CN105709772B - A kind of synthesis gas alkene catalyst and its preparation method and application - Google Patents
A kind of synthesis gas alkene catalyst and its preparation method and application Download PDFInfo
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Abstract
The present invention discloses 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, 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, and modified aluminium oxide supports are then made after aging, drying, roasting；（2）Step（1）The modified aluminium oxide supports of preparation are using unsaturated impregnation zinc solution, dry roasting；（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 and auxiliary agent manganese, and preparation of low carbon olefines by synthetic gas catalyst is made after drying, roasting.The catalyst has the characteristics of long-term operation activity stability is 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 is mainly by 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
（It 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 the chemical industrial expansion important in inhibiting in some rich gas oil starvations area.
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 more than ten plant chemistry such as niobium, gallium, praseodymium, scandium, indium, cerium, lanthanum, ytterbium
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 is applied and preparing low-carbon olefin, and achieves certain effect, but is due to need practical laser technology, is made
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
Open a kind of for preparation of ethylene by use of synthetic gas, propylene, iron/activated-carbon catalyst of butene reaction, carrier, Fe are used as using activated carbon
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
Lower CO conversion ratios are up to 96-99%, and CH compounds selectivity is up to 69.5% in gas-phase product, and wherein ethene, propylene, butylene are in CHization
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 using aluminum oxide as carrier of present invention offer is low
Carbene hydrocarbon catalyst and preparation method thereof, the catalyst has the characteristics of long-term operation activity stability is 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）Immediately at 95-110 DEG C after the isometric saturation dipping organic compounds containing nitrogen aqueous solution of alumina support, dipping
Lower 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 made modified aluminium oxide supports after aging, drying, 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 and auxiliary agent manganese, through drying, roasting
Or else saturation sprays impregnating metal auxiliary agent afterwards, then preparation of low carbon olefines by synthetic gas catalyst is made 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.Drying temperature is 90-150 DEG C after aging, 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 the one or more in zinc chloride, zinc nitrate or zinc sulfate.Zinc salt
Solution is that the mass fraction of zinc salt in the aqueous solution of zinc salt, zinc solution is 5-10%.
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, can also be by existing method system
It is standby.Support shapes can be spherical, bar shaped, piece type.Using spherical and bar shaped to be best.
The inventive method, step（3）Middle organic amine includes 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, the one or more preferably in diethylamine, triethylamine, morphine.
Step of the present invention（3）In, the fountain solution containing adsorbent is impregnated, using unsaturation dipping, 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
Have after the fountain solution of adsorbent, can be dried under the decomposition temperature no more than selected adsorbent, can also direct impregnation contain 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, be may also pass through
Health carries out next step again, and conditioned time is 0.5~8h.
The inventive method, step（4）The amount of middle unsaturated spray impregnating metal auxiliary agent potassium solution is molten for carrier saturated absorption
The 50-90% of liquid measure.Fe and auxiliary agent K and Mn mass ratio are respectively in the preparation of low carbon olefines by synthetic gas catalyst of preparation（65~
75）：（0.5~5）：（23~34）.Active metal solution or compounding agent solution preparation method are that known to technical staff, its solution is dense
Degree can be adjusted by the consumption of each compound, so as to prepare the catalyst of specified activity component and auxiliary agent content.Required activity
The raw material of component and auxiliary agent is generally the compound of the types such as salt, oxide or acid, and such as source of iron is generally from ferric nitrate, chlorination
One or more in iron, ferric sulfate, one or more of the potassium resource in potassium nitrate, potassium carbonate, potassium chloride, manganese source is typically come
From manganese nitrate or manganese chloride.
The inventive method, step（4）In add 2-15%, preferably 5- in the solution containing active metal iron and auxiliary agent manganese
10% ammonium citrate in mass.The decentralization of active component can be improved using the iron salt solutions containing ammonium citrate are added,
The active component iron catalyst of little crystal grain is prepared, so as to significantly improve the selectivity of low-carbon alkene.
The inventive method, step（4）By dry and calcination stepses after dipping, the condition of the drying and roasting is normal
Rule, for example, drying steps are dried 8-24 hours at 50-150 DEG C, 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, using Fe as active component, using K and Mn as
Fe weight percentage is 0.5%-20% in auxiliary agent, catalyst, and auxiliary agent is K and Mn, Fe and auxiliary agent K and Mn matter in catalyst
Measuring 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, 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 the outer surface and outside duct of zinc solution mainly to alumina support are impregnated using unsaturated
Surface is mainly modified.The above-mentioned inside and outside duct to alumina support, which carries out uneven modification, to be made 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 and manganese by way of adsorbent occupy-place
Content is gradually increased by outer from interior, and potassium content is distributed in eggshell type, significantly improves the selectivity of catalyst.The thing of the catalyst
Change performance, catalytic activity, the stability of long-term operation and be obtained for raising, the combination property of catalyst is protruded.
Embodiment
The process and effect of the present invention is 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 after terminating at 95 DEG C immediately, dries pyrrole processed
The adsorbance of the pyridine aqueous solution is aging 7h at the 60% of alumina support saturated absorption amount of solution, 60 DEG C, and 24 are dried in 100 DEG C
Hour, then it is calcined 5 hours obtained 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, 5h, the lower roasting 6h of 850 DEG C of roastings are dried at 120 DEG C.Carrier unsaturation spray 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, in 100 DEG C of dry 5h after spray dipping.By final catalyst Fe content
9wt% is counted, and the carrier of absorption 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, Fe, K and Mn mass ratio are 70：3：28 meter incipient impregnations
Manganese nitrate and potassium nitrate mixed liquor, 100 DEG C of dryings 16 hours are calcined 4 hours, gained catalyst is designated as C-1 in 550 DEG C.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, to be reduced 5 hours at pure 350 DEG C of 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
As a result it 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 is dried 8 hours in 120 DEG C, modified aluminas is then calcined 3 hours to obtain in 400 DEG C
Carrier.Above-mentioned modified aluminium oxide supports use unsaturated impregnation mass fraction for 10% zinc sulfate solution, dipping temperature
Spend for 60 DEG C, dip time 2h, pickup is the 40% of alumina support saturated absorption amount of solution, 10h dried at 90 DEG C,
900 DEG C of roasting 4h.Carrier unsaturation spray dipping aqueous morphine solution after roasting, aqueous morphine solution spray volume is used carrier
The mass content of morphine is the 2% of carrier quality in the 10% of total saturated water adsorptive value, aqueous morphine solution, health 5h after spray dipping,
In 90 DEG C of dry 8h.By final catalyst Fe content 9wt%, manganese content for 3.6wt% based on, the carrier of absorption morphine is using isometric
Impregnation ferric nitrate and manganese nitrate aqueous solution, 100 DEG C of dryings 16 hours are calcined 4 hours in 550 DEG C.By in catalyst
Fe, K and Mn mass ratio are 70：3：28 meters, unsaturation spray dipping potassium nitrate solution, pickup is carrier saturated absorption solution
The 80% of amount, 100 DEG C of drying 16 hours, roasting 4 hours in 550 DEG C, gained catalyst is designated as C-2, 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 be the same as Example 1, system
Obtain catalyst and be designated as C-3,300h evaluation results are shown in Table 1.
Example 4
In addition to the ammonium citrate that mass fraction is 10% is added in the iron nitrate aqueous solution of dipping, remaining be the same as Example 1,
Obtained catalysis is designated as C-4, and 300 evaluation results are shown in Table 1.
Example 5
Be the same as Example 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 obtained catalyst is designated as C-5, and 300h evaluation results are shown in Table 1.
Implement 6
Be the same as Example 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 remaining be the same as Example 1, obtained catalyst is designated as C-6, 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, catalysis is made in remaining be the same as Example 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, remaining be the same as Example 1, obtained catalyst is designated as B-2, and 300h evaluates knot
Fruit is shown in Table 1.
The reactivity worth of the catalyst of table 1
Claims (22)
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）Done immediately at 95-110 DEG C after the isometric saturation dipping organic compounds containing nitrogen aqueous solution of alumina support, dipping
Dry 0.5-1h, is dried to the 30- that the adsorbance of the organic compounds containing nitrogen aqueous solution is alumina support saturated absorption amount of solution
60%, modified aluminium oxide supports are then made after aging, drying, 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 and auxiliary agent manganese, after drying, roasting again
Unsaturation spray impregnating metal auxiliary agent potassium solution, then preparation of low carbon olefines by synthetic gas catalyst is made after drying, roasting；
Wherein, step（1）Described in the organic compounds containing nitrogen aqueous solution organic compounds containing nitrogen be monoethanolamine, diethanol amine,
One or more in triethanolamine and pyridine, aging temperature is 50-95 DEG C, and ageing time is 0.5-10h, and temperature is dried after aging
Spend for 90-150 DEG C, drying time is 0.5-36h, roasting is calcined 2-15 hours at 280-500 DEG C.
2. according to the method described in 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. according to the method described in claim 1, it is characterised in that：Step（2）After drying 2h- is calcined at 800 DEG C ~ 900 DEG C
8h。
4. according to the method described in 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.
5. according to the method described in 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.
6. according to the method described in 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 that drying temperature is 80- after 40-60 DEG C, dipping
150 DEG C, drying time is 2-15h.
7. according to the method described in 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.
8. according to the method described in 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.
9. method according to claim 8, 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.
10. method according to claim 9, it is characterised in that：Step（3）Middle organic amine is diethylamine, triethylamine, morphine
In one or more.
11. according to the method described in claim 1, it is characterised in that：Step（3）Middle fountain solution of the dipping containing adsorbent, is adopted
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。
12. according to the method described in claim 1, it is characterised in that：Step（3）After middle fountain solution of the dipping containing adsorbent,
Dried under the decomposition temperature no more than selected adsorbent, or direct impregnation contains the solution of active metal iron, drying temperature
For 60 DEG C~150 DEG C, drying time 0.5h~20h.
13. method according to claim 12, it is characterised in that：Drying temperature is 80 DEG C~120 DEG C, and drying time is 1h
~6h.
14. according to the method described in claim 1, it is characterised in that：Step（4）The preparation of low carbon olefines by synthetic gas catalysis of middle preparation
Fe and auxiliary agent K and Mn mass ratio are respectively in agent（65~75）：（0.5~5）：（23~34）.
15. according to the method described in claim 1, it is characterised in that：Step（4）Middle unsaturated spray impregnating metal auxiliary agent potassium is molten
The amount of liquid is the 50-90% of carrier saturated absorption amount of solution.
16. according to the method described in claim 1, it is characterised in that：Source of iron is one kind in ferric nitrate, iron chloride, ferric sulfate
Or it is several, potassium resource is the one or more in potassium nitrate, potassium carbonate, potassium chloride, and manganese source is manganese nitrate or manganese chloride.
17. according to the method described in claim 1, it is characterised in that：Step（4）Solution containing active metal iron and auxiliary agent manganese
In add the ammonium citrates of 2-15% in mass.
18. method according to claim 17, it is characterised in that：Step（3）It is molten containing active metal iron and auxiliary agent manganese
The ammonium citrates of 5-10% in mass are added in liquid.
19. according to the method described in claim 1, it is characterised in that：Step（4）By dry and calcination stepses after dipping, do
Dry step is dried 8-24 hours at 50-150 DEG C, and calcination stepses are calcined 2-10 hours at 350-700 DEG C.
20. preparation of low carbon olefines by synthetic gas catalyst prepared by a kind of use claim 1-19 either method, it is characterised in that：Institute
Catalyst is stated using Fe as active component, using K and Mn as auxiliary agent, in catalyst Fe weight percentage be 0.5%-20%, Fe with
Auxiliary agent K and Mn mass ratio is respectively（65~75）：（0.5~5）：（23~34）.
21. the restoring method of catalyst described in claim 20, 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,
Pressure is 0.5-2MPa.
22. restoring method according to claim 21, it is characterised in that：Volume content of the chlorine in gaseous mixture is 1-
5%。
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