CN105709768B

CN105709768B - A kind of preparation method of synthesis gas alkene catalyst

Info

Publication number: CN105709768B
Application number: CN201410723832.6A
Authority: CN
Inventors: 李�杰; 张信伟; 张舒东; 孙晓丹; 尹泽群; 刘全杰
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2014-12-04
Filing date: 2014-12-04
Publication date: 2018-03-13
Anticipated expiration: 2034-12-04
Also published as: CN105709768A

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 cushioning liquid of the isometric saturation dipping ammonium salt-containing of alumina support, it is the 30 60% of alumina support saturated absorption amount of solution to dry to the adsorbance of the cushioning liquid of ammonium salt-containing, and modified aluminium oxide supports are then made after aging, drying, roasting；（2）Step（1）The modified aluminium oxide supports of preparation use 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 advantageous to commercial Application and popularization.

Description

A kind of preparation method of synthesis gas alkene catalyst

Technical field

The present invention relates to a kind of synthesis gas alkene catalyst and preparation method thereof, it is steady to relate in particular to a kind of high activity 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 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 Compound solution, acid solution, the cushioning liquid of ammonium salt-containing, the mode such as hydro-thermal process impregnation 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 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）The aqueous buffer solution of alumina support isometric saturation dipping ammonium salt-containing, after dipping immediately at 95-110 DEG C 0.5-1h is dried, is dried to the 30-60% that the adsorbance of the cushioning liquid of ammonium salt-containing is alumina support saturated absorption amount of solution, Then modified aluminium oxide supports are made after aging, drying, roasting；

（2）Step（1）The modified aluminium oxide supports of preparation use unsaturated impregnation zinc solution, dry after 1h-10h is calcined at 700 DEG C ~ 1000 DEG C, is preferably calcined 2h-8h 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）The aqueous buffer solution ammonium salt of middle ammonium salt-containing can be selected from ammonium acetate, ammonium formate, carbonic acid One or more in ammonium, ammonium hydrogen carbonate etc..The weight concentration of ammonium salt is 1%-35%, preferably 5%-20% in cushioning liquid.Always Change temperature be 50-95 DEG C, preferably 60 ~ 80 DEG C, ageing time 0.5-10h, preferably 2-5h.Drying temperature is 90- after aging 150 DEG C, drying time 0.5-36h, 8-24h is dried preferably at 100-120 DEG C.Roasting is calcined 2-15 at 280-500 DEG C Hour, 3-5 hours are calcined 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 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, 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 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（3）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（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 known to technical staff, and its solution is dense Degree can be adjusted by the dosage 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, 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 are 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）It is by dry and calcination stepses, the condition of the drying and roasting after middle dipping Conventional, for example, drying steps dry 8-24 hours at 50-150 DEG C, it is small that calcination stepses are calcined 2-10 at 350-700 DEG C When.

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 uses the cushioning liquid saturation oxide impregnation alumina supporter of ammonium salt-containing first, after quick fraction is dried The cushioning liquid of ammonium salt is concentrated in the internal gutter of carrier, and the cushioning liquid of ammonium salt mainly carries out part to carrier inside and changed Property.Then using unsaturated dipping zinc solution, mainly the outer surface to alumina support and outside channel surfaces are mainly changed Property.The above-mentioned inside and outside duct to alumina support, which carries out uneven modification, makes the inside and outside duct physico-chemical property of alumina support bright Aobvious difference, inhibit the carbochain of the low-carbon alkene of generation to increase and be hydrogenated with saturation while improving active to greatest extent, improve The conversion ratio of carbon monoxide.The inventive method made by way of adsorbent occupy-place active component iron and auxiliary agent manganese content by it is outer from Interior gradually increase, auxiliary agent potassium are distributed in eggshell type, significantly improve the selectivity of catalyst.The physical and chemical performance of the catalyst, urge Change activity, the stability of long-term operation is obtained for raising, the combination property protrusion of catalyst.

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）, will The ammonium carbonate solution saturation that mass concentration is 5% sprays oxide impregnation aluminium, dries 1h after terminating at 95 DEG C immediately, dries system The adsorbance of ammonium carbonate solution is the 60% of alumina support saturated absorption amount of solution, aging 7h at 60 DEG C, is done in 100 DEG C Dry 24 hours, then it is calcined 5 hours obtained modified aluminium oxide supports at 300 DEG C.Above-mentioned modified aluminium oxide supports are using unsaturated The zinc nitrate aqueous solution that impregnation mass fraction is 5% is sprayed, dipping temperature is 50 DEG C, and dip time 3h, pickup is oxygen Change the 20% of alumina supporter saturated absorption amount of solution, 5h, the lower roasting 6h of 850 DEG C of roastings are dried at 120 DEG C.Carrier insatiable hunger after roasting Triethylamine aqueous solution is impregnated with spray, triethylamine aqueous solution spray volume is the 35% of the total saturated water adsorptive value of used carrier, triethylamine The mass content of triethylamine is the 8% of carrier quality in the aqueous solution, in 100 DEG C of dry 5h after spray dipping.By final catalyst Fe Content 9wt% is counted, and adsorbs the carrier of triethylamine using equi-volume impregnating dipping iron nitrate aqueous solution, 100 DEG C of dryings 16 hours, It is calcined 4 hours in 550 DEG C.It is 3.6wt% by manganese content in catalyst, Fe, K and Mn mass ratio are 70：3：28 meters are isometric Impregnate manganese nitrate and potassium nitrate mixed liquor, 100 DEG C of dryings 16 hours, be calcined 4 hours in 550 DEG C, gained catalyst is designated as C- 1.The reaction result that C-1 catalyst synthesis gas directly prepares low-carbon alkene is as shown in table 1.

Catalyst Evaluation Test 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% ammonium acetate aqueous solution saturation sprays oxide impregnation aluminium by mass concentration, is stood after terminating 0.5h is dried i.e. at 110 DEG C, it is alumina support saturated absorption amount of solution to dry to the adsorbance of ammonium acetate aqueous solution 40%, aging 4 hours at 80 DEG C, dried 8 hours in 120 DEG C, modified aluminas load then be calcined 3 hours to obtain in 400 DEG C Body.Above-mentioned modified aluminium oxide supports use unsaturated impregnation mass fraction as 10% zinc sulfate solution, dipping temperature For 60 DEG C, dip time 2h, pickup is the 40% of alumina support saturated absorption amount of solution, the dry 10h at 90 DEG C, 900 DEG C roasting 4h.The unsaturated spray dipping aqueous morphine solution of carrier after roasting, aqueous morphine solution spray volume is that used carrier is total The 10% of saturated water adsorptive value, the mass content of morphine is the 2% of carrier quality in aqueous morphine solution, health 5h after spray dipping, 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 leaching Stain method impregnates ferric nitrate and manganese nitrate aqueous solution, 100 DEG C of dryings 16 hours, is calcined 4 hours in 550 DEG C.By Fe in catalyst, K and Mn mass ratio is 70：3：28 meters, unsaturation spray dipping potassium nitrate solution, pickup is carrier saturated absorption amount of solution 80%, 100 DEG C of dryings 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 iron nitrate aqueous solution of dipping, remaining is the same as embodiment 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 with embodiment 1, Obtained catalysis is 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

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）The isometric saturation of alumina support impregnates the aqueous buffer solution of ammonium salt-containing, is dried immediately at 95-110 DEG C after dipping 0.5-1h, the 30-60% for alumina support saturated absorption amount of solution is dried to the adsorbance of the cushioning liquid of ammonium salt-containing, then Modified aluminium oxide supports are made after aging, drying, roasting；

（2）Step（1）The modified aluminium oxide supports of preparation use 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, then preparation of low carbon olefines by synthetic gas catalyst is made after drying, roasting；

Wherein, step（1）The aqueous buffer solution ammonium salt of middle ammonium salt-containing is one in ammonium acetate, ammonium formate, ammonium carbonate, ammonium hydrogen carbonate Kind is several.
2. according to the method for claim 1, it is characterised in that：The weight concentration of ammonium salt is 1%-35% in cushioning liquid.
3. according to the method for claim 1, it is characterised in that：Step（1）Aging temperature is 50-95 DEG C, and ageing time is 0.5-10h, drying temperature is 90-150 DEG C after aging, drying time 0.5-36h, is calcined and is calcined 2-15 at 280-500 DEG C Hour.
4. according to the method for claim 1, it is characterised in that：Step（2）After drying 2h- is calcined at 800 DEG C ~ 900 DEG C 8h。
5. according to the method for claim 1, it is characterised in that：Step（2）Middle zinc salt includes zinc chloride, zinc nitrate or sulfuric acid One or more in zinc.
6. according to the method for claim 1, it is characterised in that：Step（2）Middle zinc solution be zinc salt the aqueous solution, zinc salt The mass fraction of zinc salt is 5-10% in solution.
7. according to the method for 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 1-5h, dipping temperature are 40-60 DEG C, and drying temperature is 80- after dipping 150 DEG C, drying time 2-15h.
8. according to the method for 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. according to the method for claim 1, it is characterised in that：Step（3）Middle organic amine is fatty amine, hydramine, acid amides, fat One or more in cyclammonium or aromatic amine.
10. according to the method for claim 9, it is characterised in that：Step（3）Middle organic amine is monoethyl amine, diethylamine, three second Amine, ethylenediamine, hexamethylene diamine, tert-butylamine, monoethanolamine, diethanol amine, triethanolamine, dimethylformamide, propionamide, butyryl One or more in amine, pyridine, morphine, aniline, diphenylamines, naphthalidine, dinaphthylamine.
11. according to the method for claim 10, it is characterised in that：Step（3）Middle organic amine be diethylamine, triethylamine, One or more in coffee.
12. according to the method for 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。
13. according to the method for 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.
14. according to the method for claim 13, it is characterised in that：Drying temperature is 80 DEG C~120 DEG C, drying time 1h ~6h.
15. according to the method for claim 1, it is characterised in that：Step（4）The preparation of low carbon olefines by synthetic gas catalyst of preparation Middle Fe and auxiliary agent K and Mn mass ratio is respectively（65~75）：（0.5~5）：（23~34）.
16. according to the method for 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.
17. 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.
18. according to the method for 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.
19. according to the method for claim 18, it is characterised in that：Step（4）It is molten containing active metal iron and auxiliary agent manganese The ammonium citrates of 5-10% in mass are added in liquid.
20. according to the method for claim 1, it is characterised in that：Step（4）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 21. preparation of low carbon olefines by synthetic gas catalyst prepared using claim 1-20 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）.
22. the restoring method of catalyst described in claim 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 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.
23. restoring method according to claim 22, it is characterised in that：Volume content of the chlorine in gaseous mixture is 1- 5%。