PRECIOUS METAL-CARRYING MATERIAL AND USE THEREOF

专利摘要:

公开号:BE1020386A3
申请号:E201200536
申请日:2012-08-09
公开日:2013-08-06
发明作者:Tomonori Kawabata；Mitsuaki Kumazawa；Tetsuro Yonemoto
申请人:Sumitomo Chemical Co；
IPC主号:

专利说明:

DESCRIPTION
Title of the Invention PREMIUM METAL-CARRYING MATERIAL AND USE THEREOF Technical field
The present invention relates to a noble metal-containing carrier material, and to its use.
State of the art
Alkylene oxides such as propylene oxide are usually produced by using a noble metal-containing support material as a first catalyst to obtain hydrogen peroxide from hydrogen and oxygen, and then by using a titanium silicate as a second catalyst in the same reactor for the reaction of the obtained hydrogen peroxide with an olefin such as propylene. The term "titanium silicate" refers to a compound in which some of the silicon atoms in a silica backbone have been replaced by titanium atoms.
Patent literature 1 describes palladium tetramine chloride supported on activated carbon as a noble metal-containing support material that can serve as the first catalyst. It further discloses a process for producing propylene oxide from oxygen, hydrogen, and propylene using a titanium silicate as the second catalyst.
Reference list
Patent literature [Patent literature 1] JP 2008-201776 A Summary of the invention Technical problem
It is an object of this invention to provide a new catalyst that produces a high yield of alkylene oxide when used in combination with a titanium silicate-containing catalyst in a reaction for the production of an alkylene oxide from oxygen, hydrogen and an olefin.
Solution for the problem
The invention is the result of much careful research by the present inventors regarding the production method as described above.
Specifically, the present invention relates to the following.
A noble metal-containing support material comprising a noble metal γ and a support as component components, wherein the ratio of a desorbed amount of hydrogen to an adsorbed amount of carbon monoxide is in the range of 0.01 to 0.40 (will also be referred to below) as "the current noble metal bearing material").
Here, the "desorbed amount of hydrogen" is a value calculated from the sum of the peak areas of the desorbed component with a maximum value in the range of 50 ° C to 350 ° C, as observed in accordance with a temperature-programmed desorption method with a program speed of 10 ° C / min, with respect to a sample kept under vacuum at 50 ° C for 8 hours or more, under a normal pressure of a helium gas stream at 50 ° C for 1 hour, then under normal pressure of a hydrogen gas stream at 50 ° C for 2 hours, and further kept under normal pressure of a helium gas stream at 50 ° C for 1 hour, and thereby obtained, while the "adsorbed amount of carbon monoxide" is the value "that is obtained by a metal surface measurement based on the carbon monoxide pulse method, from a sample that is kept under vacuum at 50 ° C for 8 hours or more, then under a normal pressure of a helium gas stream at 50 ° C for 1 hour, under a normal pressure of a hydrogen gas stream at 50 ° C for 2 hours, and furthermore a normal pressure of a helium gas stream is maintained at 50 ° C for 1 hour and is thereby obtained.
2. The noble metal-containing support material as described in 1, wherein the peaks of the desorbed component having a maximum value in the range of 50 ° C to 350 ° C as observed in a temperature-programmed desorption process with a program speed of 10 ° C / min have no maximum value between 50 ° C and 210 ° C, and have one or more maximum values in the range of 210 ° C to 350 ° C.
3. A noble metal-containing support material as described in 1. or 2., which is obtained by contacting a support with a noble metal dispersion comprising noble metal particles, so that a 0.5% by weight aqueous dispersion of noble metal particles has a streaming potential in the range from 10 peq / g to 50 peq / g.
4. The noble metal-containing support material as described in 3., wherein the noble metal particles are obtained by mixing an acid-containing solution with either (a) a precursor of a noble metal particle such that a 0.5% by weight aqueous dispersion has a streaming potential in the range of 50 peq / g to 300 peq / g, or (b) a mixture of a precursor of a precious metal particle with a solvent.
The noble metal-containing support material * as described in 4. wherein the acid is hydrochloric acid.
6. The noble metal-containing support material as described in 3., wherein the noble metal particles are obtained using an oxidizing agent for the partial oxidation of either (a) a precursor of a noble metal particle such that a 0.5% by weight aqueous dispersion has a streaming potential in the range from 50 peq / g to 300 peq / g, or (b) a mixture of a precursor of a precious metal particle with a solvent.
7. The noble metal-containing support material as described in 6., wherein the oxidizing agent is oxygen and / or sodium nitrite.
The noble metal-containing support material as described in any of 1 to 7. wherein the noble metal is palladium.
The noble metal-containing support material as described in any of 1 to 8, wherein the support comprises at least one species selected from a group consisting of activated carbon, alumina, titanium oxide and zirconium oxide.
A method for producing hydrogen peroxide, comprising a step of reacting oxygen with hydrogen in the presence of a noble metal-containing support material as described in any of 1 to 9. (hereinafter, this will be referred to as "the current method for producing hydrogen peroxide ").
A method for producing alkylene oxide comprising a step of reacting oxygen, hydrogen, and an olefin in the presence of a noble metal-containing support material as described in any of 1 to 9. and a titanium silicate-containing catalyst (hereinafter referred to as also be referred to as "the current method for producing alkylene oxide"). 12. The method as described in 11. wherein the olefin is propylene.
The method as described in 11 or 12., wherein the titanium silicate-containing catalyst comprises titanium silicate particles with an X-ray diffraction pattern pattern with peaks at the positions indicated by the lattice distances d / A of 12.4 ± 0.8 10.8 ± 0.5 9.0 ± 0.3 6.0 ± 0.3 3.9 ± 0.3 and 3.4 ± 0.1.
The method as described in any of 11 to 13. wherein the step is a step of reacting oxygen, hydrogen and an olefin in the presence of a solvent.
The method as described in 14. wherein the solvent is an organic solvent.
The method as described in 14. wherein the solvent is a mixed solvent comprising an organic solvent and water.
17. The method as described in 15. or 16., wherein the organic solvent is acetonitrile.
Advantageous Effects Of The Invention
The present invention can provide a new catalyst capable of producing a high alkylene oxide yield when used in combination with a titanium silicate-containing catalyst in a reaction vessel for the production of an alkylene oxide from oxygen, hydrogen and olefin.
Brief description of the drawings
FIG. 1 a) is a graph showing the hydrogen desorption spectrum of the current noble metal-containing support material (A), and FIG. 1 b) illustrates a method for calculating a desorbed amount of hydrogen.
FIG. 2 a) is a graph showing the hydrogen desorption spectrum of the reference noble metal-containing support material (1), and FIG. 2 b) illustrates a method for calculating a desorbed amount of hydrogen.
Description of the Embodiments
The present noble metal-containing support material comprises a noble metal and a support as component components, wherein the ratio (MH2 / MCO) of a desorbed amount of hydrogen (MH2) to an adsorbed amount of carbon monoxide (MCO) is in the range of 0.01 to 0.40.
The "desorbed amount of hydrogen (MH2)" is the value calculated from the sum of the peak areas of the desorbed component with a maximum value in the range of 50 ° C to 350 ° C, as observed in accordance with a temperature-programmed desorption method with a program speed of 10 ° C / min, with respect to a sample kept under vacuum at 50 ° C for 8 hours or more, under a normal pressure of a helium gas stream at 50 ° C for 1 hour, then under a normal pressure of a hydrogen gas stream at 50 ° C for 2 hours, and further kept under normal pressure of a helium gas stream at 50 ° C for 1 hour, and thereby obtained.
The "desorbed amount of hydrogen (MH2)" can be calculated from the hydrogen desorption spectrum obtained with a temperature-programmed desorption method with the following equipment and measurement conditions.
• Detector: TPD-1-ATw, fully automatic thermal desorption spectrometer by Bel Japan, Ine.
• Gas flow: 50 ml / min i • Sample weight: about 0.15 g • Pre-treatment: Vacuum treatment at 50 ° C for 8 hours, followed by a treatment under normal pressure of a helium gas stream at 50 ° C for 1 hour, a normal pressure of a hydrogen gas stream at 50 ° C for 2 hours and a normal pressure of a helium gas stream at 50 ° C for 1 hour, in this order.
• Conditions Measurement: Hydrogen desorption spectrum by a temperature-programmed desorption process under normal pressure of a helium gas stream, with a program speed of 10 ° C / min.
• Detection: Quadrupool MS
• detected fragment: m / z = 2 • Calculation of MH2: The sum of the peak areas for the desorbed components with a maximum in the range of 50 ° C to 350 ° C was calculated.
For example, the upper limit of MH2 may be 0.10 cm 3 / g or less, and preferably 0.08 cm 3 / g or less, while the lower limit of MH 2 may be 0.01 cm 3 / g or more, and preferably 0.03 cm 3. / g or more.
The "adsorbed amount of carbon monoxide (MCO)" is a value measured according to a metal surface measurement based on the carbon monoxide pulse method, of a sample that is kept under vacuum at 50 ° C for 8 hours or more, kept under a normal pressure of a helium gas stream at 50 ° C for 1 hour, then under a normal pressure of a hydrogen gas stream at 50 ° C for 2 hours, and further kept under a normal pressure of a helium gas stream at 50 ° C for 1 hour, and thereby obtained. ,
The "adsorbed amount of carbon monoxide (MCO)" can be calculated after measurement with the following equipment and measurement conditions.
• Detector: BEL-METAL-3SP metal dispersion rate measuring instrument by Bel Japan, Ine.
• Gas flow: 50 ml / min • Sample weight: approximately 0.15 g • Pre-treatment: Vacuum treatment at 50 ° C for 8 hours, followed by treatment under normal pressure of a helium gas stream at 50 ° C for 1 hour, normal pressure of a hydrogen gas stream at 50 ° C for 2 hours, and a normal pressure of a helium gas stream at. 50 ° C for 1 hour, in this order.
• Conditions: Carbon monoxide pulse injection under normal pressure of a helium gas stream, measurement of carbon monoxide adsorption.
The upper limit of MCO may be, for example, 1.00 cm 3 / g or less and preferably 0.50 cm 3 / g or less, while the lower limit of MCO may be 0.10 cm 3 / g or more, and preferably 0.20 cm 3 / g. can be g or more.
The noble metal-containing support material according to the present embodiment can have an MH2 / MCO ratio in the range of 0.01 to 0.40, but preferably the peaks of the desorbed component have a maximum value in the range of 50 ° C to 350 ° C as observed in the temperature programmed desorption process with the program speed of 10 ° C / min no maximum value between 50 ° C and 210 ° C, and they have one or more maximum values in the range of 210 ° C to 350 ° C.
Examples of the support include oxides such as silicon oxide, aluminum oxide, titanium oxide, zirconium oxide and niobium oxide, hydroxides such as niobic acid, zirconic acid, tungstic acid and titanium acid, carbon, and mixtures of the foregoing. Activated carbon, aluminum oxide, titanium oxide and zirconium oxide are preferred examples.
The noble metal content may be, for example, 0.00001 parts by weight or more to 100 parts by weight of the current noble metal-containing support material, with 0.01 parts by weight or more being preferred, with 0.1 parts by weight or more being more preferred, wherein a range of 0.01 parts by weight to 20 parts by weight is even more preferred, and wherein a range of 0.1 parts by weight to 5 parts by weight is particularly preferred.
The noble metal-containing support material can be obtained, for example, by contacting a support with a noble metal dispersion containing noble metal particles.
As a general range, the noble metal particles have an average particle size in the range of 1 nm to 200 nm, and preferably contain an iron component in the range of 0.1% to 3% by weight relative to the total. More preferably, the streaming potential of the noble metal particles as a 0.5% by weight aqueous dispersion is in the range of 10 peq / g to 50 peq / g. Precious metal particles that meet this condition have a shorter lifespan but exhibit superior catalytic activity. Their streaming potential is measured using a streaming potential meter (PCD-03-PH by Mutec, Germany as a specific example).
In another embodiment of the noble metal particles, parts of the surface of the noble metal particles may form oxides and / or hydroxides, and preferably at least about 25 ° A of the surfaces of the noble metal particles are covered by oxides and / or hydroxides.
The "noble metal dispersion" used for the production of the noble metal-containing support material can be obtained, for example, by treatment (a) of a precursor of a noble metal particle, or (b) a mixture of a precursor of a noble metal particle and a solvent, by one of the following methods A or B.
Method A: Mixing component (a) or (b) with an acid-containing solution.
Method B: partial oxidation of component (a) or (b) with an oxidizing agent to cover the particle surfaces with an oxide and / or hydroxide.
The "precursor of a noble metal particle" can be obtained by reducing a noble metal salt (preferably both a noble metal salt and an iron salt) in water, an organic solvent or a mixture of both, in the presence of a reducing agent.
A preferred "precious metal particle precursor" has a streaming potential in the range of 50 to 300 peq / g as a 0.5 weight% aqueous dispersion, because a precious metal particle precursor that meets this condition, a longer life and superior controllability will show.
The "noble metal salt" can be, for example, a chloride, nitrate, sulfate, acetate or organic acid salt of palladium, platinum, ruthenium, rhodium, iridium, osmium or gold, or a combination of the foregoing. Specific examples include gold chloride, palladium chloride, palladium nitrate, palladium acetate, and ruthenium chloride, as well as combinations thereof.
i
Examples of "iron salts" include organic acid salts of iron such as iron acetate, inorganic salts of iron such as iron chloride, iron nitrate and iron sulfate, and combinations of the foregoing.
Examples of an "organic solvent" include alcohols such as 4-hydroxy-4-methyl-2-pentanone and tetrahydrofurfuryl alcohol, ethers such as propylene glycol monomethyl ether and diethylene glycol monoethyl ether, and combinations of the foregoing.
Examples of the "reducing agent" include iron sulfate, iron ammonium sulfate, iron oxalate, trisodium citrate, tartaric acid, L (+) ascorbic acid, sodium borohydride, and sodium hypophosphite. Preferred examples include iron sulfate and iron ammonium sulfate.
The following is a detailed explanation of a method in which both a precursor of a noble metal particle and a mixture of a precursor of a noble metal particle with a solvent prepared in the above-described manner (a) are mixed with an acid-containing solution (referred to below is also referred to as "method A"), or (b) is partially oxidized with an oxidizing agent (also referred to below as "method B").
In method A, the acid may be, for example, an inorganic acid such as nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, perchloric acid, boric acid or fluorosulfonic acid, an organic acid such as formic acid, acetic acid, propionic acid or tartaric acid, or a combination of the foregoing. Preferred examples are hydrochloric acid, phosphoric acid and organic acids.
The acid is usually used in the form of a solution prepared by dissolving in a solvent, where "solvent" refers to water, or an alcohol, ether, ester or ketone, or any of the foregoing, with water being preferred.
The concentration of the acid in the solution can be between 0.01% by weight and 99% by weight, with a preferred range of between 0.1% by weight and 50% by weight.
Both the precursor of a noble metal particle or a mixture of the precursor of a noble metal particle and the solvent are mixed with the acid-containing solution at a temperature in the range of, for example, 0 ° C to 100 ° C, and preferably 20 ° C to 80 ° C . The duration for mixing the precursor of a noble metal particle or a mixture of the precursor of a noble metal particle and the solvent with the acid-containing solution can be in the range of 0.1 hours to 240 hours, and preferably between 0.5 hours and 24 hours.
For Method B, the "oxidizing agent" may be, for example, oxygen, hydrogen peroxide, ozone, a permanganate, an alkali metal or alkaline earth metal nitrate or nitrite, or any combination thereof. It is preferably a combination of oxygen and an alkali metal or alkaline earth metal nitrite. It is preferably a combination of oxygen and sodium nitrite.
The oxidizing agent will be added in varying amounts depending on the type, but is preferably an amount whereby some parts of the noble metal particle surface (with at least about 25% most desired) being converted to metal oxides and / or hydroxides. More particularly, the oxidizing agent can be added in the range of 0.01 mole to 0.2 mole, and preferably in the range of 0.02 mole to 0.15 mole, to 1 mole of the total of metals. The oxidizing conditions are not particularly limited, and may include heating and stirring, if necessary. ,
The method for producing a noble metal-containing carrier material can be, for example, a conventional loading method by impregnation, dipping, wet adsorption, ion exchange or solvent evaporation, or any combination of the foregoing.
The solvents used for such wet loading processes can be, for example, aqueous solvents, non-aqueous solvents or mixtures thereof. Such solvents are preferably those that can maintain stability as uniform colloidal solutions.
Examples of such solvents include aqueous solvents such as purified water, ion exchange water, tap water, and industrial water; alcohols such as methanol, ethanol, isopropanol, hexanol and octanol; hydrocarbon solvents such as pentane, petroleum ether, hexane, cyclohexane, benzene, toluene and xylene; ketones such as acetone, ethyl methyl ketone, cyclohexanone and acetophenone; halogenated hydrocarbon-based solvents such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, tetrachloroethane, propyl chloride, chlorobenzene, dichlorobenzene and methyl fluoride; esters such as methyl acetate, ethyl acetate and propyl acetate; ethers such as diethyl ether, dipropyl ether, tetrahydrofuran and dioxane; nitriles such as acetonitrile and propionitrile; organic acids such as acetic acid and propionic acid; amines such as dimethylamine, trimethylamine, triethylamine, propylamine and aniline; and amides such as dimethylformamide, diethylformamide and dimethylacetamide, with water being preferred. These solvents can be used alone or in any desired combination.
There are no special limitations on the amount of solvent used, but it is preferably an amount sufficient for thorough contact with the entire support. A greatly excessive amount of solvent will require a long time to dry up, but conversely, too little solvent will not readily allow a uniform dispersion on the support.
The system used for loading with a wet loading method can be based on stationary loading, stirring, circulating a solution, solvent refluxing or the like, or a combination thereof.
The noble metal-containing support material can be obtained in the manner described above. When an excess of solvent or noble metal-containing solution is present with the resulting noble metal-containing material, it will usually be desirable to separate and remove the excess portion, or to evaporate the excess solvent or the noble metal-containing solution and to evaporate the current noble metal-containing support material. regain.
The method for achieving this can be an ordinary solid-liquid separation process with steps such as filtration, centrifugal separation and decantation. Evaporation of the excess solvent or the noble metal-containing solution can be carried out, for example, by natural evaporation, evaporation under reduced pressure, ventilation evaporation or bubble evaporation for air circulation.
The noble metal-containing support material obtained as described above can be used as such, or if necessary, can be subjected to normal heat treatment in an oven or the like, or heated with an inert gas, reduced with a reducing gas such as hydrogen, carbon monoxide, methane ethane, propane, butane, ethylene, propylene, butene or butadiene, oxidized with an agent such as air, or treated with any combination of the above suitable pre-treatment or activating treatment, for use as a catalyst for the reaction.
The noble metal-containing support material as a catalyst can be used as a catalyst for the production of hydrogen peroxide from oxygen and hydrogen. It can also be used as a catalyst for the production of an alkylene oxide from hydrogen, oxygen and an olefin. The noble metal-containing support material as a catalyst can be used in conjunction with a titanium silicate-containing catalyst (either in integrated form or separately) to obtain a high yield of an alkylene oxide from oxygen, hydrogen, and an olefin.
The noble metal-containing support material as a catalyst also has a high selectivity for alkylene oxides and a low selectivity for alkanes, based on hydrogen (i.e., the product has a low content of by-products such as propane).
A process for producing hydrogen peroxide according to this embodiment will now be described. The process for the preparation of hydrogen peroxide comprises a step of reacting oxygen with hydrogen in the presence of the current noble metal-containing support material. "*
Oxygen and hydrogen are required for this step and can be obtained from any source. For oxygen, high-purity oxygen gas produced by cryogenic separation, oxygen gas produced by an economical pressure exchange process or air can be used.
The molar ratio of hydrogen and oxygen used in step (H 2: C> 2) can be in the range of 1:50 to 50: 1, with for example 1:10 to 10:01 being a preferred range, and where 1: 5 to 5: 1 is a more preferred range.
An inert gas can also be used in the oxygen and hydrogen step for dilution. Examples of suitable inert gases include helium, argon, nitrogen, methane, ethane, propane, and carbon dioxide, with nitrogen being preferred. By using an inert gas in the reactor, the oxygen and hydrogen levels in the reaction mixture can advantageously be maintained within the explosion limit.
The process can also be carried out in the presence of a solvent. The solvent can be water, an organic solvent or a mixture of both. Examples of organic solvents include alcohol solvents with 1 to 12 carbon atoms, such as methanol, ethanol, isopropyl alcohol and glycerol, ketone solvents with 3 to 12 carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexenone, nitrile solvents with 2 to 12 12 carbon atoms such as acetonitrile, propionitrile, isobutyronitrile, butyronitrile and benzonitrile, ether solvents such as diethyl ether, tetrahydrofuran and propylene glycol dimethyl ether, aliphatic hydrocarbon solvents with 5 to 12 carbon atoms such as pentane, cyclopentane, hexane, cyclohexide, chloroform, chloroform, ethylene, chloroform, aromatic hydrocarbon solvents with 6 to 12 carbon atoms such as benzene, toluene, xylene and chlorobenzene, ester solvents such as ethyl acetate, butyl acetate and propylene glycol diacetate, and any mixture of the foregoing. Preferably only a nitrile solvent or alcohol solvent is used, or a mixture of a nitrile solvent or alcohol solvent with water. A preferred example is a mixture of acetonitrile and methanol with water.
When a mixture of water and an organic solvent is used, the water / organic solvent ratio (weight ratio) can be in the range of 90:10 to 0.01: 99.99, for example with a preferred range of 50:50 to 0.1: 99, 9.
The process for the preparation of hydrogen peroxide can be carried out in any desired mode, such as continuous flow, semi-batch or batch mode, although continuous flow is preferred. The current noble metal-containing support material can also be used in a suspension or a fixed bed.
The reaction temperature for the production of hydrogen peroxide can be in the range of 0 ° C to 100 ° C, for example with a preferred range of 20 ° C to 60 ° C. The lower limit for the reaction pressure for the production of hydrogen peroxide can be at least 0.1 MPa, and preferably 1 MPa, while the upper limit can be 20 MPa and preferably 10 MPa.
It will often be advantageous to carry out the process for producing hydrogen peroxide in the presence of an acid.
An acid used in the present method for producing hydrogen peroxide can be an inorganic acid, such as nitric acid, sulfuric acid, phosphoric acid, hydrochloric acid, or hydrobromic acid, or an organic acid such as pyrophoric acid or acetic acid.
The amount of acid used may be in the range of 0.1 ppm to 1000 ppm to 1 part by weight of the reaction mixture, with a preferred range between 0.1 ppm and 100 ppm, and a more preferred preferred range of between 1 ppm up to 10 ppm.
A method for producing an ethylene oxide according to this embodiment will now be described. Specifically, the process comprises a step of reacting oxygen, hydrogen, and an olefin in the presence of a noble metal-containing support material and a titanium silicate-containing catalyst.
Examples of titanium silicate-containing catalysts include catalysts referred to as titanium silicate particles. The titanium silicate particles have a structure with a tetra-coordinated Ti atom in which the ultraviolet and visible absorption spectrum in the wavelength range of 200 nm to 400 nm has an absorption peak maximum in the wavelength range of 210 nm to 230 nm (see Chemical Communications 1026 1027 (2002) Fig. 2 (d), (e), for example). The ultraviolet and visible absorption spectrum can be measured by the diffuse reflection method, using an ultraviolet and visible light spectrophotometer equipped with a reflection sensor.
When the titanium silicate particles are to be used, for example as a catalyst in a process for producing hydrogen peroxide by reacting oxygen and hydrogen in the presence of the present noble metal-containing support material (i.e., in the current process for producing hydrogen peroxide), titanium silicate particles can be were previously contacted with hydrogen peroxide. The hydrogen peroxide provided for the contact may have a concentration in the range of 0.0001% by weight to 50% by weight, for example.
Examples of titanium silicate particles include the following titanium silicates listed as 1 to 7.
Crystalline titanium silicates with pores formed by 10-membered oxygen rings: TS-1 with an MFI structure (e.g. US 4,410,501 B) TS-2 with an MEL structure (e.g. Journal of Catalysis 130, 440-446, (1991 )), Ti-ZSM-48 with an MRE structure (e.g. Zeolites 15, 164-170, (1995)) and Ti-FER with an FER structure (e.g. Journal of Materials Chemistry 8, 1685-1686 (1998)) , based on the IZA (International Zeolite Association) structure code.
2. Crystalline titanium silicates with pores formed by 12-membered oxygen rings:
Ti-Beta with a BEA structure (e.g. Journal of Catalysis 199.41-47 (2001)), Ti-ZSM-12 with an MTW structure (e.g. Zeolite 15, 236-242, (1995)), Ti-MOR with an MOR structure (e.g., The Journal of Physical Chemistry B 102, 9297-9303 (1998)), Ti-ITQ-7 with an ISV structure (e.g., Chemical Communications 761-762, (2000)), Ti-MCM -68 with an MSE structure (e.g., Chemical Communications 6224-6226 (2008)) and Ti-MWW with an MWW structure (e.g., Chemistry Letters 774-775, (2000)).
3. Crystalline titanium silicates with pores formed by 14-membered oxygen rings:
Ti-UTD-1 with a DON structure (e.g., Studies in Surface Science and Catalysis 15, 519-525, (1995)).
4. Layered titanium silicates with pores formed by 10-membered oxygen rings:
Ti-ITQ-6 (for example, Angewandte Chemie International Edition 39, 1499-1501, (2000)).
5. Layered titanium silicates with pores formed by 12-membered oxygen rings:
Ti-MVWV precursors (e.g. EP 1731515 A1), Ti-YNU-1 ^ (e.g. Angewandte Chemie International Edition 43, 236-240 (2004)), Ti-MCM-36 (e.g. Catalysis Letters 113, 160 -164 (2007) ), Ti-MCM-56 (e.g., Microporous and Mesoporous Materials 113, 435-444 (2008)).
6. Mesoporous titanium silicates:
Ti-MCM-41 (e.g., Microporous Materials 10, 259-271, (1997)), Ti-MCM-48 (e.g., Chemical Communications 145-146, (1996)), Ti-SBA-15 (e.g., Chemistry of Materials 14 , 1657-1664, (2002)).
7. Silylated titanium silicates:
Compounds that are silylated are from the above titanium silicates such as silylated Ti-MWW.
As used herein, "pore" refers to an opening formed by Si-0 bonds or Ti-0 bonds. The pores can be, for example, half-cup pores, known as "side pockets" (i.e., it is not necessary that they penetrate the primary particles of the titanium silicate).
The expression "not less than an X-membered oxygen ring" (X being an integer) will be used below to indicate that at least X oxygen atoms form the ring structure either (a) on a cross-section on the narrowest part of the pore or (b) at the entrance of the pore. In general, titanium silicate particles can be confirmed to have pores that are no smaller than an X-membered oxygen ring by analysis of the X-ray diffraction pattern, and if the structure is known, it can be easily confirmed by comparison with the X-ray diffraction pattern.
"Layered titanium silicate" is a term that includes all titanium silicates with a layered structure, such as layered precursors of crystalline titanium silicates or titanium silicates that result from the expansion between layers of crystalline titanium silicates. A layered structure can be confirmed with an electron microscope or by analyzing the X-ray diffraction pattern. "Layered precursor" is a titanium silicate that forms a crystalline titanium silicate by treatment such as dehydrating condensation. That the layered titanium silicate has pores that are no smaller than a 12-membered oxygen ring can be easily confirmed by analysis of the structure of the corresponding crystalline titanium silicate.
"Mesoporous titanium silicate" is a term comprising all titanium silicates with regular mesopores. "Regular mesopores" indicates a structure with a regularly recurring arrangement of mesopores. A mesopore is a pore with a pore size of 2 nm to 10 nm.
The term "silylated titanium silicate" refers to a compound obtained by treating each of said titanium silicates listed as 1 to 4. above, using a silylating agent. Examples of silylating agents include 1,1,1,3,3,3-hexamethyldisilazane and trimethylchlorosilane (as described in EP 1488853 A1, for example). The silylated titanium silicate can also be mixed with a hydrogen peroxide solution (this can be referred to as "hydrogen peroxide treatment"). The concentration of the hydrogen peroxide solution used for such hydrogen peroxide treatment can be in the range of 0.0001% by weight to 50% by weight for example. The solvent of the hydrogen peroxide solution can be, for example, water or the same solvent used in the present process for producing alkylene oxide. The temperature for the hydrogen peroxide treatment can be in the range of 0 ° C to 100 ° C, for example, with a preferred range of 0 ° C to 60 ° C. The mixing time will depend on the hydrogen peroxide concentration, but is generally in the range of 10 minutes to 10 hours, the preferred range being 1 hour to 3 hours.
The preferred type of titanium silicate particles consists of titanium silicate with pores no smaller than a 12-membered oxygen ring. The titanium silicate can be either crystalline or layered titanium silicate. Titanium silicate with pores no smaller than a 12-membered oxygen ring specifically include Ti-MVWV and Ti-MWW precursors.
The titanium silicate particles with pores not smaller than a 12-membered oxygen ring exhibit most preferably an X-ray diffraction pattern with peaks at the following positions, as lattice distances.
<Positions of peaks in X-ray diffraction pattern as lattice distances (lattice distance d / angstrom)> 12.4 ± 0.8, 10.8 ± 0.5, 9.0 ± 0.3, 6.0 ± 0.3, 3.9 ± 0.3, 3.4 ± 0.1
The X-ray diffraction pattern can be measured in the following manner.
A conventional commercially available X-ray diffraction apparatus with copper K-alpha radiation as a line source can be used. For example, the titanium silicate particle can be analyzed using a RINT2500V X-ray diffraction device from Rigaku Corp.
(Measurement conditions)
• Output: 40 kV - 300 mA
• Scanning zone: 2Θ = 0.75 to 20 ° • Scanning speed: 1 ° / min
Specific examples of titanium silicate particles that exhibit such an X-ray diffraction pattern (with peaks at said positions representing lattice distances) include Ti-MWW precursors (e.g. those mentioned in JP 2005-262.164 A), Ti-YNU-1 (e.g. those mentioned in Angewandte Chemie International Edition 43, 236-240 (2004)), Ti-MWW compounds that are crystalline titanium silicates with a MWW structure based on the IZA (International Zeolite Association) structure code (for example, those mentioned in JP 2003-327425 A) and Ti-MCM -68 compounds that are crystalline titanium silicates with an MSE structure based on the IZA structure code (for example, those mentioned in JP 2.008-50.186 A).
A Ti-MWW precursor is a titanium silicate that has a layered structure and forms Ti-MWW through dehydrating condensation. The dehydrating condensation will usually be carried out by heating the Ti-MWW precursor at a temperature higher than 200 ° C and not higher than 1000 ° C, and preferably between 300 ° C and 650 ° C. During the production process, the Ti-MWW precursor can also be treated with a structural control agent, as described below. The resulting Ti-MWW precursor can then be subjected to repeated treatments with a structural control agent. The Ti-MWW precursors thus obtained also fall under the term "Ti-MWW precursor" for the purpose of the invention.
Such a Ti-MWW precursor can be used as a catalyst for various forms of oxidation reactions. The molar ratio of silicon and nitrogen (Si / N ratio) in the Ti-MWW precursor can be in the range of 5 to 100, for example, with 10 to 20 being the preferred range.
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The following are specific methods for producing Ti-MWW precursors.
(1) First method: a method comprising a step of heating a mixture containing a structural control agent, a compound containing an element from Group 13 of the Periodic Table (hereinafter referred to as "Group 13 element-containing compound"), a silicon-containing compound, a titanium-containing compound and water (hereinafter referred to as "step (1-1)"), and a step of mixing the layered compound obtained in step (1-1) with an acid.
(2) Second method: a method comprising a step of heating a mixture containing a structural control agent, a Group 13 element-containing compound, a silicon-containing compound and water (hereinafter referred to as "step (2-1)") ), and a step of mixing the layered compound obtained in step (2-1) with a titanium-containing compound and an acid.
(3) Third method: a method comprising a step of heating a mixture containing a structural control agent, a Group 13 element-containing compound, a silicon-containing compound, a titanium-containing compound and water (hereinafter the "step (3-1) "), and a step of mixing the layered compound obtained in step (3-1) with a titanium-containing compound and an acid.
(4) Fourth method: a method comprising a step of first obtaining a layered borosilicate by heating a mixture comprising a structural control agent, a Group 13 element-containing compound, a silicon-containing compound and water (preferably after removal of structural control agent by contact with an acid or the like), annealing to obtain a B-MWW, subsequently removing boron from the B-MWW with an acid or the like, and then combining it with a structural control agent, a titanium-containing compound and water, heating the resulting mixture to obtain a layered compound, and then contacting this compound with about 6 M nitric acid (see: Chemical Communication 1026-1027 (2002), for example).
Ti-MWW precursors obtained by any of the first to fourth methods are preferably subjected to a further treatment with a structural control agent to adjust the molar ratio of silicon and nitrogen (Si / N ratio) to the prescribed values (e.g., values in the range of 10 to 20).
For example, the titanium silicate-containing catalyst can be mixed with the structural control agent and water in an airtight pressure-resistant container such as an autoclave, wherein the container is sealed and the contents can rest or be stirred, under heat and pressure, to obtain a liquid mixture of from which the solid product is separated by filtration, centrifugal separation or the like. Alternatively, the components can be mixed in a glass flask under atmospheric pressure, with or without stirring, and the solid product can be separated from the resulting liquid mixture by filtration, centrifugal separation or the like.
The titanium silicate-containing catalyst can also be flushed with, for example, water. The rinsing can be performed with a suitable adjustment of the amount of washing solution, or while the pH of the rinsing filtrate is being monitored. The rinsed product can then be dried by blow-drying, drying under reduced pressure, vacuum freeze-drying or the like in a temperature range of 0 ° C to 200 ° C, for example, until no further weight loss occurs,
The temperature of the mixing procedure can be in the range of 0 ° C to 250 ° C, for example, with a preferred range of between 20 ° C and 200 ° C, and a more preferred range of between 50 ° C and 180 ° C.
The duration of the mixing procedure can be in a range of 1 hour and 720 hours, for example, with two hours to 720 hours being preferred, with 4 hours to 720 hours being more preferred, and 8 hours to 720 hours being particularly preferred has. The pressure during mixing is not particularly limited, and can be an overpressure from 0 MPa to 10 MPa, for example.
The amount of titanium-containing compound used in the above-described methods may be in the range of 0.001 to 1 part by weight, for example, as the weight of titanium atoms in the titanium-containing compound relative to 1 part by weight of the layered compound obtained with a range of 0.01 to 0.5 parts by weight being preferred. "*
The acid used in the aforementioned processes may be, for example, an inorganic acid such as nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, boric acid or fluorosulfonic acid, an organic acid such as formic acid, acetic acid, propionic acid or tartaric acid, or any combination of the aforementioned . Preferably, the acid comprises at least one inorganic acid with a higher oxidation-reduction potential than tetravalent titanium. The "inorganic acid with a higher oxidation-reduction potential than tetravalent titanium" can be nitric acid, perchloric acid, fluorosulfonic acid, a combination of nitric acid and sulfuric acid, or a combination of nitric acid and boric acid, for example.
The acid will usually be used in the form of a solution prepared by dissolving in a solvent. Here, "solvent" refers to, for example, water or an alcohol, ether, ester or ketone solvent, or any mixture of the aforementioned, with water being preferred. The concentration of the acid in the solution can be between 0.01 mol / l and 20 mol / l, for example. When an inorganic acid is used, its concentration is preferably in the range of 1 mol / l to 5 mol / l.
The "Element 13 of the Periodic System" used in the process for producing a Ti-MWW precursor may be present in a boron-containing compound, aluminum-containing compound or gallium-containing compound, for example, among which boron-containing compounds are preferred.
Examples of boron-containing compounds include boric acid, boric acid salts, boron oxide, boron halides and trialkyl boron compounds with alkyl groups of 1 to 4 coolant atoms, with boric acid being preferred. Sodium aluminate is an example of an aluminum-containing compound. Gallium oxide is an example of a gallium-containing compound.
The amount of Group 13 element-containing compound used in the process for producing a Ti-MWW precursor can be in the range of 0.01 mole to 10 mole to 1 mole of silicon in the silicon-containing compound, with a preferred range from 0.1 mol to 5 mol.
Examples of the "silicon-containing compound" that can be used in the process for producing a Ti-MWW precursor include silica, silicates, silica, silicon halides, tetraalkyl orthosilicates, and colloidal silicon with preferred examples of orthosilicic acid, metasilicic acid, metadisilicic acid. Examples of silicates include alkali metal silicates such as sodium silicate and potassium silicate and alkaline earth metal silicates such as calcium silicate and magnesium silicate.
Examples of silicon oxides include crystalline silica such as quartz, and amorphous silica such as fumed silica, with fumed silica being a preferred example. The "fumed silica" can be any commercially available product with a BET specific surface area of 50 m2 / g to 380 m2 / g. The controllability is facilitated if the BET specific surface area is 50 m2 / g to 200 m2 / g, while the solubility in aqueous solutions is improved if the BET specific surface area is 100 m2 / g to 380 m2 / g.
Examples of silicon halides are silicon tetrachloride and silicon tetrafluoride.
Examples of tetraalkyl orthosilicates are tetramethyl orthosilicate and tetra ethyl orthosilicate.
Examples of the "titanium-containing compound" used in the process for producing a Ti-MWW precursor include titanium alkoxides, titanates, titanium oxides, titanium halides, inorganic salts of titanium, and organic acid salts of titanium.
Examples of titanium alkoxides include titanium alkoxides with alkoxy groups of 1 to 4 carbon atoms, such as tetra-methyl orthotitanate, tetraethyl orthotitanate, tetraisopropyl orthotitanate and tetra-n-butyl orthotitanate, among which titanium alkoxides are preferred examples, and wherein tetra-n butyl orthotitanate is a particularly preferred example.
Titanium acetate is an example of an organic acid salt of titanium, while examples of inorganic acid salts of titanium include titanium nitrate, titanium sulfate, titanium phosphate and titanium perchlorate.
Titanium tetrachloride is an example of a titanium halide, and titanium dioxide is an example of a titanium oxide.
The "water" used in the process for producing a Ti-MWW precursor can be purified water, such as distilled water or ion exchange water. The amount of water used may be in the range of 5 moles to 20 moles to 1 mole of silicon in the silicon-containing compound, with a preferred range being 10 moles to 50 moles.
Examples of structural control agents for use in the process for producing a Ti-MWW precursor (i.e., structural control agents that form a zeolite with an MWW structure in the long term) include piperidine, hexamethyleneimine, N, N, N-trimethyl-1-adamantane ammonium salts (e.g., N, N, N-trimethyl-1-adamantane ammonium hydroxide, Ν, Ν, Ν-trimethyl-1-adamantane ammonium iodide and the like) and octyltrimethylammonium salts (e.g., octyltrimethylammonium hydroxide, octyltri-methylammonium bromide and the like) ( see Chemistry Letters 916-917 (2007), for example). Preferred examples include piperidine and hexamethylene imine. Each of these compounds can be used alone, or two or more of them can be used mixed in any desired ratio.
The amount of structural control agent used may be in the range of 0.1 mole to 5 mole to 1 mole of silicon in the silicon-containing compound, with a preferred range of 0.5 mole to 3 mole.
The amount of the structural control agent used to treat the Ti-MWW precursor with the structural control agent may, for example, be in the range of 0.01 to 100 parts by weight to 1 part by weight of the titanium silicate, the preferred range being 0.1 up to 10 parts by weight.
The amount of the current noble metal-containing support material used for the reaction in the present method for producing alkylene oxide will differ depending on the type and reaction conditions, but is preferably in the range of 0.01 to 20 parts by weight to 100 parts by weight of the entire mixture comprising the acetonitrile-containing solvent, the current noble metal-containing support material, the titanium silicate-containing catalyst, and the starting materials used in the reactor. A more preferred range is between 0.1 and 10 parts by weight, and even more preferred range is between 0.5 and 8 parts by weight.
An "acetonitrile-containing solvent" is a solvent containing acetonitrile, but it may also contain solvents other than acetonitrile. Examples of solvents other than acetonitrile include organic solvents other than acetonitrile and water. The acetonitrile is preferably present in a weight ratio of 50% or more in the acetonitrile-containing solvent, with a preferred range of between 60% and 100%.
The "olefin", as one of the starting materials for the reaction in the present method for producing alkylene oxide, can be an optionally substituted hydrocarbyl compound, or a compound wherein hydrogen is attached to a carbon atom that is part of an olefinic double bond.
Examples of "hydrocarbyl group" substituents include hydroxyl groups, halogen atoms, carbonyl groups, alkoxycarbonyl groups, cyano groups, and nitro groups. Examples of hydrocarbon groups include saturated hydrocarbon groups such as alkyl groups.
Specific examples of olefins include olefins with 2 to 10 carbon atoms and cycloalkenes with 4 to 10 carbon atoms.
Examples of "olefins with 2 to 10 carbon atoms" include ethylene, propylene, butene, pentene, hexene, heptene, octene, noneen, decene, 2-butene, isobutene, 2-pentene, 3-pentene, 2-hexene, 3-hexene , 4-methyl-1-pentene, 2-heptene, 3-heptene, 2-octene, 3-octene, 2-nonen, 3-nonen, 2-decene and 3-decene. Examples of "C4-10 cycloalkenes" include cyclobutene, cyclopieninene, cyclohexene, cycloheptene, cyclooctene, cyclononene and cyclodecene.
Examples of preferred olefins include olefins with 2 to 10 carbon atoms, more preferably olefins with 2 to 5 carbon atoms, with propylene being particularly preferred.
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When the olefin is propylene, it can be produced by, for example, thermal decomposition, catalytic cracking of heavy oil or catalytic conversion of methanol.
The propylene can be purified propylene, or crude propylene obtained without a purification process. The propylene preferably has a purity of at least 90 volume% and more preferably at least 95 volume%.
The propylene may contain impurities such as propane, cyclopropane, methyl acetylene, propadiene, butadiene, butanes, butenes, ethylene, ethane, methane, and hydrogen.
The propylene can be in the form of a gas or a liquid. In this case, the "liquid" can be: (i) liquid propylene alone, or (ii) a mixture of propylene oxide dissolved in an organic solvent or a mixture of an organic solvent and water. A "gas" can be: (i ) gaseous propylene alone, or (ii) a mixture of gaseous propylene with nitrogen, hydrogen gas, or another gas component.
The amount of propylene or other olefin will depend on its type and reaction conditions, but as an example, it can be 0.01 part by weight or more to 100 parts by weight of the mixture comprising the acetonitrile-containing solvent, the titanium silicate-containing catalyst and the starting materials in the reaction system, and this is more preferably 0.1 parts by weight or more.
The content of titanium atoms in the titanium silicate of the titanium silicate-containing catalyst used for the present process for producing alkylene oxide can be in the range of 0.001 to 0.1 mole to 1 mole of silicon atoms, with a preferred range of 0.005 to 0, 05 mol. The weight ratio of the noble metal to titanium silicate (weight of noble metal / weight of titanium silicate) can be in the range of 0.01% by weight to 100% by weight, and is preferably between 0.1% by weight and 20% by weight.
The solvent for the current method for producing alkylene oxide can be the same type of solvent used in the current method for producing hydrogen peroxide. It is preferably a nitrile solvent alone or a mixture of a nitrile solvent with water and it is preferably a mixture of acetonitrile and water.
When a mixture of water and an organic solvent is used, the water / organic solvent ratio (weight ratio) may be in the range of 90:10 to 0.01: 99.99, for example, with a preferred range of between 50: 50 and 0.1: 99.9.
It will often be advantageous to carry out the current process for producing alkylene oxide in the presence of a buffering agent. Here, "buffering agent" refers to a compound comprising an anion and a cation that exhibit a pH buffering action. The buffering agent is preferably dissolved in the reaction mixture, but the buffering agent can also be included in the current noble metal-bearing support material. The buffering agent can be used in an amount in the range of 0.001 mmol / kg to ¢ 100 mmol / kg, relative to 1 kg of the solvent.
The reaction temperature for the present method for producing alkylene oxide can be in the range of 0 ° C to 200 ° C, for example, with a preferred range of 40 ° C to 150 ° C. The reaction pressure (overpressure) can be 0.1 MPa or more, for example preferably an overpressure of 1 MPa or more, and even more preferably an overpressure of 10 MPa or more, and even more preferably an overpressure of 20 MPa or more.
An ammonium salt, alkylammonium salt, alkylaryl ammonium salt or the like can be added to the reaction system of the present process for producing alkylene oxide.
The addition of a buffering agent to the reaction system can prevent a reduction in the catalytic activity and further increase the catalytic activity and it will lead to an improvement in the utilization efficiency of oxygen and hydrogen. Here, "buffering agent" refers to a salt or other compound that exhibits a buffering action on the hydrogen ion concentration of the solution. Such buffers can be included in amounts up to the solubility in the mixture comprising the acetonitrile-containing solvent, the current noble metal-containing support material and the starting materials in the reaction system. A preferred range is between 0.001 mmol and 100 mmol, up to 1 kg of the mixture.
The buffering agent may be one comprising: (1) an anion selected from the group consisting of sulfate ion, hydrogen sulfate ion, carbonate ion, hydrogen carbonate ion, phosphoric acid ion, hydrogen phosphate ion, dihydrogen phosphate ion, hydrogen pyrophosphate ion, pyrophosphate ion, halide ion, nitraation, hydroxide ion and carboxylate ion with 1 to 10 carbon atoms, and (2) a cation selected from ammonium ion, alkyl ammonium ions with 1 to 20 carbon atoms, alkylarylammonium ions with 7 to 20 carbon atoms, alkali metals and alkaline earth metals.
