• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Provided is a method for upgrading a bio-based material, the method comprising the steps of pre-treating bio-renewable oil(s) and/or fat(s) to provide a biobased fresh feed material, hydrotreating the bio-based fresh feed material, followed by separation, to provide a bio-propane composition.
    公开号:FI20196063A1
    申请号:FI20196063
    申请日:2019-12-06
    公开日:2020-12-31
    发明作者:Antti Ojala；Jukka Myllyoja；Jaana Makkonen；De Velde Rogier Van；John Jamieson
    申请人:Neste Oyj；
    IPC主号:
    专利说明:

    [0119] [0119]. The active material may comprise a purification catalyst or catalysts as described in WO2016/023973A1, paragraph [0061], [0062], [0063], and/or
    [0064] [0064]. The purification treatment may be a purification treatment as described in EP2679656A1, paragraphs [0043] to [0082]. The purification treatment may be a purification treatment as described in US2010/0331502A1, paragraphs [0092] to [0119], and/or paragraph [0126], and/or Example 2. The purification — treatment may be a purification treatment as described in W02016/023973A1, paragraphs [0056] to [0067]. The purification treatment may be a purification treatment as described in WO03/048087A1, p. 11, II. 12 - p. 15, II. 29, and/or p. 16, Il. 1 - p. 21, II. 2, and/or p.23, II. 14 - p. 24, II. 13, and/or Example 1 and/or Example 2. Typically, impurities deactivate or foul the active material during purification treatment. Thus, the active material may be regenerated to at least partially regain its purification activity. Any regeneration process suitable for re- activating the active material may be used. For example, the active material may be regenerated as described in WO2016/023973A1, paragraphs p. 12, II. 3-10, or as described in EP2679656A1, paragraphs [0108] to [0118], or as described in WO03/048087A1, p. 24, II. 14 - p. 25 II. 32. For example, a CuO catalyst may be regenerated by contacting the CuO catalyst with Hz. A CuO: o catalyst may be regenerated by contacting the CuO: catalyst with molecular > oxygen. A zeolitic molecular sieve may be regenerated by applying heat and N contacting the zeolitic molecular sieve with an inert gas flow, such as a nitrogen © flow. = N The purification treatment may comprise at least one of the following steps: i) S contacting at least a portion of the dehydrogenation product with a CuO catalyst 2 to remove oxygen, ii) contacting at least a portion of the dehydrogenation N product with Hz to remove dienes / alkynes by hydrogenation, iii) contacting at least a portion of the dehydrogenation product with a CuO; catalyst to remove CO by oxidation, or iv) contacting at least a portion of the dehydrogenation product with a zeolitic molecular sieve to remove CO.
    Optionally, the purification treatment may comprises removing secondary impurities, such as at least one of COS, H2S, or CS,, by contacting at least a portion of the dehydrogenation product with anactivated alumina catalyst, such as Selexorb™. The method of the present invention may comprise subjecting at least a portion of the dehydrogenation product to a polymerisation treatment to form polymers.
    The portion of the dehydrogenation product subjected to the polymerisation — treatment may be obtained directly from the dehydrogenation process or from the purification treatment described in the previous sections.
    Optionally, the portion of the dehydrogenation product subjected to the polymerisation treatment may partially have been subjected to the purification treatment described in the previous sections and partially be obtained directly from the dehydrogenation process.
    As mentioned previously, due to the low amount of CO, CO2, and dienes / alkynes in the dehydrogenation product formed in the manufacture or dehydrogenation step, subjecting the dehydrogenation product or a portion thereof to a purification treatment before polymerisation may be redundant.
    Conseguently, the method of the present invention may comprise subjecting the propylene fraction (i.e. the bio-propylene composition) of the dehydrogenation product to a polymerisation treatment to form polypropylene without further o purification.. & N The polymerisation treatment may include solution polymerisation, gas-phase © fluidized bed polymerisation, slurry phase polymerisation, such as bulk = polymerisation, high-pressure polymerisation, or a combination thereof.
    The N polymerisation treatment may be performed in one or more polymerisation S reactors.
    Each of the one or more polymerisation reactors may comprise 2 multiple polymerisation zones.
    The composition of the feed fed to the N polymerisation zones may vary between the zones.
    For example, different portions of the dehydrogenation product may be fed to different zones and a comonomer may optionally be fed to one or more of the polymerisation zones.
    The comonomer fed to the polymerisation zones may be a different comonomer for different polymerisation zones.
    The polymerisation reactor may, for example, be a continuous stirred tank type reactor, a fluidised bed type reactor, such as a gas-phase fluidised bed reactor, or a stirred gas- phase type reactor in horizontal or vertical configuration.
    Preferably, the polymerisation treatment is catalytic polymerisation.
