CN105709771B - A kind of preparation of low carbon olefines by synthetic gas catalyst and preparation method thereof - Google Patents
A kind of preparation of low carbon olefines by synthetic gas catalyst and preparation method thereof 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）By carrier of aluminum oxide using unsaturated impregnation zinc solution, dry roasting；（2）Using fountain solution impregnation steps of the unsaturated infusion process containing adsorbent（1）Carrier after roasting, wherein the organic amine that it is 2~15 that described adsorbent, which is carbon number, the addition of described adsorbent accounts for step（1）1% ~ 10% of vehicle weight after roasting；（3）Step（2）Carrier containing adsorbent impregnates the solution containing active metal iron and auxiliary agent manganese after drying, and or else saturation sprays impregnating metal auxiliary agent potassium after drying, roasting, then 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 preparation of low carbon olefines by synthetic gas catalyst and preparation method thereof, relate in particular to a kind of high living
Property load-type iron-based preparation of low carbon olefines by synthetic gas catalyst of stability 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 cost is high.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
The mode such as compound solution, acid solution, the cushioning liquid of ammonium salt-containing, the hydro-thermal process of sugar is carried out at dipping to silica-gel carrier
Reason, prepares Fe base silica gel supported synthesis gas and directly prepares light olefins catalyst, reduce Fe and SiO2Between carrier
Strong interaction.But above-mentioned Fe bases silica gel supported synthesis gas directly prepares the work of the long-term operation of light olefins catalyst
Property stability still 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）By carrier of aluminum oxide using unsaturated impregnation zinc solution, dry after at 700 DEG C ~ 1000 DEG C
1h-10h is calcined, preferably 2h-8h is calcined at 800 DEG C ~ 900 DEG C；
（2）Using fountain solution impregnation steps of the unsaturated infusion process containing adsorbent（1）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（1）Vehicle weight after roasting
1% ~ 10%；
（3）Step（2）Carrier impregnation containing adsorbent contains the solution of active metal iron and auxiliary agent manganese, through drying, roasting
Impregnating metal auxiliary agent potassium solution again, then preparation of low carbon olefines by synthetic gas catalyst is made after drying, roasting afterwards.
The inventive method, step（1）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（1）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（1）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（2）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（2）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（3）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）.Dipping solution preparation method is that known to technical staff, its solution concentration can pass through each chemical combination
The consumption of thing is adjusted, so as to prepare the catalyst of specified activity component and auxiliary agent content.The original of required active component and auxiliary agent
Material is generally the compound of the types such as salt, oxide or acid, as source of iron is generally from ferric nitrate, iron chloride, ferric sulfate
One or more, one or more of the potassium resource in potassium nitrate, potassium carbonate, potassium chloride, manganese source is generally from manganese nitrate or chlorine
Change manganese.
The inventive method, step（3）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（3）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 carries out uneven modification, the i.e. main appearance to carrier using zinc solution to alumina support
Face and outside channel surfaces carry out mainly modified and internal channel surfaces are modified and act on weaker, make the interior of alumina support
Outer duct physico-chemical property is significantly different, to greatest extent improve activity while inhibit generation low-carbon alkene carbochain increase and
Saturation is hydrogenated with, the conversion ratio of carbon monoxide is improved.The inventive method contains active component iron by way of adsorbent occupy-place
Amount and auxiliary agent manganese content are gradually increased by outer from interior, and potassium content is distributed into eggshell type, significantly improves the selectivity of catalyst.Should
The physical and chemical performance of catalyst, catalytic activity, the stability of long-term operation are obtained for raising, and the combination property of catalyst is dashed forward
Go out.
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）, adopt
The zinc nitrate aqueous solution for being 5% with unsaturated spray impregnation mass fraction, dipping temperature is 50 DEG C, dip time 3h, leaching
Stain amount is dry 5h at the 20% of alumina support saturated absorption amount of solution, 120 DEG C, the lower roasting 6h of 850 DEG C of roastings.After roasting
Carrier unsaturation spray dipping triethylamine aqueous solution, triethylamine aqueous solution spray volume is the total saturated water adsorptive value of used carrier
35%, the mass content of triethylamine is the 8% of carrier quality in triethylamine aqueous solution, in 100 DEG C of dry 5h after spray dipping.By most
Whole catalyst Fe content 9wt%, manganese content are counted for 3.6wt%, and the carrier of absorption triethylamine impregnates nitric acid using equi-volume impregnating
Iron and manganese nitrate aqueous solution, 100 DEG C of dryings 16 hours are calcined 4 hours in 550 DEG C.By the quality of Fe, K and Mn in catalyst
Than for 70：3：28 meters, unsaturation spray dipping potassium nitrate solution, pickup is the 60% of carrier saturated absorption amount of solution, 100 DEG C
Dry 16 hours, be calcined 4 hours in 550 DEG C, gained catalyst is designated as C-1.C-1 catalyst synthesis gas directly prepares low-carbon alkene
The reaction result of hydrocarbon 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, unsaturated impregnation mass fraction is used 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 ferric nitrate and manganese nitrate mixed aqueous solution of dipping, remaining
Be the same as Example 1, obtained catalyst is designated as C-3, and 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 ferric nitrate and manganese nitrate mixed aqueous solution of dipping, its
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 to reduce catalyst 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）By carrier of aluminum oxide using unsaturated impregnation zinc solution, dry after roasting at 700 DEG C ~ 1000 DEG C
1h-10h；
（2）Using fountain solution impregnation steps of the unsaturated infusion process containing adsorbent（1）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（1）1% of vehicle weight after roasting
~10%；
（3）Step（2）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.
2. according to the method described in claim 1, it is characterised in that：Step（1）After drying 2h- is calcined at 800 DEG C ~ 900 DEG C
8h。
3. according to the method described in claim 1, it is characterised in that：Step（1）Middle zinc salt includes zinc chloride, zinc nitrate or sulfuric acid
One or more in zinc.
4. according to the method described in claim 1, it is characterised in that：Step（1）Middle zinc solution is the aqueous solution of zinc salt, zinc salt
The mass fraction of zinc salt is 5-10% in solution.
5. according to the method described in claim 1, it is characterised in that：Step（1）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.
6. according to the method described in claim 1, it is characterised in that：Step（1）The pickup of middle zinc solution is carrying alumina
The 20-50% of body saturated absorption amount of solution.
7. according to the method described in claim 1, it is characterised in that：Step（2）Middle organic amine include fatty amine, hydramine, acid amides,
One or more in aliphatic cyclic amine or aromatic amine.
8. the method according to claim 1 or 7, it is characterised in that：Step（2）Middle organic amine include monoethyl amine, diethylamine,
Triethylamine, ethylenediamine, hexamethylene diamine, tert-butylamine, monoethanolamine, diethanol amine, triethanolamine, dimethylformamide, propionamide, fourth
One or more in acid amides, pyridine, morphine, aniline, diphenylamines, naphthalidine, dinaphthylamine.
9. method according to claim 8, it is characterised in that：Step（2）Middle organic amine is diethylamine, triethylamine, morphine
In one or more.
10. according to the method described in claim 1, it is characterised in that：Step（2）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。
11. according to the method described in claim 1, it is characterised in that：Step（2）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.
12. method according to claim 11, it is characterised in that：Drying temperature is 80 DEG C~120 DEG C, and drying time is 1h
~6h.
13. according to the method described in claim 1, it is characterised in that：Step（2）Fountain solution dipping of the middle dipping containing adsorbent
After end, next step is directly carried out, or next step is carried out again by health, conditioned time is 0.5~8h.
14. according to the method described in claim 1, it is characterised in that：Step（3）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（3）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（3）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（3）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：Should
Catalyst is using Fe as active component, using K and Mn as auxiliary agent, and Fe weight percentage is 0.5%-20% in catalyst, and Fe is with helping
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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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1083415A (en) * | 1992-09-03 | 1994-03-09 | 中国科学院大连化学物理研究所 | Iron manganese catalyst for preparation of low carbon olefines by synthetic gas and building-up reactions |
| CN102441393A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst by taking modified alumina as carrier and application thereof |
| CN102989511A (en) * | 2011-09-08 | 2013-03-27 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst, and preparation and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7348293B2 (en) * | 2003-12-05 | 2008-03-25 | Chevron U.S.A. Inc. | Homogeneous modified-alumina Fischer-Tropsch catalyst supports |
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2014
- 2014-12-04 CN CN201410723982.7A patent/CN105709771B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1083415A (en) * | 1992-09-03 | 1994-03-09 | 中国科学院大连化学物理研究所 | Iron manganese catalyst for preparation of low carbon olefines by synthetic gas and building-up reactions |
| CN102441393A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst by taking modified alumina as carrier and application thereof |
| CN102989511A (en) * | 2011-09-08 | 2013-03-27 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst, and preparation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Copper-modified alumina as a support for iron Fischer–Tropsch synthesis catalysts;Kamonchanok Pansanga 等;《Applied Catalysis A: General》;20071101;第332卷(第1期);第130-137页 * |
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