CN102441383B - Method for preparing low-carbon olefine catalyst by loading iron-based synthetic gas - Google Patents
Method for preparing low-carbon olefine catalyst by loading iron-based synthetic gas Download PDFInfo
- Publication number
- CN102441383B CN102441383B CN201010510864XA CN201010510864A CN102441383B CN 102441383 B CN102441383 B CN 102441383B CN 201010510864X A CN201010510864X A CN 201010510864XA CN 201010510864 A CN201010510864 A CN 201010510864A CN 102441383 B CN102441383 B CN 102441383B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- hours
- silica gel
- organic compounds
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing a low-carbon olefine catalyst by a loading iron-based synthetic gas, which comprises the following steps of: firstly carrying out surface modification on a silica gel carrier by using silica gel as a carrier, and then loading a metal auxiliary agent and an active component Fe by using an immersion method, wherein the surface modification method of the silica gel carrier comprises the following step of carrying out immersion treatment by using the acidic solution of sugar. After the silica gel carrier adopted is modified, the strong interaction between the carrier and the active component is overcome, and the activity and the selectivity of the catalyst are improved. The catalyst prepared by using the method is suitable for a reaction process of producing low-carbon olefines of ethylene, propylene, butane and the like by the synthetic gas.
Description
Technical field
The present invention relates to a kind of preparation method of load-type iron-based preparation of low carbon olefines by synthetic gas catalyst, relate in particular to a kind of take modified silica-gel as carrier, add that metal promoter modifies low-cost and be easy to the preparation method of the high activity iron-based preparation of low carbon olefines by synthetic gas catalyst of commercial Application.
Background technology
The low-carbon alkene such as ethene, propylene is important basic organic chemical industry raw material, and along with the development of chemical industry, its demand is more and more large.Up to now, the approach of the low-carbon alkenes such as preparing ethylene, propylene is mainly by the light oil cracking process, and along with the exhaustion day by day of petroleum resources in global range, following energy resource structure certainly will shift.Compare with petroleum resources, coal is relative with natural gas resource abundant, and exploitation has great importance take coal and natural gas as main low-carbon alkene production technology.From the directly exploitation of preparing ethylene, propylene technology of synthesis gas (can be converted to by natural gas and coal), not only can reduce the dependence to petroleum resources, and to some chemical industrial expansion important in inhibitings in rich gas oil starvation area.
CN1065026A discloses a kind of preparation of ethylene by use of synthetic gas method, the preparation method who relates to catalyst is chemical precipitation method, mechanical mixing, adopted noble metal or rare metal, planted chemical element such as niobium, gallium, praseodymium, scandium, indium, cerium, lanthanum, ytterbium etc. more than ten, ethylene selectivity is 65%-94%, but the CO conversion ratio is very low, 10%, 12% and 15% left and right only, CO recycles the consumption that certainly will bring the energy, and the catalyst cost is high.
CN01144691.9 discloses nanocatalyst of a kind of preparation of ethylene by use of synthetic gas, propylene and preparation method thereof, adopts laser pyrolysis processes to prepare with Fe in conjunction with the combination technique of solid phase reaction
3C is that main Fe base nano-catalyst is used and preparing low-carbon olefin, and has obtained certain effect, but due to the practical laser technology of needs, makes preparation technology more loaded down with trivial details, and raw material adopts Fe (CO)
5, the cost compare of catalyst is high, the industrialization difficulty.
CN03109585.2 discloses a kind of iron/activated-carbon catalyst for the synthesis of gas ethene processed, propylene, butene reaction, adopt active carbon as carrier, Fe is as the activated centre, adopt vacuum impregnation technology successfully Fe to be loaded on active carbon, make Fe and auxiliary agent be able to high degree of dispersion on active carbon, thereby the raising catalytic effect, and greatly reduce the cost of catalyst.And catalyst CO conversion ratio under the condition that circulates without raw material can reach 96-99%, and in gas-phase product, the CH compound selective reaches 69.5%, therein ethylene, propylene, butylene selectively reaching more than 68% in the CH compound.But active carbon affects service life and the stability of catalyst as catalyst carrier bad mechanical strength but also shaping of catalyst difficulty not only, is unfavorable for commercial Application.
