CN106669717A

CN106669717A - Catalyst for preparing unsaturated hydrocarbons, and preparation method thereof

Info

Publication number: CN106669717A
Application number: CN201510750226.8A
Authority: CN
Inventors: 李�杰; 张信伟; 张舒冬; 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: 2015-11-09
Filing date: 2015-11-09
Publication date: 2017-05-17

Abstract

The invention discloses a catalyst for preparing unsaturated hydrocarbons, and a preparation method thereof. The preparation method comprises: (1) impregnating an alumina carrier in an ammonium salt-containing buffer solution in an equal volume and saturated manner, and drying until the adsorption amount of the ammonium salt-containing buffer solution is 30-60% of the saturation absorption solution amount of the alumina carrier; (2) preparing the mixed aqueous solution of a nickel salt and a gallium salt, and impregnating the mixed aqueous solution by using an unsaturated impregnation method; (3) impregnating the calcined carrier obtained in the step (2) with an adsorbent-containing wetting liquid by using an unsaturated impregnation method; and (4) impregnating an active metal iron-containing solution by using the adsorbent-containing carrier obtained in the step (3), drying, calcining, impregnating with a metal auxiliary agent, drying, and calcining to prepare the syngas-to-low-carbon-olefin catalyst. According to the present invention, the catalyst has high activity and high stability after the long term running, and is beneficial to industrial application and popularization.

Description

A kind of catalyst of unsaturated hydrocarbons processed and preparation method thereof

Technical field

The present invention relates to a kind of catalyst of unsaturated hydrocarbons processed and preparation method thereof, relates in particular to load-type iron-based preparation of low carbon olefines by synthetic gas catalyst of a kind of high-activity stable and preparation method thereof.

Background technology

The low-carbon alkenes such as ethylene, propylene are important basic organic chemical industry raw materials, and with the development of chemical industry, its demand is more and more big.So far, mainly by light oil cracking process, with the increasingly depleted of petroleum resources in global range, following energy resource structure certainly will be shifted the approach of the low-carbon alkene such as preparing ethylene, propylene.Compared with petroleum resources, coal and natural gas resource relative abundance are developed the low-carbon alkene production technology based on coal and natural gas and are had great importance.From synthesis gas（Can be converted to by natural gas and coal）Directly preparing ethylene, the exploitation of propylene technology, can not only reduce the dependence to petroleum resources, and to some rich gas oil starvation area chemistry industrial expansion important in inhibiting.

CN1065026A discloses a kind of preparation of ethylene by use of synthetic gas method, the preparation method for being related to catalyst is chemical precipitation method, mechanical mixing, noble metal or rare metal are employed, such as niobium, gallium, praseodymium, scandium, indium, cerium, lanthanum, ytterbium etc. more than ten plants chemical element, and ethylene selectivity is 65%-94%, but CO conversion ratios are very low, only 10%, 12% and 15% or so, CO recycle and certainly will bring the consumption of the energy, and catalyst high cost.CN01144691.9 discloses nanocatalyst of a kind of preparation of ethylene by use of synthetic gas, propylene and preparation method thereof, adopts laser pyrolysis processes to be prepared for Fe with reference to the combination technique of solid state reaction₃The application of Fe base nano-catalysts and preparing low-carbon olefin based on C, and certain effect is achieved, but due to needing practical laser technology, make preparation technology comparatively laborious, raw material adopts Fe (CO)₅, the cost of catalyst is higher, and industrialization is difficult.CN03109585.2 disclose it is a kind of for preparation of ethylene by use of synthetic gas, propylene, butene reaction ferrum/activated-carbon catalyst, using activated carbon as carrier, Fe is used as active center, successfully Fe is loaded on the activated carbon using vacuum impregnation technology, enable Fe and auxiliary agent high degree of dispersion on the activated carbon, so as to improve catalytic effect, and greatly reduce the cost of catalyst.And catalyst under conditions of without feedstock circulation CO conversion ratios up to 96-99%, up to 69.5%, the wherein selectivity of ethylene, propylene, butylene in CH compounds is up to more than 68% for CH compounds selectivity in gas-phase product.But activated carbon is as catalyst carrier, and not only bad mechanical strength but also shaping of catalyst are difficult, affect the service life and stability of catalyst, are unfavorable for commercial Application.

CN102441383A, CN101940958A, CN102441400A, CN102441384A be respectively adopted organic compounds containing nitrogen solution, the mode such as acid solution, the buffer solution of ammonium salt-containing, hydrothermal treatment consists 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 interaction between carrier.But the activity stability of the long-term operation that above-mentioned Fe bases silica gel supported synthesis gas directly prepares light olefins catalyst still needs further raising.

The content of the invention

For the deficiencies in the prior art, the present invention provides a kind of iron-based support type preparation of low carbon olefines by synthetic gas catalyst with aluminium oxide as carrier and preparation method thereof, the characteristics of the catalyst has long-term operation activity stability high, is conducive to commercial Application and popularization.

A kind of preparation method of preparation of low carbon olefines by synthetic gas catalyst, comprises the steps：

（1）Alumina support equal-volume saturation impregnates the aqueous buffer solution of ammonium salt-containing, at 95-110 DEG C 0.5-1h is dried after dipping immediately, it is dried to the 30-60% that the adsorbance of the buffer solution of ammonium salt-containing is alumina support saturated absorption amount of solution, modified aluminium oxide supports is then obtained Jing after aging, dry, roasting；

（2）Prepare the mixed aqueous solution of nickel salt and gallium salt, step（1）The modified aluminium oxide supports of preparation are dried roasting 1h-10h, the roasting 2h-8h preferably at 800 DEG C ~ 900 DEG C at 700 DEG C ~ 1000 DEG C using the above-mentioned mixed aqueous solution of unsaturated impregnation；

（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, the addition of described adsorbent accounts for step（2）1% ~ 10% of vehicle weight after roasting；

（4）Step（3）Carrier impregnation containing adsorbent contains the solution of active metal ferrum, and preparation of low carbon olefines by synthetic gas catalyst is obtained after drying, roasting after impregnating metal auxiliary agent, then drying, roasting again.

The inventive method step（1）The aqueous buffer solution ammonium salt of middle ammonium salt-containing can be one or more in ammonium acetate, ammonium formate, ammonium carbonate, ammonium hydrogen carbonate etc..The weight concentration of ammonium salt is 1%-35%, preferably 5%-20% in buffer solution.Aging temperature is 50-95 DEG C, and preferably 60 ~ 80 DEG C, ageing time is 0.5-10h, preferred 2-5h.Aging rear baking temperature is 90-150 DEG C, and drying time is 0.5-36h, is preferably dried 8-24h at 100-120 DEG C.Roasting roasting 2-15 hours at 280-500 DEG C, the roasting 3-5 hours preferably at 300-450 DEG C.

The inventive method, step（2）Middle nickel salt is one or more in Nickel dichloride., nickel nitrate or nickel sulfate, and gallium salt is one or more in Ganite (Fujisawa)., gallium chloride, gallium sulfate.The concentration of nickel ion is 0.1-5mol/L in mixed aqueous solution, and the molar concentration of gallium ion is two times of nickel ion molar concentration.

The inventive method, step（2）Pickup is the 5-60%, preferred 20-50% of alumina support saturated absorption amount of solution.Dip time is 1-5h, and dipping temperature is 40-60 DEG C.Baking temperature is 80-150 DEG C after dipping, and drying time is 2-15h.

The inventive method, step（2）Middle alumina support can adopt existing commercial goods, it is also possible to prepare by existing method.Support shapes can be spherical, bar shaped, piece type.With spherical and bar shaped as best.

The inventive method, step（3）Middle organic amine includes one or more in fatty amine, hydramine, amide, aliphatic cyclic amine or aromatic amine.Specifically include one or more in monoethyl amine, diethylamine, triethylamine, ethylenediamine, hexamethylene diamine, tert-butylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylformamide, propionic acid amide., butyramide, pyridine, morphine, aniline, diphenylamines, naphthalidine, dinaphthylamine, one or more in preferred diethylamine, triethylamine, morphine.

Step of the present invention（3）In, the fountain solution containing adsorbent is impregnated, using unsaturated dipping, spray preferably with unsaturation, wherein the volume ratio of unsaturated dipping dip amount used and carrier saturated absorption amount of solution is 0.05 ~ 0.4.After fountain solution of the dipping containing adsorbent, can be dried under the decomposition temperature less than selected adsorbent, it is also possible to which direct impregnation contains the solution of active metal ferrum, wherein baking temperature is generally 60 DEG C～150 DEG C, 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 evenly spread on alumina support.After the dipping dipping of the fountain solution containing adsorbent terminates, next step can be directly carried out, may also pass through health preserving carries out again next step, and conditioned time is 0.5～8h.

The inventive method, step（4）Middle auxiliary agent is K and Mn.Fe is respectively with the mass ratio of auxiliary agent K and Mn in the preparation of low carbon olefines by synthetic gas catalyst of preparation（65~75）：（0.5~5）：（23~34）.Active component Fe and metal promoter K, Mn are supported on carrier by infusion process, generally using incipient impregnation.Dipping method is known to technical staff.After with the solution impregnating carrier containing active metal or auxiliary agent, need through dry and roasting.Active metal solution or compounding agent solution preparation method are that known to technical staff, its solution concentration can be adjusted by the consumption of each compound, so as to prepare the catalyst of specified activity component and auxiliary agent content.The raw material of required active component and auxiliary agent is generally the compound of the types such as salt, oxide or acid, as source of iron is generally from one or more in ferric nitrate, iron chloride, iron sulfate, one or more of potassium resource in potassium nitrate, potassium carbonate, potassium chloride, manganese source is generally from manganese nitrate or manganese chloride.

The inventive method, step（4）In add 2-15%, preferred 5-10% ammonium thiocyanates in mass in the solution containing active metal ferrum.The dispersion of active component can be improved using the iron salt solutions containing ammonium thiocyanate 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）The middle solution impregnating carrier used containing active metal component and auxiliary agent, after dipping through drying and calcination stepses, the drying and roasting condition be it is conventional, for example, drying steps are dried 8-24 hours, calcination stepses roasting 2-10 hours at 350-700 DEG C at 50-150 DEG C.

Preparation of low carbon olefines by synthetic gas catalyst prepared by a kind of employing above method, with Fe as active component, with K and Mn as auxiliary agent, the weight percentage of Fe is 0.5%-20% in catalyst, and auxiliary agent is that K and Mn, Fe are respectively with the mass ratio of auxiliary agent K and Mn in catalyst（65~75）：（0.5~5）：（23~34）.

The method of reducing of above-mentioned preparation of low carbon olefines by synthetic gas catalyst, is reduced using the gaseous mixture of chlorine and hydrogen, and volume content of the chlorine in gaseous mixture is 0.5-10%, it is preferred that 1-5%, reduction temperature is 300-450 DEG C, and the recovery time is 3-10 hours, and pressure is 0.5-2MPa.The selectivity of butylene can be improved using above-mentioned method of reducing.

Initially with the buffer solution saturation oxide impregnation alumina supporter of ammonium salt-containing, in the internal gutter that the buffer solution of ammonium salt concentrates on carrier Jing after quick fraction is dried, the buffer solution of ammonium salt mainly carries out partially modified the inventive method to carrier inside.Then mainly it is modified using the outer surface main to alumina support of mixed aqueous solution and outside channel surfaces of nickel salt and gallium salt.The above-mentioned inside and outside duct to alumina support carries out uneven modified making the inside and outside duct physico-chemical property of alumina support significantly different, inhibit the carbochain of the low-carbon alkene of generation to increase and be hydrogenated with saturation while improving activity to greatest extent, improve the conversion ratio of carbon monoxide.The inventive method makes active component iron content gradually be increased in by outer by way of adsorbent occupy-place, significantly improves selectivity of catalyst.The physical and chemical performance of the catalyst, catalysis activity, the stability of long-term operation are obtained for raising, and the combination property of catalyst is projected.

Specific embodiment

The process and effect of the present invention are further illustrated with reference to embodiment, but following examples do not constitute the restriction to the inventive 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 company limited, and following examples and comparative example use the aluminium oxide）By the ammonium carbonate solution saturation spray oxide impregnation aluminum that mass concentration is 5%, at 95 DEG C 1h is dried after end immediately, the adsorbance of drying ammonium carbonate solution processed is the 60% of alumina support saturated absorption amount of solution, aging 7h at 60 DEG C, it is dried 24 hours in 100 DEG C, then in 300 DEG C of roastings, 5 hours prepared modified aluminium oxide supports.Above-mentioned modified aluminium oxide supports are respectively the nickel nitrate of 0.5mol/L, 1mol/L, Ganite (Fujisawa). mixed aqueous solution using unsaturated spray impregnation nickel, gallium molar concentration, dipping temperature is 50 DEG C, dip time 3h, pickup is the 20% of alumina support saturated absorption amount of solution, 5h, roasting 6h under 850 DEG C of roastings are dried at 120 DEG C.The unsaturated spray dipping triethylamine aqueous solution of carrier after roasting, triethylamine aqueous solution spray volume is the 35% of the total saturated water adsorptive value of used carrier, and the mass content of triethylamine is the 8% of carrier quality in triethylamine aqueous solution, and 5h is dried at 100 DEG C after spray dipping.Based on final catalyst Fe content 9wt%, the carrier for adsorbing triethylamine impregnates iron nitrate aqueous solution, 100 DEG C of dryings 16 hours, roasting 4 hours in 550 DEG C using equi-volume impregnating.It is 3.6wt% by manganese content in catalyst, the mass ratio of Fe, K and Mn is 70：3：28 meter incipient impregnation manganese nitrates and potassium nitrate mixed liquor, 100 DEG C of dryings 16 hours, roasting 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, and to reduce 5 hours at 350 DEG C of pure hydrogen, pressure is 1.0MPa.Switching and merging gas is reacted after cooling.Reaction effluent is collected respectively by hot trap, cold-trap.Reaction condition is 280 DEG C, 1200h^-1, 2.0MPa, H₂/CO=1（Mol ratio）.The 300h reaction results that C-1 catalyst synthesis gas directly prepares low-carbon alkene are as shown in table 1.

Example 2

Weigh commercial alumina, it is that 20% ammonium acetate aqueous solution saturation sprays oxide impregnation aluminum by mass concentration, at 110 DEG C 0.5h is dried after end immediately, it is the 40% of alumina support saturated absorption amount of solution to be dried to the adsorbance of ammonium acetate aqueous solution, aging 4 hours at 80 DEG C, it is dried in 120 DEG C 8 hours, then roasting obtains modified aluminium oxide supports in 3 hours in 400 DEG C.Above-mentioned modified aluminium oxide supports are respectively the nickel nitrate of 1.5mol/L, 3mol/L, Ganite (Fujisawa). mixed aqueous solution using unsaturated spray impregnation nickel, gallium molar concentration, dipping temperature is 60 DEG C, dip time 2h, pickup is the 40% of alumina support saturated absorption amount of solution, 10h, 900 DEG C of roasting 4h are dried at 90 DEG C.The unsaturated spray dipping aqueous morphine solution of carrier after roasting, aqueous morphine solution spray volume is the 10% of the total saturated water adsorptive value of used carrier, and the mass content of morphine is the 2% of carrier quality in aqueous morphine solution, and oxygen life 5h, at 90 DEG C 8h is dried after spray dipping., with embodiment 1, prepared catalyst is designated as C-2 for remaining, and 300h evaluation results are shown in Table 1.

Example 3

In addition to the ammonium thiocyanate that mass fraction is 5% is added in the iron nitrate aqueous solution of dipping,, with embodiment 1, prepared catalyst is designated as C-3 for remaining, and 300h evaluation results are shown in Table 1.

Example 4

In addition to the ammonium thiocyanate that mass fraction is 10% is added in the iron nitrate aqueous solution of dipping, remaining is designated as C-4 with embodiment 1, prepared catalysis, and 300 evaluation results are shown in Table 1.

Example 5

With embodiment 1, difference is that catalyst is reduced using the gaseous mixture of chlorine and hydrogen, and volume content of the chlorine in gaseous mixture is 5%, and prepared catalyst is designated as C-5, and 300h evaluation results are shown in Table 1.

Implement 6

With embodiment 1, difference is that catalyst is reduced using the gaseous mixture of chlorine and hydrogen, and volume content of the chlorine in gaseous mixture is 1%, and, with embodiment 1, prepared catalyst is designated as C-6 for remaining, and 300h evaluation results are shown in Table 1.

Comparative example 1

In addition to the nickel nitrate of 0.5mol/L, 1mol/L, Ganite (Fujisawa). mixed aqueous solution is respectively using saturation spray dipping nickel, gallium molar concentration,, with embodiment 1, prepared catalyst is designated as B-1 for remaining, and 300h evaluation results are shown in Table 1.

Comparative example 2

In addition to dipping triethylamine aqueous solution is not sprayed,, with embodiment 1, prepared catalyst is designated as B-2 for remaining, and 300h evaluation results are shown in Table 1.

The reactivity worth of the catalyst of table 1

Claims

1. a kind of preparation method of preparation of low carbon olefines by synthetic gas catalyst, it is characterised in that：Comprise the steps：

（2）Prepare the mixed aqueous solution of nickel salt and gallium salt, step（1）The modified aluminium oxide supports of preparation are dried the roasting 1h-10h at 700 DEG C ~ 1000 DEG C using the above-mentioned mixed aqueous solution of unsaturated impregnation；

2. method according to claim 1, it is characterised in that：Step（1）The aqueous buffer solution ammonium salt of middle ammonium salt-containing is one or more in ammonium acetate, ammonium formate, ammonium carbonate, ammonium hydrogen carbonate.

3. method according to claim 1, it is characterised in that：The weight concentration of ammonium salt is 1%-35% in buffer solution.

4. method according to claim 1, it is characterised in that：Step（1）Aging temperature is 50-95 DEG C, and ageing time is 0.5-10h, and aging rear baking temperature is 90-150 DEG C, and drying time is 0.5-36h, roasting roasting 2-15 hours at 280-500 DEG C.

5. method according to claim 1, it is characterised in that：Step（1）After drying at 800 DEG C ~ 900 DEG C roasting 2h-8h.

6. method according to claim 1, it is characterised in that：Step（2）Middle nickel salt is one or more in Nickel dichloride., nickel nitrate or nickel sulfate, and gallium salt is one or more in Ganite (Fujisawa)., gallium chloride, gallium sulfate.

7. method according to claim 1, it is characterised in that：Step（2）The concentration of nickel ion is 0.1-5mol/L in mixed aqueous solution, and the molar concentration of gallium ion is two times of nickel ion molar concentration.

8. method according to claim 1, it is characterised in that：Step（1）Pickup is the 5-60% of alumina support saturated absorption amount of solution, and dip time is 1-5h, and dipping temperature is 40-60 DEG C, and baking temperature is 80-150 DEG C after dipping, and drying time is 2-15h.

9. method according to claim 1, it is characterised in that：Step（1）Pickup is the 20-50% of alumina support saturated absorption amount of solution.

10. method according to claim 1, it is characterised in that：Step（2）Middle organic amine includes one or more in fatty amine, hydramine, amide, aliphatic cyclic amine or aromatic amine.

11. methods according to claim 1 or 7, it is characterised in that：Step（2）Middle organic amine includes one or more in monoethyl amine, diethylamine, triethylamine, ethylenediamine, hexamethylene diamine, tert-butylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylformamide, propionic acid amide., butyramide, pyridine, morphine, aniline, diphenylamines, naphthalidine, dinaphthylamine.

12. methods according to claim 11, it is characterised in that：Step（2）Middle organic amine is one or more in diethylamine, triethylamine, morphine.

13. methods according to claim 1, it is characterised in that：Step（2）Middle fountain solution of the dipping containing adsorbent, is sprayed using unsaturation, wherein the volume ratio of unsaturated dipping dip amount used and carrier saturated absorption amount of solution is 0.05 ~ 0.4.

14. methods according to claim 1, it is characterised in that：Step（2）After middle fountain solution of the dipping containing adsorbent, be dried under the decomposition temperature less than selected adsorbent, or direct impregnation contains the solution of active metal ferrum, baking temperature is 60 DEG C～150 DEG C, drying time 0.5h～20h.

15. methods according to claim 14, it is characterised in that：Baking temperature is 80 DEG C～120 DEG C, and drying time is 1h～6h.

16. methods according to claim 1, it is characterised in that：Step（2）After middle fountain solution of the dipping containing adsorbent dipping terminates, next step is directly carried out, or next step is carried out again through health preserving, conditioned time is 0.5～8h.

17. methods according to claim 1, it is characterised in that：Step（3）Middle auxiliary agent is K and Mn, and Fe is respectively with the mass ratio of auxiliary agent K and Mn in the preparation of low carbon olefines by synthetic gas catalyst of preparation（65~75）：（0.5~5）：（23~34）.

18. methods according to claim 1, it is characterised in that：Step（3）Middle active component Fe and metal promoter K, Mn are supported on carrier by infusion process.

19. methods according to claim 14, it is characterised in that：Source of iron is one or more in ferric nitrate, iron chloride, iron sulfate, and potassium resource is one or more in potassium nitrate, potassium carbonate, potassium chloride, and manganese source is manganese nitrate or manganese chloride.

20. methods according to claim 1, it is characterised in that：Step（3）2-15% ammonium thiocyanates in mass are added in solution containing active metal ferrum.

21. methods according to claim 20, it is characterised in that：Step（3）5-10% ammonium thiocyanates in mass are added in solution containing active metal ferrum.

22. methods according to claim 1, it is characterised in that：Step（3）The middle solution impregnating carrier used containing active metal component and auxiliary agent, through dry and calcination stepses after dipping, drying steps are dried 8-24 hours, calcination stepses roasting 2-10 hours at 350-700 DEG C at 50-150 DEG C.

Preparation of low carbon olefines by synthetic gas catalyst prepared by a kind of 23. employing claim 1-12 either method, it is characterised in that：With Fe as active component, with K and Mn as auxiliary agent, the weight percentage of Fe is 0.5%-20% to the catalyst in catalyst, and Fe is respectively with the mass ratio of auxiliary agent K and Mn（65~75）：（0.5~5）：（23~34）.

The method of reducing of catalyst described in 24. claim 23, it is characterised in that：Reduced using the gaseous mixture of chlorine and hydrogen, volume content of the chlorine in gaseous mixture is 0.5-10%, reduction temperature is 300-450 DEG C, and the recovery time is 3-10 hours, and pressure is 0.5-2MPa.

25. method of reducing according to claim 24, it is characterised in that：Volume content of the chlorine in gaseous mixture is 1-5%.