CN105080561B - A kind of load-type iron-based catalyst and preparation method thereof - Google Patents
A kind of load-type iron-based catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN105080561B CN105080561B CN201410184818.3A CN201410184818A CN105080561B CN 105080561 B CN105080561 B CN 105080561B CN 201410184818 A CN201410184818 A CN 201410184818A CN 105080561 B CN105080561 B CN 105080561B
- Authority
- CN
- China
- Prior art keywords
- solution
- catalyst
- preparation
- method described
- drying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of load-type iron-based catalyst and preparation method thereof.The present invention discloses a kind of preparation method of preparation of low carbon olefines by synthetic gas catalyst, comprises the following steps：（1）By carrier of aluminum oxide using unsaturated impregnation zinc solution, dry after roasting 1h 10h at 700 DEG C ~ 1000 DEG C；（2）Using fountain solution impregnation steps of the unsaturated infusion process containing adsorbent（1）Carrier after roasting, wherein the organic amine that it is 2~15 that described adsorbent, which is carbon number, the addition of described adsorbent accounts for step（1）1% ~ 10% of vehicle weight after roasting；（3）Step（2）Carrier containing adsorbent impregnates the solution containing active metal iron after drying, the impregnating metal auxiliary agent, then preparation of low carbon olefines by synthetic gas catalyst is made after drying, roasting again after drying, roasting.The catalyst has the characteristics of long-term operation activity stability is high, is conducive to commercial Application and popularization.
Description
Technical field
The present invention relates to a kind of preparation of low carbon olefines by synthetic gas catalyst and preparation method thereof, relate in particular to a kind of high living
Property load-type iron-based preparation of low carbon olefines by synthetic gas catalyst of stability and preparation method thereof.
Background technology
The low-carbon alkenes such as ethene, propylene are important basic organic chemical industry raw materials, with the development of chemical industry, its demand
Amount is more and more big.So far, the approach of the low-carbon alkene such as preparing ethylene, propylene is mainly by light oil cracking process, with complete
The increasingly depleted of petroleum resources in the range of ball, following energy resource structure certainly will be shifted.Compared with petroleum resources, coal and natural
Gas resource relative abundance, develops the low-carbon alkene production technology based on coal and natural gas and has great importance.From synthesis gas
（It can be converted to by natural gas and coal）Direct preparing ethylene, the exploitation of propylene technology, can not only reduce to petroleum resources according to
Rely, and to the chemical industrial expansion important in inhibiting in some rich gas oil starvations area.
CN1065026A discloses a kind of preparation of ethylene by use of synthetic gas method, and the preparation method for being related to catalyst is chemical precipitation
Method, mechanical mixing employs noble metal or rare metal, and more than ten plant chemistry such as niobium, gallium, praseodymium, scandium, indium, cerium, lanthanum, ytterbium
Element, ethylene selectivity is 65%-94%, but CO conversion ratios are very low, only 10%, 12% and 15% or so, and CO is recycled and certainly will brought
The consumption of the energy, and catalyst cost is high.CN01144691.9 discloses the nano-catalytic of a kind of preparation of ethylene by use of synthetic gas, propylene
Agent and preparation method thereof, uses the combination technique of laser pyrolysis processes combination solid phase reaction to be prepared for Fe3Fe bases nanometer based on C
Catalyst is applied and preparing low-carbon olefin, and achieves certain effect, but is due to need practical laser technology, is made
Preparation technology is comparatively laborious, and raw material uses Fe (CO)5, the cost of catalyst is higher, and industrialization is difficult.CN03109585.2 is public
Open a kind of for preparation of ethylene by use of synthetic gas, propylene, iron/activated-carbon catalyst of butene reaction, carrier, Fe are used as using activated carbon
As activated centre, successfully Fe is loaded on the activated carbon using vacuum impregnation technology, Fe and auxiliary agent is highly dispersed at
On activated carbon, so as to improve catalytic effect, and the cost of catalyst is greatly reduced.And catalyst is in the condition without feedstock circulation
Lower CO conversion ratios are up to 96-99%, and CH compounds selectivity is up to 69.5% in gas-phase product, and wherein ethene, propylene, butylene are in CHization
Selectivity in compound is up to more than 68%.But activated carbon is used as catalyst carrier not only bad mechanical strength but also shaping of catalyst
Difficulty, influences the service life and stability of catalyst, is unfavorable for commercial Application.
CN102441383A, CN101940958A, CN102441400A, CN102441384A are respectively adopted nitrogenous organic
The mode such as compound solution, acid solution, the cushioning liquid of ammonium salt-containing, the hydro-thermal process of sugar is carried out at dipping to silica-gel carrier
Reason, prepares Fe base silica gel supported synthesis gas and directly prepares light olefins catalyst, reduce Fe and SiO2Between carrier
Strong interaction.But above-mentioned Fe bases silica gel supported synthesis gas directly prepares the work of the long-term operation of light olefins catalyst
Property stability still need further raising.
The content of the invention
In view of the shortcomings of the prior art, a kind of iron-based support type synthesis gas system using aluminum oxide as carrier of present invention offer is low
Carbene hydrocarbon catalyst and preparation method thereof, the catalyst has the characteristics of long-term operation activity stability is high, is conducive to industry
Using and promote.
A kind of preparation method of preparation of low carbon olefines by synthetic gas catalyst, comprises the following steps：
（1）By carrier of aluminum oxide using unsaturated impregnation zinc solution, dry after at 700 DEG C ~ 1000 DEG C
1h-10h is calcined, preferably 2h-8h is calcined at 800 DEG C ~ 900 DEG C；
（2）Using fountain solution impregnation steps of the unsaturated infusion process containing adsorbent（1）Carrier after roasting, wherein institute
The adsorbent stated is the organic amine that carbon number is 2~15, and the addition of described adsorbent accounts for step（1）Vehicle weight after roasting
1% ~ 10%；
（3）Step（2）Carrier impregnation containing adsorbent contains the solution of active metal iron, is impregnated again after drying, roasting
Metal promoter, then preparation of low carbon olefines by synthetic gas catalyst is made after drying, roasting.
The inventive method, step（1）Middle zinc salt includes the one or more in zinc chloride, zinc nitrate or zinc sulfate.Zinc salt
Solution is that the mass fraction of zinc salt in the aqueous solution of zinc salt, zinc solution is 5-10%.
The inventive method, step（1）The pickup of middle zinc solution is the 5- of alumina support saturated absorption amount of solution
60%, preferably 20-50%.Dip time is 1-5h, and dipping temperature is 40-60 DEG C.Drying temperature is 80-150 DEG C after dipping, is dried
Time is 2-15h.
The inventive method, step（1）Middle alumina support can use existing commercial goods, can also be by existing method system
It is standby.Support shapes can be spherical, bar shaped, piece type.With spherical to be best.
The inventive method, step（2）Middle organic amine includes one kind in fatty amine, hydramine, acid amides, aliphatic cyclic amine or aromatic amine
Or it is several.Specifically include monoethyl amine, diethylamine, triethylamine, ethylenediamine, hexamethylene diamine, tert-butylamine, monoethanolamine, diethanol amine, three
One kind in monoethanolamine, dimethylformamide, propionamide, butyramide, pyridine, morphine, aniline, diphenylamines, naphthalidine, dinaphthylamine
Or several, the one or more preferably in diethylamine, triethylamine, morphine.
Step of the present invention（2）In, the fountain solution containing adsorbent is impregnated, using unsaturation dipping, preferably with unsaturation
Spray, wherein the volume ratio of unsaturated dipping dip amount used and carrier saturated absorption amount of solution is 0.05 ~ 0.4.Dipping contains
Have after the fountain solution of adsorbent, can be dried under the decomposition temperature no more than selected adsorbent, can also direct impregnation contain work
Property metallic iron solution, wherein drying temperature is generally 60 DEG C~150 DEG C, and 80 DEG C~120 DEG C are preferably, drying time 0.5h~
20h, preferably 1h~6h.When spraying the fountain solution containing adsorbent, the shower nozzle that atomizing effect should be selected good makes solution uniformly divide
It is scattered on alumina support.After fountain solution dipping of the dipping containing adsorbent terminates, next step can be directly carried out, be may also pass through
Health carries out next step again, and conditioned time is 0.5~8h.
The inventive method, step（3）Middle auxiliary agent is K and Mn.Fe is with helping in the preparation of low carbon olefines by synthetic gas catalyst of preparation
Agent K and Mn mass ratio is respectively（65~75）：（0.5~5）：（23~34）.Active component Fe and metal promoter K, Mn pass through dipping
Method is supported on carrier, generally using incipient impregnation.Dipping method is known to technical staff.With containing active metal or helping
, it is necessary to by drying and being calcined after the solution impregnating carrier of agent.Active metal solution or compounding agent solution preparation method are technology people
Known to member, its solution concentration can be adjusted by the consumption of each compound, so as to prepare specified activity component and auxiliary agent contains
The catalyst of amount.The raw material of required active component and auxiliary agent is generally the compound of the types such as salt, oxide or acid, such as source of iron
Be generally from the one or more in ferric nitrate, iron chloride, ferric sulfate, potassium resource in potassium nitrate, potassium carbonate, potassium chloride one
Plant or several, manganese source is generally from manganese nitrate or manganese chloride.
The inventive method, step（3）In add 2-15% in the solution containing active metal iron, preferably 5-10% is with quality
The ammonium citrate of meter.The decentralization of active component can be improved using the iron salt solutions containing ammonium citrate are added, is prepared small
The active component iron catalyst of crystal grain, so as to significantly improve the selectivity of low-carbon alkene.
The inventive method, step（3）It is middle with the solution impregnating carrier containing active metal component and auxiliary agent, through overdrying after dipping
Dry and calcination stepses, the condition of the drying and roasting is conventional, for example, drying steps dry 8-24 at 50-150 DEG C
Hour, calcination stepses are calcined 2-10 hours at 350-700 DEG C.
Preparation of low carbon olefines by synthetic gas catalyst prepared by a kind of use above method, using Fe as active component, using K and Mn as
Fe weight percentage is 0.5%-20% in auxiliary agent, catalyst, and auxiliary agent is K and Mn, Fe and auxiliary agent K and Mn matter in catalyst
Measuring ratio is respectively（65~75）：（0.5~5）：（23~34）.
The restoring method of above-mentioned preparation of low carbon olefines by synthetic gas catalyst, is reduced using the gaseous mixture of chlorine and hydrogen,
Volume content of the chlorine in gaseous mixture is 0.5-10%, and preferably 1-5%, reduction temperature is 300-450 DEG C, and the recovery time is 3-10
Hour, reduction pressure is 0.5-2MPa.The selectivity of butylene can be improved using above-mentioned restoring method.
The inventive method carries out uneven modification, the i.e. main appearance to carrier using zinc solution to alumina support
Face and outside channel surfaces carry out mainly modified and internal channel surfaces are modified and act on weaker, make the interior of alumina support
Outer duct physico-chemical property is significantly different, to greatest extent improve activity while inhibit generation low-carbon alkene carbochain increase and
Saturation is hydrogenated with, the conversion ratio of carbon monoxide is improved.The inventive method contains active component iron by way of adsorbent occupy-place
Amount is gradually increased by outer from interior, significantly improves the selectivity of catalyst.The physical and chemical performance of the catalyst, catalytic activity, long week
The stability of phase operating is obtained for raising, and the combination property of catalyst is protruded.
Embodiment
The process and effect of the present invention is further illustrated with reference to embodiment, but following examples are not constituted to the present invention
The limitation of method.
Example 1
Weigh commercially available ball-aluminium oxide（Pore volume is 0.96ml/g, and specific surface area is 286.81m2/ g, saturated water adsorptive value is
145ml/g, is provided by Fushun branch company of Sinopec catalyst Co., Ltd, and following examples and comparative example use the oxidation
Aluminium）, use unsaturated spray impregnation mass fraction for 5% zinc nitrate aqueous solution, dipping temperature is 50 DEG C, during dipping
Between 3h, pickup is the 20% of alumina support saturated absorption amount of solution, and 5h, the lower roasting 6h of 850 DEG C of roastings are dried at 120 DEG C.
Carrier unsaturation spray dipping triethylamine aqueous solution after roasting, triethylamine aqueous solution spray volume is that the total saturation of used carrier is inhaled
The mass content of triethylamine is the 8% of carrier quality in the 35% of water, triethylamine aqueous solution, in 100 DEG C of dryings after spray dipping
5h.Based on final catalyst Fe content 9wt%, the carrier of absorption triethylamine impregnates iron nitrate aqueous solution using equi-volume impregnating,
100 DEG C of dryings 16 hours, are calcined 4 hours in 550 DEG C.It is 3.6wt%, Fe, K and Mn mass ratio by manganese content in catalyst
For 70：3：28 meter incipient impregnation manganese nitrates and potassium nitrate mixed liquor, 100 DEG C of drying 16 hours, roasting 4 hours in 550 DEG C,
Gained catalyst is designated as C-1.The reaction result that C-1 catalyst synthesis gas directly prepares low-carbon alkene is as shown in table 1.
Catalyst Evaluation Test is carried out in the continuous fixed bed reactors of high pressure, to be reduced 5 hours at pure 350 DEG C of hydrogen, pressure
Power is 1.0MPa.Switching and merging gas is reacted after cooling.Reaction effluent is collected by hot trap, cold-trap respectively.Reaction condition is
280 DEG C, 1200h-1, 2.0MPa, H2/CO=1（Mol ratio）.C-1 catalyst synthesis gas directly prepares the 300h reactions of low-carbon alkene
As a result it is as shown in table 1.
Example 2
Commercial alumina is weighed, unsaturated impregnation mass fraction is used for 10% zinc sulfate solution, dipping temperature
Spend for 60 DEG C, dip time 2h, pickup is the 40% of alumina support saturated absorption amount of solution, 10h dried at 90 DEG C,
900 DEG C of roasting 4h.Carrier unsaturation spray dipping aqueous morphine solution after roasting, aqueous morphine solution spray volume is used carrier
The mass content of morphine is the 2% of carrier quality in the 10% of total saturated water adsorptive value, aqueous morphine solution, oxygen life 5h after spray dipping,
In 90 DEG C of dry 8h.Remaining be the same as Example 1, obtained catalyst is designated as C-2, and 300h evaluation results are shown in Table 1.
Example 3
In addition to the ammonium citrate that mass fraction is 5% is added in the iron nitrate aqueous solution of dipping, remaining be the same as Example 1, system
Obtain catalyst and be designated as C-3,300h evaluation results are shown in Table 1.
Example 4
In addition to the ammonium citrate that mass fraction is 10% is added in the iron nitrate aqueous solution of dipping, remaining be the same as Example 1,
Obtained catalysis is designated as C-4, and 300 evaluation results are shown in Table 1.
Example 5
Be the same as Example 1, difference is to reduce catalyst using the gaseous mixture of chlorine and hydrogen, and chlorine is mixed
The volume content closed in gas is 5%, and obtained catalyst is designated as C-5, and 300h evaluation results are shown in Table 1.
Implement 6
Be the same as Example 1, difference is that catalyst is reduced using the gaseous mixture of chlorine and hydrogen, and chlorine is in mixing
Volume content in gas is 1%, and remaining be the same as Example 1, obtained catalyst is designated as C-6, and 300h evaluation results are shown in Table 1.
Comparative example 1
In addition to using saturation and spraying impregnating effect fraction for 5% zinc nitrate aqueous solution, catalysis is made in remaining be the same as Example 1
Agent is designated as B-1, and 300h evaluation results are shown in Table 1.
Comparative example 2
In addition to dipping triethylamine aqueous solution is not sprayed, remaining be the same as Example 1, obtained catalyst is designated as B-2, and 300h evaluates knot
Fruit is shown in Table 1.
The reactivity worth of the catalyst of table 1
Claims (22)
1. a kind of preparation method of preparation of low carbon olefines by synthetic gas catalyst, it is characterised in that：Comprise the following steps：
（1）By carrier of aluminum oxide using unsaturated impregnation zinc solution, dry after roasting at 700 DEG C ~ 1000 DEG C
1h-10h；
（2）Using fountain solution impregnation steps of the unsaturated infusion process containing adsorbent（1）Carrier after roasting, wherein described
Adsorbent is the organic amine that carbon number is 2~15, and the addition of described adsorbent accounts for step（1）1% of vehicle weight after roasting
~10%；
（3）Step（2）Carrier impregnation containing adsorbent contains the solution of active metal iron, the impregnating metal again after drying, roasting
Auxiliary agent, then preparation of low carbon olefines by synthetic gas catalyst is made after drying, roasting.
2. according to the method described in claim 1, it is characterised in that：Step（1）After drying 2h- is calcined at 800 DEG C ~ 900 DEG C
8h。
3. according to the method described in claim 1, it is characterised in that：Step（1）Middle zinc salt includes zinc chloride, zinc nitrate or sulfuric acid
One or more in zinc.
4. according to the method described in claim 1, it is characterised in that：Step（1）Middle zinc solution is the aqueous solution of zinc salt, zinc salt
The mass fraction of zinc salt is 5-10% in solution.
5. according to the method described in claim 1, it is characterised in that：Step（1）The pickup of middle zinc solution is carrying alumina
The 5-60% of body saturated absorption amount of solution, dip time is 1-5h, and dipping temperature is that drying temperature is 80- after 40-60 DEG C, dipping
150 DEG C, drying time is 2-15h.
6. according to the method described in claim 1, it is characterised in that：Step（1）The pickup of middle zinc solution is carrying alumina
The 20-50% of body saturated absorption amount of solution.
7. according to the method described in claim 1, it is characterised in that：Step（2）Middle organic amine include fatty amine, hydramine, acid amides,
One or more in aliphatic cyclic amine or aromatic amine.
8. the method according to claim 1 or 7, it is characterised in that：Step（2）Middle organic amine include monoethyl amine, diethylamine,
Triethylamine, ethylenediamine, hexamethylene diamine, tert-butylamine, monoethanolamine, diethanol amine, triethanolamine, dimethylformamide, propionamide, fourth
One or more in acid amides, pyridine, morphine, aniline, diphenylamines, naphthalidine, dinaphthylamine.
9. method according to claim 8, it is characterised in that：Step（2）Middle organic amine is diethylamine, triethylamine, morphine
In one or more.
10. according to the method described in claim 1, it is characterised in that：Step（2）Middle fountain solution of the dipping containing adsorbent, is adopted
Sprayed with unsaturation, wherein the volume ratio of unsaturated dipping dip amount used and carrier saturated absorption amount of solution for 0.05 ~
0.4。
11. according to the method described in claim 1, it is characterised in that：Step（2）After middle fountain solution of the dipping containing adsorbent,
Dried under the decomposition temperature no more than selected adsorbent, or direct impregnation contains the solution of active metal iron, drying temperature
For 60 DEG C~150 DEG C, drying time 0.5h~20h.
12. method according to claim 11, it is characterised in that：Drying temperature is 80 DEG C~120 DEG C, and drying time is 1h
~6h.
13. according to the method described in claim 1, it is characterised in that：Step（2）Fountain solution dipping of the middle dipping containing adsorbent
After end, next step is directly carried out, or next step is carried out again by health, conditioned time is 0.5~8h.
14. according to the method described in claim 1, it is characterised in that：Step（3）Middle auxiliary agent is K and Mn, the synthesis gas system of preparation
Fe and auxiliary agent K and Mn mass ratio are respectively in light olefins catalyst（65~75）：（0.5~5）：（23~34）.
15. according to the method described in claim 1, it is characterised in that：Step（3）Middle active component Fe and metal promoter K, Mn lead to
Infusion process is crossed to support on carrier.
16. method according to claim 14, it is characterised in that：Source of iron is one kind in ferric nitrate, iron chloride, ferric sulfate
Or it is several, potassium resource is the one or more in potassium nitrate, potassium carbonate, potassium chloride, and manganese source is manganese nitrate or manganese chloride.
17. according to the method described in claim 1, it is characterised in that：Step（3）Added in solution containing active metal iron
The ammonium citrates of 2-15% in mass.
18. method according to claim 17, it is characterised in that：Step（3）Added in solution containing active metal iron
The ammonium citrates of 5-10% in mass.
19. according to the method described in claim 1, it is characterised in that：Step（3）It is middle with molten containing active metal component and auxiliary agent
By dry and calcination stepses after liquid impregnated carrier, dipping, drying steps are dried 8-24 hours at 50-150 DEG C, calcination stepses
It is calcined 2-10 hours at 350-700 DEG C.
20. preparation of low carbon olefines by synthetic gas catalyst prepared by a kind of use claim 1-19 either method, it is characterised in that：Should
Catalyst is using Fe as active component, using K and Mn as auxiliary agent, and Fe weight percentage is 0.5%-20% in catalyst, and Fe is with helping
Agent K and Mn mass ratio is respectively（65~75）：（0.5~5）：（23~34）.
21. the restoring method of catalyst described in claim 20, it is characterised in that：Gone back using the gaseous mixture of chlorine and hydrogen
Original, volume content of the chlorine in gaseous mixture is 0.5-10%, and reduction temperature is 300-450 DEG C, and the recovery time is 3-10 hours,
Reduction pressure is 0.5-2MPa.
22. restoring method according to claim 21, it is characterised in that：Volume content of the chlorine in gaseous mixture is 1-
5%。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410184818.3A CN105080561B (en) | 2014-05-05 | 2014-05-05 | A kind of load-type iron-based catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410184818.3A CN105080561B (en) | 2014-05-05 | 2014-05-05 | A kind of load-type iron-based catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105080561A CN105080561A (en) | 2015-11-25 |
| CN105080561B true CN105080561B (en) | 2017-08-22 |
Family
ID=54562426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410184818.3A Active CN105080561B (en) | 2014-05-05 | 2014-05-05 | A kind of load-type iron-based catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105080561B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1289647A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Process for preparing catalyst with non-uniform distribution of active metals |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101026536B1 (en) * | 2009-06-12 | 2011-04-01 | 한국화학연구원 | Fe-based catalyst for the reaction of Fischer-Tropsch synthesis and preparation method thereof |
| CN102441383B (en) * | 2010-10-12 | 2013-06-19 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefine catalyst by loading iron-based synthetic gas |
| CN102441393B (en) * | 2010-10-12 | 2016-01-13 | 中国石油化工股份有限公司 | A kind of take modified aluminas as fischer-tropsch synthetic catalyst and the application thereof of carrier |
| CN102527401B (en) * | 2010-12-30 | 2014-06-25 | 中国科学院大连化学物理研究所 | Catalyst used in preparation of methane and coproduction of low-carbon olefin by conversion of syngas, preparation method for catalyst and application of catalyst |
| CN102989511B (en) * | 2011-09-08 | 2015-04-29 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst, and preparation and application thereof |
-
2014
- 2014-05-05 CN CN201410184818.3A patent/CN105080561B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1289647A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Process for preparing catalyst with non-uniform distribution of active metals |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105080561A (en) | 2015-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105080563B (en) | A kind of hydrogenation catalyst and preparation method thereof | |
| CN102441383B (en) | Method for preparing low-carbon olefine catalyst by loading iron-based synthetic gas | |
| CN103586046B (en) | Catalyst for preparing light olefins from synthetic gas and preparation method thereof | |
| CN114939433A (en) | Composite catalyst for directly preparing light aromatic hydrocarbon by carbon dioxide hydrogenation, preparation and application thereof | |
| CN106669721A (en) | Iron-based supported catalyst and preparation method thereof | |
| CN107970954B (en) | Catalyst for preparing butadiene by oxidative dehydrogenation of butylene and preparation method thereof | |
| CN105709770B (en) | A kind of preparation of low carbon olefines by synthetic gas catalyst and preparation method thereof | |
| CN106669718B (en) | A kind of synthesis gas alkene catalyst and its preparation method and application | |
| CN105709768B (en) | A kind of preparation method of synthesis gas alkene catalyst | |
| CN105709773B (en) | A kind of synthesis gas alkene catalyst and its preparation method and application | |
| CN106669723B (en) | A kind of catalyst for synthesis gas reaction and its preparation method and application | |
| CN105080562B (en) | A kind of CO hydrogenation catalysts and its preparation method and application | |
| CN105709830B (en) | A kind of synthesis gas alkene catalyst and preparation method thereof | |
| CN106669719B (en) | A kind of producing light olefins catalyst and preparation method thereof | |
| CN105709775B (en) | A kind of ferrum-based catalyst and its preparation method and application | |
| CN105080561B (en) | A kind of load-type iron-based catalyst and preparation method thereof | |
| CN105642307B (en) | A kind of load-type iron-based catalyst and preparation method thereof | |
| CN105709771B (en) | A kind of preparation of low carbon olefines by synthetic gas catalyst and preparation method thereof | |
| CN105709774B (en) | A kind of preparation method of synthesis gas alkene catalyst | |
| CN105080560B (en) | A kind of iron-based hydrogenation catalyst and preparation method thereof | |
| CN105709791B (en) | A kind of preparation method of load-type iron-based catalyst | |
| CN105709772B (en) | A kind of synthesis gas alkene catalyst and its preparation method and application | |
| CN106669720A (en) | Hydrogenation catalyst, preparation method and applications thereof | |
| CN105709769B (en) | A kind of synthesis gas alkene catalyst and preparation method thereof | |
| CN105709767B (en) | A kind of ferrum-based catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |