CN105080561A - Supported iron-based catalyst and preparation method thereof - Google Patents
Supported iron-based catalyst and preparation method thereof Download PDFInfo
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Abstract
A supported iron-based catalyst and a preparation method thereof. The invention discloses a preparation method of a catalyst for preparing a low carbon olefin by synthetic gas including the following steps: (1) immersing an alumina carrier into a zinc salt solution by using an unsaturated immersion method, and roasting at 700-1000 DEG C for 1-10 hours after drying; (2) immersing the roasted carrier in step (1) into a fountain solution containing an adsorbent by using the unsaturated immersion method, wherein the adsorbent is an organic amine with 2-15 carbons, and the addition of the adsorbent is 1%-10% of the weight of the roasted carrier in step (1); (3) immersing the dried carrier containing the adsorbent in step (2) into a solution containing an active metal iron; immersing the carrier into a metal auxiliary agent after drying and roasting; and getting the catalyst for preparing the low carbon olefin by synthetic gas after drying and roasting. The catalyst has high activity and stability in long-time running, and facilitates the industrial application and popularization.
Description
Technical field
The present invention relates to a kind of preparation of low carbon olefines by synthetic gas Catalysts and its preparation method, relate in particular to the load-type iron-based preparation of low carbon olefines by synthetic gas Catalysts and its preparation method of a kind of high-activity stable.
Background technology
The low-carbon alkene such as ethene, propylene is important basic organic chemical industry raw material, and along with the development of chemical industry, its demand is more and more large.Up to now, the approach of the low-carbon alkene such as preparing ethylene, propylene is mainly through light oil cracking process, and along with the exhaustion day by day of petroleum resources in global range, following energy resource structure certainly will shift.Compared with petroleum resources, coal and natural gas resource relative abundance, develop and have great importance based on the low-carbon alkene production technology of coal and natural gas.From the exploitation of the direct preparing ethylene of synthesis gas (can be converted to by natural gas and coal), propylene technology, the dependence to petroleum resources not only can be reduced, and to some chemical industrial expansion important in inhibitings in rich gas oil starvations area.
CN1065026A discloses a kind of preparation of ethylene by use of synthetic gas method, the preparation method relating to catalyst is chemical precipitation method, mechanical mixing, have employed noble metal or rare metal, such as niobium, gallium, praseodymium, scandium, indium, cerium, lanthanum, ytterbium etc. more than ten plant chemical element, and ethylene selectivity is 65%-94%, but CO conversion ratio is very low, only 10%, 12% and about 15%, CO recycle the consumption that certainly will bring the energy, and catalyst cost is high.CN01144691.9 discloses the nanocatalyst and preparation method thereof of a kind of preparation of ethylene by use of synthetic gas, propylene, adopts laser pyrolysis processes to prepare in conjunction with the combination technique of solid phase reaction with Fe
3c is main Fe base nano-catalyst application and preparing low-carbon olefin, and achieves certain effect, but due to the practical laser technology of needs, makes preparation technology more loaded down with trivial details, and raw material adopts Fe (CO)
5, the cost compare of catalyst is high, industrialization difficulty.CN03109585.2 discloses a kind of iron/activated-carbon catalyst for the synthesis of gas ethene, propylene, butene reaction, adopt active carbon as carrier, Fe is as activated centre, adopt vacuum impregnation technology successfully by Fe load on the activated carbon, Fe and auxiliary agent is made to be able to high degree of dispersion on the activated carbon, thus raising catalytic effect, and greatly reduce the cost of catalyst.And catalyst CO conversion ratio under without the condition of feedstock circulation can reach 96-99%, in gas-phase product, CH compound selective reaches 69.5%, and wherein selective in CH compound of ethene, propylene, butylene reaches more than 68%.But active carbon, as catalyst carrier not only bad mechanical strength but also shaping of catalyst difficulty, affects service life and the stability of catalyst, is unfavorable for commercial Application.
CN102441383A, CN101940958A, CN102441400A, CN102441384A adopt organic compounds containing nitrogen solution, the acid solution of sugar, the mode such as cushioning liquid, hydrothermal treatment consists of ammonium salt-containing to carry out impregnation process to silica-gel carrier respectively, prepare Fe base silica gel supported synthesis gas and directly prepare light olefins catalyst, reduce Fe and SiO
2strong interaction between carrier.But the activity stability that above-mentioned Fe base silica gel supported synthesis gas directly prepares the long-term operation of light olefins catalyst still needs to be improved further.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of take aluminium oxide as the iron-based support type preparation of low carbon olefines by synthetic gas Catalysts and its preparation method of carrier, and this catalyst has the high feature of long-term operation activity stability, is conducive to commercial Application and popularization.
A preparation method for preparation of low carbon olefines by synthetic gas catalyst, comprises the steps:
(1) be that carrier adopts unsaturated impregnation zinc solution with aluminium oxide, after drying at 700 DEG C ~ 1000 DEG C roasting 1h-10h, preferably roasting 2h-8h at 800 DEG C ~ 900 DEG C;
(2) carrier of unsaturated infusion process after containing fountain solution impregnation steps (1) roasting of adsorbent is adopted, wherein said adsorbent to be carbon number be 2 ~ 15 organic amine, the addition of described adsorbent accounts for 1% ~ 10% of the vehicle weight after step (1) roasting;
(3) step (2) contains the solution of active metal iron containing the carrier impregnation of adsorbent, impregnating metal auxiliary agent again after drying, roasting, then drying, obtained preparation of low carbon olefines by synthetic gas catalyst after roasting.
The inventive method, in step (1), zinc salt comprises one or more in zinc chloride, zinc nitrate or zinc sulfate.Zinc solution is the aqueous solution of zinc salt, and in zinc solution, the mass fraction of zinc salt is 5-10%.
The inventive method, in step (1), the pickup of zinc solution is the 5-60% of alumina support saturated absorption amount of solution, preferred 20-50%.Dip time is 1-5h, and dipping temperature is 40-60 DEG C.After dipping, baking temperature is 80-150 DEG C, and drying time is 2-15h.
The inventive method, in step (1), alumina support can adopt existing commercial goods, also can prepare by existing method.Support shapes can be spherical, bar shaped, flap-type.With spherical be best.
The inventive method, in step (2), organic amine comprises one or more in fatty amine, hydramine, acid amides, aliphatic cyclic amine or aromatic amine.Specifically comprise one or more in monoethyl amine, diethylamine, triethylamine, ethylenediamine, hexamethylene diamine, tert-butylamine, monoethanolamine, diethanol amine, triethanolamine, dimethyl formamide, propionamide, butyramide, pyridine, morphine, aniline, diphenylamines, naphthalidine, dinaphthylamine, one or more in preferred diethylamine, triethylamine, morphine.
In step of the present invention (2), the fountain solution of dipping containing adsorbent, adopt unsaturated dipping, preferably adopt unsaturated spraying, the immersion liquid amount that wherein unsaturated dipping is used and the volume ratio of carrier saturated absorption amount of solution are 0.05 ~ 0.4.Dipping, can be dry under the decomposition temperature being no more than selected adsorbent containing after the fountain solution of adsorbent, also direct impregnation can contain the solution of active metal iron, wherein baking temperature is generally 60 DEG C ~ 150 DEG C, 80 DEG C ~ 120 DEG C preferably, and drying time, 0.5h ~ 20h, was preferably 1h ~ 6h.When spraying the fountain solution containing adsorbent, the shower nozzle that atomizing effect is good should be selected, dissolution homogeneity is distributed on alumina support.After the fountain solution dipping of dipping containing adsorbent terminates, directly can carry out next step, also can be passed through health and carry out next step again, conditioned time is 0.5 ~ 8h.
The inventive method, in step (3), auxiliary agent is K and Mn.In the preparation of low carbon olefines by synthetic gas catalyst of preparation, the mass ratio of Fe and auxiliary agent K and Mn is respectively (65 ~ 75): (0.5 ~ 5): (23 ~ 34).Active component Fe and metal promoter K, Mn support on carrier by infusion process, usually adopt incipient impregnation.Dipping method is known by technical staff.After the solution impregnating carrier containing active metal or auxiliary agent, need through super-dry and roasting.Active metal solution or compounding agent solution preparation method are known by technical staff, and its solution concentration regulates by the consumption of each compound, thus prepares the catalyst of specified activity component and auxiliary agent content.The raw material of required active component and auxiliary agent is generally the compound of the types such as salt, oxide or acid, from one or more in ferric nitrate, iron chloride, ferric sulfate as source of iron, potassium source is from one or more in potassium nitrate, potash, potassium chloride, and manganese source is generally from manganese nitrate or manganese chloride.
The inventive method, adds 2-15%, preferred 5-10% ammonium citrate in mass containing in the solution of active metal iron in step (3).Adopt the iron salt solutions added containing ammonium citrate can improve the decentralization of active component, prepare the active component iron catalyst of little crystal grain, thus significantly improve the selective of low-carbon alkene.
The inventive method, with the solution impregnating carrier containing active metal component and auxiliary agent in step (3), through super-dry and calcination steps after dipping, the condition of described drying and roasting is all conventional, such as, drying steps is dry 8-24 hour at 50-150 DEG C, and calcination steps is roasting 2-10 hour at 350-700 DEG C.
A kind of preparation of low carbon olefines by synthetic gas catalyst adopting above method to prepare, take Fe as active component, with K and Mn for auxiliary agent, in catalyst, the weight percentage of Fe is 0.5%-20%, in catalyst, auxiliary agent is that the mass ratio of K and Mn, Fe and auxiliary agent K and Mn is respectively (65 ~ 75): (0.5 ~ 5): (23 ~ 34).
The method of reducing of above-mentioned preparation of low carbon olefines by synthetic gas catalyst, adopt the gaseous mixture of chlorine and hydrogen to reduce, the volume content of chlorine in gaseous mixture is 0.5-10%, preferred 1-5%, reduction temperature is 300-450 DEG C, and the recovery time is 3-10 hour, and reduction pressure is 0.5-2MPa.Adopt above-mentioned method of reducing can improve the selective of butylene.
The inventive method adopts zinc solution to carry out uneven modification to alumina support, namely the main outer surface to carrier and outside channel surfaces carry out main modification and to carry out modifying function to internal channel surfaces more weak, make the inside and outside duct physico-chemical property of alumina support obviously different, put forward the highly active carbochain of the low-carbon alkene of generation that simultaneously inhibits to greatest extent to increase and hydrotreated lube base oil, improve the conversion ratio of carbon monoxide.The inventive method makes active component iron content by increasing gradually from interior outward by the mode of adsorbent occupy-place, significantly improves the selective of catalyst.The stability of the physical and chemical performance of this catalyst, catalytic activity, long-term operation is obtained for raising, and the combination property of catalyst is given prominence to.
Detailed description of the invention
Further illustrate process of the present invention and effect below in conjunction with embodiment, but following examples do not form the restriction to the inventive method.
Example 1
(pore volume is 0.96ml/g, and specific area is 286.81m to take commercially available ball-aluminium oxide
2/ g, saturated water adsorptive value is 145ml/g, thered is provided by Fushun branch company of Sinopec catalyst Co., Ltd, following examples and comparative example all use this aluminium oxide), adopt unsaturated spray impregnation mass fraction to be the zinc nitrate aqueous solution of 5%, dipping temperature is 50 DEG C, dip time 3h, pickup is dry 5h, roasting 6h under 850 DEG C of roastings at 20%, 120 DEG C of alumina support saturated absorption amount of solution.Carrier after roasting unsaturated spray dipping triethylamine aqueous solution, triethylamine aqueous solution spray volume is 35% of the total saturated water adsorptive value of used carrier, and in triethylamine aqueous solution, the mass content of triethylamine is 8% of carrier quality, at 100 DEG C of dry 5h after spray dipping.By final catalyst Fe content 9wt%, the carrier of absorption triethylamine adopts equi-volume impregnating dipping iron nitrate aqueous solution, 100 DEG C of dryings 16 hours, roasting 4 hours in 550 DEG C.By Fe content in catalyst be 3.6wt%, Fe, the mass ratio of K and Mn is that 70:3:28 counts incipient impregnation manganese nitrate and potassium nitrate mixed liquor, 100 DEG C of dryings 16 hours, roasting 4 hours in 550 DEG C, gained catalyst is designated as C-1.The reaction result that C-1 catalyst synthesis gas directly prepares low-carbon alkene is as shown in table 1.
Catalyst Evaluation Test carries out in the continuous fixed bed reactors of high pressure, and to reduce 5 hours at pure hydrogen 350 DEG C, pressure is 1.0MPa.After cooling, switching and merging gas reacts.Reaction effluent is collected by hot trap, cold-trap respectively.Reaction condition is 280 DEG C, 1200h
-1, 2.0MPa, H
2/ CO=1(mol ratio).The 300h reaction result that C-1 catalyst synthesis gas directly prepares low-carbon alkene is as shown in table 1.
Example 2
Take commercial alumina, adopt unsaturated impregnation mass fraction to be the zinc sulfate solution of 10%, dipping temperature is 60 DEG C, dip time 2h, and pickup is 40% of alumina support saturated absorption amount of solution, dry 10h at 90 DEG C, 900 DEG C of roasting 4h.Carrier after roasting unsaturated spray dipping aqueous morphine solution, aqueous morphine solution spray volume is 10% of the total saturated water adsorptive value of used carrier, and in aqueous morphine solution, the mass content of morphine is 2% of carrier quality, and the raw 5h of oxygen after spray dipping, at 90 DEG C of dry 8h.All the other are with embodiment 1, and obtained catalyst is designated as C-2, and 300h evaluation result is in table 1.
Example 3
Except in the iron nitrate aqueous solution of dipping, to add mass fraction be except the ammonium citrate of 5%, all the other are with embodiment 1, and obtained catalyst is designated as C-3, and 300h evaluation result is in table 1.
Example 4
Except in the iron nitrate aqueous solution of dipping, to add mass fraction be except the ammonium citrate of 10%, all the other are with embodiment 1, and obtained catalysis is designated as C-4, and 300 evaluation results are in table 1.
Example 5
With embodiment 1, difference is to adopt the gaseous mixture of chlorine and hydrogen to reduce to catalyst, and the volume content of chlorine in gaseous mixture is 5%, and obtained catalyst is designated as C-5, and 300h evaluation result is in table 1.
Implement 6
With embodiment 1, difference is that catalyst adopts the gaseous mixture of chlorine and hydrogen to reduce, and the volume content of chlorine in gaseous mixture is 1%, and all the other are with embodiment 1, and obtained catalyst is designated as C-6, and 300h evaluation result is in table 1.
Comparative example 1
Except the saturated spray impregnating effect mark of employing is except the zinc nitrate aqueous solution of 5%, all the other are with embodiment 1, and obtained catalyst is designated as B-1, and 300h evaluation result is in table 1.
Comparative example 2
Except not spraying dipping triethylamine aqueous solution, all the other are with embodiment 1, and obtained catalyst is designated as B-2, and 300h evaluation result is in table 1.
The reactivity worth of table 1 catalyst
Claims (22)
1. a preparation method for preparation of low carbon olefines by synthetic gas catalyst, is characterized in that: comprise the steps:
(1) be that carrier adopts unsaturated impregnation zinc solution with aluminium oxide, after drying at 700 DEG C ~ 1000 DEG C roasting 1h-10h;
(2) carrier of unsaturated infusion process after containing fountain solution impregnation steps (1) roasting of adsorbent is adopted, wherein said adsorbent to be carbon number be 2 ~ 15 organic amine, the addition of described adsorbent accounts for 1% ~ 10% of the vehicle weight after step (1) roasting;
(3) step (2) contains the solution of active metal iron containing the carrier impregnation of adsorbent, impregnating metal auxiliary agent again after drying, roasting, then drying, obtained preparation of low carbon olefines by synthetic gas catalyst after roasting.
2. method according to claim 1, is characterized in that: after step (1) drying at 800 DEG C ~ 900 DEG C roasting 2h-8h.
3. method according to claim 1, is characterized in that: in step (1), zinc salt comprises one or more in zinc chloride, zinc nitrate or zinc sulfate.
4. method according to claim 1, is characterized in that: in step (1), zinc solution is the aqueous solution of zinc salt, and in zinc solution, the mass fraction of zinc salt is 5-10%.
5. method according to claim 1, it is characterized in that: in step (1), the pickup of zinc solution is the 5-60% of alumina support saturated absorption amount of solution, and dip time is 1-5h, and dipping temperature is 40-60 DEG C, after dipping, baking temperature is 80-150 DEG C, and drying time is 2-15h.
6. method according to claim 1, is characterized in that: in step (1), the pickup of zinc solution is the 20-50% of alumina support saturated absorption amount of solution.
7. method according to claim 1, is characterized in that: in step (2), organic amine comprises one or more in fatty amine, hydramine, acid amides, aliphatic cyclic amine or aromatic amine.
8. the method according to claim 1 or 7, is characterized in that: in step (2), organic amine comprises one or more in monoethyl amine, diethylamine, triethylamine, ethylenediamine, hexamethylene diamine, tert-butylamine, monoethanolamine, diethanol amine, triethanolamine, dimethyl formamide, propionamide, butyramide, pyridine, morphine, aniline, diphenylamines, naphthalidine, dinaphthylamine.
9. method according to claim 8, is characterized in that: in step (2), organic amine is one or more in diethylamine, triethylamine, morphine.
10. method according to claim 1, is characterized in that: the fountain solution of dipping containing adsorbent in step (2), adopt unsaturated spraying, the immersion liquid amount that wherein unsaturated dipping is used and the volume ratio of carrier saturated absorption amount of solution are 0.05 ~ 0.4.
11. methods according to claim 1, it is characterized in that: in step (2), dipping is containing after the fountain solution of adsorbent, dry under the decomposition temperature being no more than selected adsorbent, or direct impregnation contains the solution of active metal iron, baking temperature is 60 DEG C ~ 150 DEG C, drying time 0.5h ~ 20h.
12. methods according to claim 11, is characterized in that: baking temperature is 80 DEG C ~ 120 DEG C, and drying time is 1h ~ 6h.
13. methods according to claim 1, is characterized in that: after in step (2), the fountain solution dipping of dipping containing adsorbent terminates, directly carry out next step, or carry out next step again through health, conditioned time is 0.5 ~ 8h.
14. methods according to claim 1, is characterized in that: in step (3), auxiliary agent is K and Mn, and in the preparation of low carbon olefines by synthetic gas catalyst of preparation, the mass ratio of Fe and auxiliary agent K and Mn is respectively (65 ~ 75): (0.5 ~ 5): (23 ~ 34).
15. methods according to claim 1, is characterized in that: in step (3), active component Fe and metal promoter K, Mn are supported on carrier by infusion process.
16. methods according to claim 14, is characterized in that: source of iron is one or more in ferric nitrate, iron chloride, ferric sulfate, and potassium source is one or more in potassium nitrate, potash, potassium chloride, and manganese source is manganese nitrate or manganese chloride.
17. methods according to claim 1, is characterized in that: add 2-15% ammonium citrate in mass in the solution of step (3) containing active metal iron.
18. methods according to claim 17, is characterized in that: add 5-10% ammonium citrate in mass in the solution of step (3) containing active metal iron.
19. methods according to claim 1, it is characterized in that: with the solution impregnating carrier containing active metal component and auxiliary agent in step (3), through super-dry and calcination steps after dipping, drying steps is dry 8-24 hour at 50-150 DEG C, and calcination steps is roasting 2-10 hour at 350-700 DEG C.
20. 1 kinds of preparation of low carbon olefines by synthetic gas catalyst adopting claim 1-19 either method to prepare, it is characterized in that: this catalyst take Fe as active component, with K and Mn for auxiliary agent, in catalyst, the weight percentage of Fe is that the mass ratio of 0.5%-20%, Fe and auxiliary agent K and Mn is respectively (65 ~ 75): (0.5 ~ 5): (23 ~ 34).
The method of reducing of catalyst described in 21. claims 20, it is characterized in that: adopt the gaseous mixture of chlorine and hydrogen to reduce, the volume content of chlorine in gaseous mixture is 0.5-10%, and reduction temperature is 300-450 DEG C, recovery time is 3-10 hour, and reduction pressure is 0.5-2MPa.
22. method of reducing according to claim 21, is characterized in that: the volume content of chlorine in gaseous mixture is 1-5%.
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| CN1289647A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Process for preparing catalyst with non-uniform distribution of active metals |
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