• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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  • 优先权
    • 专利摘要:
    The present invention is a guard catalyst comprising alumina support and molybdenum and / or tungsten and nickel and / or cobalt supporting the alumina support, wherein the total ammonia integral endotherm of the alumina support is adsorption heat does not exceed 25 J / g, and the percentage of the ammonia integral endotherm with ammonia differential heat of at least 100 kJ / mol does not exceed 10% of the total ammonia integral endotherm. It relates to a catalyst. Compared with the catalysts of the prior art, the protective catalysts have higher catalytic activity and lower coke precipitation rate, lower pore volume reduction rate, better activity stability and higher strength.
    公开号:KR20020024566A
    申请号:KR1020010059363
    申请日:2001-09-25
    公开日:2002-03-30
    发明作者:샤오홍 강；구이 왕；웨이헹 동；균헤 양；리 쥬
    申请人:차이나 페트로리움 앤드 케미컬 코포레이션；추후보정；리서치 인스티튜트 오브 페트롤리움 프로세싱 시노펙；
    IPC主号:
    专利说明:

    GUARD CATALYST AND A PROCESS FOR ITS PREPARATION
    [5] TECHNICAL FIELD The present invention relates to a guard catalyst and a method for preparing the same, and more particularly, to a protective catalyst containing tungsten and / or molybdenum and nickel and / or cobalt and a method for producing the same.
    [6] Hydrogenated feedstocks are generally converted to coke deposits and metal sulfides, thereby blocking pores and catalyzing during hydrogenation and precipitation on the surfaces of catalysts such as resins, asphaltenes, carbon residues and iron, etc. It contains a small amount of impurities that rapidly reduce the activity of the. Therefore, a catalyst layer or a reactor in which a protective catalyst is stacked is generally installed on top of the main catalyst layer to prevent the impurities, thereby preventing deactivation of the catalyst by passing hydrogenated raw materials through the layer and the reactor. do.
    [7] For the purpose of laminating the metal and the precipitated coke, the protective catalyst has many pores in order to precipitate as much as possible therein resins, asphaltenes and metals. During the reaction, if the strength of the protective catalyst is not sufficient due to the undulation of temperature, the catalyst tends to be crushed and the pressure drop in the catalyst layer increases, so the protective catalyst should have a very high strength. Therefore, the development of a protective catalyst with high strength and large pore size, large pore volume and low inactivation rate is very important.
    [8] U.S. Patent 4,448,896 discloses a protective catalyst for removing sulfur and heavy metals, the catalyst comprising (1) at least one metal element selected from the group consisting of metals of Groups VIB and VII as active elements of the catalyst And (2) a porous support of activated alumina. Such a support material is prepared by molding a mixture of carbon black powder and a precursor of activated alumina or activated alumina, and calcining the dried mixture in an appeal-containing atmosphere to exhaust the carbon black powder. The catalyst has a pore volume of 100-350m 2 / g, and preferably has a specific surface area of 200-300m 2 / g, 0.5-1.5ml / g , preferably from 0.5-1.5ml / g. It is desirable that the pores having a diameter of 35.7-100 kPa are at least 90% of the total pore volume, peaking at diameters smaller than 100 kPa and peaking in the range of 100-1000 kPa. The volume of pores having a diameter of 37,5-100 mm 3 is at least 0.2 ml / g, preferably 0.4-0.7 ml / g, and the volume of pores having a diameter of 100-1000 mm 3 is at least 0.2 ml / g and preferably 0.2-0.5 ml / g. The catalyst uses carbon black powder as a pore expander and the prepared catalyst has a large pore volume. However, the strength of the catalyst is greatly reduced because the amount of the carbon black powder is 10% or more. In addition, the use of a large amount of carbon black powder is not suitable for temperature control upon calcination of the catalyst support material, and the temperature rise easily occurs.
    [9] Chinese patent 1,179,356A discloses a catalyst support and a method of making the same. The catalyst support consists of γ-alumina and has a pore volume of 0.65-0.88 ML / G and a specific surface area of 225-290 M 2 / G. The pore volume having a diameter of 7-13 nm occupies 80-95% of the total pore volume, the pores having a diameter of 7 nm or less occupy 2-15% of the total pore volume, and the pores having a diameter of 13 nm or more are total Occupies 2-15% of pore volume. The method of preparing the catalyst support includes adding a pseudo-boehmite dry gel, adding an aqueous alkali solution to 20-60 wt% of the pseudo-boehmite dry gel, and after sufficient kneading Adding 40-60wt% of the boehmite dry gel to the acidic aqueous solution, molding by ejection after sufficient kneading, drying at 80-140 ° C. for 1-5 hours, 700- for 2-5 hours Calcination at 900 ° C. The catalyst has a large pore volume, large specific surface area and concentrated pore dispersion. However, the catalyst is prepared primarily by the addition of an aqueous alkali solution and the addition of an acidic aqueous solution. Although peptization is reduced and the pore diameter is expanded by the neutralization reaction, the strength of the support material is impaired.
    [10] Chinese patent 1,160,602A discloses a large pore alumina support and a method for producing the same. The alumina support has a pore volume of 0.8-1.2 ml / g, the most possible pore diameter is 15-20 nm, density is 0.5-0.6 g / ml and specific surface area is 110-200 m 2 / g. The method for preparing the alumina support includes mixing Ga-boehmite with distilled water or an aqueous solution, kneading the mixture with plastic water, molding with an extruder, drying and calcining. An improvement is the addition of pore dilators of combustible solid particles and the addition of pore dilators comprising boron compounds that react with phosphorus, silicon or ga-boehmite or alumina. The alumina support also has the disadvantage of having low strength.
