CN101940958B - Method for preparing low-carbon olefin catalyst by loading iron-based synthetic gas - Google Patents
Method for preparing low-carbon olefin catalyst by loading iron-based synthetic gas Download PDFInfo
- Publication number
- CN101940958B CN101940958B CN2009100125025A CN200910012502A CN101940958B CN 101940958 B CN101940958 B CN 101940958B CN 2009100125025 A CN2009100125025 A CN 2009100125025A CN 200910012502 A CN200910012502 A CN 200910012502A CN 101940958 B CN101940958 B CN 101940958B
- Authority
- CN
- China
- Prior art keywords
- silica gel
- sugar
- acid solution
- catalyst
- hours
- 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
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 load-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 carries out impregnation process for the acid solution that adopts sugar.
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; The steamed bun stuffed with sugar that the acid solution of used sugar uses is drawn together various water-soluble sugar of fitting; Like various monose or disaccharide; Specifically comprise the aqueous solution such as fructose, glucose, sucrose, maltose, the preferably sucrose acid solution.Concrete method of modifying to silica-gel carrier is that the acid solution of a certain amount of silica gel with sugar mixed, and fully stirs back drying, roasting.Silica gel is 1: 1.5～1: 15 with the mass ratio that adopts the acid solution contain sugar to mix, and is preferably 1: 4～1: 12.The mass concentration of sugar is 1%-35% in the acid solution of sugar, preferred 5%-20%.The acid solution pH that contains sugar is 0.1-6.5, and preferred pH value is 1-3, can use the pH value of inorganic acid arbitrarily or organic acid regulator solution, is preferably hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetate etc.Silica gel is 50-95 ℃ with the acid solution mixing temperature that contains sugar, is preferably 60～80 ℃, and the mixed processing time is 0.5-10h, preferred 2-5h.Mixing the back is 50-150 ℃ in dry temperature, and be 0.5-36h drying time, preferably dry 8-24h under 60-120 ℃.Roasting is at 600-1200 ℃ of following roasting 2-15 hour, preferably at 800-1000 ℃ of following roasting 4-10 hour.Wherein silica gel mixes with the acid solution that contains sugar and follow-up drying and roasting can be carried out once, also can carry out repeatedly repeatedly, as 2～5 times.Roasting process adopts vacuum condition or under inert gas atmosphere, carries out.
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 0.25%-10% to major catalyst Fe in the catalyst, preferred 4%-8%.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): (23～34): (0.5～5).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; With silica gel is carrier; With surface modification silica gel is carrier, is active component with Fe, is auxiliary agent with K and Mn; To account for the weight percentage of support modification silica gel be 0.25%-10% 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): (23～34): (0.5～5), the surface modifying method of surface modification silica-gel carrier carries out impregnation process for the acid solution that adopts sugar to silica gel.
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 acid solution of sugar 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 88.2% 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.Be that 5% the aqueous solution equals 3 with the sulphur acid for adjusting pH value with the sucrose mass concentration; And make that the mass ratio of silica gel and mixed solution is 1: 4; In temperature is under 60 ℃ silica gel and sucrose acid solution fully to be mixed stirring 2 hours; In 60 ℃ dry 24 hours, roasting 10 hours in vacuum or the nitrogen atmosphere in 800 ℃ then.
By final catalyst K content 0.03wt%, take by weighing potassium nitrate 0.0234g and be dissolved in 48ml, add in the carrier silica gel after the above-mentioned modification and flood, 60 ℃ of dryings 24 hours, roasting 10 hours in vacuum or the nitrogen atmosphere in 350 ℃.By final catalyst Fe content 4wt%, take by weighing ferric nitrate 8.6808g and be dissolved in 48ml, 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 1.41wt%; Take by weighing manganese nitrate 1.3830g and be dissolved in 48ml, 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=2 (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, drip distilled water to just moistening, the volume of consume water is 48ml.Be that 15% the aqueous solution equals 2 with the salt acid for adjusting pH value with the sucrose mass concentration; And make that the mass ratio of silica gel and mixed solution is 1: 9; In temperature is under 70 ℃ silica gel and sucrose acid solution fully to be mixed stirring 3.5 hours; In 100 ℃ dry 16 hours, vacuum baking 8 hours in 900 ℃ then.
By final catalyst K content 0.25wt%, take by weighing potassium nitrate 0.1939g and be dissolved in 48ml, add in the carrier silica gel after the above-mentioned modification and flood, 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or the nitrogen atmosphere in 550 ℃.By final catalyst Fe content 6wt%, take by weighing ferric nitrate 13.0212g and be dissolved in 48ml, add 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 1.41wt%; Take by weighing manganese nitrate 2.3450g and be dissolved in 48ml; Add 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, drip distilled water to just moistening, the volume of consume water is 48ml.Be that 20% the aqueous solution equals 1 with the sulphur acid for adjusting pH value with the sucrose mass concentration; And make that the mass ratio of silica gel and mixed solution is 1: 12; In temperature is under 80 ℃ silica gel and sucrose acid solution fully to be mixed stirring 5 hours; In 120 ℃ dry 8 hours, vacuum baking 4 hours in 1000 ℃ then.
By final catalyst K content 0.53wt%, take by weighing potassium nitrate 0.1939g 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 8wt%, take by weighing ferric nitrate 17.3616g 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 1.41wt%; Take by weighing manganese nitrate 3.5438g and be dissolved in 48ml; 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
(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.Be that 5% the aqueous solution equals 3 with the sulphur acid for adjusting pH value with the sucrose mass concentration; And make that the mass ratio of silica gel and mixed solution is 1: 4; In temperature is under 60 ℃ silica gel and sucrose acid solution fully to be mixed stirring 2 hours; In 60 ℃ dry 24 hours, roasting 10 hours in vacuum or the nitrogen atmosphere in 800 ℃ then.
By final catalyst K content 0.03wt%, take by weighing potassium nitrate 0.0234g and be dissolved in 48ml, add in the carrier silica gel after the above-mentioned modification and flood, 60 ℃ of dryings 24 hours, roasting 10 hours in vacuum or the nitrogen atmosphere in 350 ℃.By final catalyst Fe content 4wt%, take by weighing ferric nitrate 8.6808g and be dissolved in 48ml, 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 1.41wt%; Take by weighing manganese nitrate 1.3830g and be dissolved in 48ml, 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-4.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, drip distilled water to just moistening, the volume of consume water is 48ml.Be that 15% the aqueous solution equals 2 with the sulphur acid for adjusting pH value with glucose quality concentration; And make that the mass ratio of silica gel and mixed solution is 1: 9; In temperature is under 70 ℃ silica gel and the acid solution of glucose fully to be mixed stirring 3.5 hours; In 100 ℃ dry 16 hours, vacuum baking 8 hours in 900 ℃ then.
By final catalyst K content 0.25wt%, take by weighing potassium nitrate 0.1939g and be dissolved in 48ml, add in the carrier silica gel after the above-mentioned modification and flood, 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or the nitrogen atmosphere in 550 ℃.By final catalyst Fe content 6wt%, take by weighing ferric nitrate 13.0212g and be dissolved in 48ml, add 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 1.41wt%; Take by weighing manganese nitrate 2.3450g and be dissolved in 48ml; Add 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, drip distilled water to just moistening, the volume of consume water is 48ml.Be that 15% the aqueous solution equals 2 with the sulphur acid for adjusting pH value with the fructose mass concentration; And make that the mass ratio of silica gel and mixed solution is 1: 9; In temperature is under 70 ℃ silica gel and fructose acid solution fully to be mixed stirring 3.5 hours; In 100 ℃ dry 16 hours, vacuum baking 8 hours in 900 ℃ then.
By final catalyst K content 0.25wt%, take by weighing potassium nitrate 0.1939g and be dissolved in 48ml, add in the carrier silica gel after the above-mentioned modification and flood, 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or the nitrogen atmosphere in 550 ℃.By final catalyst Fe content 6wt%, take by weighing ferric nitrate 13.0212g and be dissolved in 48ml, add 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 1.41wt%; Take by weighing manganese nitrate 2.3450g and be dissolved in 48ml; Add 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, drip distilled water to just moistening, the volume of consume water is 48ml.Be that 15% the aqueous solution equals 2 with the sulphur acid for adjusting pH value with the maltose mass concentration; And make that the mass ratio of silica gel and mixed solution is 1: 9; In temperature is under 70 ℃ silica gel and the acid solution of maltose fully to be mixed stirring 3.5 hours; In 100 ℃ dry 16 hours, vacuum baking 8 hours in 900 ℃ then.
By final catalyst K content 0.25wt%, take by weighing potassium nitrate 0.1939g and be dissolved in 48ml, add in the carrier silica gel after the above-mentioned modification and flood, 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or the nitrogen atmosphere in 550 ℃.By final catalyst Fe content 6wt%, take by weighing ferric nitrate 13.0212g and be dissolved in 48ml, add 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 1.41wt%; Take by weighing manganese nitrate 2.3450g and be dissolved in 48ml; Add 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, drip distilled water to just moistening, the volume of consume water is 48ml.Be that 15% the aqueous solution equals 2 with the sulphur acid for adjusting pH value with the sucrose mass concentration; And make that the mass ratio of silica gel and mixed solution is 1: 9; In temperature is under 70 ℃ silica gel and sucrose acid solution fully to be mixed stirring 3.5 hours; In 100 ℃ dry 16 hours, vacuum baking 8 hours in 900 ℃ then.With above-mentioned sucrose acid solution handle with dry, calcination process after silica gel be 15% with mass concentration once more; The sucrose acidic aqueous solution of pH=2 mixes; And make that the mass ratio of silica gel and mixed solution is 1: 9; In temperature is under 70 ℃ silica gel and sucrose acid solution fully to be mixed to stir 3.5 hours, in 100 ℃ dry 16 hours, and vacuum baking 8 hours in 900 ℃ then.
By final catalyst K content 0.25wt%, take by weighing potassium nitrate 0.1939g and be dissolved in 48ml, add in the carrier silica gel after the above-mentioned modification and flood, 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or the nitrogen atmosphere in 550 ℃.By final catalyst Fe content 6wt%, take by weighing ferric nitrate 13.0212g and be dissolved in 48ml, add 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 1.41wt%; Take by weighing manganese nitrate 2.3450g and be dissolved in 48ml; Add 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 0.25wt%, take by weighing potassium nitrate 0.1939g and be dissolved in 48ml, add in the carrier silica gel after the above-mentioned modification and flood, 100 ℃ of dryings 16 hours, roasting 4 hours in vacuum or the nitrogen atmosphere in 550 ℃.By final catalyst Fe content 6wt%, take by weighing ferric nitrate 13.0212g and be dissolved in 48ml, add 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 1.41wt%; Take by weighing manganese nitrate 2.3450g and be dissolved in 48ml; Add 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
| Catalyst | CO conversion ratio (%) | CH selectivity (%) | C 1Selectivity (wt%) | C 2° selectivity (wt%) | C 2 ＝Selectivity (wt%) | C 3° selectivity (wt%) | C 3 ＝Selectivity (wt%) | C 4° selectivity (wt%) | C 4 ＝Selectivity (wt%) |
| C-B | 21.8 | 88.5 | 39.8 | 13.4 | 2.8 | 21.7 | 1.5 | 18.8 | 2.0 |
| C-1 | 90.2 | 87.2 | 22.5 | 8.4 | 14.7 | 5.4 | 28.5 | 8.4 | 12.1 |
| C-2 | 93.5 | 91.5 | 21.7 | 6.7 | 16.8 | 4.8 | 29.1 | 7.6 | 13.3 |
| C-3 | 92.7 | 89.1 | 23.9 | 8.7 | 13.9 | 5.9 | 26.8 | 8.1 | 12.7 |
| C-4 | 90.3 | 87.5 | 23.5 | 7.3 | 15.7 | 5.7 | 27.6 | 8.8 | 11.4 |
| C-5 | 92.3 | 88.5 | 22.5 | 7.1 | 16.3 | 4.4 | 28.6 | 7.4 | 13.7 |
| C-6 | 88.2 | 86.5 | 21.6 | 7.8 | 15.3 | 5.4 | 27.5 | 8.5 | 13.9 |
| C-7 | 89.4 | 85.9 | 23.4 | 8.3 | 15.4 | 6.4 | 26.0 | 8.3 | 12.2 |
| C-8 | 90.7 | 90.6 | 21.9 | 9.7 | 15.9 | 4.9 | 25.8 | 8.1 | 13.7 |
CH representes hydro carbons, C
2° expression 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 load-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 carries out impregnation process for the acid solution that adopts sugar; The acid solution of sugar is that the acid solution of silica gel with sugar mixed to the surface modifying method of silica-gel carrier, carries out drying, roasting after the stirring.
2. according to the described method of claim 1, it is characterized in that: the steamed bun stuffed with sugar that the acid solution of said sugar uses is drawn together various monose or disaccharide.
3. according to claim 1 or 2 described methods; It is characterized in that: sugar acid solution impregnation process silica gel the time; Silica gel is 1: 1.5～1: 15 with the mass ratio that the acid solution of sugar mixes, and the mass concentration of sugar is 1%-35% in the acid solution of sugar, and the acid solution pH that contains sugar is 0.1-6.5; Silica gel is 50-95 ℃ with the acid solution mixing temperature of sugar, and the mixed processing time is 0.5-10h.
4. according to claim 1 or 2 described methods; It is characterized in that: sugar acid solution impregnation process silica gel the time; Silica gel is 1: 4～1: 12 with the mass ratio that the acid solution of sugar mixes, and the mass concentration of sugar is 5%-20% in the acid solution of sugar, and the acid solution pH that contains sugar is 1-3; Silica gel is 60～80 ℃ with the acid solution mixing temperature of sugar, and the mixed processing time is 2-5h.
5. according to the described method of claim 1, it is characterized in that: described baking temperature is 50-150 ℃, and be 0.5-36h drying time, and roasting was at 600-1200 ℃ of following roasting 2-15 hour.
6. according to the described method of claim 1, it is characterized in that: silica gel mixes with the acid solution that contains sugar and follow-up drying and roasting are carried out once, perhaps carries out repeatedly repeatedly.
7. according to the described method of claim 1, it is characterized in that: roasting process adopts vacuum condition or under inert gas atmosphere, carries out.
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 0.25%-10% 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): (23～34): (0.5～5).
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. the load-type iron-based preparation of low carbon olefines by synthetic gas catalyst of the said method preparation of a claim 1; With surface modification silica gel is carrier; 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 0.25%-10% 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): (23～34): (0.5～5) is characterized in that: the surface modifying method of surface modification silica-gel carrier carries out impregnation process for the acid solution that adopts sugar to silica gel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100125025A CN101940958B (en) | 2009-07-09 | 2009-07-09 | Method for preparing low-carbon olefin catalyst by loading iron-based synthetic gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100125025A CN101940958B (en) | 2009-07-09 | 2009-07-09 | Method for preparing low-carbon olefin catalyst by loading iron-based synthetic gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101940958A CN101940958A (en) | 2011-01-12 |
| CN101940958B true CN101940958B (en) | 2012-07-18 |
Family
ID=43433277
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100125025A Active CN101940958B (en) | 2009-07-09 | 2009-07-09 | Method for preparing low-carbon olefin catalyst by loading iron-based synthetic gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101940958B (en) |
Families Citing this family (9)
| 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 |
| 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 |
| 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 |
| 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 |
| CN105709830B (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 preparation method thereof |
| 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 |
| 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 |
| 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 |
| CN110368983A (en) * | 2018-04-13 | 2019-10-25 | 株式会社模范 | A kind of preparation method of synthesis gas synthesis aviation kerosine catalyst and thus obtained catalyst and its application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1187215A (en) * | 1995-06-08 | 1998-07-08 | 住友金属矿山株式会社 | Hydrotreating catalyst composition, preparation and use thereof |
| JP2006297313A (en) * | 2005-04-21 | 2006-11-02 | National Institute Of Advanced Industrial & Technology | Method for manufacturing catalyst for hydrogenating light oil |
| CN1958162A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Method for preparing carrier of alumina |
| CN101554595A (en) * | 2009-05-18 | 2009-10-14 | 浙江大学 | Catalyst support used for olefinic polymerization as well as preparation method and application thereof |
-
2009
- 2009-07-09 CN CN2009100125025A patent/CN101940958B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1187215A (en) * | 1995-06-08 | 1998-07-08 | 住友金属矿山株式会社 | Hydrotreating catalyst composition, preparation and use thereof |
| JP2006297313A (en) * | 2005-04-21 | 2006-11-02 | National Institute Of Advanced Industrial & Technology | Method for manufacturing catalyst for hydrogenating light oil |
| CN1958162A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Method for preparing carrier of alumina |
| CN101554595A (en) * | 2009-05-18 | 2009-10-14 | 浙江大学 | Catalyst support used for olefinic polymerization as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101940958A (en) | 2011-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101940958B (en) | Method for preparing low-carbon olefin catalyst by loading iron-based synthetic gas | |
| CN102441383B (en) | Method for preparing low-carbon olefine catalyst by loading iron-based synthetic gas | |
| CN101920200B (en) | Method for preparing long-life cobalt-based catalyst for Fischer-Tropsch synthesis | |
| CN103586046B (en) | Catalyst for preparing light olefins from synthetic gas 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 | |
| CN114939433A (en) | Composite catalyst for directly preparing light aromatic hydrocarbon by carbon dioxide hydrogenation, preparation and application thereof | |
| CN105080563B (en) | A kind of hydrogenation catalyst and preparation method thereof | |
| CN112570031A (en) | Catalyst suitable for preparing high-carbon hydrocarbon by carbon dioxide hydrogenation and preparation and application thereof | |
| CN111151287B (en) | Alkaline oxide modified boron nitride catalyst and preparation method and application thereof | |
| CN102908957A (en) | Method for Fischer-Tropsch synthesis | |
| CN113877583A (en) | Catalyst in process for producing 1, 5-pentanediol by biological furfuryl alcohol hydrogen ring-opening, preparation and application | |
| CN110871075B (en) | Iron-cobalt-potassium-loaded zirconium dioxide catalyst, preparation method and application thereof | |
| CN103586045B (en) | A kind of producing light olefins Catalysts and its preparation method | |
| 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 | |
| CN106669721A (en) | Iron-based supported catalyst and preparation method thereof | |
| CN102441384B (en) | Method for preparing low-carbon olefin catalyst by high-activity-stability carrier-type iron-based synthetic gas | |
| CN110327923B (en) | Biomass sugar alcohol hydrogenolysis catalyst and preparation method and application thereof | |
| CN106140227A (en) | A kind of catalyst with modified aluminas as carrier and its preparation method and application | |
| CN101623651A (en) | Catalyst for preparing propylene by methyl alcohol and/or dimethyl ether and preparation method thereof | |
| CN1318131C (en) | Catalyst foir preparing ethylene by using ethane as raw material oxidized by carbon dioxide, and its prepn. method | |
| CN110079355B (en) | Aviation fuel oil synthesized by methyl isobutyl ketone aldol condensation and synthesis method | |
| CN105080562A (en) | CO hydrogenation catalyst, preparation method and application thereof | |
| CN106669723A (en) | Catalyst for synthesis gas reaction and preparation method and application thereof | |
| CN106669720A (en) | Hydrogenation catalyst, preparation method and applications thereof | |
| CN106669719A (en) | Low-carbon olefin preparation 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 | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |