CN103372437B - The preparation method of copper-zinc system catalyst - Google Patents

The preparation method of copper-zinc system catalyst Download PDF

Info

Publication number
CN103372437B
CN103372437B CN201210442596.1A CN201210442596A CN103372437B CN 103372437 B CN103372437 B CN 103372437B CN 201210442596 A CN201210442596 A CN 201210442596A CN 103372437 B CN103372437 B CN 103372437B
Authority
CN
China
Prior art keywords
solution
catalyst
copper
zinc
concentration
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201210442596.1A
Other languages
Chinese (zh)
Other versions
CN103372437A (en
Inventor
王海涛
徐学军
刘东香
冯小萍
王继锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Original Assignee
China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Fushun Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to CN201210442596.1A priority Critical patent/CN103372437B/en
Publication of CN103372437A publication Critical patent/CN103372437A/en
Application granted granted Critical
Publication of CN103372437B publication Critical patent/CN103372437B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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)

Abstract

The invention discloses a kind of preparation method of copper-zinc system catalyst.The method loads water purification in retort, passes into a certain amount of CO 2rear and stream adds the metal salt solution of cupric and zinc, sodium aluminate solution carries out plastic, prepares copper-zinc system catalyst after aging under agitation through shaping.The method can improve the physico-chemical property of catalyst, increases the specific area of catalyst, increases coordinative role between main active metal component copper and promoter metal component zinc, improve the dispersiveness of active phase, improves activity and the stability of catalyst.This catalyst is suitable to catalst for synthesis of methanol especially.

