CN102091628B - Method for preparing low-carbon mixed alcohol catalyst by synthesis gas - Google Patents
Method for preparing low-carbon mixed alcohol catalyst by synthesis gas Download PDFInfo
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- CN102091628B CN102091628B CN201010554957A CN201010554957A CN102091628B CN 102091628 B CN102091628 B CN 102091628B CN 201010554957 A CN201010554957 A CN 201010554957A CN 201010554957 A CN201010554957 A CN 201010554957A CN 102091628 B CN102091628 B CN 102091628B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 22
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 title abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims description 16
- 230000001376 precipitating effect Effects 0.000 claims description 15
- 238000000975 co-precipitation Methods 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 239000000320 mechanical mixture Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 229910016341 Al2O3 ZrO2 Inorganic materials 0.000 abstract 5
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 239000008367 deionised water Substances 0.000 description 26
- 229910021641 deionized water Inorganic materials 0.000 description 26
- 239000007789 gas Substances 0.000 description 25
- 150000003839 salts Chemical class 0.000 description 17
- 238000005303 weighing Methods 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000012423 maintenance Methods 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000002816 fuel additive Substances 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 239000003254 gasoline additive Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 description 1
- 229910017816 Cu—Co Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 210000002268 wool Anatomy 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing low-carbon mixed alcohol (with 1 to 5 carbon atoms) catalyst by synthesis gas (CO and H2), which belongs to the technical field of chemical industry. The method is characterized by comprising the following steps of: preparing (CuO-ZnO-Al2O3-ZrO2)-MgO composite oxide by compounding MgO and CuO-ZnO-Al2O3-ZrO2; and with (CuO-ZnO-Al2O3-ZrO2)-MgO as a catalyst and synthesis gas as raw gas, preparing C1-C5 mixed alcohol under the conditions of heating and pressurizing. The (CuO-ZnO-Al2O3-ZrO2)-MgO catalyst prepared by the method of the invention has higher time space yield of C2-C5 mixed alcohol than that of CuO-ZnO-Al2O3-ZrO2 catalyst.
Description
Technical field
The present invention relates to a kind of from synthesis gas (CO+H
2) making the Catalysts and its preparation method of MAS (carbon number is 1～5 alcohol), a kind of preparation (CuO-ZnO-Al more specifically says so
2O
3-ZrO
2The method of)-MgO catalyst belongs to chemical technology field.
Background technology
Catalyzing carbon monoxide hydrogenation synthesizing low carbon mixed alcohol (C
1～C
5Alcohol) be one of important channel of coal resources clean utilization.Along with growing to even greater heights of environmental requirement, receive special concern from the research of preparing low-carbon mixed alcohol by synthetic gas.C wherein
2～C
5Mixed alcohol is eco-friendly liquid fuel additive (not sulfur-bearing, nitrogen, an aromatic compound etc.), and its surcharge is high, can directly substitute the gasoline additive that the methyl tertiary butyl ether(MTBE) (MTBE) with potentially contaminated property becomes the high-quality cleaning.Produce synthesis gas by coal, act as a fuel or gasoline additive from preparing low-carbon mixed alcohol by synthetic gas again, application promise in clinical practice is arranged.
