CN110368949A - A kind of CO adds hydrogen low-carbon alcohols GaFe base catalyst and preparation method and application - Google Patents
A kind of CO adds hydrogen low-carbon alcohols GaFe base catalyst and preparation method and application Download PDFInfo
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- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
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Abstract
The invention discloses a kind of CO to add hydrogen low-carbon alcohols GaFe base catalyst, belongs to chemical technology field.Catalyst not metallic components Cu, using Ga and Fe as active component, mass percent accounts for 20 ~ 60%；Auxiliary agent is one or more of K, La, Zn, Mn, In, and mass percent accounts for 30 ~ 60%；Carrier is by CeO2、ZrO2、SiO2、Al2O3In any one or it is two or more compound and obtain, calculating by mass percentage is 5 ~ 20%.Catalyst preparation is using sol-gal process, coprecipitation, precipitating sedimentation or Complete Liquid-phast process.Catalyst preparation process of the present invention is simple, is applicable to a variety of reaction bed-type, good catalyst activity, C under relatively mild reaction condition2+Alcohol selectivity is high.
Description
Technical field
The invention belongs to chemical technology fields, and in particular to a kind of CO adds the GaFe base catalyst and system of hydrogen low-carbon alcohols
Preparation Method and application.
Background technique
It is one of the important channel that Coal Clean efficiently utilizes by the low-carbon alcohols based on CO preparation of ethanol by hydrogenating, low-carbon alcohols are not only
It can be used as fuel directly to burn, easily methyl tertiary butyl ether(MTBE) (MTBE) can be replaced to be used to improve the pungent of gasoline as fuel additive
Alkane value, while having broad application prospects as chemical products and large industrial chemicals.Synthesizing alcohol fuel is developed in recent years
The extensive concern for gradually causing people with high added value low-carbon alcohols fuel technology, meets the road of the strategic development of China's coal chemical industry.
Currently, the large-scale production of global industry ethyl alcohol mainly passes through grain fermentation method ethylene hydration method, due to China
Populous, per capita cultivated land is less, and the cost of fermentation method and energy consumption are excessively high, and needs to consume a large amount of crops as former
The problem of material, this inevitably results in " striving grain with people ".Based on the current resources situation of China's " few gas rich in coal and poor in oil ", exploitation is with coal
Technology path of the raw material through synthesis gas preparation low-carbon alcohols, can both give full play to the resources advantage of rich coal resources in China, subtract
Few coal such as directly burns at the extensives bring ecological problem, can also reduce the dependence to petroleum, while alleviating China's grain
Food consumes the problems such as excessive pressure, therefore present study realistic meaning is huge.
Industrialization is also not implemented in low carbon alcohol by synthetic gas, is primarily limited to the deficiency of catalyst.Catalysis used at present
Agent mainly includes two major classes: I: noble metal Rh base catalyst；II: non-precious metal catalyst.United States Patent (USP) US4377643 is disclosed
A kind of catalyst containing Rh, but its activity is lower and has a large amount of CH4It generates, it is subsequent also by the various auxiliary agents of addition, but imitate
Fruit is accidentally obvious.The country also have the relevant noble metal Rh catalyst of many patent reports, as CN102029173A,
CN102268045A,CN101428229A.Non-precious metal catalyst mainly by molybdenum series catalyst, urge by modified synthesizing methanol synthesis
Agent and modified Fischer-Tropsch synthetic catalyst three classes composition.Such catalyst mainly includes following components: Cu, Co, Mo, Fe, Mn, Zn
Deng, such as patent CN105944723 A, CN101804354 A, CN107890872A.But due to joined in such catalyst
Ni metal, though Cu is a kind of excellent synthol catalytic active center, the generation of same easily promotion water gas shift reaction,
Generate more CO2, great waste is caused for unstripped gas, economy is not high.From the point of view of present case, Rh catalyst
It is expensive, it is difficult to reach industrialized purpose, Cu modified F-T synthetic catalyst has more CO2It generates, Mo series catalysts
Activity is low, and contains micro sulphur in product, and later separation is difficult, and new height is badly in need of in the breakthrough of Yao Shixian low-carbon alcohol catalyst
Imitate the exploitation of catalyst.
Summary of the invention
The present invention provides a kind of CO the GaFe base catalyst and its preparation method and the application that add hydrogen low-carbon alcohols, and the purpose is to avoid
The serious problem of water gas shift reaction on conventional Cu base catalyst, to improve C under relatively mild conditions2+The selection of OH
Property.
A kind of CO adds hydrogen low-carbon alcohols GaFe base catalyst, not metallic components Cu, using Ga and Fe as active component, auxiliary agent
Including one or more of K, La, Zn, Mn, In, carrier is by CeO2、ZrO2、SiO2、Al2O3One or more of group
It closes.
The GaFe base catalyst, in terms of total weight percent: active component accounts for 10 ~ 60%, preferably 30 ~ 50%；Auxiliary agent
Account for 5 ~ 30%, preferably 10 ~ 20%；Carrier accounts for 5 ~ 20%, preferably 10 ~ 15%.
The GaFe base method for preparing catalyst includes: that (a) utilizes sol-gal process, the precipitation method, precipitating deposition legal system
Obtained presoma (b) is dried, roasting, or presoma is dispersed in atoleine by standby catalyst precursor
In, and heat GaFe base catalyst is made under an inert atmosphere.
Sol-gal process described in step (a) is using citric acid as complexing agent, and ethylene glycol is dispersing agent in 50 ~ 95 DEG C of temperature
Precursor sol is made in lower hydrolyze of degree；The precipitation method are by KOH, K2CO3, urea and catalyst component (Fe, Ga, K,
La, Zn, Mn, In, Zr, Al, Ce, Si) it is made into co-precipitation after the solution of respective concentration；The precipitating sedimentation is will
KOH、K2CO3, urea and the active metallic element in catalyst, auxiliary element cocurrent be deposited on carrier.
Presoma described in step (b) dry 12 at 80 ~ 120 DEG C ~ for 24 hours, it is dry after sample at 300 ~ 500 DEG C
Roast 4 ~ 12h；Or drying, roasting are not directly dispersing in atoleine in 260 ~ 320 DEG C of 6 ~ 12h of heating presoma.
The GaFe base catalyst hydrolysis temperature is 50 ~ 95 DEG C；Active component, auxiliary agent and carrier element come in catalyst
From in nitrate, citrate, acetate；Precipitating reagent is K2CO3, one of KOH or urea or a variety of.
Any GaFe base catalyst adds reaction condition when applying in hydrogen low-carbon alcohols in CO are as follows: and pressure 1 ~
6MPa, 200 ~ 400 DEG C of temperature, GHSV=1000 ~ 8000 h-1, H2/CO=0.5~4。
GaFe base catalyst of the present invention, not metallic components Cu；Provided CO adds the method for hydrogen low-carbon alcohols, according to heat
The difference of processing mode, can be used for different reaction bed-type, and it is mild under conditions of can effectively avoid traditional Cu base catalyst
The serious problem of water gas shift reaction, can increase substantially C2+Alcohol selectivity, has good prospects for commercial application.
Specific embodiment
Below specific embodiment it is above-mentioned to the present invention provided by a kind of CO add hydrogen low-carbon alcohols GaFe base catalyst
Preparation and application are further described in detail.
Embodiment 1
It weighs 1.2 g zirconium nitrates, 13.6g ferric nitrate and 7.2g gallium nitrate respectively to be dissolved in the deionized water of 150mL, in magnetic force
It is completely dissolved under stirring, and is heated to 40 DEG C in water-bath；16.5g potassium carbonate is weighed again to be dissolved in 150mL deionized water, it will
Solution of potassium carbonate is added drop-wise in GaFeZr salting liquid with 3mL/min rate until forming uniform and stable sediment, aged at room temperature 2
It after h, filters, 12 h is dried at 100 DEG C, the solid after drying is in 400 DEG C of 5 h of roasting.Obtained solid is ground, tabletting, is broken
Broken, sieving obtains the catalyst of 40 ~ 60 mesh, by this catalyst in H2The lower 300 DEG C of reduction of atmosphere, 250 DEG C, 4MPa, H2/ CO=1,
GHSV=2000 h-1Under conditions of carry out activity rating, as a result: CO conversion ratio is 8.9 (C-mol %), C2+Alcohol is selectively
20.9(C-mol %)。
Embodiment 2
0.6 g zirconium nitrate, 13.6g ferric nitrate, 3.5g zinc nitrate and 14.4 g gallium nitrates are weighed respectively is dissolved in going for 150 mL
It in ionized water, then weighs 18.5g potassium carbonate and is dissolved in 150mL deionized water, by two kinds of solution with 3mL/min rate cocurrent drop
Be added in beaker until forming uniform and stable sediment, after 2 h of aged at room temperature, filter, dry 12 h at 100 DEG C, after 400
DEG C roasting 5 h obtain solid.Obtained solid is ground, tabletting, broken, sieving obtain the catalyst of 40 ~ 60 mesh, this is urged
Agent 300 DEG C of reduction, 280 DEG C, 3MPa, H under CO atmosphere2The h of/CO=1, GHSV=2000-1Under conditions of carry out activity rating,
As a result: CO conversion ratio is 10.6 (C-mol %), C2+Alcohol is selectively 35.5 (C-mol %).
Embodiment 3
Weigh respectively 6.0g cerous nitrate, 2.4g lanthanum nitrate, 3.6g ferric nitrate and 14.4 g gallium nitrates be dissolved in 150mL go from
It in sub- water, then weighs 20.5g potassium carbonate and is dissolved in 150mL deionized water, two kinds of solution are added drop-wise to 3mL/min rate cocurrent
Until forming uniform and stable sediment in beaker, after 2 h of aged at room temperature, filter, dry 12 h at 100 DEG C, after at 500 DEG C
It roasts 12 h and obtains solid.Obtained solid is ground, tabletting, broken, sieving obtain the catalyst of 40 ~ 60 mesh, this is urged
Agent 300 DEG C of reduction, 300 DEG C, 6 MPa, H under CO atmosphere2The h of/CO=2, GHSV=8000-1Under conditions of carry out activity rating,
As a result: CO conversion ratio is 8.9 (C-mol %), C2+Alcohol is selectively 27.5 (C-mol %).
Embodiment 4
The deionization that 3.5 g aluminum nitrates, 6.2g manganese nitrate, 5.0g ferric nitrate and 7.2g gallium nitrate are dissolved in 150mL is weighed respectively
It in water, then weighs 26.6g potassium hydroxide and is dissolved in 150mL deionized water, by above two solution with 3mL/min rate cocurrent drop
Be added in beaker until forming uniform and stable sediment, after aged at room temperature 2h, filter, dry 24 h at 100 DEG C, after 300
DEG C roasting 8 h obtain solid.Obtained solid is ground, tabletting, broken, sieving obtain the catalyst of 40 ~ 60 mesh, this is urged
Agent 300 DEG C of reduction, 250 DEG C, 6 MPa, H under synthesis gas atmosphere2The h of/CO=0.5, GHSV=8000-1Under conditions of live
Property evaluation, as a result: CO conversion ratio is 12.9 (C-mol %), C2+Alcohol is selectively 23.6 (C-mol %).
Embodiment 5
1.2 g zirconium nitrates, 3.5 g aluminum nitrates, 6.2g manganese nitrate, 5.0g ferric nitrate and 7.2g gallium nitrate is weighed respectively to be dissolved in
It in the deionized water of 150mL, then weighs 35.8g carbon urea and is dissolved in 150mL deionized water, by above two solution with 3mL/
Min rate cocurrent is added drop-wise in beaker after the sediment that formation is uniform and stable, aged at room temperature 2h, is filtered, dry at 120 DEG C
18 h, after in 500 DEG C of 6 h of roasting obtain solid.Obtained solid is ground, tabletting, broken, being sieved obtains 40 ~ 60 purposes
Catalyst restores this catalyst for 300 DEG C, 220 DEG C, 1 MPa, H under synthesis gas atmosphere2The h of/CO=4, GHSV=1000-1Item
Activity rating is carried out under part, as a result: CO conversion ratio is 14.6 (C-mol %), C2+Alcohol is selectively 38.3 (C-mol %).
Embodiment 6
5.6 g ethyl orthosilicates are weighed to be dissolved in the deionized water dissolved with a certain amount of citric acid, it is rear to be added dissolved with 10.8g nitric acid
Iron, 3.4g zinc nitrate and 5.2g gallium nitrate ethylene glycol solution, stir 1h under magnetic stirring；By resulting mixed solution at 80 DEG C
Continue colloidal sol of the heating hydrolysis until forming stable homogeneous in water-bath, gained colloidal sol is dried for 24 hours at 80 DEG C, 500 DEG C of roasting 10h
Afterwards, tabletting is sieved to obtain the catalyst granules of 40 ~ 60 mesh, this catalyst is fitted into fixed bed reactors and is fixed with filler,
400 DEG C of the normal pressure reduction under synthesis gas atmosphere by this catalyst, and in 250 DEG C, 3MPa, H2/CO=2、GHSV=5000 h-1Item
Activity rating is carried out under part, as a result: CO conversion ratio is 18.0 (C-mol %), C2+Alcohol is selectively 30.6 (C-mol %).
Embodiment 7
The colloidal dispersion that embodiment 6 is obtained is in 300mL atoleine, in N2300 are progressively heated at by room temperature under atmosphere
DEG C and maintain 8h to obtain catalyst.This catalyst is fitted into paste state bed reactor 280 DEG C of the normal pressure reduction under synthesis gas atmosphere,
And in 250 DEG C, 3MPa, H2/CO=2、GHSV=2000 h-1Under conditions of carry out activity rating, as a result: CO conversion ratio is 15.5
(C-mol %), C2+Alcohol is selectively 35.2 (C-mol %).
Embodiment 8
In deionized water by the commercialized alumina dispersion of 3.0g, then will dissolved with 10.8g ferric nitrate, 3.4g zinc nitrate and
It the solution of 5.2g gallium nitrate and is added in the above-mentioned suspension containing aluminium oxide dissolved with the potassium hydroxide solution cocurrent of 30.8g, to
Precipitating is completed, and is filtered, filter cake is directly dispersing in atoleine, and be heat-treated to 320 DEG C of maintenance 12h in a nitrogen atmosphere and obtain
To slurried catalyst, this catalyst is fitted into paste state bed reactor 280 DEG C of the normal pressure reduction under synthesis gas atmosphere, and 250
℃、5MPa、H2/CO=4、GHSV=4000 h-1Under conditions of carry out activity rating, as a result: CO conversion ratio is 13.4 (C-mol
%), C2+Alcohol is selectively 29.0 (C-mol %).
Embodiment 9
10.6 g aluminium isopropoxides are weighed to be dissolved in the deionized water dissolved with a certain amount of citric acid, it is rear to be added dissolved with 12.2g lemon
Sour iron, 4.3g zinc citrate, 5.2g manganese citrate and 6.4g gallium citrate ethylene glycol solution, stir 1h under magnetic stirring；
Resulting mixed solution is continued to colloidal sol of the heating hydrolysis until forming stable homogeneous in 95 DEG C of water-baths, by gained colloidal sol 80
It is dried at DEG C for 24 hours, after 500 DEG C of roasting 10h, tabletting is sieved to obtain the catalyst granules of 40 ~ 60 mesh, this catalyst is packed into fixed bed
450 DEG C of the normal pressure reduction under synthesis gas atmosphere in reactor, and in 250 DEG C, 2MPa, H2/CO=2、GHSV=4000 h-1Condition
Lower carry out activity rating, as a result: CO conversion ratio is 12.1 (C-mol %), C2+Alcohol is selectively 36.3 (C-mol %).
Embodiment 10
Weigh 10.6 g aluminium isopropoxides, 5.6 g ethyl orthosilicates are dissolved in the deionized water dissolved with a certain amount of citric acid, it is rear plus
Enter dissolved with 10.8g ferric nitrate, 3.4g zinc nitrate, 4.8g manganese nitrate and 6.4g gallium nitrate ethylene glycol solution, under magnetic stirring
Stir 1h；Resulting mixed solution is continued to colloidal sol of the heating hydrolysis until forming stable homogeneous in 95 DEG C of water-baths, by gained
Colloidal sol is directly dispersing in atoleine, and is heat-treated to 280 DEG C of maintenance 10h in a nitrogen atmosphere and is obtained slurried catalyst, will
This catalyst is fitted into paste state bed reactor 280 DEG C of the normal pressure reduction under synthesis gas atmosphere, and in 250 DEG C, 4MPa, H2/CO=2、
GHSV=2000 h-1Under conditions of carry out activity rating, as a result: CO conversion ratio is 15.9 (C-mol %), C2+Alcohol is selectively
40.2 (C-mol %)。
Claims (10)
1. a kind of CO adds hydrogen low-carbon alcohols GaFe base catalyst, it is characterised in that: using Ga and Fe as active component, auxiliary agent include K,
One or more of La, Zn, Mn, In, carrier CeO2、ZrO2、SiO2、Al2O3One of or any several combinations.
2. a kind of CO as described in claim 1 adds hydrogen low-carbon alcohols GaFe base catalyst, it is characterised in that: the GaFe base is urged
Agent is by weight percentage: active component accounts for 10 ~ 60%；Auxiliary agent accounts for 5 ~ 30%；Carrier accounts for 5 ~ 20%.
3. a kind of CO as described in claim 1 adds hydrogen low-carbon alcohols GaFe base catalyst, it is characterised in that: the GaFe base is urged
Agent is by weight percentage: active component accounts for 30 ~ 50%；Auxiliary agent accounts for 10 ~ 20%；Carrier accounts for 10 ~ 15%.
4. a kind of CO as described in claim 1 adds hydrogen low-carbon alcohols GaFe base catalyst, it is characterised in that preparation method includes
Following the description:
(a) catalyst precursor is prepared using sol-gal process, the precipitation method, precipitating sedimentation；
(b) by catalyst precursor dry 12 at 80 ~ 120 DEG C ~ for 24 hours, it is dry after sample roast 4 at 300 ~ 500 DEG C ~
12h；Or catalyst precursor is dispersed in atoleine 6 ~ 12h of heat treatment under 260 ~ 320 DEG C of inert atmospheres.
5. a kind of CO as claimed in claim 4 adds hydrogen low-carbon alcohols GaFe base catalyst, it is characterised in that: the colloidal sol is solidifying
Glue method is using citric acid as complexing agent, and ethylene glycol is dispersing agent, hydrolyzes at 50 ~ 95 DEG C and precursor sol is made.
6. a kind of CO as claimed in claim 4 adds hydrogen low-carbon alcohols GaFe base catalyst, it is characterised in that: the precipitation method
For precipitating reagent and catalyst component are made into co-precipitation after the solution of respective concentration.
7. a kind of CO as claimed in claim 4 adds hydrogen low-carbon alcohols GaFe base catalyst, it is characterised in that: the precipitating is heavy
Area method is that the active metallic element in precipitating reagent and catalyst, auxiliary element cocurrent are deposited on carrier.
8. a kind of CO as claimed in claim 4 adds hydrogen low-carbon alcohols GaFe base catalyst, it is characterised in that: active in catalyst
Component, auxiliary agent and carrier element are from nitrate, citrate, acetate.
9. a kind of CO as claimed in claim 5 adds hydrogen low-carbon alcohols GaFe base catalyst, it is characterised in that: the precipitating reagent
For K2CO3, KOH, one of urea or a variety of.
10. a kind of any CO adds hydrogen low-carbon alcohols GaFe base catalyst according to claim 1 ~ 9, it is characterised in that: GaFe
Base catalyst adds in the reaction of hydrogen low-carbon alcohols in CO, use condition are as follows: 1 ~ 6MPa of pressure, 200 ~ 400 DEG C of temperature, GHSV=1000 ~
8000h-1, H2/CO=0.5~4。
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| CN113856687A (en) * | 2021-11-04 | 2021-12-31 | 太原理工大学 | Preparation method of doped ZnO catalyst and preparation method for synthesizing higher alcohol by using doped ZnO catalyst |
| CN114618463A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Composite catalyst and preparation method and application thereof |
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| CHARLES BEASLEY ET.AL: "Efect of Gallium Additions on Reduction, Carburization and Fischer–Tropsch Activity of Iron Catalysts", 《CATALYSIS LETTERS》 * |
| TOMOYUKI INUI ET.AL: "Highly effective synthesis of ethanol by CO2 balanced multi-functional FT-type composite catalysts", 《APPLIED CATALYSIS A: GENERAL》 * |
| 董伟兵等: "预热液体石蜡对CuZnAl催化剂合成低碳醇的影响", 《天然气化工—C1化学与化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114618463A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Composite catalyst and preparation method and application thereof |
| CN114618463B (en) * | 2020-12-10 | 2023-11-17 | 中国科学院大连化学物理研究所 | Composite catalyst and preparation method and application thereof |
| CN113731428A (en) * | 2021-09-08 | 2021-12-03 | 常州大学 | CeO (CeO)2Preparation method and application of nano triangular plate supported CuO catalyst |
| CN113856687A (en) * | 2021-11-04 | 2021-12-31 | 太原理工大学 | Preparation method of doped ZnO catalyst and preparation method for synthesizing higher alcohol by using doped ZnO catalyst |
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| CN110368949B (en) | 2022-07-01 |
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