CN101259415A - Preparation of CO hydrogenation synthesizing low carbon mixed alcohol catalyst - Google Patents
Preparation of CO hydrogenation synthesizing low carbon mixed alcohol catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 19
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims description 29
- 230000002194 synthesizing effect Effects 0.000 title claims description 15
- 239000010949 copper Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000007747 plating Methods 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 239000008139 complexing agent Substances 0.000 claims abstract description 8
- 230000000694 effects Effects 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 235000019441 ethanol Nutrition 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- MSWMMJONWLTTGS-UHFFFAOYSA-N 2-hydroxy-2-oxoacetate;triethylazanium Chemical compound OC(=O)C(O)=O.CCN(CC)CC MSWMMJONWLTTGS-UHFFFAOYSA-N 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000006104 solid solution Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000012669 liquid formulation Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 206010013786 Dry skin Diseases 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000000975 co-precipitation Methods 0.000 abstract description 6
- 238000007772 electroless plating Methods 0.000 abstract description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- 230000003213 activating effect Effects 0.000 abstract 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 abstract 1
- 230000000630 rising effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 12
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 10
- 239000012065 filter cake Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000003254 gasoline additive Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017816 Cu—Co Inorganic materials 0.000 description 1
- 229910017813 Cu—Cr 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
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910007746 Zr—O Inorganic materials 0.000 description 1
- WOIHABYNKOEWFG-UHFFFAOYSA-N [Sr].[Ba] Chemical compound [Sr].[Ba] WOIHABYNKOEWFG-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003788 bath preparation Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing a lower carbon mixed alcohol catalyst through CO hydrogenation synthesis and belongs to the technical field of the chemical industry. The method is characterized by adopting copper electrolyte and a metal oxide carrier as the raw materials and preparing a loading type Cu-based catalyst by an electroless plating method; taking CO and H2 as the raw materials and preparing the lower carbon mixed alcohol under the conditions of temperature and pressure rising as well as the existence of the Cu-based catalyst. The copper electrolyte contains cupric salt, a complexing agent and a reducing agent; the metal oxide is a sosoloid of ZrO2 and Ce0.5Zr0.5O2. The electroless plating method is to deposit trace amount of copper acetate on the carrier, uses KBH4 for activating and then loads the cupric salt in the plating solution on the carrier to obtain the Cu-based catalyst under the action of the complexing agent and the reducing agent. The Cu-based catalyst prepared by the invention has higher activity and selectivity of generating the lower carbon alcohol than the catalyst prepared by the traditional coprecipitation method.
Description
Technical field
The present invention relates to a kind of CO hydrogenation synthesizing low carbon mixed alcohol catalyst and preparation method thereof, the catalyst based method of a kind of Cu of preparation of saying so more specifically belongs to chemical technology field.
Background technology
Research by the direct synthesizing low-carbon mixed alcohol of synthesis gas starts from nineteen twenty.Twice oil crisis since the seventies in last century and countries in the world make people produce bigger interest to synthesizing low-carbon mixed alcohol to the pay attention to day by day of environmental requirement.The direct synthesizing low-carbon mixed alcohol of synthesis gas becomes one of relatively more active field of domestic and international research.At present, states such as Germany, the U.S., Canada, Italy and China all bring into use methyl alcohol or ethanol to act as a fuel, and add MAS or methyl tertiary butyl ether(MTBE) (MTBE) simultaneously and burn with gasoline as cosolvent.Take all factors into consideration from Technological Economy, by coal or the natural gas production synthesis gas that sets out, the synthetic again MAS that contains methyl alcohol of synthesis gas acts as a fuel or gasoline additive is reasonably, and Application in Chemical Engineering prospect is preferably arranged.From the world energy sources structure, coal accounts for 78.9%, and oil only accounts for 6.6%.As coal producer the biggest in the world, the energy resource structure characteristics of the few oil of the rich coal of China are more obvious.From the utilization of resources and point of view of environment protection, utilize high effect cleaning coal resources technology, exploitation " green fuel " has important strategic meaning and application prospect.CO catalytic hydrogenation synthesizing low-carbon mixed alcohol is one of important channel of coal resources clean utilization, and MAS progressively shows especially in the using value of fuel and chemical field in recent years, and correlative study becomes increasingly active.Wherein, CO synthesizing methanol by hydrogenating or isobutanol are the emphasis of research.This is because methyl alcohol is one of clean and relatively cheap desirable substitute fuel of comparison, isobutanol is one of well behaved cosolvent, isobutanol dehydration generates isobutene, can produce methyl tertiary butyl ether(MTBE) (MTBE) gasoline additive or isobutene dimerization with the methyl alcohol reaction that generates simultaneously, hydrogenation is produced isooctane.In addition, isobutanol still is basic Organic Chemicals, can be used for making antioxidant, paint solvent, flavorant, fine-chemical intermediate etc., the chemical reagent of the salts such as strontium barium, lithium that also can be used to purify and as senior solvent.
External more existing patented technologies about synthesizing low-carbon mixed alcohol.As the cooperative development of The Dow Chemical Co. (US) 2030 Dow Center, Abbott Road, Midland, Michigan 48640, and union carbide corporation with MoS
2Sygmol technology (US4675344 and EP0235886) for catalyst; France Petroleum Institute's exploitation is the IFP technology (US 4122110) of catalyst with Cu-Co; What Germany Lurgi company developed is the Octamix technology (US 4031123 and US 2327066) of catalyst with Cu-Zn; Italy Snam and Denmark Tops Φ e company develops is the MAS (technology WO/1989/011468) etc. of catalyst with Cu-Cr.These patented technologies differ from one another, and wherein C2+ alcohol content is higher in the product of Sygmol and IFP technology; Octamix process using low-pressure process Cu-series catalyst, space-time yield height, water content are low, and its product structure is expected further to improve.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, and the selectivity of isobutanol and space-time yield are lower.
At home, patent CN1428192, CN1481934, CN1179993 has reported the Preparation of catalysts method of CO hydrogenation preparing low-carbon alcohols, Preparation of catalysts needs the multistep dipping, and catalyst activity also needs to add Mn, various alkaline-earth metal even noble metal Rh except Cu, complicated process of preparation, and C in the product
3～C
5Alcohol selectivity and yield are lower.
In China, the industry of synthesis gas synthesizing methanol has had suitable basis, and the present invention adopts this new method of chemical plating to prepare support type Cu catalyst on the basis of traditional C u Preparation of catalysts method, uses ZrO
2Or Ce
0.5Zr
0.5O
2Solid solution is carrier, and the preparation method is simple, and then improves catalyst based hydrogenation activity and MAS selectivity and the space-time yield in the reaction of CO hydrogenation synthesizing low carbon mixed alcohol of Cu.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of CO hydrogenation synthesizing low carbon mixed alcohol copper-based catalysts uses the selectivity that the catalyst based catalyst that makes than traditional coprecipitation method of Cu that this method makes has higher activity and generates low-carbon alcohols.
The preparation that the present invention proposes is used for the method for CO hydrogenation synthesizing low carbon mixed alcohol carried copper-base catalyst, it is characterized in that: adopting copper electrolyte and metal oxide carrier is raw material, prepares carried copper-base catalyst with the method for chemical plating; With CO and H
2Be raw material, under the condition that heat pressurization and described copper-based catalysts exist, prepare MAS.
(1) described copper electrolyte contains mantoquita, complexing agent and reducing agent, wherein is reducing agent with formaldehyde, and soluble copper salt is main salt, and the ethanedioic acid triethylammonium tetrakis is a complexing agent, adopts NaOH to regulate the pH value, and electroplate liquid formulation is as follows:
Main salt: mantoquita: 2.5g/L;
Ethanedioic acid triethylammonium tetrakis: 7.4g/L;
Formaldehyde: 3.0g/L;
PH value: 12;
(2) described metal oxide is ZrO
2And Ce
0.5Zr
0.5O
2Solid solution.The method of described chemical plating is the Schweinfurt green of precipitation trace on carrier and uses KBH
4Activation loads on the mantoquita in the plating bath afterwards and obtains copper-based catalysts on the carrier under the effect of complexing agent and reducing agent.The step of described chemical plating process is: the Schweinfurt green of 40ml absolute ethyl alcohol adding 0.2g is added drop-wise to ZrO after being heated to 80 ℃ of formation colloidal solutions
2Perhaps Ce
0.5Zr
0.5O
2In the carrier, evaporate to dryness ethanol obtains pressed powder again.Then with 5ml KBH
4The aqueous solution (0.4mol/L) joins reaction activation in the above-mentioned pressed powder, till no bubble produces.Under 50 ℃, the carrier after the activation is joined in the plating bath, behind the reaction 30min, filter, wash neutrality, at 110 ℃ of dry 12h, obtain support type Cu catalyst.