Existing many Patent publish about the catalyst and the technology of synthesizing low-carbon mixed alcohol.More representational catalyst and technology have following several kinds; For example, the exploitation of German Lurgi company is the Octamix technology (European patent EP-0034338-A2 number, U.S. Pat-No. 4513100, US-4031123 number and US-2327066 number) of catalyst principal component with Cu-Zn; France Petroleum Institute exploitation be the IFP technology (U.S. US-4122110 number, US-4291126 number) of catalyst principal component with Cu-Co; The cooperative development of The Dow Chemical Co. (US) 2030 Dow Center, Abbott Road, Midland, Michigan 48640, and union carbide corporation with MoS
2Be the Sygmol technology of catalyst main component (U.S. Pat-No. 4675344 and European patent EP-No. 0235886).These patented technologies differ from one another, wherein C in the product of Sygmol and IFP technology
2+Alcohol content is higher; Octamix process using low-pressure process has higher space-time yield, and water content is low, and its products distribution is expected further improvement.But the composition of the catalyst that uses in these patented technologies is comparatively complicated, and preparation technology is comparatively loaded down with trivial details, has plenty of severe reaction conditions.On the other hand, also Patent publish having been arranged uses the catalyst of rhodium-containing to make C from synthesis gas
2The technology of alcohol, Li (the Na)/Rh-Mn-Fe/SiO that No. 96112685 a kind of rhodium-containing is provided like Chinese patent
2Catalyst, oxygenate overall selectivitys such as methyl alcohol, ethanol, acetaldehyde, propyl alcohol can reach more than 90%, but CO conversion ratio very low (about below 6～7%), catalyst preparation process are more loaded down with trivial details, and rhodium metal costs an arm and a leg.Though the Cu-Zn-Al catalyst of the modification of Lurgi company development has the activity that generates low-carbon alcohols preferably, C
2+The selectivity of alcohol is also not high, and reaction condition is also comparatively harsh.
The present invention is through MgO and CuO-ZnO-Al
2O
3-ZrO
2Compound (the CuO-ZnO-Al that makes
2O
3-ZrO
2)-MgO composite oxide catalysts is with traditional CuO-ZnO-Al
2O
3-ZrO
2Catalyst is compared, and catalyst of the present invention has higher C
2～C
5The space-time yield of mixed alcohol.
Summary of the invention
The purpose of this invention is to provide a kind of being used for from synthesis gas system C
1～C
5The Catalysts and its preparation method of mixed alcohol.Use (the CuO-ZnO-Al that this method makes
2O
3-ZrO
2)-MgO catalyst is than traditional CuO-ZnO-Al
2O
3-ZrO
2Catalyst has higher C
1～C
5Mixed alcohol space-time yield, especially C
2～C
5The space-time yield of mixed alcohol improves a lot.
The synthesis gas system C that is used for provided by the invention
1～C
5(the CuO-ZnO-Al of mixed alcohol
2O
3-ZrO
2)-MgO Catalysts and its preparation method is characterized in that: through mechanical mixing or coprecipitation with MgO and CuO-ZnO-Al
2O
3-ZrO
2Compound, roasting at a certain temperature makes (CuO-ZnO-Al
2O
3-ZrO
2)-MgO composite oxides.Use (the CuO-ZnO-Al of the inventive method preparation
2O
3-ZrO
2)-MgO is a raw material as catalyst, with the synthesis gas, under the condition of warming and pressurizing, can make C efficiently
1～C
5Mixed alcohol.
(the CuO-ZnO-Al of the inventive method preparation
2O
3-ZrO
2In the)-MgO catalyst, CuO-ZnO-Al
2O
3-ZrO
2With the mass percent of MgO be (CuO-ZnO-Al
2O
3-ZrO
2): 85～35%, MgO:15～65%, wherein CuO-ZnO-Al
2O
3-ZrO
2Composition (mol ratio) be Cu:40～50%, Zn:30～40%, Al:5～15%, Zr:5～15%.
Adopt coprecipitation preparation (CuO-ZnO-Al
2O
3-ZrO
2The detailed process of)-MgO catalyst comprises:
(1) preparation raw material salt and precipitant solution
In different ratio preparation Cu (NO
3)
2, Zn (NO
3)
2, Al (NO
3)
3, ZrO (NO
3)
2And Mg (NO
3)
2Aqueous metal salt, preparation KOH and K
2CO
3The mixed precipitant aqueous solution.
(2) deposition, aging and last handling process
Aqueous metal salt and the precipitating reagent aqueous solution simultaneously and drip add, produce deposition, wear out then, filtration, washing, drying, place the Muffle furnace roasting to powder at last, obtain (CuO-ZnO-Al
2O
3-ZrO
2)-MgO.
Adopt mechanical mixing preparation (CuO-ZnO-Al
2O
3-ZrO
2The detailed process of)-MgO catalyst comprises:
(1) preparation CuO-ZnO-Al
2O
3-ZrO
2
Preparation Cu (NO
3)
2, Zn (NO
3)
2, Al (NO
3)
3And ZrO (NO
3)
2Aqueous metal salt, preparation KOH and K
2CO
3The mixed precipitant aqueous solution, aqueous metal salt and the precipitating reagent aqueous solution simultaneously and drip add, produce deposition, wear out then, filtration, washing, drying, place the Muffle furnace roasting to powder at last, obtain CuO-ZnO-Al
2O
3-ZrO
2
(2) preparation MgO
MgO can be from Mg (NO
3)
2Set out, adopt traditional precipitation method to make; Also direct commodity in use MgO.
(3) CuO-ZnO-Al
2O
3-ZrO
2Compound with MgO
Take by weighing CuO-ZnO-Al according to a certain percentage
2O
3-ZrO
2And MgO, carry out mechanical mixture, roasting in Muffle furnace then obtains (CuO-ZnO-Al
2O
3-ZrO
2)-MgO.
The present invention is unstripped gas with the synthesis gas, at warming and pressurizing and (CuO-ZnO-Al
2O
3-ZrO
2Prepare C under the condition that)-MgO catalyst exists
1～C
5Mixed alcohol.The synthesis gas that the present invention uses is the gaseous mixture of carbon monoxide and hydrogen ratio=1: 1.Carry out above-mentioned reaction by method of the present invention, under heating, carry out.Reaction temperature is generally 250～350 ℃; Carry out above-mentioned reaction by the inventive method, carry out adding to depress, the pressure of synthesis gas is generally 6MPa.
The specific embodiment
Below in conjunction with embodiment technical scheme of the present invention is done further explanation.
Embodiment 1
(1) 50% (CuO-ZnO-Al
2O
3-ZrO
2)-50%MgO Preparation of catalysts (coprecipitation)
Take by weighing 1.41g Cu (NO
3)
2, 1.74g Zn (NO
3)
2, 0.49g Al (NO
3)
3, 0.35g ZrO (NO
3)
2And 6.67gMg (NO
3)
2Join in the 100ml deionized water, be made into aqueous metal salt; Take by weighing 3.37g KOH and 4.14g K
2CO
3Join in the 120ml deionized water, be made into the precipitating reagent aqueous solution.Measure the 80ml deionized water in addition and put into flask, place water-bath constant temperature at 65 ℃, under stirring, be added drop-wise to the aqueous metal salt and the precipitating reagent aqueous solution simultaneously in the deionized water of above-mentioned flask, precipitation process is regulated and maintenance pH value=9.Dropwise continued and stirred mother liquor 1 hour; Filter then, filter cake washs 3 times with 80 ℃ hot deionized water, washes 2 times with deionized water at normal temperature again; Use washing with alcohol 2 times at last again; Filter cake is placed in the baking oven 110 ℃ of dryings 12 hours, places Muffle furnace 400 ℃ of following roastings of air 3 hours afterwards, promptly obtains 50% (CuO-ZnO-Al
2O
3-ZrO
2)-50%MgO catalyst.
(2) at 50% (CuO-ZnO-Al
2O
3-ZrO
2)-50%MgO carries out synthesis gas system C under existing
1～C
5The reacting synthesis gas system C of mixed alcohol
1～C
5Carry out in the miniature fixed bed movable reactor that is reflected at stainless steel tube liner quartz ampoule (internal diameter 10mm) of mixed alcohol.Take by weighing 50% (CuO-ZnO-Al
2O
3-ZrO
2)-50%MgO catalyst 0.5g is loaded on the quartz ampoule middle part, and beds is all filled silica wool in two ends up and down.Before the reaction, catalyst is at H
2/ N
2Gaseous mixture (V
N2/ V
H2=4/1) rises to 270 ℃ from room temperature with 1 ℃/min in, reduced 4 hours down at 270 ℃.Be adjusted to 250 ℃ of reaction temperatures then, switch to unstripped gas (V again
H2/ V
CO=1/1), under 6MPa pressure, react, raw gas flow is by mass flowmenter control (air speed is 6000mL/g/h), and reaction pressure is by pressure maintaining valve and counterbalance valve control, and reaction bed temperature is measured and control by thermocouple and temperature controller.The reaction tube exit gas carries out online detection and assay products with online gas-chromatography down in insulation (150 ℃) after reducing pressure.The sample analysis of 250 ℃ of reactions is warming up to 300 ℃ to beds and reacts after finishing, and the reaction tube exit gas carries out online detection and assay products with online gas-chromatography equally.The sample analysis of 300 ℃ of reactions is warming up to 350 ℃ to beds and reacts after finishing, and the reaction tube exit gas carries out online detection and assay products with online gas-chromatography equally.Calculate the space-time yield of CO conversion rate and pure ethers product according to the chromatography result, reaction result is listed in table 1.
Embodiment 2
(1) 35% (CuO-ZnO-Al
2O
3-ZrO
2)-65%MgO Preparation of catalysts (coprecipitation)
Take by weighing 0.87g Cu (NO
3)
2, 0.833g Zn (NO
3)
2, 0.3g Al (NO
3)
3, 0.21g ZrO (NO
3)
2And 8.21gMg (NO
3)
2Join in the 100ml deionized water, be made into aqueous metal salt; Take by weighing 3.37g KOH and 4.14g K
2CO
3Join in the 120ml deionized water, be made into the precipitating reagent aqueous solution.Measure the 80ml deionized water in addition and put into flask, place water-bath constant temperature at 65 ℃, under stirring, be added drop-wise to the aqueous metal salt and the precipitating reagent aqueous solution simultaneously in the deionized water of above-mentioned flask, precipitation process is regulated and maintenance pH value=9.Other follow-up step promptly obtains 35% (CuO-ZnO-Al with embodiment 1
2O
3-ZrO
2)-65%MgO catalyst.
(2) at 35% (CuO-ZnO-Al
2O
3-ZrO
2)-65%MgO carries out synthesis gas system C under existing
1～C
5The reaction response operation of mixed alcohol is with embodiment 1 (2).Reaction result is listed in table 2.
Embodiment 3
(1) 70% (CuO-ZnO-Al
2O
3-ZrO
2)-30%MgO Preparation of catalysts (coprecipitation)
Take by weighing 2.283g Cu (NO
3)
2, 2.186g Zn (NO
3)
2, 0.788gAl (NO
3)
3, 0.561g ZrO (NO
3)
2And 4.872gMg (NO
3)
2Join in the 100ml deionized water, be made into aqueous metal salt; Take by weighing 3.37g KOH and 4.14g K
2CO
3Join in the 120ml deionized water, be made into the precipitating reagent aqueous solution.Measure the 80ml deionized water in addition and put into flask, place water-bath constant temperature at 65 ℃, under stirring, be added drop-wise to the aqueous metal salt and the precipitating reagent aqueous solution simultaneously in the deionized water of above-mentioned flask, precipitation process is regulated and maintenance pH value=9.Other follow-up step promptly obtains 70% (CuO-ZnO-Al with embodiment 1
2O
3-ZrO
2)-30%MgO.
(2) at 70% (CuO-ZnO-Al
2O
3-ZrO
2)-30%MgO carries out synthesis gas system C under existing
1～C
5The reaction response operation of mixed alcohol is with embodiment 1 (2).Reaction result is listed in table 3.
Embodiment 4
(1) 85% (CuO-ZnO-Al
2O
3-ZrO
2)-15%MgO Preparation of catalysts (coprecipitation)
Take by weighing 3.153g Cu (NO
3)
2, 3.019g Zn (NO
3)
2, 1.088gAl (NO
3)
3, 0.775g ZrO (NO
3)
2And 2.821gMg (NO
3)
2Join in the 100ml deionized water, be made into aqueous metal salt; Take by weighing 3.37g KOH and 4.14g K
2CO
3Join in the 120ml deionized water, be made into the precipitating reagent aqueous solution.Measure the 80ml deionized water in addition and put into flask, place water-bath constant temperature at 65 ℃, under stirring, be added drop-wise to the aqueous metal salt and the precipitating reagent aqueous solution simultaneously in the deionized water of above-mentioned flask, precipitation process is regulated and maintenance pH value=9.Other follow-up step promptly obtains 85% (CuO-ZnO-Al with embodiment 1
2O
3-ZrO
2)-15%MgO catalyst.
(2) at 85% (CuO-ZnO-Al
2O
3-ZrO
2)-15%MgO carries out synthesis gas system C under existing
1～C
5The reaction response operation of mixed alcohol is with embodiment 1 (2).Reaction result is listed in table 4.
Embodiment 5
(1) 50% (CuO-ZnO-Al
2O
3-ZrO
2)-50%MgO (mechanical mixture) Preparation of catalysts
Prepare CuO-ZnO-Al earlier
2O
3-ZrO
2Oxide: take by weighing 4.35g Cu (NO
3)
2, 4.05g Zn (NO
3)
2, 1.50gAl (NO
3)
3With 1.07g ZrO (NO
3)
2Join in the 100ml deionized water, be made into aqueous metal salt; Take by weighing 3.37g KOH and 4.14g K
2CO
3Join in the 120ml deionized water, be made into the precipitating reagent aqueous solution.Measure the 80ml deionized water in addition and put into flask, place water-bath constant temperature at 65 ℃, under stirring, be added drop-wise to the aqueous metal salt and the precipitating reagent aqueous solution simultaneously in the deionized water of above-mentioned flask, precipitation process is regulated and maintenance pH value=7.Other follow-up step promptly obtains CuO-ZnO-Al with embodiment 1
2O
3-ZrO
2
MgO and CuO-ZnO-Al
2O
3-ZrO
2Compound: take by weighing commercially available reagent MgO1.00g (before using in the air 400 ℃ roasting 3 hours) and CuO-ZnO-Al
2O
3-ZrO
21.00g mix, be diluent with ethanol, mechanical mixture stirred 10 hours, and evaporate to dryness ethanol then, solid are placed in the baking oven 110 ℃ of dryings 12 hours, place Muffle furnace 400 ℃ of following roastings of air 3 hours afterwards, promptly obtain 50% (CuO-ZnO-Al
2O
3-ZrO
2)-50%MgO (mechanical mixture) catalyst.
(2) at 50% (CuO-ZnO-Al
2O
3-ZrO
2)-50%MgO (mechanical mixture) carries out synthesis gas system C under existing
1～C
5The reaction of mixed alcohol
Operation is with embodiment 1 (2).Reaction result is listed in table 5.
Comparative example 1
(1) CuO-ZnO-Al
2O
3-ZrO
2Preparation of catalysts
Take by weighing 4.35g Cu (NO
3)
2, 4.05g Zn (NO
3)
2, 1.50g Al (NO
3)
3With 1.07g ZrO (NO
3)
2Join in the 100ml deionized water, be made into aqueous metal salt; Take by weighing 3.37g KOH and 4.14g K
2CO
3Join in the 120ml deionized water, be made into the precipitating reagent aqueous solution.Measure the 80ml deionized water in addition and put into flask, place water-bath constant temperature at 65 ℃, under stirring, be added drop-wise to the aqueous metal salt and the precipitating reagent aqueous solution simultaneously in the deionized water of above-mentioned flask, precipitation process is regulated and maintenance pH value=7.Other follow-up step promptly obtains CuO-ZnO-Al with embodiment 1
2O
3-ZrO
2Catalyst.
(2) at CuO-ZnO-Al
2O
3-ZrO
2Carry out synthesis gas system C under existing
1～C
5The reaction of mixed alcohol
Operation is with embodiment 1 (2).Reaction result is listed in table 6.
Table 1 embodiment 1 (50% (CuO-ZnO-Al
2O
3-ZrO
2)-50%MgO catalyst) reaction result
Annotate: total pure ether products refers to: dimethyl ether+methyl alcohol+C
2～C
5The summation of alcohol (down together).
Table 2 embodiment 2 (35% (CuO-ZnO-Al
2O
3-ZrO
2)-65%MgO catalyst) reaction result
Table 3 embodiment 3 (70% (CuO-ZnO-Al
2O
3-ZrO
2)-30%MgO catalyst) reaction result
Table 4 embodiment 4 (85% (CuO-ZnO-Al
2O
3-ZrO
2)-15%MgO catalyst) reaction result
Table 5 embodiment 5 (mechanical mixture 50% (CuO-ZnO-Al
2O
3-ZrO
2)-50%MgO catalyst) reaction result
Table 6 comparative example 1 (CuO-ZnO-Al
2O
3-ZrO
2Catalyst) reaction result
Claims (1)
1. Preparation of catalysts method from the synthesis gas preparation MAS is characterized in that: this method is through MgO and CuO-ZnO-Al
2O
3-ZrO
2Compound (the CuO-ZnO-Al that makes
2O
3-ZrO
2)-MgO composite oxides are with (CuO-ZnO-Al
2O
3-ZrO
2)-MgO is catalyst, is unstripped gas with the synthesis gas, under the condition of warming and pressurizing, makes C
1～C
5Mixed alcohol; Said at (CuO-ZnO-Al
2O
3-ZrO
2In the)-MgO catalyst, CuO-ZnO-Al
2O
3-ZrO
2With the mass percent of MgO be (CuO-ZnO-Al
2O
3-ZrO
2): 85～35%, MgO:15～65%; Said at CuO-ZnO-Al
2O
3-ZrO
2In, the molar percentage of each metal is Cu:40～50%, Zn:30～40%, Al:5～15%, Zr:5～15%; MgO and CuO-ZnO-Al
2O
3-ZrO
2Compound employing mechanical mixing or coprecipitation; Adopt coprecipitation to prepare MgO and CuO-ZnO-Al
2O
3-ZrO
2Compound the time, precipitating reagent adopts KOH and K
2CO
3Mixed aqueous solution, and KOH and K
2CO
3Mol ratio be 2/1～1/1; Adopt mechanical mixing to prepare MgO and CuO-ZnO-Al
2O
3-ZrO
2Compound the time, CuO-ZnO-Al
2O
3-ZrO
2Make by the precipitation method earlier, again by certain quality percentage and MgO mechanical mixture, and through 400 ℃ of roastings.
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| US9656931B2 (en) | 2012-12-20 | 2017-05-23 | Sekisui Chemical Co., Ltd. | Catalyst for alcohol synthesis, apparatus for producing alcohol and method for producing alcohol |
| CN103613483B (en) * | 2013-11-14 | 2015-07-29 | 中国科学院广州能源研究所 | A kind of layering loading catalyst prepares the application in low-carbon alcohol at synthetic gas |
| CN104368356A (en) * | 2014-11-05 | 2015-02-25 | 南京工业大学 | Catalyst for producing low-carbon mixed alcohol by using synthesis gas as well as preparation method and application of catalyst |
| CN108409530B (en) * | 2018-03-09 | 2021-02-19 | 吴辉胜 | Device and method for producing low-carbon mixed alcohol by using organic wastes |
| CN113856687A (en) * | 2021-11-04 | 2021-12-31 | 太原理工大学 | Preparation method of doped ZnO catalyst and preparation method for synthesizing higher alcohol by using doped ZnO catalyst |
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|---|---|---|---|---|
| CN1124933A (en) * | 1993-06-01 | 1996-06-19 | 伊斯曼化学公司 | Catalyst compositions and the use thereof in the hydrogenation of carboxylic acid esters |
| CN1891337A (en) * | 2005-07-07 | 2007-01-10 | 浙江工业大学 | Preparation method for synthesizing methanol catalyst |
| CN1974006A (en) * | 2006-12-14 | 2007-06-06 | 太原理工大学 | Slurry catalyst and its prepn |
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| CN1124933A (en) * | 1993-06-01 | 1996-06-19 | 伊斯曼化学公司 | Catalyst compositions and the use thereof in the hydrogenation of carboxylic acid esters |
| CN1891337A (en) * | 2005-07-07 | 2007-01-10 | 浙江工业大学 | Preparation method for synthesizing methanol catalyst |
| CN1974006A (en) * | 2006-12-14 | 2007-06-06 | 太原理工大学 | Slurry catalyst and its prepn |
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