CN101612577B - Inverse transformation catalyst for carbon dioxide and preparation method thereof - Google Patents
Inverse transformation catalyst for carbon dioxide and preparation method thereof Download PDFInfo
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- CN101612577B CN101612577B CN200910305043XA CN200910305043A CN101612577B CN 101612577 B CN101612577 B CN 101612577B CN 200910305043X A CN200910305043X A CN 200910305043XA CN 200910305043 A CN200910305043 A CN 200910305043A CN 101612577 B CN101612577 B CN 101612577B
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- transformation catalyst
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Abstract
The invention discloses an inverse transformation catalyst for carbon dioxide. The catalyst is a precipitation type multi-component heterogeneous catalyst which mainly uses a Fe and Zn oxide (ZnFe2O4) as an active component, uses Al2O3 as a carrier and uses SrO as an assistant. The catalyst has good catalytic conversion activity, and has good selectivity at the same time. The invention also discloses a preparation method for the inverse transformation catalyst for the carbon dioxide.
Description
Technical field
The invention belongs to catalyst technical field, particularly a kind of carbon dioxide inverse transformation catalysis and preparation method thereof.
Background technology
Along with the continuous increase of the industrial development and the organic type of energy of human use, CO in the atmosphere
2Concentration also continue to rise.By CO
2" greenhouse effects " that bring have caused the extensive concern of countries in the world.In recent years, with CO
2For the chemical synthesis of raw material receives pay attention to day by day.With CO
2Use as carbon resource, not only can reduce CO
2Environmental problems such as greenhouse effects are eliminated in discharging, also can develop new carbon resource for chemical industry simultaneously.
But directly with CO
2Be the feedstock production organic product, as with CO
2Be feedstock production methyl alcohol, exist the low problem of conversion ratio and selectivity.With CO
2Being transformed into CO, is the feedstock production organic product again with CO, can solve the low problem of conversion ratio and selectivity; Also can improve simultaneously the output of product; Like the technology of commercial production methyl alcohol, transforming under the condition that load, compression load, synthetic air speed do not improve, through with CO
2Be transformed into CO, adjustment CO, CO
2Ratio can improve methanol output about 10%.
At present commercial Application with CO
2The technology that is transformed into CO mainly adopts CO
2And O
2Gas coke prepares the mode of high-purity CO.This technology is applicable to those needs CO and does not need H
2Synthesis technique and larger device.Therefore, this technology is except the range of application limitation, and also existing owing to adopting coke is that raw material exists shortcomings such as dust, sulphur, raw material transportation.
Another kind of with CO
2The method that is transformed into CO is that H is being arranged
2Under the condition of source of the gas, with CO
2Inversion changes CO into.As everyone knows, the key reaction of Water gas shift/WGS is under the uniform temperature condition, and CO in the gas and steam react under the effect of catalyst, generates H
2And CO
2, its reaction equation is following:
CO+H
2O (vapour) → CO
2+ H
2+ 41.12kJ/mol
The back reaction of this transformationreation is called reverse shift reaction, and the reaction equation of reverse shift reaction is following:
CO
2+ H
2→ CO+H
2O (vapour)-41.12kJ/mol
H is being arranged
2Under the condition of source of the gas, with CO
2Inversion changes CO into can overcome employing CO
2And O
2Gas coke prepares the existing deficiency of CO, but CO
2The reaction needed that inversion changes CO into has suitable catalyst to exist.And it is at present domestic at CO
2Inverse transformation catalyst and the research of this type of process aspect are almost blank, therefore are necessary to develop a kind of CO
2Inversion changes the catalyst of CO into.
Summary of the invention
The objective of the invention is to overcome unsuitable, eco-friendly CO in the prior art
2The deficiency of inverse transformation catalyst provides a kind of environmental friendliness, has active, the good CO optionally of good catalyzed conversion
2Inverse transformation catalyst.Another object of the present invention is to provide this Preparation of catalysts method.
In order to realize the foregoing invention purpose, the inventor provides following technical scheme through series of experimental research:
A kind of inverse transformation catalyst for carbon dioxide, it is the polynary multiphase catalyst of mainly being made up of active component, carrier and auxiliary agent of sedimentation type, it is characterized in that: said active component is by Fe
2O
3Form with ZnO, (crystalline form of Fe, Zn oxide is ZnFe
2O
4), said carrier is Al
2O
3, said auxiliary agent is SrO, MnO
2Or La
2O
3
The active component of said inverse transformation catalyst for carbon dioxide and auxiliary agent preferably add with the form of nitrate, precipitate with sodium carbonate, and said carrier is preferably 200 orders～300 purpose Al
2O
3Fine powder.
The weight proportion of each primary raw material is preferred in the said inverse transformation catalyst for carbon dioxide: Fe
2O
335～55 parts, 35～45 parts of ZnO, Al
2O
310～20 parts, SrO, MnO
2Or La
2O
32～10 parts.
The column of the preferred Φ 3.5～5.0mm of the shape of said inverse transformation catalyst for carbon dioxide * H3.5～5.0mm.
Also comprise 1～5 part of lubricant in the said inverse transformation catalyst for carbon dioxide, said lubricant is graphite, stearate or paraffin.
A kind of preparation method of inverse transformation catalyst for carbon dioxide of the present invention may further comprise the steps:
(1), in the nitrate solid of active component, auxiliary agent, add deionized water, being mixed with each constituent content summation is the nitrate solution of 30g/L～60g/L;
(2), in nitrate solution, adding fineness is 200 orders～300 purpose Al
2O
3Powder mixes;
(3), using mass content at normal temperatures is that 10% sodium carbonate liquor carries out neutralization-precipitation reaction;
(4), neutralization precipitation finish after with reaction mass shelf ageing 1h～3h, cross and filter filter cake, with deionized water with Cake Wash to neutral (washing 3 times), at 100 ℃～150 ℃ dry 1h～3h, then in 550 ℃～650 ℃ ± 20 ℃ roasting 2h～4h;
(5), add lubricant in the material after roasting; Mill mixes 0.5h～2h in the ball mill mixing machine; Making material fineness >=250 orders, is 8%～12% deionized water then by material gross weight adding percentage by weight, and the material after mixing with water is through after the preliminary treatment; Be pressed into catalyst granules by former again, promptly get catalyst of the present invention.
Compared with prior art, the present invention has following beneficial effect: the inventor is through lot of test, and providing with Fe, Zn oxide is active component, with Al
2O
3Be carrier, with SrO, MnO
2Or La
2O
3Carbon dioxide inverse conversion catalyst for auxiliary agent.Detect through test, carbon dioxide inverse conversion catalyst of the present invention has good catalytic conversion activity, possesses good selectivity.Carbon dioxide inverse conversion catalyst of the present invention do not need to be applied to H with respect to utilizing coke to prepare CO
2Synthesis technique and larger device, inverse transformation technology is removed has continuous production, pollutes outside the characteristics such as little, the organic synthesis technology that needing also can be widely used in hydrogen source with install.After adopting inverse transformation technology, reduced atmosphere pollution greatly, its social benefit also is significant.Because the CO in present industrial by-product gas and the waste gas
2Concentration is high, can be used as source of the gas in order to produce organic products such as methyl alcohol, ethanol, formic acid like fermentation gas, lime furnace gas, synthetic ammonia manufacture gas, oil plant manufacture gas, coke oven and heavy oil combustion gas etc. more.Not only prevented CO
2Discharging has been created new benefit source for enterprise again to the harm of atmosphere.
CO
2The research success of inverse transformation Catalytic processes and catalyst provides inverse transformation process basic technology data and homemade inverse transformation catalyst for methanol production reaches the synthetic enterprise of relevant organic series products.According to preresearch estimates, with regard to methanol production, utilize inverse transformation technology to increase production about 10%.But because inverse transformation catalytic unit separate configurations, separate with main system, thereby adopt this project devoid of risk, no matter the old and new factory adopts the effect that all can receive energy-saving and cost-reducing raising the output behind the inverse transformation catalysis technique.The configuration of its effect size and inverter, the technological parameter of employing, and inverse transformation catalyst and even the average relevant system of management of water.Therefore for domestic production enterprise, inverse transformation technology and catalyst have wide application market.
Description of drawings
Fig. 1 is the preparation flow sketch map of carbon dioxide inverse transformation catalysis of the present invention.
The specific embodiment
Below in conjunction with the specific embodiment and Test Example the present invention is made further detailed description.But should this be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment, allly all belong to scope of the present invention based on the technology that content of the present invention realized.
Embodiment 1
The inverse transformation catalyst for carbon dioxide of present embodiment is with Fe, Zn oxide (ZnFe
2O
4) be active component, with Al
2O
3Being carrier, is auxiliary agent with SrO, is the polynary multiphase catalyst of sedimentation type of lubricant with graphite, wherein, and the weight portion proportioning such as the table 1 of each component:
Table 1 embodiment 1 forms proportioning
| Form | ?Fe 2O 3 | ?ZnO | ?SrO | ?Al 2O 3 | Graphite |
| Proportioning | ?40 | ?40 | ?5 | ?15 | 1 |
The preparation flow of present embodiment inverse transformation catalyst for carbon dioxide is as shown in Figure 1, and present embodiment Preparation of catalysts method mainly comprises the steps:
(1), in proportion take by weighing the nitrate solid of each active component, auxiliary agent, add deionized water, being mixed with each constituent content summation is the nitrate solution of 30g/L;
(2), in nitrate solution, adding fineness is 200 purpose Al
2O
3Powder mixes;
(3), using mass content at normal temperatures is that 10% sodium carbonate liquor carries out neutralization-precipitation reaction;
(4), neutralization precipitation finish after with reaction mass shelf ageing 1h～3h, cross and filter filter cake, with deionized water with Cake Wash to neutral (washing 3 times), at 100 ℃～150 ℃ dry 1h～3h, then in 550 ℃～650 ℃ ± 20 ℃ roasting 2h～4h;
(5), add lubricant in the material after roasting; Mill mixes 0.5h～2h in the ball mill mixing machine, makes material fineness >=250 orders, is 8%～12% deionized water then by material gross weight adding percentage by weight; The cylindrical catalyst finished product of Φ 3.5 * H3.5mm is processed in granulation, moulding.
Embodiment 2
The inverse transformation catalyst for carbon dioxide of present embodiment is with Fe, Zn oxide (ZnFe
2O
4) be active component, with Al
2O
3Be carrier, with MnO
2Being auxiliary agent, is the polynary multiphase catalyst of sedimentation type of lubricant with graphite, wherein, and the weight portion proportioning such as the table 2 of each component:
Table 2 embodiment 2 forms proportioning
| Project | ?Fe 2O 3 | ?ZnO | MnO 2 | ?Al 2O 3 | Graphite |
| Proportioning | ?55 | ?35 | 10 | ?10 | 5 |
The preparation flow of present embodiment inverse transformation catalyst for carbon dioxide is as shown in Figure 1, and present embodiment Preparation of catalysts method mainly comprises the steps:
(1), in proportion take by weighing the nitrate of Fe, Zn, Mn, add deionized water, being mixed with each constituent content summation is the nitrate solution of 60g/L;
(2), in nitrate solution, adding fineness is 300 purpose Al
2O
3Powder mixes;
(3), using mass content at normal temperatures is that 10% sodium carbonate liquor carries out neutralization-precipitation reaction;
(4), neutralization precipitation finish after with reaction mass shelf ageing 1h～3h, cross and filter filter cake, with deionized water with Cake Wash to neutral (washing 3 times), at 100 ℃～150 ℃ dry 1h～3h, then in 550 ℃～650 ℃ ± 20 ℃ roasting 2h～4h;
(5), add lubricant in the material after roasting; Mill mixes 0.5h～2h in the ball mill mixing machine, makes material fineness >=250 orders, is 8%～12% deionized water then by material gross weight adding percentage by weight; The cylindrical catalyst finished product of Φ 3.5 * H3.5mm is processed in granulation, moulding.
Embodiment 3
The inverse transformation catalyst for carbon dioxide of present embodiment is with Fe, Zn oxide (ZnFe
2O
4) be active component, with Al
2O
3Be carrier, with MnO
2Being auxiliary agent, is the polynary multiphase catalyst of sedimentation type of lubricant with paraffin, wherein, and the weight portion proportioning such as the table 3 of each component:
Table 3 embodiment 3 forms proportioning
| Component | ?Fe 2O 3 | ?ZnO | ?La 2O 3 | ?Al 2O 3 | Paraffin |
| Proportioning | ?35 | ?45 | ?2 | ?18 | 3 |
The preparation flow of present embodiment carbonoxide inverse transformation catalyst is as shown in Figure 1, and its method mainly comprises the steps: to take by weighing Fe, the Zn of said proportioning, the nitrate solution of La, and in its solution, to add fineness be 200 orders～300 purpose Al
2O
3Powder; After mixing, carry out titration with the sodium carbonate liquor of mass content 10%, after neutralization precipitation finishes with the reaction mass shelf ageing after 1 hour～3 hours; Filter, wash (washing 3 times); Filter cake is sent in the ball mill mixing machine after 2 hours～4 hours in 550 ℃～650 ℃ ± 20 ℃ roastings in calciner 100 ℃～150 ℃ dryings 1 hour～3 hours then, adds the paraffin mill and mixes 0.5 hour～2 hours; Add water then and carry out granulation, moulding, process the cylindrical catalyst finished product of Φ 3.5 * 3.5mm.
Test Example
The inventor has carried out conversion ratio and optionally evaluation to the inverse transformation catalyst for carbon dioxide of the foregoing description 1～3, and process conditions and mensuration result see table 4:
Carbon dioxide conversion and selectivity computing formula
Conversion ratio=(CO+CH
4) (mol%)/(CO+CO
2+ CH
4) (mol%)
Selectivity=CO (mol%)/(CO+CH
4) (mol%)
Table 4 conversion ratio and optionally evaluation
Claims (5)
1. inverse transformation catalyst for carbon dioxide, it is the polynary multiphase catalyst of mainly being made up of active component, carrier and auxiliary agent of sedimentation type, it is characterized in that: said active component is by Fe
2O
3Form with ZnO, said carrier is Al
2O
3, said auxiliary agent is SrO, MnO
2Or La
2O
3, wherein the weight proportion of each component is Fe
2O
335～55 parts, 35～45 parts of ZnO, Al
2O
310～20 parts, SrO, MnO
2Or La
2O
32～10 parts.
2. inverse transformation catalyst for carbon dioxide according to claim 1 is characterized in that: said active component and auxiliary agent add with the form of nitrate, precipitate with sodium carbonate, and said carrier is 200 orders～300 purpose Al
2O
3Fine powder.
3. inverse transformation catalyst for carbon dioxide according to claim 1 is characterized in that: the column of the preferred Φ 3.5～5.0mm of the shape of said inverse transformation catalyst for carbon dioxide * Η 3.5～5.0mm.
4. inverse transformation catalyst for carbon dioxide according to claim 1 is characterized in that: also comprise 1～5 part of lubricant in the said inverse transformation catalyst for carbon dioxide, said lubricant is graphite, stearate or paraffin.
5. a kind of preparation method of the said inverse transformation catalyst for carbon dioxide of claim 1 is characterized in that may further comprise the steps:
(1), in the nitrate of the nitrate of the nitrate of Fe and Zn and Sr, Mn or La, add deionized water, being mixed with each constituent content summation is the nitrate solution of 30g/L～60g/L;
(2), in nitrate solution, adding fineness is 200 orders～300 purpose Al
2O
3Powder mixes;
(3), using mass content at normal temperatures is that 10% sodium carbonate liquor carries out neutralization-precipitation reaction;
(4), neutralization precipitation finish after with reaction mass shelf ageing 1h～3h, cross and filter filter cake, with deionized water with Cake Wash to neutral, at 100 ℃～150 ℃ dry 1h～3h, then in 550 ℃～650 ℃ ± 20 ℃ roasting 2h～4h;
(5), add lubricant in the material after roasting, mill mixes 0.5h～2h in the ball mill mixing machine, makes material fineness >=250 orders, and adding percentage by weight by the material gross weight then is 8%～12% deionized water, and moulding promptly gets inverse transformation catalyst for carbon dioxide.
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| CN101612577B true CN101612577B (en) | 2012-02-08 |
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| CN103230799B (en) * | 2013-04-08 | 2016-06-08 | 中国科学院广州能源研究所 | A kind of Cu-Zn for reverse water-gas-shift reaction is catalyst based, its preparation method and application |
| CN108373138B (en) * | 2018-03-14 | 2020-05-05 | 中国成达工程有限公司 | Synthetic gas preparation system and preparation process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87100517A (en) * | 1987-01-17 | 1988-08-03 | 中国科学院大连化学物理研究所 | Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst |
| CN101183585A (en) * | 2007-09-26 | 2008-05-21 | 广东风华高新科技股份有限公司 | MnZn ferrite material and method of manufacturing the magnetic core |
-
2009
- 2009-07-30 CN CN200910305043XA patent/CN101612577B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87100517A (en) * | 1987-01-17 | 1988-08-03 | 中国科学院大连化学物理研究所 | Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst |
| CN101183585A (en) * | 2007-09-26 | 2008-05-21 | 广东风华高新科技股份有限公司 | MnZn ferrite material and method of manufacturing the magnetic core |
Non-Patent Citations (1)
| Title |
|---|
| JP特开200434021A 2004.02.05 |
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Address after: No. 5 high tech Zone Gaopeng road in Chengdu city of Sichuan Province in 610041 Patentee after: Southwest Chemical Research & Design Institute Co., Ltd. Address before: No. 5 high tech Zone Gaopeng road in Chengdu city of Sichuan Province in 610041 Patentee before: Xinan Chemical Research & Design Inst. |