CN102441383A - 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
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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 is handled for adopting the organic compounds containing nitrogen solution impregnation.
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; Method of modifying to silica-gel carrier adopts the organic compounds containing nitrogen solution impregnation to handle; Organic compounds containing nitrogen can be to be selected from monoethanolamine, diethanol amine, triethanolamine and the pyridine etc. one or more, and 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 used nitrogen-containing compound, like ethanol, acetone etc.The weight concentration of organic compounds containing nitrogen is 1%-35% in the organic compounds containing nitrogen solution, 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.
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 silica-gel carrier is handled for adopting the organic compounds containing nitrogen solution impregnation.
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, organic compounds containing nitrogen solution 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 70.2% 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, drip distilled water to first profit, the volume of consume water is 48ml, is 20% pyridine solution 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 8 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% diethanolamine solution 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 5% ethanolamine solutions 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% triethanolamine 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 is to 48g, adds in the carrier silica gel after the above-mentioned modification to flood 60 ℃ of dryings 24 hours, roasting 10 hours in vacuum or the nitrogen atmosphere in 350 ℃.By final catalyst Fe content 3wt%, take by weighing ferric nitrate 6.6303g, adding distil water is to 48g, adds 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 50% manganese nitrate 3.0716g; Adding distil water is to 48g, adds 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 30g, drip distilled water to just moistening, the volume of consume water is 48ml, is 15% ethanolamine solutions 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 manganese nitrate 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% ethanolamine solutions 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% ethanolamine solutions 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 the mixed solution of 15% monoethanolamine and diethanol amine 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 (12)
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 is handled for adopting the organic compounds containing nitrogen solution impregnation.
2. according to the described method of claim 1, it is characterized in that: organic compounds containing nitrogen is selected from one or more in monoethanolamine, diethanol amine, triethanolamine and the pyridine, and the weight concentration of organic compounds containing nitrogen is 1%-35%.
3. according to claim 1 or 2 described methods, it is characterized in that: the weight concentration of organic compounds containing nitrogen is 5%-20%.
4. according to the described method of claim 1, it is characterized in that: the organic compounds containing nitrogen solution impregnation is handled and is adopted 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: organic compounds containing nitrogen 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: organic compounds containing nitrogen solution impregnation treatment 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: the weight percentage of said active component cobalt is 5%-35%.
9. according to the described method of claim 1, it is characterized in that: organic compounds containing nitrogen solution adopts the aqueous solution or organic solution.
10. 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).
11. according to the described method of claim 10, 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.
12. load-type iron-based preparation of low carbon olefines by synthetic gas catalyst; 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 0.5%-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) is characterized in that: the surface modifying method of surface modification silica-gel carrier is handled for adopting the organic compounds containing nitrogen solution impregnation.
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