The mantoquita that adopts is a copper sulphate.
The carrier that adopts is ZrO
2And Ce
0.5Zr
0.5O
2
99.99%) and hydrogen (H the synthesis gas that the present invention uses is carbon monoxide (CO purity:
2Purity: gaseous mixture 99.999%), CO/H
2Ratio be 1: 2.
Carry out above-mentioned reaction by method of the present invention, under heating, carry out.Reaction temperature is generally 300 ℃.
Carry out above-mentioned reaction by the inventive method, carry out adding to depress.The pressure of synthesis gas is generally 6MPa.
Description of drawings
Fig. 1 support C e
0.5Zr
0.5O
2XRD spectra
Fig. 2 carrier ZrO
2XRD spectra
The specific embodiment
Below in conjunction with being that embodiment is described further technical scheme of the present invention.
Embodiment 1,
(1) support C e
0.5Zr
0.5O
2Preparation
Ce (NO with 21.71g
3)
36H
2ZrO (the NO of O and 13.36g
3)
22H
2O (mol ratio 1: 1) mixing is dissolved in the 600ml deionized water, is mixed with the aqueous solution that concentration of metal ions is about 0.17mol/L.Measure the concentrated ammonia liquor of 100ml 25wt%, be diluted to 1000mL as precipitating reagent with deionized water.Under vigorous stirring, above-mentioned salting liquid is splashed in the ammoniacal liquor.After dropwising, continue to stir 0.5h, obtain hydrogel behind the static aging 10h, behind the suction filtration hydrogel spend deionised water to filtrate for neutral, use absolute ethanol washing filter cake suction filtration more then, repeat twice, with the filter cake that obtains in mobile N
2Dry 10h under 110 ℃ in the atmosphere is then in the N that flows
2In at 270 ℃, 350 ℃, under 550 ℃ respectively roasting 5h obtain the faint yellow solid powder, XRD (Fig. 1) the analysis showed that this pressed powder is the Ce-Zr-O solid solution.
(2) Cu10/Ce
0.5Zr
0.5O
2The electroless plating method preparation
Plating bath preparation: the plating bath (regulating the pH value with NaOH is 12) that is mixed with 1000ml with 2.5g copper sulphate, 7.4g ethanedioic acid triethylammonium tetrakis, 7.4mL40% formaldehyde and deionized water.The 40ml absolute ethyl alcohol is added the Schweinfurt green of 0.2g, be heated to 80 ℃ and be added drop-wise to 4g Ce after forming colloidal solutions
0.5Zr
0.5O
2In the powder, evaporate to dryness ethanol obtains pressed powder again, adds 5ml KBH then
4The aqueous solution (0.4mol/L) activation is transferred in the above-mentioned plating bath again.Under 50 ℃, stirring reaction is until there not being bubble to generate.With sedimentation and filtration, spend deionised water filtrate for neutral, dry 12h under 110 ℃.The load capacity of Cu is 10wt% in the gained catalyst, and catalyst is designated as Cu10/Ce
0.5Zr
0.5O
2-chemical plating.
(3) reaction of CO hydrogenation synthesizing low carbon mixed alcohol
The hydrogenation reaction of CO is to carry out in the miniature fixed bed flowing reactive tubular reactor of stainless steel tube liner quartz ampoule (internal diameter 10mm, high 350mm), and loaded catalyst is 0.5ml.Catalyst is through reducing gases (V before the reaction
N2/VH2=4/1) behind temperature programming to the 250 ℃ reduction 12h, rises to reaction temperature (300 ℃), switch to CO/H
2Unstripped gas reacts under 6Mp pressure, and raw gas flow is controlled by mass flowmenter, 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 is after the cooling of chuck cold water, again through ice-water bath cold-trap reception coercibility product, and incoagulability tail gas is used gas-chromatography (TCD, TDX-01 packed column, H after counterbalance valve is decompressed to normal pressure
2Do carrier gas) carry out on-line analysis, containing the oxygen organic product is that interior mark carries out off-line analysis with gas-chromatography (FID, OV-17 capillary column) with ethyl acetate.Reaction result is listed in table 1.
Embodiment 2
(1) preparation of carrier is with embodiment 1 (1)
(2) Cu5/Ce
0.5Zr
0.5O
2Preparation
Except the consumption of copper sulphate is the 1.3g, other method is the same with the method for preparing catalyst among the embodiment 1 (2) with step, and the Cu load capacity of catalyst is 5wt%, obtains catalyst and is designated as Cu5/Ce
0.5Zr
0.5O
2-chemical plating.
(3) reaction is with embodiment 1 (3).Reaction result is listed in table 1.
Embodiment 3
(1) ZrO
2Preparation
With 26.73g ZrO (NO
3)
22H
2O is dissolved in the ZrO (NO that the 600ml deionized water obtains 0.17mol/L
3)
2The aqueous solution is measured the concentrated ammonia liquor of 100ml 25wt%, spends the dried up 1000mL of being diluted to as precipitating reagent.Under vigorous stirring, above-mentioned salting liquid is splashed in the ammoniacal liquor.Precipitation finishes the back and continues to stir 0.5h, obtains hydrogel after leaving standstill aging 10h, and suction filtration also spends deionised water to filtrate neutrality, uses the absolute ethanol washing filter cake then, and suction filtration repeats twice, with the filter cake that obtains in mobile N
2Dry 10h under 110 ℃ in the atmosphere is then in the N that flows
2In at 270 ℃, 350 ℃, under 550 ℃ respectively roasting 5h obtain the white solid powder, XRD (Fig. 2) the analysis showed that this pressed powder is ZrO
2
(2) Cu10/ZrO
2The electroless plating method preparation
Remove 4g Ce
0.5Zr
0.5O
2Change 4g ZrO into
2Outside, other method is identical with embodiment 1 (2) with step, and the Cu load capacity of catalyst is 10wt%, and catalyst is designated as Cu10/ZrO
2-chemical plating.
(3) reaction is with embodiment 1 (3).Reaction result is listed in table 1.
Comparative example 1:
(1) co-precipitation Cu10-Ce
0.5Zr
0.5O
2Preparation of catalysts
With 10.86g Ce (NO
3)
36H
2O and 6.68g ZrO (NO
3)
22H
2O and 2.78g Cu (NO
3)
26H
2O is dissolved in the 300ml water, and the control concentration of metal ions is 2mol/L, drips the K of 2mol/L then
2CO
3Solution after dropwising, continues to stir 0.5h, static aging 10h.The absolute ethanol washing filter cake is used in washing then, and suction filtration repeats twice, with the filter cake that obtains in mobile N
2Dry 10h under 110 ℃ in the atmosphere is then in the N that flows
2In at 270 ℃, 350 ℃, 550 ℃ of following respectively roasting 5h, the Cu content of gained catalyst is 10wt%, catalyst is designated as Cu10-Ce
0.5Zr
0.5O
2-co-precipitation.
(2) reaction is with embodiment 1 (3).Reaction result is listed in table 1.
Comparative example 2:
(1) co-precipitation Cu10-ZrO
2Preparation of catalysts
With 13.36g ZrO (NO
3)
22H
2O and 2.78g Cu (NO
3)
26H
2O is dissolved in the 300ml water, and the control concentration of metal ions is 2mol/L, drips the K of 2mol/L then
2CO
3Solution after dropwising, continues to stir 0.5h, static aging 10h.The absolute ethanol washing filter cake is used in washing then, and suction filtration repeats twice, with the filter cake that obtains in mobile N
2Dry 10h under 110 ℃ in the atmosphere is then in the N that flows
2In at 270 ℃, 350 ℃, 550 ℃ of following respectively roasting 5h, the Cu content of gained catalyst is 10wt%, catalyst is designated as Cu10-ZrO
2-co-precipitation.
(2) reaction is with embodiment 1 (3).Reaction result is listed in table 1.
Table one
Reaction condition: temperature: 300 ℃; Pressure: 6Mp; Air speed: 10000h
-1H
2/ CO=2
*Total alcohol: refer to C
1-C
4The summation of alcohol.
Claims (9)
1, a kind of preparation method of CO hydrogenation synthesizing low carbon mixed alcohol catalyst is characterized in that: adopting copper electrolyte and metal oxide carrier is raw material, prepares carried copper-base catalyst with chemical plating method; With CO and H
2Be raw material, under the condition that heat pressurization and copper-based catalysts exist, prepare MAS.
2, preparation method according to claim 1 is characterized in that: described copper electrolyte contains mantoquita, complexing agent and reducing agent, wherein is reducing agent with formaldehyde, soluble copper salt is main salt, the ethanedioic acid triethylammonium tetrakis is a complexing agent, adopts NaOH to regulate the pH value, and electroplate liquid formulation is as follows:
Main salt: mantoquita: 2.5g/L;
Ethanedioic acid triethylammonium tetrakis: 7.4g/L;
Formaldehyde: 3.0g/L;
PH value: 12;
3, preparation method according to claim 1 is characterized in that: described metal oxide is ZrO
2And Ce
0.5Zr
0.5O
2Solid solution.
4, preparation method according to claim 1 is characterized in that: described chemical plating method is the Schweinfurt green of precipitation trace on carrier and uses KBH
4Activation loads on the mantoquita in the plating bath afterwards and obtains copper-based catalysts on the carrier under the effect of complexing agent and reducing agent, the concrete steps of chemical plating process are:
(1) absolute ethyl alcohol is added Schweinfurt green be heated to 80 ℃ form colloidal solutions after, be added drop-wise to ZrO
2Perhaps Ce
0.5Zr
0.5O
2In the carrier, evaporate to dryness ethanol obtains pressed powder again;
(2) with KBH
4The aqueous solution (0.4mol/L) joins reaction activation in the above-mentioned pressed powder, till no bubble produces;
(3) under 50 ℃, the carrier after the activation is joined in the plating bath, after the reaction, filter, wash neutrality, 110 ℃ of dryings, obtain support type Cu catalyst.
5, according to claim 1 or 4 described preparation methods, it is characterized in that: the mantoquita of employing is a copper sulphate.
6, according to claim 1 or 4 described preparation methods, it is characterized in that: the carrier of employing is ZrO
2And Ce
0.5Zr
0.5O
2
99.99%) and hydrogen (H 7, preparation method according to claim 1 is characterized in that: described synthesis gas is a carbon monoxide (CO purity:
2Purity: gaseous mixture 99.999%), CO/H
2Ratio be 1: 2.
8, preparation method according to claim 1 is characterized in that: described reaction temperature is 300 ℃.
9, preparation method according to claim 1 is characterized in that: the pressure of described synthesis gas is 6MPa.
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| CNA2008101051429A CN101259415A (en) | 2008-04-25 | 2008-04-25 | Preparation of CO hydrogenation synthesizing low carbon mixed alcohol catalyst |
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|---|---|---|---|
| CNA2008101051429A CN101259415A (en) | 2008-04-25 | 2008-04-25 | Preparation of CO hydrogenation synthesizing low carbon mixed alcohol catalyst |
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Family
ID=39960229
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102000576A (en) * | 2010-11-30 | 2011-04-06 | 复旦大学 | Catalyst for toluene exhaust gas catalytic combustion and preparation method thereof |
| CN102068989A (en) * | 2010-12-02 | 2011-05-25 | 河北工业大学 | Method for preparing ZrO2 nanotube supported copper catalyst |
| CN103007907A (en) * | 2012-12-21 | 2013-04-03 | 清华大学 | Preparation method of high-efficiency quantitative supported nano iron |
| CN113617345A (en) * | 2021-08-13 | 2021-11-09 | 厦门欧米克生物科技有限公司 | Catalyst and preparation method and application thereof |
-
2008
- 2008-04-25 CN CNA2008101051429A patent/CN101259415A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102000576A (en) * | 2010-11-30 | 2011-04-06 | 复旦大学 | Catalyst for toluene exhaust gas catalytic combustion and preparation method thereof |
| CN102000576B (en) * | 2010-11-30 | 2013-06-12 | 复旦大学 | Catalyst for toluene exhaust gas catalytic combustion and preparation method thereof |
| CN102068989A (en) * | 2010-12-02 | 2011-05-25 | 河北工业大学 | Method for preparing ZrO2 nanotube supported copper catalyst |
| CN102068989B (en) * | 2010-12-02 | 2012-10-03 | 河北工业大学 | Method for preparing ZrO2 nanotube supported copper catalyst |
| CN103007907A (en) * | 2012-12-21 | 2013-04-03 | 清华大学 | Preparation method of high-efficiency quantitative supported nano iron |
| CN113617345A (en) * | 2021-08-13 | 2021-11-09 | 厦门欧米克生物科技有限公司 | Catalyst and preparation method and application thereof |
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