Description

The preparation method of copper-zinc system catalyst
Technical field
The present invention relates to a kind of preparation method of copper-zinc system catalyst, be specifically related to a kind of preparation method of the copper-zinc system catalyst for the synthesis of methyl alcohol with high activity, good heat resistance.
Background technology
Methyl alcohol is a kind of extremely important industrial chemicals, be widely used in organic synthesis, dyestuff, fuel, medicine, coating and national defense industry, its output is only second to synthetic ammonia and ethene, occupies third place in the world, methanol demands amount and the production capacity sustainable growth along with industrial development in recent years.
Industrial methyl alcohol is generally with containing H 2, CO, CO 2synthesis gas produce under certain pressure, temperature and catalyst existence condition.In generally adopting in the world at present, low-pressure vapor phase method synthesizing methanol, used catalyst is essentially the mixed oxide of copper, zinc, aluminium.CuO, ZnO, Al in catalst for synthesis of methanol 2o 3the effect of three components is variant, and CuO is main active component, ZnO and Al 2o 3for auxiliary agent.Method for preparing catalyst is generally the mixing subcarbonate first using coprecipitation to generate (comprise and flow, instead to add, just add coprecipitation) copper zinc, and then add aluminium hydroxide in pulping process, generate slurry through washing, drying, roasting, compression molding.The research of current catalyst preparing mainly concentrates on optimization and the improvement of preparation method and technique, catalyst activity is improved by changing the ratio of catalytic component, the size of crystal grain, the size of specific area and pore-size distribution, improve copper-based catalysts poor heat stability, the selective low problem short with the life-span.Method for preparing catalyst is different, and the performance of gained catalyst can differ larger.
CN 1810357A adopts a traditional step coprecipitation to prepare a kind of catalst for synthesis of methanol.By the nitrate mixed solution of Cu, Zn, Al, Li and NaCO 3solution stream is titrated in the deionized water of a small amount of high-speed stirred, keeps the pH of solution between 7 ~ 8 simultaneously, aging, suction filtration, washing, dries to obtain catalyst precarsor, and catalyst precarsor is dried, roasting obtains finished product.The method adopts a typical step coprecipitation to prepare catalyst for methanol, in preparation process, with the addition of LiNO 3.
CN 1329938A discloses a kind of preparation method of catalst for synthesis of methanol, and this catalyst is made up of the oxide of copper, zinc, aluminium.Preparation process a: part makes coprecipitate containing copper, zinc, aluminium compound by coprecipitation, another part makes coprecipitate containing copper, zinc compound with co-precipitation.The equal thermal decomposition of above-mentioned coprecipitate is the oxide of metal, then by these two kinds of co-precipitation mixing, washing, dry, roasting, and shaping obtained catalyst.
CN 1660490A discloses a kind of preparation method of catalst for synthesis of methanol, its preparation process is: coprecipitation is prepared in methanol synthesis catalyst process and added a small amount of Surfactant OP, or fractional precipitation is prepared in methanol synthesis catalyst process and is added a small amount of Surfactant OP, obtained a kind of catalst for synthesis of methanol.
CN 101574649A discloses a kind of preparation method of catalst for synthesis of methanol, step is reacted by the mixed aqueous solution of the aqueous solution of aluminum soluble salt and alkali metal hydroxide-carbonate, generate a kind of transparent meta-aluminate aqueous solution, then it is carried out coprecipitation reaction with containing the copper of water-soluble high-molecular compound, the transparent aqueous solution of zinc salt, generate the mixing co-precipitation of a kind of copper, zinc, aluminium, then through washing, drying, granulation process, roasting, beat that sheet is shaping can obtain a kind of highly active catalst for synthesis of methanol.
The catalst for synthesis of methanol method of above-mentioned patent Introduction is by adding new auxiliary agent (Li and surfactant), changing the presoma of catalyst preparation process (step process changes two steps or three step process into) and change Al, come the structure of regulating catalyst, surface acidic-basic property, electronic property, to improve the activity of existing catalyst, selective or life-span.But improve catalst for synthesis of methanol key that the is active and life-span be to increase the specific area of catalyst and active ingredient copper and co-catalyst zinc distribute more evenly, above patent does not all relate to.
Summary of the invention
For above-mentioned deficiency of the prior art, the invention provides the preparation method of simple, the easy-operating copper-zinc system catalyst of a kind of technique, the catalyst of the method gained is suitable to catalst for synthesis of methanol especially, the specific area of this catalyst is higher, it is more even that active ingredient copper and co-catalyst zinc distribute, and improves the activity of copper-zinc system catalyst and the service life of heat endurance and catalyst.
Inventor is found by a large amount of experiments, passes into CO when copper, zinc metal salt solution and sodium metaaluminate plastic 2gas, carries out precipitation reaction and prepares catalst for synthesis of methanol, can increase the specific area of catalyst, makes CuO and ZnO uniform load to carrier A l 2o 3on, active phase crystal grain is little, and decentralization is high, and activity is combined closely with carrier, which adds the effect that ZnO promotes Cu dispersion, substantially increases catalyst activity, simultaneously Al 2o 3the increase of specific area, increases activated centre quantity, and can hinder copper particle sintered, carbon deposit, improves the heat resistance of catalyst.
The preparation method of copper-zinc system catalyst of the present invention, comprises the following steps:
(1), by wiring solution-forming A soluble in water for the soluble-salt of Cu, Zn, preparation sodium aluminate solution B;
(2), in retort load water purification, pass into CO 2, add CO 2aluminium in the total amount of gas and solution B is with Al 2o 3the mol ratio of meter is 2 ~ 8, is preferably 3 ~ 6;
(3), by solution A, solution B stream adds step (2) passes into CO 2retort in plastic, then aging under agitation;
(4), the material that obtains of step (3) through washing, filter, dry, roasting, compression molding, obtains copper-zinc system catalyst.
Cu, Zn soluble-salt described in step (1) is nitrate and/or acetate, copper (Cu in solution A 2+) concentration is 1.0 ~ 6.0mol/L, is preferably 2.0 ~ 4.0mol/L, zinc (Zn in solution A 2+) concentration is 0.5 ~ 5.0mol/L, be preferably 1.0 ~ 3.0mol/L, copper/zinc atom mol ratio is 0.1 ~ 10.0, and be preferably 0.2 ~ 5.0, (copper+zinc)/aluminium atomic molar ratio is 0.1 ~ 10.0, is preferably 3.0 ~ 8.0.In solution B, sodium metaaluminate concentration is 1.0 ~ 6.0mol/L, is preferably 2.0 ~ 4.0mol/L.
Step loads water purification in (2) in retort, logical CO 2rear retort preferably seals.The CO passed into 2the volumetric concentration of gas is 20v% ~ 99v%, is preferably 40v% ~ 95v%.Add CO 2aluminium in the total amount of gas and solution B is (with Al 2o 3meter) mol ratio be 2 ~ 8, be preferably 3 ~ 6.Described water purification typically refers to not containing the water of heteroion, such as deionized water.
Described in step (3), the condition of plastic is as follows: reaction temperature is 30 ~ 90 DEG C, is preferably 40 ~ 80 DEG C.During plastic, pH value controls is 6.0 ~ 11.0, and be preferably 7.0 ~ 9.0, gelation time is 0.2 ~ 4.0 hour, is preferably 0.5 ~ 3 hour.Aging temperature 50 ~ 100 DEG C after plastic, is preferably 60 ~ 90 DEG C, and it is 6.0 ~ 11.0 that aging pH value controls, and be preferably 7.0 ~ 10.0, ageing time is 0.5 ~ 5.0 hour, is preferably 1.0 ~ 3.0 hours.
Step (4) described washing spends deionized water, and wash temperature controls at 30 ~ 90 DEG C, is preferably 40 ~ 70 DEG C.Filter cake is dry under 50 ~ 150 DEG C of conditions, and baking temperature preferably 60 ~ 120 DEG C, 0.5 ~ 24.0 hour drying time, is preferably 1 ~ 16 hour drying time.300 ~ 360 DEG C of roastings 1 ~ 16 hour, be preferably 2 ~ 10 hours.
Copper-zinc system catalyst of the present invention, with the weight of catalyst for benchmark, the composition of catalyst comprises, in mass fraction: CuO is 20% ~ 75%, ZnO is 15% ~ 50%, Al 2o 3be 5% ~ 30%; Preferably CuO is 30% ~ 60%, ZnO is 20% ~ 40%, Al 2o 3be 6% ~ 30%.
Compared to method of the prior art, the copper-zinc system catalyst prepared by method of the present invention is adopted to have higher activity, the feature of Heat stability is good, suitable to catalst for synthesis of methanol especially.
Detailed description of the invention
The solution of the present invention and effect is further illustrated below by embodiment.In the present invention, wt% is mass fraction.
In the present invention, specific area and pore volume adopt low temperature liquid nitrogen determination of adsorption method.
Embodiment 1
In dissolving tank 1, add 500mL water, add 155gCu (NO 3) 23H 2o and 114gZn (NO 3) 26H 2o dissolves, and preparating acid sex work solution A, adds 500mL water in dissolving tank 2, then adds sodium metaaluminate 41 grams dissolving, prepares alkaline working solution B.Add 1000mL water in retort, in water purification, pass into the CO that volumetric concentration is 80v% 2, hermetically sealed can, temperature rises to 60 DEG C, and plastic in retort solution A, solution B stream being added sealing, gelling temperature 60 DEG C, gelation time 1.5 hours, during plastic, the pH value of slurries controls to be 8.5.CO in water purification neutralization reaction tank 2al in the total amount of gas and alkaline working solution B 2o 3mol ratio is 3.5.After plastic aging 3 hours, aging temperature was 75 DEG C, and pH value is 9.0.After material filtering, wash 2 times with water, filter cake is in 60 DEG C of dryings, 330 DEG C of roastings 5 hours after 8 hours, and the material after roasting adds appropriate graphite and hydraulic pressure is in blocks, and compressing tablet obtains final catalyst A.
The composition of catalyst A, in mass fraction, as follows: CuO is 50%; ZnO is 36%; Al 2o 3be 14%.The character of catalyst: specific area is 141m 2/ g, pore volume is 0.351cm 3/ g.
Embodiment 2
In dissolving tank 1, add 500mL water, add 170gCu (NO 3) 23H 2o and 78gZn (NO 3) 26H 2o dissolves, and preparating acid sex work solution A, adds 500mL water in dissolving tank 2, then adds sodium metaaluminate 58 grams dissolving, prepares alkaline working solution B.Add 500mL water in retort, in water purification, pass into the CO that concentration is 85v% 2, hermetically sealed can, temperature rises to 65 DEG C.Plastic in retort solution A, solution B stream being added sealing, gelling temperature 65 DEG C, gelation time 1 hour, the pH value of plastic slurries is 7.6.CO in water purification neutralization reaction tank 2al in the total amount of gas and alkaline working solution B 2o 3mol ratio is 4.5.After plastic aging 2 hours, aging temperature was 75 DEG C, and pH value is 7.8.After material filtering, wash 4 times with water, filter cake is in 110 DEG C of dryings, 350 DEG C of roastings 5 hours after 8 hours, and the material after roasting adds appropriate graphite and hydraulic pressure is in blocks, and compressing tablet obtains final catalyst B.
The composition of catalyst B, in mass fraction, as follows: CuO is 52%; ZnO is 30%; Al 2o 3be 18%.The character of catalyst: specific area is 149m 2/ g, pore volume is 0.367cm 3/ g.
Embodiment 3
In dissolving tank 1, add 500mL water, add 197gCu (NO 3) 23H 2o and 92gZn (NO 3) 26H 2o dissolves, and preparating acid sex work solution A, adds 500mL water in dissolving tank 2, then adds sodium metaaluminate 35 grams dissolving, prepares alkaline working solution B, add 500mL water in retort, pass into the CO that concentration is 90v% in water purification 2, hermetically sealed can, temperature rises to 70 DEG C.Plastic in retort solution A, solution B stream being added sealing, gelling temperature 70 DEG C, gelation time 1.5 hours, the pH value of plastic slurries is 8.0.CO in water purification neutralization reaction tank 2al in the total amount of gas and alkaline working solution B 2o 3mol ratio is 3.8.After plastic aging 3.0 hours, aging temperature was 75 DEG C, and pH value is 8.2.After material filtering, wash 2 times with water, filter cake is 120 DEG C of dryings after 5 hours, and 330 DEG C of roastings 6 hours, the material after roasting adds appropriate graphite and hydraulic pressure is in blocks, and compressing tablet obtains final catalyst C.
The composition of catalyst C, in mass fraction, as follows: CuO is 55%; ZnO is 34%; Al 2o 3be 11%.The character of catalyst: specific area is 165m 2/ g, pore volume is 0.389cm 3/ g.
Embodiment 4
In dissolving tank 1, add 500mL water, add 215gCu (NO 3) 23H 2o and 183gZn (NO 3) 26H 2o dissolves, and preparating acid sex work solution A, adds 500mL water in dissolving tank 2, then adds sodium metaaluminate 32 grams dissolving, prepares alkaline working solution B, add 1000mL water in retort, pass into the CO that concentration is 88v% in water purification 2, hermetically sealed can, temperature rises to 75 DEG C.Plastic in retort solution A, solution B stream being added sealing, gelling temperature 75 DEG C, gelation time 2 hours, the pH value of plastic slurries is 7.6.CO in water purification neutralization reaction tank 2al in the total amount of gas and alkaline working solution B 2o 3mol ratio is 4.2.After plastic aging 2.5 hours, aging temperature was 80 DEG C, and pH value is 8.0.After material filtering, wash 4 times with water, filter cake was 100 DEG C of dryings 6 hours, and 350 DEG C of roastings 4 hours, the material after roasting adds appropriate graphite and hydraulic pressure is in blocks, and compressing tablet obtains final catalyst D.
The composition of catalyst D, in mass fraction, as follows: CuO is 58%; ZnO is 32%; Al 2o 3be 10%.The character of catalyst: specific area is 188m 2/ g, pore volume is 0.403cm 3/ g.
Comparative example 1
By method for preparing catalyst disclosed in CN 101574649A, preparation forms identical reference agent E with the catalyst of embodiment 3.
Take Al (NO 3) 39H 2o71g, adds deionized water 200ml stirring and dissolving, takes NaOH40g, NaCO 350g is molten with 500ml deionized water altogether.Under the condition of 35 DEG C, by NaOH-NaCO 350g solution slowly adds Al (NO 3) 3, control terminal pH>=12, obtain water white sodium aluminate solution, for subsequent use.
Take Cu (NO 3) 23H 2o197g, Zn (NO 3) 26H 2o92g is dissolved in 250ml deionized water; Take 1g polyvinyl alcohol, be dissolved in 250ml deionized water.Then by these two kinds of solution mixing, blue-tinted transparent solution is made.
Solution containing sodium metaaluminate and copper nitrate-zinc nitrate is flowed reaction under the condition of 70 DEG C, and to control pH value in reaction be 7.8.React complete continuation and stir 60 minutes at the reaction temperatures, material passes through washing, then in an oven in 110 DEG C of dryings 4 hours, roasting 4 hours at 350 DEG C in Muffle furnace, cold go after add the deflocculated graphite of 2wt% and the deionized water of 3wt%, beat sheet after being mixed shaping, gained catalyst sample E.
The composition of catalyst E, in mass fraction, as follows: CuO is 55%; ZnO is 34%; Al 2o 3be 11%.The character of catalyst: specific area is 75m 2/ g, pore volume is 0.12cm 3/ g.
Comparative example 2
The catalst for synthesis of methanol that comparative example 2 adopts traditional handicraft to prepare, preparation forms identical reference agent F with the catalyst of embodiment 3.
Take Cu (NO 3) 23H 2o197g, Zn (NO 3) 26H 2o92g is dissolved in wiring solution-forming A in 850mL deionized water, is heated to 70 DEG C; Take 106 grams of Na 2cO 3be dissolved in wiring solution-forming B in 1000ml deionized water, be heated to 70 DEG C; Under the condition stirred, by solution A and solution B and stream adds in the retort that 500ml deionized water is housed, gelation time is 1 hour, and controlling endpoint pH is 7.8, continues to stir 30min and precipitates color and become blue-green from blueness, keep precipitation temperature 80 DEG C; Static 2 hours, in obtained slip, add 22gAl (OH) 3, then after filtration, wash to Na +content≤0.035wt%, the filter cake obtained is 110 DEG C of oven dry, then 320 DEG C of roastings 4 hours, the material after roasting adds appropriate graphite and hydraulic pressure is in blocks, obtains catalyst F.
The composition of catalyst F, in mass fraction, as follows: CuO is 55%; ZnO is 34%; Al 2o 3be 11%.The character of catalyst: specific area is 81m 2/ g, pore volume is 0.14cm 3/ g.
Embodiment 5
Catalst for synthesis of methanol is pulverized for 16-40 order, adopt low-concentration hydrogen (H before use 2/ N 2=3/97(volume ratio)) hydrogen nitrogen mixed gas reduction 16 ~ 20h, the highest reduction temperature is 235 DEG C.Miniature fixed-bed reactor carries out the activity rating of catalyst.Loaded catalyst is 5ml, and unstripped gas consists of CO/H 2/ CO 2/ N 2=12/70/3/15(volume ratio), reaction pressure is 5.0MPa, and air speed is 10000h -1, reaction temperature is 250 DEG C, measures CO and CO 2conversion ratio be catalyst initial activity.Then catalyst is being synthesized by 450 DEG C of heat treatment 5h in atmosphere, then dropping to 250 DEG C of mensuration CO and CO 2conversion ratio be active after heat treatment, i.e. heat resistance.Product chromatographic, the space-time yield gmL of methanol -1h -1namely the grams of every milliliter of product methyl alcohol per hour, the results are shown in Table 1.Find out from result of the test, methanol synthesis catalyst of the present invention has the selective of high activity, heat resistance and excellence.
The evaluation of table 1 catalyst activity and heat resistance experimental result
Catalyst Initial activity, % Initial activity, % Heat-resisting rear activity, % Heat-resisting rear activity, % Methyl alcohol space-time yield, (gmL -1·h -1） Methyl alcohol is selective, %
CO CO 2 CO CO 2
A 95.18 87.45 86.32 77.84 3.05 95.04
B 92.18 88.12 85.74 80.39 2.99 94.85
C 95.59 85.01 87.10 78.95 3.01 96.34
D 93.07 87.41 86.67 81.51 3.15 95.21
E 78.96 73.11 64.08 59.54 1.56 83.52
F 80.63 76.99 64.23 57.74 1.81 82.11

Claims (8)

1. a preparation method for copper-zinc system catalyst, comprising:
(1), by wiring solution-forming A soluble in water for the soluble-salt of Cu, Zn, preparation sodium aluminate solution B;
(2), in retort load water purification, pass into CO 2, add CO 2aluminium in the total amount of gas and solution B is with Al 2o 3the mol ratio of meter is 2 ~ 8;
(3), by solution A, solution B stream adds step (2) passes into CO 2retort in plastic, then aging under agitation;
(4), the material that obtains of step (3) through washing, filter, dry, roasting, compression molding, obtains copper-zinc system catalyst;
Cu, Zn soluble-salt described in step (1) is nitrate and/or acetate, and in solution A, copper concentration is 1.0 ~ 6.0mol/L, and zinc concentration is 0.5 ~ 5.0mol/L; In solution B, sodium metaaluminate concentration is 1.0 ~ 6.0mol/L;
In step (2), the CO passed into 2the volumetric concentration of gas is 20v% ~ 99v%;
Gelation Conditions described in step (3): reaction temperature is 30 ~ 90 DEG C, pH value is 6.0 ~ 11.0, and gelation time is 0.2 ~ 4.0 hour; Aging temperature 50 ~ 100 DEG C after plastic, it is 6.0 ~ 11.0 that aging pH value controls, and ageing time is 0.5 ~ 5.0 hour.
2. in accordance with the method for claim 1, it is characterized in that in step (1) solution A, copper concentration is 2.0 ~ 4.0mol/L, zinc concentration is 1.0 ~ 3.0mol/L; In solution B, sodium metaaluminate concentration is 2.0 ~ 4.0mol/L.
3. in accordance with the method for claim 1, it is characterized in that, in step (2), adding CO 2aluminium in the total amount of gas and solution B is with Al 2o 3the mol ratio of meter is 3 ~ 6.
4. in accordance with the method for claim 1, it is characterized in that in described solution A, copper/zinc atom mol ratio is 0.1 ~ 10.0, and (copper+zinc)/aluminium atomic molar ratio is 0.1 ~ 10.0.
5. in accordance with the method for claim 1, it is characterized in that in described solution A, copper/zinc atom mol ratio is 0.2 ~ 5.0, and (copper+zinc)/aluminium atomic molar ratio is 3.0 ~ 8.0.
6. in accordance with the method for claim 1, it is characterized in that Gelation Conditions described in step (3): reaction temperature is 40 ~ 80 DEG C, pH value is 7.0 ~ 10.0, and gelation time is 0.5 ~ 3.0 hour; After plastic, aging temperature is 60 ~ 90 DEG C, and it is 7.0 ~ 10.0 that aging pH value controls, and ageing time is 1.0 ~ 3.0 hours.
7. in accordance with the method for claim 1, it is characterized in that the temperature of step (4) described washing controls at 30 ~ 90 DEG C; Filter cake is dry under 50 ~ 150 DEG C of conditions, and 0.5 ~ 24.0 hour drying time, 300 ~ 360 DEG C of roastings 1 ~ 16 hour.
8. in accordance with the method for claim 1, it is characterized in that described copper-zinc system catalyst, with the weight of catalyst for benchmark, the composition of catalyst comprises, in mass fraction: CuO is 20% ~ 75%, ZnO is 15% ~ 50%, Al 2o 3be 5% ~ 30%.
CN201210442596.1A 2012-04-13 2012-11-08 The preparation method of copper-zinc system catalyst Active CN103372437B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210442596.1A CN103372437B (en) 2012-04-13 2012-11-08 The preparation method of copper-zinc system catalyst

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201210107896 2012-04-13
CN2012101078964 2012-04-13
CN201210107896.4 2012-04-13
CN201210442596.1A CN103372437B (en) 2012-04-13 2012-11-08 The preparation method of copper-zinc system catalyst

Publications (2)

Publication Number Publication Date
CN103372437A CN103372437A (en) 2013-10-30
CN103372437B true CN103372437B (en) 2015-08-12

Family

ID=49458648

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210442596.1A Active CN103372437B (en) 2012-04-13 2012-11-08 The preparation method of copper-zinc system catalyst

Country Status (1)

Country Link
CN (1) CN103372437B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104069870B (en) * 2014-07-07 2016-05-18 太原理工大学 A kind of catalyst of synthesising gas systeming carbinol and preparation method and application
CN107774262B (en) * 2016-08-31 2019-11-15 中国石油化工股份有限公司 The preparation method of copper zinc catalyst
CN107774263B (en) * 2016-08-31 2019-11-15 中国石油化工股份有限公司 A kind of preparation method of catalst for synthesis of methanol
CN107790138B (en) * 2016-08-31 2019-11-15 中国石油化工股份有限公司 A kind of copper zinc catalyst and preparation method thereof
CN110314688A (en) * 2018-03-28 2019-10-11 国家能源投资集团有限责任公司 Methanol synthesis catalyst and preparation method thereof
CN114192149B (en) * 2021-12-29 2024-05-10 上海方民科技有限公司 Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101298052A (en) * 2008-06-20 2008-11-05 华东理工大学 Copper zinc catalyst and precursor, preparation and use thereof
CN101574649A (en) * 2009-05-25 2009-11-11 来安县迅能催化剂有限公司 Methanol catalyst preparation method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101298052A (en) * 2008-06-20 2008-11-05 华东理工大学 Copper zinc catalyst and precursor, preparation and use thereof
CN101574649A (en) * 2009-05-25 2009-11-11 来安县迅能催化剂有限公司 Methanol catalyst preparation method

Also Published As

Publication number Publication date
CN103372437A (en) 2013-10-30

Similar Documents

Publication Publication Date Title
CN103372437B (en) The preparation method of copper-zinc system catalyst
CN103372441B (en) Preparation method of methanol synthesis catalyst
CN101791556B (en) Octanol hydrorefining catalyst and preparation method thereof
CN103372440B (en) Preparation method of methanol synthesis catalyst
CN107469813B (en) A kind of carried noble metal hydrogenation catalyst and its preparation and application
CN103372439B (en) The preparation method of catalst for synthesis of methanol
CN103372445B (en) Preparation method of copper-zinc series catalyst
CN108499564A (en) Catalyst in a kind of building-up process of methyl glycollate and preparation method thereof, application
CN103480377A (en) Preparation method of copper based catalyst for methanol synthesis
CN114054041B (en) Dimethyl oxalate hydrogenation catalyst, preparation method and application thereof
CN103372444B (en) A kind of preparation method of copper-based catalysts
CN105214672A (en) A kind of preparation method of the catalyst for methanol that maximizes
CN110833834A (en) Preparation method of supported ruthenium-copper bimetallic catalyst, product and application thereof
CN102059121A (en) Lanthanum-modified nickel-copper octanol hydrorefining catalyst and preparation and application thereof
CN102416325A (en) Preparation method of isobutyl ketone synthesis catalyst
CN112221509B (en) Preparation method of high-stability methanol synthesis catalyst
CN103801302B (en) A kind of preparation method containing copper zinc catalyst
CN112264026B (en) Preparation method of high-activity high-selectivity methanol synthesis catalyst
CN103372443B (en) Preparation method of copper-based catalyst
CN103801301B (en) A kind of preparation method of Cu-contained catalyst
CN107952490A (en) A kind of preparation method of silver-raney copper catalyst, catalyst prepared therefrom and application
CN101869845B (en) Catalyst for selective hydrogenation of dehydroisophytol for synthesizing isophytol
CN105964267B (en) A kind of Cu-series catalyst for synthesizing methanol and preparation method thereof
CN103372442B (en) Preparation method of copper-containing catalyst
CN103372438B (en) A kind of preparation method of Cu-contained catalyst

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant