CN108855086A - Catalyst and its preparation method and application and the method that mixed alcohol is prepared as raw material using synthesis gas - Google Patents
Catalyst and its preparation method and application and the method that mixed alcohol is prepared as raw material using synthesis gas Download PDFInfo
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- 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
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- 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
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- 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
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
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Abstract
The present invention relates to technical field of petrochemical industry, discloses a kind of catalyst and its preparation method and application and in the method that synthesis gas prepares mixed alcohol as raw material, the active component of the catalyst is CuaCobAlcMd, wherein a：b：c：D is the molar ratio of Cu, Co, Al, M, and a：b：c：D is 1：0.5-4：0.01-1：At least one of 0-1, M Mn, Zr, Ce, Mg, Mo, Re, K, Na and Cs.Catalyst of the invention is particularly suitable for paste state bed reactor, and using being preceding not required to by pre-reduction treatment, in the reaction of synthesis gas mixed alcohol, alcohol distribution and good stability with high reactivity, high CO conversion ratio, the selectivity of high alcohol and high C2-C4.
Description
Technical field
The present invention relates to technical field of petrochemical industry, and in particular to a kind of catalyst and its preparation method and application and one
The method that kind prepares mixed alcohol as raw material using synthesis gas.
Background technique
As the consumption of petroleum resources increases, the synthesis gas produced by natural gas or coal or reproducible biomass resource
(CO and H2Mixed gas) preparation low-carbon alcohols cause great concern.Low carbon mixed alcohol is free of aromatic series, also not sulfur-bearing,
Fuel and chemical field are widely used.Low carbon mixed alcohol can be used as clean gasoline additive, since it is with very high octane number
And explosion-proof and anti-seismic performance is superior, can substitute the additive that MTBE etc. is more toxic；In addition, low-carbon alcohols are also used as coal liquid
One of means of change realize the alkylation of coal and solubilized and as liquefied petroleum gas substitute etc..
Currently, there are four types of the catalyst of the direct synthesizing low-carbon mixed alcohol of synthesis gas of report：Using Rh as the noble metal of representative
Catalyst, the catalst for synthesis of methanol of modification, the Mo base catalyst of modification and the fischer-tropsch synthetic catalyst of modification.Wherein, with Rh
The features such as though noble metal catalyst for representative has good hydrogenation activity, and ethanol selectivity is preferable, and it is expensive, easy in inactivation
It limits its application.Modified catalst for synthesis of methanol operating condition is harsh, and product is still based on methanol.Modified Mo base is urged
Though agent has unique resistance to SO_2, and aqueous less in product, low-carbon alcohol content is higher, the hydrogen-carbon ratio requirement to unstripped gas
Harshness, and the catalyst promoter easily with CO formed carbonyls, cause the loss of its constituent element, thus its stability by
Limitation.
In modified fischer-tropsch synthetic catalyst Cu-Co base catalyst in a mild condition it is with higher activity and low-carbon alcohols
Selectivity, it is considered to be the higher alcohols synthesis catalyst with application prospect.In Cu-Co base catalyst, the main function of Cu is
The non-Dissociative of hydrogen dissociation and CO, Co can then dissociate CO to increase carbochain and hydrogenation reaction, i.e. Cu-Co synergistic effect life
At low carbon mixed alcohol.Document [Chinese Journal of Catalysis, 2013,34 (1):116-129],[Angew
Chem IntEd Engl, 2014,53 (25):6397-401] in report, copper-cobalt alloy plays an important role to the synthesis of low-carbon alcohols.
The framework metal alloy catalyst of fusion method preparation can make metal component be uniformly distributed to form alloy, and have
The features such as high intensity, high activity, high thermal stability and longer service life.Report is used for the bone of synthesis gas mixed alcohol at present
The report of frame metal alloy catalyst is seldom.Chinese patent application CN101164692A reports a kind of system of skeletal Co catalysts
It is ready for use on Fischer-Tropsch synthesis and prepares hydrocarbon product activity and selectivity with higher.Chinese patent application CN105080545A
Report a kind of skeleton alloy catalyst for synthesis gas isobutanol, the selectivity of the catalyst alcohol is up to 60%, isobutanol
Account for 30% or more of total alcohol.Chinese patent application CN105085185A reports a kind of method for preparing plasticizer alcohol, this method
Cu-Co-Fe base catalyst is prepared, for synthesizing syngas conversion reactor, wherein the selectivity of plasticizer alcohol is 20% or so.
Be not only related to alcohol synthesis reaction in the reaction of synthesis gas mixed alcohol directly processed, in addition there are Fischer-Tropsch synthesis and
Water gas shift reaction, these reactions are all strong exothermal reactions, and are selected from the reaction of thermodynamic analysis synthesis gas mixed alcohol
Selecting property is greatly influenced by temperature, and heat transfer is controlled in reaction process, so as to react can be stable progress, and in fixed bed
React and unavoidably will lead to hot-spot, make catalyst inactivation, selectivity declines.Paste state bed reactor due to have compared with
High production efficiency, mass-and heat-transfer performance is good, and reaction temperature profile uniformly control easy to operate can effectively avoid hot-spot
Caused by temperature runaway phenomena such as.
Chinese patent application CN 101384363A discloses a kind of preparation method of slurry bed system alcohol synthetic catalyst, this is urged
Alkali metal formate is supported on Cu/MgO solid catalyst by agent, can load one or both of Na, Pd simultaneously.China
Patent application CN102179251A discloses a kind of synthesizing methanol by fluidized bed catalyst and preparation method thereof, and the catalyst is by copper
Zinc (aluminium zirconium can be contained) active component presoma and binder composition.Chinese patent application CN102802783A discloses a kind of methanol
Synthetic method, catalyst are made of the oxide of one or more of copper zinc-aluminium and further auxiliary, auxiliary agent have Mg, Cr, Mn,
V、Ti、Zr、Ta、Mo、W、Si。
The catalyst activity component that above-mentioned patent application is related to is existed in oxide form, and slurry bed system is directly applied to
It must be restored in advance when reactor, and the reduction in paste state bed reactor is extremely difficult, and generates in product and be with methanol
It is main.It is therefore desirable to develop the synthesis gas mixed alcohol catalyst of a kind of suitable paste state bed reactor being not required to by prereduction.
Summary of the invention
The purpose of the invention is to overcome the above-mentioned problems in the prior art, a kind of catalyst and its preparation are provided
Methods and applications and a kind of method for preparing mixed alcohol as raw material using synthesis gas, catalyst of the invention are particularly suitable for slurry
Bed reactor, and using being preceding not required to by pre-reduction treatment, in the reaction of synthesis gas mixed alcohol, have high reactivity,
The selectivity of high CO conversion ratio, high alcohol and the alcohol distribution of high C2-C4 and good stability.
To achieve the goals above, in a first aspect, the present invention provides a kind of catalyst, the active component of the catalyst is
CuaCobAlcMd, wherein a：b：c：D is the molar ratio of Cu, Co, Al, M, and a：b：c：D is 1：0.5-4：0.01-1：0-1, M are
At least one of Mn, Zr, Ce, Mg, Mo, Re, K, Na and Cs.
Second aspect, the present invention provides the preparation method of catalyst of the present invention, this method includes：Will by copper,
The fusant solidification of the alloy of cobalt, aluminium and optionally at least one metal M composition, then carries out aqueous slkali for the alloy after solidification
Extracting processing is to extract most aluminium out；Or the product that aqueous slkali extracting is handled is immersed in the salting liquid of metal M.
The third aspect, the present invention provides catalyst of the present invention to prepare the anti-of mixed alcohol by raw material of synthesis gas
Application in answering.
Fourth aspect, the present invention provides a kind of method for preparing mixed alcohol as raw material using synthesis gas, this method includes：It will
Synthesis gas is contacted with catalyst of the present invention.
Compared with prior art, catalyst particle size of the invention is evenly distributed, wear-resisting, and wear-resistant index is high, urges before reaction
Agent does not need to be restored, and reaction temperature and pressure are lower, can be applied to paste state bed reactor or fixed bed reactors simultaneously,
It is particularly suitable for paste state bed reactor transformation of synthetic gas mixed alcohol.In addition, in the reaction of synthesis gas mixed alcohol, it is of the invention
Catalyst has the alcohol distribution of high reactivity, high CO conversion ratio, the selectivity of high alcohol and high C2-C4, Yi Jiliang
Good stability.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
In a first aspect, the active component of the catalyst is Cu the present invention provides a kind of catalystaCobAlcMd, wherein
a：b：c：D is the molar ratio of Cu, Co, Al, M, and a：b：c：D is 1：(0.5-4)：(0.01-1)：(0-1), M Mn, Zr, Ce,
At least one of Mg, Mo, Re, K, Na and Cs.
In catalyst of the invention, in order to make catalyst have higher reactivity, higher CO conversion ratio, more is had both
The alcohol of the selectivity of high alcohol and higher C2-C4 are distributed, under preferable case, a：b：c：D is 1：(1-3)：(0.01-0.1)：
(0.1-0.8)。
In catalyst of the invention, in order to further increase the reactivity of catalyst, the selection of CO conversion ratio, alcohol is improved
Property and C2-C4 alcohol distribution, under preferable case, at least one of M Mn, Zr, Ce, Mg and K.The present inventor is grinding
It is had been surprisingly found that in studying carefully, when M is at least two in Mn, Zr, Ce, Mg and K, at least three kinds preferably in Mn, Zr, Ce, Mg and K
When, be capable of it is more apparent improve CO conversion ratio, alcohol selectivity and C2-C4 alcohol distribution, it is therefore preferable that in the case of, M Mn, Zr,
At least two in Ce, Mg and K, at least three kinds further preferably in Mn, Zr, Ce, Mg and K.And the present inventor
Further study show that when the group merging that M is Mn and/or Mg, Zr and/or Ce and K is combined with special ratios, it can be more into one
Step improves the reactivity of catalyst, the alcohol distribution of CO conversion ratio, the selectivity of alcohol and C2-C4 is improved, it is therefore preferred that M is
Mn and/or Mg, Zr and/or Ce and K combination (i.e. M is made of three dvielements, one kind be Mn and/or Mg, one kind be Zr and/
Or Ce, another kind of is K)；It is further preferred that the content of Mn and/or Mg are rubbed on the basis of the total mole number of M for 20-50
The content of your %, Zr and/or Ce are 50-80 moles of %, and the content of K is 0-15 moles of %.
In catalyst of the invention, under preferable case, the granular size of the catalyst is 8-400 mesh, further preferably
It is still more preferably 80-200 mesh for 50-300 mesh.
Second aspect, the present invention provides the preparation method of catalyst of the present invention, this method includes：Will by copper, cobalt,
(quick) solidification of the fusant of the alloy of aluminium and optionally at least one metal M composition, then carries out alkali for the alloy after solidification
Solution extracting processing is to extract most aluminium out；Or the salt that the product that aqueous slkali extracting is handled is immersed in metal M is molten
In liquid.
In method of the invention, the dosage between type and copper, cobalt, aluminium, metal M for metal M be can refer to above
Corresponding description is selected, and it is no longer repeated herein.
It include using atwirl by fusant (quick) cured method in the case of process of the present invention it is preferred
The rotation speed of single roller or the cooling fusant of double roller, the list roller or double roller is 500-1500 revs/min and (may make fusant with big
In the cooling rate rapid curing of 1000 DEG C/s), or by fusant (quick) cured method include use 1300 DEG C with
The cooling fusant of the mode of upper spray atomization and deposition.
In the case of process of the present invention it is preferred, the method for the aqueous slkali extracting processing includes：Under stiring, will consolidate
Alloy after change has been heated in the aqueous slkali of extraction temperature, reacts the aluminium in alloy sufficiently with aqueous slkali, consolidate
Body catalyst, wherein extraction temperature is 10-100 DEG C (further preferably 40-90 DEG C), and the concentration of aqueous slkali is 2-40 weight
It measures % (further preferably 10-20 weight %), extraction times are 5-600min (further preferably 30-120min), alloy
Granular size is 8-400 mesh (further preferably 50-300 mesh is still more preferably 80-200 mesh), the weight of alloy and alkali
Than being 1:1-10 (further preferably 1:1.5-4).
In method of the invention, the granular size of catalyst can be by before carrying out aqueous slkali extracting processing, to solid
The granular size of alloy after change control it is accomplished, and the control method be this field conventional method (such as pass through ball
Grinding machine is ground), this is well known to those skilled in the art, and details are not described herein.
In the case of process of the present invention it is preferred, the aqueous slkali is soluble strong base solution, further preferably alkali gold
Belong to and/or the hydroxide solution of alkaline-earth metal, is still more preferably NaOH solution, KOH solution and Ba (OH)2In solution
At least one, much further preferably from NaOH solution and/or KOH solution.
It will be understood by those skilled in the art that can be made by the condition for controlling aforementioned aqueous slkali extracting processing
The molar ratio of each element is in range described previously in catalyst activity component.
In the case of process of the present invention it is preferred, the salting liquid of the metal M is alkali metal salt soln, further preferably
It is still more preferably KNO for the nitrate solution of alkali metal and/or the carbonate solution of alkali metal3Solution, K2CO3Solution,
Cs2CO3Solution and CsNO3At least one of solution.Wherein, the concentration of the salting liquid of metal M can be 0.01-1mol/L, leaching
The time of stain can be 1-24h.The condition of dipping is controlled in aforementioned range, can make the amount of alkali metal in catalyst to be
0.001-1 moles of %.
In method of the invention, the catalyst product that aqueous slkali extracting is handled can use distilled water or deionized water
(50-100 DEG C) washing then with dehydrated alcohol displacement distilled water or deionized water, and is saved to neutral (pH value 6.0-8.0)
In dehydrated alcohol, preferably saved under conditions of having inert gas or hydrogen shield；Or aqueous slkali extracting is handled to obtain
Catalyst product be immersed in the salting liquid of metal M, use dehydrated alcohol after then being washed 3-5 times with distilled water or deionized water
It washs and is stored in dehydrated alcohol, preferably saved under conditions of having inert gas or hydrogen shield.
The third aspect, the present invention provides catalyst of the present invention to prepare the anti-of mixed alcohol by raw material of synthesis gas
Application in answering.
Preferably, the mixed alcohol is the mixed alcohol of C1-C5, the further preferably mixed alcohol of C2-C4.
Fourth aspect, the present invention provides a kind of method for preparing mixed alcohol as raw material using synthesis gas, this method includes：It will
Synthesis gas is contacted with catalyst of the present invention.
Of the invention prepares in the method for mixed alcohol by raw material of synthesis gas, and the contact can be in paste state bed reactor
It carries out, can also be carried out in fixed bed reactors.
Under preferable case, contact carries out in paste state bed reactor, and this method includes：First catalyst and organic solvent are mixed
Conjunction forms slurries, then contacts synthesis gas with slurries, wherein the condition of the contact includes：Temperature is 180-450
DEG C, pressure 0.5-15MPa, H2Molar ratio with CO is 0.5-10：1, on the basis of the weight of organic solvent, catalyst it is dense
Degree is 5-40 weight %, and the air speed of synthesis gas is 0.5-10NL/ (gcath).In the present invention, mentioned pressure is gauge pressure.
Preferably, the organic solvent is at least one of atoleine, decahydronaphthalene and diphenyl ether.
Embodiment
The present invention will be described in detail by way of examples below, but is not intended to limit the present invention.Following embodiment
In comparative example, unless otherwise instructed, method used is the conventional method of this field, and each material used is commercially available to be obtained
, subscript indicates the molar ratio of each element in the composition of each catalyst.
The content of each element is measured with inductively coupled plasma direct-reading spectrometer (ICP) in catalyst.
The calculation formula of CO conversion ratio is：XCO=100 × [(nCO)in-(nCO)out]/(nCO)in, wherein XCOFor CO conversion
Rate, (nCO)inFor the molal quantity of CO in charging, (nCO)outFor the molal quantity of CO in discharging.
The calculation formula of the selectivity of a certain alcohol is：YAlcohol=N × 100 × nAlcohol/(nCO)in, wherein YAlcoholFor the choosing of the alcohol
Selecting property, N are the carbon atom number contained in the alcohol, nAlcoholFor the molal quantity of the alcohol in discharging, (nCO)inFor mole of CO in charging
Number；The selectivity of total alcohol is the sum of the selectivity of each alcohol.
Embodiment 1
The present embodiment is for illustrating catalyst and preparation method thereof of the invention.
640g Cu, 1180g Co, 2000g Al, 25g Mg, 90g Zr and 140g Ce are added in graphite crucible,
It is heated to melting in coreless induction furnace, then be sprayed onto the molten liquid from crucible nozzle on the copper roller that one revolving speed is 800 revs/min, copper
Lead to cooling water in roller, molten liquid is thrown away after being quickly cooled down along copper roller tangent line, forms band-like alloy, and band-like alloy passes through ball mill
Being ground to particle diameter is 100-200 mesh, obtains master alloy.Under stiring, 50g master alloy is slowly added into and fills 500 grams
In the three-necked flask of 20wt% sodium hydrate aqueous solution, its temperature is controlled as 70 DEG C and constant temperature stirs 1 hour.Stop heating and stirs
After mixing, decantation liquid, being washed with 90 DEG C of deionized water to pH value is 7, then catalyst is immersed in the KNO of 0.10mol/L3
24 hours in solution, first it is washed with deionized 3 times, then washed and be stored in dehydrated alcohol with dehydrated alcohol, is catalyzed
Agent C-1, calculates after measured, and the group of catalyst becomes Cu1Co2Mg0.11Zr0.1Ce0.11K0.05Al0.05。
Embodiment 2
The present embodiment is for illustrating catalyst and preparation method thereof of the invention.
640g Cu, 1180g Co, 2000g Al, 55g Mn and 180g Zr are added in graphite crucible, in coreless induction furnace
In be heated to melting, then by the molten liquid 1500 DEG C temperature carry out spray atomization and deposition, formed alloy, the alloy pass through
Ball mill grinding to particle diameter is 100-200 mesh, obtains master alloy.Under stiring, 50g master alloy is slowly added into and is filled
1500 grams of 20wt%Ba (OH)2In the three-necked flask of aqueous solution, its temperature is controlled as 60 DEG C and constant temperature stirs 1.5 hours.Stop
After heating and stirring, decantation liquid is 7 with 90 DEG C of distillation water washings to pH value, catalyst is then immersed in 0.1mol/L
KNO324 hours in solution, first it is washed with distilled water 4 times, then washed and be stored in dehydrated alcohol with dehydrated alcohol, obtains
Catalyst C-2, calculates after measured, and the group of catalyst becomes Cu1Co2Mn0.11Zr0.2K0.05Al0.05。
Embodiment 3
The present embodiment is for illustrating catalyst and preparation method thereof of the invention.
640g Cu, 1180g Co, 2100g Al, 25g Mg and 280g Ce are added in graphite crucible, in coreless induction furnace
In be heated to melting, then it is to lead in copper roller on 800 revs/min of copper roller which is sprayed onto a revolving speed from crucible nozzle
Cooling water, molten liquid are thrown away after being quickly cooled down along copper roller tangent line, form band-like alloy, and band-like alloy passes through ball mill grinding extremely
Particle diameter is 250-350 mesh, obtains master alloy.Under stiring, 50g master alloy is slowly added into and fills 500 grams of 20wt%
In the three-necked flask of sodium hydrate aqueous solution, its temperature is controlled as 70 DEG C and constant temperature stirs 1 hour.After stopping heating and stirring,
Decantation liquid is 7 with 90 DEG C of distillation water washings to pH value, then catalyst is immersed in the K of 0.05mol/L2CO3In solution
It 24 hours, is first washed with distilled water 3 times, then washed and be stored in dehydrated alcohol with dehydrated alcohol, obtains catalyst C-3, pass through
The group of measure and calculation, catalyst becomes Cu1Co2Mg0.11Ce0.2K0.05Al0.05。
Embodiment 4
The present embodiment is for illustrating catalyst and preparation method thereof of the invention.
640g Cu, 590g Co, 1400g Al, 55g Mn and 180g Zr are added in graphite crucible, in coreless induction furnace
It is heated to melting, then the molten liquid is sprayed on the copper roller that a revolving speed is 600 revs/min from crucible nozzle, is led in copper roller cold
But water, molten liquid are thrown away after being quickly cooled down along copper roller tangent line, form band-like alloy, band-like alloy by ball mill grinding to
Grain diameter is 80-180 mesh, obtains master alloy.Under stiring, 50g master alloy is slowly added into and fills 750 grams of 10wt% hydrogen-oxygens
In the three-necked flask for changing aqueous solutions of potassium, its temperature is controlled as 90 DEG C and constant temperature stirs 40 minutes.After stopping heating and stirring, decantation
Liquid is 7 with 90 DEG C of distillation water washings to pH value, then catalyst is immersed in the KNO of 0.1mol/L324 is small in solution
When, it is first washed with distilled water 3 times, then washed and be stored in dehydrated alcohol with dehydrated alcohol, obtains catalyst C-4, after measured
It calculates, the group of catalyst becomes Cu1Co1Mn0.11Zr0.2K0.05Al0.01。
Embodiment 5
The present embodiment is for illustrating catalyst and preparation method thereof of the invention.
640g Cu, 1770g Co, 3000g Al, 75g Mg and 560g Ce are added in graphite crucible, in coreless induction furnace
In be heated to melting, then it is to lead in copper roller on 1500 revs/min of copper roller which is sprayed onto a revolving speed from crucible nozzle
Cooling water, molten liquid are thrown away after being quickly cooled down along copper roller tangent line, form band-like alloy, and band-like alloy passes through ball mill grinding extremely
Particle diameter is 200-300 mesh, obtains master alloy.Under stiring, 50g master alloy is slowly added into and fills 1330 grams of 15wt%
In the three-necked flask of sodium hydrate aqueous solution, its temperature is controlled as 50 DEG C and constant temperature stirs 2 hours.After stopping heating and stirring,
Decantation liquid is 7 with 90 DEG C of distillation water washings to pH value, then catalyst is immersed in the KNO of 0.1mol/L324 in solution
Hour, it is first washed with distilled water 3 times, then washed and be stored in dehydrated alcohol with dehydrated alcohol, catalyst C-5 is obtained, through surveying
Devise a stratagem is calculated, and the group of catalyst becomes Cu1Co3Mg0.33Ce0.4K0.05Al0.1。
Embodiment 6
According to the method for embodiment 1, unlike, the composition of M changes in catalyst, and step is specific as follows：
640g Cu, 1180g Co, 2000g Al, 9.6g Mg, 90g Zr and 140g Ce are added in graphite crucible,
It is heated to melting in coreless induction furnace, then be sprayed onto the molten liquid from crucible nozzle on the copper roller that one revolving speed is 800 revs/min,
Lead to cooling water in copper roller, molten liquid is thrown away after being quickly cooled down along copper roller tangent line, forms band-like alloy, and band-like alloy passes through ball milling
It is 100-200 mesh that machine, which is ground to particle diameter, obtains master alloy.Under stiring, 50g master alloy is slowly added into and fills 500
In the three-necked flask of gram 25wt% sodium hydrate aqueous solution, control that its temperature is 80 DEG C and constant temperature stirs 1 hour.Stop heating and
After stirring, decantation liquid, being washed with 90 DEG C of deionized water to pH value is 7, and catalyst is then immersed in 0.10mol/L's
KNO324 hours in solution, first it is washed with deionized 3 times, then washed and be stored in dehydrated alcohol with dehydrated alcohol, obtains
Catalyst C-6, calculates after measured, and the group of catalyst becomes Cu1Co2Mg0.04Zr0.13Ce0.15K0.05Al0.05。
Embodiment 7
According to the method for embodiment 1, unlike, the composition of M changes in catalyst, and step is specific as follows：
640g Cu, 1180g Co, 2000g Al, 53g Mg, 45.5g Zr and 70g Ce are added in graphite crucible,
It is heated to melting in coreless induction furnace, then be sprayed onto the molten liquid from crucible nozzle on the copper roller that one revolving speed is 800 revs/min,
Lead to cooling water in copper roller, molten liquid is thrown away after being quickly cooled down along copper roller tangent line, forms band-like alloy, and band-like alloy passes through ball milling
It is 100-200 mesh that machine, which is ground to particle diameter, obtains master alloy.Under stiring, 50g master alloy is slowly added into and fills 500
In the three-necked flask of gram 25wt% sodium hydrate aqueous solution, control that its temperature is 80 DEG C and constant temperature stirs 1 hour.Stop heating and
After stirring, decantation liquid, being washed with 90 DEG C of deionized water to pH value is 7, and catalyst is then immersed in 0.10mol/L's
KNO324 hours in solution, first it is washed with deionized 3 times, then washed and be stored in dehydrated alcohol with dehydrated alcohol, obtains
Catalyst C-7, calculates after measured, and the group of catalyst becomes Cu1Co2Mg0.22Zr0.05Ce0.05K0.05Al0.05。
Embodiment 8
According to the method for embodiment 1, unlike, the amount of Co and Al changes in the composition of catalyst, and step is specific
It is as follows：
640g Cu, 295g Co, 1200g Al, 25g Mg, 90g Zr and 140g Ce are added in graphite crucible,
It is heated to melting in coreless induction furnace, then be sprayed onto the molten liquid from crucible nozzle on the copper roller that one revolving speed is 800 revs/min, copper
Lead to cooling water in roller, molten liquid is thrown away after being quickly cooled down along copper roller tangent line, forms band-like alloy, and band-like alloy passes through ball mill
Being ground to particle diameter is 100-200 mesh, obtains master alloy.Under stiring, 50g master alloy is slowly added into and fills 500 grams
In the three-necked flask of 25wt% sodium hydrate aqueous solution, its temperature is controlled as 80 DEG C and constant temperature stirs 1 hour.Stop heating and stirs
After mixing, decantation liquid, being washed with 90 DEG C of deionized water to pH value is 7, then catalyst is immersed in the KNO of 0.10mol/L3
24 hours in solution, first it is washed with deionized 3 times, then washed and be stored in dehydrated alcohol with dehydrated alcohol, is catalyzed
Agent C-8, calculates after measured, and the group of catalyst becomes Cu1Co0.5Mg0.11Zr0.1Ce0.11K0.05Al0.01。
Embodiment 9
According to the method for embodiment 1, unlike, the amount of Co and Al changes in the composition of catalyst, and step is specific
It is as follows：
640g Cu, 2360g Co, 3800g Al, 75g Mg, 270g Zr and 420g Ce are added in graphite crucible,
It is heated to melting in coreless induction furnace, then be sprayed onto the molten liquid from crucible nozzle on the copper roller that one revolving speed is 800 revs/min,
Lead to cooling water in copper roller, molten liquid is thrown away after being quickly cooled down along copper roller tangent line, forms band-like alloy, and band-like alloy passes through ball milling
It is 100-200 mesh that machine, which is ground to particle diameter, obtains master alloy.Under stiring, 50g master alloy is slowly added into and fills 500
In the three-necked flask of gram 10wt% sodium hydrate aqueous solution, control that its temperature is 70 DEG C and constant temperature stirs 1 hour.Stop heating and
After stirring, decantation liquid, being washed with 90 DEG C of deionized water to pH value is 7, and catalyst is then immersed in 0.1mol/L's
KNO324 hours in solution, first it is washed with deionized 3 times, then washed and be stored in dehydrated alcohol with dehydrated alcohol, obtains
Catalyst C-9, calculates after measured, and the group of catalyst becomes Cu1Co4Mg0.31Zr0.3Ce0.33K0.05Al1。
Embodiment 10
According to the method for embodiment 1, unlike, the group of catalyst becomes Cu1Co2Al0.05, step is specific as follows：
640g Cu, 1180g Co and 1820g Al are added in graphite crucible, are heated to melting in coreless induction furnace, so
The molten liquid is sprayed onto afterwards on the copper roller that a revolving speed is 800 revs/min from crucible nozzle, cooling water, molten liquid warp are led in copper roller
It is thrown away after rapid cooling along copper roller tangent line, forms band-like alloy, band-like alloy is 100- by ball mill grinding to particle diameter
200 mesh, obtain master alloy.Under stiring, 50g master alloy is slowly added into and fills 500 grams of 20wt% sodium hydrate aqueous solutions
Three-necked flask in, controlling its temperature is that 70 DEG C and constant temperature stir 1 hour.After stopping heating and stirring, decantation liquid, with 90 DEG C
Deionized water to wash to pH value be 7, then wash and is stored in dehydrated alcohol with dehydrated alcohol, obtain catalyst C-10, warp
The group of measure and calculation, catalyst becomes Cu1Co2Al0.05。
Embodiment 11
According to the method for embodiment 1, unlike, the group of catalyst becomes Cu1Co2Mn0.2Al0.05, step is specific as follows：
640g Cu, 1180g Co, 2000g Al and 110g Mn are added in graphite crucible, are heated in coreless induction furnace
Then the molten liquid is sprayed on the copper roller that a revolving speed is 800 revs/min from crucible nozzle, cooling water is led in copper roller, melts by melting
Melt liquid to throw away after being quickly cooled down along copper roller tangent line, forms band-like alloy, band-like alloy is by ball mill grinding to particle diameter
For 100-200 mesh, master alloy is obtained.Under stiring, 50g master alloy is slowly added into and fills 500 grams of 20wt% sodium hydroxides
In the three-necked flask of aqueous solution, its temperature is controlled as 70 DEG C and constant temperature stirs 1 hour.After stopping heating and stirring, decantation liquid,
Being washed with 90 DEG C of deionized water to pH value is 7, then is washed and be stored in dehydrated alcohol with dehydrated alcohol, obtains catalyst C-
11, it calculates after measured, the group of catalyst becomes Cu1Co2Mn0.2Al0.05。
Embodiment 12
According to the method for embodiment 1, unlike, the group of catalyst becomes Cu1Co2Mg0.2Al0.05, step is specific as follows：
640g Cu, 1180g Co, 2000g Al and 50g Mg are added in graphite crucible, are heated in coreless induction furnace
Then the molten liquid is sprayed on the copper roller that a revolving speed is 800 revs/min from crucible nozzle, cooling water is led in copper roller, melts by melting
Melt liquid to throw away after being quickly cooled down along copper roller tangent line, forms band-like alloy, band-like alloy is by ball mill grinding to particle diameter
For 100-200 mesh, master alloy is obtained.Under stiring, 50g master alloy is slowly added into and fills 500 grams of 20wt% sodium hydroxides
In the three-necked flask of aqueous solution, its temperature is controlled as 70 DEG C and constant temperature stirs 1 hour.After stopping heating and stirring, decantation liquid,
Being washed with 90 DEG C of deionized water to pH value is 7, then is washed and be stored in dehydrated alcohol with dehydrated alcohol, obtains catalyst C-
12, it calculates after measured, the group of catalyst becomes Cu1Co2Mg0.2Al0.05。
Embodiment 13
According to the method for embodiment 1, unlike, the group of catalyst becomes Cu1Co2Zr0.1Ce0.11Al0.05, step is specific
It is as follows：
640Cu, 1180g Co, 2000g Al, 140g Ce and 90g Zr are added in graphite crucible, in coreless induction furnace
It is heated to melting, then the molten liquid is sprayed on the copper roller that a revolving speed is 800 revs/min from crucible nozzle, is led in copper roller cold
But water, molten liquid are thrown away after being quickly cooled down along copper roller tangent line, form band-like alloy, band-like alloy by ball mill grinding to
Grain diameter is 100-200 mesh, obtains master alloy.Under stiring, 50g master alloy is slowly added into and fills 500 grams of 20wt% hydrogen
In the three-necked flask of aqueous solution of sodium oxide, its temperature is controlled as 70 DEG C and constant temperature stirs 1 hour.After stopping heating and stirring, strain
Liquid is removed, being washed with 90 DEG C of deionized water to pH value is 7, then is washed and be stored in dehydrated alcohol with dehydrated alcohol, is obtained
Catalyst C-13, calculates after measured, and the group of catalyst becomes Cu1Co2Zr0.1Ce0.11Al0.05。
Embodiment 14
According to the method for embodiment 1, unlike, the group of catalyst becomes Cu1Co2Re0.2Al0.05, step is specific as follows：
640g Cu, 1180g Co, 2000g Al and 300g Re are added in graphite crucible, are heated in coreless induction furnace
Then the molten liquid is sprayed on the copper roller that a revolving speed is 800 revs/min from crucible nozzle, cooling water is led in copper roller, melts by melting
Melt liquid to throw away after being quickly cooled down along copper roller tangent line, forms band-like alloy, band-like alloy is by ball mill grinding to particle diameter
For 100-200 mesh, master alloy is obtained.Under stiring, 50g master alloy is slowly added into and fills 500 grams of 20wt% sodium hydroxides
In the three-necked flask of aqueous solution, its temperature is controlled as 70 DEG C and constant temperature stirs 1 hour.After stopping heating and stirring, decantation liquid,
Being washed with 90 DEG C of deionized water to pH value is 7, then is washed and be stored in dehydrated alcohol with dehydrated alcohol, obtains catalyst C-
14, it calculates after measured, the group of catalyst becomes Cu1Co2Re0.2Al0.05。
Embodiment 15
According to the method for embodiment 1, unlike, the group of catalyst becomes Cu1Co2K0.05Al0.05, step is specific as follows：
640g Cu, 1180g Co and 2000g Al are added in graphite crucible, are heated to melting in coreless induction furnace, so
The molten liquid is sprayed onto afterwards on the copper roller that a revolving speed is 800 revs/min from crucible nozzle, cooling water, molten liquid warp are led in copper roller
It is thrown away after rapid cooling along copper roller tangent line, forms band-like alloy, band-like alloy is 100- by ball mill grinding to particle diameter
200 mesh, obtain master alloy.Under stiring, 50g master alloy is slowly added into and fills 500 grams of 20wt% sodium hydrate aqueous solutions
Three-necked flask in, controlling its temperature is that 70 DEG C and constant temperature stir 1 hour.After stopping heating and stirring, decantation liquid, with 90 DEG C
Deionized water wash to pH value be 7, then catalyst is immersed in the KNO of 0.10mol/L324 hours in solution, first spend
Ion water washing 3 times, then washed and be stored in dehydrated alcohol with dehydrated alcohol, catalyst C-15 is obtained, is calculated after measured, is urged
The group of agent becomes Cu1Co2K0.05Al0.05。
Embodiment 16
According to the method for embodiment 1, unlike, the group of catalyst becomes Cu1Co2Cs0.05Al0.05, step is specifically such as
Under：
640g Cu, 1180g Co and 2000g Al are added in graphite crucible, are heated to melting in coreless induction furnace, so
The molten liquid is sprayed onto afterwards on the copper roller that a revolving speed is 800 revs/min from crucible nozzle, cooling water, molten liquid warp are led in copper roller
It is thrown away after rapid cooling along copper roller tangent line, forms band-like alloy, band-like alloy is 100- by ball mill grinding to particle diameter
200 mesh, obtain master alloy.Under stiring, 50g master alloy is slowly added into and fills 500 grams of 20wt% sodium hydrate aqueous solutions
Three-necked flask in, controlling its temperature is that 70 DEG C and constant temperature stir 1 hour.After stopping heating and stirring, decantation liquid, with 90 DEG C
Deionized water wash to pH value be 7, then catalyst is immersed in the CsNO of 0.1mol/L324 hours in solution, first spend
Ion water washing 3 times, then washed and be stored in dehydrated alcohol with dehydrated alcohol, catalyst C-16 is obtained, is calculated after measured, is urged
The group of agent becomes Cu1Co2Cs0.05Al0.05。
Comparative example 1
According to the method for embodiment 1, unlike, the group of catalyst becomes Co1Al0.04, step is specific as follows：
1180g Co and 2000g Al are added in graphite crucible, is heated to melting in coreless induction furnace, then melts this
Melt liquid to be sprayed onto from crucible nozzle on the copper roller that a revolving speed is 800 revs/min, cooling water is led in copper roller, molten liquid is through being quickly cooled down
It is thrown away afterwards along copper roller tangent line, forms band-like alloy, band-like alloy is 100-200 mesh by ball mill grinding to particle diameter, is obtained
To master alloy.Under stiring, 50g master alloy is slowly added into three mouthfuls of burnings for filling 500 grams of 20wt% sodium hydrate aqueous solutions
In bottle, its temperature is controlled as 70 DEG C and constant temperature stirs 1 hour.After stopping heating and stirring, decantation liquid, with 90 DEG C of deionization
Water washing to pH value is 7, is washed and is stored in dehydrated alcohol with dehydrated alcohol, obtained catalyst D-1, calculate after measured, urge
The group of agent becomes Co1Al0.04。
Comparative example 2
According to the method for embodiment 1, unlike, the group of catalyst becomes Cu1Co2, step is specific as follows：
640g Cu and 1180g Co are added in graphite crucible, are heated to melting in coreless induction furnace, then by the melting
Liquid is sprayed on the copper roller that a revolving speed is 800 revs/min from crucible nozzle, cooling water is led in copper roller, molten liquid is after being quickly cooled down
It is thrown away along copper roller tangent line, forms band-like alloy, band-like alloy is 100-200 mesh by ball mill grinding to particle diameter, is obtained
Master alloy.Under stiring, 50g master alloy is slowly added into the three-necked flask for filling 500 grams of 20wt% sodium hydrate aqueous solutions
In, its temperature is controlled as 70 DEG C and constant temperature stirs 1 hour.After stopping heating and stirring, decantation liquid, with 90 DEG C of deionized water
Washing to pH value is 7, is washed and is stored in dehydrated alcohol with dehydrated alcohol, obtained catalyst D-2, calculate after measured, is catalyzed
The group of agent becomes Cu1Co2。
Comparative example 3
Catalyst D-3 is prepared according to the method for embodiment 3 in patent application CN101164692A, the group of the catalyst becomes
Cu0.04Co1.5Al0.33The molar ratio of each element (under be designated as), i.e. Co88.5Al8.9Cu2.6The weight ratio of each element (under be designated as).
Comparative example 4
Catalyst D-4 is prepared according to the method for embodiment 7 in CN 105085185A, the group of the catalyst becomes
Cu57.32Co5.68Fe22.87Ce2.10Al12.03The weight ratio of each element (under be designated as).
Test example 1-16
The reaction that test example 1-16 is used to illustrate catalyst of the invention for paste state bed reactor synthesis gas mixed alcohol
Effect.
Using paste state bed reactor, the obtained catalyst of embodiment 1-16 and atoleine are mixed to form slurries respectively,
On the basis of the weight of atoleine, the concentration of catalyst is 10 weight %, then seals into reactor, is passed through synthesis gas and sets
Air in reactor is changed, then at 300 DEG C of reaction temperature, reaction pressure 5.0MPa, agitator speed 800rpm, H2With CO's
Molar ratio is 2.0, and for volume space velocity to be reacted under the conditions of 4.0NL/ (gcath), reaction result is as shown in table 1.
Test example 17
According to the method for test example 1, the difference is that, answering pressure is 3.0MPa.
Test example 18
According to the method for test example 1, the difference is that, reaction temperature is 230 DEG C.
Comparative experimental example 1-4
According to the method for test example 1, the difference is that, catalyst is substituted with the catalyst that comparative example 1-4 is obtained respectively.Reaction
The results are shown in Table 1.
Table 1
Can be seen that by the result of table 1 and use catalyst of the invention is former with synthesis gas in paste state bed reactor
Expect Synthesis of mixed alcohols, be not required to before use by pre-reduction treatment, which has high reactivity, high CO conversion
The alcohol of rate, the selectivity of high alcohol and high C2-C4 is distributed.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of catalyst, which is characterized in that the active component of the catalyst is CuaCobAlcMd, wherein a：b：c：D be Cu,
The molar ratio of Co, Al, M, and a：b：c：D is 1：0.5-4：0.01-1：In 0-1, M Mn, Zr, Ce, Mg, Mo, Re, K, Na and Cs
At least one.
2. catalyst according to claim 1, wherein a：b：c：D is 1：1-3：0.01-0.1：0.1-0.8.
3. catalyst according to claim 1 or 2, wherein at least one of M Mn, Zr, Ce, Mg and K, preferably
At least two in Mn, Zr, Ce, Mg and K, it is at least three kinds further preferably in Mn, Zr, Ce, Mg and K, further excellent
It is selected as the combination of Mn and/or Mg, Zr and/or Ce and K；Still further preferably, on the basis of the total mole number of M, Mn and/or
The content of Mg is that the content of 20-50 moles of %, Zr and/or Ce are 50-80 moles of %, and the content of K is 0-15 moles of %.
4. the preparation method of catalyst described in any one of claim 1-3, which is characterized in that this method includes：It will be by
The fusant solidification for the alloy that copper, cobalt, aluminium and optionally at least one metal M are formed, then carries out alkali for the alloy after solidification
Solution extracting processing is to extract most aluminium out；Or the salt that the product that aqueous slkali extracting is handled is immersed in metal M is molten
In liquid.
5. according to the method described in claim 4, wherein, by the cured method of fusant include using atwirl single roller or
The rotation speed of double roller cooling fusant, the list roller or double roller is 500-1500 revs/min, or
It include using fusant cooling by the way of 1300 DEG C or more spray atomization and depositions by the cured method of fusant.
6. method according to claim 4 or 5, wherein the aqueous slkali extracts the method handled and includes：Under stiring,
Alloy after solidification is heated in the aqueous slkali of extraction temperature, wherein extraction temperature is 10-100 DEG C, aqueous slkali
Concentration is 2-40 weight %, and extraction times 5-600min, alloying pellet size is 8-400 mesh, and the weight ratio of alloy and alkali is
1:1-10。
7. method according to any one of claims 4 to 6, wherein the aqueous slkali is soluble strong base solution, excellent
It is selected as the hydroxide solution of alkali metal and/or alkaline-earth metal, further preferably NaOH solution, KOH solution and Ba (OH)2It is molten
At least one of liquid；And/or
The salting liquid of the metal M is alkali metal salt soln, the preferably carbonic acid of the nitrate solution of alkali metal and/or alkali metal
Salting liquid, further preferably KNO3Solution, K2CO3Solution, Cs2CO3Solution and CsNO3At least one of solution.
8. catalyst answering in the reaction for preparing mixed alcohol as raw material using synthesis gas described in any one of claim 1-3
With；
Preferably, the mixed alcohol is the mixed alcohol of C1-C5, the further preferably mixed alcohol of C2-C4.
9. a kind of method for preparing mixed alcohol as raw material using synthesis gas, which is characterized in that this method includes：By synthesis gas and right
It is required that catalyst described in any one of 1-3 contacts.
10. according to the method described in claim 9, wherein, the contact in paste state bed reactor or fixed bed reactors into
Row；
Preferably, the contact carries out in paste state bed reactor, and this method includes：Catalyst and organic solvent are first mixed into shape
At slurries, then synthesis gas is contacted with slurries, wherein the condition of the contact includes：Temperature is 180-450 DEG C, pressure
Power is 0.5-15MPa, H2Molar ratio with CO is 0.5-10：1, on the basis of the weight of organic solvent, the concentration of catalyst is
5-40 weight %, the air speed of synthesis gas are 0.5-10NL/ (gcath)；
Preferably, the organic solvent is at least one of atoleine, decahydronaphthalene and diphenyl ether.
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| CN110280261A (en) * | 2019-06-19 | 2019-09-27 | 中国科学院山西煤炭化学研究所 | It is a kind of by the catalyst and its preparation method of the direct synthesizing alcohol of synthesis gas and application |
| CN112495385A (en) * | 2020-11-26 | 2021-03-16 | 中国科学院山西煤炭化学研究所 | CuCo-based composite catalyst for preparing higher alcohol from synthesis gas and preparation method and application thereof |
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| CN105080545A (en) * | 2014-05-23 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst used for CO hydrogenation to prepare isobutanol, and method for preparing isobutanol through CO hydrogenation |
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