Examples of carboxylate ions with 1 to 10 carbon atoms include acetation, formation, acetation. propionate ion, butyrate ion, valerate ion, caproate ion, caprylaate ion, capraate ion and benzoate ion.
Examples of alkyl ammonium ions with 1 to 20 carbon atoms include tetramethyl ammonium hydroxide, tetraethyl ammonium, tetra-n-propyl ammonium, tetra-n-butyl ammonium and cetyl trimethyl ammonium.
Examples of cations selected from a group consisting of alkali metals and alkaline earth metals include lithium cation, sodium cation, potassium cation, rubidium cation, cesium cation, magnesium cation, calcium cation, Strontium cation, and barium cation.
Preferred examples of buffering agents include ammonium salts. of carboxylic acids with 1 to 10 carbon atoms, such as ammonium sulphate, ammonium hydrogen sulphate, ammonium carbonate, ammonium hydrogen carbonate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, ammonium hydrogen pyrophosphate, ammonium pyrophosphate, ammonium benzoate and ammonium acetate, ammonium salts of inorganic ammonium salts such as ammonium ammonium nitrate ammonium acetate, wherein the preferred ammonium salts are ammonium benzoate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
The reaction in the process for producing alkylene oxide is preferably carried out in a continuous manner. For example, the starting materials can be continuously fed to an epoxidized reaction vessel containing an acetonitrile-containing solvent and a catalyst, and the reaction can be conducted in the epoxidized reaction vessel for the production of alkylene oxide.
When hydrogen peroxide is to be produced from oxygen and hydrogen in the reaction in the process for producing alkylene oxide, the partial pressure ratio of oxygen and hydrogen in the oxygen / hydrogen mixed gas supplied to the reactor may be in the range of oxygen : hydrogen = 1:50 to 50: 1, with a preferred range oxygen: hydrogen = 1:10 to 10: 1. A partial oxygen pressure higher than oxygen: hydrogen = 1:50 is preferred because it tends to increase the production rate of alkylene oxide, while a partial oxygen pressure of less than oxygen: hydrogen = 50: 1 is preferred because it tends to reduce the production of by-products obtained when the carbon / carbon double bonds of the olefin are reduced with hydrogen, and thus increase the selectivity to alkylene oxide.
The mixture of oxygen and hydrogen is preferably treated in the presence of a dilution gas. The "dilution gas" can be nitrogen, argon, carbon dioxide, methane, ethane, propane or the like, with nitrogen and propane being preferred, and with nitrogen being particularly preferred.
When oxygen, hydrogen, olefin and the dilution gas are to be treated as a mixture, the mixing ratio (starting from nitrogen gas as the dilution gas) is preferably a total of 4.9 volume% or less for hydrogen and the olefin, 9 volume % or less for oxygen, and nitrogen as the residual gas, or a total of 50 volume% or more for hydrogen and the olefin, 50 volume% or less for oxygen, and nitrogen gas as the residual gas.
The oxygen that is used can be oxygen or air that contains oxygen. The oxygen gas can be the product of an inexpensive pressure change process, or, if necessary, the high-purity oxygen can be produced by cryogenic separation. The oxygen supply can be in the range of 0.005 to 10 moles to 1 mole of the olefin, the preferred range being 0.05 to 5 moles.
The hydrogen can be obtained by steam conversion of a hydrocarbon. The hydrogen can have a purity of 80 volume% or more, and preferably 90 volume% or more. The hydrogen feed may be in the range of 0.05 mole to 10 mole to 1 mole of the olefin, with a preferred range of 0.05 mole to 5 mole.
Preferably, a quinoid compound is added to the reaction system for the production of hydrogen peroxide from oxygen and hydrogen by the current method for producing alkylene oxide, because this will further increase the selectivity for the alkylene oxide.
Examples of quinoid compounds include compounds represented by formula (1):
(1) wherein R 1, R 2, R 3, and R 4 each independently represent a hydrogen atom, or R 1 and R 2, or R 3 and R 4 may be joined together to form a benzene ring that may have a substituent or a naphthalene ring that may have a substituent together with carbon atoms to which R1, R2, R3 and R4 are each attached, and X and Y are each independently an oxygen atom or NH group.
Examples of compounds of formula (1) include: 1) quinone compounds (1A) of formula (1) wherein R1, R2, R3 and R4 are hydrogen, and X and Y are both oxygen atoms, 2) quinonimine compounds (1B) of formula (1) ) wherein R1, R2, R3 and R4 are hydrogen atoms, X is an oxygen atom and Y is an NH group, and 3) quinone diimine compounds (1C) of formula (1) wherein R1, R2, R3 and R4 are hydrogen atoms, and X and Y are NH groups.
Examples of other compounds represented by formula (1) include anthraquinone compounds represented by formula (2):
(2) wherein X and Y have the same definitions as for formula (1) and R5, R6, R7 and R8 are each independently hydrogen, a hydroxyl group or an alkyl group (for example, an alkyl group with 1 to 5 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group or pentyl group).
In formula (1), X and Y are preferably an oxygen atom.
Examples of compounds represented by formula (1) include quinone compounds such as benzoquinone and naphthoquinone; anthraquinones; 2-alkyl anthraquinone compounds such as 2-ethyl anthraquinone, 2-t-butyl anthraquinone, 2-amyl anthraquinone, 2-methyl anthraquinone, 2-butyl anthraquinone, 2-t-amyl anthraquinone, 2-isopropyl anthraquinone, 2-s-butyl anthraquinone; polyalkylanthraquinone compounds such as 1,3-diethylanthraquinone, 2,3-dimethylanthraquinone, 1,4-dimethylanthraquinone and 2,7-dimethylanthraquinone; polyhydroxyanthraquinone compounds such as 2,6-dihydroxyanthraquinone; p-quinoid compounds such as naphthoquinone, 1,4-phenanthraquinone; and o-quinoid compounds such as 1,2-phenanthraquinone, 3,4-phenanthraquinone and 9,10-phenanthraquinone. Preferred compounds include anthraquinone and 2-alkyl anthraquinone compounds (compounds of formula (2) wherein X and Y are an oxygen atom, R5 is an alkyl group, R6 is a hydrogen atom, and R7 and R8 are a hydrogen atom).
The amount of such quinoid compounds used in the reaction of the present method for producing alkylene oxide can be in the range of 0.001 to 500 mmol, for example, for 1 kg of solvent, with a preferred range of 0.01 mmol to 50 mmol.
The quinoid compound can be prepared by oxidizing the dihydro form of the quinoid compound in the reactor with oxygen. For example, a quinoid compound such as 9,10-anthracendiol or hydrogenated compound such as hydrochihon can be added to the liquid phase and oxidized by the oxygen in the reactor to generate a quinoid compound.
Examples of dihydroforms of quinoid compounds include compounds represented by formula (3):
(3) (wherein R 1, R 2, R 3, R 4, X and Y have the same meanings as above), which are dihydro forms of compounds represented by formula (1), and compounds represented by formula (4):
(4) (wherein X, Y, R5, R6, R7 and R8 have the same meanings as above), which are dihydro forms of compounds represented by formula (2).
Preferred compounds of this type represented by formula (3) and formula (4) include dihydro forms corresponding to the aforementioned preferred quinoid compounds. Also, X and Y in the compounds represented by formula (3) and formula (4) are preferably oxygen atoms.
f
Examples
The invention will now be further illustrated by the following examples.
<Analyzers used in the examples> (Elementanâlyse)
The content of Pd (palladium), Ti (titanium), Si (silicon) and B (boron) of the current noble metal-containing support materials, the noble metal particles and the precursors of the noble metal particles was measured by a method based on alkali fusion nitric acid solution -ICP luminescence analysis. Specifically, a 20 mg sample was measured in a platinum crucible and covered with sodium carbonate, and then fused with a gas burner. After the fusion, the contents of the platinum crucible were heated to melt with purified water and nitric acid, and after replenishing to a constant volume with purified water, the elements in the measurement solution were quantified with an ICP emission analyzer (ICPS-8000 from Shimadzu) Corp.).
The N (nitrogen) content of a sample weighed to 10-20 mg was measured with an oxygen circulating combustion / TCD detection system using a SUMIGRAPH (product of Sumitomo Chemical Analysis Center) (reaction temperature: 850 ° C, reduction temperature: 600 ° C). The separation column used was a column filled with porous polymer beads, with acetoanilide as the reference sample.
(X-ray diffraction (XRD))
The X-ray diffraction patterns of the current noble metal carrier material, the noble metal particles, and the precursors of the noble metal particles were measured with the following equipment and measurement conditions.
• Equipment: RINT2500V from Rigaku Corp.
• Line source: Cu K-alpha radiation
• Output: 40 kV-300 mA
• Scanning zone: 2Θ = 0.75 to 20 ° • Scanning speed: 1 ° / min (Ultraviolet and visible absorption spectrum (UV-Vis))
The current noble metal-containing support material, the noble metal particles and the precursors of the noble metal particles were thoroughly ground with an agate mortar and pelletized (7 mmcp) to prepare a measurement sample. The ultraviolet and visible absorption spectrum of the sample was measured with the following equipment and measurement conditions.
• Equipment: Diffuse reflection sensor (Praying Mantis, from HARRICK) • Accessories: Ultraviolet and visible spectrophotometer (V-7100 from JASCO Corp.) • Pressure: Air pressure • Measured value: reflection • Data acquisition time: 0.1 second • Bandwidth: 2 nm • Measured wavelength: 200-900 nm • Slit height: Semi-open 'r • Data acquisition interval: 1 nm.
• Baseline compensation (reference): BaS04 pellets (7 mm <p) (Measuring streaming potential of an aqueous dispersion of precious metal particles)
The "streaming potential" of the noble metal particles was measured by titration with the following equipment and measurement conditions with an aqueous dispersion of noble metal particles obtained by dispersing noble metal particles in water in an amount for a final concentration of 0.5% by weight.
• Equipment: Streaming potential meter (PCD-03-PH from Mutec) • Titrant: 0.001 N Poly-DADMAC solution from Metron.
(Average particle size measurement)
The average particle sizes of the noble metal particles and the precursor of the noble metal particles were measured with the following equipment.
• Equipment: MICROTRAC particle size distribution meter (Nikkiso Co., Ltd) (Measurement of the hydrogen desorption spectrum for the noble metal-containing carrier material)
The desorbed amount of hydrogen (MH2) from the current noble metal-containing support material was calculated based on the hydrogen desorption spectrum, measured by temperature-programmed desorption using the following equipment and measurement conditions.
• Equipment: TPD-1-ATw, fully automatic thermal desorption spectrometer by Bel Japan, Ine.
• Gas flow: 50 ml / minute (for pre-treatment, measurement and plotting calibration curves) • Sample weight: about 0.15 g • Pre-treatment: Vacuum treatment at 50 ° C for 8 hours, followed by treatment under normal pressure of a helium gas flow at 50 ° C for 1 hour, a normal pressure of a solid gas flow at 50 ° C for 2 hours and a normal pressure of a helium gas flow at 50 ° C for 1 hour, in this order.
• Measurement conditions: Hydrogen desorption spectrum by temperature-programmed desorption under normal pressure of a helium gas stream with a temperature rise of 10 ° C / min.
• Detection: Quadrupool MS
• Detected fragment: m / z = 2 • Calculation of MH2: The sum of the areas under the peaks for the desorbed component with a maximum in the range of 50 ° C to 350 ° C was calculated.
Conditions for plotting calibration curves: Circulation (30 minutes) at normal pressure of a hydrogen gas diluted to 5% with helium.
FIG. 1 a) shows an example of a hydrogen dispersion spectrum for the current noble metal-containing support material (A), and FIG. 2 a) shows a hydrogen desorption spectrum for another noble metal-containing support material (1) as a reference. The abscissa of the spectrum shows the sample temperature. The results show that the noble metal-containing support material A of the invention has no maximum between 50 ° C and 210 ° C, and one maximum between 210 ° C and 350 ° C. It is also shown that the noble metal-containing support material 1 has one maximum between 50 ° C and 210 ° C, and one maximum has between 210 ° C and 350 ° C. The MH2 was calculated using waveform analysis software by Bel Japan, Ine. In each graph, the line connecting the origin of the first peak in the hydrogen desorption spectrum and the minimum between 210 ° C and 350 ° C, plotted against the measurement time as the abscissa (graph insertion) was used as a background to the surface. value (a) from the baseline compensated spectrum. The background was then subtracted from the spectrum calibration conditions, and the surface value (b) was calculated for about 5 minutes of circulation under normal pressure of a hydrogen gas diluted to 5% with helium. MH2 per 1 g of catalyst was calculated with the following formula based on the total hydrogen flow during the period ((c), units: seconds). The surface value (b) was 5,355,802,000 and the time (c) was 213 seconds.
MH2 = [surface value (a) * 50 χ time (c) χ 5] / [surface value (b) χ 60 χ 100 χ sample weight (g)]
The calculated MH 2 was 0.038 cm 3 / g cat for the current noble metal-containing support material (A), and 0.122 cm 3 / g cat for the reference noble metal-containing support material (1).
(Measurement of adsorbed amount of carbon monoxide (MCO)) MCO of the current noble metal-containing support material was calculated after measuring the metal surface by the carbon monoxide pulse method with the following equipment and measurement conditions.
• Detector: BEL-METAL-3SP measuring equipment for measuring the metal dispersion speed by Bel Japan, Ine.
• Gas flow rate: 50 ml / min * • Sample weight: about 0.15 g • Pre-treatment: Vacuum treatment at 50 ° C for 8 hours, followed by treatment under normal pressure of a helium gas stream at 50 ° C for 1 hour, a normal pressure of a hydrogen gas stream at 50 ° C for 2 hours and a normal pressure of a helium gas stream at 50 ° C for 1 hour, in this order.
• Measurement conditions: carbon monoxide pulse injection repeatedly at 0.45 cm3, each under normal pressure of a helium gas stream at 50 ° C, adsorption measurement. The measurement was performed twice and the average value was calculated.
(Example 1: Preparation of an aqueous monodispersion of noble metal particles (P-1))
A mixed metal salt solution was prepared by adding 9.6 g of palladium nitrate dihydrate and 0.1 g of aqueous iron citrate to 100 g of purified water. After subsequently adding 200 g of aqueous trisodium citrate as a stabilizer of the mixed metal salt solution, 81.2 g of aqueous iron sulfate with a concentration of 25% by weight was added as a reducing agent, and the resulting mixture was stirred under a nitrogen atmosphere for 20 hours for a liquid noble metal to prepare a mixture. The palladium particles were separated and collected from the noble metal mixture with the aid of a centrifugal separator. The palladium particles were rinsed with 1% by weight aqueous hydrochloric acid and then dispersed in purified water.
The dispersion was subjected to wet milling using a nanomizer system (LA-33-S from Nanomizer, Ine) to prepare an aqueous monodispersion (P-1) of the noble metal particles. The palladium concentration of the aqueous monoflow press (P-1) was 3.1% by weight as palladium metal. (ICP luminescence analysis), and the Fe content was 0.42% by weight relative to Pd (ICP luminescence analysis). The streaming potential of an aqueous dispersion of the noble metal particles at a concentration of 0.5% by weight was 156 peq / g and the average particle size was 10 nm. j (Example 2: Pre-treatment of the carrier)
After rinsing 20 g of activated carbon with a pore volume of 1.22 cc / g (activated carbon of Wako Pure Chemical Industries, Ltd., powder form) using 10 liters of hot water at 100 ° C, it was dried at 150 ° C for 6 hours under a stream of nitrogen to prepare "flushed activated carbon". The pore volume of the activated carbon was calculated from the nitrogen gas adsorption near a relative pressure of 0.99 in an absorption isotherm obtained by adsorption of nitrogen gas at a liquid nitrogen temperature on the sample, pre-dried under vacuum at 150 ° C for 4 hours , using AU-TOSORB 6 by Quanta Chrome Corp.
(Example 3: Preparation of precious metal dispersion (A))
A noble metal dispersion (A) was prepared by mixing 2.164 g of an aqueous mono dispersion (P1) of noble metal particles obtained in Example 1.40 g of distilled water and 0.004 g of hydrochloric acid (Wako Pure Chemical Industries, Ltd), stirring in air for 30 minutes at 20 ° C and then rinsing with an ultra filter membrane. The palladium concentration of the noble metal dispersion (A) was 2.5% by weight as palladium metal (ICP luminescence analysis) and the Fe content was 0.42% by weight relative to Pd (ICP luminescence analysis). The streaming potential of an aqueous dispersion of noble metal particles at a concentration of 0.5% by weight was 29 peq /,, and the average particle size was 10 nm.
(Example 4: Preparation of the current noble metal-bearing support material (A))
After adding 20 g of the flushed activated carbon obtained in Example 2 and 300 ml of water in a 1-liter rrijate flask, the mixture was stirred in air at 20 ° C. A 100 ml of an aqueous solution comprising 7.78 g of the noble metal dispersion (A) obtained in Example 3 was slowly added dropwise to the carrier suspension in air at room temperature. After completion of the dropwise addition, the suspension was stirred at room temperature for 8 hours in air. After stirring, the moisture in the suspension was removed with a rotary evaporator and the residue was dried under vacuum at 80 ° C for 6 hours to obtain the current noble metal-containing support material (A), including palladium supported on activated carbon. The palladium concentration of the current noble metal-containing support material (A) was 1.1% by weight as palladium metal (ICP luminescence analysis).
Only one hydrogen desorption peak (at 235 ° C) was observed in the range of 50 ° C to 350 ° C in temperature-programmed desorption with a program speed of 10 ° C / min. MH2 was 0.038 cm3 / g and MCO was 0.20 cm3 / g, and therefore MH2 / MCO was 0.19.
(Example 5: Preparation of precious metal dispersion (B))
After mixing 2.164 g of the aqueous monodispersion (P-1) of noble metal particles obtained in Example 1 with 40 g of distilled water and 0.008 g of sodium nitrite (Wako Pure Chemical Industries, Ltd), the mixture was stirred and bubbled for 1 hour with bubbling of air at 20 ° C at a flow rate of 0.2 ml / min and then rinsed with an ultrafilter membrane to prepare the noble metal dispersion (B). The palladium concentration of the noble metal dispersion (B) was 2.1% by weight as palladium metal (ICP luminescence analysis), and the Fe content was 0.52% by weight relative to Pd (ICP lumyriescence analysis). The streaming potential of an aqueous dispersion of the noble metal particles at a concentration of 0.5% by weight was 38 peq / g, and the average particle size was 10 nm.
(Example 6: Preparation of the current noble metal carrier material (B))
After adding 6 g of the flushed activated carbon obtained in Example 2 and 300 ml of water in a 1-liter volumetric flask, the mixture was stirred in air at 20 ° C. A 100 ml of an aqueous solution comprising 2.91 g of the noble metal dispersion (B) obtained in Example 5 was slowly added dropwise to the carrier suspension in air at room temperature.
After completion of the dropwise addition, the suspension was stirred at room temperature for 8 hours in air. After stirring, the moisture in the suspension was removed with a rotary evaporator and the residue was dried under vacuum at 80 ° C for 6 hours to obtain the current noble metal-containing support material (B), including palladium supported on activated carbon. The palladium concentration of the current noble metal-containing support material (B) was 0.95% by weight as palladium metal (ICP luminescence analysis).
Only one hydrogen desorption peak (at 253 ° C) was observed in the range of 50 ° C to 350 ° C in temperature-programmed desorption with a program speed of 10 ° C / min. MH2 was 0.043 cm3 / g and the carbon monoxide adsorption (MCO) was 0.21 cm3 / g, and therefore MH2 / MCO was 0.21.
(Example 7: Preparation of the current noble metal-containing support material (C))
After adding 6 g of zirconium oxide (RSC-100 of Daiichi Kigenso Kagaku Kogyo Co., Ltd) and 300 ml of water in a 1-liter volumetric flask, the mixture was stirred in air at 20 ° C. A 100 ml aqueous solution comprising 2.91 g of the noble metal dispersion (B) obtained in Example 5 was slowly added dropwise to the carrier suspension in air at room temperature. After completion of the dropwise addition, the suspension was stirred at room temperature for 8 hours in air. After stirring, the moisture in the suspension was removed with a rotary evaporator and the residue was dried under vacuum at 80 ° C for 6 hours to obtain the noble metal-containing support material (C), including palladium supported on zirconium oxide. The palladium concentration of the current noble metal-containing support material (G) was 1.05% by weight as palladium metal (ICP luminescence analysis).
(Example 8: Preparation of noble metal dispersion (C))
A mixture of 2.164 g of the aqueous monodispersion (P-1) of noble metal particles obtained in Example 1, with 40 g of distilled water and 0.5 g of acetic acid (Wako Pure Chemical Industries, Ltd) was mixed in a glass vessel with a volume of about 50 cc. The mixture was stirred in air at 20 ° C for 30 minutes to prepare the noble metal dispersion (C).
(Example 9: Preparation of the current noble metal-containing support material (D))
After adding 6 g of activated carbon with a pore volume of 1.22 cc / g (activated carbon of Wako Pure Chemical Industries, Ltd., powder form) and 300 ml of water in a 1-liter volumetric flask, the contents were stirred in air at 20 ° C. The total amount of the noble metal dispersion (C) obtained in Example 8 was slowly added dropwise to the carrier suspension in air at room temperature. After completion of the dropwise addition, the suspension was stirred at room temperature for 8 hours in air. After stirring, the filtrate was separated from the suspension by filtration to obtain a residue. The residue was washed with 3 liters of warm water and then dried under vacuum for 6 hours to obtain the current noble metal-containing support material (D), including palladium supported on activated carbon.
The palladium concentration of the current noble metal-containing support material (D) was 0.94% by weight as palladium metal (ICP luminescence analysis). Only one hydrogen desorption peak (at 276 ° C) was observed in the range of 50 ° C to 350 ° C in temperature-programmed desorption with a program speed of 10 ° C / min. MH2 was 0.025 cm3 / g and MCO was 0.16 cm3 / g, and therefore MH2 / MCO was 0.16.
(Example 10: Preparation of the noble metal dispersion (D))
A mixture of 2.164 g of the aqueous monodispersion (P-1) of noble metal particles obtained in Example 1 with 40 g of distilled water and 0.5 g of phosphoric acid (Kanto Kagaku Co., Ltd) was mixed in a glass vessel with a volume of approximately 50 cc. The mixture was stirred in air at 20 ° C for 30 minutes to prepare the noble metal dispersion (D).
(Example 11: Preparation of the current noble metal-containing support material (E))
After adding 6 g of activated carbon with a pore volume of 1.22 cc / g (activated carbon of Wako Pure Chemical Industries, Ltd., powder form) and 300 ml of water in a 1-liter flask, the contents were stirred in air at 20 ° C. The total amount of the noble metal dispersion (D) obtained in Example 11 was slowly added dropwise to the carrier suspension in air at room temperature. After completion of the dropwise addition, the suspension was stirred at room temperature for 8 hours in air. After stirring, the filtrate was separated from the suspension by filtration to obtain a residue. The residue was washed with 3 liters of warm water and then dried under vacuum for 6 hours to obtain the current noble metal-containing support material (E), including palladium supported on activated carbon.
The palladium concentration of the current noble metal-containing support material (E) was 1.02% by weight as palladium metal (ICP luminescence analysis). Only one hydrogen desorption peak (at 262 ° C) was observed in the range of 50 ° C to 350 ° C in temperature-programmed desorption with a program speed of 10 ° C / min. MH2 was 0.022 cm3 / g and MCO was 0.19 cm3 / g, and therefore MH2 / MCO was 0.12.
(Reference example 1: Production of reference noble metal-containing carrier material (1))
After adding 18 g of the flushed activated carbon obtained in Example 2 and 300 ml of water in a 1-liter volumetric flask, the mixture was stirred in air at 20 ° C. One 100 ml of an aqueous solution comprised the 5.88 g of the aqueous monodispersion (P-1) of the noble metal particles obtained in Example 1 was slowly added dropwise to the carrier suspension in air at room temperature. After completion of the dropwise addition, the suspension was stirred at room temperature for 8 hours in air. After stirring, the moisture in the suspension was removed with a rotary evaporator and the residue was dried under vacuum at 80 ° C for 6 hours to obtain a reference noble metal-containing support material (1), including palladium supported on activated carbon. The palladium concentration of the reference noble metal-containing support material (1) was 1.09% by weight as palladium metal (ICP luminescence analysis). Two hydrogen desiccation peaks (at 113 ° C and 230 ° C) were observed in the range of 50 ° C to 350 ° C in temperature-programmed desorption at a program speed of 10 ° C / min. MH2 was 0.122 cm3 / g and MCO was 0.28 cm3 / g, and therefore MH2 / MCO was 0.47.
(Reference example 2: Preparation of reference noble metal-containing carrier material (2))
A mixture of 3 g of the activated carbon described in
Example 2 (non-rinsed) and 225 ml of acetonitrile (Nacalai Tesque, Ine.) Was added to a 1-liter flask and the mixture was stirred in air at 20 ° C. To this carrier suspension was slowly added dropwise 35 ml of acetonitrile comprising 0.0647 g of palladium acetate (Aldrich Co.) in air at room temperature. After completion of the dropwise addition, the suspension was stirred at room temperature for 8 hours in air. After stirring, the moisture in the suspension was removed with a rotary evaporator and the residue was dried under vacuum at 80 ° C for 6 hours to obtain a reference noble metal carrier material (2) comprising palladium supported on activated carbon. The palladium concentration of the reference noble metal-containing support material (2) was 1.07% by weight as palladium metal (ICP luminescence analysis). Two hydrogen desorption peaks (at 167 ° C and 261 ° C) were observed in the range of from 0 ° C to 350 ° C in temperature-programmed desorption with a program speed of 10 ° C / min. MH2 was 0.17 cm3 / g and MCO 0.23 cm3 / g, and therefore MH2 / MCO was 0.74.
(Comparative Example 1: Production of comparative noble metal-containing support material (1))
A comparative noble metal-containing support material (1) was prepared according to the method described in Example 1 of JP 2008-201776 A.
Specifically, 6 g of activated carbon with a pore volume of 1.22 cc / g (activated carbon of Wako Pure Chemical Industries, Ltd., powder form) and 425 ml of water were added to a 1-liter volumetric flask, and the contents were stirred in air at 20 ° C. To this carrier suspension was slowly added dropwise 75 ml of an aqueous solution comprising 0.60 mmol of palladium tetramine chloride in air at 20 ° C. After completion of the dropwise addition, the suspension was stirred in air at 20 ° C for 6 hours. After stirring, the moisture in the suspension was removed with a rotary evaporator and the residue was dried under vacuum at 80 ° C for 6 hours to obtain a noble metal-containing support material (1) for comparison (comparison noble metal-containing support material (1)), comprising palladium supported on activated carbon. The palladium concentration of the noble metal-containing support material (1) for comparison * was 1.14% by weight as palladium metal (ICP luminescence analysis). Two hydrogen desorption peaks (at 185 ° C and 258 ° C) were observed in the range of 50 ° C to 350 ° C in temperature-programmed desorption with a program speed of 10 ° C / min. MH2 was 0.125 cm 3 / g and MCO was 0.19 cm 3 / g, and therefore MH 2 / MCO was 0.66. j (Example 12: Production of titanium silicate-containing catalyst)
A combination of 899 g of piperidine and 2402 g of ion exchange water, mixed under an air atmosphere at room temperature (22 ° C), was stirred. To this mixture, 46 g of TBOT (tetra-n-butyl orthotitanate) was added dropwise and dissolved with stirring. After TBOT dissolution was completed, 565 g of boric acid was added and dissolved with stirring. Then 410 g of fumed silica (Cab-O-Sil M7D from Cabot) was added and dissolved under an air atmosphere with stirring and the mixture was further aged for 1.5 hours. After transferring the outdated solution in a 5-liter autoclave equipped with two anchor-type stirrers, the autoclave was sealed. An airtight seal test was conducted at 1.5 MPa (gauge pressure) using argon gas and then the pressure was released and the autoclave was sealed. The contents of the autoclave were heated to 150 ° C for 8 hours while the anchor-type stirrers were rotated. After keeping the reaction product in the autoclave at the same temperature for 120 hours, it was cooled to obtain a suspension. The resulting suspension was filtered, and then the filtered solid was rinsed with ion exchange water until the pH of the rinsed filtrate reached 10. The rinsed solid was then dried until a further weight loss was observed (drying temperature: 50 ° C). The dried product was rinsed with ion exchange water and then dried until approximately 520 g of a layered compound was obtained. This procedure was repeated 6 times to obtain a total of 3120 g of the layered compound. j
In a glass-coated metal container (200 liters, fitted with a jacket and reflux tube), 3 kg of the layered compound, 158 kg of 2 M aqueous nitric acid and 0.38 kg of TBOT were placed in an air atmosphere at an outside air temperature of 20 ° C to 30 ° C. The container temperature temperature was raised to 115 ° C, this temperature was maintained for 9 hours and then raised to 124 ° C, and the mixture was then refluxed for 7 hours at the same temperature. After the reflux, the mantle heating was interrupted and the contents were cooled to room temperature. The contents were filtered, and the filtered solid was rinsed with ion exchange water until the pH of the rinsed filtrate reached about 5.
The rinsed solid was dried until no more weight loss was observed (drying temperature: 80 ° C) to obtain a white solid that was further pulverized into a white powder. A portion of the white powder was packaged in a glass tube and heated from room temperature to 530 ° C for 2 hours under a nitrogen flow of 6 liters (0 ° C, 1 atm) / hour, and after being kept at the same temperature for 2 hours , the nitrogen stream was replaced with an air stream of 6 L (0 ° C, 1 atm) / hour, and the powder was kept at 530 ° C for 4 hours.
In a 1.5 liter autoclave, 150 g of the white powder were annealed in the above manner, 30 g of piperidine and 600 g of ion exchange water, under an air atmosphere at room temperature. The contents were dissolved in the same atmosphere with stirring at the same temperature and further aged for 1.5 hours. After transferring the aged solution into a 1.5 liter autoclave equipped with an anchor-type stirrer, the autoclave was closed. An airtight seal test was performed at 1.0 MPa (gauge pressure) with argon gas, and then the pressure was released and the autoclave was sealed.
The contents of the autoclave were heated to 150 ° C for 4 hours while the anchor-type stirrer was rotated. The content was then kept at a temperature within a range of 150 ° C to 170 ° C, and focused at 160 ° C, and was heated for 1 day. After heating, the contents of the autoclave were cooled to obtain a suspension. After filtering the suspension, the filtered solid was rinsed with filtered ion exchange water, heated to 100 ° C, until the rinsed filtrate reached a pH of about 9 to obtain a white solid.
The white solid was thoroughly dried at 150 ° C using a vacuum dryer, and was then pulverized to obtain a white powder. Elemental analysis showed that the white powder had a Ti content of 2.0 mass% and an Si content of 36 mass%. The results of XRD and an analysis of the ultraviolet and visible absorption spectrum confirmed that the white powder was a titanium silicate (Ti-MWW precursor).
(Example 13: Current process for producing hydrogen peroxide (hydrogen peroxide (A))
After loading a 0.5-liter autoclave with 0.06 g of this noble metal-containing carrier material (A), it was supplied with a source gas with a nitrogen / hydrogen / oxygen volume ratio of 90.9 / 4.7 / 4.4 at a feed rate of 18 l / hour and with a solvent (water / acetonitrile = 20/80 (weight ratio)) at a feed rate of 171 g / hour, and the reaction mixture was extracted from the autoclave through a filter in a continuous reaction. The reaction was carried out at a temperature of 40 ° C, a gauge pressure of 0.8 MPa and a residence time of 45 minutes.
Gas chromatography analysis of the liquid phase and the gas phase 4.5 hours after the start of the reaction showed a hydrogen peroxide yield of 0.59 mmol / hour (weight concentration: 0.023%).
(Reference example 3: Reference method for the preparation of hydrogen peroxide (Reference hydrogen peroxide (1) production) Hydrogen peroxide was produced by the same method as in Example 12, except for using the reference noble metal-containing support material (1) obtained in Reference example 1 instead of the current one precious metal-containing carrier material (Â).
Gas chromatography analysis of the liquid phase and the gas phase 4.5 hours after the start of the reaction showed a hydrogen peroxide yield of 0.46 mmol / hour (weight concentration: 0.018%).
(Example 14: Current process for producing alkylene oxide (propylene oxide (A))
After loading a 0.5 liter autoclave with 1.14 g of the titanium silicate-containing catalyst obtained in Example 12, 0.53 g of the current noble metal-containing support material (A) obtained in Example 4, and 117 g of a water / acetonitrile = 30/70 (weight ratio) solution, the autoclave was closed. A source gas was then added to the autoclave with an oxygen / hydrogen / nitrogen / propylene volume ratio of 3.8 / 3.1 / 93.0 / 86.9 / 6.3 with a feed rate of 107 Nl / hour, and a water / acetonitrile solution = 30/70 (weight ratio) containing 0.7 mmol / kg of anthraquinone and 3.0 mmol / kg of diammonium hydrogen phosphate at a feed rate of 117 g / hour, and the reaction mixture was extracted from the autoclave through a filter in a continuous response. The reaction was carried out at a temperature of 60 ° C, a gauge pressure of 0.8 MPa and a residence time of 60 minutes. Sampling was carried out 2 hours and 5 hours after the start of the reaction, with analysis of the sampled liquid phase and gas phase by gas chromatography, and the results showed a propylene oxide yield of 60.0 mmol / g (noble metal-containing support material) / hour and an op hydrogen-based selectivity for propylene oxide (propylene oxide yield / hydrogen consumption x 100) of 84% (average of the values after 2 hours and 5 hours).
(Example 15: Current process for producing alkylene oxide (propylene oxide (B))
Propylene oxide was produced by the same method as in Example 14, except for using the current noble metal-containing support material (B) obtained in Example 6 instead of the current noble-metal-containing support material (A). Sampling was carried out 2 hours and 5 hours after the start of the reaction, with analysis of the sampled liquid phase and the gas phase by gas chromatography, and the results showed a propylene oxide yield of 55.5 mmol / g (noble metal-containing support material) / hour and an op hydrogen based selectivity to propylene oxide (propylene oxide yield / hydrogen consumption x 100) of 84% (average of the values after 2 hours and 5 hours). r (Example 16: Current method for producing alkylene oxide (propylene oxide (C).)
Propylene oxide was produced by the same method as Example 14, except for using the current noble metal-containing support material (C) obtained in Example 7 instead of the current noble-metal-containing support material (A). Sampling was performed 2 hours and 5 hours after the start of the reaction, with analysis of the sampled liquid phase and the gas phase with gas chromatography, and the results showed a propylene oxide yield of 78.5 mmol / g (noble metal-containing support material) / hour and a hydrogen-based selectivity for propylene oxide (propylene oxide yield / hydrogen consumption x 100) of 86% (average of the values after 2 hours and 5 hours).
, (Example 17: Current process for producing alkylene oxide (propylene oxide (D))
Propylene oxide was produced by the same method as in Example 14, except for using the current noble metal-containing support material (D) obtained in Example 9 instead of the current noble-metal-containing support material (A). Sampling was performed 2 hours and 5 hours after the start of the reaction, with analysis of the sampled liquid phase and the gas phase with gas chromatography, and the results showed a propylene oxide yield of 42.1 mmol / g (noble metal-containing support material) / hour and a hydrogen-based selectivity for propylene oxide (propylene oxide yield / hydrogen consumption x 100) of 89% (average of the values after 2 hours and 5 hours).
(Example 18: Current process for producing alkylene oxide (propylene oxide (E))
Propylene oxide was produced by the same method as in Example 14, except for using the current noble metal-containing support material (E) obtained in Example 11 instead of the current noble-metal-containing support material (A). Sampling was performed 2 hours and 5 hours after the start of the reaction, with analysis of the sampled liquid phase and the gas phase with gas chromatography, and the results showed a propylene oxide yield of 32.3 mmol / g (noble metal-containing support material) / hour and a hydrogen-based selectivity for propylene oxide (propylene oxide yield / hydrogen consumption x 100) of 81% (average of the values after 2 hours and 5 hours).
(Reference example 4: Reference method for the preparation of alkylene oxide (Reference propylene oxide production (1))
Propylene oxide was produced by the same method as in Example 15, except with the reference noble metal-containing support material (1) obtained in Reference Example 1 instead of the current noble-metal-containing support material (A). Sampling was carried out 2 hours and 5 hours after the start of the reaction, with analysis of the sampled liquid phase and the gas phase with gas chromatography and the results showed a propylene oxide yield of 70.2 mmol / g (noble metal-containing support material) / hour and a hydrogen based selectivity for propylene oxide (propylene oxide yield / hydrogen consumption x 100) of 72% (average of the values after 2 hours and 5 hours).
(Reference example 5: Reference method for the preparation of alkylene oxide (Reference propylate oxide (2))
Propylene oxide was produced by the same method as in Example 15, except for using the reference noble metal-containing support material (2) obtained in Reference Example 2 instead of the current noble-metal-containing support material (A). Sampling was carried out 2 hours and 5 hours after the start of the reaction, with analysis of the sampled liquid phase and the gas phase with gas chromatography and the results showed a propylene oxide yield of 56.8 mmol / g (noble metal-containing support material) / hour and an op hydrogen based selectivity for propylene oxide (propylene oxide yield / hydrogen consumption x 100) of 65% (average of the values after 2 hours and 5 hours).
(Comparative Example 2: Alkylene oxide comparative production (1))
Propylene oxide was produced by the same method as in Example 15, except with the comparative noble metal-containing support material (1) obtained in Comparative Example 1, instead of the current noble-metal-containing support material (A). Sampling was carried out 2 hours and 5 hours after the start of the reaction, with analysis of the sampled liquid phase and the gas phase with gas chromatography and the results showed a propylene oxide yield of 30.0 mmol / g (noble metal-containing support material) / hour and an op hydrogen-based selectivity to propylene oxide (propylene oxide yield / hydrogen consumption x 100) of 59% (average of the values after 2 hours and 5 hours).
The experimental results for the production of propylene oxide are summarized in Table 1. As can be seen in the table, did the combined use increase of the present noble metal-containing support material with a titanium silicate-containing catalyst, the yield of propylene oxide from oxygen, hydrogen and propylene. The noble metal-containing support material as a catalyst of the present invention was also shown to have a high hydrogen-based selectivity for alkylene oxide. [Table 1]
* 1 [mmol (propylene oxide) / g (noble metal-containing support material) / hour] * 2: [%] mmol (propylene oxide) / mmol (hydrogen supplied) x 100 (Example 19: Current process for producing alkylene oxide (propylene oxide (A1) )
After loading a 0.3 liter autoclave with 2.28 g of titanium silicate-containing catalyst obtained in Example 12, 0.63 g of the current noble metal-containing support material (A) obtained in Example 4, 3.0 g of PTFE zeolite (Teflon Boiling Storie) and 90.5 g of a water / acetonitrile = 30/70 (weight ratio) solution, the autoclave was sealed.
A source gas was then supplied with an oxygen / hydrogen / nitrogen volume ratio of 3.2 / 3.8 / 93.0 with a feed rate of 284 l / hour, containing a solution of water / acetonitrile ^ = 30/70 (weight ratio) 0.7 mmol / kg anthraquinone and 3.0 mmol / kg diammonium hydrogen phosphate with a feed rate of 135 g / hour, and propylene with a feed rate of 54 g / hour, wherein the reaction mixture was withdrawn from the autoclave via a filter in a continuous reaction . The reaction was carried out at a temperature of 50 ° C, a pressure of 6.0 MPa, and a residence time of 40 minutes.
Sampling was performed at 2, 3 and 4 hours after the start of the reaction, with analysis of the sampled liquid phase and the gas phase with gas chromatography, and the results showed a propylene oxide yield of 306.5 mmol / g (noble metal-containing support material). material) / hour, a hydrogen-based selectivity for propylene oxide (propylene oxide yield / hydrogen consumption x 100) of 85% and a selectivity for propane (propane yield / (total propylene oxide, propylene glycol and propane yield) x 100) of 6.3 % (average values of 2, 3 and 4 hours).
(Example 20: Current process for producing alkylene oxide (propylene oxide (B1))
Propylene oxide was produced by the same method as in Example 19, except for using the current noble metal-containing support material (B) obtained in Example 6 instead of the current noble-metal-containing support material (A). Sampling was carried out 2, 3 and 4 hours after the start of the reaction, with analysis of the sampled liquid phase and the gas phase with gas chromatography, and the results showed a propylene oxide yield of 356.6 mmol / g (noble metal-containing support material) / hour, a hydrogen-based selectivity for propylene oxide (propylene oxide yield / hydrogen consumption x 100) of 68% and a selectivity for propane (propane yield / (total propylene oxide, propylene glycol and propane yield) x 100) of 3.5% (average values of 2, 3 and 4 hours).
(Reference example 5: Reference method for the preparation of alkylene oxide (Reference propylene oxide (3)))
Propylene oxide was produced by the same method as in Example 19, except for using the reference noble metal-containing support material (1) obtained in Reference Example # 1 instead of the current noble-metal-containing support material (A). Sampling was performed 2, 3 and 4 hours after the start of the reaction, with analysis of the sampled liquid phase and the gas phase with gas chromatography, and the results showed a propylene oxide yield of 281.4 mmol / g (noble metal-containing support material) / hour, a hydrogen-based selectivity for propylene oxide (propylene oxide yield / hydrogen consumption x 100) of 74% and a selectivity for propane (propane yield / (total propylene oxide, propylene glycol and propane yield) x 100) of 7.5% (average values of 2, 3 and 4 hours).
The experimental results for the production of propylene oxide are summarized in Table 2. As can be seen in the table, the combined use of the current noble metal-containing support material with a titanium silicate-containing catalyst increased the yield of propylene oxide from oxygen, hydrogen and propylene. The noble metal-containing support material as a catalyst according to the invention was shown to have high hydrogen-based selectivity for alkylene oxide and low hydrogen-based selectivity for alkane (i.e., producing a low content of by-products such as propane).
[Table 2]
* 1 [mmol (propylene oxide) / g (noble metal-containing carrier material) / hour] * 2: [%] mmol (propylene oxide) / mmol (hydrogen supplied) x 100 * 3 [%] mmol (propane) / mmol (total propylene oxide, propylene glycol and propane) x 100 (Example 21: Current process for producing alkylene oxide (propylene oxide (A2))
After loading a 0.3 liter autoclave with 2.28 g of titanium silicate-containing catalyst obtained in Example 12, 1.06 g of the current noble metal-containing support material (A) obtained in Example 4, 3.0 g of PTFE zeolite (Teflon Boiling Stone) and 90 g of a water / acetonitrile = 30/70 (weight) solution, the autoclave was sealed.
A source gas was then supplied with an oxygen / hydrogen / nitrogen volume ratio 3.2 / 3.8 / 93.0 with a feed rate of 284 l / hour, a solution of water / acetonitrile = 30/70 (weight ratio) containing 0, 7 mmol / kg anthraquinone and 3.0 mmol / kg diammonium hydrogen phosphate with a feed rate of 90 g / hour, and propylene with a feed rate of 36 g / hour, the reaction mixture being extracted from the autoclave via a filter in a continuous reaction. The reaction was carried out at a temperature of 50 ° C, a pressure of 4.0 MPa and a residence time of 60 minutes. Sampling was performed 3, 4, 5 and 6 hours after the start of the reaction, with analysis of the sampled liquid phase and the gas phase with gas chromatography and the results showed a propylene oxide yield of 339.0 mmol / g (noble metal-containing support material) / hour, a hydrogen-based selectivity for propylene oxide (propylene oxide yield / hydrogen consumption x 100) of 75% and a selectivity propane (propane yield / (total propylene oxide, propylene glycol and propane yield) x 100) of 2, 1% (average values at 3, 4, 5 and 6 hours).
(Reference example 6: Reference method for the preparation of alkylene oxide (Reference propylene oxide (5))
Propylene oxide was produced by the same method as in Example 21, except for using the reference noble metal-containing support material (1) obtained in Reference Example 1 instead of the current noble-metal-containing support material (A). Sampling was carried out 3, 4, 5 and 6 hours after the start of the reaction, with analysis of the sampled liquid phase and the gas phase with gas chromatography and the results showed a propylene oxide yield of 166.4 mmol / g (noble metal-containing support material). -al) / hour, a hydrogen-based selectivity for propylene oxide (propylene oxide yield / hydrogen consumption x 100) of 66% and a selectivity for propane (propane yield / (total propylene oxide, propylene glycol and propane yield) x 100) of 4 , 4% (average values at 3, 4.5 and 6 hours).
(Reference example 7: Reference method for the preparation of alkylene oxide (Reference propylene oxide (6))
Propylene oxide was produced by the same method as in Example 21, except for using the reference noble metal-containing support material (2) obtained in Reference Example 2 instead of the current noble-metal-containing support material (A). Sampling was performed 3, 4, 5 and 6 hours after the start of the reaction, with analysis of the sampled liquid phase and the gas phase with gas chromatography and the results showed a propylene oxide yield of 161.7 mmol / g (noble metal-containing support material). aal) / hour, a hydrogen-based propylene oxide selectivity (propylene oxide yield / hydrogen consumption x 100) of 62% and a propane selectivity (propane yield / (total propylene oxide, propylene glycol and propane yield) x 100) of 8, 3% (average values at 3, 4.5 and 6 hours).
(Comparative Example 3: comparative method for the preparation of alkylene oxide (Propylene oxide comparative production (2)))
Propylene oxide was produced by the same method as in Example 21 except for using the comparative noble metal-containing support material (1) obtained in Comparative Example 1 instead of the current noble-metal-containing support material (A). Sampling was performed 3, 4, 5 and 6 hours after the start of the reaction, with analysis of the sampled liquid phase and the gas phase with gas chromatography and the results showed a propylene oxide yield of 118.7 mmol / g (noble metal-containing support material ) / hour, a hydrogen-based selectivity for propylene oxide (propylene oxide yield / hydrogen consumption x 100) of 55% and a selectivity for propane (propane yield / (total propylene oxide, propylene glycol and propane yield) x 100) of 12.6 % (average values at 3, 4, 5 and 6 hours).
The experimental results for the production of propylene oxide are summarized in Table 3. As can be seen in the table, the combined use of the current noble metal-containing support material with a titanium silicate-containing catalyst increased the yield of propylene oxide from oxygen, hydrogen and propylene. The noble metal-containing support material as a catalyst was also shown to have high hydrogen-based selectivity for alkylene oxide and low hydrogen-based selectivity for alkane (i.e., producing a low content of by-products such as propane).
[Table 3]
* 1 [mmol (propylene oxide) / g (precious metal support) / hour] * 2: [%] mmol (propylene oxide) / mmol (hydrogen supplied) x 100 * 3 [%] mmol (propane) / mmol (total propylene oxide, propylene glycol and propane) x 100.
Industrial applicability
The invention can provide a new catalyst capable of producing a high yield of alkylene oxide when used in combination with a titanium silicate-containing catalyst, in a reaction for the production of an alkylene oxide from oxygen, hydrogen and an olefin.

权利要求:
Claims (17)
[1]
A noble metal-containing support material comprising a noble metal and a support as component components, wherein the ratio of a desorbed amount of hydrogen to an adsorbed amount of carbon monoxide is in the range of 0.01 to 0.40; wherein the "desorbed amount of hydrogen" is a value calculated from the sum of the peak areas of the desorbed component with a maximum value in the range of 50 ° C to 350 ° C as observed in accordance with a temperature-programmed desorption with a program speed of 10 ° C / min, with respect to a sample kept under vacuum at 50 ° C for 8 hours or more, under a normal pressure of a helium gas stream at 50 ° C for 1 hour / then under a normal pressure of a hydrogen gas stream at 50 ° C for 2 hours, and further kept under normal pressure of a helium gas stream at 50 ° C for 1 hour, and thereby obtained, while the "adsorbed amount of carbon monoxide" is the value measured is determined by a metal surface measurement based on the carbon monoxide pulse method, of a sample that is kept under vacuum at 50 ° C for 8 hours or more, under normal pressure is maintained at a helium gas stream at 50 ° C for 1 hour, then under a normal pressure of a hydrogen gas stream at 50 ° C for 2 hours, and further under a normal pressure of a helium gas stream at 50 ° C for 1 hour and is thereby obtained.
[2]
The noble metal-containing support material according to claim 1, wherein the peaks of the desorbed component with a maximum value in the range of 50 ° C to 350 ° C as observed in a temperature-programmed desorption process with a program speed of 10 ° C / min no maximum have a value between 50 ° C and 210 X, and have one or more maximum values in the range of 210 ° C to 350 ° C.
[3]
The noble metal-containing support material according to claim 1 or 2, which is obtained by contacting a support with a noble metal dispersion comprising noble metal particles, so that a 0.5% by weight aqueous dispersion of noble metal particles has a streaming potential in the range of 10 peq / g up to 50 peq / g.
[4]
The noble metal-containing support material according to claim 3, wherein the noble metal particles are obtained by mixing an acid-containing solution with either (a) a precursor of a noble metal particle such that a 0.5% by weight aqueous dispersion has a streaming potential in the range of 50 peq / g to 300 peq / g, or (b) a mixture of a precursor of a noble metal particle with a solvent. ψ
[5]
The noble metal-containing support material according to claim 4, wherein the acid is hydrochloric acid.
[6]
The noble metal-containing support material according to claim 3, wherein the noble metal particles are obtained using an oxidant for the partial oxidation of either (a) a precursor of a noble metal particle such that a 0.5% by weight aqueous dispersion has a streaming potential in the range of 50 peq / g to 300 peq / g, or (b) a mixture of a precursor of a precious metal particle with a solvent.
[7]
The noble metal-containing support material according to claim 6, wherein the oxidizing agent is oxygen and / or sodium nitrite.
[8]
The noble metal-containing support material according to any of claims 1 to 7, wherein the noble metal is palladium.
[9]
The noble metal-containing support material according to any of claims 1 to 8, wherein the support comprises at least one species selected from a group consisting of activated carbon, aluminum oxide, titanium oxide and zirconium oxide.
[10]
A method for producing hydrogen peroxide, comprising: a step of reacting oxygen with hydrogen in the presence of a noble metal-containing support material according to any of claims 1 to 9. »
[11]
A method for producing alkylene oxide, comprising a step of reacting oxygen, hydrogen, and an olefin in the presence of a noble metal-containing support material according to any of claims 1 to 9 and a titanium silicate-containing catalyst.
[12]
The method of claim 11, wherein the olefin is propylene.
[13]
The method according to claim 11 or 12, wherein the titanium silicate-containing catalyst comprises titanium silicate particles with an X-ray diffraction pattern pattern with peaks at the positions indicated by the lattice distances d / A of f12.4 ± 0.8 10.8 ± 0.5 9 , 0 ± 0.3 6.0 ± 0.3 3.9 ± 0.3 and 3.4 ± 0.1.
[14]
The method of any of claims 11 to 13, wherein the step is a step of reacting oxygen, hydrogen, and an olefin in the presence of a solvent. i
[15]
The method of claim 14, wherein the solvent is an organic solvent.
[16]
The method of Claim 14, wherein the solvent is a mixed solvent comprising an organic solvent and water.
[17]
The method of claim 15 or 16, wherein the organic solvent is acetonitrile.

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

EP0978316A1|1998-08-05|2000-02-09|Enichem S.p.A.|New catalyst, process for the production of hydrogen peroxide and its use in oxidation processes|

---

US6498259B1|2001-10-19|2002-12-24|Arco Chemical Technology L.P.|Direct epoxidation process using a mixed catalyst system|

---

WO2008090997A1|2007-01-24|2008-07-31|Sumitomo Chemical Company, Limited|Method for producing propylene oxide|

---

WO2009001948A1|2007-06-27|2008-12-31|Sumitomo Chemical Company, Limited|Method for producing propylene oxide|

---

WO2009119901A1|2008-03-28|2009-10-01|Sumitomo Chemical Company, Limited|Producion method of propylene oxide|

---

WO2010087519A1|2009-02-02|2010-08-05|Sumitomo Chemical Company, Limited|Method for producing propylene oxide using a noble metal catalyst supported on silylated active carbon|

---

WO2011096459A1|2010-02-03|2011-08-11|Sumitomo Chemical Company, Limited|Method for producing propylene oxide|

---

IT1127311B|1979-12-21|1986-05-21|Anic Spa|SYNTHETIC, CRYSTALLINE, POROUS MATERIAL CONSTITUTED BY SILICON AND TITANIUM OXIDES, METHOD FOR ITS PREPARATION AND ITS USES|

---

AU2003211252A1|2002-03-04|2003-09-16|Sumitomo Chemical Company, Limited|Method for improving crystalline titanosilicate catalyst having mww structure|

---

JP4241068B2|2002-03-07|2009-03-18|昭和電工株式会社|Method for producing MWW type zeolite material|

---

JP4433843B2|2004-03-22|2010-03-17|住友化学株式会社|Propylene oxide production catalyst and propylene oxide production method|

---

JP4923248B2|2006-08-23|2012-04-25|国立大学法人横浜国立大学|Titanosilicate and process for producing the same|CN103949289B|2014-04-15|2016-06-29|华东师范大学|The preparation method of a kind of composite Ti-Si Borate cocatalyst and application thereof|

---

CN108097243B|2017-12-26|2021-04-02|江西省汉氏贵金属有限公司|Alkali modified activated carbon supported palladium catalyst and preparation method thereof|

法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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JP2011173600A|JP2013034948A|2011-08-09|2011-08-09|Noble metal-supported material and use thereof|

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JP2011173600|2011-08-09|

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