Compare the active carbon silica supports and not only have acid resistance, heat resistance (can at 500～600 ℃ of lower long reactions) and wearability, and silica is easy to moulding, specific area is larger, and all have controllability, be more suitable for as catalyst carrier.In the reaction of alkene, few silica that adopts is mainly because Fe and SiO as carrier but directly prepare at the base supported synthesis gas of Fe at present
2Strong interaction between carrier causes part Fe to be difficult to be reduced, and is difficult to reach comparatively ideal reactivity.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind ofly take modified silica-gel as carrier, add the preparation method of the iron-based preparation of low carbon olefines by synthetic gas catalyst that metal promoter modifies.The silica-gel carrier that the present invention adopts has overcome the strong interaction between carrier and active component after modification, improved the activity of catalyst.
The preparation method that iron-based support type synthesis gas of the present invention directly prepares the catalyst of alkene comprises following process: take silica gel as carrier, at first silica-gel carrier is carried out surface modification, then adopt infusion process carried metal auxiliary agent and active component Fe; Wherein the surface modifying method of silica-gel carrier is for adopting the organic compounds containing nitrogen solution impregnation to process.
Iron-based support type synthesis gas of the present invention directly prepares in the preparation method of catalyst of alkene, and silica-gel carrier can adopt existing silica gel product, and as macropore or pore dry microspheres etc., silica gel can adopt commodity on demand, also can be by existing method preparation.
Iron-based support type synthesis gas of the present invention directly prepares in the preparation method of catalyst of alkene, method of modifying to silica-gel carrier adopts the organic compounds containing nitrogen solution impregnation to process, organic compounds containing nitrogen can be one or more that are selected from monoethanolamine, diethanol amine, triethanolamine and pyridine etc., organic compounds containing nitrogen solution generally can adopt the aqueous solution or organic solution, preferred aqueous solutions, organic solution adopts the organic solvent that can dissolve nitrogen-containing compound used, as ethanol, acetone etc.In organic compounds containing nitrogen solution, the weight concentration of organic compounds containing nitrogen is 1%-35%, is preferably 5%-20%.Dipping can adopt saturated dipping or supersaturation dipping, carries out drying after dipping, also can proceed calcination process.The impregnation process temperature is 50-95 ℃, is preferably 60～80 ℃, and the impregnation process time is 2-150h, preferred 10-100h.Baking temperature is 50-150 ℃, and be 0.5-36h drying time, preferably dry 8-24h under 60-120 ℃.Roasting is at 280-600 ℃ of lower roasting 2-15 hour, preferably at 300-500 ℃ of lower roasting 4-10 hour.
In the preparation method of iron-based support type preparing low-carbon olefin catalyst of the present invention, in catalyst, to account for the weight percentage of support modification silica gel be 0.5%-20% to major catalyst Fe, preferred 3%-12%.Also contain auxiliary agent in catalyst, auxiliary agent such as K, Mn etc., the mass ratio of Fe and auxiliary agent K and Mn is respectively (65～75): (0.5～5): (23～34).The carrying method of metal promoter and active component Fe preferably first floods alkali metal promoter K, then floods active component Fe, the step impregnation method of final impregnating Mn.The dipping process of metal promoter and active component Fe can adopt method well known to those skilled in the art.As adopt following process: first adopt the solution impregnation modified silica gel carrier that contains additive alkali metal K element salt, then adopt the solution impregnation that contains active metal component Fe salt, adopt at last the solution impregnation that contains promoter metal Mn salt, can comprise drying steps and calcination steps after per step dipping.Drying steps under 50-150 ℃ dry 8-24 hour, calcination steps was at 350-700 ℃ of lower roasting 2-10 hour.
A kind of load-type iron-based preparation of low carbon olefines by synthetic gas catalyst of the present invention, take silica gel as carrier, take surface modification silica gel as carrier, take Fe as active component, take K and Mn as auxiliary agent, in catalyst, to account for the weight percentage of support modification silica gel be 0.5%-20% to Fe, in catalyst, auxiliary agent is K and Mn, the mass ratio of Fe and auxiliary agent K and Mn is respectively (65～75): (0.5～5): (23～34), the surface modifying method of silica-gel carrier is for adopting the organic compounds containing nitrogen solution impregnation to process.
Adopt the present invention's preparation take modified silica-gel as carrier, K and Mn are that the ferrum-based catalyst of auxiliary agent has following advantage:
1, the processing of organic compounds containing nitrogen solution to silica-gel carrier overcome the strong interaction between carrier and active component, improved the activity of catalyst.The conversion ratio of CO is brought up to more than 70.2% by 21.8%, and C
2 =～C
4 =selectively also bring up to (not modification as a comparison) more than 55.4% by 15.8%.