    The — polymerisation treatment may specifically comprise contacting at least a portion of the dehydrogenation product with a polymerisation catalyst optionally in the presence of molecular hydrogen to form polymers.
    Preferably, the contacting is performed in one or more polymerisation reactors.
    In embodiments, wherein the polymerisation treatment is a catalytic polymerisation treatment, the molecular weight of the formed polymers may be regulated, for example, by the presence of hydrogen in the polymerisation treatment or by controlling the reaction temperature, depending on the polymerisation catalyst(s) employed.
    In embodiments, wherein the polymerisation treatment is a catalytic polymerisation treatment, the polydispersity is preferably mainly controlled by the catalyst employed.
    The polymerisation treatment may be a polymerisation treatment forming polymers having monomodal, bimodal, or multimodal molecular weight distributions. o Bimodality or multimodality may be achieved by employing a bi-functional > catalyst system in one reaction media (i.e. one reactor or polymerisation zone), N or with a typical catalyst (i.e non-bi-functional) but with variable reaction media © (i.e. combination of multiple polymerisation zones or multiple polymerisation = reactors with different feeds). Other properties of the polymers formed in the N polymerisation treatment, such as polarity, unsaturation content and/or S polydispersity, may be controlled by controlling the reaction temperature, 2 pressure and residence time, or through injecting a predetermined type and N amount of co- and/or termonomers to the polymerisation process at a predetermined location, e.g. in one or more of the polymerisation zones optionally comprised in the polymerisation reactor(s). Optionally, the density, elastic modulus and other properties of the polymers formed in the polymerisation treatment may be controlled by introducing to the polymerisation treatment a comonomer or combinations of multiple monomers, for example at least one of ethylene (in polypropylene production), propylene (in polyethylene production), 1-butene, 1-hexene (also (1,5- hexadiene), 1- octane (also 1,7-octadiene) and 1-decene (also 1,9 -octadiene) or higher alpha olefins or alpha-omega dienes. In certain embodiments, the polymerisation treatment may be a slurry polymerisation treatment comprising dissolving in a diluent, such as propane, propene or hexane, at least a portion of the dehydrogenation product together with molecular hydrogen, and optionally a comonomer, to form a solution, and contacting the solution with a catalyst to form polymers. The polymerisation treatment may be a polymerisation treatment as described in EP2679656A1, paragraphs [0090] - [0097]. The polymerisation treatment may be a polymerisation treatment as described in US2010/0331502A1, paragraphs [0050] - [0066], and/or paragraphs [0123] - [0125], and/or Example 3. The polymerisation treatment may be a polymerisation treatment as described in W02016/023973, paragraphs [0006] - [0020], and/or paragraphs [0024] -[0043]. The method may comprise a combination of a o purification treatment and a polymerisation treatment as described in > US2010/0331502A1, paragraphs [0092] - [0119]. Polypropylene (PP), or co- N or terpolymers thereof, is thus formed in the polymerisation treatment. © Polypropylenes of different density ranges and product classes, such as = homopolymers, high crystallinity homo-polymers, random co-polymers, impact N co-polymers, block co/terpolymers, hetero-phasic co-polymers, or combinations S thereof may be formed in the polymerisation treatment of the propylene 2 fraction. Similarly, the process conditions and catalysts mentioned inN
    WQ09924478 Al, WO9924479 Ai, or WO0068315A1 may be used in the present invention.
    An example of a polymerisation catalyst for catalytic polymerisation is Ziegler type catalysts, which utilise aluminum alkyl compounds, such as trimethylaluminum, triethylaluminum, tri-isobutylaluminum, methylaluminoxane (MAO), or tri-n-hexylaluminum as co-catalyst activators to activate titanium or vanadium sites on the catalyst, such as titanium tetrachloride.
    The aluminium alkyl compounds can additionally be used as scavengers of polymerisation poisons in the reaction media.
    Preferable polymerisation catalysts which may be employed in accordance with the invention are furthermore those mentioned in EP0591224, EP1028985, which are herewith incorporated by reference in their entirety.
    The polymerisation catalyst for catalytic polymerisation may be supported if desired or required by the process.
    The support material may be magnesium dichloride or silica support onto which active sites and optionally internal donors, such as benzoate, phthalate, diether, or succinate may be impregnated.
