CN104959148A

CN104959148A - Catalyst for preparing mixed alcohols from synthetic gas and preparation method therefor and application thereof

Info

Publication number: CN104959148A
Application number: CN201510391000.3A
Authority: CN
Inventors: 孙予罕; 杨彦章; 钟良枢; 王新星; 齐行振; 吕东; 于飞; 王慧; 吴秀章; 卢卫民; 李克健; 李晋平; 刘斌; 孙志强
Original assignee: China Shenhua Coal to Liquid Chemical Co Ltd; Shanghai Advanced Research Institute of CAS; Shanxi Luan Environmental Energy Development Co Ltd
Current assignee: China Shenhua Coal to Liquid Chemical Co Ltd; Shanghai Advanced Research Institute of CAS; Shanxi Luan Environmental Energy Development Co Ltd
Priority date: 2015-07-06
Filing date: 2015-07-06
Publication date: 2015-10-07

Abstract

The invention provides a catalyst for preparing mixed alcohols from synthetic gas. The catalyst contains the following ingredients: cobalt and manganese, wherein the mole ratio of cobalt to manganese is (0.1-10): 1. During the operation of synthesis reaction for preparing the mixed alcohols from the synthetic gas, the catalyst provided by the invention has high activity, high total alcohol selectivity, high C2+ alcohol selectivity and high C6+ alcohol selectivity, can operate at a relatively low temperature, such as temperature of 200-250 DEG C and has the advantages of high synthetic gas conversion capability, low cost, simplicity and convenience in preparation and easiness in industrial amplification.

Description

A kind of catalyst for the synthesis of gas mixed alcohol and preparation method and application

Technical field

The present invention relates to a kind of catalyst and preparation method and application, particularly relate to a kind of cobalt manganese-based catalyst for the synthesis of gas mixed alcohol and preparation method and application.

Background technology

China is the developing country of a rich coal oil starvation, and along with day by day highlighting of environmental problem, the efficient plot finding coal utilizes to become and solves the task of top priority that China does not solve energy resource structure and issues about the cities' development.In addition, China's natural gas resource is abundanter, and the economic interests weakness brought of directly burning, and utilization rate is not high, is therefore that intermediate product or the finished product of the motor vehicle fuel that added value is higher or chemicals has high economic worth by conversion of natural gas.

C based on syngas catalytic conversion ₁chemistry is the important channel realizing coal and the conversion of natural gas clean and effective.Now realize industrializedly comprising methanol-fueled CLC reaction, Fischer-Tropsch synthesis or F-T hydrocarbon reaction and the direct producing light olefins of methyl alcohol etc.As C ₁an essential industry application of chemistry, synthesis gas catalyzes and synthesizes the problem in science that mixed alcohol is the attempt solution of researcher always.This is because mixed alcohol not only directly can be used as the fuel of the modern means of communication such as automobile, also can as the intermediate product of fuel additive or fine chemical product; And mixed alcohol effectively can reduce the concentration of nitrogen oxide in tail gas or oxysulfide when using as fuel.From the angle of high value added product, mixed alcohol particularly higher alcohols has more wide economic worth and application prospect.Higher alcohols refer generally to the monohydric alcohol comprising more than 6 carbon atoms in molecule, are mainly used in surfactant, synthesis plasticizer, washing agent, surfactant, cosmetics and other fine chemical products.Prepare that the method for higher alcohol is current two kinds: directly chemical synthesis and the preparation of animal and plant fat direct hydrogenation.The former can large-scale production, but is but overly dependent upon oil product, also has that flow process is longer, technical sophistication, cost are higher and the shortcoming such as side reaction is more simultaneously; The latter is difficult to large-scale industrial production, is limited by the supply of raw material simultaneously.By synthesis gas directly catalyze and synthesize mixed alcohol especially higher alcohols due to this reaction scheme short, product added value is high, therefore can as a kind of alternative preparing higher alcohols.

In order to make Synthetic holography be mixed alcohol reaction temperature and and improve mixed alcohol selective, be necessary to develop high performance mixed alcohol catalyst.Current, there is the report of synthesis gas mixed alcohol catalyst, 4 kinds of main mixed alcohol catalysts can be divided into.

1) modified methanol synthetic catalyst (ZnO/Cr ₂o ₃, Cu/ZnO/Al ₂o ₃): in methanol synthesis catalyst, add appropriate alkaline-earth metal or alkali metals modified forms; Lugi company of Germany and Italian Snam company develop such catalyst the earliest, and typical patent has U.S. US 4513100 and EP 0034338A2.In this type of catalyst activity and product, isobutanol content is higher, but mixed alcohol synthetic reaction condition is harsher, and (pressure is 14 ~ 20MPa, temperature is 350 ~ 450 DEG C), water content higher (being generally 30 ~ 50%) in product, higher alcohol selective lower (being generally less than 35%).