    [11] Chinese patent 1,103,009A discloses a process for producing alumina having a double pore structure. The alumina is prepared by mixing and molding two kinds of alumina or carbon black powders, surfactants, peptizing agents, precursors with other pore dispersions in aqueous solution, followed by drying and calcining. More specifically, the method for preparing the alumina comprises mixing alumina of the second class and the precursor having a uniform RLORHD dispersion, carbon in a ratio of 1: 0.05-0.1, 0.05-0.1: 0.02-0.05 with the mixed alumina Mixing black powder, surfactant, peptizer and aqueous solution, molding, drying at 100-130 ° C., calcining at 550-650 ° C. for 1-4 hours. In the alumina, the volume of pores having a diameter of 100-200 mm 3 occupies at least 50% of the total pore volume, and the volume of pores having a diameter of 1000 mm 3 or more occupies 5-30% of the total pore volume. The alumina support material produced by the method has higher strength. Compared to the method disclosed in US Pat. No. 4,448,896, the method uses less carbon black powder and has industrial applicability.
    [12] The alumina backing itself itself has some acidity at its site due to coke precipitation. Silica is generally used as catalyst support to reduce the coke precipitation. However, silica is difficult to mold and lowers the strength of the catalyst. When alumina is used as a support, the strength of the catalyst is improved, but the catalyst shows a tendency of coke precipitation. All of the above prior art do not consider the problem of coke precipitation of the catalyst.
    [13] It is an object of the present invention to overcome the problems of coke sedimentation tendency and low strength and to provide a protective catalyst with no tendency to coke sedimentation and having higher strength. It is another object of the present invention to provide a method for preparing the catalyst.
    [14] The protective catalyst provided by the present invention includes an alumina support and molybdenum and / or tungsten and nickel and / or cobalt supporting the alumina support. The total ammonia integral adsorption heat of the alumina support material does not exceed 25 J / g, wherein the percentage of the ammonia integral endotherm with ammonia differential adsorption heat of 100 kJ / mol or more It does not exceed 10% of the ammonia integral endothermic amount.
    [15] The method for preparing the catalyst according to the present invention comprises the steps of mixing the hydrated ammonia, carbon black powder, organic pore dilator, peptizator and aqueous solution, molding by extrusion, drying step, calcining ( calcine), injecting the metal component, followed by drying and calcining again, wherein the carbon black powder is titrated and the pH of the wet powder is at least 8. The amount of each component is from 0.03 to 0.05 with respect to weight 1 of alumina, the weight of organic pore dilator is 0.05-0.2 and the weight of peptizer is 002-0.05.
    [16] In the preferred catalyst provided by the present invention, the total ammonia integral endothermic amount of the ammonia support material is 20-25 J / g, wherein the percentage of the ammonia integral endothermic amount having ammonia fine endothermic amount of 100 kJ / mol or more is total ammonia. Account for 7-10% of the integral endotherm. The alumina is various aluminas that satisfy the above conditions, such as γ-alumina, η-alumina, and the like, preferably γ-alumina.
    [1] 1 is a dispersion of iron precipitated on a catalyst according to the present invention.
    [2] 2 is a dispersion diagram of iron precipitated on a reference catalyst.
    [3] 3 is a graph showing the removal rate of carbon residues in the flow as a function of time.
    [4] 4 is a structural flowchart of an apparatus for determining an endothermic amount of an alumina support material.
    [17] The method for determining the ammonia integral endothermic amount and the ammonia derivative endothermic amount is as follows:
    [18] 1. Appliances used
    [19] The instrument used was a HT-1000 ° C Calvet model high temperature microcalorimeter (manufactured by Cetaram, France).
    [20] 2. Determination of endothermic amount
    [21] The process of determining the endothermic amount will be described next with drawings.
    [22] As shown in FIG. 4, the six valves 13 approach the “sam” (ling) position. Two 1.0000 g of alumina are accurately measured and placed in the reference cell 10 of the sample cell 16 and calorimeter 20, respectively. High purity nitrogen enters the flow stabilization valve 7 through the line 6 in the cylinder 5 and the flow rate is controlled at 15 ml / min. The high purity nitrogen then enters the reference cell 10 of the calorimeter 20 through the flow meter 8 and line 9 and is poured into the alumina support 11 within the reference cell 10. The nitrogen is then line 12, six valves 13 (the nitrogen is not yet in contact with the sampling tube 14) and the sample cell of the calorimeter 20 via line 15 ( 16) and poured into the ammonia support 11 in the sample cell 16. The nitrogen is then discharged or analyzed via line 17. The temperature of the reference cell 10 and the sample cell 16 is continuously maintained at 420K, which is measured by the thermal couple 18 introduced into the calorimeter 920. On the other hand, high purity ammonia is continuously supplied from the cylinder 22 to the flow control valves 25 and 26 through the line 23 and the pressure stabilization valve 24. After the flow rate is regulated by flow control valves 25 and 26, the high purity ammonia enters buffer 28 through line 27, and then line 29, flow meter 30, line 31, six valves 13 (through the sampling tube 14) exit the line 32. After 12 hours of flushing of the thermostat, the six valves 13 are switched to the "sample in" position, at which point the ammonia in line 31 passes through the six valves (sampling tube ( 14) is discharged directly to line 32). Nitrogen in line 12 carries ammonia in sampling tube 14 and enters sample cell 16 through sampling tube 14. Ammonia is absorbed into the ammonia support 11 in the sample cell 16 and heat is released. The effect of the exotherm is detected by a thermopile 19 of the calorimeter 20, which is transmitted to the microvolt amplifier 21 in the form of a thermal potential, amplified and recorded, and the result of the calculation is Appears on the record counter. The amount of each ammonia introduced and the result of each calculation are recorded and the differential endothermic amount q (kJ / mol ammonia, abbreviated kJ / mol) of the ammonia is calculated by the following equation: q = kn / ad, where q is Ammonia differential endothermic amount, k is a calorie constant (kJ / count), n is an integral count (count), ad is the input amount (mmol) of each ammonia. The measurement is continued until the amount of differential endotherm generated by two adjacent ammonia inputs becomes constant. Before the differential endothermic amount generated by the two adjacent ammonia inputs becomes constant, the average value of the differential ammonia endothermic amount is multiplied by the total ammonia input amount before the differential endothermic amount generated by the two adjacent ammonia inputs becomes constant, Dividing by the weight of the catalyst in the sample cell yields the total ammonia integral endothermic amount (J / g-catalyst, abbreviated as J / g) of the catalyst. The average value of the ammonia fine endothermic amount is 100 kJ / mol or more, which is multiplied by the total amount of charged ammonia that generates the ammonia fine endothermic amount of 100 kJ / mol or more, divided by the weight of the catalyst in the sample cell and ammonia or more The ammonia integral endothermic amount which has a differential endothermic amount is computed. The calorie constant correction method is an EJP constant-current supply method, applying a Joule current of a voltage of 6.2 V and a current of 10 mA to a Joule cell that is automatically adjusted in the calorimeter for 120 s, and each counting unit that is a calorie constant. Recording the integral coefficient of the calorific effect to obtain energy corresponding to (coefficient).
    [23] Each ammonia dose is controlled by the sampling tube 14 of the six valves 13. Although the volume of the sampling tube 14 is limited, the temperature and pressure of each introduced ammonia are different, so the amount of ammonia at the other temperature and pressure is corrected. In addition, when measuring the differential endothermic amount of the alumina tries to more accurately determine the differential endothermic amount of the alumina, the amount of ammonia in the sampling tube at the different temperature and pressure should be corrected. The method of correcting the input amount of ammonia involves absorbing ammonia in the sampling tube 14 with 180 ml of diluent at different temperatures and pressures, and determining the appropriate amount of ammonia with 0.1 N hydrochloric acid.
    [24] Purity, amount of impurities and the origin of high purity nitrogen and ammonia are shown in Table 1.
    [25] gasPurity,%Impurity content, ppmmanufacturer H 2 OH 2 CCOC n H High purity99.999<2.<<<1<0.-Beijing High purity99.999<1<---<2Beijing
    [26] According to one preferred embodiment of the present invention, the catalyst has the following pore dispersion: the volume of pores having a diameter of 100-200 mm 3 corresponds to 50-90% of the total volume, the pores having a diameter of 200-1000 mm 3 The volume of corresponds to 5-30% of the total pore volume, the volume of the pores having a diameter of 1000mm 3 or more corresponds to 5-40% of the total pore volume, the remaining volume is included as pores having a diameter of 100mm or less.
    [27] According to one more preferred embodiment of the invention, the catalyst has the following pore dispersion: the volume of pores having a diameter of 100-200 mm 3 corresponds to 55-80% of the total volume and has a diameter of 200-1000 mm 3 The pore volume corresponds to 5-20% of the total pore volume, the volume of the pores having a diameter of 1000 mm or more corresponds to 8-25% of the total pore volume, and the remaining volume is included as pores having a diameter of 100 mm or less. .
    [28] In the catalyst provided by the present invention, the content of molybdenum and / or tungsten is 1-10 wt% and preferably 4-9 wt%, based on the total weight of the catalyst and the oxide calculated. Or the amount of cobalt is 0.5-3 wt% and preferably 0.5-2.5 wt%.
    [29] In the process for preparing the catalyst provided by the present invention, the hydrated alumina is generally one or more hydrates used as precursors of alumina support materials such as bayerite, ga-boehmite and boehmite. Alumina, Ga-boehmite is preferred. Ga-boehmite is prepared by various conventional methods such as aluminum sulphate method or CO 2 -sodium meta-aluminate method.
    [30] The carbon black powder may be ethylene carbon black, channel black, or medical carbon black generally used in industry. The inventors of the present invention have found that the measured pH when the carbon black powder is wet is lower than 8 and the projection of the present invention is not obtained by using the carbon black powder directly. The inventors of the present invention have found that the pH of the wet carbon black powder has a great influence on the properties of the alumina support. In order to achieve the object of the present invention and to meet the demand of the endothermic amount of the alumina support, the pH of the wet carbon black powder should be measured. According to the present invention, the method for measuring the pH of the wet carbon black powder comprises mixing a nitrogen-containing alkali compound solution and the carbon black powder, adding an acid solution such that at least pH of the mixed solution is 8, and at least pH It is filtered to obtain a wet carbon black powder having 8, preferably 8-12. The nitrogen-containing alkali compound solution is at least one selected from the group consisting of aqueous solutions of water-soluble ammonia, organic amines and urea, preferably water-soluble ammonia. The acid solution is one or more selected from the group consisting of various organic and inorganic acids, preferably an organic acid in which nitric acid, hydrochloric acid and 1-5 carbon atoms are present, with nitric acid being particularly preferred.
    [31] The organic pore extenders are selected from one or more from polymerized alcohols and polymerized ethers that do not contain nitrogen, such as polyethylene glycols and polyvinyl alcohols of different molecular weights. It is also selected from one or more nonionic surfactants, such as, for example, linear polyether primary alcohols. The organic pore swelling agent may also be a mixture of polymerized alcohol and polymerized ethers and nonionic surfactants free of nitrogen. The peptizing agent may be selected from one or more conventionally used peptising agents such as soluble aluminum salts, organic acids and inorganic acids.
    [32] In the process provided by the present invention, suitable amounts of lubricants and / or extruders such as starch, cellulose and the like are well known to those skilled in the art and are added to the mixture for extrusion. The catalyst is prepared in various forms depending on the needs of the catalyst, such as cylinders, trilobal, quarterfoils, butterflies, and the like.
    [33] In the method provided by the present invention, the drying and calcining temperature of the molded alumina support material is a conventional drying and calcining temperature, for example the drying temperature is a normal temperature of 300 ° C and preferably 90-150 ° C. The calcination temperature is 500-700 ° C. and preferably 550-650 ° C., the calcination time is at least 0.5 hours and preferably 1-8 hours.
    [34] In addition, after the addition of a metal element, the drying and calcining temperature of the alumina is a conventional drying and calcining temperature, for example, the drying temperature is a normal temperature of 200 ℃ and preferably 90-150 ℃, the calcining temperature is 300 -600 ° C and preferably 450-550 ° C, the calcination time is at least 0.5 hours and preferably 1-8 hours.
    [35] The operating conditions of the protective catalyst according to the present invention are conventional conditions, for example, the reaction temperature is 230-420 ° C and preferably 300-410 ° C; The reaction pressure is 0.3-18 MPa and preferably 0.7-15 MPa; The liquid time-space velocity is 1-20 h −1 and preferably 2-10 h −1 ; The hydrogen / oil volume ratio is 90-2000 and preferably 200-1000.
    [36] The following examples are intended to illustrate the present invention in more detail, and do not limit the scope of the present invention.
    [37] Example
    [38] Example 1
    [39] Preparation of Catalysts According to the Invention
    [40] 1.5 g of clothing carbon black powder (manufactured by Dijin Carbon Black Co., Ltd.) is mixed with 20 ml of water-soluble ammonia at a concentration of 65 wt%. With a nitric acid solution at a concentration of 65 wt%, the pH of the mixture is titrated to 9. After filtration, the obtained wet carbon black powder was mixed with Ga-boehmite (trade name is aluminum hydroxide dry gel and manufactured by Changling Catalyst Co., Ltd., 65 wt% solids) and 2 g of a surfactant (under drying), and a linear poly Ether alcohol (trademark SA-20, manufactured by Dijin Assistant Co., Ltd.) is added. The mixture is milled for 5 minutes and 1.2 g of peptizer and aluminum nitrate (manufactured by Beijing Chemical Industries) are added. The milling is continued for 10 minutes (alumina: carbon black powder: organic pore dilator: peptizer = 1: 0.045: 0.061: 0.036). The resulting mixture is extruded into a trilobal strip with a circumscribed diameter of 1.8 mm, which is dried at 120 ° C. for 4 hours and calcined at 600 ° C. to obtain catalyst support Z1. Table 2 shows the total ammonia integral endothermic amount of the support material Z1, and shows the percentage of the ammonia integral endothermic amount having ammonia fine endothermic amount of 100 kJ / mol or more in the total ammonia integral endothermic amount. 40 g of support Z1 was charged with ammonium paramolybdate containing 26 ml of mixed nickel nitrate mixed solution and 19.7 g / l nickel oxide and 83.7 g / l molybdenum oxide, followed by catalyst Dry at 120 ° C. and calcined at 480 ° C. for 4 hours to obtain C1. The metal content and physicochemical properties of catalyst C1 are shown in Table 3-5. Here, the contents of Nigel, Molybdenum and Tungsten are obtained by calculation. The specific surface area, pore volume and pore dispersion rate are determined by the mercury intrusion method. The compressive strength is mentioned in "Analytical Methods of the Petroleum Industry (PIPP Test Method)" (pp. 66-67, Science Press, 1990).
    [41] Comparative Example 1
    [42] Catalyst prepared according to the method of Chinese patent 1103009A.
    [43] The catalyst is prepared by the method of Example 1, except that the 1.8 g of carbon black powder is used directly without titrating the pH with water-soluble ammonia and nitric acid. Reference support material ZB2 and reference catalyst CB1 are obtained. Table 2 shows the percentage of ammonia integral endothermic amount having ammonia fine endothermic amount of 100 kJ / mol or more in the total ammonia integral endothermic amount and total ammonia integral endothermic amount of the support material ZB1. Table 3-5 shows the composition and physicochemical properties of the catalyst CB1.
    [44] Comparative Example 2
    [45] Preparation of Reference Catalyst.
    [46] The support and catalyst are prepared according to the method of Example 1 of US Pat. No. 4,448,896. Except for the pseudo-boehmite and carbon black powder on Example 1, an unsuitable pH is used, and the boehmite and carbon black powder of Example 1 of US Pat. No. 4,448,896 is used instead. Extrusion conditions, drying and drying temperature and time, injection solution is the same as in Example 1 of the present invention. Reference catalyst ZB2 and reference catalyst CB2 are obtained. Table 2 shows the percentage of the ammonia integral endotherm having the ammonia derivative endothermic amount of 100 kJ / mol or more in the total ammonia integral endothermic amount and the total ammonia integral endothermic amount of the support material ZB2. Table 3-5 shows the composition and physicochemical properties of catalyst CB2.
    [47] Comparative Example 3
    [48] Preparation of Reference Catalyst.
    [49] 1.5 g of garment carbon black powder (same as Example 1) was uniformly mixed with 33 g (dry basis) of Ga-boehmite (same as Example 1), and 2 g of the surfactant of Example 1 was added do. The mixture is milled for 5 minutes, to which 39.2 g of 4.3 wt% water soluble nitrate solution is added, and the mixture is kneaded. Then 18.8 g of 2.1 wt% aqueous ammonia is added. The mixture is molded by extrusion, dried and calcined according to the method of Example 1 to obtain the reference catalyst support ZB3. The support material ZB3 is injected into the metal element, dried and calcined according to the method of Example 1 to obtain the reference catalyst CB3. Table 2 shows the percentage of the ammonia integral endotherm having the ammonia derivative endothermic amount of 100 kJ / mol or more in the total ammonia integral endothermic amount and the total ammonia integral endothermic amount of the support material ZB3. Table 3-5 shows the composition and physicochemical properties of catalyst CB3.
    [50] Comparative Example 4
    [51] Preparation of Reference Catalyst.
    [52] The catalyst is prepared as EK in the method of Comparative P 4 except that the acid solution is 7.1 g and the amount of water-soluble ammonia is 3.4 g. Reference support material ZB4 and reference catalyst CB4 are obtained. Table 2 shows the percentage of the ammonia integral endotherm having the ammonia derivative endothermic amount of 100 kJ / mol or more in the total ammonia integral endothermic amount and the total ammonia integral endothermic amount of the support material ZB4. Table 3-5 shows the composition and physicochemical properties of catalyst CB4.
    [53] Example 2
    [54] Preparation of the catalyst according to the invention.
    [55] The catalyst support and the catalyst were titrated at 10.0 and the nickel oxide and molybdenum oxide contents of the mixed solution of nickel nitrate and ammonium paramolybdate were 23.1 g / l and 92.3 g / l, respectively. Prepared according to the method of Example 1. Support material Z2 and catalyst C2 are obtained. Table 2 shows the percentage of ammonia integral endothermic amount having ammonia differential endothermic amount of 100 kJ / mol or more in the total ammonia integral endothermic amount and total ammonia integral endothermic amount. Table 3-5 shows the composition and physicochemical properties of Catalyst C2.
    [56] Example 3
    [57] Preparation of the catalyst according to the invention.
    [58] 3 g of polyethylene glycol (molecular weight 1500, Tantai Fine Chemicals, Tanjin) is used in place of 2 g of SA-20 and 1.2 g of nitric acid is used in place of 1.2 g of aluminum nitrate (alumina: carbon black) Powder: organic pore dilator: peptizer = 1: 0.039: 0.12: 0.036), a mixed solution of nickel nientite and ammonium metatungsten containing 24.9 g / l nickel oxide and 96.3 g / l turnsten oxide Prepared according to Example 1, except that the mixed solution of nickel sslxmfpdlxm and Ammonium metatungsten of Example 1 was substituted. Catalyst support Z3 and catalyst C3 are obtained. Table 2 shows the percentage of ammonia integral endothermic amount having ammonia differential endothermic amount of 100 kJ / mol or more in the total ammonia integral endothermic amount and total ammonia integral endothermic amount. Table 3-5 shows the composition and physicochemical properties of Catalyst C3.
    [59] Example 4
    [60] Preparation of the catalyst according to the invention.
    [61] The catalyst support and the catalyst were each mixed solution of nickel nitrate and ammonium paramolybdate with 35.4 g / l nickel oxide and 1344.83 g / l molybdenum oxide and 11.8 g / l nickel oxide and 73.7 g / l, respectively. Molybdenum oxide, wherein the temperature is 500 ℃ and 550 ℃, respectively, and the calcination time is prepared by the method of Example 1 except that it is 8 hours and 4 hours, respectively. Catalysts C4 and C5 are obtained. Table 3-5 shows the composition and physicochemical properties of the catalyst.
    [62] Example numberSupport material numberTotal Ammonia Integral Endotherm, J / gPercentage of ammonia integral endotherm with ammonia fine endothermic amount of 100 kJ / mol or more,% of total ammonia integral endothermic amount OneZ 1229.78 Comparative Example 1ZB 13710.32 Comparative Example 2ZB 24011.62 Comparative Example 3ZB 35612.41 Comparative Example 4ZB 44511.60 2Z 2258.80 3Z 3219.88
    [63] Example numberCatalyst numberMetal content in the catalyst, wt% Nickel oxideMolybdenum oxideTungsten oxide OneC11.25.1- Comparative Example 1CB11.25.1- Comparative Example 2CB21.25.1- 3 in comparisonCB31.25.1- Comparative Example 4CB41.25.1- 2C21.45.6- 3C31.5-5.8 4C42.18.0- 5C50.74.5-
    [64] Example numberCatalyst numberPore volume ml / gSpecific surface area m 2 / gStrength N / mm OneC10.6518016.2 Comparative Example 1CB10.5118510.5 Comparative Example 2CB20.6815010.03 Comparative Example 3CB30.741528.2 Comparative Example 4CB40.6518010.4 2C20.6417214.7 3C30.6517713.5 4C40.6618215.1 5C50.7217814.3
    [65] Example numberCatalyst numberPore dispersion rate,% <100Å<100-200Å200-500 yen500-1000Å> 1000Å OneC18.267.44.46.014.0 2C28.065.24.86.715.3 3C38.067.64.26.713.5 4C48.255.04.79.114.0 5C58.064.75.59.212.6
    [66] As shown in Table 2, the total ammonia integral endothermic amount of all catalyst supports according to the present invention does not exceed 25 J / g, and the percentage of ammonia integral endothermic amount having ammonia fine endothermic amount of 100 kJ / mol or more in the total ammonia integral endothermic amount is While less than 10%, the conventional catalyst support is the opposite.
    [67] As shown in Table 4, the catalyst according to the present invention has a higher strength. The strength of all catalysts according to the invention is at least 13.5 N / mm, while the strength of all conventional catalysts does not exceed 10.5 N / mm.
    [68] Example 6
    [69] The following examples show the catalytic efficacy of the catalysts according to the invention.
    [70] Puffs of naphtha's natural oils until iron naphthenate contains 100 ppm of iron to obtain feed oil 1 # (its characteristics are shown in Table 6) to evaluate the steel and coke-sedimentation-resistance performance Light vacuum gas oil (LVGO) is added, which is a further refined oil (containing 27 ppm of iron). To a 0.5 l vibratory pressure furnace 10 g of catalyst C1 of 40-60 mesh and 200 ml of the feed oil 1 # are added. After the air was filled with hydrogen, the pressure furnace was pressurized with hydrogen at 4 MPa and heated at 380 ° C. The pressure is raised to 8 MPa. The reaction proceeds for 2 hours at a stirring rate of 60 times / minute. The pressure stripped off with hydrogen for 1 hour. After the oil and catalyst are separated, the iron content in the resulting oil is analyzed. The amount of coke precipitate and mercury intrusion pore volume are determined after toluene solex extraction. The results are shown in Table 7, wherein a method for determining coke precipitate is mentioned in "Analytical Methods in the Petrochemical Industry (RIPP Test Method)" (PP. 418-419, Science Press, 1990). A method for determining the iron content is mentioned in "Analytical Methods in the Oil and Chemical Industry (RIPP Test Method)" (PP. 380-383, Science Press, 1990).
    [71] The dispersion of iron precipitated in the radial direction of the particles of the catalyst C1 is observed with an electron probe micro-scanning analyzer (model EPM 8100Q, Shimazu, Japan). The results are shown in FIG.
    [72] Comparative Example 5-8
    [73] The comparative example below shows the catalytic efficiency of the reference catalyst.
    [74] The catalyst was evaluated according to the method of Example 6 except that the reference catalysts CB1 to CB4 prepared in Comparative Examples 1-4 were used in place of C1, respectively. The carbon precipitation, steel removal rate, and pore volume reduction rate of the catalysts CB1-Cb4 are shown in Table 7. The dispersion of iron precipitated in the radial direction of the particles of the catalyst C1 is observed with an electron probe micro-scanning analyzer (model EPM 8100Q, Shimazu, Japan). The results are shown in FIG.
    [75] Comparative Example 7-10
    [76] The comparative example below shows the catalytic efficiency of the reference catalyst.
    [77] The activity of the catalyst is evaluated according to the method of example 6 except that catalysts C2-C5 are used in place of C1. The evaluation results are shown in Table 7.
    [78] Supply oil numberOne #2 # Supply oil nameIron naphtelate with furfural refined oil LVGO from naphtha's natural oilsLVGO, a furfural refined oil of naphtha's natural oils Density (20 ° C), g / cm 2 0.97160.9807 Viscosity (40 ° C), mm 2 / s50.163.2 Carbon residue, wt%1315.2 Iron content, ppm10027.2
    [79] Example numberCatalyst numberCarbon precipitation, wt%Steel removal rate, wt%Pore volume reduction rate,% 6C16.885.215.0 Comparative Example 5CB110.565.340.2 Comparative Example 6CB215.882.138.0 Comparative Example 7CB314.780.124.1 Comparative Example 8CB418.880.930.4 7C28.287.420.1 8C38.887.315.3 9C46.084.313.0 10C58.082.721.9
    [80] The results in Table 7 show that the activity of the catalyst provided by the present invention for steelmaking is significantly higher than the activity of the reference catalyst and the rate of reduction of the amount of coke precipitation and pore volume is significantly lower than that of the reference catalyst. The results in FIGS. 1 and 2 show that the iron precipitated on the catalyst provided by the present invention is more uniformly dispersed and there is no significant difference in iron content between the center and the surface. However, the dispersion of the precipitated catalyst on the reference catalyst CB1 is very heterogeneous. The amount of iron precipitated at the surface of the catalyst particles is significantly higher than at the center portion. This means that the catalyst provided by the present invention has a greater ability to precipitate iron.
    [81] Example 11
    [82] This example shows the stability of the catalyst according to the invention.
    [83] Feed oil 2 # in Table 6 is used as a raw material to evaluate the stability of catalyst C1 in removing carbon residues. The reaction is carried out in a 100 ml continuous bottom-flow reactor with 100 ml of 40-60 mesh catalyst. The reaction conditions are a temperature of 380 ° C., a pressure of 10 MPa, a hydrogen / oil volume ratio of 800 and a liquid time-space velocity of 10 h −1 . Line 1 of FIG. 3 shows the removal rate of the carbon residue as a function of time.
    [84] Comparative Example 9-11
    [85] The following comparative example shows the stability of the activity of the reference catalyst.
    [86] The stability of the activity of the catalyst is evaluated according to the method of Example 11 except that the reference catalysts CB1, CB2 and CB3 are used in place of catalyst C1, respectively. The results are shown in lines 2, 3 and 4 of FIG. 3, respectively.
    [87] From the results in FIG. 3, it can be seen that the reduction rate of the carbon residue removal activity of the catalyst according to the present invention is slower than that of the reference catalyst, and the catalyst according to the present invention has higher activity stability.
    [88] Advantages of the protective catalyst according to the invention are as follows:
    [89] 1. Compared with the conventional catalyst, the catalyst according to the present invention has higher catalytic activity. For example, 10 g of the catalyst according to the invention, containing 1.2 wt% nickel oxide and 5.1 wt% molybdenum oxide, is fed a feed containing 100 ppm of iron on 0.5 l in a stirred pressure reaction at a temperature of 380 ° C. and a pressure of 8 MPa. The iron is removed (iron deferrization) from 200 ml of oil, and the iron removal rate is 65-82% when the conventional catalyst contains the same amount of molybdenum and nickel and is used under the same conditions, whereas the catalyst according to the present invention Is 85% or more after 2 hours of reaction.
    [90] 2. The catalyst provided by the present invention has less precipitation of coke, resulting in lower rate of reduction of pore volume and better activity stability. For example, 10 g of the catalyst according to the invention containing 1.2 wt% nickel oxide and 5.1 wt% molybdenum oxide remove iron from 200 ml of feed oil containing 100 ppm of iron on 0.5 l in a stirred pressure reaction, The coke sedimentation rate is only 6.8% and the pore volume reduction rate is 15% after 2 hours reaction, but the coke sedimentation rate is 10.5- when the conventional catalyst contains the same amount of molybdenum and nickel and is used under the same conditions. It increases to 18.8% and decreases the pore volume by 24-40%. As another example, the catalyst according to the invention containing 1.2 wt% nickel oxide and 5.1 wt% molybdenum oxide has a temperature of 380 ° C., a pressure of 10 MPa, a hydrogen / oil volume ratio of 800 and a liquid time of 10 h −1 . Under the conditions of space velocity, the carbon residue of 200 ml of feed oil containing 15,2 wt% of carbon residue on 100 ml of continuous bottom-flow reactor is removed, the removal rate of which is still 70 wt after 3000 hours of reaction. On the other hand, the removal rate of the carbon residue after 3000 hours of reaction when the conventional catalyst is used under the same conditions and containing the same content of molybdenum and nickel is 32-65 wt%.
    [91] 3. The protection catalyst according to the present invention has a higher strength. For example, the strengths of all catalysts according to the present invention are 13.5 N / mm or more, while the strengths of all the catalysts in the past are 10.5 N / mm or less. Therefore, the catalyst according to the present invention has the advantage of extending the operating time in the process.
    [92] The protective catalyst according to the invention can be used as a protective agent for feed oils having a high content of impurities and is particularly suitable for use in frontmounted beds for protecting downstream main catalysts.
    权利要求:
    Claims (19)
    [1" claim-type="Currently amended] In the guard catalyst,
    The catalyst comprises an alumina support and molybdenum and / or tungsten and nickel and / or cobalt supporting the alumina support,
    Here, the total ammonia integral adsorption heat of the alumina support material does not exceed 25 J / g, and the percentage of the ammonia integral endotherm having ammonia differential adsorption heat of 100 kJ / mol or more is A protective catalyst, characterized in that it does not exceed 10% of the total ammonia integral endotherm.
    [2" claim-type="Currently amended] The total ammonia integral endothermic amount of the ammonia support material is 20-25 J / g, and the percentage of the ammonia integral endothermic amount having ammonia fine endothermic amount of 100 kJ / mol or more is 7% of the total ammonia integral endothermic amount. Protection catalyst, characterized by -10%.
    [3" claim-type="Currently amended] The protective catalyst according to claim 1 or 2, wherein the alumina is γ-alumina.
    [4" claim-type="Currently amended] The method of claim 1,
    The catalyst has the following pore dispersions:
    The volume of pores with a diameter of 100-200 mm 3 corresponds to 50-90% of the total pore volume, and the volume of pores with a diameter of 200-1000 mm corresponds to 5-30% of the total pore volume. The volume of the pores having 5 to 40% of the total pore volume, the remaining volume is a protective catalyst, characterized in that the pores having a diameter of less than 100Å.
