CN105498756B - The catalyst of hydrogenation of carbon dioxide methanol - Google Patents
The catalyst of hydrogenation of carbon dioxide methanol Download PDFInfo
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- CN105498756B CN105498756B CN201410498074.2A CN201410498074A CN105498756B CN 105498756 B CN105498756 B CN 105498756B CN 201410498074 A CN201410498074 A CN 201410498074A CN 105498756 B CN105498756 B CN 105498756B
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Abstract
The preparation method of catalyst, catalyst and the synthetic method of methanol the present invention relates to hydrogenation of carbon dioxide methanol, mainly solve the problems, such as that the catalyst activity of hydrogenation of carbon dioxide methanol in the prior art is not high, catalyst of the invention by using hydrogenation of carbon dioxide methanol, in terms of mass parts, including following components：(1) 85~99 parts of carrier；(2) technical solution selected from least one of Pd, Pt or Cu 1~15 part of active element preferably solves the technical problem, available in the industrial production of methanol.
Description
Technical field
The preparation method of catalyst, catalyst and the synthesis side of methanol the present invention relates to hydrogenation of carbon dioxide methanol
Method.
Background technology
With CO in air2The increase of concentration, its adverse effect that may be brought cause national governments and scientific research personnel
Extensive concern, reduce CO2The research effectively recycled to it while discharge becomes focus of attention.Methanol conduct
One of basic organic, and a kind of important clean fuel, therefore recycle the mistake of synthesizing methanol by hydrogenating carbon dioxide
Journey is subject to widely studied.And the research and development of catalyst are to realize the industrialized key of synthesizing methanol by hydrogenating carbon dioxide.
Copper-based catalysts are the dominant catalysts of current carbon dioxide direct hydrogenation reaction, and majority is in synthesising gas systeming carbinol
Developed on the basis of catalyst.Its main active component is divided into Cu or Cu/ZnO, but most researchs are all by activity
Component CuO/ZnO is supported on other carriers, such as SiO2、ZrO2、Al2O3、TiO2Deng, then helped by adding other into catalyst
Agent is modified, to further improve catalyst activity.Such as patent CN103263926, (synthesizing methanol by hydrogenating carbon dioxide is catalyzed
Agent and preparation method and application), a kind of efficient copper-based catalysts are disclosed, it is made of oxide, and in terms of metal, various metals rub
You are at ratio：[n(Cu)+n(Zn)+n(MA)]:[n (Al)+n (MB)]=2-15, n (Cu):N (Zn)=0.5-4, n (MA):n(Zn)
=0-1, n (MB):N (Al)=0-9；Wherein MA represents monovalence or bivalent metal ion, and MB represents trivalent or quadrivalent metallic ion,
But the activity of the catalyst need to be improved.
The content of the invention
The first technical problem to be solved by the present invention is to solve the catalysis of hydrogenation of carbon dioxide methanol in the prior art
The problem of agent activity is not high, there is provided a kind of catalyst of new hydrogenation of carbon dioxide methanol, the catalyst are active high
Feature.
The second technical problem to be solved by the present invention is the preparation using catalyst described in one of above-mentioned technical problem
Method.
The third technical problem to be solved by the present invention uses the conjunction of one of the above-mentioned technical problem methanol of the catalyst
Into method.
To solve one of above-mentioned technical problem, technical scheme is as follows：The catalysis of hydrogenation of carbon dioxide methanol
Agent, in terms of mass parts, including following components：
(1) carrier, 85~99 parts
(2) selected from least one of Pd, Pt or Cu active element, 1~15 part.
In above-mentioned technical proposal, the carrier preferably is selected from SiO2、Al2O3、In2O3、TiO2And ZrO2At least one of, institute
State carrier and be such as, but not limited to In2O3、ZrO2、In2O3And ZrO2, when the carrier is In2O3And ZrO2When, ZrO2And In2O3's
Mass ratio is preferably≤1.In is used when at the same time2O3And ZrO2When, there is synergistic effect in terms of catalyst activity is improved.
To solve the two of above-mentioned technical problem, technical scheme is as follows：Any one of one of above-mentioned technical problem
The preparation method of catalyst, comprises the following steps described in the technical solution：
A, the compound solution of the desired amount of active element is mixed with the carrier；
B, drying；
C, roast.
Active metallic element exists with compound state in the catalyst that above-mentioned preparation method obtains, in order to make storage more stable,
Or use and be more convenient, preferably further included after step c：D, active element is reduced to simple substance from compound state.
In above-mentioned technical proposal, when the carrier uses In at the same time2O3And ZrO2When, it is prepared into using following four methods
The carrier arrived is suitable for the present invention, but to make the carrier that Zr and In salt-mixture co-precipitation preparation methods obtain with alkali or basic salt
Best results, In2O3And ZrO2Synergistic effect it is most prominent：
Method one：By aequum In2O3Powder and ZrO2Powder mechanical mixture obtains carrier；
Method two：By the desired amount of In2O3Mixed with aequum Zr compound solutions, dry, roasting obtains carrier；
Method three：By the desired amount of ZrO2Mixed with aequum In compound solutions, dry, roasting obtains carrier；
Method four：It is precipitating reagent with alkali or basic salt, makes Zr and In mixing salt solutions that co-precipitation occur and obtain carrier forerunner
Body, dry, roasting obtains carrier.
Zr compounds described in the above method two or method three, In compound Zr and In salt-mixture preferably nitrates, such as
Zirconium nitrate, zirconyl nitrate.
As the citing of method two, such as by the desired amount of In2O3Mixed with aequum zirconyl nitrate or zirconium nitrate solution,
When standing 1~24 is small, when drying 10-24 is small at 70-100 DEG C, roasted when roasting 3-5 is small at dried 400-600 DEG C of sample
Obtain carrier.
As the citing of method three, such as by the desired amount of In2O3Mixed with aequum zirconyl nitrate or zirconium nitrate solution,
When standing 1~24 is small, when drying 10-24 is small at 70-100 DEG C, roasted when roasting 3-5 is small at dried 400-600 DEG C of sample
Obtain carrier.
As the citing of method four, for example, by the desired amount of zirconium nitrate and indium nitrate be configured to metal total concentration for 0.5~
The mixed solution of 1.5mol/L.It is 0.5~1.5mol/L by mixed liquor and concentration under conditions of heating keeps 60-70 DEG C of constant temperature
Na2CO3Solution carries out co-precipitation.It is 7-8 persistently to be stirred in precipitation process and keep pH value of solution.Room temperature after the completion of titration
When aging 6~24 is small, filtering, washing to no sodium ion.When sediment dry 10-24 at 70-100 DEG C is small, dried sample
When roasting 3-5 is small at 400-600 DEG C of product, up to the carrier.
In above-mentioned technical proposal, drying temperature is preferably 100-120 DEG C in the step b.
In above-mentioned technical proposal, when drying time is preferably 10-24 small in the step b.
It is that the temperature roasted in the step c is preferably 400-600 DEG C in above-mentioned technical proposal.
In above-mentioned technical proposal, when the time roasted in the step c is preferably 3-5 small.
In above-mentioned technical proposal, the reducing agent used in the step d is not particularly limited, for example, can use hydrogen,
Hydrazine hydrate, formic acid and its at least one of salt or formaldehyde are used as reducing agent.When using hydrogen as reducing agent, in order to make also
Former process lenitively carries out, and can use the gas dilution hydrogen such as nitrogen, helium.Such as the condition of reduction can be：With containing 3~
10% (volume) H2Nitrogen hydrogen mixed gas 180-230 DEG C reduce 1-3 it is small when.
To solve the three of above-mentioned technical problem, technical scheme is as follows：The synthetic method of methanol, with carbon dioxide
It is raw material with hydrogen, carries out reaction preparation in the presence of catalyst described in any one technical solution of one of above-mentioned technical problem
Methanol.
For the synthetic reaction of methanol, key of the invention is the selection of catalyst, and other process conditions are for example reacted
Temperature, reaction pressure, raw material proportioning, air speed etc., those skilled in the art can rationally determine.As an example, reaction temperature
It can be 200~370 DEG C；Reaction pressure can be 2~6-MPa；The volume ratio of hydrogen and carbon dioxide can be 2~4；Raw material
Air speed can be 3000~30000mL/ (hg).It is beneficial to control to make hydrogenation reaction steady, or is conducive to improve choosing
Selecting property, can also add inert diluent, such as inert diluent can be but not limited to nitrogen, C1~C4Saturated hydrocarbons etc..
The catalyst of the present invention is when being used for hydrogenation of carbon dioxide methanol, and the high conversion rate of carbon dioxide is up to 16%, methanol
High selectivity achieves beneficial technique effect, available in the industrial production of methanol up to 75%.
Below by embodiment, the present invention is described in detail：
Embodiment
【Embodiment 1】
Catalyst preparation
By the ZrO of 500 grams of palladium nitrate aqueous solution (containing 25 grams of palladium) and 975 gram of 100~120 mesh2Powder mixes, quiet at room temperature
Put 12 it is small when, at 110 DEG C it is dry 12 it is small when, then when roasting 4 is small at 500 DEG C of air atmosphere, natural cooling, before obtaining catalyst
Body.In 16MPa lower sheetings, the particle for crushing, being sieved into 40-60 mesh, then in the hydrogen nitrogen mixture of hydrogen content 5v%
Catalyst is obtained when 200 DEG C of reductase 12s are small in atmosphere.
Methanol-fueled CLC
The synthesis of methanol carries out in fixed bed reactors.Methanol synthesis reaction condition：Reaction temperature is 270 DEG C, reaction
Pressure 4MPa, hydrogen:Carbon dioxide:Nitrogen volume ratio is 60:20:20, GHSV=15000mL/ (hg).
For ease of comparing, by the composition of catalyst, preparation process and methanol synthesis reaction, the results are shown in table 1.
【Embodiment 2】
Catalyst preparation
By the In of 500 grams of palladium nitrate aqueous solution (containing 25 grams of palladium) and 975 gram of 100~120 mesh2O3Powder mixes, quiet at room temperature
Put 12 it is small when, at 110 DEG C it is dry 12 it is small when, then when roasting 4 is small at 500 DEG C of air atmosphere, natural cooling, before obtaining catalyst
Body.In 16MPa lower sheetings, the particle for crushing, being sieved into 40-60 mesh, then in the hydrogen nitrogen mixture of hydrogen content 5v%
Catalyst is obtained when 200 DEG C of reductase 12s are small in atmosphere.
Methanol-fueled CLC
The synthesis of methanol carries out in fixed bed reactors.Methanol synthesis reaction condition：Reaction temperature is 270 DEG C, reaction
Pressure 4MPa, hydrogen:Carbon dioxide:Nitrogen volume ratio is 60:20:20, GHSV=15000mL/ (hg).
For ease of comparing, by the composition of catalyst, preparation process and methanol synthesis reaction, the results are shown in table 1.
【Embodiment 3】
It is prepared by carrier
By the ZrO of 100~120 mesh2The In of powder and 100~120 mesh2O3Powder is according to 0.5:1 mass ratio mixing conduct
Carrier.
Catalyst preparation
Palladium nitrate aqueous solution 500 grams (containing 25 grams of palladium) is mixed with 975 grams of carriers, when standing 12 is small at room temperature, at 110 DEG C
It is dry 12 it is small when, then when roasting 4 is small at 500 DEG C of air atmosphere, natural cooling, obtains catalyst precarsor.Pushed in 16MPa
Piece, the particle for crushing, being sieved into 40-60 mesh, then 200 DEG C of reductase 12s in the hydrogen nitrogen mixture atmosphere of hydrogen content 5v%
Hour obtains catalyst.
Methanol-fueled CLC
The synthesis of methanol carries out in fixed bed reactors.Methanol synthesis reaction condition：Reaction temperature is 270 DEG C, reaction
Pressure 4MPa, hydrogen:Carbon dioxide:Nitrogen volume ratio is 60:20:20, GHSV=15000mL/ (hg).
For ease of comparing, by the composition of catalyst, preparation process and methanol synthesis reaction, the results are shown in table 1.
【Embodiment 4】
It is prepared by carrier
According to ZrO2With In2O3Mass ratio is 0.5:1, by the In of 1000 gram of 100~120 mesh2O3Powder containing 45w% with aoxidizing
The zirconyl nitrate solution mixing of zirconium, be stored at room temperature 12 it is small when, stir lower 90 DEG C of dryings 12 it is small when, at dried 500 DEG C of sample
Roast 4 it is small when roast to obtain carrier.
Catalyst preparation
Palladium nitrate aqueous solution 500 grams (containing 25 grams of palladium) is mixed, room temperature with 100~120 mesh powder of 975 grams of above-mentioned carriers
It is lower stand 12 it is small when, at 110 DEG C it is dry 12 it is small when, then when roasting 4 is small at 500 DEG C of air atmosphere, natural cooling, is catalyzed
Agent precursor.In 16MPa lower sheetings, the particle for crushing, being sieved into 40-60 mesh, then mixed in the hydrogen nitrogen of hydrogen content 5v%
Close and obtain catalyst when 200 DEG C of reductase 12s are small in atmosphere.
Methanol-fueled CLC
The synthesis of methanol carries out in fixed bed reactors.Methanol synthesis reaction condition：Reaction temperature is 270 DEG C, reaction
Pressure 4MPa, hydrogen:Carbon dioxide:Nitrogen volume ratio is 60:20:20, GHSV=15000mL/ (hg).
For ease of comparing, by the composition of catalyst, preparation process and methanol synthesis reaction, the results are shown in table 1.
【Embodiment 5】
It is prepared by carrier
According to ZrO2With In2O3Mass ratio is 0.5:1, by the ZrO of 500 gram of 100~120 mesh2Powder and 4500 grams of indium nitrates
Aqueous solution (contains In2O31000 grams of meter) mixing, be stored at room temperature 12 it is small when, stir lower 90 DEG C of dryings 12 it is small when, dried sample
Roast to obtain carrier when roasting 4 is small at 500 DEG C.
Catalyst preparation
Palladium nitrate aqueous solution 500 grams (containing 25 grams of palladium) is mixed, room temperature with 100~120 mesh powder of 975 grams of above-mentioned carriers
It is lower stand 12 it is small when, at 110 DEG C it is dry 12 it is small when, then when roasting 4 is small at 500 DEG C of air atmosphere, natural cooling, is catalyzed
Agent precursor.In 16MPa lower sheetings, the particle for crushing, being sieved into 40-60 mesh, then mixed in the hydrogen nitrogen of hydrogen content 5v%
Close and obtain catalyst when 200 DEG C of reductase 12s are small in atmosphere.
Methanol-fueled CLC
The synthesis of methanol carries out in fixed bed reactors.Methanol synthesis reaction condition：Reaction temperature is 270 DEG C, reaction
Pressure 4MPa, hydrogen:Carbon dioxide:Nitrogen volume ratio is 60:20:20, GHSV=15000mL/ (hg).
For ease of comparing, by the composition of catalyst, preparation process and methanol synthesis reaction, the results are shown in table 1.
【Embodiment 6】
It is prepared by carrier
According to ZrO2And In2O3Mass ratio be 0.5:1 prepares the zirconyl nitrate nitre that metallic element total concentration is 0.9mol/L
Sour indium mixed aqueous solution.Under conditions of heating keeps 65 DEG C of constant temperature, the Na by mixed aqueous solution with concentration for 1mol/L2CO3It is water-soluble
Liquid carries out co-precipitation.The pH of mixed liquor is 7-8 after maintenance cocurrent during co-precipitation.Mixed liquor room temperature after cocurrent
When aging 12 is small, filtering, washing to no sodium ion.Filter cake at 90 DEG C it is dry 12 it is small when, roast at dried 500 DEG C of sample
4 it is small when, up to the carrier.
Catalyst preparation
Palladium nitrate aqueous solution 500 grams (containing 25 grams of palladium) is mixed with 975 grams of above-mentioned 100~120 mesh powder of carrier, at room temperature
Stand 12 it is small when, at 110 DEG C it is dry 12 it is small when, then when roasting 4 is small at 500 DEG C of air atmosphere, natural cooling, obtains catalyst
Precursor.In 16MPa lower sheetings, the particle for crushing, being sieved into 40-60 mesh, then mixed in the hydrogen nitrogen of hydrogen content 5v%
Catalyst is obtained when 200 DEG C of reductase 12s are small in atmosphere.
Methanol-fueled CLC
The synthesis of methanol carries out in fixed bed reactors.Methanol synthesis reaction condition：Reaction temperature is 270 DEG C, reaction
Pressure 4MPa, hydrogen:Carbon dioxide:Nitrogen volume ratio is 60:20:20, GHSV=15000mL/ (hg).
For ease of comparing, by the composition of catalyst, preparation process and methanol synthesis reaction, the results are shown in table 1.
【Embodiment 7】
It is prepared by carrier
According to ZrO2And In2O3Mass ratio be 0.8:1 prepares the zirconyl nitrate nitric acid that metallic element total concentration is 1mol/L
Indium mixed aqueous solution.Under conditions of heating keeps 65 DEG C of constant temperature, the Na by mixed aqueous solution with concentration for 1mol/L2CO3Aqueous solution
Carry out co-precipitation.The pH of mixed liquor is 7-8 after maintenance cocurrent during co-precipitation.Mixed liquor room temperature after cocurrent is old
Change 12 it is small when, filtering, washing is to no sodium ion.Filter cake at 80 DEG C it is dry 12 it is small when, roast 3 at dried 500 DEG C of sample
Hour, up to the carrier.
Catalyst preparation
Palladium nitrate aqueous solution 500 grams (containing 50 grams of palladium) is mixed with 950 grams of above-mentioned 100~120 mesh powder of carrier, at room temperature
Stand 12 it is small when, at 110 DEG C it is dry 12 it is small when, then when roasting 4 is small at 400 DEG C of air atmosphere, natural cooling, obtains catalyst
Precursor.In 16MPa lower sheetings, the particle for crushing, being sieved into 40-60 mesh, then mixed in the hydrogen nitrogen of hydrogen content 5v%
Catalyst is obtained when 200 DEG C of reductase 12s are small in atmosphere.
Methanol-fueled CLC
The synthesis of methanol carries out in fixed bed reactors.Methanol synthesis reaction condition：Reaction temperature is 270 DEG C, reaction
Pressure 4MPa, hydrogen:Carbon dioxide:Nitrogen volume ratio is 60:20:20, GHSV=15000mL/ (hg).
For ease of comparing, by the composition of catalyst, preparation process and methanol synthesis reaction, the results are shown in table 1.
Table 1
Note：Methanol synthesis reaction condition：Reaction temperature is 270 DEG C, reaction pressure 4MPa, hydrogen:Carbon dioxide:Nitrogen
Product is than being 60:20:20, GHSV=15000mL/ (hg).
Claims (10)
1. the catalyst of hydrogenation of carbon dioxide methanol, in terms of mass parts, including following components：
(1) carrier, 85~99 parts；Wherein, the carrier uses In2O3And ZrO2；
(2) selected from least one of Pd, Pt active element, 1~15 part；
Wherein, the carrier ZrO2And In2O3Mass ratio≤1.
2. catalyst according to claim 1, it is characterized in that the carrier also contains SiO2、Al2O3And TiO2In at least
It is a kind of.
3. the preparation method of catalyst described in claim 1, comprises the following steps：
A, the compound solution of the desired amount of active element is mixed with the carrier；
B, drying；
C, roast.
4. preparation method according to claim 3, it is characterized in that being further included after step c：
D, active element is reduced to simple substance from compound state.
5. preparation method according to claim 3, it is characterized in that drying temperature is 100-120 DEG C in the step b.
6. preparation method according to claim 3, it is characterized in that when drying time is 10-24 small in the step b.
7. preparation method according to claim 3, it is characterized in that the temperature roasted in the step c is 400-600 DEG C.
8. preparation method according to claim 3, it is characterized in that when the time roasted in the step c is 3-5 small.
9. preparation method according to claim 4, it is characterized in that the step d uses hydrogen, hydrazine hydrate, formic acid and its salt
Or at least one of formaldehyde reducing agent reduction.
10. the synthetic method of methanol, using carbon dioxide and hydrogen as raw material, exists in any catalyst of claim 1-2
Under carry out reaction and prepare methanol.
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| WO2020049081A1 (en) * | 2018-09-06 | 2020-03-12 | Total S.A. | Noble metal promoted supported indium oxide catalyst for the hydrogenation of co2 to methanol and process using said catalyst |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109999833A (en) * | 2019-05-07 | 2019-07-12 | 盐城工学院 | A kind of catalyst and preparation method thereof for synthesizing methanol by hydrogenating carbon dioxide |
| CN110586064B (en) * | 2019-09-27 | 2023-03-31 | 天津大学 | Lithium-doped zirconium oxide loaded indium oxide catalyst and preparation method and application thereof |
| CN111701586B (en) * | 2020-06-09 | 2021-07-02 | 山西大学 | Photocatalytic reduction of CO2Construction method and application of Pickering microbubble system for preparing methanol |
| KR20220000433A (en) * | 2020-06-25 | 2022-01-04 | 현대자동차주식회사 | Catalyst for conversion of carbon dioxide to methanol by hydrogenation, and method for preparing the same |
| CN116173947B (en) * | 2021-11-29 | 2024-07-12 | 中国华能集团清洁能源技术研究院有限公司 | Hydrogenation catalyst and preparation method and application thereof |
| CN114405505B (en) * | 2022-01-25 | 2023-10-31 | 上海工程技术大学 | Platinum modified indium-based oxide catalyst and preparation method and application thereof |
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| US20040216818A1 (en) * | 2003-03-31 | 2004-11-04 | Atlantic Research Corporation | Iridium-catalyzed hydrogen peroxide based monopropellant system |
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| WO2020049081A1 (en) * | 2018-09-06 | 2020-03-12 | Total S.A. | Noble metal promoted supported indium oxide catalyst for the hydrogenation of co2 to methanol and process using said catalyst |
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