CN101830776B - Method for synthesizing ethanol - Google Patents
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- CN101830776B CN101830776B CN 201010177750 CN201010177750A CN101830776B CN 101830776 B CN101830776 B CN 101830776B CN 201010177750 CN201010177750 CN 201010177750 CN 201010177750 A CN201010177750 A CN 201010177750A CN 101830776 B CN101830776 B CN 101830776B
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000010949 copper Substances 0.000 claims abstract description 41
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 claims abstract description 36
- 239000007789 gas Substances 0.000 claims abstract description 29
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 25
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000008016 vaporization Effects 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 23
- 238000005303 weighing Methods 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 18
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 15
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims description 14
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 11
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 claims description 10
- 230000009466 transformation Effects 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 8
- 238000009834 vaporization Methods 0.000 claims description 8
- QQZWEECEMNQSTG-UHFFFAOYSA-N Ethyl nitrite Chemical compound CCON=O QQZWEECEMNQSTG-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000013067 intermediate product Substances 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims description 4
- XEEVLJKYYUVTRC-UHFFFAOYSA-N oxomalonic acid Chemical compound OC(=O)C(=O)C(O)=O XEEVLJKYYUVTRC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- DBKKFIIYQGGHJO-UHFFFAOYSA-N diethyl 2-oxopropanedioate Chemical compound CCOC(=O)C(=O)C(=O)OCC DBKKFIIYQGGHJO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- -1 oxalic acid diester Chemical class 0.000 abstract description 15
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- 239000007795 chemical reaction product Substances 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract 4
- 235000006408 oxalic acid Nutrition 0.000 abstract 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 229960001866 silicon dioxide Drugs 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 8
- 238000000855 fermentation Methods 0.000 description 6
- 230000004151 fermentation Effects 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000004464 cereal grain Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012262 fermentative production Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000003317 industrial substance Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 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
- 238000001556 precipitation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- LOMVENUNSWAXEN-NUQCWPJISA-N dimethyl oxalate Chemical group CO[14C](=O)[14C](=O)OC LOMVENUNSWAXEN-NUQCWPJISA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for synthesizing ethanol, which comprises the following steps of: 1, preparing oxalic acid diester through coupling reaction of carbon monoxide and nitrite under the catalysis of an alumina-supported palladium catalyst; 2, pre-heating and vaporizing the oxalic acid diester and mixing with hydrogen; carrying out catalytic hydrogenation reaction on the mixed gas on a silicon dioxide-supported copper catalyst, and then cooling and distilling the reaction product to obtain ethanol. The preparation method of the invention realizes over 80% of selectivity and high yield of ethanol, and the gas used in synthesis process can be completely converted through circulation, thereby establishing a good foundation for research on the industry of synthesizing ethanol frombiomass.
Description
Technical field
The invention belongs to technical field of organic synthesis, refer more particularly to a kind of method of synthesizing alcohol.
Background technology
Ethanol is commonly called as alcohol, is a kind of clean fuel.Oil substitutes such as exploitation fuel alcohol, taking measures to save petroleum resources is one of emphasis of the Tenth Five-Year Plan (2001-2005) outline.Vehicle-use alcohol gasoline is a kind of new automobile fuel that denatured fuel ethanol and gasoline are mixed by a certain percentage and form.It can effectively improve performance and the quality of oil product, reduces the discharging of principal pollutant such as carbon monoxide, hydrocarbon polymer and does not influence the rideability of automobile.Ethanol petrol is the present development priority of renewable energy source in the world as a kind of novel clean fuel, meets China's energy substitution strategy and renewable energy source developing direction.Ethanol also is a kind of important chemical material, can be as the raw material of industrial chemical and polymkeric substance.
At present, the method for industrial production ethanol mainly is the direct aquation method of fermentation method and ethene.Fermentation legal system ethanol is to grow up on the basis of wine brewing, in the quite long period of history, once is unique commercial run of producing ethanol.The massfraction of ethanol in fermented liquid is about 6%-10%, and contains some other organic impurity, can obtain 95% industrial alcohol through rectifying.Yet at present the raw material of fermentation method ethanol still comes from cereal grain fermentation method and can only utilize 6-carbon sugar in the biomass, and can't utilize 5-carbon sugar and xylogen in the biomass.In addition, the raw material of fermentation method ethanol mainly still comes from cereal grain (stalk cellulose disassociation fermentation conversion rate is also too low) at present, and cereal grain fermentative production of ethanol and people strive grain, and grain price goes up thereupon, and restriction cereal grain fermentative production of ethanol is give stricted orders by country at present.The direct aquation method of ethene is exactly under the condition that heating, pressurization and catalyzer exist, and ethene and water direct reaction are produced ethanol.Ethene obtains from petroleum cracking, thereby its production cost and throughput seriously depend on petroleum industry.
Synthetic gas is to be main ingredient with carbon monoxide and hydrogen, as a kind of unstripped gas of industrial chemicals.Synthetic gas can derive from the partial oxidation of gasifying biomass, coal gasification and Sweet natural gas and reform, thereby the advantage of aboundresources and Sustainable development is arranged from the synthetic gas synthesizing alcohol.Experience a nearly century though direct method is produced the research of ethanol, still be faced with stern challenge.Though the homogeneous catalysis process can obtain higher ethanol selectivity, owing to use expensive catalysts, higher working pressure and loaded down with trivial details catalyst separating and removal process have limited the practical application of this technology.For heterogeneous catalysis process, because the carbochain that the formation of C-C key is subjected to dynamic (dynamical) restriction and contains the intermediate of two carbon atoms increases fast, cause the selectivity of ethanol and yield all lower.Thereby seek one efficiently the operational path of synthesizing alcohol have important practical significance.
Summary of the invention
The invention provides the method that a kind of selectivity is good, yield is high and be easy to realize industrialized synthesizing alcohol.
A kind of method of synthesizing alcohol comprises:
(1) carbon monoxide and nitrous acid ester carry out linked reaction under the catalysis of alumina load palladium catalyst, prepare oxalate diester;
(2) mix with oxalate diester heating vaporization and with hydrogen, mixed gas carries out catalytic hydrogenation reaction at silicon dioxide carried copper catalyst, and reaction product obtains ethanol through cooling, distillation.
It is palladium that carbon monoxide and nitrous acid ester carry out linked reaction catalyst system therefor activeconstituents, and carrier is the α-Al with vesicular structure
2O
3, specific surface area is 3～30m
2/ g, catalyzer are that the pickling process by routine obtains.Catalyzer needs reduction activation before use, to guarantee the catalytic activity of catalyzer.
The used nitrous acid ester of linked reaction can be methyl nitrite or ethyl nitrite, can be selected from the commercially available prod, also can be prepared by Sodium Nitrite, sulfuric acid and alcohol according to method well known in the art; Perhaps, generated by nitrogen protoxide, oxygen and alcohol reaction, described alcohol is methyl alcohol or ethanol.Of the present invention is to be the feedstock production nitrous acid ester with nitrogen protoxide, oxygen and alcohol, concrete operations step reference literature US 4353843.
Oxalate diester is dimethyl oxalate or oxalic acid diethyl ester, is prepared by corresponding methyl nitrite or ethyl nitrite respectively.
Linked reaction is carried out in fixed-bed reactor, and the product oxalate diester that generates after the condensation is collected from the bottom of reactor, if the preparation oxalic acid diethyl ester, its cooling back is liquid, directly collects; If dimethyl oxalate, because its cooling back is solid, so for follow-up reinforced convenience, can adopt C
1～C
4Alkyl alcohol collect, collection method can be with reference to patent documentation EP 0046983, what obtain is the alcoholic solution of dimethyl oxalate, can handle and directly use in the catalytic hydrogenation reaction; Selected alcohol has solvability preferably to dimethyl oxalate, and can not react with dimethyl oxalate, can not participate in follow-up catalytic hydrogenation reaction.The by product nitrogen protoxide that reaction generates can further change into nitrous acid ester and recycle; Linked reaction is carried out under normal pressure, and temperature of reaction is 100～150 ℃; Carbon monoxide: the volume ratio of methyl nitrite is: 1.1～2: 1, and the total gas volume air speed of carbon monoxide and nitrous acid ester is 900～4500h
-1
Barkite catalytic hydrogenation reaction catalyst system therefor active ingredient is copper, and carrier is unbodied silicon-dioxide.Catalyzer obtains by the Preparation by Uniform Precipitation of routine, adopts to make precipitation agent with ammoniacal liquor or urea, and in-situ deposition is on the nano SiO 2 particle that silicon sol forms or be deposited on the silicon-dioxide for preparing in advance.The specific surface area of catalyzer is 150～400m
2/ g.Catalyzer needs reduction activation before use, to guarantee the catalytic activity of catalyzer.
Catalytic hydrogenation reaction also is to carry out in fixed-bed reactor, mix with oxalate diester preheating vaporization and with hydrogen, gas mixture feeds in the fixed-bed reactor and carries out catalytic hydrogenation reaction at silicon dioxide carried copper catalyst, temperature of reaction is 220～300 ℃, reaction pressure is 0.5～6MPa, the mol ratio of oxalate diester and hydrogen is 1: 10～500, (refer to that it is 101.325 kPas with pressure that temperature is 0 ℃) under the normal conditions, the residence time of oxalate diester on catalyzer is 0.5～20s, and reaction product obtains ethanol after condensation and distillation.
The main component that the main raw material carbon monoxide that the present invention is used and hydrogen are synthetic gas can derive from the gas that number of ways such as gasifying biomass, gasification and gas by partial oxidation of natural reformation produce.Can be pure carbon monoxide and hydrogen, also can be the hydrogen that contains the carbon monoxide of small quantity of hydrogen and contain a small amount of carbon monoxide, can also contain the rare gas element of picture nitrogen and carbonic acid gas etc. in the gas.
The beneficial effect that the present invention has is embodied in: the ethanol that method provided by the invention is synthetic, and selectivity and yield are higher; The industry that can be the biomass synthesizing alcohol is established good research basis.
Embodiment
Embodiment 1
(1) preparation alumina load palladium catalyst: take by weighing 5g α-Al
2O
3, be that 0.5% charge capacity takes by weighing 0.063g Pd (NO by weight percentage
3)
22H
2O is mixed with steeping fluid, and solvent is deionized water, is 15m with specific surface area then
2Carrier α-Al of/g
2O
3Soak 10h in steeping fluid, 80 ℃ of following transpiring moistures obtain solid, again the gained solid are dried 12h down at 120 ℃, and 400 ℃ of following roasting 2h namely get alumina load palladium catalyst (Pd/ α-Al
2O
3).
(2) preparation dimethyl oxalate: the internal diameter of stainless steel fixed-bed reactor is 8mm, and the consumption of alumina load palladium catalyst is 2ml, and catalyzer is used 50ml/min CO reductase 12 h under 350 ℃ of conditions before use.Unstripped gas carbon monoxide and methyl nitrite (wherein, methyl nitrite is to prepare according to document US 4353843) are from top to bottom by reactor (volume ratio of carbon monoxide and methyl nitrite is 1.4: 1), and the volume space velocity of unstripped gas is 2500h
-1, product is collected product gas chromatogram on-line analysis with the methyl alcohol of 0.46ml/min 40 ℃ of following condensations.Be reflected under the normal pressure and carry out, temperature of reaction is 120 ℃, and the mass percent concentration of the product mesoxalic acid dimethyl ester of collection is 20%.
(3) prepare silicon dioxide carried copper catalyst: take by weighing 15.25g Cu (NO
3)
23H
2The O solid, be that 30% charge capacity prepares copper catalyst by mass percentage, the steps include: under agitation, the cupric nitrate solid that takes by weighing is dissolved in the 200ml deionized water, and the adding strong aqua reaches 10 up to the pH value of solution, take by weighing the alkaline silica sol of 37.4g 25%, then above-mentioned two kinds of liquid are added drop-wise in the flask that fills 50ml distilled water simultaneously, the pH value of control solution is 9.Add the back and continue to stir 4h, heating makes pH value reach 6-7 under 90 ℃ of conditions then.Filter, wash 5 times, 120 ℃ of oven dry, 450 ℃ of roasting 4h namely get described copper catalyst, and specific surface area is 294m
2/ g.
(4) preparation ethanol: the internal diameter of stainless steel fixed-bed reactor is 8mm, and the consumption of copper catalyst is 3ml, and catalyzer is used 50ml/min H before use
2Under 350 ℃ of conditions, reduce 4h.The methanol solution of the intermediate product dimethyl oxalate that obtains in the step (2) is through vaporization and and H
2Mix back feeding fixed-bed reactor and react, temperature of reaction is 250 ℃, and reaction pressure is 2MPa.Condensed product liquid is the certain hour sampling analysis at interval, the chromatogram on-line analysis of uncooled gas, and the mol ratio of hydrogen and dimethyl oxalate is 100, the residence time is 8.6s (under the normal conditions).The transformation efficiency 100% of dimethyl oxalate, the selectivity of ethanol are 65%, and the selectivity of n-propyl alcohol is 9%, and the selectivity of Virahol is 8%.
Embodiment 2
Prepare alumina load palladium catalyst, dimethyl oxalate and silicon dioxide carried copper catalyst according to embodiment 1;
Temperature of reaction is 280 ℃ in the preparation ethanol step, the mol ratio of hydrogen and dimethyl oxalate is 350, the residence time is 5.7s (under the normal conditions), other conditions are with embodiment 1, the transformation efficiency 100% of dimethyl oxalate, the selectivity of ethanol is 83%, and the selectivity of n-propyl alcohol is 12%, and the selectivity of Virahol is 1%.
Embodiment 3
Prepare alumina load palladium catalyst, dimethyl oxalate and silicon dioxide carried copper catalyst according to embodiment 1;
Temperature of reaction is 290 ℃ in the preparation ethanol step, and the residence time is 3s (under the normal conditions), and other conditions are with embodiment 2, the transformation efficiency 100% of dimethyl oxalate, and the selectivity of ethanol is 75%, and the selectivity of n-propyl alcohol is 7%, and the selectivity of Virahol is 5%.
Embodiment 4
(1) prepares the alumina load palladium catalyst according to embodiment 1 same method;
(2) prepare the reaction product that the methyl alcohol of using 0.21ml/min in the dimethyl oxalate step instead is collected condensation, other conditions are with embodiment 1, and the mass percent concentration of the product mesoxalic acid dimethyl ester of collection is 35%;
(3) prepare silicon dioxide carried copper catalyst: take by weighing 14.26g Cu (NO
3)
23H
2The O solid is that 40% charge capacity prepares copper catalyst by mass percentage, the steps include: under agitation, and cupric nitrate solid and the 10.63g urea that takes by weighing is dissolved in the 300ml deionized water, drips the acidic silicasol of 22.5g 25% then.After adding, continue to stir 3h.Under 90 ℃, make hydrolysis of urea reach 7 until pH value then.Filter, wash 5 times, 120 ℃ of oven dry, 450 ℃ of roasting 4h namely get described copper catalyst, and specific surface area is 319m
2/ g.
(4) preparation ethanol: the internal diameter of stainless steel fixed-bed reactor is 8mm, and the consumption of copper catalyst is 3ml, and catalyzer is used 50ml/min H before use
2Under 350 ℃ of conditions, reduce 4h.The methanol solution of the intermediate product dimethyl oxalate that obtains in the step (2) is through vaporization and and H
2Mix back feeding fixed-bed reactor and react, temperature of reaction is 230 ℃, and reaction pressure is 3MPa.Condensed product liquid is the certain hour sampling analysis at interval, the chromatogram on-line analysis of uncooled gas, the mol ratio of hydrogen and dimethyl oxalate is 400, the residence time is 4.8s (under the normal conditions), the transformation efficiency 100% of dimethyl oxalate, the selectivity of ethanol is 58%, and the selectivity of n-propyl alcohol is 12%, and the selectivity of Virahol is 12%.
Embodiment 5
Prepare according to embodiment 1 and to prepare dimethyl oxalate and silicon dioxide carried copper catalyst among alumina load palladium catalyst and the embodiment 4;
Temperature of reaction is 270 ℃ in the preparation ethanol step, and reaction pressure is 4MPa, and the residence time is 4.3s (under the normal conditions), other conditions are with embodiment 4, the transformation efficiency 100% of dimethyl oxalate, and the selectivity of ethanol is 85%, the selectivity of n-propyl alcohol is 9%, and the selectivity of Virahol is 2%.
Embodiment 6
(1) prepares the alumina load palladium catalyst according to embodiment 1 same method and prepare silicon dioxide carried copper catalyst with embodiment 4 identical methods;
(2) preparation oxalic acid diethyl ester: the internal diameter of stainless steel fixed-bed reactor is 8mm, and the consumption of alumina load palladium catalyst is 1.5ml, and catalyzer is used 50ml/min CO reductase 12 h under 350 ℃ of conditions before use.Unstripped gas carbon monoxide and ethyl nitrite (wherein, ethyl nitrite is to prepare according to document US 4353843) are from top to bottom by reactor (carbon monoxide and ethyl nitrite volume ratio are 1.8: 1), and the volume space velocity of unstripped gas is 3100h
-1, product is collected after condensation, product gas chromatogram on-line analysis.Be reflected under the normal pressure and carry out, temperature of reaction is 135 ℃, and the mass percent concentration of the product mesoxalic acid diethyl ester of collection is 96%.
(3) preparation ethanol: the internal diameter of stainless steel fixed-bed reactor is 8mm, and the consumption of copper catalyst is 3ml, and catalyzer is used 50ml/min H before use
2Under 350 ℃ of conditions, reduce 4h.The intermediate product oxalic acid diethyl ester that obtains in the step (2) is through vaporization and and H
2Mix back feeding fixed-bed reactor and react, temperature of reaction is 280 ℃, and reaction pressure is 3MPa.Condensed product liquid is the certain hour sampling analysis at interval, the chromatogram on-line analysis of uncooled gas, the mol ratio of hydrogen and oxalic acid diethyl ester are 150, and the residence time is 18s (under the normal conditions), the transformation efficiency 98% of oxalic acid diethyl ester, the selectivity of ethanol are 78%.
Embodiment 7
According to embodiment 1 prepare the alumina load palladium catalyst, embodiment 4 prepares silicon dioxide carried copper catalyst and embodiment 6 prepares oxalic acid diethyl ester;
The mol ratio of hydrogen and oxalic acid diethyl ester is 300 in the preparation ethanol step, and other conditions are with embodiment 6, the transformation efficiency 100% of oxalic acid diethyl ester, and the selectivity of ethanol is 83%.
Claims (3)
1. the method for a synthesizing alcohol comprises:
(1) preparation alumina load palladium catalyst: take by weighing 5g α-Al
2O
3, be that 0.5% charge capacity takes by weighing 0.063g Pd (NO by weight percentage
3)
22H
2O is mixed with steeping fluid, and solvent is deionized water, is 15m with specific surface area then
2Carrier α-Al of/g
2O
3Soak 10h in steeping fluid, 80 ℃ of following transpiring moistures obtain solid, again the gained solid are dried 12h down at 120 ℃, and 400 ℃ of following roasting 2h namely get the alumina load palladium catalyst;
(2) preparation dimethyl oxalate: the internal diameter of stainless steel fixed-bed reactor is 8mm, and the consumption of alumina load palladium catalyst is 2ml, and the alumina load palladium catalyst is used 50ml/minCO reductase 12 h under 350 ℃ of conditions before use; By reactor, wherein the volume ratio of carbon monoxide and methyl nitrite is 1.4: 1 from top to bottom for unstripped gas carbon monoxide and methyl nitrite, and the volume space velocity of unstripped gas is 2500h
-1, product is collected 40 ℃ of following condensations with the methyl alcohol of 0.46ml/min, is reflected under the normal pressure and carries out, and temperature of reaction is 120 ℃, and the mass percent concentration of the product mesoxalic acid dimethyl ester of collection is 20%;
(3) prepare silicon dioxide carried copper catalyst: take by weighing 15.25g Cu (NO
3)
23H
2The O solid, be that 30% charge capacity prepares copper catalyst by mass percentage, the preparation process of copper catalyst is: under agitation, the cupric nitrate solid that takes by weighing is dissolved in the 200ml deionized water, and the adding strong aqua reaches 10 up to the pH of solution value, take by weighing the alkaline silica sol of 37.4g25%, then above-mentioned two kinds of liquid are added drop-wise in the flask that fills 50ml distilled water simultaneously, the pH value of control solution is 9; Add the back and continue to stir 4h, heating makes the pH value reach 6-7 under 90 ℃ of conditions then, filters, wash 5 times, and 120 ℃ of oven dry, 450 ℃ of roasting 4h prepare described copper catalyst, and specific surface area is 294m
2/ g;
(4) preparation ethanol: the internal diameter of stainless steel fixed-bed reactor is 8mm, and the consumption of copper catalyst is 3ml, and copper catalyst is used 50ml/min H before use
2Under 350 ℃ of conditions, reduce 4h; With the methanol solution of the intermediate product dimethyl oxalate that obtains in the step (2) through vaporization and and H
2Mixing back feeding fixed-bed reactor reacts, temperature of reaction is 280 ℃, reaction pressure is 2MPa, the mol ratio of hydrogen and dimethyl oxalate is 350, the residence time is 5.7s, and the transformation efficiency that reaction finishes the back dimethyl oxalate is 100%, and the selectivity of ethanol is 83%, the selectivity of n-propyl alcohol is 12%, and the selectivity of Virahol is 1%.
2. the method for a synthesizing alcohol comprises:
(1) preparation alumina load palladium catalyst: take by weighing 5g α-Al
2O
3, be that 0.5% charge capacity takes by weighing 0.063g Pd (NO by weight percentage
3)
22H
2O is mixed with steeping fluid, and solvent is deionized water, is 15m with specific surface area then
2Carrier α-Al of/g
2O
3Soak 10h in steeping fluid, 80 ℃ of following transpiring moistures obtain solid, again the gained solid are dried 12h down at 120 ℃, and 400 ℃ of following roasting 2h namely get the alumina load palladium catalyst;
(2) preparation dimethyl oxalate: the internal diameter of stainless steel fixed-bed reactor is 8mm, and the consumption of alumina load palladium catalyst is 2ml, and the alumina load palladium catalyst is used 50ml/minCO reductase 12 h under 350 ℃ of conditions before use; By reactor, wherein the volume ratio of carbon monoxide and methyl nitrite is 1.4: 1 from top to bottom for unstripped gas carbon monoxide and methyl nitrite, and the volume space velocity of unstripped gas is 2500h
-1, product is collected 40 ℃ of following condensations with the methyl alcohol of 0.21ml/min, is reflected under the normal pressure and carries out, and temperature of reaction is 120 ℃, and the mass percent concentration of the product mesoxalic acid dimethyl ester of collection is 35%;
(3) prepare silicon dioxide carried copper catalyst: take by weighing 14.26g Cu (NO
3)
23H
2The O solid, be that 40% charge capacity prepares copper catalyst by mass percentage, the preparation process of copper catalyst is: under agitation, cupric nitrate solid and the 10.63g urea that takes by weighing is dissolved in the 300ml deionized water, drips the acidic silicasol of 22.5g25% then; After adding, continue to stir 3h; Under 90 ℃, make hydrolysis of urea reach 7 until the pH value then; Filter, wash 5 times, 120 ℃ of oven dry, 450 ℃ of roasting 4h namely get described copper catalyst, and specific surface area is 319m
2/ g;
(4) preparation ethanol: the internal diameter of stainless steel fixed-bed reactor is 8mm, and the consumption of copper catalyst is 3ml, and copper catalyst is used 50ml/min H before use
2Under 350 ℃ of conditions, reduce 4h; The methanol solution of the intermediate product dimethyl oxalate that obtains in the step (2) is through vaporization and and H
2Mixing back feeding fixed-bed reactor reacts, temperature of reaction is 270 ℃, reaction pressure is 4MPa, the mol ratio of hydrogen and dimethyl oxalate is 400, the residence time is 4.3s, and the transformation efficiency that reaction finishes the back dimethyl oxalate is 100%, and the selectivity of ethanol is 85%, the selectivity of n-propyl alcohol is 9%, and the selectivity of Virahol is 2%.
3. the method for a synthesizing alcohol comprises:
(1) preparation alumina load palladium catalyst: take by weighing 5g α-Al
2O
3, be that 0.5% charge capacity takes by weighing 0.063g Pd (NO by weight percentage
3)
22H
2O is mixed with steeping fluid, and solvent is deionized water, is 15m with specific surface area then
2Carrier α-Al of/g
2O
3Soak 10h in steeping fluid, 80 ℃ of following transpiring moistures obtain solid, again the gained solid are dried 12h down at 120 ℃, and 400 ℃ of following roasting 2h namely get the alumina load palladium catalyst;
(2) preparation oxalic acid diethyl ester: the internal diameter of stainless steel fixed-bed reactor is 8mm, and the consumption of alumina load palladium catalyst is 1.5ml, and the alumina load palladium catalyst is used 50ml/minCO reductase 12 h under 350 ℃ of conditions before use; By reactor, wherein carbon monoxide and ethyl nitrite volume ratio are 1.8: 1 from top to bottom for unstripped gas carbon monoxide and ethyl nitrite, and the volume space velocity of unstripped gas is 3100h
-1, product is collected after condensation, is reflected under the normal pressure to carry out, and temperature of reaction is 135 ℃, and the mass percent concentration of the product mesoxalic acid diethyl ester of collection is 96%;
(3) prepare silicon dioxide carried copper catalyst: take by weighing 14.26g Cu (NO
3)
23H
2The O solid, be that 40% charge capacity prepares copper catalyst by mass percentage, the preparation process of copper catalyst is: under agitation, cupric nitrate solid and the 10.63g urea that takes by weighing is dissolved in the 300ml deionized water, drips the acidic silicasol of 22.5g25% then; After adding, continue to stir 3h; Under 90 ℃, make hydrolysis of urea reach 7 until the pH value then; Filter, wash 5 times, 120 ℃ of oven dry, 450 ℃ of roasting 4h namely get described copper catalyst, and specific surface area is 319m
2/ g;
(4) preparation ethanol: the internal diameter of stainless steel fixed-bed reactor is 8mm, and the consumption of copper catalyst is 3ml, and copper catalyst is used 50ml/min H before use
2Under 350 ℃ of conditions, reduce 4h; The intermediate product oxalic acid diethyl ester that obtains in the step (2) is through vaporization and and H
2Mix back feeding fixed-bed reactor and react, temperature of reaction is 280 ℃, and reaction pressure is 3MPa, the mol ratio of hydrogen and oxalic acid diethyl ester is 300, the residence time is 18s, and reaction finishes the transformation efficiency 100% of back oxalic acid diethyl ester, and the selectivity of ethanol is 83%.
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| CN102350358B (en) * | 2011-08-10 | 2013-08-21 | 天津大学 | Preparation method and application of catalyst for preparing ethanol by oxalate hydrogenation |
| CN105085167B (en) * | 2015-08-28 | 2017-04-12 | 天津大学 | Two-section method process for preparing alcohol by oxalic ester hydrogenation |
| CN106378128B (en) * | 2016-09-30 | 2018-12-21 | 中国科学院福建物质结构研究所 | A kind of CO synthesis of oxalate Pd/Al2O3The preparation method of catalyst |
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| Cu/SiO2催化剂上草酸二甲酯加氢反应的研究;李竹霞等;《化学反应工程与工艺》;20040630;第20卷(第2期);121-128 * |
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