CN105709770B - 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）Unsaturated impregnation zinc solution, dry roasting are used by carrier of aluminum oxide；（2）Using fountain solution impregnation steps of the unsaturated infusion process containing adsorbent（1）Carrier after roasting；（3）Step（2）Saturation co-impregnation contains the mixed solution of active metal iron, auxiliary agent manganese and auxiliary agent potassium to carrier containing adsorbent after drying, the or else saturation spray impregnating metal auxiliary agent potassium solution, then preparation of low carbon olefines by synthetic gas catalyst is made after drying, roasting after drying, roasting.The catalyst has the characteristics of long-term operation activity stability is high, is advantageous 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, relates 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 shift.Compared with petroleum resources, coal and natural
Gas resource relative abundance, develop the low-carbon alkene production technology based on coal and natural gas and have great importance.From synthesis gas
（It can be converted to by natural gas and coal）The exploitation of direct preparing ethylene, 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, employ noble metal or rare metal, such as the kind chemistry of niobium, gallium, praseodymium, scandium, indium, cerium, lanthanum, ytterbium etc. more than ten
Element, ethylene selectivity 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, the combination technique of laser pyrolysis processes combination solid phase reaction is used to be prepared for Fe3Fe base nanometers based on C
Catalyst is applied and preparing low-carbon olefin, and achieves certain effect, but due to needing practical laser technology, makes
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 be used for preparation of ethylene by use of synthetic gas, propylene, iron/activated-carbon catalyst of butene reaction, 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
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 as catalyst carrier not only bad mechanical strength but also shaping of catalyst
Difficulty, the service life and stability of catalyst are influenceed, is unfavorable for commercial Application.
CN102441383A, CN101940958A, CN102441400A, CN102441384A are respectively adopted nitrogenous organic
The modes such as compound solution, the acid solution of sugar, the cushioning liquid of ammonium salt-containing, hydro-thermal process are 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 needs further to be improved.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of low using aluminum oxide as the iron-based support type synthesis gas system of carrier
Carbene hydrocarbon catalyst and preparation method thereof, the catalyst have the characteristics of long-term operation activity stability is high, are advantageous 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）Unsaturated impregnation zinc solution is used by carrier of aluminum oxide, is dried after at 700 DEG C ~ 1000 DEG C
1h-10h is calcined, is preferably calcined 2h-8h 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 saturation co-impregnation containing adsorbent contains the mixing of active metal iron, auxiliary agent manganese and auxiliary agent potassium
Solution, the or else saturation spray impregnating metal auxiliary agent potassium solution, then synthesis gas system is made after drying, roasting after drying, roasting
Light olefins catalyst.
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 the aqueous solution of zinc salt, and the mass fraction of zinc salt is 5-10% in zinc solution.
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
It is or 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, is impregnated using unsaturation, preferably with unsaturation
Spray, wherein the volume ratio of the dip amount and carrier saturated absorption amount of solution used in unsaturated dipping is 0.05 ~ 0.4.Dipping contains
After having 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 good shower nozzle of atomizing effect should be selected, solution is uniformly divided
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（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, the amount of unsaturation spray impregnation aids potassium is the 40%-70% of potassium total amount in catalyst.The synthesis gas system of preparation
Fe and auxiliary agent K and Mn mass ratio are respectively in light olefins catalyst（65~75）：（0.5~5）：（23~34）.Dipping solution system
Preparation Method is known to technical staff, and its solution concentration can be adjusted by the dosage of each compound, so as to prepare specified work
The catalyst of property component and auxiliary agent content.The raw material of required active component and auxiliary agent is generally the types such as salt, oxide or acid
Compound, as source of iron is generally from the one or more in ferric nitrate, iron chloride, ferric sulfate, potassium resource is from potassium nitrate, carbonic acid
One or more in potassium, potassium chloride, manganese source are generally from manganese nitrate or manganese chloride.
The inventive method, step（3）In add 2- in the mixed solution containing active metal iron, auxiliary agent manganese and auxiliary agent potassium
The ammonium citrate of 15%, preferably 5-10% in mass.Activearm can be improved using the iron salt solutions containing ammonium citrate are added
The decentralization divided, 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 dry 8-24 hours at 50-150 DEG C, calcination stepses are calcined 2-10 hours at 350-700 DEG C.
It is a kind of using above method prepare preparation of low carbon olefines by synthetic gas catalyst, using Fe as active component, using K and Mn as
Auxiliary agent, Fe weight percentage is 0.5%-20% in 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%, preferably 1-5%, and reduction temperature is 300-450 DEG C, recovery time 3-10
Hour, pressure 0.5-2MPa.The selectivity of butylene can be improved using above-mentioned restoring method.
The inventive method carries out uneven modification to alumina support using zinc solution, i.e., mainly to the appearance of carrier
Face and outside channel surfaces carry out mainly modified and that internal channel surfaces are modified with effect is weaker, make the interior of alumina support
Outer duct physico-chemical property is significantly different, inhibited while improving active to greatest extent generation low-carbon alkene carbochain increase and
Saturation is hydrogenated with, improves the conversion ratio of carbon monoxide.The inventive method contains active component iron by way of adsorbent occupy-place
Amount and auxiliary agent manganese content significantly improve the selectivity of catalyst by being distributed outside from interior gradually increase, potassium content into eggshell type.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 formed to the present invention
The limitation of method.
Example 1
Weigh commercial alumina（Pore volume is 0.96ml/g, specific surface area 286.81m2/ g, saturated water adsorptive value 145ml/
G, provided by Fushun branch company of Sinopec catalyst Co., Ltd, 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 are 50 DEG C, dip time 3h, leaching
Stain amount is the 20% of alumina support saturated absorption amount of solution, and 5h, the lower roasting 6h of 850 DEG C of roastings are dried at 120 DEG C.After roasting
The unsaturated spray dipping triethylamine aqueous solution of carrier, 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 for adsorbing triethylamine is contained using equi-volume impregnating dipping
The mixed solution of active metal iron, auxiliary agent manganese and auxiliary agent potassium, 100 DEG C of dryings 16 hours, is calcined 4 hours in 550 DEG C.By catalysis
Fe, K and Mn mass ratio are 70 in agent：3：28 meters, unsaturation spray dipping potassium nitrate solution, pickup is carrier saturated absorption
The 60% of amount of solution, the amount of unsaturation spray impregnation aids potassium is 45% of potassium total amount in catalyst.100 DEG C of dryings 16 hours,
It is calcined 4 hours in 550 DEG C, gained catalyst is designated as C-1.C-1 catalyst synthesis gas directly prepares the reaction result of low-carbon alkene
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, uses unsaturated impregnation mass fraction as 10% zinc sulfate solution, dipping temperature
To spend for 60 DEG C, dip time 2h, 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, 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, adsorb the carrier of morphine using isometric
Impregnation contains the mixed solution of active metal iron, auxiliary agent manganese and auxiliary agent potassium, 100 DEG C of dryings 16 hours, is roasted in 550 DEG C
Burn 4 hours.It is 70 by the mass ratio of Fe, K and Mn in catalyst：3：28 meters, unsaturation spray dipping potassium nitrate solution, pickup
For the 80% of carrier saturated absorption amount of solution, the amount of unsaturation spray impregnation aids potassium is 65% of potassium total amount in catalyst.100℃
Dry 16 hours, be calcined 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
With embodiment 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 same embodiment 1, obtained catalysis are designated as C-4, and 300 evaluation results are shown in Table 1.
Example 5
With embodiment 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
With embodiment 1, difference is that catalyst is reduced using the gaseous mixture of chlorine and hydrogen, and chlorine is mixing
Volume content in gas is 1%, and, with embodiment 1, obtained 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 as 5% zinc nitrate aqueous solution, catalysis is made with embodiment 1 in remaining
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, obtained catalyst is designated as B-2,300h evaluation knots for remaining
Fruit is shown in Table 1.
The reactivity worth of the catalyst of table 1
Claims (22)
- A kind of 1. preparation method of preparation of low carbon olefines by synthetic gas catalyst, it is characterised in that：Comprise the following steps：（1）Unsaturated impregnation zinc solution is used by carrier of aluminum oxide, drying is calcined after 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）The mixing that carrier saturation co-impregnation containing adsorbent contains active metal iron, auxiliary agent manganese and auxiliary agent potassium is molten Liquid, the or else saturation spray impregnating metal auxiliary agent potassium solution, then obtained synthesis gas system is low after drying, roasting after drying, roasting Carbene hydrocarbon catalyst.
- 2. according to the method for 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 for 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 for claim 1, it is characterised in that：Step（1）Middle zinc solution be zinc salt the aqueous solution, zinc salt The mass fraction of zinc salt is 5-10% in solution.
- 5. according to the method for 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 1-5h, dipping temperature are 40-60 DEG C, and drying temperature is 80- after dipping 150 DEG C, drying time 2-15h.
- 6. according to the method for 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 for 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. according to the method for 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 for 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 for 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, drying temperature is 60 DEG C~150 DEG C, drying time 0.5h~20h.
- 12. according to the method for claim 11, it is characterised in that：Drying temperature is 80 DEG C~120 DEG C, drying time 1h ~6h.
- 13. according to the method for 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 for 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 for 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, and the amount of unsaturation spray impregnation aids potassium is potassium total amount in catalyst 40%-70%。
- 16. according to the method for 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 for claim 1, it is characterised in that：Step（3）Contain active metal iron, auxiliary agent manganese and auxiliary agent The ammonium citrates of 2-15% in mass are added in the mixed solution of potassium.
- 18. according to the method for claim 17, it is characterised in that：Step（3）Contain active metal iron, auxiliary agent manganese and auxiliary agent The ammonium citrates of 5-10% in mass are added in the mixed solution of potassium.
- 19. according to the method for claim 1, it is characterised in that：Step（3）By dry and calcination stepses after dipping, do Dry step dries 8-24 hours at 50-150 DEG C, and calcination stepses are calcined 2-10 hours at 350-700 DEG C.
- A kind of 20. preparation of low carbon olefines by synthetic gas catalyst prepared using claim 1-19 either method, it is characterised in that：Should Catalyst is using Fe as active component, and using K and Mn as auxiliary agent, 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 are 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 (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101224425A (en) * | 2008-01-30 | 2008-07-23 | 中国科学院山西煤炭化学研究所 | Co catalyst with controllable Fischer-Tropsch product distribution, preparing and applications thereof |
| 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 |
| CN103801403A (en) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | Hydrotreating catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7452844B2 (en) * | 2001-05-08 | 2008-11-18 | Süd-Chemie Inc | High surface area, small crystallite size catalyst for Fischer-Tropsch synthesis |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101224425A (en) * | 2008-01-30 | 2008-07-23 | 中国科学院山西煤炭化学研究所 | Co catalyst with controllable Fischer-Tropsch product distribution, preparing and applications thereof |
| 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 |
| CN103801403A (en) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | Hydrotreating catalyst and preparation method thereof |
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