CN110152675A - The method of low carbon alcohol by synthetic gas catalyst, preparation method and low carbon alcohol by synthetic gas - Google Patents
The method of low carbon alcohol by synthetic gas catalyst, preparation method and low carbon alcohol by synthetic gas Download PDFInfo
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- CN110152675A CN110152675A CN201910430364.6A CN201910430364A CN110152675A CN 110152675 A CN110152675 A CN 110152675A CN 201910430364 A CN201910430364 A CN 201910430364A CN 110152675 A CN110152675 A CN 110152675A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—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
- B01J23/78—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 alkali- or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- 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
- C07C29/153—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 characterised by the catalyst used
- C07C29/156—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 characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
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Abstract
The invention discloses a kind of methods of low carbon alcohol by synthetic gas catalyst, preparation method and low carbon alcohol by synthetic gas.Wherein, active element mass percent is Cu:10%~35% in the catalyst, Fe:5%~40%, Zr:3%~20%, Co:1%~15%, M:0.01~2%, Si:3%~30%, wherein M is one of alkali metal or alkali earth metal or several.It applies the technical scheme of the present invention, low carbon alcohol by synthetic gas catalyst has the carrier zirconium oxide of enhancing catalyst stability, and introduce and improve F- T synthesis constituent element such as group VIII element and alkali metal or the alkaline earth metal content with stronger carbochain growing ability, to improve the target product C2+ alcohol selectivity and structural stability of catalyst, increase the service life of catalyst.
Description
Technical field
The present invention relates to chemical technology fields, in particular to a kind of low carbon alcohol by synthetic gas catalyst, its preparation side
The method of method and low carbon alcohol by synthetic gas.
Background technique
Low carbon mixed alcohol (alcohol-based mixtures of C1~C6) since its high-octane rating both may be used as clean gasoline additive,
The dimethyl tertiary butyl ether (MTBE) with carcinogenesis is substituted, can also be used as excellent clean vehicle fuel and for oil product,
And it has huge economic value as chemicals itself or large Chemical Manufacture raw material.Therefore, in current China
It is becoming tight stone oil supply day under methanol alternative fuel market continued downturn background, develops substitution methanol combustion by source of coal
Material, it is highly selective to produce mixed alcohol (the especially higher alcohol of C2 or more), with high economic benefit and important strategy meaning
Justice.
Chinese patent authorization publication number (104128186 B of CN) describes a kind of catalyst of synthesis gas preparation low-carbon alcohols
And preparation method thereof, low-carbon alcohols, which are produced, using two kinds of group lease making mechanical mixture grindings of AlOOH and industrial methanol synthetic catalyst closes
At catalyst, which is used for fixed bed synthesis gas reaction, total alcohol of low-carbon alcohols selectively reaches 50%, wherein C2+ alcohol
Selectivity is 20%.This catalyst belongs to carbinol-modified CuZnAl catalyst, although preparation is simple, due to being prepared
AlOOH and catalyst for methanol in Cu, Zn isoreactivity component be only mechanical mixture, do not carry out molecular level and be combined into
Key, therefore its stability is poor, the consequence for easily causing active component to be easily lost；And its C2+ alcohol is selectively only 20%,
The selectivity of target product is too low, does not have industrial prospect.
Chinese patent authorization publication number (103191741 B of CN) describes a kind of copper and iron nucleocapsid catalysis of synthesis of low-carbon alcohol
Agent and preparation method, the catalyst only have the characteristics that structure novel, active poor, the big portion of the conversion per pass of CO of catalyst
Divide 20% or so.And this catalyst has Workflow mildly inconvenient as fixed bed catalyst in industrialized application
The inevitable disadvantage of operation.
Summary of the invention
The present invention is intended to provide the side of a kind of low carbon alcohol by synthetic gas catalyst, preparation method and low carbon alcohol by synthetic gas
Method increases making for catalyst to solve to improve the target product C2+ alcohol selectivity and structural stability of catalyst in the prior art
Use the service life.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of low carbon alcohol by synthetic gas catalyst.
Active element mass percent is Cu:10%~35% in the catalyst, Fe:5%~40%, Zr:3%~20%, Co:1%
~15%, M:0.01~2%, Si:3%~30%, wherein M is one of alkali metal or alkali earth metal or several
Kind.
Further, active element mass percent is Cu:10%~35% in catalyst, Fe:10%~35%, Zr:
5%~18%%, Co:2%~13%, M:0.05%~1.8%, Si:5%~30%, wherein M is alkali metal or alkaline earth gold
Belong to one of element or several.
According to another aspect of the present invention, a kind of preparation method of above-mentioned low carbon alcohol by synthetic gas catalyst is provided.It should
Copper nitrate, ferric nitrate, zirconium nitrate, cobalt nitrate are dissolved in deionized water that be made into mixing molten the following steps are included: S1 by preparation method
Liquid carries out precipitation reaction as precipitating reagent using the carbonate solution of alkali metal or alkaline-earth metal, by filtering or being centrifuged point
From obtaining catalyst Precursors and precipitated liquid；Catalyst Precursors obtained in S1 are added water to be beaten by S2, and binder silicon is then added,
It stirs evenly；Catalyst after molding is roasted, it is low to obtain synthesis gas system by S3 by slurries drying and moulding obtained in S2
Carbon alcohol catalyst.
It further, include that carbonate solution is added continuously in mixed solution in precipitation reaction, precipitating terminates in S1
After carry out aging reaction, obtained precipitating is filtered after aging reaction and is washed with deionized, is centrifugated and goes to clean
Ion.
Further, in S1, the conductivity of the clear liquid as obtained by control deionized water washing precipitating is golden to correspond to control alkali
The content that category or alkaline-earth metal retain in catalyst Precursors.
Further, the temperature of precipitation reaction is 20~100 DEG C, and pH is 4~9.
Further, the temperature of aging reaction is 20~100 DEG C, and the time is 1~5h.
Further, in S2, catalyst Precursors add the volume after water is added in water mashing equal to the volume of precipitated liquid.
Further, in S2, the mode that binder silicon is added is that binder silicon is added in the slurries after being beaten, the temperature of slurries
Degree is kept for 20~100 DEG C；Either 20~50 DEG C of binder silicon is added in the slurries of room temperature.
In accordance with a further aspect of the present invention, a kind of method of low carbon alcohol by synthetic gas is provided.This method includes following step
It is rapid: above-mentioned low carbon alcohol by synthetic gas catalyst to be added in the solvent in paste state bed reactor, using hydrogen under normal pressure through 300
DEG C temperature programmed reduction activated for 24 hours after catalyst；Then higher alcohols synthesis reaction is carried out in paste state bed reactor, instead
Answering temperature is 200~280 DEG C, reaction pressure is 5.0MPa~7.0MPa, air speed is 2000~10000h-1, H2/ CO molar ratio is
1~4:1,400~1200rpm of agitator speed.
It applies the technical scheme of the present invention, low carbon alcohol by synthetic gas catalyst has the carrier oxygen of enhancing catalyst stability
Change zirconium, and introduce and improve have stronger carbochain growing ability F- T synthesis constituent element such as group VIII element and alkali metal or
Person's alkaline earth metal content increases making for catalyst to improve the target product C2+ alcohol selectivity and structural stability of catalyst
Use the service life.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
For the shortcomings that catalyst, the invention proposes following technical proposals described in background technique.
A kind of typical embodiment according to the present invention provides a kind of low carbon alcohol by synthetic gas catalyst.In the catalyst
Active element mass percent is Cu:10%~35%, Fe:5%~40%, Zr:3%~20%, Co:1%~15%, M:
0.01~2%, Si:3%~30%, wherein M is one of alkali metal or alkali earth metal or several.Wherein, living
Property element mainly in the form of various single or composite oxides or hydroxide etc. exist.
Since Fe has the ability of dissociation CO, adsorbs and forms methylene etc. after CO dissociation plus hydrogen thereon and make C chain growth,
And Cu is the active component of synthesizing methanol, has CO insertions function.The synergistic effect of the two eventually leads to the generation of low-carbon alcohols.
Cu-Fe base catalyst has preferable activity to synthesis of low-carbon alcohol reaction, and required operating condition is more mild, catalyst
Raw material is cheap and easy to get.In addition, can effectively improve the stabilization of catalyst after adding suitable carrier and auxiliary agent to catalyst
Property.Cu-Fe alloying pellet is formed in synthesis of low-carbon alcohol becoming apparent from for the synergistic effect performance for making iron-copper bi-metal, promotes
The progress of synthesis of low-carbon alcohol reaction.
Zirconium oxide has good stability as carrier, can be stabilized in high temperature, strongly reducing atmosphere, by Cu-
Fe alloying pellet supports the surface of Zirconia carrier, effectively inhibits the sintering and reunion of Cu-Fe alloying pellet, improves
The stability of catalyst；Furthermore Zirconia carrier itself has certain catalytic effect to synthesis of low-carbon alcohol reaction, is conducive to improve
The activity and the selectivity of C2+ alcohol of reaction.In addition, due to the addition of adhesive silicon sol, compared to no Si catalyst, alcohol distribution
To methanol deviate, cause C2+ alcohol reduce, this is the aspect of performance change the most apparent, trace it to its cause may be due to silicon with
Iron forms stable iron silicon tetrahedral structure, and the iron in reduction process is caused to be difficult to restore, to reduce the chain growth of iron
Effect, so that the reduction of the selectivity of the longer C2+ alcohol of carbochain.In order to solve that caused C2+ alcohol after silicon is added selectively to be lower, first
The problem of alcohol selectively increases increases carbochain using the content for increasing Fischer-Tropsch constituent element such as Fe, Co, K etc., reaches and increases C2+ alcohol
The purpose of selectivity.
It applies the technical scheme of the present invention, low carbon alcohol by synthetic gas catalyst has the carrier oxygen of enhancing catalyst stability
Change zirconium, and introduce and improve have stronger carbochain growing ability F- T synthesis constituent element such as group VIII element and alkali metal or
Person's alkaline earth metal content increases making for catalyst to improve the target product C2+ alcohol selectivity and structural stability of catalyst
Use the service life.
Preferably, active element mass percent is Cu:10%~35% in catalyst, Fe:10%~35%, Zr:
5%~18%%, Co:2%~13%, M:0.05%~1.8%, Si:5%~30%, wherein M is alkali metal or alkaline earth gold
Belong to one of element or several.
A kind of typical embodiment according to the present invention provides a kind of preparation side of above-mentioned low carbon alcohol by synthetic gas catalyst
Method.Copper nitrate, ferric nitrate, zirconium nitrate, cobalt nitrate are dissolved in deionized water and being made into the following steps are included: S1 by the preparation method
Mixed solution, using the carbonate solution of alkali metal or alkaline-earth metal as precipitating reagent carry out precipitation reaction, by filtering or
Centrifuge separation, obtains catalyst Precursors and precipitated liquid；Catalyst Precursors obtained in S1 are added water to be beaten by S2, are then added viscous
Agent silicon is tied, is stirred evenly；Catalyst after molding is roasted, is synthesized by S3 by slurries drying and moulding obtained in S2
Gas low-carbon alcohol catalyst.
Wherein, the copper nitrate in S1, ferric nitrate, zirconium nitrate, cobalt nitrate also could alternatively be chlorate or sulfate, still
The heteroion of addition may have an adverse effect to catalyst, so nitrate is the most suitable.
It preferably, include that carbonate solution is added continuously in mixed solution in precipitation reaction, after precipitating in S1
Carry out aging reaction, obtained precipitating filter after aging reaction and is washed with deionized, be centrifugated go to clean from
Son.Slurries drying and moulding can carry out spray drying forming using spray drying tower.The carbonate of alkali metal or alkaline-earth metal
Solution is the solution of the carbonate of potassium carbonate or sodium carbonate or otheralkali metal or alkaline-earth metal.
A kind of typical embodiment according to the present invention, in S1, the clear liquid as obtained by control deionized water washing precipitating
Conductivity corresponds to control alkali metal or the content that retains in catalyst Precursors of alkaline-earth metal.
Preferably, the temperature of precipitation reaction is 20~100 DEG C, and pH is 4~9.It at this point in the reaction can be to avoid temperature
Excessively high or catalyst primary particle size caused by pH is excessively high is meticulous, the loss in washing process；Illustrate to precipitate in addition, pH is too low
Underdosage, nitrate cannot react precipitating completely, therefore controlling pH is 4~9, it is preferred that precipitation reaction terminate it is optimal
Alkalescence condition pH=7~8 are relatively good.
Preferably, the temperature of aging reaction is 20~100 DEG C, and the time is 1~5h.Under the conditions of this temperature, be conducive to live
The combination of reaction and uniform close between property constituent element；Again will not be too high because of temperature, catalyst granules is meticulous, and catalyst is caused to exist
It is lost in washing process.
Preferably, in S2, catalyst Precursors add the volume after water is added in water mashing equal to the volume of the precipitated liquid.
Preferably, in S2, binder silicon is added in the slurries after mashing, and the temperature of slurries is kept for 20~100 DEG C；Either
20~50 DEG C of binder silicon is added in the slurries of room temperature.Room temperature silicon positive adding manner into the warm slurries of band under high-speed stirred
It is much better, be conducive to uniformly intersperse among in slurries；The warm silica solution of band can make crystal grain grow up, and crystal grain adds after growing up
Meeting is unfavorable for dispersion and uniformity of the silica solution in slurries so that part reunion.A kind of typical embodiment party according to the present invention
Formula provides a kind of method of low carbon alcohol by synthetic gas.Method includes the following steps: by above-mentioned low carbon alcohol by synthetic gas catalyst
It is added in the solvent in paste state bed reactor, using hydrogen under normal pressure after 300 DEG C of temperature programmed reductions are activated for 24 hours
Catalyst；Then higher alcohols synthesis reaction is carried out in paste state bed reactor, reaction temperature is 200~280 DEG C, reaction pressure is
5.0MPa~7.0MPa, air speed are 2000~10000h-1, H2/ CO molar ratio be 1~4:1, agitator speed 400~
1200rpm。
Beneficial effects of the present invention are further illustrated below in conjunction with embodiment.
Embodiment 1
It is dissolved in deionized water with copper nitrate, ferric nitrate, zirconium nitrate, cobalt nitrate according to molar ratio 0.6:0.7:0.2:0.1
Sufficiently dissolution is made into mixed solution；Precipitating reagent uses solution of potassium carbonate, and continuous feed and being sufficiently stirred makes at 60 DEG C of water-bath
Precipitating uniformly mixing, reaction end pH value are 7.5, in 60 DEG C of aging 2h after precipitating, after aging simultaneously by precipitating filtering
6 times (washing is until cleaning solution conductivity is down to 100us/cm or less) are washed repeatedly with deionized water to be centrifuged,
Washing plus water are to sediment total Water before every time.
By gained sediment plus water mashing (water is to sediment total Water before), addition binder silicon be (binder silicon
Mode is in the slurries after mashing is added, and the temperature of slurries is kept for 20~100 DEG C；Either 20~50 DEG C of binder silicon is added
In the slurries of room temperature), it is stirred well to uniformly；Spray drying forming is carried out using spray drying tower, by catalyst after molding
It is roasted, obtains finished catalyst particle.The active element quality group of gained fresh catalyst becomes: Cu:20.27%, Fe:
21.32%, Zr:8.96%, Co:3.28%, Si:14.47%, K:0.18%.
In 1L gas one way by the way that 500ml atoleine is added in stirred tank evaluating apparatus, 15g spray drying is then added
Then catalyst seals reactor.Catalyst after reductase 12 4h at 300 DEG C is activated under normal pressure, in reaction temperature
260 DEG C, pressure 6.0Mpa, air speed 4000h-1 carry out low-carbon alcohols conjunction under conditions of agitator speed 1000rpm, hydrogen-carbon ratio 2:1
At reaction.Long-term operation 500 hours with this condition, catalyst runs stability are active (CO conversion ratio) fall off rate institute
Evaluation results, the C2+ alcohol of acquirement are selectively shown in Table 1.
Embodiment 2
Catalyst preparation process and performance evaluation process are same as Example 1, only change active element in catalyst
Mass percent, the fresh catalyst activity element quality group being prepared becomes: Cu:19.86%, Fe:5.42%, Zr:
8.96%, Co:1.08%, Si:15.51%, K:0.002%.Catalyst performance evaluation the results are shown in Table 1.
Embodiment 3
Catalyst preparation process and performance evaluation process are same as Example 1, only change active element in catalyst
Mass percent, the fresh catalyst activity element quality group being prepared becomes: Cu:19.25%, Fe:28.89%, Zr:
9.09%, Co:10.32%, Si:16.01%, K:0.98%.Catalyst performance evaluation the results are shown in Table 1.
Embodiment 4
Catalyst preparation process and performance evaluation process are same as Example 1, only change active element in catalyst
Mass percent, the fresh catalyst activity element quality group being prepared becomes: Cu:21.06%, Fe:19.46%, Zr:
3.61%, Co:3.02%, Si:16.18%, K:0.16%.Catalyst performance evaluation the results are shown in Table 1.
Embodiment 5
Catalyst preparation process and performance evaluation process are same as Example 1, only change active element in catalyst
Mass percent, the fresh catalyst activity element quality group being prepared becomes: Cu:21.18%, Fe:19.51%, Zr:
14.78%, Co:4.01%, Si:13.95%, K:0.17%.Catalyst performance evaluation the results are shown in Table 1.
Embodiment 6
Catalyst preparation process and performance evaluation process are same as Example 1, only change active element in catalyst
Mass percent, the fresh catalyst activity element quality group being prepared becomes: Cu:19.73%, Fe:20.19%, Zr:
9.55%, Co:3.16%, Si:22.75%, K:0.17%.Catalyst performance evaluation the results are shown in Table 1.
Embodiment 7
Catalyst preparation process and performance evaluation process are same as Example 1, only change active element in catalyst
Mass percent, the fresh catalyst activity element quality group being prepared becomes: Cu:10.33%, Fe:39.85%, Zr:
3.76%, Co:1.46%, Si:3.56%, K:0.02%.Catalyst performance evaluation the results are shown in Table 1.
Embodiment 8
Catalyst preparation process and performance evaluation process are same as Example 1, only change active element in catalyst
Mass percent, the fresh catalyst activity element quality group being prepared becomes: Cu:34.55%, Fe:5.13%, Zr:
3.84%, Co:1.73%, Si:3.81%, K:0.03%.Catalyst performance evaluation the results are shown in Table 1.
Embodiment 9
Catalyst preparation process and performance evaluation process are same as Example 1, only change active element in catalyst
Mass percent, the fresh catalyst activity element quality group being prepared becomes: Cu:33.67%, Fe:5.62%, Zr:
3.34%, Co:1.21%, Si:29.72%, K:0.04%.Catalyst performance evaluation the results are shown in Table 1.
Embodiment 10
Catalyst preparation process and performance evaluation process are same as Example 1, only change active element in catalyst
Mass percent, the fresh catalyst activity element quality group being prepared becomes: Cu:10.86%, Fe:37.98%, Zr:
3.35%, Co:1.28%, Si:28.77%, K:0.03%.Catalyst performance evaluation the results are shown in Table 1.
1 target product C2+ alcohol Selectivity and activety rate of descent table of table
| Embodiment | C2+ alcohol selectivity, % | Active rate of descent (%/h) |
| Embodiment 1 | 56.29 | 0.0008 |
| Embodiment 2 | 43.98 | 0.0017 |
| Embodiment 3 | 49.66 | 0.0025 |
| Embodiment 4 | 46.32 | 0.0098 |
| Embodiment 5 | 43.15 | 0.0019 |
| Embodiment 6 | 40.73 | 0.0026 |
| Embodiment 7 | 53.98 | 0.0102 |
| Embodiment 8 | 54.56 | 0.0198 |
| Embodiment 9 | 29.87 | 0.0002 |
| Embodiment 10 | 26.22 | 0.0003 |
It can be seen from the above description that the above embodiments of the present invention realized the following chievements:
1) target product C2+ alcohol selectivity is high；
2) long-term operation stability is good, and the service life is long.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of low carbon alcohol by synthetic gas catalyst, which is characterized in that active element mass percent is in the catalyst,
Cu:10%~35%, Fe:5%~40%, Zr:3%~20%, Co:1%~15%, M:0.01~2%, Si:3%~
30%, wherein M is one of alkali metal or alkali earth metal or several.
2. low carbon alcohol by synthetic gas catalyst according to claim 1, which is characterized in that active element in the catalyst
Mass percent is Cu:10%~35%, Fe:10%~35%, Zr:5%~18%%, Co:2%~13%, M:0.05%
~1.8%, Si:5%~30%, wherein M is one of alkali metal or alkali earth metal or several.
3. a kind of preparation method of low carbon alcohol by synthetic gas catalyst as claimed in claim 1 or 2, which is characterized in that including
Following steps:
Copper nitrate, ferric nitrate, zirconium nitrate, cobalt nitrate are dissolved in deionized water and are made into mixed solution by S1, using alkali metal or
The carbonate solution of alkaline-earth metal carries out precipitation reaction as precipitating reagent and obtains catalyst Precursors by filtering or being centrifugated
And precipitated liquid；
Catalyst Precursors obtained in the S1 are added water to be beaten by S2, and binder silicon is then added, stirs evenly；
Catalyst after molding is roasted slurries drying and moulding obtained in the S2 by S3, obtains the synthesis gas system
Low-carbon alcohol catalyst.
4. preparation method according to claim 3, which is characterized in that include by institute in the S1, in the precipitation reaction
It states carbonate solution to be added continuously in the mixed solution, aging reaction is carried out after precipitating, the aging reaction terminates
Obtained precipitating is filtered afterwards and is washed with deionized, is centrifugated removal heteroion.
5. the preparation method according to claim 4, which is characterized in that heavy by control deionized water washing in the S1
The conductivity of gained clear liquid of forming sediment corresponds to control alkali metal or the content that retains in the catalyst Precursors of alkaline-earth metal.
6. the preparation method according to claim 4, which is characterized in that the temperature of the precipitation reaction is 20~100 DEG C, pH
It is 4~9.
7. the preparation method according to claim 4, which is characterized in that the temperature of the aging reaction is 20~100 DEG C, when
Between be 1~5h.
8. preparation method according to claim 3, which is characterized in that in the S2, catalyst Precursors add to be added in water mashing
Volume after entering water is equal to the volume of the precipitated liquid.
9. preparation method according to claim 3, which is characterized in that in the S2, the mode that binder silicon is added is institute
It states in the slurries after mashing is added in binder silicon, the temperature of the slurries is kept for 20~100 DEG C；Either 20~50 DEG C of bonding
Agent silicon is added in the slurries of room temperature.
10. a kind of method of low carbon alcohol by synthetic gas, which comprises the following steps:
Low carbon alcohol by synthetic gas catalyst as claimed in claim 1 or 2 is added in the solvent in paste state bed reactor, is used
The hydrogen catalyst after 300 DEG C of temperature programmed reductions are activated for 24 hours under normal pressure；
Then higher alcohols synthesis reaction is carried out in the paste state bed reactor, reaction temperature is 200~280 DEG C, reaction pressure
It is 2000~10000h for 5.0MPa~7.0MPa, air speed-1, H2/ CO molar ratio be 1~4:1, agitator speed 400~
1200rpm。
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| CN114849725A (en) * | 2022-05-16 | 2022-08-05 | 河南省科学院 | Red mud-based catalyst for synthesizing low-carbon alcohol and preparation method and application thereof |
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| CN114849725A (en) * | 2022-05-16 | 2022-08-05 | 河南省科学院 | Red mud-based catalyst for synthesizing low-carbon alcohol and preparation method and application thereof |
| CN114849725B (en) * | 2022-05-16 | 2024-01-23 | 河南省科学院 | Red mud-based catalyst for synthesizing low-carbon alcohol and preparation method and application thereof |
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