CN101757943B - Catalyst for synthesizing methanol by hydrogenating carbon dioxide, preparation method and application thereof - Google Patents
Catalyst for synthesizing methanol by hydrogenating carbon dioxide, preparation method and application thereof Download PDFInfo
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- CN101757943B CN101757943B CN2009101632366A CN200910163236A CN101757943B CN 101757943 B CN101757943 B CN 101757943B CN 2009101632366 A CN2009101632366 A CN 2009101632366A CN 200910163236 A CN200910163236 A CN 200910163236A CN 101757943 B CN101757943 B CN 101757943B
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- methanol
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 197
- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 21
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002808 molecular sieve Substances 0.000 claims abstract description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 13
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- 238000000975 co-precipitation Methods 0.000 claims abstract description 3
- 238000007654 immersion Methods 0.000 claims abstract description 3
- 229910017518 Cu Zn Inorganic materials 0.000 claims abstract 2
- 229910017752 Cu-Zn Inorganic materials 0.000 claims abstract 2
- 229910017943 Cu—Zn Inorganic materials 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 22
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims description 4
- 238000004448 titration Methods 0.000 claims description 4
- -1 Hydrogen Chemical class 0.000 claims description 3
- 230000001588 bifunctional effect Effects 0.000 claims description 3
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000012495 reaction gas Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 4
- 229910004631 Ce(NO3)3.6H2O Inorganic materials 0.000 claims 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 2
- 239000000377 silicon dioxide Substances 0.000 claims 2
- 239000000126 substance Substances 0.000 abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 abstract description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000003245 coal Substances 0.000 description 9
- 238000011161 development Methods 0.000 description 8
- 230000018109 developmental process Effects 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- VODBHXZOIQDDST-UHFFFAOYSA-N copper zinc oxygen(2-) Chemical compound [O--].[O--].[Cu++].[Zn++] VODBHXZOIQDDST-UHFFFAOYSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010036590 Premature baby Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
Abstract
The invention discloses a catalyst for combining methanol by hydrogenating carbon dioxide and a preparation method thereof. A Cu-Zn-Ce-Zr-HZSM-5 catalyst for synthesizing the methanol by hydrogenating the carbon dioxide is prepared by using a HZSM-5 molecular sieve as a carrier, using cerium and zirconium as auxiliary agents and adopting a cocurrent coprecipitation immersion method, the mol ratio of Cu to Zn is 2-4: 1, the mol ratio of Ce to Zr is 1-3: 1, the content of Cu-Zn is 30-70% by weight, and the content of HZSM-5 is 5-50% by weight. The invention has the advantages of simple preparation technology of the catalyst, low energy consumption and production cost in a preparation process, high intensity of the catalyst and long service life, and is free from pollution. The economical efficiency of the utilization of CO2 in chemical industry can be obviously increased and the purposes of saving energy, reducing emission and changing the waste into the value are achieved.
Description
Technical field
The present invention relates to a kind of method of preparing methanol by hydrogenating carbon dioxide, further relate to raw catelyst that synthesizing methanol by hydrogenating carbon dioxide uses and its production and application.
Background technology
The raising of the development of World Economics, the increase of population and living standards of the people will constantly increase the demand of the energy (coal, oil, natural gas etc.), will cause the energy shortage situation serious day by day, world energy sources in short supply directly restricting development of global economy.Therefore the energy starved effective way is all actively being sought to solve by each state.Current, the energy of China is based on coal and oil, and the output of natural gas has very big growth in recent years.But the ratio that accounts in the energy total flow can be very not big.Particularly point out be China be in the world a few energy based on one of country of coal, coal accounts for about 3/4ths of energy aggregate consumption, because it is backward in technique, nearly 85% coal directly burns, coal directly burns, discharging a large amount of sulfide, nitrogen oxide, flue dust and carbon dioxide, is the present primary pollution source of China; In addition, along with economic development, the auto industry volume of production and marketing heightens, and its direct result is an automobile exhaust pollution.Though the oil product of petroleum refining is than the coal cleaning, the China's oil resource can not satisfy the demands, and also reduces gradually on the quality, brings very big difficulty for refining premium-type gasoline, diesel oil., natural gas quite limited and coal bed gas resource in view of rich coal resources, the petroleum resources of China distribute apart from can the center far and the pipe network system of China is very undeveloped, regenerative resource can not account for the very national conditions of great share in decades in total energy balance, from the STRATEGIES OF SUSTAINABLE DEVELOPMENT viewpoint, make rational use of resources, effective use of energy sources, seeking novel clean energy resource has become a urgent and great research topic.
A large amount of uses of fossil fuel are CO
2The main source of isothermal chamber gas, in all greenhouse gases, CO
2Contribution maximum to greenhouse effects is discharged into the CO in the atmosphere
23/4 cause by combustion of fossil fuel.According to the prediction of USDOE, the CO of annual row in atmosphere
2Measure and to reach 26 * 10 in 2100
9About t, CO
2Sharply riseing of discharge capacity having a strong impact on the original balance of the ecosystem.By catalyzed conversion with CO
2Be converted into chemical products and have multiple meanings such as environment, resource and economic benefit.Synthesizing methanol is all the time as CO
2A direction of catalyzed conversion research was being made progress aspect the improvement of catalyst performance, the catalytic mechanism research in recent years to some extent, but since the restriction of thermodynamical equilibrium, CO
2The conversion ratio and the selectivity of methyl alcohol also lower.Utilize the CO of industrial discharge
2The direct synthesizing methanol of catalytic hydrogenation not only can alleviate CO
2To the pollution of atmospheric environment, can also obtain broad-spectrum chemical products methyl alcohol, reached the purpose of changing waste into valuable, this process especially for large-scale steel plant, power plant, petrochemical plant, has more remarkable economic efficiency.Therefore, to CO
2Carry out effective recycling, make tellurian CO
2Realize benign cycle, can either alleviating energy crisis, can reduce the influence of greenhouse effects again, have the double meaning that solves energy security problem and environmental issue.
Methyl alcohol is important chemical material, also is a kind of fuel.The purposes of industrial methanol is very extensive, except that can be used as many organic good solvents, is mainly used in industrial production such as synthetic fibers, formaldehyde, plastics, medicine, agricultural chemicals, dyestuff, synthetic protein, is a kind of basic Organic Chemicals; Methyl alcohol can be made into the industrial of various different purposes or civil new-type fuel with gasoline (diesel oil) or the mixing of other materials.
The methyl alcohol general trend of market development was pretty good in recent years, the consumption figure continuous increasing of world methanol.Over more than 10 year, by CO
2The research of synthesizing methanol by hydrogenating is deeply being carried out always.Though because problems such as hydrogen source, catalyst, the not industrialization as yet at present of this technology was because of it both can solve CO
2Waste gas utilize problem, but the new way of Development and Production methyl alcohol again, so its correlative study receives concern more and more widely.Following methanol industry development prospect will be very wide, because consider from national economic development, energy strategy safety guarantee aspect, it is ripe to popularize the methanol fuel condition in an all-round way.
CO
2One of key of synthesizing methanol by hydrogenating reaction is a catalyst.Be used for this catalyst for reaction and develop prematurity still, majority is improved and is made by CO synthesizing methanol by hydrogenating catalyst system therefor, the also laboratory research fields that are confined to of relevant both at home and abroad report, research emphasis more concentrate on mostly reaction mechanism research, active component, carrier selection and investigate different preparation methods, reaction condition influence to catalyst performance.Because CO
2Chemical inertness and the unfavorable factor on the thermodynamics, make CO
2Be difficult to activating and reducing, exist that conversion ratio is low, accessory substance reaches the not high shortcoming of methyl alcohol selectivity more with the catalyst of conventional method preparation, therefore, study new catalyst, the reactivity and the selectivity of raising catalyst seem very necessary.
Summary of the invention
The objective of the invention is to adopt H
2With the abundant carbon resource CO of nature
2As unstripped gas, in fixed bed reactors, with CO
2Be converted into target product methyl alcohol, thereby obtain higher CO
2Conversion ratio and methyl alcohol selectivity.
The present invention finishes according to the following steps:
At first make a certain proportion of copper, zinc, cerium, zirconium solution, then and Na
2CO
3Precipitating reagent and stream are titrated in the suspension of HZSM-5 molecular sieve, with obtaining the methanol synthesis catalyst of not moulding after washing of precipitate, drying, the roasting, the catalyst granulation are placed in the fixed bed reactors, feed a certain proportion of H
2With CO
2, at pressure 1～5MPa, reaction just can generate methyl alcohol under the condition of temperature 200～300 degree.
Concrete processing step of the present invention is: 1. earlier with a certain proportion of Cu (NO
3)
23H
2O, Z
n(NO
3)
36H
2O, Ce (NO
3)
36H
2O and Zr (NO
3)
45H
2O wiring solution-forming A soluble in water is again with Na
2CO
3Wiring solution-forming B soluble in water, then solution A and solution B and stream are titrated among the suspension C of HZSM-5 molecular sieve, keep mixing speed 300r/min, dropping temperature is 20 ℃～80 ℃, dropping time 60min～120min, the rate of addition of regulating A and B solution in the titration process is 7 with the pH value that keeps system, drip follow-up continuous stirring 30min fully, filter then, washing is until no sodium ion, dry 12h～24h under 100～130 ℃, obtain the presoma of catalyst, presoma is following 200 ℃～800 ℃ roasting 3h～8h of air atmosphere, obtains methanol synthesis catalyst; 2. catalyst is carried out compressing tablet, granulation, when synthesizing methanol by hydrogenating carbon dioxide reacts, select 20～40 purpose catalyst to pack in the fixed bed reactors, with containing volume ratio 10%H
2Hydrogen nitrogen mixed gas bifunctional catalyst is carried out temperature programmed reduction, the control heating rate is 1 ℃/min, catalyst switches to raw material reaction gas H then at 300 ℃ of constant temperature reduction 8h
2With CO
2, at pressure 1.0～5.0MPa, 200～300 ℃ of temperature, hydrogen-carbon ratio H
2/ CO
2Carry out the methyl alcohol synthetic reaction under=1.0～5.0 the condition.
In above-mentioned technology, during the preparation methanol synthesis catalyst, during the preparation methanol synthesis catalyst, the mol ratio of Ce/Zr is 6/4, and the mol ratio of Ce/Zr is 1: 1, when the mass content of HZSM-5 is 30% preparation methanol synthesis catalyst, temperature of precipitation is 70 ℃, drips time 120min, needs to continue to stir 30min after dripping off, aging 120min, 300 ℃ of sintering temperatures.
Traditional synthesizing methanol by hydrogenating carbon dioxide catalyst all is at synthesising gas systeming carbinol CuO-ZnO-Al
2O
3Carry out modification on the catalyst, the selectivity of prepared catalyst carbon dioxide conversion and methyl alcohol is low, a large amount of CO gases of by-product, and the easy inactivation of catalyst, and the selectivity and the CO of the prepared catalyst methyl alcohol of the present invention
2Conversion ratio all is significantly improved.
Compared with prior art, the present invention has the following advantages:
1. adopt cerium zirconium sosoloid to do auxiliary agent and HZSM-5 molecular sieve and do carrier and can increase the specific area of catalyst and the decentralization of copper, improved CO greatly
2Conversion ratio and the selectivity of methyl alcohol; Obtain purposes chemical products methyl alcohol very widely, increased CO
2The economy of chemical utilization reaches the purpose that changes harmful to treasure, and especially produces CO for richness
2With the refinery that has than the sufficient hydrogen source, this process has remarkable economic efficiency;
2. adopt co-precipitation immersion process for preparing catalyst have that flow process is short, energy consumption is low, pollution-free, the advantage that production cost is low helps suitability for industrialized production;
3. catalyst component is simple, adopts cerium zirconium sosoloid to do the chain carrier that auxiliary agent can be stablized lower valency, thereby improves CO
2The stability of hydrogenation reaction improves catalyst activity, prolongs life of catalyst;
4. adopting the HZSM-5 molecular sieve to do the decentralization that carrier can increase the specific area of catalyst and copper can utilize it to select the yield that the type effect increases methyl alcohol again;
5. the fixed bed reaction technological process is short, simple to operate.
The specific embodiment
Further specify flesh and blood of the present invention with example below, but content of the present invention is not limited to this.
Concrete processing step of the present invention is: 1. earlier with a certain proportion of Cu (NO
3)
23H
2O, Zn (NO
3)
36H
2O, Ce (NO
3)
36H
2O and Zr (NO
3)
45H
2O wiring solution-forming A soluble in water is again with Na
2CO
3Wiring solution-forming B soluble in water, then solution A and solution B and stream are titrated among the suspension C of HZSM-5 molecular sieve, keep mixing speed 300r/min, dropping temperature is 20 ℃～80 ℃, dropping time 60min～120min, the rate of addition of regulating A and B solution in the titration process is 7 with the pH value that keeps system, drip follow-up continuous stirring 30min fully, filter then, washing is until no sodium ion, dry 12h～24h under 100～130 ℃, obtain the presoma of catalyst, presoma is following 200 ℃～800 ℃ roasting 3h～8h of air atmosphere, obtains methanol synthesis catalyst; 2. catalyst is carried out compressing tablet, granulation, when synthesizing methanol by hydrogenating carbon dioxide reacts, select 20～40 purpose catalyst to pack in the fixed bed reactors, with containing volume ratio 10%H
2Hydrogen nitrogen mixed gas bifunctional catalyst is carried out temperature programmed reduction, the control heating rate is 1 ℃/min, catalyst switches to raw material reaction gas H then at 300 ℃ of constant temperature reduction 8h
2With CO
2, at pressure 1.0～5.0MPa, 200～300 ℃ of temperature, hydrogen-carbon ratio H
2/ CO
2Carry out the methyl alcohol synthetic reaction under=1.0～5.0 the condition.
In above-mentioned technology, during the preparation methanol synthesis catalyst, during the preparation methanol synthesis catalyst, the mol ratio of Ce/Zr is 6/4, and the mol ratio of Ce/Zr is 1: 1, and the mass content of HZSM-5 is 30% of a catalyst total amount.During the preparation methanol synthesis catalyst, temperature of precipitation is 70 ℃, drips time 120min, needs to continue to stir 30min after dripping off, aging 120min, 300 ℃ of sintering temperatures.
The catalyst that makes according to the method described above carries out active testing in fixed bed reactors.
Embodiment 1
(1) implementation condition
Select the copper zinc atom for use than being that 6/4 CuO-ZnO is as catalyst.Industry CO
2And H
2Be reactor feed gas (CO
2/ H
2=1/3), but the temperature programmed control fixed bed reactors, operating temperature is 250 ℃, and operating pressure is 3.0Mpa, and loaded catalyst 1g, hydrogen gas flow are 22.5ml/min, CO
2Gas flow is 7.5ml/min.
(2) result of implementation
CO
2The selectivity of the methyl alcohol that the direct reaction result of hydrogenation obtains is 35.4%, CO
2Conversion ratio is 11%.
Embodiment 2
(1) implementation condition
Select the copper zinc atom for use than be 6/4 CuO-ZnO/HZSM-5 (Si/Al=25) as catalyst, wherein HZSM-5 content is 30% (wt%).Industry CO
2And H
2Be reactor feed gas (CO
2/ H
2=1/3), but the temperature programmed control fixed bed reactors, operating temperature is 250 ℃, and operating pressure is 3.0Mpa, and loaded catalyst 1g, hydrogen gas flow are 22.5ml/min, CO
2Gas flow is 7.5ml/min.
(2) result of implementation
CO
2The selectivity of the methyl alcohol that the direct reaction result of hydrogenation obtains is 38%, CO
2Conversion ratio is 15%.
Embodiment 3
(1) implementation condition
Select the copper zinc atom for use than be 6/4 CuO-ZnO/HZSM-5 (Si/Al=38) as catalyst, wherein HZSM-5 content is 30% (wt%).Industry CO
2And H
2Be reactor feed gas (CO
2/ H
2=1/3), but the temperature programmed control fixed bed reactors, operating temperature is 250 ℃, and operating pressure is 3.0Mpa, and loaded catalyst 1g, hydrogen gas flow are 22.5ml/min, CO
2Gas flow is 7.5ml/min.
(2) result of implementation
CO
2The selectivity of the methyl alcohol that the direct reaction result of hydrogenation obtains is 43%, CO
2Conversion ratio is 17%.
Embodiment 4
(1) implementation condition
Select the copper zinc atom for use than be 6/4 CuO-ZnO/HZSM-5 (Si/Al=50) as catalyst, wherein HZSM-5 content is 50% (wt%).Industry CO
2And H
2Be reactor feed gas (CO
2/ H
2=1/3), but the temperature programmed control fixed bed reactors, operating temperature is 250 ℃, and operating pressure is 3.0Mpa, and loaded catalyst 1g, hydrogen gas flow are 22.5ml/min, CO
2Gas flow is 7.5ml/min.
(2) result of implementation
CO
2The selectivity of the methyl alcohol that the direct reaction result of hydrogenation obtains is 41%, CO
2Conversion ratio is 15.7%.
Embodiment 5
(1) implementation condition
Select for use the copper zinc atom than the CuO-ZnO-CeO that is 6/4
2-ZrO
2/ HZSM-5 (Si/Al=25) is as catalyst, and wherein HZSM-5 content is 30% (wt%), and copper zinc oxide content is 56% (wt%), and the cerium atomic percent zirconium is 1/1.Industry CO
2And H
2Be reactor feed gas (CO
2/ H
2=1/3), but the temperature programmed control fixed bed reactors, operating temperature is 250 ℃, and operating pressure is 3.0Mpa, and loaded catalyst 1g, hydrogen gas flow are 22.5ml/min, CO
2Gas flow is 7.5ml/min.
(2) result of implementation
CO
2The selectivity of the methyl alcohol that the direct reaction result of hydrogenation obtains is 46.7%, CO
2Conversion ratio is 22.4%
Embodiment 6
(1) implementation condition
Select for use the copper zinc atom than the CuO-ZnO-CeO that is 6/4
2-ZrO
2/ HZSM-5 (Si/Al=38) is as catalyst, and wherein HZSM-5 content is 30% (wt%), and copper zinc oxide content is 56% (wt%), and the cerium atomic percent zirconium is 1/1.Industry CO
2And H
2Be reactor feed gas (CO
2/ H
2=1/3), but the temperature programmed control fixed bed reactors, operating temperature is 250 ℃, and operating pressure is 3.0Mpa, and loaded catalyst 1g, hydrogen gas flow are 22.5ml/min, CO
2Gas flow is 7.5ml/min.
(2) result of implementation
CO
2The selectivity of the methyl alcohol that the direct reaction result of hydrogenation obtains is 51.8%, CO
2Conversion ratio is 25.6%
Embodiment 7
(1) implementation condition
Select for use the copper zinc atom than the CuO-ZnO-CeO that is 6/4
2-ZrO
2/ HZSM-5 (Si/Al=50) is as catalyst, and wherein HZSM-5 content is 30% (wt%), and copper zinc oxide content is 56% (wt%), and the cerium atomic percent zirconium is 1/1.Industry CO
2And H
2Be reactor feed gas (CO
2/ H
2=1/3), but the temperature programmed control fixed bed reactors, operating temperature is 250 ℃, and operating pressure is 3.0Mpa, and loaded catalyst 1g, hydrogen gas flow are 22.5ml/min, CO
2Gas flow is 7.5ml/min.
(2) result of implementation
CO
2The selectivity of the methyl alcohol that the direct reaction result of hydrogenation obtains is 50.6%, CO
2Conversion ratio is 24.1%.
Claims (7)
1. the catalyst of a synthesizing methanol by hydrogenating carbon dioxide, it is characterized in that: with the HZSM-5 molecular sieve make carrier, the cerium zirconium is made auxiliary agent, adopt and flow the co-precipitation immersion process for preparing and go out synthesizing methanol by hydrogenating carbon dioxide Cu-Zn-Ce-Zr-HZSM-5 catalyst, wherein the mol of Cu/Zn ratio is 2～4: 1, the mol ratio of Ce/Zr is 1～3: 1, the Cu-Zn mass content is 30%～70%, and the mass content of HZSM-5 is 5%～50%.
2. a synthesizing methanol by hydrogenating carbon dioxide Preparation of catalysts method is characterized in that comprising the steps:
Earlier with Cu (NO
3)
2.3H
2O, Zn (NO
3)
3.6H
2O, Ce (NO
3)
3.6H
2O and Zr (NO
3)
4.5H
2O wiring solution-forming A soluble in water is again with Na
2CO
3Wiring solution-forming B soluble in water, then solution A and solution B and stream are titrated among the suspension C of HZSM-5 molecular sieve, keep mixing speed 300r/min, dropping temperature is 20 ℃～80 ℃, dropping time 60min～120min, keeping the pH value of system in the titration process is 7～8, drip follow-up continuous stirring 30min fully, filter then, wash until no sodium ion, dry 12h～24h under 100～130 ℃, obtain the presoma of catalyst, presoma is following 200 ℃～800 ℃ roasting 3h～8h of air atmosphere, obtains methanol synthesis catalyst.
3. synthesizing methanol by hydrogenating carbon dioxide Preparation of catalysts method according to claim 2, it is characterized in that: during the preparation methanol synthesis catalyst, the mol ratio of Ce/Zr is 6/4, the mass content of HZSM-5 is 30%, temperature of precipitation is 70 ℃, drips time 120min, needs to continue to stir 30min after dripping off, aging 120min, 300 ℃ of sintering temperatures.
4. synthesizing methanol by hydrogenating carbon dioxide Preparation of catalysts method according to claim 2 is characterized in that: used HZSM-5 molecular sieve is that silica alumina ratio is 25,38 and 50 molecular sieve.
5. the preparation method of a synthesizing methanol by hydrogenating carbon dioxide, its feature comprises the steps:
1. earlier with a certain proportion of Cu (NO
3)
2.3H
2O, Zn (NO
3)
3.6H
2O, Ce (NO
3)
3.6H
2O and Zr (NO
3)
4.5H
2O wiring solution-forming A soluble in water is again with Na
2CO
3Wiring solution-forming B soluble in water, then solution A and solution B and stream are titrated among the suspension C of HZSM-5 molecular sieve, keep mixing speed 300r/min, dropping temperature is 20 ℃～80 ℃, dropping time 60min～120min, keeping the pH value of system in the titration process is 7～8, drip follow-up continuous stirring 30min fully, filter then, wash until no sodium ion, dry 12h～24h under 100～130 ℃, obtain the presoma of catalyst, presoma is following 200 ℃～800 ℃ roasting 3h～8h of air atmosphere, obtains methanol synthesis catalyst;
2. catalyst is carried out compressing tablet, granulation, when synthesizing methanol by hydrogenating carbon dioxide reacts, select 20～40 purpose catalyst to pack in the fixed bed reactors, with containing volume ratio 10%H
2Hydrogen nitrogen mixed gas bifunctional catalyst is carried out temperature programmed reduction, the control heating rate is 1 ℃/min, catalyst switches to raw material reaction gas H then at 300 ℃ of constant temperature reduction 8h
2With CO
2, at pressure 1.0～5.0MPa, 200～300 ℃ of temperature, hydrogen-carbon ratio H
2/ CO
2Carry out the methyl alcohol synthetic reaction under=1.0～5.0 the condition.
6. the preparation method of synthesizing methanol by hydrogenating carbon dioxide according to claim 5, it is characterized in that: during the preparation methanol synthesis catalyst, the mol ratio of Ce/Zr is 6/4, the mass content of HZSM-5 is 30%, temperature of precipitation is 70 ℃, drips time 120min, needs to continue to stir 30min after dripping off, aging 120min, 300 ℃ of sintering temperatures.
7. the preparation method of synthesizing methanol by hydrogenating carbon dioxide according to claim 5, it is characterized in that: used HZSM-5 molecular sieve is that silica alumina ratio is 25,38 and 50 molecular sieve.
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| CN102600851A (en) * | 2012-03-05 | 2012-07-25 | 昆明理工大学 | Preparation method of catalyst for synthesizing methanol by carbon dioxide hydrogenation |
| CN106311249A (en) * | 2015-07-02 | 2017-01-11 | 中国科学院大连化学物理研究所 | Catalyst for synthesis of methanol by hydrogenation of carbon dioxide at normal pressure as well as preparation method and application thereof |
| CN106345515B (en) * | 2016-07-31 | 2018-07-06 | 合肥学院 | A kind of preparation method of Ce-Zn-Co-Cu mixing and dopings ZSM-5 zeolite molecular sieve |
| CN106390978B (en) * | 2016-09-14 | 2019-04-09 | 中国科学院大连化学物理研究所 | A kind of high temperature resistant synthesizing methanol by hydrogenating carbon dioxide catalyst and its preparation and application |
| CN110833843B (en) * | 2018-08-16 | 2021-03-16 | 中国科学院大连化学物理研究所 | Catalyst for synthesizing methanol by carbon dioxide hydrogenation |
| CN113617296B (en) * | 2020-05-08 | 2023-08-25 | 北京机械设备研究所 | Carbon dioxide catalytic hydrogenation system and method |
| CN115770612A (en) * | 2022-12-06 | 2023-03-10 | 中国科学院青岛生物能源与过程研究所 | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method and application thereof |
| CN116393160A (en) * | 2023-04-03 | 2023-07-07 | 浙江大学 | Catalytic CO 2 Preparation method of Cu-Zn-Al-molecular sieve catalyst for preparing methanol by hydrogenation |
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| EP1010464B1 (en) * | 1998-12-17 | 2004-09-22 | Agency Of Industrial Science And Technology | Palladium ceria supported catalyst and process for the synthesis of methanol |
| CN101513615A (en) * | 2009-03-28 | 2009-08-26 | 大连理工大学 | Carbon dioxide-synthesized methanol catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1010464B1 (en) * | 1998-12-17 | 2004-09-22 | Agency Of Industrial Science And Technology | Palladium ceria supported catalyst and process for the synthesis of methanol |
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