CN101244971A - Synthesis method for producing ethylene with high-efficiency dehydration of biological ethyl alcohol - Google Patents
Synthesis method for producing ethylene with high-efficiency dehydration of biological ethyl alcohol Download PDFInfo
- Publication number
- CN101244971A CN101244971A CNA200810010514XA CN200810010514A CN101244971A CN 101244971 A CN101244971 A CN 101244971A CN A200810010514X A CNA200810010514X A CN A200810010514XA CN 200810010514 A CN200810010514 A CN 200810010514A CN 101244971 A CN101244971 A CN 101244971A
- Authority
- CN
- China
- Prior art keywords
- ethanol
- ethylene
- molecular sieve
- catalyst
- biological
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 250
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000005977 Ethylene Substances 0.000 title claims abstract description 52
- 235000019441 ethanol Nutrition 0.000 title claims description 75
- 230000018044 dehydration Effects 0.000 title claims description 25
- 238000006297 dehydration reaction Methods 0.000 title claims description 25
- 238000001308 synthesis method Methods 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000002808 molecular sieve Substances 0.000 claims abstract description 38
- 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 38
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 239000007789 gas Substances 0.000 claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000010189 synthetic method Methods 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 13
- 238000012986 modification Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910001868 water Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001257 actinium Chemical class 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910052680 mordenite Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052755 nonmetal Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 17
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000003795 desorption Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 42
- 239000011261 inert gas Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000001476 alcoholic effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000012018 catalyst precursor Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 229910004631 Ce(NO3)3.6H2O Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a synthesis method for dehydrating biological ethanol to prepare ethylene, belongs to the technical field of the synthesis chemical project and relates to a preparation of the ethylene. The invention provides a method for dehydrating the biological ethanol to prepare the ethylene under the function of a nanometer molecular sieve catalyst. Under the normal pressure and in a certain temperature range, a fixed bed reactor which uses the nanometer molecular sieve as the catalyst and uses the liquid biological ethanol as a raw material, and while the inertia gas is used for adjusting the partial pressure of the gas ethanol in the preheating section of the reactor, the desorption of the generated ethylene from the catalyst is strengthened so as to achieve the aim of efficiently dehydrating and synthesizing the ethylene by the ethanol. The synthesis method of dehydrating the biological ethanol to prepare the ethylene of the invention is outstandingly characterized in that: (1) the nanometer molecular sieve is applied in dehydrating the biological ethanol to prepare the ethylene; (2) while the inertia gas is used for adjusting the partial pressure of the gas ethanol, the desorption of the generated ethylene from the catalyst is strengthened; (3) the catalyst is good in stability, reaction is low in temperature, ethanol is high in conversion, ethylene is high in selectivity, environment is not polluted and the process is simple. A nanometer HZSM-5 molecular sieve is used as the catalyst, and 95(v/v) percent of liquid ethanol is used as the raw material (the ethanol weight space velocity is 1.2 hours<-1>), the nitrogen is used for adjusting the partial pressure of the gas ethanol in the preheating section of the reactor, the ethanol conversion is more than 99 percent and the ethylene selectivity is more than 98 percent in the reaction time of 600 hours under the reaction temperature of 240 DEG C.
Description
Technical field
The invention belongs to the synthetic chemistry field of engineering technology, relate to the synthetic method of bio-ethanol dehydration system ethene.
Background technology
Producing ethylene from dehydration of ethanol can be traced back to 1797, and before 1945, most in the world ethene all are to be made by ethanol dehydration.Along with developing rapidly of petroleum chemical industry, the appearance of a large amount of cheap oils and Sweet natural gas, the thermo-cracking of hydro carbons such as petroleum naphtha or Sweet natural gas is produced ethene, has replaced the route of producing ethylene from dehydration of ethanol gradually.The discharging that is accompanied by greenhouse gases is exhausted day by day to non-renewable fossil resource such as the serious harm of environment for human survival and oil, especially in recent years the first mate of fossil resource price such as oil is gone up, and the route of producing ethylene from dehydration of ethanol has bigger development potentiality and space.Along with people to the attention of renewable resources and the continuous development of biotechnology, the production technology of non-grain bio-ethanol reaches its maturity, output is increasing.This makes with the bio-ethanol is that raw material carries out large-scale chemical process, reduction has great realistic meaning to the dependence of fossil resources such as oil and the discharging of greenhouse gases.In addition, the ethene purity height that the ethanol dehydration method is produced produces many by products unlike petroleum law, in order to separate purification and to utilize these by products, must set up the machinery of a whole set of processing treatment simultaneously, causes gross investment big, and the construction period is long; And the Ethanol Method investment is little, the construction period is short, income is fast, production equipment is small and exquisite flexibly, production operation is convenient, technical requirements is not high.
In the synthetic method of bio-ethanol dehydration system ethene, crucial problem is a catalyzer.Traditional related catalyzer of producing ethylene from dehydration of ethanol process is mainly oxide compound and inorganic salt etc., and most widely used is alumina system.The shortcoming of aluminium oxide catalyst is that catalytic activity is low, and it mainly shows temperature of reaction height (360-450 ℃), the low (0.4-0.6h of weight space velocity
-1), unit output ethene energy consumption height, and to the concentration requirement harshness of feed ethanol, ethanol conversion reduces along with the increase of material concentration.
Since the eighties in 20th century, it is developed that the micron grain ZSM-5 molecular sieve is applied to the research of catalysis ethanol dehydration system ethene.This catalyzer has not etching apparatus, the transformation efficiency height, and characteristics such as Heat stability is good, temperature of reaction are also along with the difference of the method for the modification when of sial in the molecular sieve and difference (250-400 ℃).Because the duct of micron grain ZSM-5 molecular sieve is long, active site is many in the duct, is unfavorable for the diffusion of ethene in the duct and by-product molecule thereof, causes the duct of molecular sieve to stop up inactivation because of carbon distribution, thereby below 300 ℃, micron grain ZSM-5 catalyst stability is low.With CN 86101615A (1986.3.8) is example, the poor stability of the grain ZSM-5 molecular sieve catalyst of micron below 300 ℃, need constantly improve temperature of reaction and keep activity of such catalysts, 10 days have only been moved in the 250-300 ℃ of interval, after rising to 380 ℃ temperature of reaction, the stability of catalyzer just reached under the constant situation of temperature of reaction steady running 20 days.
In addition, also owing to use in the process of micron grain ZSM-5 catalyst producing ethylene from dehydration of ethanol, there is a large amount of oil reservoirs in the liquid emission, reduced the yield of ethene, increased the burden of wastewater treatment, so micron grain ZSM-5 catalyzer is not widely used in the technology of producing ethylene from dehydration of ethanol.
Comprehensively above-mentioned, the synthetic method of exploitation efficient cryogenic, environmental protection, bio-ethanol dehydration system ethene has very reality and long-range meaning.
[reference]:
US patent 4,234,752(1980)
US patent 4,873,392(1989-10-10)
N.K.Kochar，R.Merims，and A.S.Padia，Chem.Eng.Progr.77(1981)66
R.Le Van Mao，T.M.Nguyen and G.P.McLaughlin，Appl.Catal.48(1989)265
T.M.Nguyen，R.Le Van Mao，Appl.Catal.58(1990)119.
William R.Moser，Robert W.Thompson，Chen-Chou Chiang，and Hao Tong，J.Catal.117(1989)19.
CN 86101615A 1986.3.8
Pan Lvrang, Li He, petrochemical complex, 14 (3), 154 (1985)
Pan Lvrang, Speciality Petrochemicals, 4,41 (1986)
Pan Lvrang, Li He, petrochemical complex, 16 (11), 764 (1987)
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of efficient cryogenic, environmental protection, producing ethylene with high-efficiency dehydration of biological ethyl alcohol.The crystal grain that the present invention makes full use of nano molecular sieve is little, the duct is short, be difficult for carbon distribution, characteristics such as specific surface area is big, active height, when utilizing in the rare gas element conditioned reaction device gas alcoholic acid dividing potential drop, strengthen the desorption behavior of ethene on catalyzer that generates, suppressed the generation of many carbon component.
Technical solution of the present invention is that a kind of synthetic method of producing ethylene with high-efficiency dehydration of biological ethyl alcohol, this method are under normal pressure, 200-300 ℃ of temperature of reaction, with liquid bio ethanol is raw material, and nano molecular sieve is a catalyzer, and the weight space velocity of liquid ethanol is 0.5-4h
-1,, be 60-120KPa with the rare gas element adjustments of gas bio-ethanol dividing potential drop of gauge pressure 0.2-0.3Mpa at the preheating section of reactor.Described nano molecular sieve comprises mordenite, ZSM-5, ZSM-11, SAPO-34, ZSM-22, MCM-22, ZSM-48, β zeolite or several combination allotments in them, preferred ZSM-5 molecular sieve.Described nano molecular sieve grain-size is the 20-300 nanometer, preferred 50-100 nanometer.Nano molecular sieve catalyst is to carry out steam treatment at low temperatures, and treatment temp is 350-450 ℃.Described nano molecular sieve catalyst is to be oxide modifying, used oxide compound comprises IA-VA metal oxide, IB-VIIIB transition metal oxide, group of the lanthanides or actinium series rare-earth oxide or IIIA-VIA nonmetal oxide, preferably magnesium modification, zinc modification, manganese modification, cerium modified, phosphorus modification or silicon modification.Rare gas element is nitrogen, helium or water vapour.The concentration range of bio-ethanol is 10-99%.In the time of with the rare gas element adjustments of gas ethanol dividing potential drop of 0.2-0.3Mpa (gauge pressure), strengthened the ethene desorption on the nano molecular sieve catalyst in the conversion zone, suppress the generation of many carbon component, to reach the ethanol conversion height, selectivity of ethylene is high and catalyst stability is good.
With nanometer HZSM-5 molecular sieve catalyst is example:
(1) preparation of efficient nano HZSM-5 bio-ethanol dehydration catalyst for making ethylene: with SiO
2: Al
2O
3=20-60 (mol ratio), the HZSM-5 molecular sieve and the α-Al of grain-size 50-100 nanometer
2O
3.H
2O is by butt weight ratio 1-10: add the 1.0-5.0% sesbania powder of butt weight in 1 mixture of forming and the aqueous nitric acid of 5-15% (V/V) mixes the extruding slivering, at 80-100 ℃ down after dry 8-10 hour, in muffle furnace, reduce to room temperature after roasting 2-6 hour for 450-600 ℃; On this basis, under 350-450 ℃ temperature, be 1-5h with the air speed
-1Water vapor carry out steam and handled 1-6 hour, after reduce to room temperature; The above two one of the basis on, carry out oxide modifying according to the method in the right 5.With cerium oxide (CeO
2) be modified as example, detailed process is described: with the cerium oxide (CeO of parent weight 0.1-10%
2) be converted to normal cerous nitrate (Ce (NO
3)
3.6H
2O), (volume of solution and the volume ratio of catalyst Precursors are about 5-10: 1) to be configured to cerous nitrate solution.Catalyst Precursors be impregnated in the cerous nitrate solution, leave standstill 8-10 hour under the room temperature after, evaporation drying in 80-100 ℃.Then the exsiccant sample is inserted in the muffle furnace, after 400-600 ℃ of roasting 2-5 hour, reduce to room temperature.
(2) Application of Catalyst method: with the experimental data is that example is described as follows: restrain (g) catalyst loading in the reactor constant temperature zone with 1, under rare gas element (nitrogen) protection of 0.25Mpa (gauge pressure), 400-550 ℃ of activation is after 2-5 hour, and temperature is reduced to 240 ℃ (± 3); 95 (V/V) % liquid ethanol is with weight space velocity 1.2h
-1Injecting reactor is depressed into set-point with the gas alcoholic acid branch in the nitrogen conditioned reaction device preheating section of 0.25Mpa (gauge pressure), in the reaction process, keeps the pressure and the stability of flow of rare gas element (nitrogen).
The invention has the beneficial effects as follows: it is existing shortcoming in the synthetic method of catalyzer producing ethylene from dehydration of ethanol that this method has overcome with aluminum oxide or micron grain ZSM-5 molecular sieve, has that temperature of reaction is low, catalyst activity is high, the life-span is long, Heat stability is good; The ethanol conversion height, the selectivity of ethylene height; Not etching apparatus, simple, easy and simple to handle, the environmental protection of technology.
Embodiment
Embodiment 1
With SiO
2: Al
2O
3=26 (mol ratios), the HZSM-5 molecular sieve (powder) of grain-size 50-100 nanometer and α .Al
2O
3.H
2O (powder) mixes the extruding slivering by the 3.0% sesbania powder of adding butt weight and the aqueous nitric acid of 12% (V/V) in the mixture of 70: 30 compositions of butt weight ratio, drying is after 8 hours in 85 ℃ of thermostat containers, sample is inserted in the muffle furnace, with 6 ℃/minute speed temperature is warming up to 540 ℃ and reduce to room temperature at 540 ℃ after down keeping 3 hours from 30 ℃, note is made catalyst A.
1 gram (g) catalyst A sample is inserted the stainless steel tubular type reactor middle part (constant temperature zone) of long 40cm, internal diameter 0.8cm, and the non-constant temperature zone of reactor is filled inert ceramic balls.Under the protection of nitrogen gas of 0.25Mpa (gauge pressure), after 450 ℃ (constant temperature zones) activate 2 hours down, cool the temperature to 240 ℃ (constant temperature zones).Liquid starting material ethanol is gone into reactor by infusion, and the alcoholic acid weight space velocity is 1.2h
-1At the preheating section of reactor, be 86Kpa with the nitrogen adjustments of gas alcoholic acid dividing potential drop of 0.25Mpa (gauge pressure).Reactor outlet material after gas-liquid separator separates, the gas sample by the gas chromatograph analysis of fid detector (4mm * 2m modification GDX103 packed column, nitrogen is carrier gas, 35 ℃ of initial column temperatures, 150 ℃ of Sample Room temperature, 150 ℃ of detector temperatures; Column temperature kept 20 minutes by 35 ℃ of temperature programmings to 130 ℃ and at 130 ℃), the liquid sample is by the gas chromatograph analysis (2mm * 3m modification GDX101 packed column, hydrogen is carrier gas, 105 ℃ of column temperatures, 150 ℃ of Sample Room temperature, 150 ℃ of detector temperatures) of TCD detector.The composition of gas sample: C
1(methane), C
2(ethene and ethane), C
3(propylene and propane), C
4(butylene and butane mixture), C
5(carbon 5 mixtures), ether, unreacted ethanol and C
6(carbon 6 mixtures); The composition of liquid sample: water, the acetaldehyde of minute quantity, unreacted ethanol.Reacted ethanol conversion＞99%, selectivity of ethylene＞98% 600 hours.
Comparative example 1
Press embodiment 1, increase inert gas flow, the ethanol differential pressure drop in the reactor preheating section is low to moderate 80Kpa, reacts ethanol conversion＞99%, selectivity of ethylene＞98% 240 hours.
Comparative example 2
Press embodiment 1, reduce inert gas flow, the ethanol dividing potential drop in the reactor preheating section increases to 92Kpa, reacts ethanol conversion＞99%, selectivity of ethylene＞98% 300 hours.
Comparative example 3
The HZSM-5 molecular sieve of grain-size 50-100 nanometer is replaced by grain-size 1-2 μ m HZSM-5 molecular sieve, press the preparation method of embodiment 1, make corresponding micron HZSM-5 molecular sieve catalyst, application method is identical with embodiment 1, ethanol dividing potential drop 86Kpa in the reactor preheating section, move after 96 hours ethanol conversion 93.6%, selectivity of ethylene 93.7%.
Comparative example 4
Press comparative example 3, increase inert gas flow, the ethanol differential pressure drop in the reactor preheating section is low to moderate 80Kpa, moves after 96 hours ethanol conversion 91.9%, selectivity of ethylene 91.6%.
Comparative example 5
Press comparative example 3, reduce inert gas flow, the ethanol dividing potential drop in the reactor preheating section increases to 92Kpa, moves after 96 hours, and ethanol conversion is 92.4%, selectivity of ethylene 92.2%.
Table 1. catalyst A contrasts with the operation result of " comparative example 1 " to " comparative example 5 "
| Catalyzer | The ethanol dividing potential drop | Temperature of reaction | Reaction times | Ethanol conversion | Selectivity of ethylene |
| Kpa | ℃ | hr | ％ | ％ |
| Catalyst A | 86 | 240 | 50 100 150 300 500 600 630 | 99.94 99.90 99.78 99.70 99.26 99.03 98.83 | 98.13 98.24 98.34 98.54 98.68 98.46 98.32. |
| Comparative example 1 | 80 | 240 | 50 100 150 240 280 | 99.74 99.50 99.23 99.02 98.31 | 98.45 98.61 98.72 98.43 98.16 |
| Comparative example 2 | 92 | 240 | 50 100 150 300 330 | 99.88 99.70 99.56 99.04 98.56 | 98.07 98.34 98.57 98.30 98.11 |
| Comparative example 3 | 86 | 240 | 10 20 30 50 96 | 99.83 99.20 98.08 96.63 93.62 | 97.86 98.35 97.59 96.62 93.73 |
| Comparative example 4 | 80 | 240 | 10 20 30 50 96 | 99.14 98.56 97.47 96.08 91.94 | 98.46 98.41 97.52 96.23 91.62 |
| Comparative example 5 | 92 | 240 | 10 20 30 50 96 | 99.70 99.27 98.51 97.11 92..43 | 98.23 98.38 97.86 96.84 92.21 |
Embodiment 2
With SiO
2: Al
2O
3=26 (mol ratios), the HZSM-5 molecular sieve (powder) of grain-size 50-100 nanometer and α-Al
2O
3.H
2O (powder) mixes the extruding slivering by the 3.0% sesbania powder of adding butt weight and the aqueous nitric acid of 12% (V/V) in the mixture of 70: 30 compositions of butt weight ratio, drying is after 8 hours in 85 ℃ of thermostat containers, sample is inserted in the muffle furnace, temperature is warming up to 540 ℃ and reduce to room temperature at 540 ℃ after down keeping 3 hours from 30 ℃ with 6 ℃/minute speed.Then with sample under 410 ℃ temperature, be 2h with the air speed
-1Water vapor carry out steam and handle after 3.5 hours, reduce to room temperature, note is made catalyst B.Application method and embodiment 1 are identical, the alcoholic acid dividing potential drop 86Kpa in the reactor preheating section, 430 hours run durations, ethanol conversion＞99%, selectivity of ethylene＞98%.
Comparative example 6
Press embodiment 2, increase inert gas flow, the ethanol differential pressure drop in the reactor preheating section is low to moderate 80Kpa, 180 hours run duration, ethanol conversion＞99%, selectivity of ethylene＞98%.
Comparative example 7
Press embodiment 2, reduce inert gas flow, the ethanol dividing potential drop in the reactor preheating section increases to 92Kpa, 270 hours run duration, ethanol conversion＞99%, selectivity of ethylene＞98%.
Comparative example 8
The HZSM-5 molecular sieve of grain-size 50-100 nanometer is replaced by grain-size 1-2 μ m HZSM-5 molecular sieve, press the preparation method of embodiment 2, make corresponding micron HZSM-5 molecular sieve catalyst, application method is identical with embodiment 2, ethanol dividing potential drop 86Kpa in the reactor preheating section, move after 96 hours ethanol conversion 92.8%, selectivity of ethylene 92.6%.
Comparative example 9
Press comparative example 8, increase inert gas flow, the ethanol differential pressure drop in the reactor preheating section is low to moderate 80Kpa, moves after 96 hours ethanol conversion 90.8%, selectivity of ethylene 91.1%.
Comparative example 10
Press comparative example 8, reduce inert gas flow, the ethanol dividing potential drop in the reactor preheating section increases to 92Kpa, moves after 96 hours ethanol conversion 92.1%, selectivity of ethylene 91.7%.
Table 2. catalyst B contrasts with the operation result of " comparative example 6 " to " comparative example 10 "
| Catalyzer | The ethanol dividing potential drop | Temperature of reaction | Reaction times | Ethanol conversion | Selectivity of ethylene |
| Kpa | ℃ | hr | ％ | ％ | |
| Catalyst B | 86 | 240 | 50 100 150 300 430 500 | 99.78 99.64 99.55 99.32 99.06 98.89 | 98.15 98.21 98.35 98.43 98.32 98.16 |
| Comparative example 6 | 80 | 240 | 50 100 150 180 210 | 99.40 99.21 99.09 99.01 98.54 | 98.52 98.61 98.70 98.43 98.22 |
| Comparative example 7 | 92 | 240 | 50 100 150 270 300 | 99.82 99.60 99.26 99.08 98.67 | 98.13 98.36 98.52 98.34 98.17 |
| Comparative example 8 | 86 | 240 | 10 20 30 50 96 | 99.66 99.20 98.58 97..13 92.76 | 97.67 98.31 98.15 97.32 92.57 |
| Comparative example 9 | 80 | 240 | 10 20 30 50 96 | 99.17 98.41 97.15 95.64 90.79 | 98.44 98.24 97.53 96.02 91.14 |
| Comparative example 10 | 92 | 240 | 10 20 30 50 96 | 99.74 99.20 98.43 97.93 92.08 | 98.19 98.43 97.94 97.62 91.72 |
Embodiment 3
With SiO
2: Al
2O
3=26 (mol ratios), the HZSM-5 molecular sieve of grain-size 50-100 nanometer and α .Al
2O
3.H
2O mixes the extruding slivering by the 3.0% sesbania powder of adding butt weight and the aqueous nitric acid of 12% (V/V) in the mixture of 70: 30 compositions of butt weight ratio, drying is after 8 hours in 85 ℃ of thermostat containers, sample is inserted in the muffle furnace, temperature is warming up to 540 ℃ and reduce to room temperature at 540 ℃ after down keeping 3 hours from 30 ℃ with 6 ℃/minute speed.Then with sample under 410 ℃ temperature, be 2h with the air speed
-1Water vapor carry out steam and handle after 3.5 hours, reduce to room temperature.As parent, with the cerium oxide (CeO of parent weight 3%
2) be converted to normal cerous nitrate (Ce (NO
3)
3.6H
2O), be configured to cerous nitrate solution (volume of solution and the volume ratio of catalyst Precursors are about 9: 1).Catalyst Precursors be impregnated in the cerous nitrate solution, leave standstill 10 hours under the room temperature after, evaporation drying in 85 ℃ thermostat container.Then the exsiccant sample is inserted in the muffle furnace, reduce to room temperature 540 ℃ of roastings after 3 hours, note is made catalyzer C.Application method and embodiment 1 are identical, the ethanol dividing potential drop 86Kpa in the reactor preheating section, 180 hours run durations, ethanol conversion＞99%, selectivity of ethylene＞98%.
Comparative example 11
Press embodiment 3, increase inert gas flow, the ethanol differential pressure drop in the reactor preheating section is low to moderate 80Kpa, 96 hours run durations, ethanol conversion＞99%, selectivity of ethylene＞98%.
Comparative example 12
Press embodiment 3, reduce inert gas flow, the ethanol dividing potential drop in the reactor preheating section increases to 92Kpa, 240 hours run durations, ethanol conversion＞99%, selectivity of ethylene＞98%.
Comparative example 13
The HZSM-5 molecular sieve of grain-size 50-100 nanometer is replaced by grain-size 1-2 μ m HZSM-5 molecular sieve, press the preparation method of embodiment 3, make corresponding micron HZSM-5 molecular sieve catalyst, application method is identical with embodiment 3, ethanol dividing potential drop 86Kpa in the reactor preheating section, move after 55 hours ethanol conversion 93.5%, selectivity of ethylene 93.5%.
Comparative example 14
Press comparative example 13, increase inert gas flow, the ethanol differential pressure drop in the reactor preheating section is low to moderate 80Kpa, moves after 55 hours ethanol conversion 92.1%, selectivity of ethylene 93.1%.
Comparative example 15
Press comparative example 13, reduce inert gas flow, the ethanol dividing potential drop in the reactor preheating section increases to 92Kpa, moves after 55 hours, and ethanol conversion is 93.7%, and selectivity of ethylene is 93.2%.
Table 3. catalyzer C contrasts with the operation result of " comparative example 11 " to " comparative example 15 "
| Catalyzer | The ethanol dividing potential drop | Temperature of reaction | Reaction times | Ethanol conversion | Selectivity of ethylene |
| Kpa | ℃ | hr | ％ | ％ | |
| Catalyzer C | 86 | 240 | 50 100 150 180 200 | 99.63 99.31 99.16 99.04 98.82 | 98.19 98.54 98.67 98.63 98.46 |
| Comparative example 11 | 80 | 240 | 24 48 72 96 120 | 99.32 99.20 99.12 99.03 98.45 | 98.57 98.68 98.76 98.53 98.31 |
| Comparative example 12 | 92 | 240 | 50 100 150 240 280 | 99.75 99.47 99.22 99.03 98.56 | 98.21 98.44 98.57 98.43 98.15 |
| Comparative example 13 | 86 | 240 | 10 20 30 55 | 99.18 98.15 96.14 93.53 | 98.27 97.42 96.48 93.46 |
| Comparative example 14 | 80 | 240 | 10 20 30 55 | 98.82 97.76 95.37 92.09 | 98.43 97.54 96.06 93.07 |
| Comparative example 15 | 92 | 240 | 10 20 30 55 | 99.16 98.20 96.39 93.68 | 98.28 97.89 95.78 93.21 |
2008.01.21
Claims (7)
1, a kind of synthetic method of producing ethylene with high-efficiency dehydration of biological ethyl alcohol is characterized in that, under the normal pressure, 200-300 ℃ of temperature of reaction is raw material with liquid bio ethanol, and nano molecular sieve is a catalyzer, and the weight space velocity of liquid ethanol is 0.5-4h
-1,, be 60-120KPa with the rare gas element adjustments of gas bio-ethanol dividing potential drop of gauge pressure 0.2-0.3Mpa at the preheating section of reactor.
2, according to the synthetic method of the described a kind of producing ethylene with high-efficiency dehydration of biological ethyl alcohol of claim 1, it is characterized in that, described nano molecular sieve comprises mordenite, ZSM-5, ZSM-11, SAPO-34, ZSM-22, MCM-22, ZSM-48, β zeolite or several combination allotments in them, preferred ZSM-5 molecular sieve.
According to the synthetic method of the described a kind of producing ethylene with high-efficiency dehydration of biological ethyl alcohol of claim 1, it is characterized in that 3, described nano molecular sieve grain-size is the 20-300 nanometer, preferred 50-100 nanometer.
According to the synthetic method of the described a kind of producing ethylene with high-efficiency dehydration of biological ethyl alcohol of claim 1, it is characterized in that 4, described nano molecular sieve catalyst is to carry out steam treatment at low temperatures, treatment temp is 350-450 ℃.
5, according to the synthetic method of the described a kind of producing ethylene with high-efficiency dehydration of biological ethyl alcohol of claim 1, it is characterized in that, described nano molecular sieve catalyst is to be oxide modifying, used oxide compound comprises IA-VA metal oxide, IB-VIIIB transition metal oxide, group of the lanthanides or actinium series rare-earth oxide or IIIA-VIA nonmetal oxide, preferably magnesium modification, zinc modification, manganese modification, cerium modified, phosphorus modification or silicon modification.
According to the synthetic method of the described a kind of producing ethylene with high-efficiency dehydration of biological ethyl alcohol of claim 1, it is characterized in that 6, described rare gas element is nitrogen, helium or water vapour.
According to the synthetic method of the described a kind of producing ethylene with high-efficiency dehydration of biological ethyl alcohol of claim 1, it is characterized in that 7, the concentration range of described bio-ethanol is 10-99%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200810010514XA CN101244971A (en) | 2008-02-27 | 2008-02-27 | Synthesis method for producing ethylene with high-efficiency dehydration of biological ethyl alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200810010514XA CN101244971A (en) | 2008-02-27 | 2008-02-27 | Synthesis method for producing ethylene with high-efficiency dehydration of biological ethyl alcohol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101244971A true CN101244971A (en) | 2008-08-20 |
Family
ID=39945691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200810010514XA Pending CN101244971A (en) | 2008-02-27 | 2008-02-27 | Synthesis method for producing ethylene with high-efficiency dehydration of biological ethyl alcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101244971A (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102227393A (en) * | 2008-12-01 | 2011-10-26 | 三井化学株式会社 | Method for producing olefin |
| CN103030491A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method for producing ethylene through ethanol dehydration |
| CN103121902A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing ethylene by dehydrating ethanol under catalysis |
| CN103121930A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method of catalytic dehydration by 4-hydroxyl-3-hexanone |
| CN103121929A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for producing 4-hexene-3-one by dehydration of 4-hydroxyl-3-hexanone |
| CN103121932A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Catalytic dehydrating preparation method of 4-hexen-3-ketone by 4- hydroxy-3-hexanone |
| CN103450921A (en) * | 2012-06-01 | 2013-12-18 | 中国石油天然气集团公司 | Method for selectively preparing propylene and clean gasoline through using methanol |
| WO2016107759A1 (en) * | 2014-12-31 | 2016-07-07 | Total Research & Technology Feluy | Process for preparing olefins by dehydrating alcohols with less side effects comprising addition of sulfur containing compounds |
| WO2017210812A1 (en) * | 2016-06-06 | 2017-12-14 | Rhodia Operations | Rare earth zeolite and the method of preparation thereof |
| CN108101727A (en) * | 2018-01-12 | 2018-06-01 | 温州市星峰新材料有限公司 | A kind of method of producing ethylene from dehydration of ethanol |
| CN108855205A (en) * | 2018-07-31 | 2018-11-23 | 西北化工研究院有限公司 | A kind of producing ethylene from dehydration of ethanol molecular sieve catalyst and its preparation method and application |
| CN110560151A (en) * | 2019-09-16 | 2019-12-13 | 延长中科（大连）能源科技股份有限公司 | Molecular sieve solid acid catalyst, preparation method and application thereof |
| CN111450874A (en) * | 2020-04-09 | 2020-07-28 | 中国石油大学(北京) | Metal modified mordenite, preparation method thereof and application of metal modified mordenite in preparation of ethylene by catalyzing dimethyl ether |
| CN113105300A (en) * | 2021-03-26 | 2021-07-13 | 华南理工大学 | Method for producing ethylene by homogeneous phase photocatalysis of ethanol |
| CN113758782A (en) * | 2021-09-06 | 2021-12-07 | 北京银河巴马生物技术股份有限公司 | Gaseous reinforcing means of biomaterial |
| US11260367B2 (en) | 2018-12-12 | 2022-03-01 | Instituto Nacional De Tecnologia | Catalytic system and process for the production of light olefins from ethanol |
-
2008
- 2008-02-27 CN CNA200810010514XA patent/CN101244971A/en active Pending
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102227393A (en) * | 2008-12-01 | 2011-10-26 | 三井化学株式会社 | Method for producing olefin |
| CN103030491A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method for producing ethylene through ethanol dehydration |
| CN103030491B (en) * | 2011-09-29 | 2017-04-19 | 中国石油化工股份有限公司 | Method for producing ethylene through ethanol dehydration |
| CN103121929B (en) * | 2011-11-18 | 2015-05-13 | 中国石油化工股份有限公司 | Method for producing 4-hexene-3-one by dehydration of 4-hydroxyl-3-hexanone |
| CN103121902A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing ethylene by dehydrating ethanol under catalysis |
| CN103121930A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method of catalytic dehydration by 4-hydroxyl-3-hexanone |
| CN103121929A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for producing 4-hexene-3-one by dehydration of 4-hydroxyl-3-hexanone |
| CN103121932A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Catalytic dehydrating preparation method of 4-hexen-3-ketone by 4- hydroxy-3-hexanone |
| CN103121902B (en) * | 2011-11-18 | 2015-01-07 | 中国石油化工股份有限公司 | Method for preparing ethylene by dehydrating ethanol under catalysis |
| CN103121930B (en) * | 2011-11-18 | 2015-04-08 | 中国石油化工股份有限公司 | Method of catalytic dehydration by 4-hydroxyl-3-hexanone |
| CN103450921A (en) * | 2012-06-01 | 2013-12-18 | 中国石油天然气集团公司 | Method for selectively preparing propylene and clean gasoline through using methanol |
| CN103450921B (en) * | 2012-06-01 | 2014-12-24 | 中国石油天然气集团公司 | Method for selectively preparing propylene and clean gasoline through using methanol |
| WO2016107759A1 (en) * | 2014-12-31 | 2016-07-07 | Total Research & Technology Feluy | Process for preparing olefins by dehydrating alcohols with less side effects comprising addition of sulfur containing compounds |
| US10472300B2 (en) | 2014-12-31 | 2019-11-12 | Total Research & Technology Feluy | Process for preparing olefins by dehydrating alcohols with less side effects comprising addition of sulfur containing compounds |
| WO2017210812A1 (en) * | 2016-06-06 | 2017-12-14 | Rhodia Operations | Rare earth zeolite and the method of preparation thereof |
| CN108101727B (en) * | 2018-01-12 | 2020-11-03 | 温州市星峰新材料有限公司 | Method for preparing ethylene by ethanol dehydration |
| CN108101727A (en) * | 2018-01-12 | 2018-06-01 | 温州市星峰新材料有限公司 | A kind of method of producing ethylene from dehydration of ethanol |
| CN108855205A (en) * | 2018-07-31 | 2018-11-23 | 西北化工研究院有限公司 | A kind of producing ethylene from dehydration of ethanol molecular sieve catalyst and its preparation method and application |
| CN108855205B (en) * | 2018-07-31 | 2021-03-02 | 西北化工研究院有限公司 | Molecular sieve catalyst for preparing ethylene by ethanol dehydration and preparation method and application thereof |
| US11260367B2 (en) | 2018-12-12 | 2022-03-01 | Instituto Nacional De Tecnologia | Catalytic system and process for the production of light olefins from ethanol |
| CN110560151A (en) * | 2019-09-16 | 2019-12-13 | 延长中科（大连）能源科技股份有限公司 | Molecular sieve solid acid catalyst, preparation method and application thereof |
| CN111450874A (en) * | 2020-04-09 | 2020-07-28 | 中国石油大学(北京) | Metal modified mordenite, preparation method thereof and application of metal modified mordenite in preparation of ethylene by catalyzing dimethyl ether |
| CN111450874B (en) * | 2020-04-09 | 2021-08-20 | 中国石油大学(北京) | Metal modified mordenite, preparation method thereof and application of metal modified mordenite in preparation of ethylene by catalyzing dimethyl ether |
| CN113105300A (en) * | 2021-03-26 | 2021-07-13 | 华南理工大学 | Method for producing ethylene by homogeneous phase photocatalysis of ethanol |
| CN113105300B (en) * | 2021-03-26 | 2022-05-24 | 华南理工大学 | Method for producing ethylene by homogeneous phase photocatalysis of ethanol |
| CN113758782A (en) * | 2021-09-06 | 2021-12-07 | 北京银河巴马生物技术股份有限公司 | Gaseous reinforcing means of biomaterial |
| CN113758782B (en) * | 2021-09-06 | 2024-05-28 | 北京银河巴马生物技术股份有限公司 | Biological material gas strengthening device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101244971A (en) | Synthesis method for producing ethylene with high-efficiency dehydration of biological ethyl alcohol | |
| CN104230615B (en) | The method of biomass derivatives γ-valerolactone catalytic cracking aromatic hydrocarbons and cyclopentenone | |
| CN101648140B (en) | Tungsten carbide catalyst, preparation thereof and application thereof in reaction for preparing glycol from cellulose | |
| ES2914251T3 (en) | Process for producing dienes | |
| CN110124647A (en) | Support type non-metallic catalyst, preparation method and applications | |
| JP5789306B2 (en) | Method for producing organic compounds by fermentation of biomass and zeolite catalysis | |
| CN103157502A (en) | Catalyst of preparing ethylene and propylene by carbinol and / or dimethyl ether, preparing method and application thereof | |
| CN112299962B (en) | Synthesis method of 3-methyl-2-butene-1-aldehyde diisopentenyl acetal | |
| CN103435483A (en) | Synthesis method for methyl acrylate from methyl acetate and formaldehyde | |
| CN103127945A (en) | Method for preparing catalyst used for preparing acetaldehyde through direct dehydrogenation of ethanol and application of catalyst | |
| JP5288255B2 (en) | Catalyst for producing lower olefin, process for producing the same, and process for producing lower olefin using the same | |
| JP2010042344A (en) | Catalyst for manufacturing lower olefin, method of manufacturing the same and method of manufacturing lower olefin using catalyst | |
| CN102807465B (en) | Method for producing propane and gasoline by using butane | |
| CN1161307C (en) | Catalyst for producing ethylene by carbon dioxide oxidation and dehydrogenation of ethane under low temperature | |
| CN110947417B (en) | Catalyst for producing propane and gasoline from alkane, preparation method and application | |
| Dosumov et al. | Cerium-containing catalysts for converting ethanol into ethylene | |
| CN101176850B (en) | Catalyzer for preparing ethylene by ethanol dehydration as well as preparation method and usage | |
| CN103785473B (en) | A kind of highly active catalytic cracking alkene catalyst and its preparation method and application | |
| CN102649086B (en) | Catalyst used in preparation of ethylene through ethanol dehydration | |
| CN102190543A (en) | Method for preparing ethylene by dehydrating ethanol | |
| JP5245162B2 (en) | Method for producing olefins having 3 or more carbon atoms from ethanol using zirconium-supported zeolite catalyst | |
| JP5311409B2 (en) | Method for producing olefins having 3 or more carbon atoms from ethanol | |
| US9643898B2 (en) | Alkanol to alkylene conversion using at least two different catalysts in sequential order | |
| JP2007075796A (en) | Lower hydrocarbon reforming catalyst | |
| JP6084126B2 (en) | Manufacturing method of high calorific value fuel gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080820 |