CN102266790A - Catalyst for synthesizing C2-C18 high alcohol and preparation method thereof - Google Patents
Catalyst for synthesizing C2-C18 high alcohol and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a catalyst for synthesizing C2-C18 high alcohol and a preparation method thereof. The preparation method comprises the following steps of: by taking at least one of CoO and Co3O4 as a precursor, firstly generating metal Co after a reduction activation step is carried out on the raw material, and carbonizing a part of metal Co into Co2C through a temperature-programmed carbonization method to prepare the catalyst including mixed components of Co2C and metal Co grains. The method for synthesizing high alcohol by synthesis gas in the invention has a simple process, and the synthesized liquid product is a mixture of C2-C18 high alcohol and C5-C20 naphtha/diesel oil, wherein the mass percentage of the C2-C18 high alcohol can be up to 10-40%. The preparation method disclosed by the invention has a higher economic benefit and a very strong industrial application prospect.
Description
Technical field
The present invention relates to the higher alcohols field, particularly relate to a kind of synthetic C
2-C
18The Catalysts and its preparation method of higher alcohols.
Background technology
Higher alcohols are synthetic surfactants, the main basic material of washing agent and plasticizer and other multiple fine chemistry industry, and processed goods has important application in fields such as weaving, papermaking, food, medicine, leather thereafter.Whole world C
12Above higher alcohols market every year is with 3.9% speed increment, China is a higher alcohols consumption big country, the higher alcohols market prospects are wide, fast development along with Chinese national economy, the raising day by day of living standards of the people is also progressively increasing the demand of higher alcohols series of products and derivative product thereof.
The method of industrial production higher alcohols has two classes at present: the one, and be the conversion method synthol of raw material with the natural oil, mainly contain two kinds of oil hydrogenation method and aliphatic acid hydrogenation methods, and China does not possess industrialness oil sources scale, can't realize large-scale production.The 2nd, be the chemical synthesis production higher alcohols of raw material with the petroleum derivative product, comprise ziegler process and oxo synthesis, but these two kinds of methods exist all technological process long, technical sophistication, the problem that production cost is high.
Transition metal carbide is cheap and have a catalytic performance of class noble metal.This compounds be carbon atom enter the lattice of transition metal and the class that forms have metalline between fill compound.1973, RB Levy found that tungsten carbide has shown class noble metal character in a series of catalytic reactions, as the water of catalysis oxyhydrogen reaction generation at room temperature.Co
2C is a kind of in the transition metal carbide, is found in nineteen thirty by H A Bahr and V Jessen the earliest.Co
2C has superior catalysis to generate the performance of alcohol.Xu and G.G.Volkova etc. discover, contain Co in the Cu-Co catalyst
2C, this catalyst are used for F-T when synthetic, except hydrocarbon products, also contain more C in the product
1-C
6Alcohol.
Summary of the invention
The purpose of this invention is to provide a kind of synthetic C
2-C
18The Catalysts and its preparation method of higher alcohols.
Provided by the inventionly be used for synthetic C
2-C
18The catalyst of higher alcohols comprises Co
2C nano particle and Co nano particle; Described Co
2The mass ratio of C nano particle and Co nano particle is 1-4: 1.
Described Co
2The mass ratio of C nano particle and Co nano particle is 1.5: 1; Describedly be used for synthetic C
2-C
18In the catalyst of alcohol, also comprise graphite; The quality of described graphite is the 1-15% of described catalyst gross weight, preferred 5%.Above-mentioned catalyst can only be made up of said components, also can be made up of above-mentioned two components and graphite.Particle diameter is 0.1～3 millimeter after the described shaping of catalyst.
Preparation provided by the invention is above-mentioned to be used for synthetic C
2-C
18The method of the catalyst of alcohol comprises the steps:
1) with Co
3O
4Carry out reduction activation reaction with at least a among the CoO with hydrogen or by the mist that hydrogen and inert gas are formed;
2) in the reaction system of step 1), feed carbonaceous gas and carry out carburizing reagent, carry out passivation reaction with the mist of forming by oxygen and inert gas after reaction finishes, add the graphite mixing again, obtain the described synthetic C that is used for behind the compression molding
2-C
18The catalyst of alcohol.
In the described step 1), in the described mist of being made up of hydrogen and inert gas, hydrogen content is 1-90%, preferred 30-60%, and the volume space velocity of the mist of described hydrogen and hydrogen and inert gas is 300-5000h
-1, specifically can be 200-500h
-1Or 500-2000h
-1, preferred 200～2000h
-1The temperature of described reduction activation is 473-673K, specifically can be 523-573K or 573-673K, preferred 523-673K, the time is 2-48 hour, preferred 5-10 hour, pressure is 0.05-2.00MPa, preferred 0.1-0.5MPa, the heating rate that is risen to described reduction activation temperature by room temperature is 50-100K/h, preferred 80K/h; Described Co
3O
4With CoO with both mixtures during as reactant, described Co
3O
4Be preferably 1: 1 with the mass ratio of CoO.This step can make Co
3O
4Or CoO is reduced to metal Co, thereby makes that in carbonisation subsequently a part of metal Co carbonization is Co
2C.
Described step 2) in, described carbonaceous gas and described Co
3O
4When carrying out carburizing reagent with the mixture of CoO, described Co
3O
4With the mass ratio of CoO be 1-5: 1, preferred 2: 1; Described carbonaceous gas is single-component gas or multicomponent gas, and described single-component gas is CO, CH
4, C
2H
6Or C
3H
8, described multicomponent gas is by CO, CH
4, C
2H
6And C
3H
8In any one and following gas in any one composition: hydrogen, nitrogen and argon gas; In the described multicomponent gas, the percent by volume of the described multicomponent gas of gas comprises of carbon elements is 1-90%; The volume space velocity of described carbonaceous gas is 100～5000h
-1, preferred 500～2000h
-1In the described carburizing reagent, reaction temperature is 473～673K, specifically can be 473-493K, 473-523K or 493-523K, the reaction time is 1～500 hour, specifically can be 48-120 hour, 48-300 hour or 120-300 hour, preferred 10-300 hour, reaction pressure is 0.05～2.00MPa, preferred 0.1～0.5MPa, and the heating rate that is risen to described reaction temperature by room temperature is 0.5～20K/h, specifically can be 2-15K/h or 10-15K/h, preferred 2～10K/h; The purpose of described passivation reaction is to prevent the spontaneous combustion in air of active catalyst exposure, and wherein, described inert gas is at least a in nitrogen, helium and the argon gas; In the described mist of being made up of oxygen and inert gas, the volume ratio that oxygen accounts for gaseous mixture is 0.001～0.5%, preferred 0.001～0.1% or 0.1～0.5%; The consumption of described graphite is the 1-15% of described catalyst gross weight, and is preferred 5%, and the volume space velocity of the described mist of being made up of oxygen and inert gas is 100～1000h
-1, preferred 200～500h
-1, in the described passivation reaction, reaction temperature is 278-298K, and the reaction time is 1～10 hour, and preferred 2～5 hours, pressure was 0.05-2.00MPa, is preferably 0.1MPa.
In the above-mentioned method for preparing catalyst, can pass through the modulation preparation condition, as the kind of carbonization gas, air speed, temperature programming speed, carburizing temperature and the carbonization time of carbonization gas, to Co
2The structure of C and nano metal Co, particle diameter and the ratio between the two are regulated and control, thereby obtain to have advantages of high catalytic activity and catalyst optionally.
Above-mentioned steps 1) in, Co
3O
4The available following Co of containing compound and getting, as cobalt nitrate, cobalt oxalate, citric acid cobalt or malic acid cobalt, preferred cobalt nitrate.Preparation Co
3O
4Method specifically comprise thermal decomposition method, the precipitation method etc.Wherein, thermal decomposition method prepares Co
3O
4Concrete grammar be: contain the roasting in Muffle furnace of Co compound with above-mentioned, its heating rate is 1～5K/min, and sintering temperature is 523～723K, and roasting time is 10～30 hours, and the atmosphere of roasting can be air, oxygen or nitrogen etc.
The present invention also provides synthetic C
2-C
18The method of alcohol, this method comprises the steps:
1) is used for synthetic C with described
2-C
18The catalyst of alcohol carries out the reduction activation reaction with hydrogen or by the mist that hydrogen and inert gas are formed;
2) described catalyst activated and hydrogen and carbon monoxide are reacted, obtain described C
2-C
18Alcohol.
The step 1) reduction activation reaction of said method is micro-CoO or the Co in order to generate in above-mentioned passivation reaction process
3O
4Hydrogenating reduction is a metal Co, obtains catalyst activated.In the described mist of being made up of hydrogen and inert gas, the volume ratio that hydrogen accounts for described mist is 1-90%, preferred 50-80%, and the volume space velocity of described hydrogen is 300-5000h
-1, preferred 200～2000h
-1, the volume space velocity of the mist of described hydrogen and inert gas is 300-5000h
-1, preferred 200～2000h
-1, the temperature of described reduction activation is 573-873K, preferred 623-723K, time is 2-48 hour, and preferred 5-10 hour, pressure was 0.05-2.00MPa, preferred 0.1-0.5MPa, the heating rate that is risen to described reduction activation temperature by room temperature is 20-100K/h, preferred 80K/h;
The consumption of described catalyst activated is 4ml, and reaction temperature is 430～550K, preferred 483-503K, and reaction pressure is 0.1～10.0MPa, preferred 3.0～5.0MPa, the reaction time is 45-55 hour, preferred 50 hours; The volume space velocity of described hydrogen and carbon monoxide is 100～10000h
-1, preferred 500～2000h
-1The volume ratio of described hydrogen and carbon monoxide is 1: 2; This step is carried out in fixed bed reactors.
Method by the synthesis gas synthesizing bigh carbon alcohol provided by the invention, technology is simple, and the gained fluid product is C
2～C
18Higher alcohols and C
5～C
20Naphtha, the mixture of diesel oil, wherein, C
2～C
18The quality percentage composition of higher alcohols can reach 10-40%.Higher alcohols and derivative thereof have premium properties such as unit output value height, added value be big, have obtained using widely in the every field of national economy.Wherein the market price of the high carbon straight primary alcohol of even carbon is at 15000～20000 yuan/ton, and the market price of the high carbon straight primary alcohol of odd number carbon is at 40000～50000 yuan/ton.The demand of present global higher alcohols is 2,100,000 tons/year.And China is a higher alcohols consumption big country, be that plastic products, washing agent, surfactant and other fine chemical product all have wide consumption market, so this method has very high economic benefit and very strong prospects for commercial application.
The specific embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.
Embodiment 1, preparation catalyst A
1) gets 100 gram Co (NO
3)
26H
2O puts into the Muffle furnace roasting, and heating rate is set at 3K/min, roasting 12 hours in air atmosphere under the 623K temperature.After being cooled to room temperature, obtain Co
3O
4With 10ml (9.83 gram) Co
3O
4Put into crystal reaction tube and carry out reduction activation, activation process is used hydrogen, and activation pressure is 0.1MPa, and volume space velocity is 500h
-1, heating rate is 80K/h, rises to 523K and activate 5 hours under this temperature.
2) be cooled to room temperature after, switch to CO gas and carry out the temperature programming carburizing reagent.Carbonization pressure is 0.1MPa, and the volume space velocity of CO is 500h
-1, heating rate is 10K/h, carbonization is 48 hours under the 473K temperature.
3) after the carbonization, system reduces to room temperature and switches to passivation gas, at room temperature carries out passivation, and passivation gas is for containing 0.1%O
2The O of (volume ratio)
2/ N
2Gaseous mixture, passivation pressure are 0.1MPa, and volume space velocity is 100h
-1, passivation time is 5 hours.At last catalyst is taken out from quartz reactor, add graphite, after stirring, compression molding obtains catalyst A provided by the invention, and wherein, graphite accounts for 5% of described catalyst A gross weight.
The granularity of this catalyst A is 0.5mm.By above-mentioned preparation method as can be known, this catalyst A is by Co
2C nano particle, Co nano particle and graphite are formed, and wherein, the quality of described graphite is 5% of a described catalyst gross weight, Co
2The mass ratio of C nano particle and Co nano particle is 1.5: 1.
Embodiment 2, preparation catalyst B
According to being prepared, only with the Co that obtains among the embodiment 1 with embodiment 1 identical method and condition
3O
4, directly carry out carbonization, passivation, and do not carry out reduction activation, obtain catalyst B, the granularity after this catalyst B moulding is 1mm.
Embodiment 3, preparation catalyst C
Be prepared Co according to method and the condition identical with embodiment 1
3O
4, and with gained Co
3O
4It is mixed by 1: 1 mass ratio with commercially available CoO and grind, press the identical method of embodiment 1 again, carry out reduction activation, carbonization and passivation, preparation catalyst C, the granularity after this catalyst C moulding is 2mm.By above-mentioned preparation method as can be known, this catalyst C is by Co
2C nano particle, Co nano particle and graphite are formed, and wherein, the quality of described graphite is 5% of a described catalyst gross weight, Co
2The mass ratio of C nano particle and Co nano particle is 1.5: 1.
Embodiment 4, preparation catalyst D
According to being prepared, only with the Co among the embodiment 3 with embodiment 3 identical methods and condition
3O
4Directly carry out carbonization and passivation with the CoO mixture, and do not carry out reduction activation, obtain catalyst D, the granularity after this catalyst D moulding is 1mm.
Embodiment 5, preparation catalyst E
Carry out reduction activation, carbonization and passivation according to embodiment 1 identical method and condition, only with used Co
3O
4Replace with commercially available CoO, prepare catalyst E, the granularity after this catalyst E moulding is 1mm.By above-mentioned preparation method as can be known, this catalyst E is by Co
2C nano particle, Co nano particle and graphite are formed, and wherein, the quality of described graphite is 5% of a described catalyst gross weight, Co
2The mass ratio of C nano particle and Co nano particle is 1.5: 1.
Embodiment 6, preparation catalyst F
According to embodiment 5 identical method and conditions, directly carry out carbonization and passivation, and do not carry out reduction activation, preparation catalyst F, the granularity after this catalyst F moulding is 0.5mm.
Embodiment 7, preparation catalyst G
According to being prepared with embodiment 1 identical method and condition, only the reduction activation temperature among the embodiment 1 is adjusted into 573K, obtain catalyst G provided by the invention, the granularity after this catalyst G moulding is 1mm.By above-mentioned preparation method as can be known, this catalyst G is by Co
2C nano particle, Co nano particle and graphite are formed, and wherein, the quality of described graphite is 5% of a described catalyst gross weight, Co
2The mass ratio of C nano particle and Co nano particle is 1.5: 1.
Embodiment 8, preparation catalyst H
According to being prepared with embodiment 1 identical method and condition, only the reduction activation temperature among the embodiment 1 is adjusted into 673K, obtain catalyst H provided by the invention, the granularity after this catalyst H moulding is 0.5mm.By above-mentioned preparation method as can be known, this catalyst H is by Co
2C nano particle, Co nano particle and graphite are formed, and wherein, the quality of described graphite is 5% of a described catalyst gross weight, Co
2The mass ratio of C nano particle and Co nano particle is 1.5: 1.
Embodiment 9, preparation catalyst I
According to being prepared with embodiment 1 identical method and condition, only change the carburizing temperature among the embodiment 1 into 493K, obtain catalyst I provided by the invention, the granularity after this catalyst I moulding is 1mm.By above-mentioned preparation method as can be known, this catalyst I is by Co
2C nano particle, Co nano particle and graphite are formed, and wherein, the quality of described graphite is 5% of a described catalyst gross weight, Co
2The mass ratio of C nano particle and Co nano particle is 1.5: 1.
Embodiment 10, preparation catalyst J
According to being prepared with embodiment 1 identical method, only the carburizing temperature among the embodiment 1 is adjusted into 523K, obtain catalyst J provided by the invention, the granularity after this catalyst J moulding is 1mm.By above-mentioned preparation method as can be known, this catalyst J is by Co
2C nano particle, Co nano particle and graphite are formed, and wherein, the quality of described graphite is 5% of a described catalyst gross weight, Co
2The mass ratio of C nano particle and Co nano particle is 1.5: 1.
Embodiment 11, preparation catalyst K
According to being prepared with embodiment 1 identical method and condition, only the heating rate that rises to carburizing temperature from room temperature among the embodiment 1 is adjusted into 15K/h, obtain catalyst K provided by the invention, the granularity after this catalyst K moulding is 0.5mm.By above-mentioned preparation method as can be known, this catalyst K is by Co
2C nano particle, Co nano particle and graphite are formed, and wherein described, the quality of described graphite is 5% of a described catalyst gross weight, Co
2The mass ratio of C nano particle and Co nano particle is 1.5: 1.
Embodiment 12, preparation catalyst L
According to being prepared, only the carbonization gas among the embodiment 1 is replaced by C with embodiment 1 identical method and condition
3H
8Gas obtains catalyst L provided by the invention, and the granularity after this catalyst L moulding is 1mm.By above-mentioned preparation method as can be known, this catalyst L is by Co
2C nano particle, Co nano particle and graphite are formed, and wherein, the quality of described graphite is 5% of a described catalyst gross weight, Co
2The mass ratio of C nano particle and Co nano particle is 1.5: 1.
Embodiment 13, preparation catalyst M
According to being prepared with embodiment 1 identical method and condition, only the carbonization time among the embodiment 1 is adjusted into 120 hours, obtain catalyst M provided by the invention, the granularity after this catalyst M moulding is 1mm.By above-mentioned preparation method as can be known, this catalyst M is by Co
2C nano particle, Co nano particle and graphite are formed, and wherein, the quality of described graphite is 5% of a described catalyst gross weight, Co
2The mass ratio of C nano particle and Co nano particle is 1.5: 1.
Embodiment 14, preparation C
2-C
18Higher alcohols
Arbitrary preparation gained catalyst among the foregoing description 1-13 is packed in the fixed bed reactors, and the loadings of catalyst is 4ml, carries out the in-situ activation reaction with hydrogen, obtains catalyst activated, and wherein, the air speed of hydrogen is 1000h
-1, heating rate is 80K/h, and the priming reaction temperature is 673K, and priming reaction pressure is 0.3MPa, and the priming reaction time is 10 hours; After priming reaction finishes, with temperature of reaction system reduce to switch to below the 373K that carbon monoxide and hydrogen mix with volume ratio at 2: 1 and gaseous mixture react, the air speed of this gaseous mixture is 500h
-1, reaction temperature is 493K, and reaction pressure is 3.0MPa, and the reaction time is 50 hours, obtains reactor product, comprises C
2-C
18Higher alcohols, C
1-C
4Gaseous hydrocarbon, C
5-C
20The mixture of naphtha and diesel oil and a small amount of C
21 +Solid hydrocarbons (＜3%).Reactivity worth is listed in table 1.
In order to obtain indexs such as CO conversion ratio, carbon number selectivity and liquid product composition, hydrogenation reaction product is collected with the product collecting tank, the temperature maintenance of collecting tank is at 273～293K, tail gas emptying after the counterbalance valve release, exhaust flow is measured by flowmeter, the fluid product of collecting comprises water/oily two-phase, and after the standing demix method was divided into water and oil phase two parts, analytical calculation obtained CO conversion ratio and the C in this catalytic reaction
2-C
18Indexs such as the selectivity of higher alcohols.Its tail gas adopts HP-6890 gas chromatograph, TCD detector, the on-line analysis of Porapack-Q packed column.The every 50h setting-out of liquid product once, oil phase and water HP-6890 gas chromatograph, 5%PH ME capillary column, fid detector off-line analysis.Oil-phase product is calculated and is adopted normalization method, mark in the water-phase product analysis is done with sec-butyl alcohol.
Conversion ratio and the product selectivity of CO are calculated by following formula:
Conversion ratio (%)=∑ (N
CO, in-N
CO, out)/N
CO, in* 100%
Carbon number selectivity: Si=(Ni * Ci/ ∑ Ni * Ci) * 100% (calculate product selectivity) with the C molal quantity
Liquid phase organic product selectivity: Si=Wi/ ∑ Wi * 100% (calculating product selectivity by weight)
Wherein: N
CO, in: the molal quantity of CO in the unstripped gas; N
CO, out: the molal quantity of CO in the tail gas;
Ci: carbon number; Wi: carbon number is the weight of alcohol or the hydrocarbon of i in the product;
The carbon number selectivity is meant the carbon number selectivity of each component of reaction;
Liquid phase organic product selectivity is meant each components selection in the liquid phase organic product of collecting.The liquid phase organic product of collecting comprises the component of oil phase product, and contain in the water product with C
1-C
4Alcohol is main organic products.
Ni: carbon number is the alcohol of i or the molal quantity of hydrocarbon in the product.
Table 1, catalyst are to the evaluation result of co hydrogenation system higher alcohols
Reaction condition: reacting gas is synthesis gas (H
2With CO gaseous mixture, H
2With the CO volume ratio be 2: 1), air speed is 500h
-1, reaction pressure is 3.0MPa; Reaction temperature is 493K, after stablizing in 48 hours, gets response sample analysis in 50 hours.
By evaluation result as seen, Co
3O
4Through the catalyst (catalyst A) of reduction activation, carbonization, passivation, interpolation graphite moulding preparation, reduction once more before reaction is at 493K, 3.0MPa and 500h
-1Reaction condition under, the conversion ratio of its catalysis CO hydrogenation is 16.1%, the carbon number selectivity that generates alcohol is 26.1%, wherein C in the liquid organic product
2-C
18Higher alcohols (comprise C
2-C
5Pure and mild C
6-C
18Alcohol) selectivity reaches 53.8%.As can be known, by above step, a part of Co
3O
4Carbonization becomes Co
2C, gained contains Co
2The catalyst of C and metal Co mix particles component has the selectivity of certain CO hydrogenation activity and higher generation higher alcohols.With CoO is raw material or the catalyst (catalyst C, E) that adds the CoO preparation, and the selectivity of its CO hydrogenation conversion and generation higher alcohols all decreases.With Co
3O
4Or CoO be raw material without reduction activation, and directly carry out the catalyst (catalyst B, D and F) that carbonization, passivation, the moulding of interpolation graphite make, its catalytic performance is relatively poor.The preparation condition of catalyst (G-M) has very big influence to the performance of catalyst.Such as, the catalyst that carries out the carbonization preparation under the 493K temperature has the selectivity of higher CO conversion rate and generation higher alcohols.
Claims (10)
1. one kind is used for synthetic C
2-C
18The catalyst of alcohol comprises Co
2C nano particle and Co nano particle; Described Co
2The mass ratio of C nano particle and Co nano particle is 1-4: 1.
2. catalyst according to claim 1 is characterized in that: described Co
2The mass ratio of C nano particle and Co nano particle is 1.5: 1.
3. catalyst according to claim 1 and 2 is characterized in that: describedly be used for synthetic C
2-C
18In the catalyst of alcohol, also comprise graphite; The quality of described graphite is the 1-15% of described catalyst gross weight, preferred 5%.
4. according to the arbitrary described catalyst of claim 1-3, it is characterized in that: the described catalyst that is used for the synthesis gas synthesizing bigh carbon alcohol is by Co
2C nano particle, Co nano particle and graphite are formed; Described Co
2The mass ratio of C nano particle and Co nano particle is 1-4: 1, and preferred 1.5: 1; The quality of described graphite is the 1-15% of described catalyst gross weight, preferred 5%.
5. according to the arbitrary described catalyst of claim 1-4, it is characterized in that: the particle diameter of described catalyst is the 0.1-3 millimeter.
6. according to the arbitrary described catalyst of claim 1-5, it is characterized in that: described catalyst is to prepare according to the arbitrary described method of claim 7-8.
7. one kind prepares the arbitrary described synthetic C that is used for of claim 1-6
2-C
18The method of the catalyst of alcohol comprises the steps:
1) with Co
3O
4Carry out reduction activation reaction with at least a among the CoO with hydrogen or by the mist that hydrogen and inert gas are formed;
2) in the reaction system of step 1), feed carbonaceous gas and carry out carburizing reagent, carry out passivation reaction with the mist of forming by oxygen and inert gas after reaction finishes, add the graphite mixing again, obtain the described synthetic C that is used for behind the compression molding
2-C
18The catalyst of alcohol.
8. method according to claim 7 is characterized in that: in the described step 1), in the described mist of being made up of hydrogen and inert gas, hydrogen content is 1-90%, preferred 30-60%, and the volume space velocity of described hydrogen is 300-5000h
-1, preferred 200～2000h
-1, the volume space velocity of the mist of described hydrogen and inert gas is 300-5000h
-1, preferred 200～2000
H-1, the temperature of described reduction activation is 473-673K, preferred 523-673K, and the time is 2-48 hour, preferred 5-10 hour, pressure was 0.05-2.00MPa, preferred 0.1-0.5MPa, the heating rate that is risen to described reduction activation temperature by room temperature is 50-100K/h, and preferred 80K/h uses described Co simultaneously
3O
4With CoO during as reactant, described Co
3O
4With the mass ratio of CoO be 1-5: 1, preferred 2: 1;
Described step 2) in, described carbonaceous gas is single-component gas or multicomponent gas, and described single-component gas is CO, CH
4, C
2H
6Or C
3H
8, described multicomponent gas is by CO, CH
4, C
2H
6And C
3H
8In any one and following gas in any one composition: hydrogen, nitrogen and argon gas; In the described multicomponent gas, the percent by volume of the described multicomponent gas of gas comprises of carbon elements is 1-90%; The volume space velocity of described carbonaceous gas is 100～5000h
-1, preferred 500～2000h
-1In the described carburizing reagent, reaction temperature is 473～673K, and the reaction time is 1～500 hour, preferred 10-300 hour, reaction pressure was 0.05～2.00MPa, preferred 0.1～0.5MPa, the heating rate that is risen to described reaction temperature by room temperature is 0.5～20K/h, preferred 2～10K/h; Described inert gas is selected from least a in nitrogen, helium and the argon gas; In the described mist of being made up of oxygen and inert gas, the volume ratio that oxygen accounts for gaseous mixture is 0.001～0.5%; The consumption of described graphite is the 1-15% of described catalyst gross weight, and is preferred 5%, and the volume space velocity of the described mist of being made up of oxygen and inert gas is 100～1000h
-1, preferred 200～500h
-1, in the described passivation reaction, reaction temperature is 278-298K, and the reaction time is 1～10 hour, and preferred 2～5 hours, pressure was 0.05-2.00MPa, is preferably 0.1MPa.
9. synthetic C
2-C
18The method of alcohol comprises the steps:
1) with the arbitrary described synthetic C that is used for of claim 1-6
2-C
18The catalyst of alcohol carries out the reduction activation reaction with hydrogen or by the mist that hydrogen and inert gas are formed, and obtains catalyst activated;
2) described catalyst activated and hydrogen and carbon monoxide are reacted, obtain described C
2-C
18Alcohol.
10. method according to claim 9, it is characterized in that: in the described step 1), in the described mist of being made up of hydrogen and inert gas, the volume ratio that hydrogen accounts for described mist is 1-90%, preferred 50-80%, the volume space velocity of described hydrogen is 300-5000h
-1, preferred 200～2000h
-1, the volume space velocity of the mist of described hydrogen and inert gas is 300-5000h
-1, preferred 200～2000h
-1, the temperature of described reduction activation is 573-873K, preferred 623-723K, time is 2-48 hour, and preferred 5-10 hour, pressure was 0.05-2.00MPa, preferred 0.1-0.5MPa, the heating rate that is risen to described reduction activation temperature by room temperature is 20-100K/h, preferred 80K/h.
Described step 2) in, the consumption of described catalyst activated is 4ml, and reaction temperature is 430～550K, preferred 483-503K, and reaction pressure is 0.1～10.0MPa, preferred 3.0～5.0MPa, the reaction time is 45-55 hour, preferred 50 hours; The volume space velocity of described hydrogen and carbon monoxide is 100～10000h
-1, preferred 500～2000h
-1The volume ratio of described hydrogen and carbon monoxide is 1: 2; This step is carried out in fixed bed reactors.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103586060A (en) * | 2012-08-16 | 2014-02-19 | 中国科学院大连化学物理研究所 | Catalyst used for increasing selectivity of higher carbon alcohol production via Fischer-Tropsch synthesis, and preparation method and applications thereof |
| CN104588057A (en) * | 2013-10-31 | 2015-05-06 | 中国科学院大连化学物理研究所 | Heterogeneous catalyst for synthesizing aldehydes and alcohols through olefin hydroformylation, and preparation method thereof |
| CN105582970A (en) * | 2014-10-27 | 2016-05-18 | 中国科学院大连化学物理研究所 | Catalyst for low-carbon mixed alcohol with synergistic gas as raw material and preparation method thereof |
| CN106345478A (en) * | 2016-08-28 | 2017-01-25 | 山东成泰化工有限公司 | Catalyst used for preparing high alcohols |
| CN107867686A (en) * | 2016-09-27 | 2018-04-03 | 中国科学院上海高等研究院 | Based on Co2C prepares the hollow nanostructured method of graphitization |
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2010
- 2010-06-04 CN CN2010101986382A patent/CN102266790A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103586060A (en) * | 2012-08-16 | 2014-02-19 | 中国科学院大连化学物理研究所 | Catalyst used for increasing selectivity of higher carbon alcohol production via Fischer-Tropsch synthesis, and preparation method and applications thereof |
| CN103586060B (en) * | 2012-08-16 | 2015-12-16 | 中国科学院大连化学物理研究所 | Improve FT and synthesize higher alcohols processed optionally catalyst and its preparation method and application |
| CN104588057A (en) * | 2013-10-31 | 2015-05-06 | 中国科学院大连化学物理研究所 | Heterogeneous catalyst for synthesizing aldehydes and alcohols through olefin hydroformylation, and preparation method thereof |
| CN104588057B (en) * | 2013-10-31 | 2017-05-03 | 中国科学院大连化学物理研究所 | Heterogeneous catalyst for synthesizing aldehydes and alcohols through olefin hydroformylation, and preparation method thereof |
| CN105582970A (en) * | 2014-10-27 | 2016-05-18 | 中国科学院大连化学物理研究所 | Catalyst for low-carbon mixed alcohol with synergistic gas as raw material and preparation method thereof |
| CN105582970B (en) * | 2014-10-27 | 2017-10-10 | 中国科学院大连化学物理研究所 | A kind of synthesis gas is catalyst of low carbon mixed alcohol of raw material and preparation method thereof |
| CN106345478A (en) * | 2016-08-28 | 2017-01-25 | 山东成泰化工有限公司 | Catalyst used for preparing high alcohols |
| CN107867686A (en) * | 2016-09-27 | 2018-04-03 | 中国科学院上海高等研究院 | Based on Co2C prepares the hollow nanostructured method of graphitization |
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Application publication date: 20111207 |