CN105080562B - A kind of CO hydrogenation catalysts and its preparation method and application - Google Patents
A kind of CO hydrogenation catalysts and its preparation method and application Download PDFInfo
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Abstract
The present invention discloses a kind of CO hydrogenation catalysts and its preparation method and application, and the preparation of catalyst comprises the following steps：（1）The isometric saturation dipping organic compounds containing nitrogen aqueous solution of alumina support, it is the 30 60% of alumina support saturated absorption amount of solution to dry to the adsorbance of the organic compounds containing nitrogen aqueous solution；（2）Step（1）The modified aluminium oxide supports of preparation are using unsaturated impregnation zinc solution；（3）Using fountain solution impregnation steps of the unsaturated infusion process containing adsorbent（2）Carrier after roasting；（4）Step（3）Carrier impregnation containing adsorbent contains the solution of active metal iron, the impregnating metal auxiliary agent again after drying, roasting, then preparation of low carbon olefines by synthetic gas catalyst is obtained after drying, roasting.The characteristics of catalyst has long-term operation activity stability high, is conducive to commercial Application and popularization.
Description
Technical field
The present invention relates to a kind of synthesis gas alkene catalyst and preparation method thereof, a kind of high activity is related in particular to steady
Qualitative load-type iron-based preparation of low carbon olefines by synthetic gas catalyst and preparation method thereof.
Background technology
The low-carbon alkenes such as ethene, propylene are important basic organic chemical industry raw materials, with the development of chemical industry, its demand
Amount is more and more big.So far, the approach of the low-carbon alkene such as preparing ethylene, propylene mainly passes through light oil cracking process, with complete
The increasingly depleted of petroleum resources in the range of ball, following energy resource structure certainly will be shifted.Compared with petroleum resources, coal and natural
Gas resource relative abundance, develops the low-carbon alkene production technology based on coal and natural gas and has great importance.From synthesis gas
（Can be converted to by natural gas and coal）Direct preparing ethylene, the exploitation of propylene technology, can not only reduce to petroleum resources according to
Rely, and to some rich gas oil starvations area chemistry industrial expansion important in inhibiting.
CN1065026A discloses a kind of preparation of ethylene by use of synthetic gas method, and the preparation method for being related to catalyst is chemical precipitation
Method, mechanical mixing employs noble metal or rare metal, and such as niobium, gallium, praseodymium, scandium, indium, cerium, lanthanum, ytterbium etc. more than ten plant chemistry
Element, ethylene selectivity is 65%-94%, but CO conversion ratios are very low, only 10%, 12% and 15% or so, and CO is recycled and certainly will brought
The consumption of the energy, and catalyst high cost.CN01144691.9 discloses the nano-catalytic of a kind of preparation of ethylene by use of synthetic gas, propylene
Agent and preparation method thereof, uses the combination technique of laser pyrolysis processes combination solid phase reaction to be prepared for Fe3Fe bases nanometer based on C
Catalyst application and preparing low-carbon olefin, and certain effect is achieved, but due to needing practical laser technology, make
Preparation technology is comparatively laborious, and raw material uses Fe (CO)5, the cost of catalyst is higher, and industrialization is difficult.CN03109585.2 is public
Opened it is a kind of for preparation of ethylene by use of synthetic gas, propylene, butene reaction iron/activated-carbon catalyst, using activated carbon as carrier, Fe
As activated centre, successfully Fe is loaded on the activated carbon using vacuum impregnation technology, Fe and auxiliary agent is highly dispersed at
On activated carbon, so as to improve catalytic effect, and the cost of catalyst is greatly reduced.And catalyst is in the condition without feedstock circulation
, up to 96-99%, up to 69.5%, wherein ethene, propylene, butylene are in CHization for CH compounds selectivity in gas-phase product for lower CO conversion ratios
Selectivity in compound is up to more than 68%.But activated carbon is used as catalyst carrier not only bad mechanical strength but also shaping of catalyst
Difficulty, influences the service life and stability of catalyst, is unfavorable for commercial Application.
CN102441383A, CN101940958A, CN102441400A, CN102441384A are respectively adopted nitrogenous organic
Compound solution, the mode such as acid solution, the cushioning liquid of ammonium salt-containing, hydro-thermal process impregnation process is carried out to silica-gel carrier,
Prepare Fe base silica gel supported synthesis gas and directly prepare light olefins catalyst, reduce Fe and SiO2Strong phase between carrier
Interaction.But the activity that above-mentioned Fe bases silica gel supported synthesis gas directly prepares the long-term operation of light olefins catalyst is steady
It is qualitative still to need further raising.
The content of the invention
In view of the shortcomings of the prior art, a kind of iron-based support type synthesis gas system with aluminum oxide as carrier of present invention offer is low
Carbene hydrocarbon catalyst and preparation method thereof, the characteristics of the catalyst has long-term operation activity stability high, is conducive to industry
Using and promote.
A kind of preparation method of preparation of low carbon olefines by synthetic gas catalyst, comprises the following steps：
（1）The isometric saturation dipping organic compounds containing nitrogen aqueous solution of alumina support, immediately at 95-110 DEG C after dipping
Under dry 0.5-1h, it is alumina support saturated absorption amount of solution to dry to the adsorbance of the organic compounds containing nitrogen aqueous solution
30-60%, is then obtained modified aluminium oxide supports after aging, dry, roasting；
（2）Step（1）The modified aluminium oxide supports of preparation using unsaturated impregnation zinc solution, dry after
1h-10h is calcined at 700 DEG C ~ 1000 DEG C, preferably 2h-8h is calcined at 800 DEG C ~ 900 DEG C；
（3）Using fountain solution impregnation steps of the unsaturated infusion process containing adsorbent（2）Carrier after roasting, wherein institute
The adsorbent stated is the organic amine that carbon number is 2~15, and the addition of described adsorbent accounts for step（2）Vehicle weight after roasting
1% ~ 10%；
（4）Step（3）Carrier impregnation containing adsorbent contains the solution of active metal iron, is impregnated again after drying, roasting
Metal promoter, then preparation of low carbon olefines by synthetic gas catalyst is obtained after drying, roasting.
The inventive method step（1）Organic compounds containing nitrogen can be selected from ethanol in the middle organic compounds containing nitrogen aqueous solution
One or more in amine, diethanol amine, triethanolamine and pyridine etc..Nitrogenous organic compound in the organic compounds containing nitrogen aqueous solution
The weight concentration of thing is 1%-35%, preferably 5%-20%.Aging temperature is 50-95 DEG C, and preferably 60 ~ 80 DEG C, ageing time is
0.5-10h, preferably 2-5h.Aging rear drying temperature is 90-150 DEG C, and drying time is 0.5-36h, preferably at 100-120 DEG C
Dry 8-24h.Roasting is calcined 2-15 hours at 280-500 DEG C, is calcined 3-5 hours preferably at 300-450 DEG C.
The inventive method, step（2）Middle zinc salt includes one or more in zinc chloride, zinc nitrate or zinc sulfate.Zinc salt
Solution is the aqueous solution of zinc salt, and the mass fraction of zinc salt is 5-10% in zinc solution.
The inventive method, step（2）The pickup of middle zinc solution is the 5- of alumina support saturated absorption amount of solution
60%, preferably 20-50%.Dip time is 1-5h, and dipping temperature is 40-60 DEG C.Drying temperature is 80-150 DEG C after dipping, is dried
Time is 2-15h.
The inventive method, step（2）Middle alumina support can use existing commercial goods, it is also possible to by existing method system
It is standby.Support shapes can be spherical, bar shaped, piece type.With spherical and bar shaped as best.
The inventive method, step（3）Middle organic amine includes the one kind in fatty amine, hydramine, acid amides, aliphatic cyclic amine or aromatic amine
Or it is several.Specifically include monoethyl amine, diethylamine, triethylamine, ethylenediamine, hexamethylene diamine, tert-butylamine, monoethanolamine, diethanol amine, three
One kind in monoethanolamine, dimethylformamide, propionamide, butyramide, pyridine, morphine, aniline, diphenylamines, naphthalidine, dinaphthylamine
Or several, one or more preferably in diethylamine, triethylamine, morphine.
Step of the present invention（3）In, the fountain solution containing adsorbent is impregnated, impregnated using unsaturation, preferably with unsaturation
Spray, wherein the volume ratio of unsaturated dipping dip amount used and carrier saturated absorption amount of solution is 0.05 ~ 0.4.Dipping contains
After having the fountain solution of adsorbent, can be dried under no more than the decomposition temperature of selected adsorbent, it is also possible to which direct impregnation contains work
Property metallic iron solution, wherein drying temperature is generally 60 DEG C~150 DEG C, and 80 DEG C~120 DEG C are preferably, drying time 0.5h~
20h, preferably 1h~6h.When spraying the fountain solution containing adsorbent, the shower nozzle that atomizing effect should be selected good makes solution uniformly divide
It is scattered on alumina support.After fountain solution dipping of the dipping containing adsorbent terminates, next step can be directly carried out, may also pass through
Health carries out next step again, and conditioned time is 0.5~8h.
The inventive method, step（4）Middle auxiliary agent is K and Mn.In the preparation of low carbon olefines by synthetic gas catalyst of preparation Fe with help
The mass ratio of agent K and Mn is respectively（65~75）：（0.5~5）：（23~34）.Active component Fe and metal promoter K, Mn are by dipping
Method is supported on carrier, generally using incipient impregnation.Dipping method is known to technical staff.With containing active metal or helping
, it is necessary to by drying and being calcined after the solution impregnating carrier of agent.Active metal solution or compounding agent solution preparation method are technology people
Known to member, its solution concentration can be adjusted by the consumption of each compound, be contained so as to prepare specified activity component and auxiliary agent
The catalyst of amount.The raw material of required active component and auxiliary agent is generally the compound of the types such as salt, oxide or acid, such as source of iron
One or more in ferric nitrate, iron chloride, ferric sulfate are generally from, potassium resource is from potassium nitrate, potassium carbonate, potassium chloride
Plant or several, manganese source is generally from manganese nitrate or manganese chloride.
The inventive method, step（4）In add 2-15% in the solution containing active metal iron, preferably 5-10% is with quality
The ammonium citrate of meter.The decentralization of active component can be improved using the iron salt solutions containing ammonium citrate are added, is prepared small
The active component iron catalyst of crystal grain, so as to significantly improve the selectivity of low-carbon alkene.
The inventive method, step（4）The middle solution impregnating carrier used containing active metal component and auxiliary agent, through overdrying after dipping
The condition of dry and calcination stepses, the drying and roasting is conventional, for example, drying steps dry 8-24 at 50-150 DEG C
Hour, calcination stepses are calcined 2-10 hours at 350-700 DEG C.
Preparation of low carbon olefines by synthetic gas catalyst prepared by a kind of use above method, with Fe as active component, be with K and Mn
Auxiliary agent, the weight percentage of Fe is 0.5%-20% in catalyst, and auxiliary agent is the matter of K and Mn, Fe and auxiliary agent K and Mn in catalyst
Amount ratio is respectively（65~75）：（0.5~5）：（23~34）.
The restoring method of above-mentioned preparation of low carbon olefines by synthetic gas catalyst, is reduced using the gaseous mixture of chlorine and hydrogen,
Volume content of the chlorine in gaseous mixture is 0.5-10%, and preferably 1-5%, reduction temperature is 300-450 DEG C, and the recovery time is 3-10
Hour, reduction pressure is 0.5-2MPa.The selectivity of butylene can be improved using above-mentioned restoring method.
The inventive method uses organic compounds containing nitrogen aqueous solution saturation oxide impregnation alumina supporter first, dry through quick fraction
The dry rear organic compounds containing nitrogen aqueous solution is concentrated in the internal gutter of carrier, and the organic compounds containing nitrogen aqueous solution is mainly to carrier
Inside carries out partially modified.Then zinc solution outer surface and outside duct mainly to alumina support is impregnated using unsaturated
Surface is mainly modified.The above-mentioned inside and outside duct to alumina support carries out uneven modified make inside and outside alumina support
Duct physico-chemical property is significantly different, inhibits the carbochain of the low-carbon alkene of generation to increase and add while activity is improved to greatest extent
Hydrogen saturation, improves the conversion ratio of carbon monoxide.The inventive method makes active component iron content by way of adsorbent occupy-place
Gradually increased in by outer, significantly improve the selectivity of catalyst.The physical and chemical performance of the catalyst, catalysis activity, long period
The stability of operating is obtained for raising, and the combination property of catalyst is protruded.
Specific embodiment
Process of the invention and effect are further illustrated with reference to embodiment, but following examples are not constituted to the present invention
The limitation of method.
Example 1
Weigh commercial alumina（Pore volume is 0.96ml/g, and specific surface area is 286.81m2/ g, saturated water adsorptive value is 145ml/
G, is provided by Fushun branch company of Sinopec catalyst Co., Ltd, and following examples and comparative example use the aluminum oxide）, will
Mass concentration is 5% pyridine solution saturation spray oxide impregnation aluminium, dries 1h, drying pyrrole processed after terminating at 95 DEG C immediately
The adsorbance of the pyridine aqueous solution is 60%, aging 7h at 60 DEG C of alumina support saturated absorption amount of solution, and 24 are dried in 100 DEG C
Hour, then it is calcined 5 hours prepared modified aluminium oxide supports at 300 DEG C.Above-mentioned modified aluminium oxide supports are sprayed using unsaturated
Impregnation mass fraction is 5% zinc nitrate aqueous solution, and dipping temperature is 50 DEG C, and dip time 3h, pickup is aluminum oxide
The 20% of carrier saturated absorption amount of solution, dries 5h, 850 DEG C of lower roasting 6h of roasting at 120 DEG C.The unsaturated spray of carrier after roasting
Dipping triethylamine aqueous solution is drenched, triethylamine aqueous solution spray volume is the 35% of the total saturated water adsorptive value of used carrier, and triethylamine is water-soluble
The mass content of triethylamine is the 8% of carrier quality in liquid, and 5h is dried at 100 DEG C after spray dipping.By final catalyst Fe content
9wt% is counted, and the carrier for adsorbing triethylamine impregnates iron nitrate aqueous solution, 100 DEG C of dryings 16 hours, 550 using equi-volume impregnating
It is calcined 4 hours in DEG C.It is 3.6wt% by manganese content in catalyst, the mass ratio of Fe, K and Mn is 70：3：28 meter incipient impregnations
Manganese nitrate and potassium nitrate mixed liquor, 100 DEG C of dryings 16 hours are calcined 4 hours in 550 DEG C, and gained catalyst is designated as C-1.C-1
The reaction result that catalyst synthesis gas directly prepares low-carbon alkene is as shown in table 1.
Catalyst Evaluation Test is carried out in the continuous fixed bed reactors of high pressure, is reduced 5 hours with 350 DEG C of pure hydrogen, pressure
Power is 1.0MPa.Switching and merging gas is reacted after cooling.Reaction effluent is collected by hot trap, cold-trap respectively.Reaction condition is
280 DEG C, 1200h-1, 2.0MPa, H2/CO=1（Mol ratio）.C-1 catalyst synthesis gas directly prepares the 300h reactions of low-carbon alkene
Result is as shown in table 1.
Example 2
Commercial alumina is weighed, is that 20% diethanol amine aqueous solution saturation sprays oxide impregnation aluminium by mass concentration, after terminating
0.5h is dried at 110 DEG C immediately, it is alumina support saturated absorption amount of solution to dry to the adsorbance of the diethanol amine aqueous solution
40%, aging 4 hours at 80 DEG C, in 120 DEG C dry 8 hours, then in 400 DEG C be calcined 3 hours modified aluminas
Carrier.It is 10% zinc sulfate solution that above-mentioned modified aluminium oxide supports use unsaturated impregnation mass fraction, impregnates temperature
It is 60 DEG C to spend, dip time 2h, and pickup is the 40% of alumina support saturated absorption amount of solution, and 10h is dried at 90 DEG C,
900 DEG C of roasting 4h.The unsaturated spray dipping aqueous morphine solution of carrier after roasting, aqueous morphine solution spray volume is used carrier
The 10% of total saturated water adsorptive value, the mass content of morphine is the 2% of carrier quality in aqueous morphine solution, oxygen life 5h after spray dipping,
8h is dried at 90 DEG C., with embodiment 1, prepared catalyst is designated as C-2 for remaining, and 300h evaluation results are shown in Table 1.
Example 3
In addition to the ammonium citrate that mass fraction is 5% is added in the iron nitrate aqueous solution of dipping, remaining is with embodiment 1, system
Obtain catalyst and be designated as C-3,300h evaluation results are shown in Table 1.
Example 4
Except dipping iron nitrate aqueous solution in add the ammonium citrate that mass fraction is 10% in addition to, remaining with embodiment 1,
Prepared catalysis is designated as C-4, and 300 evaluation results are shown in Table 1.
Example 5
With embodiment 1, difference is that catalyst is reduced using the gaseous mixture of chlorine and hydrogen, and chlorine is mixed
The volume content closed in gas is 5%, and prepared catalyst is designated as C-5, and 300h evaluation results are shown in Table 1.
Implement 6
With embodiment 1, difference is that catalyst is reduced using the gaseous mixture of chlorine and hydrogen, and chlorine is in mixing
Volume content in gas is 1%, and, with embodiment 1, prepared catalyst is designated as C-6 for remaining, and 300h evaluation results are shown in Table 1.
Comparative example 1
In addition to using saturation and spraying impregnating effect fraction for 5% zinc nitrate aqueous solution, remaining is obtained catalysis with embodiment 1
Agent is designated as B-1, and 300h evaluation results are shown in Table 1.
Comparative example 2
In addition to dipping triethylamine aqueous solution is not sprayed,, with embodiment 1, prepared catalyst is designated as B-2 for remaining, and 300h evaluates knot
Fruit is shown in Table 1.
The reactivity worth of the catalyst of table 1
Claims (23)
1. a kind of preparation method of preparation of low carbon olefines by synthetic gas catalyst, it is characterised in that：Comprise the following steps：
（1）The isometric saturation dipping organic compounds containing nitrogen aqueous solution of alumina support, does at 95-110 DEG C immediately after dipping
Dry 0.5-1h, it is the 30- of alumina support saturated absorption amount of solution to dry to the adsorbance of the organic compounds containing nitrogen aqueous solution
60%, modified aluminium oxide supports then are obtained after aging, dry, roasting；
（2）Step（1）The modified aluminium oxide supports of preparation using unsaturated impregnation zinc solution, dry after 700 DEG C ~
1h-10h is calcined at 1000 DEG C；
（3）Using fountain solution impregnation steps of the unsaturated infusion process containing adsorbent（2）Carrier after roasting, wherein described
Adsorbent is the organic amine that carbon number is 2~15, and the addition of described adsorbent accounts for step（2）1% of vehicle weight after roasting
~10%；
（4）Step（3）Carrier impregnation containing adsorbent contains the solution of active metal iron, the impregnating metal again after drying, roasting
Auxiliary agent, then preparation of low carbon olefines by synthetic gas catalyst is obtained after drying, roasting；
Step（1）Organic compounds containing nitrogen is monoethanolamine, diethanol amine, triethanolamine and pyrrole in the organic compounds containing nitrogen aqueous solution
One or more in pyridine, roasting is calcined 2-15 hours at 280-500 DEG C.
2. method according to claim 1, it is characterised in that：Step（1）It is nitrogenous in the organic compounds containing nitrogen aqueous solution to have
The weight concentration of machine compound is 1%-35%.
3. method according to claim 1, it is characterised in that：Step（1）Aging temperature is 50-95 DEG C, and ageing time is
0.5-10h, aging rear drying temperature is 90-150 DEG C, and drying time is 0.5-36h.
4. method according to claim 1, it is characterised in that：Step（2）After drying 2h- is calcined at 800 DEG C ~ 900 DEG C
8h。
5. method according to claim 1, it is characterised in that：Step（2）Middle zinc salt is selected from zinc chloride, zinc nitrate or sulfuric acid
One or more in zinc.
6. method according to claim 1, it is characterised in that：Step（2）Middle zinc solution is the aqueous solution of zinc salt, zinc salt
The mass fraction of zinc salt is 5-10% in solution.
7. method according to claim 1, it is characterised in that：Step（2）The pickup of middle zinc solution is carrying alumina
The 5-60% of body saturated absorption amount of solution, dip time is 1-5h, and dipping temperature is 40-60 DEG C, and drying temperature is 80- after dipping
150 DEG C, drying time is 2-15h.
8. method according to claim 1, it is characterised in that：Step（2）The pickup of middle zinc solution is carrying alumina
The 20-50% of body saturated absorption amount of solution.
9. method according to claim 1, it is characterised in that：Step（3）Middle organic amine be selected from fatty amine, hydramine, acid amides,
One or more in aliphatic cyclic amine or aromatic amine.
10. method according to claim 1, it is characterised in that：Step（3）Middle organic amine is selected from monoethyl amine, diethylamine, three
Ethamine, ethylenediamine, hexamethylene diamine, tert-butylamine, monoethanolamine, diethanol amine, triethanolamine, dimethylformamide, propionamide, butyryl
One or more in amine, pyridine, morphine, aniline, diphenylamines, naphthalidine, dinaphthylamine.
11. methods according to claim 10, it is characterised in that：Step（3）Middle organic amine be diethylamine, triethylamine,
One or more in coffee.
12. methods according to claim 1, it is characterised in that：Step（3）Middle fountain solution of the dipping containing adsorbent, adopts
Sprayed with unsaturation, wherein the volume ratio of unsaturated dipping dip amount used and carrier saturated absorption amount of solution for 0.05 ~
0.4。
13. methods according to claim 1, it is characterised in that：Step（3）After middle fountain solution of the dipping containing adsorbent,
Dried under no more than the decomposition temperature of selected adsorbent, or direct impregnation contains the solution of active metal iron, drying temperature
It is 60 DEG C~150 DEG C, drying time 0.5h~20h.
14. methods according to claim 13, it is characterised in that：Drying temperature is 80 DEG C~120 DEG C, and drying time is 1h
~6h.
15. methods according to claim 1, it is characterised in that：Step（4）Middle auxiliary agent is K and Mn, the synthesis gas system of preparation
Fe is respectively with the mass ratio of auxiliary agent K and Mn in light olefins catalyst（65~75）：（0.5~5）：（23~34）.
16. methods according to claim 1, it is characterised in that：Step（4）Middle active component Fe and metal promoter K, Mn are logical
Infusion process is crossed to support on carrier.
17. methods according to claim 15, it is characterised in that：Source of iron is the one kind in ferric nitrate, iron chloride, ferric sulfate
Or it is several, potassium resource is one or more in potassium nitrate, potassium carbonate, potassium chloride, and manganese source is manganese nitrate or manganese chloride.
18. methods according to claim 1, it is characterised in that：Step（4）Added in solution containing active metal iron
2-15% ammonium citrates in mass.
19. methods according to claim 18, it is characterised in that：Step（4）Added in solution containing active metal iron
5-10% ammonium citrates in mass.
20. methods according to claim 1, it is characterised in that：Step（4）It is middle with molten containing active metal component and auxiliary agent
Liquid impregnated carrier, by dry and calcination stepses after dipping, drying steps dry 8-24 hours, calcination stepses at 50-150 DEG C
It is calcined 2-10 hours at 350-700 DEG C.
Preparation of low carbon olefines by synthetic gas catalyst prepared by a kind of 21. use claim 1-20 either method, it is characterised in that：Should
Catalyst with Fe as active component, with K and Mn as auxiliary agent, in catalyst the weight percentage of Fe be 0.5%-20%, Fe with help
The mass ratio of agent K and Mn is respectively（65~75）：（0.5~5）：（23~34）.
The restoring method of catalyst described in 22. claims 21, it is characterised in that：Gone back using the gaseous mixture of chlorine and hydrogen
Original, volume content of the chlorine in gaseous mixture is 0.5-10%, and reduction temperature is 300-450 DEG C, and the recovery time is 3-10 hours,
Reduction pressure is 0.5-2MPa.
23. restoring method according to claim 22, it is characterised in that：Volume content of the chlorine in gaseous mixture is 1-
5%。
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