CN102441400A - Preparation method of catalyst in process of producing light olefins by high-activity load type iron-based synthesis gas - Google Patents
Preparation method of catalyst in process of producing light olefins by high-activity load type iron-based synthesis gas Download PDFInfo
- Publication number
- CN102441400A CN102441400A CN2010105108654A CN201010510865A CN102441400A CN 102441400 A CN102441400 A CN 102441400A CN 2010105108654 A CN2010105108654 A CN 2010105108654A CN 201010510865 A CN201010510865 A CN 201010510865A CN 102441400 A CN102441400 A CN 102441400A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hours
- carrier
- preparation
- silica gel
- 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.)
- Granted
Links
Abstract
The invention discloses a preparation method of a catalyst in a process of producing light olefins by high-activity load type iron-based synthesis gas. The preparation method comprises the steps of: with silicon gel as a carrier, firstly, carrying out surface modification on the silicon gel carrier, and then loading a metal additive and an active component Fe by adopting an immersion method, wherein an ammonium salt-containing buffer solution is adopted for immersion in the surface modification method of the silicon gel carrier. After the adopted silicon gel carrier is modified, the strong interaction function between the carrier and the active component is overcome, and the activity and the selectivity of the catalyst are improved. The catalyst prepared by adopting the preparation method is suitable for a reaction process for producing light olefins such as ethylene, propylene, butylene and the like by using the synthesis gas.
Description
Technical field
The present invention relates to a kind of high activity loading type iron-based preparation of low carbon olefines by synthetic gas Preparation of catalysts method; Relating in particular to a kind of is carrier with the modified silica-gel, low cost that the interpolation metal promoter is modified and the high activity iron-based preparation of low carbon olefines by synthetic gas Preparation of catalysts method that is easy to commercial Application.
Background technology
Low-carbon alkene such as ethene, propylene is important basic Organic Chemicals, and along with the development of chemical industry, its demand is more and more big.Up to now, the approach of producing low-carbon alkenes such as ethene, propylene is mainly through the light oil cracking process, and along with the exhaustion day by day of petroleum resources in the global range, following energy resource structure certainly will shift.Compare with petroleum resources, coal and natural gas resource are abundant relatively, and exploitation is that master's low-carbon alkene production technology has great importance with coal and natural gas.Exploitation from synthesis gas (can be converted to by natural gas and coal) is directly produced ethene, propylene technology not only can reduce the dependence to petroleum resources, and some chemical industrial expansions in rich gas oil starvation area are had significance.
CN1065026A discloses a kind of preparation of ethylene by use of synthetic gas method, and relating to the Preparation of catalysts method is chemical precipitation method, mechanical mixing; Adopted noble metal or rare metal, kind of chemical element surplus niobium, gallium, praseodymium, scandium, indium, cerium, lanthanum, the ytterbium etc. ten for example, ethylene selectivity is 65%-94%; But the CO conversion ratio is very low; Only about 10%, 12% and 15%, 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 combine the combination technique of solid phase reaction to prepare with Fe
3C is that main Fe base nano-catalyst is used and preparing low-carbon olefin, and has obtained certain effect, but owing to need practical laser technology, makes preparation technology more loaded down with trivial details, and raw material adopts Fe (CO)
5, the cost of catalyst is than higher, and industrialization is difficult.
CN03109585.2 discloses a kind of iron/activated-carbon catalyst that is used for preparation of ethylene by use of synthetic gas, propylene, butene reaction; Adopt active carbon as carrier; Fe adopts vacuum impregnation technology successfully Fe to be loaded on the active carbon as the activated centre, makes 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 of no raw material circulation can reach 96-99%, and the CH compound selective reaches 69.5% in the gas-phase product, and therein ethylene, propylene, the selectivity of butylene in the CH compound reach more than 68%.But active carbon influences the 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, hear resistance (can at 500～600 ℃ of following long reactions) and wearability, and silica is easy to moulding, specific area is bigger, and all have controllability, be more suitable for as catalyst carrier.Few silica that adopts mainly is because Fe and SiO as carrier in the reaction of alkene but directly prepare at the base supported synthesis gas of Fe at present
2Strong interaction between the carrier causes part Fe to be difficult to be reduced, and is difficult to reach comparatively ideal reactivity.
Summary of the invention
To the deficiency of prior art, the invention provides a kind of is carrier with the modified silica-gel, adds the iron-based preparation of low carbon olefines by synthetic gas Preparation of catalysts method that metal promoter is modified.The silica-gel carrier that the present invention adopts has overcome the strong interaction between carrier and the active component after modification, improved activity of such catalysts.
The Preparation of catalysts method that iron-based support type synthesis gas of the present invention directly prepares alkene comprises following process: be carrier with silica gel, at first silica-gel carrier carried out surface modification, adopt infusion process carried metal auxiliary agent and active component Fe then; Wherein the surface modifying method of silica-gel carrier is for adopting the cushioning liquid impregnation process of ammonium salt-containing.
Iron-based support type synthesis gas of the present invention directly prepares in the Preparation of catalysts method of alkene, and silica-gel carrier can adopt existing silica gel product, and like 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 of catalysts method of alkene; It can be to be selected from ammonium acetate, ammonium formate, ammonium carbonate, the carbonic hydroammonium etc. one or more that the method for modifying of silica-gel carrier is adopted the cushioning liquid impregnation process of ammonium salt-containing, ammonium salt.The weight concentration of ammonium salt is 1%-35% in the cushioning liquid, is preferably 5%-20%.Dipping can adopt saturated dipping or supersaturation dipping, carries out drying behind the 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 following roasting 2-15 hour, preferably at 300-500 ℃ of following roasting 4-10 hour.
In the iron-based support type preparing low-carbon olefin Preparation of catalysts method of the present invention, to account for the weight percentage of support modification silica gel be 0.5%-20% to major catalyst Fe in the catalyst, preferred 3%-12%.Also contain auxiliary agent in the 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 preferred dipping earlier of the carrying method of metal promoter and active component Fe alkali metal promoter K floods active component Fe, the step impregnation method of final impregnating Mn then.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: adopt the solution impregnation modified silica-gel carrier that contains additive alkali metal K element salt earlier; Adopt the solution impregnation that contains active metal component Fe salt then; Adopt the solution impregnation that contains promoter metal Mn salt at last, can comprise drying steps and calcination steps behind per step dipping.Drying steps descended dry 8-24 hour at 50-150 ℃, and calcination steps was at 350-700 ℃ of following roasting 2-10 hour.All roastings must be carried out under vacuum or nitrogen protection.
A kind of load-type iron-based preparation of low carbon olefines by synthetic gas catalyst of the present invention is a carrier with silica gel, is carrier with surface modification silica gel; With Fe is active component; With K and Mn is auxiliary agent, and to account for the weight percentage of support modification silica gel be 0.5%-20% to Fe in the catalyst, and auxiliary agent is K and Mn in the catalyst; 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 surface modification silica-gel carrier is for adopting the cushioning liquid impregnation process of ammonium salt-containing.
What adopt the present invention's preparation is carrier with the modified silica-gel, and K and Mn are that the ferrum-based catalyst of auxiliary agent has following advantage:
1, the solution of ammonium salt-containing has overcome the strong interaction between carrier and the active component to the processing of silica-gel carrier, has improved activity of such catalysts.The conversion ratio of CO is brought up to more than 81.2% by 21.8%, and C
2 =-C
4 =Selectivity also by 15.8% bringing up to more than 55.4% (not modification as relatively).
2, the silica-gel carrier after the modification has kept its wearability, acid resistance and mechanical strength advantages of higher, helps improving the service life of catalysis and this catalyst is shaped easily, the preparation method is simple, and technology is ripe, helps the commercial production of catalyst.
The specific embodiment
Further specify the process and the effect of the inventive method below in conjunction with embodiment.
Instance 1
(pore volume is 1.06ml/g, and specific area is 386.81m to take by weighing commercially available silica gel
2/ g, following examples are all used this silica gel) 30g, dripping distilled water to just moistening, the volume of consume water is 48ml, is 5% sal volatile with 48ml concentration, adds in the silica gel down at 50 ℃, handles 10 hours.60 ℃ of dryings 24 hours are then 280 ℃ of roastings 15 hours.By final catalyst K content 0.023wt%, take by weighing potassium nitrate 0.0179g adding distil water to 48g, add in the carrier silica gel after the above-mentioned modification and flood, 60 ℃ of dryings 24 hours were 350 ℃ of roastings 10 hours.By final catalyst Fe content 3wt%, take by weighing ferric nitrate 6.6303g adding distil water to 48g, add in the sample behind the above-mentioned dipping potassium 60 ℃ of dryings 24 hours, roasting 10 hours in vacuum or the nitrogen atmosphere in 350 ℃.By final catalyst manganese content 1.06wt%; Take by weighing 50% manganese nitrate solution 2.0716g and add water to 48g; Add in the sample behind above-mentioned dipping potassium and the iron; 60 ℃ of dryings 24 hours, roasting 10 hours in vacuum or the nitrogen atmosphere makes that the mass ratio of Fe, K and Mn is 65: 0.5: 23 in 350 ℃.The gained catalyst is designated as C-1.
The evaluating catalyst test was reduced 4 hours down for 450 ℃ with pure hydrogen in the continuous fixed bed reactors of high pressure, and pressure is 1.0MPa.The cooling back is switched synthesis gas and is reacted.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.
Instance 2
Take by weighing commercially available silica gel 30g, drip distilled water to just moistening, the volume of consume water is 48ml, is 15% sal volatile with 48ml concentration, adds down in the silica gel at 80 ℃, stirs.Handled 90 ℃ of dryings 16 hours 30 hours.By final catalyst K content 0.39wt%, take by weighing potassium nitrate 0.3042g, adding distil water is to 48g, adds in the carrier silica gel after the above-mentioned modification to flood 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or the nitrogen atmosphere in 550 ℃.By final catalyst Fe content 9wt%, take by weighing ferric nitrate 19.8909g, adding distil water is to 48g, adds in the sample behind the above-mentioned dipping potassium 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or the nitrogen atmosphere in 550 ℃.By final catalyst manganese content 3.6wt%; Take by weighing 50% manganese nitrate solution 7.0355g, adding distil water is to 48g, adds in the sample behind above-mentioned dipping potassium and the iron; Aging 3 hours; 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or the nitrogen atmosphere makes that the mass ratio of Fe, K and Mn is 70: 3: 28 in 550 ℃.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.
Instance 3
Take by weighing commercially available silica gel 30g, drip distilled water to first profit, the volume of consume water is 48ml, is 20% sal volatile with 48ml concentration, adds in the silica gel stir process 100 hours, 100 ℃ of dryings 8 hours down at 95 ℃.By final catalyst K content 0.8wt%, take by weighing potassium nitrate 0.624g and be dissolved in 48ml, add in the carrier silica gel after the above-mentioned modification and flood, 150 ℃ of dryings 8 hours, roasting 2 hours in vacuum or the nitrogen atmosphere in 700 ℃.By final catalyst Fe content 12wt%, take by weighing ferric nitrate 26.5212g and be dissolved in 48ml, add in the sample behind the above-mentioned dipping potassium 150 ℃ of dryings 8 hours, roasting 2 hours in vacuum or the nitrogen atmosphere in 700 ℃.By final catalyst manganese content 5.44wt%; Take by weighing 50% manganese nitrate solution 10.6315g, add water to 48g, add in the sample behind above-mentioned dipping potassium and the iron; Aging 3 hours; 150 ℃ of dryings 8 hours, roasting 2 hours in vacuum or the nitrogen atmosphere makes that the mass ratio of Fe, K and Mn is 75: 5: 34 in 700 ℃.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.
Instance 4
Take by weighing commercially available silica gel 30g, drip distilled water to just moistening, the volume of consume water is 48ml, is 15% ammonium acetate solution with 48ml concentration, adds down in the silica gel at 80 ℃, stirs.Aging 30 hours, 90 ℃ of dryings 16 hours.By final catalyst K content 0.023wt%, take by weighing potassium nitrate 0.0179g adding distil water to 48g, add in the carrier silica gel after the above-mentioned modification and flood, 60 ℃ of dryings 24 hours were 350 ℃ of roastings 10 hours.By final catalyst Fe content 3wt%, take by weighing ferric nitrate 6.6303g adding distil water to 48g, add in the sample behind the above-mentioned dipping potassium 60 ℃ of dryings 24 hours, roasting 10 hours in vacuum or the nitrogen atmosphere in 350 ℃.By final catalyst manganese content 1.06wt%; Take by weighing 50% manganese nitrate solution 2.0716g and add water to 48g; Add in the sample behind above-mentioned dipping potassium and the iron; 60 ℃ of dryings 24 hours, roasting 10 hours in vacuum or the nitrogen atmosphere makes that the mass ratio of Fe, K and Mn is 65: 0.5: 23 in 350 ℃.It is as shown in table 1 that C-4 catalyst synthesis gas directly prepares the reaction result of low-carbon alkene.
Instance 5
Take by weighing commercially available silica gel 30g, drip distilled water to just moistening, the volume of consume water is 48ml, is 15% ammonium bicarbonate soln with 48ml concentration, adds down in the silica gel at 80 ℃, stirs.Aging 30 hours, 90 ℃ of dryings 16 hours.By final catalyst K content 0.39wt%, take by weighing potassium nitrate 0.3042g, adding distil water is to 48g, adds in the carrier silica gel after the above-mentioned modification to flood 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or the nitrogen atmosphere in 550 ℃.By final catalyst Fe content 9wt%, take by weighing ferric nitrate 19.8909g, adding distil water is to 48g, adds in the sample behind the above-mentioned dipping potassium 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or the nitrogen atmosphere in 550 ℃.By final catalyst manganese content 3.6wt%; Take by weighing 50% manganese nitrate solution 7.0355g, adding distil water is to 48g, adds in the sample behind above-mentioned dipping potassium and the iron; Aging 3 hours; 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or the nitrogen atmosphere makes that the mass ratio of Fe, K and Mn is 70: 3: 28 in 550 ℃.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.
Instance 6
Take by weighing commercially available silica gel 30g, drip distilled water to just moistening, the volume of consume water is 48ml, is 15% ammonium formate solution with 48ml concentration, adds down in the silica gel at 80 ℃, stirs.Aging 30 hours, 90 ℃ of dryings 16 hours.By final catalyst K content 0.39wt%, take by weighing potassium nitrate 0.3042g, adding distil water is to 48g, adds in the carrier silica gel after the above-mentioned modification to flood 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or the nitrogen atmosphere in 550 ℃.By final catalyst Fe content 9wt%, take by weighing ferric nitrate 19.8909g, adding distil water is to 48g, adds in the sample behind the above-mentioned dipping potassium 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or the nitrogen atmosphere in 550 ℃.By final catalyst manganese content 3.6wt%; Take by weighing 50% manganese nitrate solution 7.0355g, adding distil water is to 48g, adds in the sample behind above-mentioned dipping potassium and the iron; Aging 3 hours; 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or the nitrogen atmosphere makes that the mass ratio of Fe, K and Mn is 70: 3: 28 in 550 ℃.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.
Instance 7
Take by weighing commercially available silica gel 30g, drip distilled water to just moistening, the volume of consume water is 48ml, is 15% ammonium acetate solution with 48ml concentration, adds down in the silica gel at 80 ℃, stirs.Aging 30 hours, 90 ℃ of dryings 16 hours.By final catalyst K content 0.39wt%, take by weighing potassium nitrate 0.3042g, adding distil water is to 48g, adds in the carrier silica gel after the above-mentioned modification to flood 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or the nitrogen atmosphere in 550 ℃.By final catalyst Fe content 9wt%, take by weighing ferric nitrate 19.8909g, adding distil water is to 48g, adds in the sample behind the above-mentioned dipping potassium 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or the nitrogen atmosphere in 550 ℃.By final catalyst manganese content 3.6wt%; Take by weighing 50% manganese nitrate solution 7.0355g, adding distil water is to 48g, adds in the sample behind above-mentioned dipping potassium and the iron; Aging 3 hours; 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or the nitrogen atmosphere makes that the mass ratio of Fe, K and Mn is 70: 3: 28 in 550 ℃.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.
Instance 8
Take by weighing commercially available silica gel 30g, drip distilled water to just moistening, the volume of consume water is 48ml, is 15% ammonium acetate solution with 48ml concentration, adds down in the silica gel at 80 ℃, stirs.Aging 30 hours, 90 ℃ of dryings 16 hours.By final catalyst K content 0.39wt%, take by weighing potassium nitrate 0.3042g, adding distil water is to 48g, adds in the carrier silica gel after the above-mentioned modification to flood 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or the nitrogen atmosphere in 550 ℃.By final catalyst Fe content 9wt%, take by weighing ferric nitrate 19.8909g, adding distil water is to 48g, adds in the sample behind the above-mentioned dipping potassium 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or the nitrogen atmosphere in 550 ℃.By final catalyst manganese content 3.6wt%; Take by weighing 50% manganese nitrate solution 7.0355g, adding distil water is to 48g, adds in the sample behind above-mentioned dipping potassium and the iron; Aging 3 hours; 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or the nitrogen atmosphere makes that the mass ratio of Fe, K and Mn is 70: 3: 28 in 550 ℃.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 by weighing commercially available silica gel, drip distilled water to just moistening, the volume of consume water is 48ml.By final catalyst K content 0.39wt%, take by weighing potassium nitrate 0.3042g, adding distil water is to 48g, adds in the carrier silica gel after the above-mentioned modification to flood 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or the nitrogen atmosphere in 550 ℃.By final catalyst Fe content 9wt%, take by weighing ferric nitrate 19.8909g, adding distil water is to 48g, adds in the sample behind the above-mentioned dipping potassium 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or the nitrogen atmosphere in 550 ℃.By final catalyst manganese content 3.6wt%; Take by weighing 50% manganese nitrate solution 7.0355g, adding distil water is to 48g, adds in the sample behind above-mentioned dipping potassium and the iron; Aging 3 hours; 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or the nitrogen atmosphere makes that the mass ratio of Fe, K and Mn is 70: 3: 28 in 550 ℃.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 representes 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 (10)
1. a high activity loading type iron-based preparation of low carbon olefines by synthetic gas Preparation of catalysts method is a carrier with silica gel, at first silica-gel carrier is carried out surface modification, adopts infusion process carried metal auxiliary agent and active component Fe then; It is characterized in that: the surface modifying method of silica-gel carrier is for adopting the cushioning liquid impregnation process of ammonium salt-containing.
2. according to the described method of claim 1, it is characterized in that: the ammonium salt of the cushioning liquid of ammonium salt-containing is selected from one or more in ammonium acetate, ammonium formate, ammonium carbonate and the carbonic hydroammonium, and the weight concentration of ammonium salt is 1%-35% in the cushioning liquid.
3. according to claim 1 or 2 described methods, it is characterized in that: the weight concentration of ammonium salt is 5%-20% in the cushioning liquid.
4. according to the described method of claim 1, it is characterized in that: the cushioning liquid impregnation process adopts saturated dipping or supersaturation dipping, carries out drying after the impregnation process, and baking temperature is 50-150 ℃, and be 0.5-36h drying time.
5. according to the described method of claim 4, it is characterized in that: carry out calcination process after dry, roasting was at 280-600 ℃ of following roasting 2-15 hour.
6. according to claim 1 or 4 described methods, it is characterized in that: cushioning liquid impregnation process temperature is 50-95 ℃, and the impregnation process time is 2-150h.
7. according to the described method of claim 6, it is characterized in that: cushioning liquid impregnation process temperature is 60～80 ℃, and the impregnation process time is 10-100h.
8. according to the described method of claim 1; It is characterized in that: to account for the weight percentage of support modification silica gel be 0.5%-20% to Fe in the catalyst; Auxiliary agent is K and Mn in the catalyst, and the mass ratio of Fe and auxiliary agent K and Mn is respectively (65～75): (0.5～5): (23～34).
9. according to the described method of claim 8, it is characterized in that: the carrying method of metal promoter and active component Fe floods active component Fe, the step impregnation method of final impregnating Mn then for flooding alkali metal promoter K earlier.
10. high activity loading type iron-based preparation of low carbon olefines by synthetic gas catalyst; With surface modification silica gel is carrier; With Fe is active component, is auxiliary agent with K and Mn, and to account for the weight percentage of support modification silica gel be 0.5%-20% to Fe in the catalyst; 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 cushioning liquid impregnation process of ammonium salt-containing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010510865 CN102441400B (en) | 2010-10-12 | 2010-10-12 | Preparation method of catalyst in process of producing light olefins by high-activity load type iron-based synthesis gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010510865 CN102441400B (en) | 2010-10-12 | 2010-10-12 | Preparation method of catalyst in process of producing light olefins by high-activity load type iron-based synthesis gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102441400A true CN102441400A (en) | 2012-05-09 |
| CN102441400B CN102441400B (en) | 2013-08-28 |
Family
ID=46004632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010510865 Active CN102441400B (en) | 2010-10-12 | 2010-10-12 | Preparation method of catalyst in process of producing light olefins by high-activity load type iron-based synthesis gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102441400B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103586046A (en) * | 2013-11-01 | 2014-02-19 | 中国石油化工股份有限公司 | Catalyst for preparing light olefins from synthetic gas and preparation method thereof |
| WO2015161700A1 (en) * | 2014-04-21 | 2015-10-29 | 武汉凯迪工程技术研究总院有限公司 | Structured iron-based catalyst for producing α-olefin from synthesis gas and preparation method and use |
| CN105709768A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method for catalyst used in preparation of olefin from synthetic gas |
| CN105709791A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method for loaded iron-based catalyst |
| CN105709767A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Iron-based 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1509816A (en) * | 2002-12-26 | 2004-07-07 | 中国科学院大连化学物理研究所 | Preparing method for catalyst with macroporous silica gel as carrier |
| CN101011662A (en) * | 2007-02-07 | 2007-08-08 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing low-carbon olefin, its preparation method and application |
| CN101219384A (en) * | 2007-01-08 | 2008-07-16 | 北京化工大学 | Catalyst for reaction of one-step conversion into low carbon olefin hydrocarbon with synthesis gas |
-
2010
- 2010-10-12 CN CN 201010510865 patent/CN102441400B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1509816A (en) * | 2002-12-26 | 2004-07-07 | 中国科学院大连化学物理研究所 | Preparing method for catalyst with macroporous silica gel as carrier |
| CN101219384A (en) * | 2007-01-08 | 2008-07-16 | 北京化工大学 | Catalyst for reaction of one-step conversion into low carbon olefin hydrocarbon with synthesis gas |
| CN101011662A (en) * | 2007-02-07 | 2007-08-08 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing low-carbon olefin, its preparation method and application |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103586046A (en) * | 2013-11-01 | 2014-02-19 | 中国石油化工股份有限公司 | Catalyst for preparing light olefins from synthetic gas and preparation method thereof |
