CN101255109A - Process for producing acrylic acid by dehydrating biomass lactic acid - Google Patents
Process for producing acrylic acid by dehydrating biomass lactic acid Download PDFInfo
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- CN101255109A CN101255109A CNA200810023342XA CN200810023342A CN101255109A CN 101255109 A CN101255109 A CN 101255109A CN A200810023342X A CNA200810023342X A CN A200810023342XA CN 200810023342 A CN200810023342 A CN 200810023342A CN 101255109 A CN101255109 A CN 101255109A
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- lactic acid
- acrylic acid
- biomass
- acid
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 title claims abstract description 116
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 105
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000004310 lactic acid Substances 0.000 title claims abstract description 58
- 235000014655 lactic acid Nutrition 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000002028 Biomass Substances 0.000 title claims abstract description 23
- 230000008569 process Effects 0.000 title abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 98
- 239000007788 liquid Substances 0.000 claims abstract description 44
- 239000002808 molecular sieve Substances 0.000 claims abstract description 31
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 230000018044 dehydration Effects 0.000 claims abstract description 26
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 26
- 230000003197 catalytic effect Effects 0.000 claims abstract description 24
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- BSYNFGPFPYSTTM-UHFFFAOYSA-N 2-hydroxypropanoic acid;hydrate Chemical compound O.CC(O)C(O)=O BSYNFGPFPYSTTM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012159 carrier gas Substances 0.000 claims abstract description 13
- 239000000047 product Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000000605 extraction Methods 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007790 solid phase Substances 0.000 claims abstract description 7
- 239000010457 zeolite Substances 0.000 claims abstract description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 238000006555 catalytic reaction Methods 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000002309 gasification Methods 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 241000282326 Felis catus Species 0.000 claims description 8
- 235000011089 carbon dioxide Nutrition 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 10
- 230000003321 amplification Effects 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- 238000010533 azeotropic distillation Methods 0.000 abstract 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 235000019260 propionic acid Nutrition 0.000 description 7
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002561 ketenes Chemical class 0.000 description 2
- WOFDVDFSGLBFAC-UHFFFAOYSA-N lactonitrile Chemical compound CC(O)C#N WOFDVDFSGLBFAC-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- JCGCKSUCGVTMNB-UHFFFAOYSA-N acetic acid;formaldehyde Chemical compound O=C.CC(O)=O JCGCKSUCGVTMNB-UHFFFAOYSA-N 0.000 description 1
- ATMLPEJAVWINOF-UHFFFAOYSA-N acrylic acid acrylic acid Chemical compound OC(=O)C=C.OC(=O)C=C ATMLPEJAVWINOF-UHFFFAOYSA-N 0.000 description 1
- -1 acrylic ester Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
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- 229920001059 synthetic polymer Polymers 0.000 description 1
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Abstract
The invention provides a process for producing acrylic acid by dehydrating biomass lactic acid, and particularly relates to a process for producing acrylic acid by catalyzing and dehydrating lactic acid obtained by fermenting biomass as a raw material. The method is characterized in that a lactic acid water solution is heated to 150-200 ℃ to be gasified to obtain lactic acid-water mixed steam, the lactic acid-water mixed steam is mixed with carrier gas, the mixed gas is continuously heated to 200-450 ℃ and then enters a gas-solid phase catalytic reactor to be dehydrated under the action of a modified Y zeolite molecular sieve catalyst to obtain reaction product gas, the reaction product gas is cooled and then subjected to gas-liquid separation to obtain an acrylic acid solution, and the acrylic acid solution is subjected to gas stripping, azeotropic distillation or extraction and rectification in sequence to obtain a crude acrylic acid product. The invention provides a process for preparing acrylic acid by biomass lactic acid dehydration for the first time, and the process can be well applied to the green catalytic amplification production of preparing acrylic acid by lactic acid dehydration by taking a modified Y zeolite molecular sieve as a catalyst, and is a novel process which meets the industrial requirement and has strong practicability.
Description
Technical field
The present invention relates to chemical technology field, being specifically related to a kind of is that the raw material dehydration generates acrylic acid technology with biomass lactic acid.
Background technology
Vinylformic acid (acrylic acid) claims to lose resin acid, molecular formula C again
3H
4O
2Vinylformic acid is colourless liquid at normal temperatures and pressures, and irritating smell is arranged, relative density 1.0511, and 12 ℃ of molten points, 141.6 ℃ of boiling points, water-soluble, ethanol and ether, chemical property is active, belongs to strong organic acid, is corrosive.Vinylformic acid and ester class series monomers thereof are the monomers of the most attractive synthetic polymer.Because of there is undersaturated double bond structure its carbonyl α and β position, can generate the thousands of stabilization of polymer that differs from one another through polymerization and method such as crosslinked.Vinylformic acid is mainly used in acrylic ester synthesizing and polyacrylic acid, and polyacrylic acid can be used for aspects such as sanitary material, washing composition, flocculation agent and dispersion agent.Acrylate then is used for industrial sectors such as synthetic paint, latex, tamanori, tanning, papermaking.
Vinylformic acid and ester class industrial production have several different methods in history, as chloroethanol method, cyanoethanol method, Reppe method, ketenes method, improvement Reppe method, formaldehyde-acetate method, acrylonitrile hydrolysis method, ethylene process, propane method, epoxyethane method, beta-propiolactone method and oxidation of propylene etc.Wherein, chloroethanol method, cyanoethanol method and ketenes method are low because of efficient, consumption is big, cost is high, progressively are eliminated.Ethylene process, propane method and epoxyethane method were also only having the people in exploitation in recent years, and technology is still not mature enough, and the large-scale production equipment of Shang Weiyou has oxidation of propylene only and monopolizes extensive vinylformic acid production plant.All vinylformic acid large production equipments all adopt oxidation of propylene production in the world at present.Oxidation of propylene built up first cover production equipment in 1969 in the U.S. by UCC company the earliest, followed Japanese catalyst chemical company (1970), Mitsubishi Chemical Ind (1973) and U.S. Celanese Corp. (1973) and founded the factory in succession.There are Japanese catalyst chemical company, Mitsubishi Chemical Ind, BASF AG and Sohio company etc. in the company that has a propylene oxidation process production techniques.The propylene oxidation technology widespread use still in the world of present Japanese catalyst chemical company.The technology of Mitsubishi Chemical Ind is also used in many cover production equipments.The technology of BASF AG is not exported, and only uses in our company's device.
Oxidation of propylene is based upon on the petrochemical complex basis, and this method is faced with difficult problems such as fossil resource shortage, production cost raising and environmental pollution at present.Different with the oil approach, biological process prepares acrylic acid key and is, the lactic acid that makes through microbial fermentation with renewable resourcess such as various starchiness or saccharic agricultural-food is raw material, be converted into vinylformic acid through catalytic dehydration, this process has that raw material is easy to get, the advantage of with low cost, comprehensive advantage such as operational safety is simple and Sustainable development.Greatly develop biological vinylformic acid project and can alleviate the current acrylic acid imbalance between supply and demand of China, alleviate the oil crisis that China faced, reduce environmental pollution.Therefore, be a technology with strategic reserves meaning of benefiting the nation and the people, its development prospect is very wide.
The acrylic acid research of biomass lactic acid catalytic dehydration system is carried out very early.1958 Holmen (USP 2859240) be that lactic acid or lactate dehydration system vinylformic acid and ester thereof carry out screening of catalyst research to raw material first.Experiment finds that the most effective catalyzer is CaSO
4/ Na
2SO
4Composite catalyst, lactic acid mass concentration are 10%, and feeding rate 10-15ml/hour can realize 68% theoretical yield during 400 ℃ of temperature of reaction.1988 Sawicki (USP 4729978) carrier, catalyzer and reaction conditions have been carried out detailed optimization research, find that the less silicon oxide of inertia is a carrier, acid more weak SODIUM PHOSPHATE, MONOBASIC is a catalyzer, charge capacity is 1.0mmol/g, inert gas flow is 20ml/min, be that 5.9 o'clock vinylformic acid output is the highest with the sodium bicarbonate for the pH regulator agent is adjusted to pH when the stock liquid flow is 0.34ml/min, can reach 58%.Yet above-mentioned research only rests on the experimental phase, biomass lactic acid catalytic dehydration system vinylformic acid is not carried out technological design research, does not also have industrialized report.
Summary of the invention
The object of the present invention is to provide a kind of biomass lactic acid catalytic dehydration to produce acrylic acid technology.
Purpose of the present invention realizes by following technical measures:
The acrylic acid production technique of a kind of biomass lactic acid catalytic dehydration system, lactic acid aqueous solution is heated to lactic acid-water mixed vapour that 150～200 ℃ of gasifications obtain to be mixed with carrier gas, enter after mixed gas continued to be heated to 200～450 ℃ in the gas-solid-phase catalytic reaction device through the effect of modified Y zeolite molecular sieve catalyst dewater reaction product gas, reaction product gas cooling obtains acrylic acid solution after its mid-boiling point of gas-liquid separator separates is 20 ℃ a acetaldehyde, and acrylic acid solution is carried through gas more successively, component distillation (perhaps extraction), technological processs such as rectifying obtain the crude acrylic acid product.
The mass concentration scope of above-mentioned lactic acid aqueous solution is 10～60%, and preferred concentration range for is 30～50%.Lactic acid aqueous solution directly is heated to 150～200 ℃ of gasifications through interchanger obtains lactic acid-water mixed vapour.The gasification of lactic acid aqueous solution also can be coupled with the condensation of reaction product gas.Lactic acid aqueous solution is directly by being that 200～450 ℃ reaction product gas is that the gas liquid exchanger of thermal source is heated to 150～200 ℃ of gasifications with temperature.
Carbonic acid gas, water vapour or nitrogen are adopted in above-mentioned carrier gas, with need be heated to 150～200 ℃ before lactic acid-the water mixed vapour mixes.Mix with lactic acid-water mixed vapour of 150～200 ℃ again, enter in the gas-solid-phase catalytic reaction device after mixed gas is continued to be heated to 200～450 ℃ and obtain reaction product gas through catalyst action.
Above-mentioned gas-solid-phase catalytic reaction device adopts isotherm formula fixed bed, adiabatic reactor reactor etc., and the reaction pressure of mixed gas in the gas-solid-phase catalytic reaction device is 0.05～1.5MPa, and temperature is 200～450 ℃.
The modified Y zeolite molecular sieve catalyst is preferably the loaded modified Y molecular sieve catalyzer of metal ion, and metal ion comprises K
+, Ca
2+, Ba
2+, La
3+Or Ru
+Deng.
The method of modifying of the Y molecular sieve catalyzer that metal ion is loaded modified is: with K
+, Ca
2+, Ba
2+, La
3+Or Ru
+Plasma, wherein K
+, Ca
2+, Ba
2+, La
3+Or Ru
+The plasma source can be its nitrate and villaumite, in the charge capacity (with the quality of ionic oxide formation thing) of 1%-10%, stirs by dipping under 60-100 ℃ of condition, loads on the NaY molecular sieve 300～750 ℃ of following incinerating modes then.
The gas that reaction produces from catalytic dehydration, (70～120 ℃) enter in the gas-liquid separator after overcooling.Gas-liquid separation adopts the bottom that the gas-liquid separator of water cooler is set.Gas-liquid separator is mainly used in separation of propylene acid and acetaldehyde, because the difference of each boiling point substance, overwhelming majority vinylformic acid, water and unreacted lactic acid accumulate in the bottom of gas-liquid separation device with the solution form, most of acetaldehyde, ethene, carbon monoxide, carbonic acid gas and carrier gas then enter in the acetaldehyde absorption tower with gaseous form, prevent the acetaldehyde contaminate environment.For preventing acroleic acid polymerization, the acrylic acid solution that cools down must keep below 100 ℃, so in the bottom of separator water cooler is set.Come out from the gas-liquid separator bottom acrylic acid solution that obtains through gas-liquid separation enters gas stripping column from the cat head of gas stripping column and carries out gas and carry, and carries by gas acetaldehyde is removed, and makes the acetaldehyde concentration in the acrylic acid solution be not more than 150mg/kg.Gas is proposed required carrier gas can adopt water vapour or nitrogen etc., and the gas-liquid separation process is carried out under negative pressure substantially, and the pressure of whole process, temperature all need maintain a stable indexes.The gas stripping column absolute pressure of top of the tower is controlled at about 300mmHg, and tower top temperature is controlled at 30～60 ℃.
Vinylformic acid and water separate existence owing to the hydrogen bond comparison difficulty that becomes, can not obtain the very high vinylformic acid of purity with simple rectifying or distillatory method.The acrylic acid solution that the present invention comes out from gas stripping column enters the azeotrope column and to adopt method of extraction to improve acrylic acid concentration (about 90%) in component distillation or the extraction tower, having chosen of entrainer or extraction agent is multiple, can select entrainers such as hexanaphthene or toluene for use, and carry out according to conventional azeotropic of industry or extraction conditions.The acrylic acid solution that comes out from gas stripping column enters azeotrope column or the extraction tower, can separate to obtain water-content and can be low to moderate vinylformic acid below 10%.The vinylformic acid of the concentration height of separating to 85% enters in the rectifying tower, and cat head distillates most of unreacted lactic acid that is, the tower stilling go out for propionic acid and the very low vinylformic acid (about 94%) of lactic acid content be the crude acrylic acid product.
Beneficial effect of the present invention: the present invention has proposed the acrylic acid technological process of acid by dehydrating biomass lactic system first, adopting gasification-catalysis-gas-liquid separation-gas to carry-technical process of azeotropic (extraction)-rectifying, is raw material obtains having high using value through catalytic dehydration crude acrylic acid monomer (the crude acrylic acid monomer contains the impurity such as propionic acid, lactic acid, water and dimer of minute quantity) with reproducible biomass lactic acid.It is during the amplification of the green catalysis of catalyzer producing acroleic acid by lactic acid dewatering is produced, to be a kind of very strong novel process of industrialization demand, practicality that satisfies that this technological process can be applied to well with the modified Y zeolite molecular sieve.
Description of drawings:
Fig. 1 is the technique for producing propenoic acid by dehydrating biomass lactic acid schema.
Among the figure, 1. gas liquid exchanger I; 2. interchanger II; 3. interchanger III; 4. condenser; 5. gas-liquid separator; 6. gas-solid catalyticreactor; 7. gas stripping column; 8. acetaldehyde absorption tower; 9. dashpot; 10. azeotrope column; 11. condenser; 12. reboiler; 13. reboiler; 14. rectifying tower; 15. condenser.
Embodiment
Process implementing example of the present invention illustrates in conjunction with Fig. 1:
Embodiment 1
(1) be that 50% lactic acid aqueous solution makes it gasification through gas liquid exchanger I 1 and reaches 180 ℃ with massfraction.
(2) nitrogen is heated to 180 ℃ through interchanger II 2, and mixes with lactic acid-water mixed vapour.Gas mixture is warming up to 350 ℃ of the required temperature of reaction through interchanger III 3.
(3) mixed gas after heating up enter gas-solid catalyticreactor 6 carry out catalyzed reaction dewater reaction product gas.Gas-solid catalyticreactor 6 adopts the isothermal calandria type fixed bed reactor, tubulation caliber 30mm, and length is 3000mm, heating medium is a fused salt, and catalyzer adopts the 1.5kgK/Y molecular sieve, and the bulk density of molecular sieve is 1.0g/ml, the catalyzed reaction temperature is 350 ℃, the mass space velocity 3.0h of raw material
-1, reaction pressure 1.5MPa.The making method of K/Y molecular sieve: with 0.4532kgKNO
3In 20L water, mix with 10kg NaY molecular sieve again, in 80 ℃ of heated and stirred 4h, dry 24h in 100 ℃ of baking ovens, dry back powder is put into 550 ℃ of roasting 4h of retort furnace, and compressing tablet is broken into pieces, and 30～50 orders sieve.
(4) mainly contain vinylformic acid, water, lactic acid, propionic acid and acetaldehyde in the reaction product gas.The gas that reaction produces from catalytic dehydration reaches 120 ℃ through interchanger I cooling back temperature, enters in the gas-liquid separator 5.Overwhelming majority vinylformic acid, water and unreacted lactic acid accumulate in the bottom of gas-liquid separator 5 with the solution form, and gaseous substance enters in the acetaldehyde absorption tower 8.The bottom of gas-liquid separator 5 is provided with water cooler, and acrylic acid solution is reduced to 80 ℃, and volume fraction is 40%.
(5) acrylic acid solution of gas-liquid separator 5 bottoms enters gas stripping column 7 from the gas stripping column cat head, carries by gas acetaldehyde is removed.It is nitrogen that gas is proposed used carrier gas, and absolute pressure of top of the tower is controlled at about 300mmHg, and tower top temperature is 60 ℃, remove acetaldehyde after the acetaldehyde mass concentration less than 150mg/kg.
(6) acrylic acid solution that comes out from gas stripping column 7 enters the azeotrope column 10, and entrainer adopts toluene, obtains mass concentration behind the azeotropic and be 90% vinylformic acid.
(7) vinylformic acid behind the azeotropic enters rectifying tower 14, obtains purity and be 94% crude acrylic acid product.The results are shown in Table 1.
(1) be that the condensation of the gasification of 60% lactic acid aqueous solution and product gas is coupled with massfraction be that massfraction is that 60% lactic acid aqueous solution is directly by being that 350 ℃ product gas is that the gas liquid exchanger I 1 of thermal source is heated to 160 ℃ with temperature.
(2) nitrogen is heated to 160 ℃ through interchanger II 2, and mixes with lactic acid-water mixed vapour, gas mixture is warming up to 250 ℃ of the required temperature of reaction through interchanger III 3.
(3) mixed gas after heating up enter gas-solid catalyticreactor 6 carry out catalyzed reaction dewater reaction product gas.Gas-solid catalyticreactor 6 adopts the isothermal calandria type fixed bed reactor, tubulation caliber 30mm, and length is 3000mm, heating medium is a fused salt, and catalyzer adopts the 1.5kgBa/Y molecular sieve, and the bulk density of molecular sieve is 1.0g/ml, the catalyzed reaction temperature is 250 ℃, the mass space velocity 3.0h of raw material
-1, reaction pressure 0.1MPa.The making method of Ba/Y molecular sieve: with 0.8342kgBa (NO
3)
2In 20L water, mix with 10kg NaY molecular sieve again, 80 ℃ of heated and stirred 4h, dry 24h in 100 ℃ of baking ovens, dry back powder is put into 550 ℃ of roasting 4h of retort furnace, and compressing tablet is broken into pieces, and 30～50 orders sieve.
(4) mainly contain vinylformic acid, water, lactic acid, propionic acid and acetaldehyde in the reaction product gas.The gas that reaction produces from catalytic dehydration reaches 110 ℃ through interchanger I cooling back temperature, enters in the gas-liquid separator 5.Overwhelming majority vinylformic acid, water and unreacted lactic acid accumulate in the bottom of gas-liquid separator 5 with the solution form, and most of acetaldehyde, ethene, carbon monoxide, carbonic acid gas and nitrogen then enter in the acetaldehyde absorption tower 8 with gaseous form.The bottom of separator 5 is provided with water cooler, and acrylic acid solution is reduced to 85 ℃, and volume fraction is 38%.
(5) acrylic acid solution of gas-liquid separator 5 bottoms enters gas stripping column 7 from the gas stripping column cat head, carries by gas acetaldehyde is removed.It is water vapour that gas is proposed required carrier gas, and absolute pressure of top of the tower is controlled at about 300mmHg, and tower top temperature is 50 ℃.The acetaldehyde mass concentration is less than 130mg/kg.
(6) acrylic acid solution that comes out from gas stripping column 7 enters the azeotrope column 10, and it is 90% vinylformic acid that entrainer adopts hexanaphthene, azeotropic to obtain mass concentration.
(7) vinylformic acid behind the azeotropic enters rectifying tower 14, obtains purity and be 94% crude acrylic acid product.The results are shown in Table 1.
(1) be that 30% lactic acid aqueous solution makes it gasification through gas liquid exchanger I 1 and reaches 180 ℃ with massfraction.
(2) carbonic acid gas is heated to 200 ℃ through interchanger II 2, and mixes with lactic acid-water mixed vapour.Gas mixture is warming up to 450 ℃ of the required temperature of reaction through interchanger III 3.
(3) mixed gas after heating up enter gas-solid catalyticreactor 6 carry out catalyzed reaction dewater reaction product gas.Gas-solid catalyticreactor 6 adopts the adiabatic reactor reactor, and catalyzer adopts 1.5kg Ca/Y molecular sieve, and the particle diameter of molecular sieve is 70um, and the catalyzed reaction temperature is 450 ℃, reaction pressure 0.1MPa.The making method of Ca/Y molecular sieve: with 0.6587kgCa (NO
3)
2In 20L water, mix with 10kg NaY molecular sieve again, in 80 ℃ of heated and stirred 4h, dry 24h in 100 ℃ of baking ovens, dry back powder is put into 550 ℃ of roasting 4h of retort furnace, and compressing tablet is broken into pieces, and 30～50 orders sieve.
(4) mainly contain vinylformic acid, water, lactic acid, propionic acid and acetaldehyde in the reaction product gas.The gas that reaction produces from catalytic dehydration, temperature reaches 70 ℃ after overcooling, enters in the gas-liquid separator 5.Overwhelming majority vinylformic acid, water and unreacted lactic acid accumulate in the bottom of gas-liquid separator 5 with the solution form, and most of acetaldehyde, ethene, carbon monoxide, carbonic acid gas and nitrogen then enter in the acetaldehyde absorption tower 8 with gaseous form.The bottom of gas-liquid separator 5 is provided with water cooler, and acrylic acid solution is reduced to 88 ℃, and volume fraction is 35%.
(5) acrylic acid solution of gas-liquid separator 5 bottoms enters gas stripping column 7 from the gas stripping column cat head, carries by gas acetaldehyde is removed.It is water vapour that gas is proposed required carrier gas, and absolute pressure of top of the tower is controlled at about 300mmHg, and tower top temperature is 30 ℃, and the acetaldehyde mass concentration is less than 110mg/kg.
(6) acrylic acid solution that comes out from gas stripping column 7 enters the extraction tower 10, and extraction agent adopts hexanaphthene, and it is 92% vinylformic acid that extraction obtains mass concentration.
(7) vinylformic acid behind the azeotropic enters rectifying tower 14, obtains purity and be 96% crude acrylic acid product.The results are shown in Table 1.
Embodiment 4
(1) be that the condensation of the gasification of 55% lactic acid aqueous solution and product gas is coupled with massfraction be that massfraction is that 55% lactic acid aqueous solution is directly by being that 350 ℃ product gas is that the gas liquid exchanger I1 of thermal source is heated to 160 ℃ with temperature.
(2) nitrogen is heated to 160 ℃ through interchanger II 2, and mixes with lactic acid-water mixed vapour, gas mixture is warming up to 250 ℃ of the required temperature of reaction through interchanger III 3.
(3) mixed gas after heating up enter gas-solid catalyticreactor 6 carry out catalyzed reaction dewater reaction product gas.Gas-solid catalyticreactor 6 adopts the isothermal calandria type fixed bed reactor, tubulation caliber 30mm, and length is 3000mm, heating medium is a fused salt, and catalyzer adopts 1.5kg La/Y molecular sieve, and the bulk density of molecular sieve is 1.0g/ml, the catalyzed reaction temperature is 250 ℃, the mass space velocity 3.0h of raw material
-1, reaction pressure 0.5MPa.The making method of La/Y molecular sieve: with 0.9558kgLa (NO
3)
36H
2O mixes with 10kg NaY molecular sieve in 20L water again, in 80 ℃ of heated and stirred 4h, and dry 24h in 100 ℃ of baking ovens, dry back powder is put into 550 ℃ of roasting 4h of retort furnace, and compressing tablet is broken into pieces, and 30～50 orders sieve.
(4) mainly contain vinylformic acid, water, lactic acid, propionic acid and acetaldehyde in the reaction product gas.The gas that reaction produces from catalytic dehydration reaches 120 ℃ through interchanger I cooling back temperature, enters in the gas-liquid separator 5.Overwhelming majority vinylformic acid, water and unreacted lactic acid accumulate in the bottom of gas-liquid separator 5 with the solution form, and most of acetaldehyde, ethene, carbon monoxide, carbonic acid gas and nitrogen then enter in the acetaldehyde absorption tower 8 with gaseous form.The bottom of separator 5 is provided with water cooler, and acrylic acid solution is reduced to 75 ℃, and volume fraction is 38%.
(5) acrylic acid solution of gas-liquid separator 5 bottoms enters gas stripping column 7 from the gas stripping column cat head, carries by gas acetaldehyde is removed.It is water vapour that gas is proposed required carrier gas, and absolute pressure of top of the tower is controlled at about 300mmHg, and tower top temperature is 50 ℃.The acetaldehyde mass concentration is less than 130mg/kg.
(6) acrylic acid solution that comes out from gas stripping column 7 enters the azeotrope column 10, and it is 91% vinylformic acid that entrainer adopts hexanaphthene, azeotropic to obtain mass concentration.
(7) vinylformic acid behind the azeotropic enters rectifying tower 14, obtains purity and be 95% crude acrylic acid product.The results are shown in Table 1.
(1) be that 55% lactic acid aqueous solution makes it gasification through gas liquid exchanger I 1 and reaches 170 ℃ with massfraction.
(2) nitrogen is heated to 170 ℃ through interchanger II 2, and mixes with lactic acid-water mixed vapour.Gas mixture is warming up to 350 ℃ of the required temperature of reaction through interchanger III 3.
(3) mixed gas after heating up enter gas-solid catalyticreactor 6 carry out catalyzed reaction dewater reaction product gas.Gas-solid catalyticreactor 6 adopts the isothermal calandria type fixed bed reactor, tubulation caliber 30mm, and length is 3000mm, heating medium is a fused salt, and catalyzer adopts 1.5kg Rb/Y molecular sieve, and the bulk density of molecular sieve is 1.0g/ml, the catalyzed reaction temperature is 350 ℃, the mass space velocity 3.0h of raw material
-1, reaction pressure 1.0MPa.The making method of Rb/Y molecular sieve: with 0.5941kgRbNO
3In 20L water, mix with 10kg NaY molecular sieve again, in 80 ℃ of heated and stirred 4h, dry 24h in 100 ℃ of baking ovens, dry back powder is put into 550 ℃ of roasting 4h of retort furnace, and compressing tablet is broken into pieces, and 30～50 orders sieve.
(4) mainly contain vinylformic acid, water, lactic acid, propionic acid and acetaldehyde in the reaction product gas.The gas that reaction produces from catalytic dehydration reaches 110 ℃ through interchanger I cooling back temperature, enters in the gas-liquid separator 5.Overwhelming majority vinylformic acid, water and unreacted lactic acid accumulate in the bottom of gas-liquid separator 5 with the solution form, and most of acetaldehyde, ethene, carbon monoxide, carbonic acid gas and nitrogen then enter in the acetaldehyde absorption tower 8 with gaseous form.The bottom of gas-liquid separator 5 is provided with water cooler, and acrylic acid solution is reduced to 76 ℃, and volume fraction is 42%.
(5) acrylic acid solution of gas-liquid separator 5 bottoms enters gas stripping column 7 from the gas stripping column cat head, carries by gas acetaldehyde is removed.It is nitrogen that gas is proposed used carrier gas, and absolute pressure of top of the tower is controlled at about 300mmHg, and tower top temperature is 60 ℃.The acetaldehyde mass concentration is less than 150mg/kg.
(6) acrylic acid solution that comes out from gas stripping column 7 enters the azeotrope column 10, and entrainer adopts toluene, obtains mass concentration behind the azeotropic and be 92% vinylformic acid.
(7) vinylformic acid behind the azeotropic enters rectifying tower 14, obtains purity and be 96% crude acrylic acid product.The results are shown in Table 1.
Table 1 embodiment reaction result
Claims (10)
1. acrylic acid production technique of biomass lactic acid catalytic dehydration system, it is characterized in that lactic acid aqueous solution is heated to lactic acid-water mixed vapour that 150～200 ℃ of gasifications obtain to be mixed with carrier gas, enter after mixed gas continued to be heated to 200～450 ℃ in the gas-solid-phase catalytic reaction device through the effect of modified Y zeolite molecular sieve catalyst dewater reaction product gas, reaction product gas cooling is after gas-liquid separation obtains acrylic acid solution, acrylic acid solution more successively through gas carry, component distillation or extraction, rectifying obtains the crude acrylic acid product.
2. the acrylic acid production technique of biomass lactic acid catalytic dehydration system according to claim 1 is characterized in that the mass concentration scope of lactic acid aqueous solution is 10～60%.
3. the acrylic acid production technique of biomass lactic acid catalytic dehydration system according to claim 2, the mass concentration that it is characterized in that lactic acid aqueous solution is 30～50%.
4. the acrylic acid production technique of biomass lactic acid catalytic dehydration system according to claim 1 is characterized in that lactic acid aqueous solution directly is heated to 150～200 ℃ of gasifications through interchanger obtains lactic acid-water mixed vapour or lactic acid aqueous solution by being that the gas liquid exchanger of thermal source is heated to 150～200 ℃ of gasifications and obtains lactic acid-water mixed vapour with the reaction product gas.
5. the acrylic acid production technique of biomass lactic acid catalytic dehydration system according to claim 1 is characterized in that carrier gas is carbonic acid gas, water vapour or nitrogen, be heated to 150～200 ℃ before lactic acid-the water mixed vapour mixes.
6. the acrylic acid production technique of biomass lactic acid catalytic dehydration system according to claim 1 is characterized in that the gas-solid-phase catalytic reaction device adopts isotherm formula fixed bed or adiabatic reactor reactor, and reaction pressure is 0.05～1.5MPa, and temperature is 200～450 ℃.
7. the acrylic acid production technique of biomass lactic acid catalytic dehydration system according to claim 1 is characterized in that the gas-liquid separator that adopts the bottom that water cooler is set carries out gas-liquid separation.
8. the acrylic acid production technique of biomass lactic acid catalytic dehydration system according to claim 1, it is characterized in that the acrylic acid solution that obtains through gas-liquid separation enters from the cat head of gas stripping column carries out gas and carries the gas stripping column, the acetaldehyde concentration of carrying in the acrylic acid solution by gas is not more than 150mg/kg.
9. the acrylic acid production technique of biomass lactic acid catalytic dehydration system according to claim 8 is characterized in that the gas stripping column tower top temperature is controlled at 30～60 ℃, and the gas stripping column tower top pressure is controlled at 300mmHg, and gas is carried and adopted carrier gas is water vapour or nitrogen.
10. the acrylic acid production technique of biomass lactic acid catalytic dehydration system according to claim 1 is characterized in that described modified Y zeolite molecular sieve catalyst is the loaded modified Y molecular sieve catalyzer of metal ion; Wherein, metal ion comprises K
+, Ca
2+, Ba
2+, La
3+, Ru
+
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