    [5" claim-type="Currently amended] The method of claim 4, wherein
    The catalyst has the following pore dispersions:
    The volume of pores with a diameter of 100-200 mm 3 corresponds to 55-80% of the total pore volume, and the volume of pores with a diameter of 200-1000 mm is 5-20% of the total pore volume. A protective catalyst, characterized in that the volume of the pores having 8-25% of the total pore volume, the remaining volume is a pore having a diameter of less than 100Å.
    [6" claim-type="Currently amended] The method of claim 1, wherein the content of molybdenum and / or tungsten is 1-10 wt%, and the amount of nickel and / or cobalt is 0.5-3 wt%, based on the total weight of the catalyst and calculated as oxide. A protective catalyst, characterized in that.
    [7" claim-type="Currently amended] 7. The method of claim 6, wherein the content of molybdenum and / or tungsten is 4-9 wt% and the amount of nickel and / or cobalt is 0.5-2.5 wt% based on the total weight of the catalyst and the calculated oxides. A protective catalyst, characterized in that.
    [8" claim-type="Currently amended] In the method of producing a catalyst of claim 1,
    The method comprises the steps of mixing hydrated ammonia, carbon black powder, organic pore dilator, peptizator and aqueous solution, molding by extrusion, drying, calcining, metal components Injecting the step, and drying and calcining again,
    Wherein the carbon black powder is titrated and the wet carbon powder has a pH of at least 8. The amount of each component is the weight of the carbon black powder relative to the weight 1 of the alumina is 0.03 to 0.05, the weight of the organic pore dilator is 0.05-0.2 and the weight of the peptizing agent is 002-0.05, characterized in that .
    [9" claim-type="Currently amended] The method of claim 8, wherein the pH of the wet carbon black powder is 8-12.
    [10" claim-type="Currently amended] The method of claim 8, wherein the hydrated alumina is pseudo-boehmite.
    [11" claim-type="Currently amended] The method of claim 8, wherein the pH of the wet carbon black powder is titrated by mixing a nitrogen-containing alkali compound solution and the carbon black powder, and adding an acid solution such that the pH of the mixed solution is at least 8. 10. And filtering to obtain a wet carbon black powder having a pH of at least 8.
    [12" claim-type="Currently amended] The method for producing a protective catalyst according to claim 11, wherein the pH of the mixture of the nitrogen-containing alkali compound solution and the carbon black powder is 8-12.
    [13" claim-type="Currently amended] The method of claim 11 or 12, wherein the nitrogen-containing alkaline compound solution is one or more selected from the group consisting of ammonia water-soluble solution, organic amine water-soluble solution and urea solution, the acid solution is nitric acid, hydrochloric acid And one or more selected from the group consisting of organic acids in which 1-5 carbon atoms are present.
    [14" claim-type="Currently amended] The method for producing a protective catalyst according to claim 13, wherein the nitrogen-containing alkali compound solution is water-soluble ammonia and the acid solution is a nitric acid solution.
    [15" claim-type="Currently amended] The method of claim 8, wherein the organic pore dilator is selected from one or more selected from the group consisting of polymerized alcohols and polymerized ethers that do not contain nitrogen, and one or more selected from the group consisting of nonionic surfactants. And also a mixture of said nitrogen-free polymerized alcohol and a mixture of polymerized ethers and nonionic surfactants.
    [16" claim-type="Currently amended] The method of claim 15, wherein the organic pore extender is selected from the group consisting of polyethylene glycol (polyetylene glycol) and polyvinyl alcohol of different molecular weight, and also linear polyether primary alcohol or mixtures thereof Method for producing a protective catalyst, characterized in that selected from.
    [17" claim-type="Currently amended] The method of claim 8, wherein the peptizing agent may be selected from one or more selected from the group consisting of soluble aluminum salts, organic acids and inorganic acids.
    [18" claim-type="Currently amended] The method of claim 8, wherein the molded alumina support material has a drying temperature of 90-150 ° C., a calcination temperature of 550-650 ° C., and a calcination time of 1-8 hours.
    [19" claim-type="Currently amended] The method of claim 8, wherein after the metal element is injected, the drying temperature is 90-150 ° C., the calcination temperature is 450-550 ° C., and the calcination time is 1-8 hours.
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    同族专利:
    公开号 | 公开日
    ITMI20011979A1|2002-03-25|
    CN1115388C|2003-07-23|
    KR100636432B1|2006-10-18|
    US20020065193A1|2002-05-30|
    CN1344781A|2002-04-17|
    ITMI20011979D0|2001-09-24|
    US6673741B2|2004-01-06|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-09-25|Priority to CN00124903.7
    2000-09-25|Priority to CN 00124903
    2001-09-25|Application filed by 차이나 페트로리움 앤드 케미컬 코포레이션, 추후보정, 리서치 인스티튜트 오브 페트롤리움 프로세싱 시노펙
    2002-03-30|Publication of KR20020024566A
    2006-10-18|Application granted
    2006-10-18|Publication of KR100636432B1
    优先权:
    申请号 | 申请日 | 专利标题
    CN00124903.7|2000-09-25|
    CN 00124903|CN1115388C|2000-09-25|2000-09-25|Hydrogenation protecting catalyst and its prepn.|
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