2, the silica-gel carrier after modification has kept its wearability, acid resistance and mechanical strength advantages of higher, is conducive to improve the service life of catalysis and this catalyst easily is shaped, the preparation method is simple, and technology is ripe, is conducive to the industrial production of catalyst.
The specific embodiment
Further illustrate process and the effect of the inventive method below in conjunction with embodiment.
Example 1
(pore volume is 1.06ml/g, and specific area is 386.81m to take commercially available silica gel
2/ g, following examples are all used this silica gel) 30g, drip distilled water to first profit, the volume that consumes water is 48ml, is 20% pyridine solution with 48ml concentration, adds silica gel under 50 ℃, processes 10 hours.60 ℃ of dryings 24 hours are then 280 ℃ of roastings 15 hours.By final catalyst K content 0.023wt%, take potassium nitrate 0.0179g adding distil water to 48g, add in the carrier silica gel after above-mentioned modification and flood, 60 ℃ of dryings 24 hours were 350 ℃ of roastings 10 hours.By final catalyst Fe content 3wt%, take ferric nitrate 6.6303g adding distil water to 48g, add in the sample after above-mentioned dipping potassium 60 ℃ of dryings 24 hours, roasting 10 hours in vacuum or nitrogen atmosphere in 350 ℃.By final catalyst manganese content 1.06wt%, take 50% manganese nitrate solution 2.0716g and add water to 48g, add in the sample after above-mentioned dipping potassium and iron, 60 ℃ of dryings 24 hours, roasting 10 hours in vacuum or nitrogen atmosphere in 350 ℃, the mass ratio that makes Fe, K and Mn is 65: 0.5: 23.The gained catalyst is designated as C-1.
Evaluating catalyst test is in the continuous fixed bed reactors of high pressure, and with reduction under 450 ℃ of pure hydrogen 8 hours, pressure was 1.0MPa.Switching synthesis gas after cooling reacts.Reaction effluent is collected by hot trap, cold-trap respectively.Reaction condition is 260-400 ℃, 1000h
-1, 2.0MPa, H
2/ CO=1 (mol ratio).It is as shown in table 1 that C-1 catalyst synthesis gas directly prepares the reaction result of low-carbon alkene.
Example 2
Take commercially available silica gel 30g, drip distilled water to first profit, the volume that consumes water is 48ml, is 15% diethanolamine solution with 48ml concentration, adds silica gel under 80 ℃, stirs.Processed 90 ℃ of dryings 16 hours 30 hours.By final catalyst K content 0.39wt%, take potassium nitrate 0.3042g, adding distil water is to 48g, adds in the carrier silica gel after above-mentioned modification to flood 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or nitrogen atmosphere in 550 ℃.By final catalyst Fe content 9wt%, take ferric nitrate 19.8909g, adding distil water is to 48g, adds in the sample after above-mentioned dipping potassium 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or nitrogen atmosphere in 550 ℃.By final catalyst manganese content 3.6wt%, take 50% manganese nitrate solution 7.0355g, adding distil water is to 48g, add in the sample after above-mentioned dipping potassium and iron, aging 3 hours, 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or nitrogen atmosphere in 550 ℃, the mass ratio that makes Fe, K and Mn is 70: 3: 28.The gained catalyst is designated as C-2.It is as shown in table 1 that C-2 catalyst synthesis gas directly prepares the reaction result of low-carbon alkene.
Example 3
Take commercially available silica gel 30g, drip distilled water to first profit, the volume that consumes water is 48ml, is 5% ethanolamine solutions with 48ml concentration, adds silica gel under 95 ℃, stir process 100 hours, 100 ℃ of dryings 8 hours.By final catalyst K content 0.8wt%, take potassium nitrate 0.624g and be dissolved in 48ml, add in the carrier silica gel after above-mentioned modification and flood, 150 ℃ of dryings 8 hours, roasting 2 hours in vacuum or nitrogen atmosphere in 700 ℃.By final catalyst Fe content 12wt%, take ferric nitrate 26.5212g and be dissolved in 48ml, add in the sample after above-mentioned dipping potassium 150 ℃ of dryings 8 hours, roasting 2 hours in vacuum or nitrogen atmosphere in 700 ℃.By final catalyst manganese content 5.44wt%, take 50% manganese nitrate solution 10.6315g, add water to 48g, add in the sample after above-mentioned dipping potassium and iron, aging 3 hours, 150 ℃ of dryings 8 hours, roasting 2 hours in vacuum or nitrogen atmosphere in 700 ℃, the mass ratio that makes Fe, K and Mn is 75: 5: 34.The gained catalyst is designated as C-3.It is as shown in table 1 that C-3 catalyst synthesis gas directly prepares the reaction result of low-carbon alkene.
