CN108014816A - A kind of preparation method and application of CO hydrogenation synthesis mixing primary alconol coproduction alkene catalyst - Google Patents
A kind of preparation method and application of CO hydrogenation synthesis mixing primary alconol coproduction alkene catalyst Download PDFInfo
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Abstract
The present invention provides a kind of preparation method and application of the catalyst of CO hydrogenation synthesis mixing primary alconol coproduction alkene.The catalyst general type is Co Mn X/AC, and carrier is activated carbon, and active component is the Co generated in Co and reaction process2The Co Co of C compositions2C double activity center, main auxiliary agent are Mn, the one or more in X Ce, Zn, Cu, La.Wherein, Co contents are 1~30wt%, and Mn contents are 0.01~10wt%, and auxiliary agent X contents are 0~10wt%.Using catalyst provided by the invention, alkene and C in Fischer-Tropsch synthetic can be improved2The selectivity of primary alconol mixed above, makes the total mass fraction of alkene and alcohol in the product be more than 50wt%, is conducive to further produce the fine chemical product such as the high valuable chemicals such as alcohol, ether, aldehyde, carboxylic acid and detergent, plasticizer, surfactant.
Description
Technical field
Method for preparing catalyst and its application the present invention relates to a kind of CO hydrogenation synthesis mixing primary alconol coproduction alkene.Specifically
, which is Co-Mn-X/AC, is a kind of activated carbon supported Co-Co2C double activity center catalyst, using Mn as
The auxiliary agent such as main auxiliary agent, auxiliary addition Ce, Cu, Zn, La is selective to improve alkene and mixing primary alconol in product.
Background technology
Using Fischer-Tropsch (FT) synthetic method, synthesis gas (CO/H is utilized2) One-step production alkene, alcohol, ether, aldehyde, acid it is contour
Chemicals is worth, is the important directions of chemical field concern in recent years.Specifically, C2~C4Low-carbon alkene be chemical industry
Important source material, available for production polyethylene, the chemicals such as polypropylene, have a vast market space.And carbon number is more than or equal to 5
Alkene can be converted into the fine chemicals such as corresponding alcohol, ether, aldehyde, acid, halide by means such as hydroformylations, have
Very high surcharge.In addition, primary alconol of the carbon number more than or equal to 2 has unique excellent performance, in multiple necks of national economy
Have a wide range of applications in domain.Wherein, C2~C5Alcohol can improve efficiency of combustion, C as excellent fuel additive6~C11It is high
Carbon alcohol can be used for producing plasticizer, C12~C18Higher alcohols can be used for producing surfactant.It is estimated that the market of high carbon primary alcohol
Price is at 10000~20000 yuan/ton, and about 13,000,000 tons of annual requirement, growth rate is about 3%.
At present, the method for industrial synthesizing low-carbon alkene mainly includes two ways of methanol-to-olefins (MTO) and petroleum cracking
Footpath, higher olefins are mainly derived from the polymerization of low-carbon alkene.Therefore, from synthesis gas, the approach that a step prepares alkene has
Shortest technology path and preferably economic benefit.The main method of synthesis mixing primary alconol is ziegler process and olefin hydroformylation
Method.Ziegler process realizes that carbochain increases using ethene as raw material, using triethyl aluminum as catalyst, then is aoxidized, hydrolyzed and separated
Technique, is made C6~C16Straight-chain even primary alconol.But this method technological process is grown, technical sophistication, development difficulty is big, catalyst
Consumption is big and security is poor.Olefin hydroformylation method is alkene and CO and H under the action of Rh bases or Co base catalyst2's
Gaseous mixture carries out hydroformylation reaction generation aldehyde, and corresponding alcohol is made in aldehyde repeated hydrogenation.But the method technological process is grown, catalyst valency
Lattice are expensive and are easily lost in.Therefore, there is an urgent need to develop technique is simple, reaction condition is gentle, raw material is easy to get and derives from a wealth of sources
Mixing primary alconol production new technology.
Can be with the direct Synthesis of mixed alcohols (C of a step by CO hydrogenation1~C6), which has the advantages that technique is simple.
US4775696 patents disclose a kind of method using synthesis gas synthesizing low-carbon mixed alcohol, its catalyst is urged for Mo, W or Re base
Agent.US4752622 and US4882630 patents provide the method using synthesis gas as unstripped gas synthesizing low-carbon mixed alcohol, use
Mo, W base catalyst of Fe, Co and Ni auxiliary agent modulation, add alkali or alkaline earth metal.US6753353 discloses a nanometer MoS2
Or W2C is as catalyst CO hydrogenation synthesizing low carbon mixed alcohols.US8048933 patents disclose one kind using synthesis gas as raw material
The method for producing low carbon mixed alcohol, the catalyst used is Mo2C, and Ni and/or Na are added as auxiliary agent, improve catalyst
Performance.CN01130481 discloses Mn-Ni-K-MoS2Catalyst, in MoS2Mn elements are introduced in the preparation of base catalyst, are made
Catalyst synthol activity is obtained to significantly improve, meanwhile, C2The selectivity of above alcohol increases.CN200610097869 is carried
For a kind of catalyst for synthesizing low-carbon alcohol from synthetic gas and preparation method thereof, catalyst key component is CuO, ZnO, Cr2O3、
Al2O3With suitable other auxiliary agents (V, Mo, Mn, Mg, Ce), there is higher CO conversion ratios and higher C2The selection of above alcohol
Property.But above by CO plus the mixed alcohol carbon number of hydroformylation step preparation than relatively low, generally C1~C6, substantially cannot be high attached
Value added C6Higher alcohols above, the low methanol proportion of added value is larger, reaches more than 40%, constrains the economy of the technology
Property.
Dalian Inst of Chemicophysics, Chinese Academy of Sciences have developed for preparing C by F- T synthesis6Higher alcohols above
Catalyst, wherein US 7670985 and CN101310856 discloses its catalyst system and is catalyzed for activated carbon supported Co bases
Agent, CO, which is hydrogenated with, under its catalytic action can directly synthesize high-carbon mixing primary alconol, C in fluid product2~C18The high selectivity of alcohol
Up to 60%, wherein distribution of the methanol in alcohol only accounts for about 2~4%.But in addition to alcohol, the CO hydrogenation reactions production of above-mentioned catalyst
A large amount of alkane are also included in thing, the olefin(e) centent of high added value is relatively low.Therefore, still need and further the catalyst is optimized.
The content of the invention
The object of the present invention is to develop catalysis that is a kind of while improving mixing primary alconol and olefin(e) centent in Fischer-Tropsch synthetic
Agent, makes to mix primary alconol in product and the total mass fraction of alkene reaches more than 50wt%, to from synthesis gas, step production
The high valuable chemicals such as alcohol, ether, aldehyde, carboxylic acid.
To realize above-mentioned target, the technical solution adopted in the present invention specifically includes：
The catalyst of a kind of CO hydrogenation synthesis alkene and mixing primary alconol, it is characterised in that the catalyst mode is Co-Mn-
X/AC.Wherein, catalyst activity component is the Co generated in Co and reaction process2The Co-Co of C compositions2C double activity center, mainly
Auxiliary agent is Mn, and X auxiliary agents are the one or more in Ce, Cu, Zn, La, and carrier is activated carbon.Alkene is the alkene of carbon number 2~30
Class compound, mixing primary alconol are the primary alcohol compound of carbon number 2~30.
Above-mentioned catalyst, the content of Co elements is 1~30wt% of catalyst weight in active component, and Mn contents are catalysis
0.01~10wt% of agent weight, auxiliary agent X content are 0~10wt% of catalyst weight.Carrier is almond activated carbon or coconut husk
Activated carbon, the particle diameter of the activated carbon is 40 μm~2cm, and specific surface area is 100~1500m2/ g, average pore size are 0.1~20nm,
Pore volume is 0.1~2.5mL/g.
Above-mentioned method for preparing catalyst comprises the following steps：
(1) activated carbon raw material is first handled with deionized water boiling washing；
(2) after using the soluble-salt of active component and auxiliary agent or the aqueous solution Immesion active carbon carrier of acid, in 323~353K
When drying 8~48 is small under air conditions, half stem-based catalyst is made；
(3) half stem-based catalysts are under nitrogen or argon gas atmosphere, 353~700K of temperature, 100~5000h of air speed-1, roasting 4
~100 it is small when, be prepared into stem-based catalyst；
(4) stem-based catalyst is in hydrogeneous atmosphere, and hydrogen content is 10~100%, 473~873K of temperature, and pressure 0~
1.0MPa, 100~5000h of air speed-1, when reductase 12~100 are small, it is prepared into activated catalyst.
(5) activated catalyst is also needed through H2/ CO gaseous mixtures are pre-processed, described to reach stabilizing active and selectivity
H in gaseous mixture2/ CO molar ratios are 0.5~4.0, and pretreatment temperature is 433~563K, and pressure is 0~6MPa, air speed 100~
10000h-1, when processing time 1~96 is small.
Above-mentioned catalyst not only can be applied to fixed bed reactors, but also can be applied to paste state bed reactor.Applied to solid
During fixed bed reactor, above-mentioned (3) (4) (5) step is in situ in fixed bed reactors to be carried out；During applied to paste state bed reactor,
(3) (4) step carries out in a fluidized bed reactor, after the completion of catalyst is transferred in paste state bed reactor progress (5) step.
Catalyst should use inert gas mode of movement when shifting.
The preferred reaction conditions of above-mentioned catalyst CO hydrogenation synthesis alkene and mixing primary alconol are 383~525K of temperature,
0~8MPa of pressure, 100~6000h of air speed-1, H2/ CO molar ratios 0.5~4.0.
In the CO hydrogenation reaction products of above-mentioned catalyst, proportion is not less than 30wt% to alkene gross mass in the product,
Proportion is not less than 20wt% to mixing primary alconol gross mass in the product, and the gross mass of alkene and mixing primary alconol is shared in the product
Ratio is not less than 50wt%.
The present invention has the following advantages compared with prior art：
Using catalyst provided by the invention, the yield that primary alconol and alkene are mixed in synthetic product can be improved at the same time, its
Proportion is not less than 50wt% to gross mass in the product.
Co-Co provided by the invention2C catalyst, utilizes Co2The class noble metal property of C, realizes CO absorption and insertion carbochain
Effect, without using noble metal, catalyst price reduction, is conducive to industrial mass production.
Catalyst provided by the invention, carrier is activated carbon, in activation of catalyst and reaction process, not with the Co of load
The difficult reducing substances such as reaction generation cobaltous silicate, cobalt aluminate, are conducive to improve the reduction degree of Co, improve catalyst life.
Beneficial effects of the present invention are：
On the basis of its higher mixing primary alconol selectivity is maintained, the selectivity of alkene is substantially increased, and produce
Alkene further can change into the chemicals such as alcohol by hydroformylation, improve the comprehensive value of CO hydrogenation products.
Embodiment
The present invention is further illustrated with subordinate list with reference to embodiments, does not carry out any restrictions to the present invention.
Embodiment 1
10Co0.3Mn0.2Zn/AC catalyst is prepared, labeled as Cat1.
Select specific surface area 960m2The cocoanut active charcoal of/g, average pore size 3.8nm, pore volume 0.6mL/g are carrier, by it
Washed repeatedly in 90 DEG C of deionized waters 20 times, when drying 20 is small under 393K, obtain absorbent charcoal carrier after purification.
4.94g cabaltous nitrate hexahydrates, 0.091g zinc nitrate hexahydrates and 0.094g manganese acetates are dissolved in 10g water, are made
Maceration extract.Impregnated with the maceration extract under room temperature 298K dry in the shade after 8.95g absorbent charcoal carriers about 10 it is small when, do not have to catalyst surface
After having flowable moisture, be placed in 313K baking ovens and dry 24h, after taking-up in nitrogen, be gradually heating to 573K roasting 20 it is small when,
Taking-up is fitted into the fixed bed reactors of a diameter of 6mm, loading 2mL, air speed 2000h-1.Catalyst gradually rises in hydrogen
Temperature to 673K reductase 12s 0 it is small when, be cooled to 423K, switching and merging gas (H2/ CO=2:1), pressure 2MPa, is warming up to 493K progress
FT reacts.Stablize 12 it is small when after, each component concentration in sampling analysis tail gas when 24 is small, and liquid product yield.Gained
The results are shown in subordinate list 1.
Embodiment 2
15Co0.3Mn3Cu/AC catalyst is prepared, labeled as Cat2.
7.41g cabaltous nitrate hexahydrates, 1.14g Gerhardites and 0.094g manganese acetates are dissolved in 10g water, leaching is made
Stain liquid.8.17g absorbent charcoal carriers are impregnated under room temperature 298K with the maceration extract, dry in the shade about 10 it is small when, do not have to catalyst surface
After flowable moisture, be placed in 313K baking ovens drying 24 it is small when, after taking-up in nitrogen, it is small to be gradually heating to 573K roastings 20
When, taking-up is fitted into the fixed bed reactors of a diameter of 6mm, loading 2ml, air speed 2000h-1.Catalyst in hydrogen by
Gradually be warming up to 673K reductase 12s 0 it is small when, be cooled to 423K, switching and merging gas (H2/ CO=2:1), pressure 2MPa, is warming up to 493K
Carry out FT reactions.Stablize 12 it is small when after, each component concentration in sampling analysis tail gas when 24 is small, and liquid product yield.
Acquired results are listed in subordinate list 1.
Embodiment 3
10Co0.5Mn1Ce0.1La/AC catalyst is prepared, labeled as Cat3.
4.94g cabaltous nitrate hexahydrates, 0.99g cerous nitrates, 0.03g lanthanum nitrate hexahydrates and 0.157g manganese acetates are dissolved in 10
In gram water, maceration extract is made.Impregnated with the maceration extract under room temperature 298K dry in the shade after 8.84g absorbent charcoal carriers about 10 it is small when, extremely
After catalyst surface does not have flowable moisture, be placed in 313K baking ovens drying 24 it is small when, after taking-up in nitrogen, be gradually heating to
When 573K roastings 20 are small, taking-up is fitted into the fixed bed reactors of a diameter of 6mm, loading 2mL, air speed 2000h-1.Catalysis
Agent be gradually heating in hydrogen 673K reductase 12s 0 it is small when, be cooled to 423K, switching and merging gas (H2/ CO=2:1), pressure
2MPa, is warming up to 493K and carries out FT reactions.Stablize 12 it is small when after, each component concentration in sampling analysis tail gas when 24 is small, with
And liquid product yield.Acquired results are listed in subordinate list 1.
Embodiment 4
10Co2Mn0.2Zn2Cu/AC catalyst is prepared, labeled as Cat4.
By 4.94g cabaltous nitrate hexahydrates, 0.091g zinc nitrate hexahydrates, 0.76 gram of Gerhardite and 0.629g acetic acid
Manganese is dissolved in 10g water, and maceration extract is made.Impregnated with the maceration extract under room temperature 298K dry in the shade after 8.6g absorbent charcoal carriers it is about 10 small
When, after there is no flowable moisture to catalyst surface, be placed in 313K baking ovens drying 24 it is small when, after taking-up in nitrogen, gradually
Be warming up to 573K roasting 20 it is small when, taking-up be fitted into the fixed bed reactors of a diameter of 6mm, loading 2mL, air speed 2000h-1.Catalyst be gradually heating in hydrogen 673K reductase 12s 0 it is small when, be cooled to 423K, switching and merging gas (H2/ CO=2:1), press
Power 2MPa, is warming up to 493K and carries out FT reactions.Stablize 12 it is small when after, each component concentration in sampling analysis tail gas when 24 is small,
And liquid product yield.Acquired results are listed in subordinate list 1.
Embodiment 5
10Co7Mn7Cu1Ce/AC catalyst is prepared, labeled as Cat5.
By 4.94g cabaltous nitrate hexahydrates, 2.66g Gerhardites, six nitric hydrate ceriums of 0.31g and 2.20g manganese acetates
It is dissolved in 10 grams of water, maceration extract is made.Impregnated with the maceration extract under room temperature 298K dry in the shade after 7.50g absorbent charcoal carriers it is about 10 small
When, after there is no flowable moisture to catalyst surface, be placed in 313K baking ovens drying 24 it is small when, after taking-up in nitrogen, gradually
Be warming up to 573K roasting 20 it is small when, taking-up be fitted into the fixed bed reactors of a diameter of 6mm, loading 2mL, air speed 2000h-1.Catalyst be gradually heating in hydrogen 673K reductase 12s 0 it is small when, be cooled to 423K, switching and merging gas (H2/ CO=2:1), press
Power 2MPa, is warming up to 493K and carries out FT reactions.Stablize 12 it is small when after, each component concentration in sampling analysis tail gas when 24 is small,
And liquid product yield.Acquired results are listed in subordinate list 1.
Embodiment 6
10Co5Mn2Zn1Ce/AC catalyst is prepared, labeled as Cat6.
By 4.94g cabaltous nitrate hexahydrates, 0.091g zinc nitrate hexahydrates, six nitric hydrate ceriums of 0.31g and 1.57g manganese acetates
It is dissolved in 10g water, maceration extract is made.Impregnated with the maceration extract under room temperature 298K dry in the shade after 8.40g absorbent charcoal carriers it is about 10 small
When, after there is no flowable moisture to catalyst surface, be placed in 313K baking ovens drying 24 it is small when, after taking-up in nitrogen, gradually
Be warming up to 573K roasting 20 it is small when, taking-up be fitted into the fixed bed reactors of a diameter of 6mm, loading 2mL, air speed 2000h-1.Catalyst be gradually heating in hydrogen 673K reductase 12s 0 it is small when, be cooled to 423K, switching and merging gas (H2/ CO=2:1), press
Power 2MPa, is warming up to 493K and carries out FT reactions.Stablize 12 it is small when after, each component concentration in sampling analysis tail gas when 24 is small,
And liquid product yield.Acquired results are listed in subordinate list 1.
Embodiment 7~8
Almond activated carbon is selected as carrier, carrier specific surface area 912m2/ g, average pore size 3.5nm, pore volume 0.43mL/
G, it is washed 20 times repeatedly in the deionized water boiled, and when drying 20 is small under 393K, obtains carried by active carbon after purification
Body.
Prepared according to method similar to Example 4 and evaluate 10Co5Mn2Zn1Ce/AC catalyst, labeled as Cat7, institute
The results are shown in subordinate list 1.
Prepared according to method similar to Example 6 and evaluation 10Co2Mn0.2Zn2Cu/AC catalyst, labeled as Cat8,
Acquired results are listed in subordinate list 1.
Comparative example 1
The formula and method of patent CN201210292413 offers are provided instead, catalyst is prepared, using similar method to it
Reaction evaluating is carried out, and compared with embodiment.Acquired results are listed in subordinate list 1.
Comparative example 1：15Co0.1Al/AC1
Comparative example 2
With the Fe of patent CN201210225885 reports100AaBbCcOxCatalyst is compared, and the results are shown in table 1.
Comparative example 2：20%Fe100Mn50Mg5K5Ox+ 80% (10%TiO2+ 90% α-Al2O3)。
Table 1
The performance of CO hydrogenation synthesis mixing primary alconol coproduction alkene on Co-Mn-X/AC catalyst
In terms of comparative result, catalyst provided by the invention on the basis of higher mixing primary alconol selectivity is maintained, into
One step improves the olefine selective in product；And with other using low-carbon alkene compared with the catalyst of principal product, this patent carries
The catalyst of confession can produce a large amount of mixing primary alconols at the same time, have the Atom economy and surcharge of higher.
Claims (10)
- A kind of 1. catalyst of CO hydrogenation synthesis mixing primary alconol coproduction alkene, it is characterised in thatThe catalyst mode is Co-Mn-X/AC, wherein, catalyst activity component is the Co generated in Co and reaction process2C is formed Co-Co2C double activity center, Mn are main auxiliary agent, and X auxiliary agents are the one or more in Ce, Cu, Zn, La, and carrier is work Property charcoal.
- 2. catalyst described in accordance with the claim 1, it is characterised in thatAlkene is the alkene of carbon number 2~30 in product, and mixing primary alconol is the primary alconol of carbon number 2~30.
- 3. catalyst described in accordance with the claim 1, it is characterised in thatIn terms of metal Co, the content of Co is 1~30wt% of catalyst weight in active component.
- 4. catalyst described in accordance with the claim 1, it is characterised in thatMn contents are 0.01~10wt% of catalyst weight, and auxiliary agent X contents are 0~10wt% of catalyst weight.
- 5. catalyst described in accordance with the claim 1, it is characterised in thatCarrier is almond activated carbon or cocoanut active charcoal, and the particle diameter of the activated carbon is 40 μm~2cm, specific surface area for 100~ 1500m2/ g, average pore size are 0.1~20nm, and pore volume is 0.1~2.5mL/g.
- 6. the preparation method of catalyst described in a kind of claim 1, it is characterised in that comprise the following steps：(1) activated carbon raw material is first handled with deionized water boiling washing；(2) it is empty in 323~353K after using the soluble-salt of active component Co and auxiliary agent or the aqueous solution Immesion active carbon carrier of acid When drying 8~48 is small under the conditions of gas, half stem-based catalyst is made；(3) half stem-based catalysts are under nitrogen or argon gas atmosphere, 353~700K of temperature, 100~5000h of air speed-1, roasting 4~ 100 it is small when, be prepared into stem-based catalyst；(4) stem-based catalyst is in hydrogeneous atmosphere, and hydrogen content is 10~100%, 473~873K of temperature, 0~1.0MPa of pressure, 100~5000h of air speed-1, when reductase 12~100 are small, it is prepared into activated catalyst；(5) activated catalyst is also needed through H2/ CO gaseous mixtures are pre-processed, to reach stabilizing active and selectivity, the gaseous mixture Middle H2/ CO molar ratios are 0.5~4.0, and pretreatment temperature is 433~563K, and pressure is 0~6MPa, 100~10000h of air speed-1, When processing time 1~96 is small.
- 7. according to the preparation method described in claim 6, it is characterised in thatThe catalyst not only can be applied to fixed bed reactors, but also can be applied to paste state bed reactor；(3) (4) (5) step is in situ in fixed bed reactors during applied to fixed bed reactors, in claim 6 carries out；During applied to paste state bed reactor, (3) (4) step carries out in a fluidized bed reactor, after the completion of catalyst is transferred to (5) step is carried out in paste state bed reactor.
- A kind of 8. application of catalyst described in claim 1, it is characterised in thatIt is 383~525K of temperature, pressure 0~8MPa, H that catalyst FT, which synthesizes alkene and the reaction condition of mixing primary alconol,2/ CO molar ratios 0.5~4.0.
- 9. according to the application described in claim 8, it is characterised in thatProportion is not less than 30wt% to alkene gross mass in the product in product.
- 10. according to the application described in claim 8, it is characterised in thatPrimary alconol gross mass is mixed in product, and proportion is not less than 20wt% in the product.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110964563A (en) * | 2018-09-28 | 2020-04-07 | 中国科学院大连化学物理研究所 | Hydrofining method for preparing mixed alcohol crude product from synthesis gas |
| CN112275304A (en) * | 2020-11-09 | 2021-01-29 | 济南大学 | Carbon-supported cobalt carbide catalyst containing auxiliary agent and preparation method and application thereof |
| WO2021043560A1 (en) | 2019-09-05 | 2021-03-11 | Thyssenkrupp Industrial Solutions Ag | Process of preparing alcohols |
| CN113522303A (en) * | 2021-06-23 | 2021-10-22 | 天津大学 | CoMnOx nano-catalyst for directly preparing low-carbon alcohol from synthesis gas, and preparation method and use method thereof |
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