    Additionally, external donors, such as ethyl p-ethoxybenzoate (PEEB), dicyclopentyldimethoxysilane (DCPMS), diisopropyldimethoxysilane (DIPS), diisobutyldimethoxysilane, cyclohexyldimethoxymethylsilane (CHMMS), dicyclopentyldimethoxysilane (DPDMS), or alkoxysilanes, such as Me(EtO)3Si, Ph(EtO)3Si, Ph2(Me0)2Si, Ph2(EtO)2Si, Ph(EtO)3Si, may be added to the o polymerisation treatment. & N In certain embodiments, the polymerisation catalyst may be stereo modifiers, © such as cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, = diisobutyldimethoxysilane, diisopropyldimethoxysilane, N isobutylisopropyldimethoxysilane, n-propyltrimethoxysilane, S isobutylmethyldimethoxysilane, tetraethoxysilane, tetramethoxysilane, 2 isobutyltriethoxysilane, n-propyltriethoxysilane, isobutyltrimethoxysilane, N and/or cyclohexylethyldimethoxysilane.
    A further example of a polymerisation catalyst for catalytic polymerisation are so called single site catalyst systems of which there are various types, such as Kaminsky type, combination type, constrained-geometry type, and late transition metal catalyst type. The polymerisation catalyst may contain a metallocene complex of zirconium, titanium, or hafnium which usually contains two cyclopentadienyl rings or monolobal eguivalents to cyclopentadienyl and either a perfluorinated boron- aromatic compound, an organoaluminum compound, or methylaluminoxane — where the rings contain various alkyl substituents, both linear and cyclic. Said rings may be linked together by bridging groups. Alternatively, the polymerisation catalyst may contain monocyclopentadienyl derivatives of titanium or zirconium, one of the carbon atoms in the cyclopentadienyl ring being additionally linked to the metal atom by a bridge. These complexes which may be contained in the polymerisation catalyst are typically converted to polymerization catalysts by reacting said complexes with methylaluminoxane or by forming ionic complexes with noncoordinative anions. Other complexes, such as cyclopentadienyl group 4 ketimide complexes, cyclopentadienyl group 4 siloxyl complexes, and/or non-cyclopentadienyl group 4 phosphinimide complexes may optionally be used for forming polymerisation catalysts. A further type of polymerisation catalysts for catalytic polymerisation is Phillips type catalysts which may comprise hexavalent chromium supported on a high- o surface-area, wide-pore oxide carrier, such as silica, alumina, titania, > aluminophosphates, or combinations where a mixture of chromium oxide and N silicon oxide (CrO3/SiO2) may be used to create active sites. 3 = The polymerisation catalyst may be a polymerisation catalyst as described in N EP2679656A1, paragraphs [0098] - [0107]. The polymerisation catalyst may be S a polymerisation catalyst as described in US2010/0331502A1, paragraphs 2 [0067] - [0091], and/or Example 1. The polymerisation catalyst may be a
    N polymerisation catalyst as described in WO2016/023973A1, paragraphs [0045] - [0055]. The properties of the polymers formed in a catalytic polymerisation treatment, such as molecular weight, molecular weight distribution, long chain branching content, density, viscosity, crystallinity, amorphous content, shear thinning behaviour, other rheological parameters, composition distribution indicators such as comonomer distribution breadth index (CDBI), comonomer distribution constant (CDC), thermal stability, melting temperature, crystallisation temperature, melt flow rate (MFR) and others, may be influenced by selection — of the catalyst type or catalysts types (as hybrid versions are available and it is possible to feed two or more different catalysts to one or more reactors), the comonomer type, comonomer content, additional monomer(s) and their type and amount(s). After the polymerisation process, the formed polymers may be further modified to form polymer material. The formed polymers may be modified via one or more extrusion or compounding steps where additional ingredients are optionally added. Such additional ingredients are, for example, stabilisation additives, impact modifiers such as plastomers or elastomers, other blend components in general, fillers such as talc's, glass fibres, carbon fibres, nanoclays or other nanomaterials, carbon black, nucleating agents (which are also possible to add in-situ during the polymerisation treatment or preparation of a polymerisation catalyst), UV stabilisers, pigments, crosslinking or o visbreaking agents such as organic peroxides, acid scavengers such as calcium > stearate, polymer processing aids for example fluoropolymers. Additional N comonomers or functional groups, such as silanes and/or maleic anhydride, may © optionally be added to the formed polymers after the polymerisation treatment = via reactive extrusion. The formed polymers may after the polymerisation N treatment be subjected to further processing steps in conversion. These optional S modifications enable production of at least partially bio-based (renewable) 2 versions of the full spectrum of fossil based polymer materials, particularly PE
    N and/or PP materials, and other materials and articles derived from these polymer materials.
    The polymers formed in the polymerisation treatment, or the polymer material derived from the formed polymers as described above, may be converted or formed to final parts or products by multiple processes such as extrusion processes for film, sheet, fibres, pipe, profiles, wires and cables, injection moulding processes, hot melt spinning, blow moulding or extrusion blow moulding processes, rotational moulding processes, hot dip coating, calendaring, compacting, chemical and/or physical foaming processes or others. — The polymer material derived from the polymers formed in the polymerisation treatment may be used as a direct substitute for fossil based polymer materials in these conversion processes.
    The polymer material derived from the polymers formed in the polymerisation treatment may optionally be blended with other types of polymers, fillers, additives, or combinations thereof and may optionally be included in composite materials or multilayer structures with other materials, such as other polymer materials, for example fossil based polypropylene, polyvinylidene chloride, polyesters, ethylene vinyl alcohol, aluminium, etc.
    The final parts or products described above may be used in a variety of applications.
    For example, said final parts or products may be used in packaging applications including food and non-food packaging, flexible packaging, heat seal, thin wall packaging, transparent packaging, packaging of dangerous goods, packaging for detergents and personal care, packaging of surfactants, o etc.
    Said final parts or products may be used in consumer goods applications > such as caps and closures, toys, bottles, watering cans, white goods and N appliances, engineering parts, crates, cartridges, leisure products, housewares, © panels and profiles, lids, shoe insoles, pipe clamps, car boot/trunk lining, = brushes, corks, ink cartridges, flippers, brushes, collector trays for perforators, N seals, hand grips, garden furniture, houseware, thin walled injection moulded S parts, co-injection moulded parts, food containers, reusable containers, 2 luggage, ice cream containers, dairy products containers, drinking cups, high N impact containers, high stiffness containers, DVD boxes, etc.
    Said final parts or products may be used in automotive applications, such as parts and assemblies for exterior, interior, under-the-bonnet, bumpers, body panels, trims, facias, dashboards, door claddings, climate control or cooling systems, air intake manifolds or battery cases, instrument panels or soft touch controls, airbag covers, roof pillar mouldings, under the hood belt or hoses, weather strips, anti- vibration systems, rocker panels or side moulding, instrument panels, structural parts, etc. Said final parts or products may be used in wire and cable applications, such as insulation, jacketing or semi-conductive materials for extra-high, high and medium voltage energy transmission and distribution in AC or DC, data or communication cables or jacketing, building wires or cables, — automotive wires or cables, photovoltaic encapsulants, etc. Said final parts or products may be used in pipe applications such as multilayer pipes, pressure pipes, gas pipes, drinking water pipes, industrial pipes, wastewater or sewage pipes, in-house plumbing or heating, mono or multi-layer onshore or offshore oil or gas pipeline coatings, pressure pipes for sandless bedding, no dig installation pipes, linings and relinings, corrugated industrial pipes, fittings, mechanical-joint compression fittings, solar heat absorbers, etc. Said final parts or products may be used in film applications, such as heavy duty bags, liners, refuse sacks, carrier bags, agricultural films, building or construction films, heavy duty shrink films, collation shrink films, fine shrink films, food packaging fill form seal (FFS) films or bags, packaging films for sanitary articles, freezer films, sanitary films, embossed release films, lamination films, label films, cling films, surface protection films, sealing layers, cereal packaging, silicon coated films, stretch hoods, etc. Said final parts or products may be used in fibre o applications, such as non-woven or technical fibres, continuous filament, > filament yarn, raffia, tapes, strapping nets, bulk fibres, etc. Other applications N wherein said final parts or products may be used in are, for example, extrusion © coating, hot melt adhesives, tie-layer adhesives, medical applications, roofing = & waterproofing membranes, carpeting, rubberized surfaces, artificial turf, N base resin for masterbatches and compounding.N
    EXAMPLES Bio-based fresh feed A triglyceridic feed comprising a mixture of vegetable and animal oils containing about 40 wt.-% of saturated C16 fatty acids, about 50 wt.-% of unsaturated C18 fatty acids, and having a glycerol equivalent content of about 10 wt.-% was first pre-treated to remove elemental impurities by bleaching. After this the pre-treated raw material stream (bio-based fresh feed material) was diluted. The diluted mixture was processed through hydrodeoxygenation (HDO) to produce a hydrotreatment effluent under the conditions specified below. The — hydrotreatment effluent was separated and purified to provide a bio-propane composition, and diesel range paraffinic hydrocarbons. Bleaching The bio-renewable oil/fat material was bleached using a conventional bleaching protocol. 2000 ppm of citric acid, 0.2 wt.-% of water and 1 wt.-% of bleaching earth were added to the pre-heated bio-renewable oil/fat material, followed by mixing for 20 min at 80 °C, dehydrating using reduced pressure, and filtering. Impurity levels in the bleached bio-renewable oil/fat material are presented in the table below. cam [oo 2
    E s | >
    Hydrodeoxygenation - Step (B) The bleached bio-renewable oil/fat material was diluted by mixing 5 w-parts of bio-based paraffinic hydrocarbons to 1 w-part of the bleached bio-renewable oil/fat material to form a hydrotreatment feed, which was adjusted with DMDS (dimethyl disulfide) to contain 20-100 wt.-ppm of S (calculated as elemental S) and hydrodeoxygenated using a sulphided metal catalyst at a temperature of 285 OC, Ha pressure of about 50 bar, and space velocity of about 0.5-1 g/g*h"!. The HDO effluent was separated at a temperature of about 40°C at the HDO reactor pressure into a gas stream and liquid stream, and water was separated and discarded from the liquid stream to obtain paraffinic hydrocarbons.
    Isomerization and fractionation of the liquid stream The paraffinic hydrocarbons were subjected to a hydroisomerization using conventional platinum-based isomerization catalyst and conventional process conditions.
    The obtained isoparaffinic hydrocarbon material was directed to fractionation.
    Diesel range hydrocarbon material meeting EN 590 requirements for automotive diesel fuel was recovered in an amount corresponding to about 83 wt-% of the bio-based fresh feed material.
    Purification of the gas stream - Step (D) The propane rich gas stream was first subjected to amine wash (Step (D)) under the following conditions: - amine flow vs. gas flow, 5.8 t/h amine solution per ton sour gas, - aqueous amine solution is 50 wt% methyl diethyl amine (MDEA), containing o 400 ppm piperazine to enhance CO; absorption in an absorber > - atreatment pressure of 4 MPa, N - gas inlet temperature: about 40°C, amine inlet temperature: about 60°C. 3 = The resulting sweet gas was then passed across a hydrogen selective membrane N (Step (E)). The propane rich retentate was then dried (Step (E)) to remove S water before the propane product was separated in an elevated pressure 2 distillator at 30 barg and 50 OC to provide a propane feed, which was N subseguently compressed to liguid form.
    The above procedure from bio-based fresh feed to purified bio-propane was repeated several times varying the feed composition, including the glycerol- equivalent content, feed sulphur level, HDO temperature and H pressure, and the separation and purification parameters, while each time operating according to the inventive method, and obtaining bio-propane compositions having the desired characteristics. Mean analysis results of the resulting bio-propane compositions are shown in table A below, as well as of the inventive bio-propane sample that was used in — the dehydrogenation tests below. Table A: Mean analysis results of bio-propane compositions | | om | oe | on | asta Property sample used in the dehy tests Eo Bp [Te] m. = pressure kPa 1390 1380 N (40°C)
    N 3 Catalytic dehydrogenation E Propane samples used in the dehydrogenation tests included a standard fossil e propane composition, a reference bio-propane composition, and a bio-propane S composition according to the invention. The bio-propane composition according 2 to the invention was prepared using the above procedure. The reference bio- N propane composition was representative of bio-propane prepared using otherwise similar procedure, but starting from a bio-renewable oil/fat material having a lower glycerol equivalent content, and using decarb-favoring conditions in the HDO step (incl. higher temperature, lower H pressure). A Sn-modified Pt catalyst known in the art (such as one prepared according to US 2003/0191351 Al) was used in the dehydrogenation experiments. Alternatively a Cr based catalyst could have been used e.g. as prepared according to US 2015/259265 Al. The experiments were carried out in a quartz fixed bed reactor with an inner — diameter of 2.66 cm and a thermocouple pocket of 4 mm in diameter. The reactor was placed in a three-zone furnace and the lines before and after the reactor as well as the bypass line were heated to 200 °C. The bio-propane composition was fed from a gas cylinder via mass flow controllers to the system with additional 5 vol-% of N2 as an internal standard. For liguid feed the gas cylinder was pressurized with N2 and pumped with either a mass flow controller or HPLC pump. The catalyst was diluted with 5 times the catalyst mass of SiC (e.g., for 5 g of catalyst 25 g of SiC). A 2cm layer of SiC was added on top of the catalyst bed corresponding to SiC mass of 19 g. The following procedure was used:
    1. Reduction of catalyst system at 550 °C with 50% H in N for 2 hours o 2. N2 flush and change oven temperature to reaction temperature of 575°C > 3. 30 min reaction at 575 °C N 4. N2 flush and change oven to regeneration temperature of 600°C for at © least 30 min = 5. Regeneration with 1.5% of Oz in Na for 15 min at 600 °C N 6. N2 flush and change oven T for at least 15 min S Steps 3 to 6 were repeated four times to evaluate the catalyst deactivation N between the first run (dehy 1) and the final run (dehy 4). The overall
    Experiment was repeated three times per setup to give a standard deviation. The results are shown in Table C below. The propane rich feed composition to the dehydrogenation reactor was analysed as follows: e Noble gases were measured on a micro-GC: Varian CP-4900, TCD, Channel 1 (Hz, N2, CH4, CO): 105 °C, carrier gas Ar, column MSSA, Channel 2 (CO), C2H4, C2He): 80 °C, carrier gas He, column PPU, Channel 3 (C3 and C4 compounds): 80°C, carrier gas He, column Al203. e Hydrocarbon composition on the following GC: Shimadzu GC2010 Plus, — FID, column Rt-Alumina BOND/MAPD, program, carrier gas He, program: 70°C 2 min — 4 °C/min — 140 °C — 10 °C/min — 230 °C 9 min. e Sulfur compounds on the following equipment: Agilent 7890B, FPD, column GS Gaspro, carrier gas He, program: 100 °C 2.5 min — 15 *C/min - 220 °C 15 min. Molar flows and elemental balances were calculated based on the GC results with following eguations: = Oin*XNoin Qout — XN, out Q * x; n; =- L v, n in — N — '*propane,in propane,out Xpropane = * 100 Npropane,in n; 2 Vp =" Q Niin ]
    N O Where O is total volume flow (mol/dm3), xi is volume fraction of compound i = measured with micro-GC, Vm is the molar volume of the gas (dm /mol), ni is the o JN molar flow of the compound i (mol/min), Xi is conversion and Yi is yield. >
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    The amount of carbon formed in the regeneration was calculated based on the gas analyser results, the CO: concentration was calculated to carbon flow by following equation: K (co, t — Xc0,,0) *Q * Mc Mot — vw m The carbon flow was then summed over the measuring interval: _ y (meq + Mc,2)/2 mc = —_— tot M The feed to the reactor was analysed always before starting the experiment.
    In addition the feedstocks were analysed for minor hydrocarbon compounds separately with GC/FID.
    In all the analyses propane concentration was calculated by reducing the other compounds from 100%. The permanent gases were analysed with p-GC.
    Table B.
    Compositions of fossil propane, reference bio-propane and inventive bio-propane composition | KSS SSS propane Bio-propane | Bio-propane Analysis of minor hydrocarbons with GC/FID Sulfur (mg/kg) 48 Jo (jo | 27845 7804 10231 3076 Unsaturates (vol ppm) 1895 dienes/alkynes (vol ppm) [2 ~~ fo Jo — | D Hydrocarbon composition at inlet as measured by GC S CH4 (vol-% 1.74 + 0.26 | 0.06 + 0.05 A CO (vol-%) 0.26 + 0.06 T CO2 (vol-%) 0.54 + 0.03 | 0.06 + 0.03 S C2H6 (vol-%) 0.71 + 0.18 4.84 + 0.04 1.56 + 0.25 I C2H4 (vol-%) E H2 (vol-% 0.86 + 0.33 |0.01+0 0 iC4H10 (vol-%) 2.63 + 0.19 0.36 + 0.01 1.04 + 0.11 S nC4H10 (vol-%) 0.33 + 0.08 0.35 + 0.01 1.29 + 0.05 O N2 (vol-%, internal standard) | 6.95 + 0.44 8.93 + 0.75 7.28 + 0.67 O 02 (vol-% 0.01 + 0.01 0.01 + 0.02 0.01 + 0.01 N C3H8 (vol-% 88.74 + 0.62 1 82.05 + 1.56 | 88.69 + 0.69 C3H6 (vol-%) 0.33 + 0.05 0 + 0.01
    As can be seen from Table B, both bio-samples exhibited lower sulfur, C4's and unsaturates contents, in particular less C3H6, while fossil propane exhibited lower C5+ and ethane contents. Main difference between the inventive and the reference bio-propane was that the latter contained CO, and a higher ratio of CO and CO; to propane.
    Table C. Conversion and coking results from catalytic dehydrogenation of fossil propane, reference bio-propane and the inventive bio-propane composition. — Propane Conversion (%) propane propane
    11.72 + 6.44 25.42 + 11.1 20.98 + 6.31 dehy 2 1 | 16.59 + 8.56 15.17 + 6.24
    3.16 + 3.7 9.01 + 6.74 12.46 + 6.96 dehy 4 3.61 + 2.51 7.17 + 6.24 12.78 + 2.98 Specific Coke (g Coke formed per 1g C fed over 1g catalyst x10” dehy 1 130.29 198.62 + 20.31 133.07 + 16.35 dehy 2 48.86 132.36 + 30.22 86.57 + 4.33 dehy 3 32.57 99.25 + 19.54 81.15 + 22.59 dehy 4 32.57 86.06 + 11.56 89.04 Characteristics High: S; Low: S; Low: S; of the propane unsaturates unsaturates unsaturates Low: CO & CO2 | High: CO & CO2 Low: CO & CO2 & C5+ Moderate: C5+ Moderate: C5+ As can be seen from Table C dehydrogenation catalyst coking results, the reference bio-propane composition formed most specific coke on the o dehydrogenation catalyst. It is assumed that the higher coking tendency is due S to the higher CO and CO. contents compared to the inventive bio-propane N composition. On the other hand the fossil propane having higher sulfur content ES deactivated the catalyst quicker resulting in significantly lower propane to z propylene conversion-% compared to both bio-propane samples, but especially o e compared to the inventive bio-propane. In general, it can be observed that the S inactivation of the catalyst (i.e. lower conversion from dehy_1 to dehy_4) S similarly results in lower specific coke values. Actually, when normalized over
    N propane conversion (not shown in Table B), the specific coke formation for the inventive sample is superior over the fossil sample. While the exact role of unsaturates (e.g. olefins and diolefins) and C5+ hydrocarbons (C5 and heavier) was not analysed in detail, the high unsaturates content in fossil propane, including presence of C3H6, may have contributed to the quicker deactivation of the catalyst thus resulting to the lower conversion- %. Unsaturates are highly reactive, and easily undergo unwanted side and secondary reactions, that may affect e.g. the structure and composition of the formed coke, and even lead into formation of so-called hard coke. Surprisingly — the higher C5+ contents of the bio-propanes did not reduce the conversion-% that much, potentially reflecting formation of a coke structure/composition that is easier to remove during catalyst regeneration.
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    权利要求:
    Claims (15)
    [1] 1. A method for upgrading a bio-based material, comprising the steps of: (A) providing a bio-based fresh feed material of bio-renewable oils and/or fats having a glycerol-equivalent content of 2 wt.-% to 60 wt.-% relative to the total weight of the bio-based fresh feed material; (B) subjecting a hydrotreatment feed comprising the bio-based fresh feed material and an optional diluent to a hydrotreatment comprising HDO in the presence of a sulphided metal catalyst and hydrogen (Hz), to provide a NN hydrotreated effluent, wherein the hydrotreatment feed comprises 10 - 10 000 wt.-ppm of sulphur-containing compound calculated as elemental S; (C) subjecting the hydrotreated effluent to gas-liquid separation so as to provide a gaseous hydrotreated material comprising Hz, bio-propane, H2O, H2S, CO, and CO, and a liquid hydrotreated material comprising paraffinic hydrocarbons; (D) subjecting the liquid hydrotreated material to fractionation, after an optional second hydrotreatment, and recovering at least diesel and/or kerosene range paraffinic hydrocarbon material; (E) subjecting the gaseous hydrotreated material to a purification step for removing H2S and CO; to obtain a H2S and CO: depleted gaseous stream; (F) subjecting the H2S and CO: depleted gaseous stream to H recovering and drying to obtain dried H2S, CO. and H depleted gaseous stream; (G) fractionating the dried H2S, CO and H depleted gaseous stream to recover a bio-propane gas composition, and optionally compressing the bio-propane 2 gas composition to obtain a liquefied bio-propane composition.
    [2] N a 2. The method according to claim 1, wherein 7 the bio-based fresh feed material has a glycerol-equivalent content of at E least 3 wt.%, preferably at least 4 wt.%, more preferably at least 5 wt.%, even & more preferably at least 6 wt.%, most preferably at least 7 wt.%, or at least 8 3 wt.%; and/or & the bio-based fresh feed material has a glycerol-equivalent content of 55 wt.% or less, preferably 50 wt.% or less, or 45 wt.% or less, or 40 wt.-% or less, or 35 wt.% or less, or 30 wt.-% or less, or 25 wt.% or less, or 20 wt.% or less; and/or the bio-based fresh feed material has a glycerol-equivalent content of 4 wt.% to 50 wt.-%, preferably 6 wt.-% to 40 wt.-%, or 7 wt.-% to 30 wt.-%.
    [3] 3. The method according to claim 1 or 2, wherein the hydrotreatment feed comprises 10 - 1 000 wt.-ppm, preferably 10 - 500 wt.-ppm, more preferably - 300 wt.-ppm of Sulphur-containing compound calculated as elemental S.
    [4] 4. The method according to any one of the preceding claims, comprising, in — step (D), subjecting the liguid hydrotreated material to fractionation after a second hydrotreatment comprising hydroisomerization, and recovering at least diesel and/or kerosene range iso-paraffinic hydrocarbon material.
    [5] 5. The method according to any one of the preceding claims, wherein the step (A) comprises a step (A') of pre-treating bio-renewable oil(s) and/or fat(s) for reducing contaminants in the oil(s) and/or fat(s) to produce the bio-based fresh feed material.