Example 4
Take commercially available silica gel 30g, drip distilled water to first profit, the volume that consumes water is 48ml, is 15% triethanolamine solution with 48ml concentration, adds silica gel under 80 ℃, stirs.Aging 30 hours, 90 ℃ of dryings 16 hours.By final catalyst K content 0.023wt%, take potassium nitrate 0.0179g, adding distil water is to 48g, adds in the carrier silica gel after above-mentioned modification to flood 60 ℃ of dryings 24 hours, roasting 10 hours in vacuum or nitrogen atmosphere in 350 ℃.By final catalyst Fe content 3wt%, take ferric nitrate 6.6303g, adding distil water is to 48g, adds in the sample after above-mentioned dipping potassium 60 ℃ of dryings 24 hours, roasting 10 hours in vacuum or nitrogen atmosphere in 350 ℃.By final catalyst manganese content 1.41wt%, take 50% manganese nitrate 3.0716g, adding distil water is to 48g, add in the sample after above-mentioned dipping potassium and iron, 60 ℃ of dryings 24 hours, roasting 10 hours in vacuum or nitrogen atmosphere in 350 ℃, the mass ratio that makes Fe, K and Mn is 65: 0.5: 23.The gained catalyst is designated as C-4.It is as shown in table 1 that C-4 catalyst synthesis gas directly prepares the reaction result of low-carbon alkene.
Example 5
Take commercially available silica gel 30g, drip distilled water to first profit, the volume that consumes water is 48ml, is 15% ethanolamine solutions with 48ml concentration, adds silica gel under 80 ℃, stirs.Aging 30 hours, 90 ℃ of dryings 16 hours.By final catalyst K content 0.39wt%, take potassium nitrate 0.3042g, adding distil water is to 48g, adds in the carrier silica gel after above-mentioned modification to flood 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or nitrogen atmosphere in 550 ℃.By final catalyst Fe content 9wt%, take ferric nitrate 19.8909g, adding distil water is to 48g, adds in the sample after above-mentioned dipping potassium 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or nitrogen atmosphere in 550 ℃.By final catalyst manganese content 3.6wt%, take manganese nitrate 7.0355g, adding distil water is to 48g, add in the sample after above-mentioned dipping potassium and iron, aging 3 hours, 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or nitrogen atmosphere in 550 ℃, the mass ratio that makes Fe, K and Mn is 70: 3: 28.The gained catalyst is designated as C-5.It is as shown in table 1 that C-5 catalyst synthesis gas directly prepares the reaction result of low-carbon alkene.
Example 6
Take commercially available silica gel 30g, drip distilled water to first profit, the volume that consumes water is 48ml, is 15% ethanolamine solutions with 48ml concentration, adds silica gel under 80 ℃, stirs.Aging 30 hours, 90 ℃ of dryings 16 hours.By final catalyst K content 0.39wt%, take potassium nitrate 0.3042g, adding distil water is to 48g, adds in the carrier silica gel after above-mentioned modification to flood 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or nitrogen atmosphere in 550 ℃.By final catalyst Fe content 9wt%, take ferric nitrate 19.8909g, adding distil water is to 48g, adds in the sample after above-mentioned dipping potassium 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or nitrogen atmosphere in 550 ℃.By final catalyst manganese content 3.6wt%, take 50% manganese nitrate solution 7.0355g, adding distil water is to 48g, add in the sample after above-mentioned dipping potassium and iron, aging 3 hours, 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or nitrogen atmosphere in 550 ℃, the mass ratio that makes Fe, K and Mn is 70: 3: 28.The gained catalyst is designated as C-6.It is as shown in table 1 that C-6 catalyst synthesis gas directly prepares the reaction result of low-carbon alkene.
Example 7
Take commercially available silica gel 30g, drip distilled water to first profit, the volume that consumes water is 48ml, is 15% ethanolamine solutions with 48ml concentration, adds silica gel under 80 ℃, stirs.Aging 30 hours, 90 ℃ of dryings 16 hours.By final catalyst K content 0.39wt%, take potassium nitrate 0.3042g, adding distil water is to 48g, adds in the carrier silica gel after above-mentioned modification to flood 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or nitrogen atmosphere in 550 ℃.By final catalyst Fe content 9wt%, take ferric nitrate 19.8909g, adding distil water is to 48g, adds in the sample after above-mentioned dipping potassium 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or nitrogen atmosphere in 550 ℃.By final catalyst manganese content 3.6wt%, take 50% manganese nitrate solution 7.0355g, adding distil water is to 48g, add in the sample after above-mentioned dipping potassium and iron, aging 3 hours, 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or nitrogen atmosphere in 550 ℃, the mass ratio that makes Fe, K and Mn is 70: 3: 28.The gained catalyst is designated as C-7.It is as shown in table 1 that C-7 catalyst synthesis gas directly prepares the reaction result of low-carbon alkene.
Example 8
Take commercially available silica gel 30g, drip distilled water to first profit, the volume that consumes water is 48ml, is the mixed solution of 15% monoethanolamine and diethanol amine with 48ml concentration, adds silica gel under 80 ℃, stirs.Aging 30 hours, 90 ℃ of dryings 16 hours.By final catalyst K content 0.39wt%, take potassium nitrate 0.3042g, adding distil water is to 48g, adds in the carrier silica gel after above-mentioned modification to flood 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or nitrogen atmosphere in 550 ℃.By final catalyst Fe content 9wt%, take ferric nitrate 19.8909g, adding distil water is to 48g, adds in the sample after above-mentioned dipping potassium 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or nitrogen atmosphere in 550 ℃.By final catalyst manganese content 3.6wt%, take 50% manganese nitrate solution 7.0355g, adding distil water is to 48g, add in the sample after above-mentioned dipping potassium and iron, aging 3 hours, 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or nitrogen atmosphere in 550 ℃, the mass ratio that makes Fe, K and Mn is 70: 3: 28.The gained catalyst is designated as C-8.It is as shown in table 1 that C-8 catalyst synthesis gas directly prepares the reaction result of low-carbon alkene.
Comparative example 1
Take commercially available silica gel, drip distilled water to just moistening, the volume that consumes water is 48ml.By final catalyst K content 0.39wt%, take potassium nitrate 0.3042g, adding distil water is to 48g, adds in the carrier silica gel after above-mentioned modification to flood 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or nitrogen atmosphere in 550 ℃.By final catalyst Fe content 9wt%, take ferric nitrate 19.8909g, adding distil water is to 48g, adds in the sample after above-mentioned dipping potassium 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or nitrogen atmosphere in 550 ℃.By final catalyst manganese content 3.6wt%, take 50% manganese nitrate solution 7.0355g, adding distil water is to 48g, add in the sample after above-mentioned dipping potassium and iron, aging 3 hours, 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or nitrogen atmosphere in 550 ℃, the mass ratio that makes Fe, K and Mn is 70: 3: 28.The gained catalyst is designated as C-B.It is as shown in table 1 that C-B catalyst synthesis gas directly prepares the reaction result of low-carbon alkene.
The reactivity worth of table 1 catalyst
CH represents hydro carbons, C
2 oExpression contains the alkane of 2 carbon, C
2 =Expression contains the alkene of 2 carbon, and the rest may be inferred for other implication.
Claims (5)
1. the preparation method of a load-type iron-based preparation of low carbon olefines by synthetic gas catalyst, take silica gel as carrier, at first carry out surface modification to silica-gel carrier, then adopts infusion process carried metal auxiliary agent and active component Fe, it is characterized in that: the surface modifying method of silica-gel carrier is for adopting the organic compounds containing nitrogen solution impregnation to process, organic compounds containing nitrogen is selected from monoethanolamine, diethanol amine, one or more in triethanolamine and pyridine, the weight concentration of organic compounds containing nitrogen is 1%-35%, the organic compounds containing nitrogen solution impregnation is processed and is adopted saturated dipping or supersaturation dipping, carry out drying after impregnation process, baking temperature is 50-150 ℃, be 0.5-36h drying time, carry out calcination process after dry, roasting was at 280-600 ℃ of lower roasting 2-15 hour, organic compounds containing nitrogen impregnation process temperature is 50-95 ℃, the impregnation process time is 2-150h, the weight percentage of described active component iron is 5%-35%, in catalyst, to account for the weight percentage of support modification silica gel be 0.5%-20% to Fe, in catalyst, auxiliary agent is K and Mn, the mass ratio of Fe and auxiliary agent K and Mn is respectively (65～75): (0.5～5): (23～34), the carrying method of metal promoter and active component Fe is for first flooding alkali metal promoter K, then flood active component Fe, the step impregnation method of final impregnating Mn.
2. it is characterized in that in accordance with the method for claim 1: the weight concentration of organic compounds containing nitrogen is 5%-20%.
3. in accordance with the method for claim 1, it is characterized in that: organic compounds containing nitrogen solution impregnation treatment temperature is 60～80 ℃, and the impregnation process time is 10-100h.
4. it is characterized in that in accordance with the method for claim 1: organic compounds containing nitrogen solution adopts the aqueous solution or organic solution.
5. a right to use requires the load-type iron-based preparation of low carbon olefines by synthetic gas catalyst of 1 described preparation method's preparation, take surface modification silica gel as carrier, take Fe as active component, take K and Mn as auxiliary agent, in catalyst, to account for the weight percentage of carrier surface modified silica-gel be 0.5%-20% to Fe, in catalyst, auxiliary agent is K and Mn, the mass ratio of Fe and auxiliary agent K and Mn is respectively (65～75): (0.5～5): (23～34) is characterized in that: the surface modifying method of surface modification silica-gel carrier is for adopting the organic compounds containing nitrogen solution impregnation to process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010510864XA CN102441383B (en) | 2010-10-12 | 2010-10-12 | Method for preparing low-carbon olefine catalyst by loading iron-based synthetic gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010510864XA CN102441383B (en) | 2010-10-12 | 2010-10-12 | Method for preparing low-carbon olefine catalyst by loading iron-based synthetic gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102441383A CN102441383A (en) | 2012-05-09 |
| CN102441383B true CN102441383B (en) | 2013-06-19 |
Family
ID=46004615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010510864XA Active CN102441383B (en) | 2010-10-12 | 2010-10-12 | Method for preparing low-carbon olefine catalyst by loading iron-based synthetic gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102441383B (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103586045B (en) * | 2013-11-01 | 2015-08-12 | 中国石油化工股份有限公司 | A kind of producing light olefins Catalysts and its preparation method |
| CN103586046B (en) * | 2013-11-01 | 2015-05-13 | 中国石油化工股份有限公司 | Catalyst for preparing light olefins from synthetic gas and preparation method thereof |
| CN105080563B (en) * | 2014-05-05 | 2017-06-06 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and preparation method thereof |
| CN105080561B (en) * | 2014-05-05 | 2017-08-22 | 中国石油化工股份有限公司 | A kind of load-type iron-based catalyst and preparation method thereof |
| CN105080562B (en) * | 2014-05-05 | 2017-06-20 | 中国石油化工股份有限公司 | A kind of CO hydrogenation catalysts and its preparation method and application |
| CN105709773B (en) * | 2014-12-04 | 2017-08-22 | 中国石油化工股份有限公司 | A kind of synthesis gas alkene catalyst and its preparation method and application |
| CN105709772B (en) * | 2014-12-04 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of synthesis gas alkene catalyst and its preparation method and application |
| CN105709769B (en) * | 2014-12-04 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of synthesis gas alkene catalyst and preparation method thereof |
| CN106669719B (en) * | 2015-11-09 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of producing light olefins catalyst and preparation method thereof |
| CN106669721A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Iron-based supported catalyst and preparation method thereof |
| CN106669720A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and applications thereof |
| CN106669717A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Catalyst for preparing unsaturated hydrocarbons, and preparation method thereof |
| CN106000289B (en) * | 2016-06-30 | 2019-08-27 | 中国海洋石油集团有限公司 | A kind of aromatic solvent naphtha refining agent and preparation method |
| CN109701628A (en) | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Composite catalyst containing phosphate aluminium molecular sieve and its application in one-step method from syngas alkene |
| CN107827691B (en) * | 2017-11-06 | 2020-09-01 | 中石化炼化工程（集团）股份有限公司 | Method for preparing low-carbon olefin from synthesis gas |
| CN110152663A (en) * | 2018-02-11 | 2019-08-23 | 中国科学院大连化学物理研究所 | It is a kind of for the catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol and its preparation and application |
| CN110369001A (en) * | 2018-04-12 | 2019-10-25 | 中国科学院大连化学物理研究所 | A method of preparing high-dispersion metal catalyst |
| CN110369002A (en) * | 2018-04-12 | 2019-10-25 | 中国科学院大连化学物理研究所 | A kind of preprocess method of oxide-based inorganic carrier |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3907968A (en) * | 1972-12-29 | 1975-09-23 | Gulf Research Development Co | Process for reducing the content of nitrogen oxides in a gaseous mixture containing the same |
| EP0705282B1 (en) * | 1992-03-20 | 1998-07-29 | The Dow Chemical Company | Use of the variation of the ratio of Mg:Ti in a catalyst to vary or control the short chain branching distribution of ethylene copolymers |
| CN101020137A (en) * | 2006-02-15 | 2007-08-22 | 中国石油天然气股份有限公司 | Catalyst for preparing heavy hydrocarbon with synthetic gas and its prepn process |
-
2010
- 2010-10-12 CN CN201010510864XA patent/CN102441383B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3907968A (en) * | 1972-12-29 | 1975-09-23 | Gulf Research Development Co | Process for reducing the content of nitrogen oxides in a gaseous mixture containing the same |
| EP0705282B1 (en) * | 1992-03-20 | 1998-07-29 | The Dow Chemical Company | Use of the variation of the ratio of Mg:Ti in a catalyst to vary or control the short chain branching distribution of ethylene copolymers |
| CN101020137A (en) * | 2006-02-15 | 2007-08-22 | 中国石油天然气股份有限公司 | Catalyst for preparing heavy hydrocarbon with synthetic gas and its prepn process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102441383A (en) | 2012-05-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| 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 | |
| CN102452878B (en) | Method for preparing low-carbon olefin by synthetic gas one-step technology | |
| CN101940958B (en) | Method for preparing low-carbon olefin catalyst by loading iron-based synthetic gas | |
| CN102441400B (en) | Preparation method of catalyst in process of producing light olefins by high-activity load type iron-based synthesis gas | |
| CN114939433A (en) | Composite catalyst for directly preparing light aromatic hydrocarbon by carbon dioxide hydrogenation, preparation and application thereof | |
| CN104549325B (en) | Catalyst for preparing low-carbon olefin from synthesis gas by one-step method, preparation method and application of catalyst | |
| CN105080563A (en) | Hydrogenation catalyst and preparation method therefor | |
| CN102908957A (en) | Method for Fischer-Tropsch synthesis | |
| CN103586045B (en) | A kind of producing light olefins Catalysts and its preparation method | |
| CN102441384B (en) | Method for preparing low-carbon olefin catalyst by high-activity-stability carrier-type iron-based synthetic gas | |
| CN106669721A (en) | Iron-based supported catalyst and preparation method thereof | |
| CN105732263A (en) | Selective hydrogenation method of trace amount of acetylene in methanol to olefin (MTO) apparatus | |
| CN114471744B (en) | Pretreatment method of iron-based catalyst and application thereof | |
| CN106140227A (en) | A kind of catalyst with modified aluminas as carrier and its preparation method and application | |
| CN105080562B (en) | A kind of CO hydrogenation catalysts and its preparation method and application | |
| CN103769097B (en) | A kind of preparation method of Co based Fischer-Tropsch synthesis catalyst | |
| CN106669718A (en) | Catalyst for preparation of olefin from synthesis gas as well as preparation method and application of catalyst | |
| CN106669719A (en) | Low-carbon olefin preparation catalyst and preparation method thereof | |
| CN105709768A (en) | Preparation method for catalyst used in preparation of olefin from synthetic gas | |
| CN106669720A (en) | Hydrogenation catalyst, preparation method and applications thereof | |
| CN105709770A (en) | Catalyst used in preparation of low-carbon olefin from synthetic gas and preparation method thereof | |
| CN106669723A (en) | Catalyst for synthesis gas reaction and preparation method and application thereof | |
| CN105709773A (en) | Catalyst used in preparation of olefin from synthetic gas, and preparation method and application thereof | |
| CN103773409A (en) | Method for directly preparing light alkene by using synthetic gas as raw material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |