CN106669722B - A kind of catalyst and preparation method thereof for hydrogen and reaction of carbon monoxide - Google Patents
A kind of catalyst and preparation method thereof for hydrogen and reaction of carbon monoxide Download PDFInfo
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- CN106669722B CN106669722B CN201510751034.9A CN201510751034A CN106669722B CN 106669722 B CN106669722 B CN 106669722B CN 201510751034 A CN201510751034 A CN 201510751034A CN 106669722 B CN106669722 B CN 106669722B
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- method described
- catalyst
- preparation
- drying
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000001257 hydrogen Substances 0.000 title claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 title abstract description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title abstract description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 title abstract description 4
- 239000000243 solution Substances 0.000 claims abstract description 62
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 48
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000007598 dipping method Methods 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 27
- 239000007789 gas Substances 0.000 claims abstract description 24
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 238000005470 impregnation Methods 0.000 claims abstract description 20
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- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 8
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
- C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/0445—Preparation; Activation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/889—Manganese, technetium or rhenium
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a kind of catalyst and preparation method thereof for hydrogen and reaction of carbon monoxide, and catalyst preparation includes the following steps：（1）Alumina support is saturated the acid solution of dipping sugar in equal volume；（2）Prepare the mixed aqueous solution of nickel salt and gallium salt, step（1）The modified aluminium oxide supports of preparation are dry 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；（4）Step（3）Carrier containing adsorbent impregnates the solution containing active metal iron and auxiliary agent manganese after drying, the or else saturation spray impregnating metal auxiliary agent potassium, then the obtained preparation of low carbon olefines by synthetic gas catalyst after drying, roasting after drying, roasting.The catalyst has the characteristics that 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 catalyst and preparation method thereof for hydrogen and reaction of carbon monoxide, relate in particular to
A kind of load-type iron-based preparation of low carbon olefines by synthetic gas catalyst 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 material, with the development of chemical industry, demand
Amount is more and more big.So far, the approach of the low-carbon alkenes such as preparing ethylene, propylene is mainly by light oil cracking process, with complete
The increasingly depleted of petroleum resources within the scope of ball, following energy resource structure certainly will shift.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）The exploitation of direct preparing ethylene, propylene technology, can not only reduce to petroleum resources according to
Rely, and to some chemical industrial expansion important in inhibiting in rich gas oil starvation 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 use the kind chemistry of noble metal or rare metal, such as 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 recyclings certainly will be brought
The consumption of the energy, and catalyst is of high cost.CN01144691.9 discloses the nano-catalytic of a kind of preparation of ethylene by use of synthetic gas, propylene
Agent and preparation method thereof uses the combination technique of laser pyrolysis processes combination solid phase reaction to be prepared for Fe3Fe 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 process is comparatively laborious, and raw material uses Fe (CO)5, the cost of catalyst is relatively high, and industrialization is difficult.CN03109585.2 is public
A kind of iron/activated-carbon catalyst being used for preparation of ethylene by use of synthetic gas, propylene, butene reaction is opened, 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 enable to be highly dispersed at
On activated carbon, to improve catalytic effect, and the cost of catalyst is greatly reduced.And catalyst is in the condition of no 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 ethylene, propylene, butylene are in CHization
The selectivity in object is closed up to 68% or more.But activated carbon is 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 modes such as buffer solution, the hydro-thermal process of compound solution, the acid solution of sugar, ammonium salt-containing carry out at dipping 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 to be further increased.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of low using aluminium oxide as the iron-based support type synthesis gas system of carrier
Carbene hydrocarbon catalyst and preparation method thereof, the catalyst have the characteristics that long-term operation activity stability is high, are conducive to industry
Using and promote.
A kind of preparation method of preparation of low carbon olefines by synthetic gas catalyst, includes the following steps：
（1）Alumina support is saturated in equal volume impregnates sugared acid solution, dry at 95-110 DEG C immediately after dipping
0.5-1h, the adsorbance of the dry acid solution to sugar are the 30-60% of alumina support saturated absorption amount of solution, are then passed through old
Change, is dry, modified aluminium oxide supports are made after roasting；
（2）Prepare the mixed aqueous solution of nickel salt and gallium salt, step（1）The modified aluminium oxide supports of preparation are soaked using unsaturated
Stain method impregnates above-mentioned mixed aqueous solution, roasts 1h-10h at 700 DEG C ~ 1000 DEG C after dry, is preferably roasted at 800 DEG C ~ 900 DEG C
Burn 2h-8h；
（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 the 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 metal promoter manganese, through drying,
Or else saturation spray impregnating metal auxiliary agent potassium solution, then the obtained preparation of low carbon olefines by synthetic gas catalysis after drying, roasting after roasting
Agent.
The method of the present invention step（1）The sugar that the acid solution of sugar used uses includes various water-soluble sugar, such as each
Kind monosaccharide or disaccharide, specifically include the aqueous solutions such as fructose, glucose, sucrose, maltose, preferably sucrose acid solution.The acid of sugar
Property solution in sugared mass concentration be 1%-35%, preferably 5%-20%.Acid solution pH containing sugar is 0.1-6.5, and preferable ph is
1-3 can use the pH value of arbitrary inorganic acid or organic acid-conditioning solution, preferably hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, first
Acid, acetic acid etc..Aging temperature be 50-95 DEG C, preferably 60 ~ 80 DEG C, ageing time 0.5-10h, preferably 2-5h.It is done after aging
Dry temperature is 90-150 DEG C, drying time 0.5-36h, the dry 8-24h preferably at 100-120 DEG C.Roasting is at 280-500 DEG C
Lower roasting 2-15 hours roasts 3-5 hours preferably at 300-450 DEG C.
The method of the present invention, step（2）Middle nickel salt is one or more of nickel chloride, nickel nitrate or nickel sulfate, and gallium salt is
One or more of gallium nitrate, gallium chloride, gallium sulfate.A concentration of 0.1-5mol/L of nickel ion in mixed aqueous solution, gallium from
The molar concentration of son is two times of nickel ion molar concentration.
The method of the present invention, step（2）Impregnation increment is the 5-60%, preferably 20-50% of alumina support saturated absorption amount of solution.
Dip time is 1-5h, and dipping temperature is 40-60 DEG C.Drying temperature is 80-150 DEG C after dipping, drying time 2-15h.
The method of the present invention, step（2）Existing commercial goods may be used in middle alumina support, can also be by existing method system
It is standby.Support shapes can be spherical shape, bar shaped, piece type.It is best with spherical and bar shaped.
The method of the present invention, step（3）Middle organic amine includes one kind in fatty amine, hydramine, amide, 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 ethanol amine, dimethylformamide, propionamide, butyramide, pyridine, morphine, aniline, diphenylamines, naphthalidine, dinaphthylamine
Or several, preferably one or more of diethylamine, triethylamine, morphine.
Step of the present invention（3）In, the fountain solution containing adsorbent is impregnated, is impregnated using unsaturation, preferably with unsaturation
It sprays, wherein the volume ratio of unsaturated dipping dip amount and carrier saturated absorption amount of solution used 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 nozzle that atomizing effect should be selected good makes solution uniformly divide
It is scattered on alumina support.After impregnating the fountain solution dipping containing adsorbent, 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 method of the present invention, step（4）The amount of middle unsaturated spray impregnating metal auxiliary agent potassium solution is that carrier saturated absorption is molten
The 50-90% of liquid measure.The mass ratio of Fe and auxiliary agent K and Mn 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 solution is dense
Degree can be adjusted by the dosage of each compound, 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 of iron, ferric sulfate, potassium resource are generally come from one or more of potassium nitrate, potassium carbonate, potassium chloride, manganese source
From manganese nitrate or manganese chloride.
The method of the present invention, step（4）In add 2-15%, preferably 5- in the solution containing active metal iron and auxiliary agent manganese
10% ammonium thiocyanate in mass.The dispersion degree of active component can be improved using the iron salt solutions containing ammonium thiocyanate are added,
The active component iron catalyst for preparing little crystal grain, to significantly improve the selectivity of low-carbon alkene.
The method of the present invention, step（4）The middle solution impregnating carrier containing active metal component and auxiliary agent, through overdrying after dipping
The condition of dry and calcination steps, the drying and roasting is conventional, for example, drying steps dry 8-24 at 50-150 DEG C
Hour, calcination steps roast 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 be with K and Mn using Fe as active component
Auxiliary agent, the weight percentage of Fe is 0.5%-20% in catalyst, and auxiliary agent is K and Mn, the matter of Fe and auxiliary agent K and Mn 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 restored 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, recovery time 3-10
Hour, pressure 0.5-2MPa.The selectivity of butylene can be improved using above-mentioned restoring method.
The method of the present invention is saturated oxide impregnation alumina supporter using the acid solution of sugar first, sugared after quick fraction is dried
Acid solution concentrates in the internal gutter of carrier, and sugared acid solution mainly carries out carrier inside partially modified.Then it adopts
With the mixed aqueous solution of nickel salt and gallium salt, mainly the outer surface to alumina support and external channel surfaces are mainly modified.On
It states and non-uniform modification is carried out to the inside and outside duct of alumina support does not make the inside and outside duct physico-chemical property of alumina support obviously not
Together, it inhibits the carbochain of the low-carbon alkene of generation to increase and add hydrogen saturation while improving activity to greatest extent, improves an oxygen
Change charcoal percent conversion.The method of the present invention made by way of adsorbent occupy-place active component iron content and auxiliary agent manganese by it is outer from it is interior by
Cumulative to add, auxiliary agent potassium is distributed at eggshell type, significantly improves the selectivity of catalyst.The physical and chemical performance of the catalyst, catalysis are lived
Property, long-term operation stability be obtained for raising, the comprehensive performance of catalyst protrudes.
Specific implementation mode
The process and effect further illustrated the present invention with reference to embodiment, but following embodiment is not constituted to the present invention
The limitation of method.
Example 1
Weigh commercial alumina（Kong Rongwei 0.96ml/g, specific surface area 286.81m2/ g, saturated water adsorptive value 145ml/
G is provided by Fushun branch company of Sinopec catalyst Co., Ltd, and following embodiment and comparative example use the aluminium oxide）, will
The aqueous solution sulphur acid for adjusting pH value that sucrose mass concentration is 5% is equal to 3, is saturated after spraying oxide impregnation aluminium immediately 95
Dry 1h at DEG C, the adsorbance of the acid solution of dry sugaring are the 60% of alumina support saturated absorption amount of solution, at 60 DEG C
Aging 7h, it is 24 hours dry in 100 DEG C, 5 hours obtained modified aluminium oxide supports are then roasted at 300 DEG C.Above-mentioned modified oxygen
It is respectively the nickel nitrate of 0.5mol/L, 1mol/L, nitre to change alumina supporter using unsaturated spray impregnation nickel, gallium molar concentration
Sour gallium mixed aqueous solution, dipping temperature are 50 DEG C, dip time 3h, and impregnation increment is alumina support saturated absorption amount of solution
20%, dry 5h at 120 DEG C, 850 DEG C of roastings are lower to roast 6h.Carrier unsaturation spray dipping triethylamine aqueous solution after roasting,
It is the 35% of the total saturated water adsorptive value of used carrier that triethylamine aqueous solution, which sprays volume, and the quality of triethylamine contains in triethylamine aqueous solution
Amount is the 8% of carrier quality, is sprayed after impregnating in 100 DEG C of dry 5h.Based on final catalyst Fe content 9wt%, triethylamine is adsorbed
Carrier iron nitrate aqueous solution is impregnated using equi-volume impregnating, 100 DEG C of dryings 16 hours roast 4 hours in 550 DEG C.It presses
The mass ratio of Fe, K and Mn are 70 in catalyst：3：28 meters, unsaturation spray dipping potassium nitrate solution, impregnation increment are saturated for carrier
The 60% of absorbent solution amount, 100 DEG C of dryings 16 hours, roasts 4 hours, gained catalyst is denoted as C-1 in 550 DEG C.C-1 is catalyzed
The reaction result that agent synthesis gas directly prepares low-carbon alkene is as shown in table 1.
Catalyst Evaluation Test carries out in the continuous fixed bed reactors of high pressure, to be restored 5 hours at 350 DEG C of pure hydrogen, presses
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（Molar ratio）.C-1 catalyst synthesis gas directly prepares the 300h reactions of low-carbon alkene
The results are shown in Table 1.
Example 2
Commercial alumina is weighed, the aqueous solution sulphur acid for adjusting pH value that sucrose mass concentration is 20% is equal to 1, saturation spray
The dry 0.5h at 110 DEG C, the dry adsorbance to sugared acid solution are carrying alumina immediately after leaching oxide impregnation aluminium
The 40% of body saturated absorption amount of solution, aging 4 hours at 80 DEG C is 8 hours dry in 120 DEG C, then roasts 3 in 400 DEG C
Hour obtains modified aluminium oxide supports.Above-mentioned modified aluminium oxide supports are using unsaturated spray impregnation nickel, gallium molar concentration
The respectively nickel nitrate of 1.5mol/L, 3mol/L, gallium nitrate mixed aqueous solution, dipping temperature are 60 DEG C, dip time 2h, dipping
Amount is the 40% of alumina support saturated absorption amount of solution, the dry 10h at 90 DEG C, 900 DEG C of roasting 4h.Carrier after roasting is not
Saturation spray dipping aqueous morphine solution, aqueous morphine solution spray 10% that volume is the total saturated water adsorptive value of used carrier, and morphine is water-soluble
The mass content of morphine is the 2% of carrier quality in liquid, and oxygen gives birth to 5h after spray dipping, in 90 DEG C of dry 8h.By final catalyst Fe
Content 9wt%, manganese content are counted for 3.6wt%, adsorb the carrier of triethylamine using equi-volume impregnating dipping ferric nitrate and manganese nitrate
Aqueous solution, 100 DEG C of dryings 16 hours, roasts 4 hours in 550 DEG C.It is 70 by the mass ratio of Fe, K and Mn in catalyst：3：28
Meter, unsaturation spray dipping potassium nitrate solution, impregnation increment are the 80% of carrier saturated absorption amount of solution, 100 DEG C of dryings 16 hours,
It is roasted 4 hours in 550 DEG C, gained catalyst is denoted as C-2, and evaluation results are shown in Table 1 by 300h.
Example 3
In addition to adding the ammonium thiocyanate that mass fraction is 5% in the iron nitrate aqueous solution of dipping, remaining is the same as embodiment 1, system
It obtains catalyst and is denoted as C-3, evaluation results are shown in Table 1 by 300h.
Example 4
In addition to adding the ammonium thiocyanate that mass fraction is 10% in the iron nitrate aqueous solution of dipping, remaining with embodiment 1,
Obtained catalysis is denoted as C-4, and 300 evaluation results are shown in Table 1.
Example 5
With embodiment 1, the difference is that being restored to catalyst using the gaseous mixture of chlorine and hydrogen, chlorine is mixed
The volume content closed in gas is 5%, and obtained catalyst is denoted as C-5, and evaluation results are shown in Table 1 by 300h.
Implement 6
With embodiment 1, the difference is that catalyst is restored using the gaseous mixture of chlorine and hydrogen, chlorine is mixing
Volume content in gas is 1%, remaining is with embodiment 1, and obtained catalyst is denoted as C-6, and evaluation results are shown in Table 1 by 300h.
Comparative example 1
Except being respectively that the nickel nitrate of 0.5mol/L, 1mol/L, gallium nitrate are mixed using spray dipping nickel, gallium molar concentration is saturated
Outside Heshui solution, remaining is with embodiment 1, and obtained catalyst is denoted as B-1, and evaluation results are shown in Table 1 by 300h.
Comparative example 2
In addition to not spraying dipping triethylamine aqueous solution, with embodiment 1, obtained catalyst is denoted as B-2,300h evaluation knots for remaining
Fruit is shown in Table 1.
The reactivity worth of 1 catalyst of table
Claims (23)
1. a kind of preparation method of preparation of low carbon olefines by synthetic gas catalyst, it is characterised in that：Include the following steps：
（1）Alumina support is saturated the acid solution of dipping sugar in equal volume, and 0.5-1h is dried at 95-110 DEG C immediately after dipping,
The adsorbance of the dry acid solution to sugar is the 30-60% of alumina support saturated absorption amount of solution, then through aging, drying,
Modified aluminium oxide supports are made after roasting；
（2）Prepare the mixed aqueous solution of nickel salt and gallium salt, step（1）The modified aluminium oxide supports of preparation are using unsaturated infusion process
Above-mentioned mixed aqueous solution is impregnated, 1h-10h is roasted at 700 DEG C ~ 1000 DEG C after dry；
（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 the adsorbent accounts for step（2）1% of vehicle weight after roasting
~10%；
（4）Step（3）Carrier impregnation containing adsorbent contains the solution of active metal iron and auxiliary agent manganese, after drying, roasting again
Unsaturation spray impregnating metal auxiliary agent potassium solution, then preparation of low carbon olefines by synthetic gas catalyst is made after drying, roasting；
Wherein, step（1）The sugar that the acid solution of sugar used uses be fructose, glucose, sucrose, one kind in maltose or
Several, the roasting roasts 2-15 hours at 280-500 DEG C.
2. according to the method described in claim 1, it is characterized in that：Step（1）Sugared mass concentration is in the acid solution of sugar
1%-35%, the acid solution pH containing sugar are 0.1-6.5.
3. according to the method described in claim 1, it is characterized in that：Step（1）Aging temperature is 50-95 in the acid solution of sugar
DEG C, ageing time 0.5-10h, drying temperature is 90-150 DEG C after aging, drying time 0.5-36h.
4. according to the method described in claim 1, it is characterized in that：Step（2）After drying 2h- is roasted at 800 DEG C ~ 900 DEG C
8h。
5. according to the method described in claim 1, it is characterized in that：Step（2）Middle nickel salt is nickel chloride, nickel nitrate or nickel sulfate
One or more of, gallium salt is one or more of gallium nitrate, gallium chloride, gallium sulfate.
6. according to the method described in claim 1, it is characterized in that：Step（2）Nickel ion is a concentration of in mixed aqueous solution
0.1-5mol/L, the molar concentration of gallium ion are two times of nickel ion molar concentration.
7. according to the method described in claim 1, it is characterized in that：Step（2）Impregnation increment is that alumina support saturated absorption is molten
The 5-60% of liquid measure, dip time 1-5h, dipping temperature are 40-60 DEG C, and drying temperature is 80-150 DEG C after dipping, when dry
Between be 2-15h.
8. according to the method described in claim 1, it is characterized in that：Step（2）Impregnation increment is that alumina support saturated absorption is molten
The 20-50% of liquid measure.
9. according to the method described in claim 1, it is characterized in that：Step（3）Middle organic amine is fatty amine, hydramine, amide, fat
One or more of cyclammonium or aromatic amine.
10. according to the method described in claim 9, it is characterized 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 of amine, pyridine, morphine, aniline, diphenylamines, naphthalidine, dinaphthylamine.
11. according to the method described in claim 10, it is characterized in that：Step（3）Middle organic amine be diethylamine, triethylamine,
One or more of coffee.
12. according to the method described in claim 1, it is characterized 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 and carrier saturated absorption amount of solution used be 0.05 ~
0.4。
13. according to the method described in claim 1, it is characterized in that：Step（3）After middle fountain solution of the dipping containing adsorbent,
Dry or direct impregnation contains the solution of active metal iron, drying temperature under the decomposition temperature no more than selected adsorbent
It is 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 described in claim 1, it is characterized in that：Step（4）The preparation of low carbon olefines by synthetic gas of middle preparation is catalyzed
The mass ratio of Fe and auxiliary agent K and Mn are respectively in agent（65~75）：（0.5~5）：（23~34）.
16. according to the method described in claim 1, it is characterized 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 described in claim 1, it is characterized in that：Source of iron is one kind in ferric nitrate, iron chloride, ferric sulfate
Or it is several, potassium resource is one or more of potassium nitrate, potassium carbonate, potassium chloride, and manganese source is manganese nitrate or manganese chloride.
18. according to the method described in claim 1, it is characterized in that：Step（4）Solution containing active metal iron and auxiliary agent manganese
In add the ammonium thiocyanates 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 thiocyanates of 5-10% in mass are added in liquid.
20. according to the method described in claim 1, it is characterized in that：Step（4）By dry and calcination steps after dipping, do
Dry step is 8-24 hours dry at 50-150 DEG C, and calcination steps roast 2-10 hours at 350-700 DEG C.
21. a kind of preparation of low carbon olefines by synthetic gas catalyst prepared using claim 1-20 either method, it is characterised in that：It should
Catalyst is using Fe as active component, using K and Mn as auxiliary agent, in catalyst the weight percentage of Fe be 0.5%-20%, Fe with help
The mass ratio of agent K and Mn is respectively（65~75）：（0.5~5）：（23~34）.
22. the restoring method of catalyst described in claim 21, it is characterised in that：It is 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%。
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| CN106669722B true CN106669722B (en) | 2018-11-06 |
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| CN101920201A (en) * | 2009-06-09 | 2010-12-22 | 中国石油化工股份有限公司 | Method for preparing cobalt-based Fischer-Tropsch synthesis catalyst |
| CN102441393A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst with modified alumina as carrier and application thereof |
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| CN101920201A (en) * | 2009-06-09 | 2010-12-22 | 中国石油化工股份有限公司 | Method for preparing cobalt-based Fischer-Tropsch synthesis catalyst |
| CN102441393A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst with modified alumina as carrier and application thereof |
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