    [6] 6. The method according to any one of the preceding claims, wherein the purification step (E) further comprises a step (E’) of recovering the H.S removed from the gaseous hydrotreated material and recycling the recovered H>S to the hydrotreatment feed. o
    [7] 7. The method according to any one of the preceding claims, wherein the bio- > propane gas composition and/or the liguefied bio-propane composition has a N propane content of at least 90 wt.-%, at least 91 wt.-%, at least 92 wt.-%, at © least 93 wt.-%, at least 94 wt.-%, at least 95 wt.-%, at least 96 wt.-%, or least = 97 wt.-%. a 3 >
    [8] 8. The method according to any one of the preceding claims, further 2 comprising a step of subjecting at least part of the bio-propane gas composition N and/or the liguefied bio-propane composition to a conversion comprising catalytic dehydrogenation to obtain a dehydrogenation effluent, followed by recovering at least bio-propylene in the dehydrogenation effluent to obtain, after optional purification, a bio-propylene composition.
    [9] 9. The method according to claim 8, further comprising (co)polymerizing at least bio-propylene of the bio-propylene composition and/or at least a derivative of bio-propylene of the bio-propylene composition, optionally together with other (co)monomer(s), to produce a bio-polymer.
    [10] 10. A liquefied bio-propane composition having a vapour pressure of 1200-1500 — kPa at 40°C and a density of 495-520 kg/m3 at 15°C, and comprising: at least 94 wt.-% of bio-propane; at most 2000 wt.-ppm of COz; at most 1000 wt.-ppm of CO; at most 15 wt.-ppm of S-containing compounds, calculated as elemental S; at most 1500 wt.-ppm of unsaturated hydrocarbons; at most 5.5 wt.-% of hydrocarbons having more than 3 carbon atoms (C3+ hydrocarbons), whereof at most 1.4 wt.-% (relative to the liguefied bio-propane composition) are hydrocarbons having 5 or more carbon atoms, and optionally at most 1500 wt.-ppm, preferably at most 1000 wt.-ppm, more preferably at most 800 wt.-ppm, even more preferably at most 500 wt.- ppm of propylene.
    [11] 11.The liguefied bio-propane composition according to claim 10 which is o produced by the method according to any one of claims 1 to 7. & N
    [12] 12.A method for upgrading a bio-based material, comprising the steps of: © (A) providing a bio-based fresh feed material of bio-renewable oils and/or fats = having a glycerol-equivalent content of 2 wt.-% to 60 wt.-% relative to the N total weight of the bio-based fresh feed material; S (B) subjecting a hydrotreatment feed comprising the bio-based fresh feed 2 material and an optional diluent to a hydrotreatment comprising HDO in the N presence of a sulphided metal catalyst and hydrogen (Hz), to provide a hydrotreated effluent, wherein the hydrotreatment feed comprises 10 - 10 000 wt.-ppm of sulphur-containing compound calculated as elemental S; (C) subjecting the hydrotreated effluent to gas-liquid separation so as to provide a gaseous hydrotreated material comprising Hz, bio-propane, H2O, H2S, CO;, and CO, and a liquid hydrotreated material comprising paraffinic hydrocarbons; (D) an optional step of subjecting the liquid hydrotreated material to fractionation, after an optional second hydrotreatment, and recovering at least diesel and/or kerosene range paraffinic hydrocarbon material; (E) subjecting the gaseous hydrotreated material to a purification step for — removing H2S and CO; to obtain a H2S and CO: depleted gaseous stream; (F) subjecting the H2S and CO: depleted gaseous stream to H. recovering and drying to obtain dried H2S, CO. and H depleted gaseous stream; (G) fractionating the dried H2S, CO and H depleted gaseous stream to recover a bio-propane gas composition, and optionally compressing the bio-propane gas composition to obtain a liquefied bio-propane composition; (H) subjecting at least part of the bio-propane gas composition and/or the liquefied bio-propane composition to a conversion comprising catalytic dehydrogenation to obtain a dehydrogenation effluent comprising bio- propylene; (I) recovering and optionally purifying a bio-propylene composition from the dehydrogenation effluent.
    [13] 13. The method according to claim 12, further comprising derivatisation of at o least part of the bio-propylene composition to obtain at least one bio-propylene > derivative, preferably at least one bio-propylene derivative selected from the N group consisting of bio-(meth)acrylic acid, bio-acrylonitrile, bio-acrolein and © bio-propylene oxide.
    [14] = N 14.The method according to claim 12 or 13, further comprising S (co)polymerizing a mixture comprising at least part of the recovered bio- 2 propylene composition and/or derivative(s) thereof and optionally co- N monomer(s) and/or additive(s) to obtain a biopolymer composition.
    [15] 15. A biopolymer composition obtainable by the method according to claim 14. o
    O
    N
    N ©
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    I jami o 0
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    O
    N
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