| JP2017518170A (en) * | 2014-04-21 | 2017-07-06 | 武▲漢凱▼迪工程技▲術▼研究▲総▼院有限公司 | Structured iron-based catalyst for the production of α-olefins from synthesis gas, and the preparation and use thereof |
| WO2015161700A1 (en) * | 2014-04-21 | 2015-10-29 | 武汉凯迪工程技术研究总院有限公司 | Structured iron-based catalyst for producing α-olefin from synthesis gas and preparation method and use |
| RU2659067C2 (en) * | 2014-04-21 | 2018-06-28 | Ухань Кайди Инджиниринг Текнолоджи Рисерч Инститьют Ко., Лтд. | Iron based structured catalyst for the α-olefin production from synthesis gas and method of its manufacturing and application |
| AU2015251402B2 (en) * | 2014-04-21 | 2017-09-14 | Wuhan Kaidi Engineering Technology Research Institute Co., Ltd. | Structured iron-based catalyst for producing alpha-olefin from synthesis gas and preparation method and use |
| CN105709767B (en) * | 2014-12-04 | 2018-01-16 | 中国石油化工股份有限公司 | A kind of ferrum-based catalyst and preparation method thereof |
| CN105709767A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Iron-based catalyst and preparation method thereof |
| CN105709791A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method for loaded iron-based catalyst |
| CN105709791B (en) * | 2014-12-04 | 2018-01-16 | 中国石油化工股份有限公司 | A kind of preparation method of load-type iron-based catalyst |
| CN105709768B (en) * | 2014-12-04 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of preparation method of synthesis gas alkene catalyst |
| CN105709768A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method for catalyst used in preparation of olefin from synthetic gas |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102441400B (en) | 2013-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102441383B (en) | Method for preparing low-carbon olefine catalyst by loading iron-based synthetic gas | |
| CN101940958B (en) | Method for preparing low-carbon olefin 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 | |
| CN104148106B (en) | Synthesis gas produces catalyst of low-carbon alkene and preparation method thereof | |
| CN102441400B (en) | Preparation method of catalyst in process of producing light olefins by high-activity load type iron-based synthesis gas | |
| CN104549325B (en) | Catalyst for preparing low-carbon olefin from synthesis gas by one-step method, preparation method and application of catalyst | |
| CN114939433A (en) | Composite catalyst for directly preparing light aromatic hydrocarbon by carbon dioxide hydrogenation, preparation and application thereof | |
| CN107913729B (en) | Composite catalyst and preparation method thereof | |
| CN104437532A (en) | Catalyst for preparing low carbon olefin by fixed bed, preparation method as well as use thereof | |
| CN103586045B (en) | A kind of producing light olefins Catalysts and its preparation method | |
| CN104549342A (en) | Iron catalyst for preparing light olefins by use of synthesis gas and preparation method of iron catalyst | |
| CN106807421B (en) | A kind of catalyst and its preparation method and application for synthesis gas mixed alcohol | |
| CN102441391B (en) | Preparation method of cobalt-based catalyst for Fischer Tropsch synthesis | |
| CN110871075B (en) | Iron-cobalt-potassium-loaded zirconium dioxide catalyst, preparation method and application thereof | |
| CN104437524B (en) | Iron-based catalyst for preparing low-carbon alkane as well as preparation method and using method of iron-based catalyst for preparing low-carbon alkane | |
| 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 | |
| CN102911695A (en) | Fischer-Tropsch synthetic method of mixed system by using different catalysts | |
| CN106140227A (en) | A kind of catalyst with modified aluminas as carrier and its preparation method and application | |
| CN106807422A (en) | Catalyst and its preparation and application for modulation synthesis gas higher alcohol performance | |
| CN103521239A (en) | Catalyst for preparing low-carbon olefin through Fischer-Tropsch synthesis and preparation method of catalyst | |
| CN1318131C (en) | Catalyst foir preparing ethylene by using ethane as raw material oxidized by carbon dioxide, and its prepn. method | |
| CN106669719A (en) | Low-carbon olefin preparation catalyst and preparation method thereof | |
| CN105080562A (en) | CO hydrogenation catalyst, preparation method and application 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 | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |