CN107774281A - The catalyst and preparation method and the method for co hydrogenation producing light olefins of a kind of co hydrogenation producing light olefins - Google Patents
The catalyst and preparation method and the method for co hydrogenation producing light olefins of a kind of co hydrogenation producing light olefins Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
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- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
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- 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
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- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
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Abstract
The invention discloses a kind of catalyst of co hydrogenation producing light olefins and preparation method and the method for co hydrogenation producing light olefins, the catalyst includes porous amorphous alloy skeleton and the molybdenum component being supported on the porous amorphous alloy skeleton, the porous amorphous alloy skeleton includes iron and silicon, and the molybdenum component is the presoma of molybdenum sulfide and/or molybdenum sulfide；Wherein, on the basis of the gross weight of catalyst and in terms of element wt, the content of iron is 45 95 weight % in the catalyst, and the content of silicon is 3 40 weight %, and the content of molybdenum is 1 10 weight %, and the content of sulphur is 0.1 5 weight %.Co hydrogenation producing light olefins are carried out using the method for the present invention, the selectivity of low-carbon alkene is good.
Description
Technical field
The present invention relates to a kind of catalyst of co hydrogenation producing light olefins and preparation method and co hydrogenation
The method of producing light olefins.
Background technology
Low-carbon alkene (C2-C4Alkene) basic organic chemical industry raw material is used as, act foot is played in modern petroleum and chemical industry
The effect of weight.Especially ethene and propylene, with the increasingly increase and the continuous expansion of application field of its demand, it is closed
Widely research, which is carried out, into method shows important day.
The method of preparing low-carbon olefins can generally be divided into two major classes:One kind is petroleum path, and another kind of is non-petroleum road
Line.So far, traditional light oil cracking method is still mainly used in the world, i.e. it is low to come preparing ethylene, propylene etc. for petroleum path
Carbon olefin.In the case where oil price is soaring, using natural gas as raw material, have via the direct or indirect producing light olefins of synthesis gas
There are technology and economic attractiveness.Such as using natural gas as raw material, the methods of passing through oxidative coupling preparing low-carbon olefins technology, with natural
Gas or coal are waste synthesis gas, and synthesis gas is made by F- T synthesis (direct method) or via methanol or dimethyl ether (indirect method)
Take low-carbon alkene technology etc..And by the technique that the direct preparing low-carbon olefins of synthesis gas are single step reaction generation purpose product, its work
Skill flow is more simpler than indirect method, more economical.
The catalyst that synthesis gas orientation is converted into low-carbon alkene reaction typically selects Fe as active component, while adds one
A little auxiliary agents；The carrier of catalyst is typically various types of molecular sieve and activated carbon.Wherein molecular sieve carried catalyst can lead to
The adjustable pore passage structure of over-molecular sieve is realized to the shape-selective of product, is attracted attention in terms of selectivity of light olefin is improved.
The Chinese invention patent CN1260823A of Exxon Corporation report converted synthesis gas into modified molecular screen it is low
The method of carbon olefin, it uses Fe3(CO)12/ ZSM-5 modified molecular sieve catalysts, in 260 DEG C, H2/ CO volume ratios are 3, GHSV
For 1000h-1Reaction condition under, the overall selectivity of ethene and propylene is 65%.
The Chinese invention patent CN92109866.9 of Dalian Chemical Physics Research Institute reports to be loaded using high-silica zeolite
Fe-Mn isoreactivity components realize the selectivity of preferable preparation of low carbon olefines by synthetic gas.Its disclosed catalyst is ferrimanganic metal
Oxide-molecular sieve (K-Fe-MnO/Silicalite-2) composite catalyst, CO conversion ratios reach 70-90%, C2-C4Alkene selects
Property is 72-74%.
But due to that in molecular sieve carried active component the pore structure of molecular sieve can be caused to change, and outer surface
Active metal do not influenceed by carrier hole structure, unfavorable to obtaining high selectivity, the effect of carrier can not fully be sent out
Wave.
The Chinese invention patent ZL03109585.2 and CN101219384A of Beijing University of Chemical Technology disclose using activated carbon as
Carrier, manganese, copper, zinc, silicon, potassium etc. is the Fe/ activated carbon catalysts of auxiliary agent, for the reaction of synthesis gas preparing low-carbon olefins,
300-400 DEG C of temperature, pressure 1-2MPa, synthesis gas air speed 400-1000h-1, the CO conversion ratios under conditions of being circulated without unstripped gas
Up to 95%, content of the hydrocarbon in gas-phase product is 69.5%, and ethene, propylene, butylene are in hydrocarbon
Selectivity is up to more than 68%.But coking is serious during the catalyst use, it is impossible to long-term operating.
Iron nano-particle is dispersed in weak property interactive mode alpha-oxidation by De Jong etc. (Science, 2012,335,835)
On aluminium or carbon nano-fiber carrier, synthesis gas is directly converted and produce C2~C4Light olefin, in CO conversion ratios 80%, low-carbon alkene
It is 50% that hydrocarbon, which accounts for hydrocarbon product mass content, and possesses relatively good anticoking capability, but the preparation process of the catalyst is answered
It is miscellaneous to be difficult to industrial applications.
For many years, some research teams have attempted to high temperature fused iron catalyst, directly raw for improving F- T synthesis
Produce the selectivity of the product of low-carbon alkene.
Chinese patent CN101757925A provides a kind of oxide by iron and co-catalyst aluminum oxide, calcium oxide, oxygen
Change the composition such as potassium, fused iron catalyst for synthesis gas production low-carbon alkene, the catalyst F- T synthesis activity and selectivity
Higher, conversion per pass reaches more than 95%, and methane selectively is less than 10%, low-carbon alkene content more than 35%.But molten iron
The mechanical performance of catalyst at high temperature is bad, may result in the blocking of beds in fixed-bed operation, or causes to flow
Change the incrustation of bed process separation equipment, limit application of the fused iron catalyst in F- T synthesis generation low-carbon alkene course of reaction.
In addition, these catalyst run into different degrees of difficulty in the program such as Repeatability, amplification preparation is prepared.Therefore
The catalyst of new structure is designed, high selectivity of light olefin is obtained, has to the commercial Application of preparation of low carbon olefines by synthetic gas
Significance.
The content of the invention
It is an object of the invention to provide a kind of catalyst of co hydrogenation producing light olefins and preparation method and an oxygen
Change the method for carbon hydrogenation producing light olefins, co hydrogenation producing light olefins, low-carbon alkene are carried out using the method for the present invention
Selectivity it is good.
To achieve these goals, the present invention provides a kind of catalyst of co hydrogenation producing light olefins, the catalysis
Agent includes porous amorphous alloy skeleton and the molybdenum component being supported on the porous amorphous alloy skeleton, described porous amorphous
Alloy skeleton includes iron and silicon, and the molybdenum component is the presoma of molybdenum sulfide and/or molybdenum sulfide；Wherein, with the gross weight of catalyst
On the basis of amount and in terms of element wt, the content of iron is 45-95 weight % in the catalyst, and the content of silicon is 3-40 weights
% is measured, the content of molybdenum is 1-10 weight %, and the content of sulphur is 0.1-5 weight %.
Preferably, on the basis of the gross weight of catalyst and in terms of element wt, the porous amorphous alloy skeleton is also
Metal M including 0.1-40 weight %, the metal M are selected from I B-group metal, group iib metal, Group IIIB metal, the
At least one of Group IVB metal, vib metals, V Group IIB metal and group VIII metal.
Preferably, the metal M is selected from least one of cobalt, manganese, copper and cerium.
Preferably, on the basis of the gross weight of catalyst and in terms of element wt, the content of iron is 70- in the catalyst
85 weight %, the content of silicon is 10-25 weight %, and the content of molybdenum is 1-3 weight %, and the content of sulphur is 2-4 weight %.
The present invention also provides a kind of preparation method of the catalyst of co hydrogenation producing light olefins, and this method includes：
A, quenching processing will be carried out after the alloy skeleton raw material mixed melting including iron and silicon, obtains foundry alloy；B, by gained in step a
Foundry alloy is stripped desiliconization, obtains porous amorphous alloy skeleton；C, by obtained by the presoma load in stepb of molybdenum sulfide
On porous amorphous alloy skeleton, the catalyst of co hydrogenation producing light olefins is obtained；Wherein, with the gross weight of catalyst
On the basis of and in terms of element wt, the content of iron is 45-95 weight % in the catalyst, and the content of silicon is 3-40 weight %,
The content of molybdenum is 1-10 weight %, and the content of sulphur is 0.1-5 weight %.
Preferably, it is selected from I B-group metal, group iib that the alloy skeleton raw material, which also includes metal M, the metal M,
In metal, Group IIIB metal, group ivb metal, vib metals, V Group IIB metal and group VIII metal at least
One kind, on the basis of the gross weight of catalyst and in terms of element wt, metal M content is 0.1-40 weights in the catalyst
Measure %.
Preferably, the metal M is selected from least one of cobalt, manganese, copper and cerium.
Preferably, the processing of quenching described in step a includes：The mixed melting liquid of alloy skeleton raw material is ejected into 600-
1000 revs/min be connected with the copper roller of cooling water, makes the mixed melting liquid cold with 1000-1600 DEG C/sec of cooling velocity
But and along copper roller tangent line throw away, obtained flakey band alloy obtains the foundry alloy through being crushed to 20-200 mesh；Step b
Described in extract desiliconization the step of include：Gained foundry alloy in step a is subjected to caustic extraction desiliconization in alkali lye, obtains alkali lye
Extract desiliconization alloy；Gained caustic extraction desiliconization alloy is subjected to acid solution extracting desiliconization in acid solution, obtains the porous amorphous
State alloy skeleton；Wherein, the condition of the caustic extraction desiliconization is：Temperature is 0-100 DEG C, and the time is 10-60 minutes, alkali lye
Molar concentration is 1-12 mol/Ls, and the alkali in alkali lye is sodium hydroxide and/or potassium hydroxide, the weight of foundry alloy and alkali in alkali lye
Amount is than being 1：(1-10)；The condition of acid solution extracting desiliconization is：Temperature is 0-100 DEG C, and the time is 10-120 minutes, acid solution
Molar concentration is 1-12 mol/Ls, and the acid in acid solution is hydrochloric acid and/or nitric acid, and foundry alloy is 1 with weight ratio sour in acid solution：
(0.4-10)；The method loaded described in step c is the precipitation method and/or infusion process.
Preferably, by porous amorphous alloy skeleton obtained by the presoma load in stepb of molybdenum sulfide described in step c
On step include：Ammoniacal liquor is added after porous amorphous alloy skeleton described in step b is mixed with ammonium thiomolybdate solution, is made
Ammonium thiomolybdate is precipitated on porous amorphous alloy skeleton, and the porous amorphous alloy skeleton for being attached with sediment is roasted
After burning, the catalyst of co hydrogenation producing light olefins is obtained.
The present invention also provides a kind of method of co hydrogenation producing light olefins, and this method includes：By carbon monoxide with
The catalyst of co hydrogenation producing light olefins provided by the present invention contacts and under hydroconversion condition in hydrogenation reactor
Carry out hydrogenation preparing low-carbon olefins.
Preferably, the hydroconversion condition includes：Temperature is 200-500 DEG C, and pressure is 0.5-15.0 MPas, and gas volume is empty
Speed is 500-100000 hours-1, the mol ratio 0.5-10 of hydrogen and carbon monoxide；The hydrogenation reactor is anti-selected from slurry bed system
Answer at least one of device, fluidized-bed reactor and fixed bed reactors.
The method for preparing catalyst of the present invention is simple, and prepared catalyst particle size is evenly distributed, structure-controllable.The present invention
Catalyst when being applied to co hydrogenation producing light olefins, catalytic efficiency, stability, the selectivity of activity and low-carbon alkene
Height, carbon dioxide selectivity are low.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of catalyst of co hydrogenation producing light olefins, and the catalyst includes porous amorphous conjunction
Golden skeleton and the molybdenum component being supported on the porous amorphous alloy skeleton, the porous amorphous alloy skeleton include iron and
Silicon, the molybdenum component are the presoma of molybdenum sulfide and/or molybdenum sulfide；Wherein, on the basis of the gross weight of catalyst and with element
Weight meter, the content of iron is 45-95 weight % in the catalyst, and the content of silicon is 3-40 weight %, and the content of molybdenum is 1-10
Weight %, the content of sulphur is 0.1-5 weight %；Preferably, it is described on the basis of the gross weight of catalyst and in terms of element wt
The content of iron is 70-85 weight % in catalyst, and the content of silicon is 10-25 weight %, and the content of molybdenum is 1-3 weight %, sulphur
Content is 2-4 weight %.Molybdenum sulfide in the molybdenum component typically with a molybdenum sulfide, molybdenum disulfide, molybdenum trisulfide simple substance or
Mixture is present.
According to the present invention, porous amorphous alloy skeleton is well-known to those skilled in the art, belongs to amorphous alloy,
The defects of arrangement in the absence of the crystal boundary present in usual crystal alloy, dislocation and segregation of its interior atoms, between component
It is connected with metallic bond and shortrange order and longrange disorder is kept in several lattice constant ranges, forms a kind of similar cluster
Structure.On the basis of the gross weight of catalyst and in terms of element wt, the porous amorphous alloy skeleton can also include
0.1-40 weight % metal M, the metal M, the metal M for preferably including 0.5-20 weight % can be selected from group ib gold
Category, group iib metal, Group IIIB metal, group ivb metal, vib metals, V Group IIB metal and group VIII gold
At least one of category, preferably is selected from least one of cobalt, manganese, copper and cerium.
According to the present invention, catalyst can be existed with shell-caryogram structure, using porous amorphous alloy skeleton as core,
Molybdenum component is the shell being wrapped on skeleton.
The present invention also provides a kind of preparation method of the catalyst of co hydrogenation producing light olefins, and this method includes：
A, quenching processing will be carried out after the alloy skeleton raw material mixed melting including iron and silicon, obtains foundry alloy；B, by gained in step a
Foundry alloy is stripped desiliconization, obtains porous amorphous alloy skeleton；C, by obtained by the presoma load in stepb of molybdenum sulfide
On porous amorphous alloy skeleton, the catalyst of co hydrogenation producing light olefins is obtained；Wherein, with the gross weight of catalyst
On the basis of and in terms of element wt, the content of iron is 45-95 weight % in the catalyst, and the content of silicon is 3-40 weight %,
The content of molybdenum is 1-10 weight %, and the content of sulphur is 0.1-5 weight %.
According to the present invention, the preparation method of porous amorphous alloy skeleton is well known to those skilled in the art, can be adopted
Prepared with the methods of quenching method, chemical reaction method and electrodeposition process, because the method for preparing catalyst of the present invention includes taking out
Desiliconization step is put forward, therefore in addition to the silicon, the inventory in other components is almost identical with the actual content in catalyst, and ability
Field technique personnel can control the content of silicon in catalyst, or the mesh according to silicon in catalyst by extracting the condition of desiliconization
Mark content and extract the condition of desiliconization and calculate the inventory of silicon.
According to the present invention, the alloy skeleton raw material can also include metal M, the metal M be selected from I B-group metal,
In group iib metal, Group IIIB metal, group ivb metal, vib metals, V Group IIB metal and group VIII metal
At least one, at least one of cobalt, manganese, copper and cerium preferably are selected from, on the basis of the gross weight of catalyst and with element wt
Count, metal M content can be 0.1-40 weight % in the catalyst, and preferably 0.5-20 weight %, more preferably 3-10 are heavy
Measure %.
According to the present invention, quenching processing, extracting desiliconization and load are well known to those skilled in the art, for example, in step a
The quenching processing can include：It is cold that the mixed melting liquid of alloy skeleton raw material is ejected into 600-1000 revs/min be connected with
But on the copper roller of water, the mixed melting liquid is cooled down with 1000-1600 DEG C/sec of cooling velocity and thrown away along copper roller tangent line,
Obtained flakey band alloy obtains the foundry alloy, wherein described copper roller can be double rods through being crushed to 20-200 mesh
Can also be single roller, described injection can be by the way of atomized spray, it is preferred to use more than 1300 DEG C of atomized spray, it is female
The size of alloy is 80-200 mesh；The step of desiliconization is extracted described in step b can include：Gained foundry alloy in step a is existed
Caustic extraction desiliconization is carried out in alkali lye, obtains caustic extraction desiliconization alloy；The caustic extraction desiliconization alloy of its Oxford gray can be with
Adopt and be washed with distilled water to pH value less than 10, it is de- that gained caustic extraction desiliconization alloy is then carried out into acid solution extracting in acid solution
Silicon, obtain the porous amorphous alloy skeleton；Wherein, the condition of the caustic extraction desiliconization can be：It can be stirred in magnetic force
Lower progress is mixed, temperature can be 0-100 DEG C, and preferably 25-100 DEG C, the time can be 10-60 minutes, and preferably 20-60 divides
Clock, the molar concentration of alkali lye can be 1-12 mol/Ls, preferably 2-10 mol/Ls, and the alkali in alkali lye can be sodium hydroxide
And/or potassium hydroxide, the weight ratio of foundry alloy and alkali in alkali lye can be 1：(1-10)；The condition of the acid solution extracting desiliconization can
Think：Temperature can be 0-100 DEG C, and preferably 50-100 DEG C, the time can be 10-120 minutes, preferably 40-120 minutes,
The molar concentration of acid solution can be 1-12 mol/Ls, and the acid in acid solution can be hydrochloric acid and/or nitric acid, foundry alloy with acid solution
The weight ratio of acid can be 1：(0.4-10)；In addition, according to the usual requirement of porous amorphous alloy skeleton adulteration, taken out in acid solution
After proposing desiliconization, the step of can also including washing porous amorphous alloy skeleton using distilled water, until washings are
Neutrality, the porous amorphous alloy skeleton after washing can preserve under conditions of inert gas or hydrogen shield；Institute in step c
The method for stating load can be the precipitation method and/or infusion process, be that those skilled in the art are known, for example, will described in step c
Step of the presoma load of molybdenum sulfide in stepb on gained porous amorphous alloy skeleton can include：By institute in step b
State after porous amorphous alloy skeleton mixes with ammonium thiomolybdate solution and add ammoniacal liquor, make ammonium thiomolybdate in porous amorphous conjunction
Precipitated on golden skeleton, after the porous amorphous alloy skeleton for being attached with sediment is calcined, obtain co hydrogenation system
The catalyst of low-carbon alkene.A kind of embodiment, by porous amorphous alloy skeleton and 1-5 weight % ammonium thiomolybdate
For the aqueous solution in 60-80 DEG C of contact, time of contact can be 0.5-2 hours, and 5-10 weight % ammoniacal liquor regulation pH value is added dropwise and has been formed
Full black precipitate, aging is stood after precipitation, the time for standing aging can be 6-10 hours, filter and be washed with deionized water
Wash, be placed in after 50-100 DEG C is dried in vacuo 2-6 hours in tube furnace in nitrogen protection and be heated to 300-400 DEG C, thermal decomposition
Catalyst is made in 2-6 hours.
The present invention also provides a kind of method of co hydrogenation producing light olefins, and this method includes：By carbon monoxide with
The catalyst of co hydrogenation producing light olefins provided by the present invention contacts and under hydroconversion condition in hydrogenation reactor
Carry out hydrogenation preparing low-carbon olefins.
According to the present invention, the method and condition of co hydrogenation producing light olefins be it is well known to those skilled in the art,
For example, the hydroconversion condition can include：Temperature is 200-500 DEG C, and pressure is 0.5-15.0 MPas, and gas volume air speed is
500-100000 hours-1, the mol ratio 0.5-10 of hydrogen and carbon monoxide；The hydrogenation reactor can be anti-selected from slurry bed system
Answer at least one of device, fluidized-bed reactor and fixed bed reactors.
The present invention will be illustrated by embodiment below, but the present invention is not therefore subject to any restriction.
The each component content of embodiment 1-5 prepared catalysts is determined using plasma emission spectrum (ICP).
Gaseous product is measured using the gas-chromatography of TCD detectors obtained by embodiment 6-10, and product liquid uses FID
The gas-chromatography of detector is measured.Hydrocarbon-selective refers to that hydro carbons accounts for the weight fraction of reaction product.
Embodiment 1-5 illustrates the method for preparing catalyst and prepared catalyst for providing the present invention.
Embodiment 1
1.5 kilograms of iron, 1.5 kilograms of silicon are added in graphite crucible, it is heated to melting in coreless induction furnace, then should
Fused solution is sprayed onto at crucible nozzle on the copper roller that a rotating speed is 600 revs/min, cooling water is led in copper roller, aluminium alloy is with 1000-
1600 DEG C/sec of cooling velocity is got rid of in water after quickly cooling down along copper roller tangent line, forms flakey band, flakey band warp
Particle diameter is ground to as less than 500 microns, obtains foundry alloy.50g foundry alloys are slowly added into and fill 500 grams of 20wt% hydrogen
In the there-necked flask of aqueous solution of sodium oxide, its temperature is controlled to be stirred 1 hour for 60 DEG C and constant temperature.After stopping heating and stirring, filter off
Liquid, add distillation water washing to pH value and be less than 10；Then it is then added in 100 grams of 20wt% HCl solution, controls temperature 80
DEG C and constant temperature stir 1 hour, with 80 DEG C of distillation water washings to pH value be 7, obtain the porous amorphous alloy skeleton.
Weigh 2g ammonium thiomolybdates to be dissolved in 98ml deionized waters, 60 DEG C are heated to, by above-mentioned porous amorphous alloy
Skeleton is added in ammonium thiomolybdate solution, and after stirring 1h, 10% ammonia spirit regulation pH to 6 or so is slowly added dropwise.60
Aging 8h is stood after being precipitated under the conditions of DEG C, filters and is washed with deionized to neutrality, sediment is put into 80 DEG C of vacuum drying chamber
Dry, sediment is put into tube furnace after drying, and is passed through nitrogen protection and is warming up to more than 300 DEG C decomposition and obtains co hydrogenation
The catalyst of producing light olefins, catalyst numbering is catalyst -1, and composition is shown in Table 1.
Embodiment 2
1.5 kilograms of iron, 1.0 kilograms of silicon and 0.1 kilogram of cobalt are added in graphite crucible, it is heated in coreless induction furnace
Melting, the fused solution is sprayed onto on the copper roller that a rotating speed is 900 revs/min at crucible nozzle, cooling water, aluminium alloy are led in copper roller
To be got rid of after 1000-1600 DEG C/sec of cooling velocity quickly cooling along copper roller tangent line in water, flakey band, scale are formed
Shape band it is ground to particle diameter be less than 500 microns, obtain foundry alloy.50g foundry alloys are slowly added into and fill 500 grams
In the there-necked flask of 20wt% sodium hydrate aqueous solutions, its temperature is controlled to be stirred 1 hour for 60 DEG C and constant temperature.Stop heating and stirring
Afterwards, liquid is filtered off, distillation water washing to pH value is added and is less than 10；Then it is then added in 100 grams of 20wt% salpeter solution, controls
Simultaneously constant temperature stirs 1 hour 80 DEG C of temperature processed, is 7 with 80 DEG C of distillation water washings to pH value, obtains the porous amorphous alloy
Skeleton.
Weigh 2g ammonium thiomolybdates to be dissolved in 98ml deionized waters, 60 DEG C are heated to, by above-mentioned porous amorphous alloy
Skeleton is added in ammonium thiomolybdate solution, and after stirring 1h, 10% ammonia spirit regulation pH to 6 or so is slowly added dropwise.60
Aging 8h is stood after being precipitated under the conditions of DEG C, filters and is washed with deionized to neutrality, sediment is put into 80 DEG C of vacuum drying chamber
Dry, sediment is put into tube furnace after drying, and is passed through nitrogen protection and is warming up to more than 300 DEG C decomposition and obtains co hydrogenation
The catalyst of producing light olefins, catalyst numbering is catalyst -2, and composition is shown in Table 1.
Embodiment 3
1.5 kilograms of iron, 1.5 kilograms of silicon and 0.2 kilogram of manganese are added in graphite crucible, it is heated in coreless induction furnace
Melt, then the fused solution is sprayed onto at crucible nozzle on the copper roller that a rotating speed is 1000 revs/min, and cooling water is led in copper roller, is closed
Golden liquid after 1000-1600 DEG C/sec of cooling velocity quickly cooling along copper roller tangent line to get rid of in water, formation flakey band,
Flakey band it is ground to particle diameter be less than 500 microns, obtain foundry alloy.50g foundry alloys are slowly added into and filled
In the there-necked flask of 500 grams of 20wt% sodium hydrate aqueous solutions, its temperature is controlled to be stirred 1 hour for 60 DEG C and constant temperature.Stop heating
After stirring, liquid is filtered off, distillation water washing to pH value is added and is less than 10；Then it is then added to 100 grams of 20wt% HNO3It is molten
In liquid, simultaneously constant temperature stirs 1 hour 80 DEG C of temperature of control, is 7 with 80 DEG C of distillation water washings to pH value, obtains the porous amorphous
State alloy skeleton.
Weigh 2g ammonium thiomolybdates to be dissolved in 98ml deionized waters, 60 DEG C are heated to, by above-mentioned porous amorphous alloy
Skeleton is added in ammonium thiomolybdate solution, and after stirring 1h, 10% ammonia spirit regulation pH to 6 or so is slowly added dropwise.60
Aging 8h is stood after being precipitated under the conditions of DEG C, filters and is washed with deionized to neutrality, sediment is put into 80 DEG C of vacuum drying chamber
Dry, sediment is put into tube furnace after drying, and is passed through nitrogen protection and is warming up to more than 300 DEG C decomposition and obtains co hydrogenation
The catalyst of producing light olefins, catalyst numbering is catalyst -3, and composition is shown in Table 1.
Embodiment 4
1.5 kilograms of iron, 1.5 kilograms of silicon and 0.2 kilogram of copper are added in graphite crucible, it is heated in coreless induction furnace
Melt, then the fused solution is sprayed onto at crucible nozzle on the copper roller that a rotating speed is 800 revs/min, and cooling water, alloy are led in copper roller
Liquid forms flakey band, squama to be got rid of after 1000-1600 DEG C/sec of cooling velocity quickly cooling along copper roller tangent line in water
Sheet-like strip it is ground to particle diameter be less than 500 microns, obtain foundry alloy.50g foundry alloys are slowly added into and fill 500
In the there-necked flask of gram 20wt% sodium hydrate aqueous solutions, its temperature is controlled to be stirred 1 hours for 60 DEG C and constant temperature.Stop heating and stir
After mixing, liquid is filtered off, distillation water washing to pH value is added and is less than 10；Then it is then added in 100 grams of 20wt% HCl solution,
Control 80 DEG C of temperature and constant temperature stirs 1 hour, be 7 with 80 DEG C of distillation water washings to pH value, obtain the porous amorphous conjunction
Golden skeleton.
Weigh 2g ammonium thiomolybdates to be dissolved in 98ml deionized waters, 60 DEG C are heated to, by above-mentioned porous amorphous alloy
Skeleton is added in ammonium thiomolybdate solution, and after stirring 1h, 10% ammonia spirit regulation pH to 6 or so is slowly added dropwise.60
Aging 8h is stood after being precipitated under the conditions of DEG C, filters and is washed with deionized to neutrality, sediment is put into 80 DEG C of vacuum drying chamber
Dry, sediment is put into tube furnace after drying, and is passed through nitrogen protection and is warming up to more than 300 DEG C decomposition and obtains co hydrogenation
The catalyst of producing light olefins, catalyst numbering is catalyst -4, and composition is shown in Table 1.
Embodiment 5
1.5 kilograms of iron, 1.5 kilograms of silicon and 0.2 kilogram of cerium are added in graphite crucible, it is heated in coreless induction furnace
Melt, then the fused solution is sprayed onto at crucible nozzle on the copper roller that a rotating speed is 600 revs/min, and cooling water, alloy are led in copper roller
Liquid forms flakey band, squama to be got rid of after 1000-1600 DEG C/sec of cooling velocity quickly cooling along copper roller tangent line in water
Sheet-like strip it is ground to particle diameter be less than 500 microns, obtain foundry alloy.50g foundry alloys are slowly added into and fill 500
In the there-necked flask of gram 20wt% sodium hydrate aqueous solutions, its temperature is controlled to be stirred 1 hours for 60 DEG C and constant temperature.Stop heating and stir
After mixing, liquid is filtered off, distillation water washing to pH value is added and is less than 10；Then it is then added in 100 grams of 20wt% HCl solution,
Control 80 DEG C of temperature and constant temperature stirs 1 hour, be 7 with 80 DEG C of distillation water washings to pH value, obtain the porous amorphous conjunction
Golden skeleton.
Weigh 2g ammonium thiomolybdates to be dissolved in 98ml deionized waters, 60 DEG C are heated to, by above-mentioned porous amorphous alloy
Skeleton is added in ammonium thiomolybdate solution, and after stirring 1h, 10% ammonia spirit regulation pH to 6 or so is slowly added dropwise.60
Aging 8h is stood after being precipitated under the conditions of DEG C, filters and is washed with deionized to neutrality, sediment is put into 80 DEG C of vacuum drying chamber
Dry, sediment is put into tube furnace after drying, and is passed through nitrogen protection and is warming up to more than 300 DEG C decomposition and obtains co hydrogenation
The catalyst of producing light olefins, catalyst numbering is catalyst -5, and composition is shown in Table 1.
The method that embodiment 6-10 provides the co hydrogenation producing light olefins of the present invention.
Embodiment 6-10
The catalyst that embodiment 6-10 is provided using 1-5 of the embodiment of the present invention is in fixed bed reactors in same reaction
Under the conditions of carry out co hydrogenation producing light olefins, specific reaction result is shown in Table 2, and specific reaction condition is：Catalyst packing
0.5 gram, 340 DEG C of reaction temperature, 2.0 MPas of reaction pressure, the mol ratio 2 of hydrogen and carbon monoxide, gas volume air speed 6000
Hour-1。
From table 2 it can be seen that carrying out co hydrogenation producing light olefins using the inventive method, CO high conversion rates are low
Carbene hydrocarbon-selective is good.
Table 1
Table 2
| Embodiment | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 |
| Catalyst is numbered | Catalyst -1 | Catalyst -2 | Catalyst -3 | Catalyst -4 | Catalyst -5 |
| CO conversion ratios, weight % | 84.1 | 84.8 | 87.1 | 89.7 | 88.4 |
| CO2Selectivity, weight % | 5.7 | 6.2 | 7.3 | 7.7 | 6.4 |
| Hydrocarbon-selective, weight % | |||||
| CH4 | 12.4 | 11.6 | 13.7 | 12.2 | 11.7 |
| C2H4 | 21.3 | 19.4 | 21.3 | 16.7 | 20.3 |
| C2H6 | 2.7 | 4.1 | 3.8 | 4.4 | 4.8 |
| C3H6 | 24.5 | 19.1 | 18.7 | 17.8 | 19.1 |
| C3H8 | 5.2 | 5.7 | 5.5 | 6.2 | 5.8 |
| C4H8 | 13.1 | 15.6 | 14.1 | 15.7 | 13.5 |
| C4H10 | 3.4 | 4.5 | 5.2 | 5.6 | 4.7 |
| C5 + | 17.4 | 20.0 | 17.7 | 21.4 | 20.1 |
| It is total | 100 | 100 | 100 | 100 | 100 |
Claims (11)
1. a kind of catalyst of co hydrogenation producing light olefins, the catalyst includes porous amorphous alloy skeleton and load
Molybdenum component on the porous amorphous alloy skeleton, the porous amorphous alloy skeleton include iron and silicon, the molybdenum component
For molybdenum sulfide and/or the presoma of molybdenum sulfide；Wherein, it is described to urge on the basis of the gross weight of catalyst and in terms of element wt
The content of iron is 45-95 weight % in agent, and the content of silicon is 3-40 weight %, and the content of molybdenum is 1-10 weight %, and sulphur contains
Measure as 0.1-5 weight %.
2. catalyst according to claim 1, wherein, on the basis of the gross weight of catalyst and in terms of element wt, institute
It is selected from I B-group metal, II B to state metal M, the metal M of the porous amorphous alloy skeleton also including 0.1-40 weight %
In race's metal, Group IIIB metal, group ivb metal, vib metals, V Group IIB metal and group VIII metal extremely
Few one kind.
3. catalyst according to claim 2, wherein, the metal M is selected from least one of cobalt, manganese, copper and cerium.
4. catalyst according to claim 1, wherein, on the basis of the gross weight of catalyst and in terms of element wt, institute
The content for stating iron in catalyst is 70-85 weight %, and the content of silicon is 10-25 weight %, and the content of molybdenum is 1-3 weight %, sulphur
Content be 2-4 weight %.
5. a kind of preparation method of the catalyst of co hydrogenation producing light olefins, this method include：
A, quenching processing will be carried out after the alloy skeleton raw material mixed melting including iron and silicon, obtains foundry alloy；
B, gained foundry alloy in step a is stripped desiliconization, obtains porous amorphous alloy skeleton；
C, on porous amorphous alloy skeleton, co hydrogenation will be obtained obtained by the presoma load in stepb of molybdenum sulfide
The catalyst of producing light olefins；
Wherein, on the basis of the gross weight of catalyst and in terms of element wt, the content of iron is 45-95 weights in the catalyst
% is measured, the content of silicon is 3-40 weight %, and the content of molybdenum is 1-10 weight %, and the content of sulphur is 0.1-5 weight %.
6. preparation method according to claim 5, wherein, the alloy skeleton raw material also includes metal M, the metal M
For selected from I B-group metal, group iib metal, Group IIIB metal, group ivb metal, vib metals, V Group IIB gold
At least one of category and group VIII metal, on the basis of the gross weight of catalyst and in terms of element wt, the catalyst
Middle metal M content is 0.1-40 weight %.
7. preparation method according to claim 6, wherein, the metal M is at least one in cobalt, manganese, copper and cerium
Kind.
8. preparation method according to claim 5, wherein, the processing of quenching described in step a includes：By alloy skeleton raw material
Mixed melting liquid be ejected into 600-1000 revs/min and be connected with the copper roller of cooling water, make the mixed melting liquid with 1000-
1600 DEG C/sec of cooling velocity cools down simultaneously to be thrown away along copper roller tangent line, obtained flakey band alloy through being crushed to 20-200 mesh,
Obtain the foundry alloy；
The step of desiliconization is extracted described in step b includes：Gained foundry alloy in step a is carried out into caustic extraction in alkali lye to take off
Silicon, obtain caustic extraction desiliconization alloy；Gained caustic extraction desiliconization alloy is subjected to acid solution extracting desiliconization in acid solution, obtains institute
State porous amorphous alloy skeleton；Wherein, the condition of the caustic extraction desiliconization is：Temperature is 0-100 DEG C, time 10-60
Minute, the molar concentration of alkali lye is 1-12 mol/Ls, and the alkali in alkali lye is sodium hydroxide and/or potassium hydroxide, foundry alloy and alkali
The weight ratio of alkali is 1 in liquid：(1-10)；The condition of acid solution extracting desiliconization is：Temperature is 0-100 DEG C, time 10-120
Minute, the molar concentration of acid solution be 1-12 mol/Ls, and the acid in acid solution is hydrochloric acid and/or nitric acid, sour in foundry alloy and acid solution
Weight ratio is 1：(0.4-10)；
The method loaded described in step c is the precipitation method and/or infusion process.
9. according to the preparation method described in claim 5, wherein, described in step c by the presoma load of molybdenum sulfide in stepb
Step on gained porous amorphous alloy skeleton includes：By porous amorphous alloy skeleton described in step b and thio molybdic acid
Ammoniacal liquor is added after ammonium salt solution mixing, ammonium thiomolybdate is precipitated on porous amorphous alloy skeleton, sediment will be attached with
After porous amorphous alloy skeleton is calcined, the catalyst of co hydrogenation producing light olefins is obtained.
10. a kind of method of co hydrogenation producing light olefins, this method include：By in carbon monoxide and claim 1-4
The catalyst of co hydrogenation producing light olefins described in any one contacts and under hydroconversion condition in hydrogenation reactor
Carry out hydrogenation preparing low-carbon olefins.
11. the method for co hydrogenation producing light olefins according to claim 10, wherein, the hydroconversion condition bag
Include：Temperature is 200-500 DEG C, and pressure is 0.5-15.0 MPas, and gas volume air speed is 500-100000 hours-1, hydrogen and one
The mol ratio 0.5-10 of carbonoxide；The hydrogenation reactor is anti-selected from paste state bed reactor, fluidized-bed reactor and fixed bed
Answer at least one of device.
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| CN114425385A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin by Fischer-Tropsch synthesis and preparation method and application thereof |
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