CN102516004A - Method for preparing low-carbon olefin by taking biomass synthetic gas as raw material with dimethyl ether two-step method - Google Patents
Method for preparing low-carbon olefin by taking biomass synthetic gas as raw material with dimethyl ether two-step method Download PDFInfo
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- dimethyl ether
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- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000002028 Biomass Substances 0.000 title claims abstract description 31
- 239000002994 raw material Substances 0.000 title claims abstract description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000003054 catalyst Substances 0.000 claims abstract description 96
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 47
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 47
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000018044 dehydration Effects 0.000 claims abstract description 17
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 17
- 239000002808 molecular sieve Substances 0.000 claims abstract description 16
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 238000011068 loading method Methods 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 56
- 239000000047 product Substances 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 239000007806 chemical reaction intermediate Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 abstract description 13
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 8
- 150000001336 alkenes Chemical class 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000035425 carbon utilization Effects 0.000 abstract 1
- 230000008569 process Effects 0.000 description 14
- 239000010949 copper Substances 0.000 description 13
- 239000011701 zinc Substances 0.000 description 13
- 239000004215 Carbon black (E152) Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- -1 dme Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 235000009508 confectionery Nutrition 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229940001007 aluminium phosphate Drugs 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供了一种以生物质合成气为原料经二甲醚两步法制备低碳烯烃的方法，以低氢碳比生物质合成气为原料，在一步固定床反应器中与二甲醚合成催化剂经合成甲醇、甲醇脱水反应制备出含有较高二甲醚含量的含氧碳氢化合物，反应产物除水后、再升高温度到120℃，在常压下通入二步固定床反应器中与二甲醚催化转化催化剂连续反应，生成低碳烯烃；所述二甲醚合成催化剂是Cu/Zn/Al甲醇合成催化剂和HZSM-5甲醇脱水催化剂组成的复合催化剂；所述二甲醚转化催化剂载体为SAPO-34和HZSM-5机械混合的分子筛，活性组分为镍，其重量担载量为0.5～1.5％。本发明的CO转化率可达到39.2-77.4％，低碳烯烃的选择性可达71.5-84.6％，合成气的碳利用率达到10.2-32.8％。本发明为我国低碳烯烃的生产提供新的技术路线。The invention provides a method for preparing low-carbon olefins by using biomass synthesis gas as a raw material through a two-step method of dimethyl ether, using biomass synthesis gas with a low hydrogen-to-carbon ratio as a raw material, and combining dimethyl ether with dimethyl ether in a one-step fixed-bed reactor Synthetic catalysts synthesize methanol and methanol dehydration to prepare oxygenated hydrocarbons with high dimethyl ether content. After dehydration, the reaction product is raised to 120°C and passed into a two-step fixed-bed reactor under normal pressure. Continuously react with the dimethyl ether catalytic conversion catalyst to generate low-carbon olefins; the dimethyl ether synthesis catalyst is a composite catalyst composed of Cu/Zn/Al methanol synthesis catalyst and HZSM-5 methanol dehydration catalyst; the dimethyl ether conversion The catalyst carrier is a molecular sieve mechanically mixed with SAPO-34 and HZSM-5, the active component is nickel, and its weight loading is 0.5-1.5%. The CO conversion rate of the invention can reach 39.2-77.4%, the selectivity of light olefins can reach 71.5-84.6%, and the carbon utilization rate of the synthesis gas can reach 10.2-32.8%. The invention provides a new technical route for the production of low-carbon olefins in my country.
Description
Technical field
The present invention provides a kind of and prepares the method for low-carbon alkene through the synthetic gas indirect method, particularly a kind ofly is used for to be raw material, to be intermediate product through dme, prepare the method for low-carbon alkene with the low hydrogen-carbon ratio biomass synthesis gas.
Technical background
The ethene overwhelming majority derives from the naphtha steam cracking technology at present, and this technology energy consumption is big, and relies on petroleum resources fully.What develop is raw material with Sweet natural gas, coal or biomass, via synthetic gas, is that intermediate product is produced the focus that low-carbon alkene is present research with methyl alcohol or dme (indirect method), also is the technology that is hopeful to substitute petroleum path most.Because indirect method prepares in the low-carbon alkene technology and prepares the technology that synthetic gas, synthesizing methanol or dme have comparative maturity with coal, Sweet natural gas or biomass.Therefore this method concentrates on methyl alcohol or development of dimethyl ether catalysis catalyst for cracking and process modification aspect
Indirect method (MTO) via methyl alcohol is by the invention of Mobil company, adopts the ZSM-5 molecular sieve, and its bigger pore passage structure makes it lower to the selectivity of ethene and propylene with strong surface acidity, generates sub products such as aromatic hydrocarbons and paraffin in a large number.American UOP and Norsk Hydro have developed silicon aluminium phosphate SAPO-34 molecular sieve, and the MTO catalytic performance of the type molecular sieve is excellent, and methanol conversion reaches 100% or near 100%, ethene and propylene selectivity almost do not have C about 60%
5Above product; But because the temperature of reaction of dimethyl ether catalysis cracking system ethene is higher, the big constructional feature of the little cage of SAPO-34 molecule sieve aperture makes low-carbon alkene in the molecular sieve cage, be easy to further add chain polymerization; Cause the degree of depth to transform, need frequent regeneration until knot carbon.And exothermic heat of reaction causes reaction bed temperature to rise, and the catalysis water byproduct also can be aggravated catalyst deactivation.On the fluidized-bed reactor, raw material consumption is about 2.659t methyl alcohol/t low-carbon alkene.The preparing propylene from methanol of LURGI (MTP) process for propylene has than highly selective.The DMTO technology of Dalian Chemical Physics Research Institute's exploitation is raw material with the dme, and its transformation efficiency reaches 100%, and selectivity of light olefin reaches more than 90%.
The synthetic gas of development is through the single stage method dme; The operational path (SDTO) of low-carbon alkene is produced in the dimethyl ether catalysis cracking, and the dual-function catalyst that utilizes metal one acidic molecular sieve to form makes synthetic gas be converted into dme; (MTO) compares with indirect method; Owing to saved the step of methyl alcohol to dimethyl ether conversion, and broken through the thermodynamics equilibrium limit of two-step approach process for synthesis of dimethyl ether, can obtain higher CO per pass conversion and dimethyl ether catalyst stability; And the simplification overall process, will be more reasonable also economically.Preliminary study shows that yield of light olefins is higher than 100g/Nm
3, the 1kg dme can be produced low-carbon alkene 532g, has demonstrated the advantage of this new technology.In the synthesis of dimethyl ether with synthesis gas one-step process; The main composite catalyst that adopts Cu-Zn methanol synthesis catalyst and acidic methanol dehydration catalyst to form; Aspect dimethyl ether conversion, often adopt modified ZSM-5 and SAPO-34 pure aluminium silicate phosphate molecule sieve catalyst.
More than research all is to be raw material with coal or Sweet natural gas, does not break away from the natural dependence to fossil energy yet, and mainly is to methyl alcohol or dimethyl ether conversion process.Continuous maturation, development along with the home and abroad biomass gasification technology; Be badly in need of opening up the field that utilizes except that generating, heat supply; The research of pure ethers Chemicals such as biogas synthesizing methanol, dme, methylcarbonate and vapour, diesel oil equal energy source fuel is just at the early-stage, also needs the further downstream high value added product-low-carbon alkene synthesis technique of exploitation biomass dme.Method at present that the biogas dimethyl ether synthesis is technological and that dimethyl ether conversion synthesizing low-carbon alkene two step process combine does not also have bibliographical information.
Summary of the invention
The purpose of this invention is to provide a kind of is raw material with the low hydrogen-carbon ratio biomass synthesis gas, adopts two-step process to prepare the method for high-content low-carbon alkene.
The present invention is a target with preparation high-content low-carbon alkene, biomass synthesis gas (H
2+ CO+CO
2) contain optionally oxygen-bearing hydrocarbon of higher dme through the preparation of single stage method synthesis process for dimethyl ether earlier, transform through dimethyl ether catalysis again, generate high-load low-carbon alkene.
In this two-step process; With the low hydrogen-carbon ratio biomass synthesis gas is raw material; The dimethyl ether synthetic catalyst effect generation dimethyl ether synthesizing reaction of in step fixed-bed reactor, forming with methanol synthesis catalyst and methanol dehydration catalyst; After reaction product dewaters, under normal pressure, feed in the two step fixed-bed reactor and dimethyl ether catalysis conversion catalyst successive reaction, generate low-carbon alkene.
Said low hydrogen-carbon ratio biomass synthesis gas is to be raw material, to be obtained H through gasification, reformation, purification by biomass
2, CO, CO
2, N
2, CH
4Mixed gas, its hydrogen-carbon ratio is lower than industrial synthetic gas, wherein (H
2-CO
2)/CO+CO
2=0.33～1.1.
Said dimethyl ether synthetic catalyst is the composite catalyst that Cu/Zn/Al methanol synthesis catalyst and HZSM-5 methanol dehydration catalyst are formed; Said dimethyl ether conversion support of the catalyst is the molecular sieve of SAPO-34 and HZSM-5 mechanically mixing, and active ingredient is a nickel, and active metal nickel loads on the carrier through pickling process, and its weight loading is 0.5～1.5%, and carrier is of a size of 20～40 orders.
Said dimethyl ether synthetic catalyst is used for the reaction that synthetic gas directly transforms preparing dimethy ether, and reaction conditions is gentle, and catalytic activity is high, and stability is strong, and synthetic gas needn't recycle, and is cost-saved.Be raw material with low hydrogen carbon biomass synthesis gas, process has obtained effect preferably in the single stage method prepared in reaction dme.
The invention has the beneficial effects as follows, low hydrogen-carbon ratio biomass synthesis gas process for synthesis of dimethyl ether and dimethyl ether conversion technology are effectively combined, with biomass synthesis gas (H
2+ CO+CO
2) be that raw material is earlier through the dme building-up reactions; Prepare and contain optionally mixture of high oxygen-bearing hydrocarbon (methyl alcohol, dme, ethanol), particularly dme, again through the dimethyl ether conversion reaction; Further generate low-carbon alkene, improve the selectivity and the synthetic gas carbon utilisation rate of low-carbon alkene.It is 39.2-77.4% that technology of the present invention can reach the CO transformation efficiency, and the selectivity of low-carbon alkene is 71.5-84.6%, and the carbon utilisation rate of synthetic gas is 10.2-32.8%.A route that has non-oil resource to prepare industrial chemicals and petrochemical complex flagship product is provided; On the one hand for effectively utilizing wide material sources, short biomass resource of regeneration period that new application approach is provided; Bring the power of sustainable development also for traditional low-carbon alkene and derivatives industry thereof, for the production of China's low-carbon alkene new technological line is provided on the other hand.
Embodiment:
Below in conjunction with embodiment the present invention is explained further details.
The concrete steps of present embodiment are: in the step fixed-bed reactor, dimethyl ether synthetic catalyst is at H
2/ N
2In the reducing gas through the temperature programmed reduction(TPR) activation; In the two step fixed-bed reactor, the dimethyl ether conversion catalyzer is earlier at N
2Be warming up to 430-450 ℃ under the atmosphere gradually, carry out activation; After catalyzer is activated, at air speed 1500～6000h
-1, 260～270 ℃ of temperature condition under feed the low hydrogen-carbon ratio biomass synthesis gas, in step fixed-bed reactor, issue living dimethyl ether synthesizing reaction in the dimethyl ether synthetic catalyst effect, reaction intermediate by dehydration, elevated temperature to 120 ℃; Under normal pressure, directly feed two step fixed-bed reactor again, under the dimethyl ether conversion catalyst action, recur the dimethyl ether conversion reaction and generate low-carbon alkene.
Dimethyl ether synthetic catalyst of the present invention is the composite catalyst that Cu/Zn/Al methanol synthesis catalyst and HZSM-5 methanol dehydration catalyst are formed.Wherein catalyst for methanol prepares as follows:
(1) with the mixed ethanol solution of cupric nitrate, zinc nitrate, aluminum nitrate, add the oxalic acid ethanolic soln that contains 1.2 times of the required oxalic acid amounts of precipitating ion fast, through stirring, co-precipitation is aging, evaporating solvent;
(2) descend each roasting 1 hour at 150 ℃, 200 ℃, 250 ℃ and 300 ℃ respectively, again at 350 ℃ of following roasting 4h;
(3) catalyst for methanol that makes is milled be the 180-200 order.
With the catalyst for methanol powder and the HZSM-5 molecular sieve powder of preparation is dispersion agent with ethanol, under magnetic agitation, both is mixed, and 110 ℃ of following dried overnight, getting 20～40 order samples behind the compressing tablet is dimethyl ether synthetic catalyst.The mass content of each component is respectively: copper 34～50%, zinc 17～26%, aluminium 2～4%, HZSM-5 molecular sieve 20～46%.
Described dimethyl ether conversion support of the catalyst is the molecular sieve of SAPO-34 and HZSM-5 mechanically mixing, and active ingredient is a nickel, through pickling process active metal nickel is loaded on the carrier, and its weight loading is 0.5～1.5%.Carrier is of a size of 20～40 orders.
The dimethyl ether conversion catalyzer prepares as follows:
(1) take by weighing the nitrate salt of nickel, be dissolved in the absolute ethyl alcohol, the weight loading of its nickel is 0.5～1.5%, stir homogeneous solution;
(2) with above-mentioned solution impregnation on SAPO-34 through the dehydration degassing, the vehicle weight loading is not less than 90%;
(3) behind step (2) the product dipping, in 100 ℃ of dryings;
(4) dried product exhibited is in 550 ℃ of calcining 4h, and presses mass ratio in 3～0.33 scopes with HZSM-5 through the dehydration degassing, and mechanically mixing is even, through 15MPa pressure lower sheeting, mills.Make the dimethyl ether conversion catalyzer.
Embodiment 1:
A: in the fixed-bed reactor, dimethyl ether synthetic catalyst is earlier through air speed 1800
-1, the V (H of pressure 0.5MPa
2)/V (N
2)=5/95 reducing gas is in temperature programming to 270 ℃, and the back is at 270 ℃ of reduction 10h;
The composite catalyst Cu/Zn/Al/HZSM-5 that the methanol synthesis catalyst of this dimethyl ether synthetic catalyst and dehydration catalyst are formed, the mass ratio Cu of each component: Zn: Al: HZSM-5=50: 26: 4: 20;
B: in two sections fixed-bed reactor, the dimethyl ether conversion catalyzer is earlier at N
2Be warming up to 450 ℃ under the atmosphere gradually, and under temperature of reaction activation 3h;
Dimethyl ether conversion Preparation of catalysts method is: the ethanolic soln of SAPO-34 molecular sieve with nickelous nitrate flooded, and after 100 ℃ of dryings, 550 ℃ of calcining 3h carry out mechanically mixing with HZSM-5, make conversion catalyst.Wherein both weight ratios are 3: 1, and wherein the weight loading of nickel is 1.5%, and the catalyst size that obtains is 20～40 orders;
C: go on foot in the fixed-bed reactor H one
2/ N
2It is 1500h that reducing gas switches to air speed
-1Biomass synthesis gas (H
2/ CO/CO
2/ CH
4/ N
2=33.1/10.7/22.1/7.05/27.1), (H wherein
2-CO
2)/(CO+CO
2)=0.33, successive reaction under 265 ℃, the condition of 5MPa, reaction product dewaters through silica gel earlier, directly feeds two step fixed-bed reactor 400 ℃ of following successive reactions after reducing to normal pressure again.
Gc per hour real-time online detects product, and reaction 5h catalyst performance stabilised is 71.2% through calculating the CO transformation efficiency, and the first step yield of dimethyl ether is 0.148g/mL/h, and each products distribution is in the second step hydrocarbon polymer: C
1° 5.78%, C
2° 4.96%, C
2 =35.9%, C
3° 4.19%, C
3 =40.3%, C
4° 2.51%, C
4 =6.28%, low-carbon alkene C
2 =～C
4 =82.6%, productivity of low carbon olefin hydrocarbon 51.4g/m
3Synthetic gas, synthetic gas carbon utilisation rate are 25.0%.
Embodiment 2:
A: in step fixed-bed reactor, dimethyl ether synthetic catalyst is earlier through air speed 1500
-1, the V (H of pressure 0.8MPa
2)/V (N
2)=5/95 reducing gas is in temperature programming to 270 ℃, and the back is at 270 ℃ of reduction 10h;
The composite catalyst Cu/Zn/Al/HZSM-5 that the methanol synthesis catalyst of this dimethyl ether synthetic catalyst and dehydration catalyst are formed, the mass ratio Cu of each component: Zn: Al: HZSM-5=34: 18: 2.4: 46;
B: in two sections fixed-bed reactor, the dimethyl ether conversion catalyzer is earlier at N
2Be warming up to 450 ℃ under the atmosphere gradually, and under temperature of reaction activation 3h;
Dimethyl ether conversion Preparation of catalysts method is: the ethanolic soln of SAPO-34 molecular sieve with nickelous nitrate flooded, and after 100 ℃ of dryings, 550 ℃ of calcining 3h carry out mechanically mixing with HZSM-5, make conversion catalyst.Wherein both weight ratios are 0.33, and wherein the weight loading of nickel is 0.5%, and the catalyst size that obtains is 20～40 orders;
C: go on foot in the fixed-bed reactor H one
2/ N
2It is 6000h that reducing gas switches to air speed
-1Biomass synthesis gas (H
2/ CO/O
2/ CH
4/ N
2=45.3/30.2/4.61/4.28/15.6), (H wherein
2-CO
2)/(CO+CO
2)=1.1, successive reaction under 265 ℃, the condition of 5MPa, reaction product dewaters through silica gel earlier, directly feeds two step fixed-bed reactor 400 ℃ of following successive reactions after reducing to normal pressure again.
Gc per hour real-time online detects product, and reaction 8h catalyst performance stabilised is 41.3% through calculating the CO transformation efficiency, and the first step yield of dimethyl ether is 0.655g/mL/h, and each products distribution is in the second step hydrocarbon polymer: C
1° 10.0%, C
2° 9.08%, C
2 =26.2%, C
3° 8.40%, C
3 =35.1%, C
4° 3.22%, C
4 =8.05%, low-carbon alkene C
2 =～C
4 =69.3%, productivity of low carbon olefin hydrocarbon 44.9g/m
3Synthetic gas, synthetic gas carbon utilisation rate are 20.6%.
Embodiment 3:
A: in step fixed-bed reactor, dimethyl ether synthetic catalyst is earlier through air speed 2000
-1, the V (H of pressure 0.6MPa
2)/V (N
2)=5/95 reducing gas is in temperature programming to 270 ℃, and the back is at 270 ℃ of reduction 10h;
The composite catalyst Cu/Zn/Al/HZSM-5 that the methanol synthesis catalyst of this dimethyl ether synthetic catalyst and dehydration catalyst are formed, the mass ratio Cu of each component: Zn: Al: HZSM-5=34: 17: 2.4: 46
B: in two sections fixed-bed reactor, the dimethyl ether conversion catalyzer is earlier at N
2Be warming up to 450 ℃ under the atmosphere gradually, and under temperature of reaction activation 3h;
Dimethyl ether conversion Preparation of catalysts method is: the ethanolic soln of SAPO-34 molecular sieve with nickelous nitrate flooded, and after 100 ℃ of dryings, 550 ℃ of calcining 3h carry out mechanically mixing with HZSM-5, make conversion catalyst.Wherein both weight ratios are 3, and wherein the weight loading of nickel is 1.5%, and the catalyst size that obtains is 20～40 orders;
C: go on foot in the fixed-bed reactor H one
2/ N
2It is 3000h that reducing gas switches to air speed
-1Biomass synthesis gas (H
2/ CO/CO
2/ CH
4/ N
2=41.5/26.9/14.2/2.89/14.6), (H wherein
2-CO
2)/(CO+CO
2)=0.66, successive reaction under 265 ℃, the condition of 5MPa, reaction product earlier through cold-trap separate liquid product, silica gel dewaters, and directly feeds two step fixed-bed reactor 400 ℃ of following successive reactions after reducing to normal pressure again.
Gc per hour real-time online detects product, and reaction 5h catalyst performance stabilised is 48.4% through calculating the CO transformation efficiency, and the first step yield of dimethyl ether is 0.490g/mL/h, and each products distribution is in the second step hydrocarbon polymer: C
1° 3.0%, C
2° 4.31%, C
2 =39.6%, C
3° 4.31%, C
3 =41.3%, C
4° 3.08%, C
4 =3.71%, low-carbon alkene C
2 =～C
4 =84.7%, productivity of low carbon olefin hydrocarbon 84.6g/m
3Synthetic gas, synthetic gas carbon utilisation rate are 32.8%.
Embodiment 4:
A: in step fixed-bed reactor, dimethyl ether synthetic catalyst is earlier through air speed 1700
-1, the V (H of pressure 0.6MPa
2)/V (N
2)=5/95 reducing gas is in temperature programming to 270 ℃, and the back is at 270 ℃ of reduction 10h;
The composite catalyst Cu/Zn/Al/HZSM-5 that the methanol synthesis catalyst of this dimethyl ether synthetic catalyst and dehydration catalyst are formed, the mass ratio Cu of each component: Zn: Al: HZSM-5=48: 25: 3.4: 24;
B: in two sections fixed-bed reactor, the dimethyl ether conversion catalyzer is earlier at N
2Be warming up to 450 ℃ under the atmosphere gradually, and under temperature of reaction activation 3h;
Dimethyl ether conversion Preparation of catalysts method is: the ethanolic soln of SAPO-34 molecular sieve with nickelous nitrate flooded, and after 100 ℃ of dryings, 550 ℃ of calcining 3h carry out mechanically mixing with HZSM-5, make conversion catalyst.Wherein both weight ratios are 0.33, and wherein the weight loading of nickel is 0.5%, and the catalyst size that obtains is 20～40 orders;
C: go on foot in the fixed-bed reactor H one
2/ N
2It is 4500h that reducing gas switches to air speed
-1Biomass synthesis gas (H
2/ CO/CO
2/ CH
4/ N
2=40.0/33.7/5.54/5.57/15.2), (H wherein
2-CO
2)/(CO+CO
2)=0.88, successive reaction under 265 ℃, the condition of 5MPa, reaction product dewaters through silica gel earlier, directly feeds two step fixed-bed reactor 400 ℃ of following successive reactions after reducing to normal pressure again.
Gc per hour real-time online detects product, and reaction 8h catalyst performance stabilised is 77.4% through calculating the CO transformation efficiency, and the first step yield of dimethyl ether is 0.262g/mL/h, and each products distribution is in the second step hydrocarbon polymer: C
1° 8.15%, C
2° 8.04%, C
2 =30.9%, C
3° 6.76%, C
3 =31.7, C
4° 5.58%, C
4 =8.91%, low-carbon alkene C
2 =～C
4 =71.5%, productivity of low carbon olefin hydrocarbon 75.1g/m
3Synthetic gas, synthetic gas carbon utilisation rate are 30.5%.
Embodiment 5:
A: in step fixed-bed reactor, dimethyl ether synthetic catalyst is earlier through air speed 1200
-1, the V (H of pressure 0.4MPa
2)/V (N
2)=5/95 reducing gas is in temperature programming to 270 ℃, and the back is at 270 ℃ of reduction 10h;
The composite catalyst Cu/Zn/Al/HZSM-5 that the methanol synthesis catalyst of this dimethyl ether synthetic catalyst and dehydration catalyst are formed, the mass ratio Cu of each component: Zn: Al: HZSM-5=34: 18: 2.4: 46;
B: in two sections fixed-bed reactor, the dimethyl ether conversion catalyzer is earlier at 1800h
-1N
2Be warming up to 450 ℃ under the atmosphere gradually, and under temperature of reaction activation 3h;
Dimethyl ether conversion Preparation of catalysts method is: the ethanolic soln of SAPO-34 molecular sieve with nickelous nitrate flooded, and after 100 ℃ of dryings, 550 ℃ of calcining 3h carry out mechanically mixing with HZSM-5, make conversion catalyst.Wherein both weight ratios are 1, and wherein the weight loading of nickel is 1%, and the catalyst size that obtains is 20～40 orders;
C: go on foot in the fixed-bed reactor H one
2/ N
2It is 4500h that reducing gas switches to air speed
-1Biomass synthesis gas (H
2/ CO/CO
2/ CH
4/ N
2=33.1/10.7/22.1/7.05/27.1), (H wherein
2-CO
2)/(CO+CO
2)=0.33, successive reaction under 265 ℃, the condition of 5MPa, reaction product earlier through cold-trap separate liquid product, silica gel dewaters, and directly feeds two step fixed-bed reactor 400 ℃ of following successive reactions after reducing to normal pressure again.
Gc per hour real-time online detects product, and reaction 6h catalyst performance stabilised is 39.2% through calculating the CO transformation efficiency, and the first step yield of dimethyl ether is 0.216g/mL/h, and each products distribution is in the second step hydrocarbon polymer: C
1° 8.67%, C
2° 7.28%, C
2 =28.4%, C
3° 6.96%, C
3 =38.5%, C
4° 7.69%, C
4 =8.15%, low-carbon alkene C
2 =～C
4 =74.3%, productivity of low carbon olefin hydrocarbon 21.1g/m
3Synthetic gas, synthetic gas carbon utilisation rate are 9.7%.
Claims (4)
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| CN106807443A (en) * | 2016-11-09 | 2017-06-09 | 浙江科技学院 | A kind of copper-zinc-based catalyst and preparation method thereof |
| CN108456127A (en) * | 2018-04-13 | 2018-08-28 | 华中科技大学 | A kind of method that biomass multistage catalytic pyrolysis prepares low-carbon alkene |
| CN108456127B (en) * | 2018-04-13 | 2020-09-08 | 华中科技大学 | Method for preparing low-carbon olefin by multistage catalytic cracking of biomass |
| CN111039738A (en) * | 2018-10-11 | 2020-04-21 | 中国科学院大连化学物理研究所 | A kind of method for producing low carbon olefin from synthesis gas |
| WO2020073598A1 (en) * | 2018-10-11 | 2020-04-16 | 中国科学院大连化学物理研究所 | Method for preparing low-carbon olefins from synthesis gas |
| CN111039738B (en) * | 2018-10-11 | 2021-08-10 | 中国科学院大连化学物理研究所 | Method for preparing low-carbon olefin from synthesis gas |
| CN110183300A (en) * | 2019-05-08 | 2019-08-30 | 国家能源投资集团有限责任公司 | A kind of process and system by the highly selective propylene processed of synthesis gas |
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| CN114605213A (en) * | 2020-12-09 | 2022-06-10 | 中国科学院大连化学物理研究所 | Method for producing propylene from synthesis gas and dimethyl ether |
| CN114605213B (en) * | 2020-12-09 | 2023-01-31 | 中国科学院大连化学物理研究所 | A method for producing propylene from synthesis gas and dimethyl ether |
| CN115521186A (en) * | 2022-10-06 | 2022-12-27 | 新疆大学 | A method for preparing low-carbon olefins from biomass through a two-step conversion process |
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