2) modified FT synthesis catalyst: because FT synthesizes the ability that the CATALYST Co of hydrocarbon reaction or Fe isoreactivity metal do not possess the non-Dissociative of CO substantially, therefore people attempt adding one in FT catalyst activity component can another metal of non-Dissociative CO (such as Cu) or metal oxide, to improving the selectivity of product of mixed alcohol.The Cu-Co mixed alcohol catalyst that this kind of catalyst is developed with IFP (IFP) is for representative, and it has multinomial patent (comprising US 4122110,4291126 and GB2118061,2158730).The mixed alcohol reaction condition gentleness (similar to low pressure methanol synthesis catalyst) of this catalyst, product alcohol is mainly C ₁-C ₆straight chain n-alkanol, accessory substance is mainly C ₁-C ₆aliphatic hydrocarbon, but less stable.

3) Mo is catalyst based: molybdenum system sulfide catalyst (patent US4882360) that this kind of catalyst is developed with DOW company of the U.S. is for representative.This catalyst system product water content is few, not only has resistance to SO_2, and higher alcohol content higher (can reach 30 ~ 70%), and lower alcohol is ethanol and normal propyl alcohol mainly; But catalyst stability and the life-span lower, this is because wherein auxiliary element very easily and form carbonyls between carbon monoxide and run off, thus reduces the activity of catalyst and selective, and the structural stability of catalyst is deteriorated.

4) Rh is catalyst based: in carried noble metal Rh catalyst, add one to two kinds of transition metal or metal oxide auxiliary agent.Such catalyst (as US 4014913 and 4096164) there is higher activity and low-carbon alcohols selective, special standby is to C ₂ ⁺alcohol selective higher, namely product is based on ethanol; Shortcoming be Rh metal at natural low memory, expensive, and catalyst is easily by CO ₂poison, therefore generally do not reach the extensive and macrocyclic requirement of industrial production.

Up to now, modified Fischer-Tropsch mixed alcohol catalyst due to activity component metal price low, greatly and easily obtain, catalytic activity is large for memory space, the selective height of alcohol and be considered to the mixed alcohol catalyst most with industrial prospect.But in current modified Fischer-Tropsch mixed alcohol catalyst, CO inserts activated centre is main mainly with Cu component, rarely has and can be used as the CO insertion metal at center or the report of oxide species about other.Therefore, be necessary to develop not containing the modified Fischer-Tropsch mixed alcohol catalyst of Cu.

Summary of the invention

The object of this invention is to provide a kind of catalyst for the synthesis of gas mixed alcohol and preparation method and application.This catalyst comprises following component: cobalt, manganese, and the mol ratio of cobalt/manganese is 0.1-10:1.Catalyst of the present invention has high activity, high total selective, high C of alcohol in the synthetic reaction operation of synthesis gas mixed alcohol ₂₊selective and the high C of alcohol ₆₊alcohol is selective, can operate, have high Synthetic holography ability at lower temperature is as 200-250 DEG C, with low cost, prepare easy and be easy to industry amplify.

A first aspect of the present invention provides a kind of catalyst for the synthesis of gas mixed alcohol, and described catalyst comprises following component: cobalt and manganese, and the mol ratio of cobalt/manganese is 0.1-10:1.

Preferably, the mol ratio of cobalt/manganese is 1-10:1.Preferred, the mol ratio of cobalt/manganese is 0.2-5:1.

Preferably, described catalyst also comprises auxiliary agent, the mol ratio of auxiliary agent/manganese not higher than 10:1, described auxiliary agent be selected from carrier component, transition metal, rare earth metal or alkaline-earth metal one or more.Preferred, the mol ratio of auxiliary agent/manganese is 5:1-1:5.

Present invention also offers a kind of catalyst for the synthesis of gas mixed alcohol, described catalyst is composed of the following components: cobalt and manganese, and the mol ratio of cobalt/manganese is 0.1-10:1.

Preferably, described catalyst is composed of the following components: cobalt, manganese and auxiliary agent, the mol ratio of auxiliary agent/manganese not higher than 10:1, described auxiliary agent be selected from carrier component, transition metal, rare earth metal or alkaline-earth metal one or more.Preferred, the mol ratio of auxiliary agent/manganese is 5:1-1:5.

Wherein, above-mentioned carrier component is selected from Al ₂o ₃, SiO ₂, TiO ₂or one or more in active carbon; One or more in above-mentioned transition metal chosen from Fe (Fe), zirconium (Zr) or zinc (Zn); Above-mentioned rare earth metal be selected from lanthanum (La) or cerium (Ce) one or more; Above-mentioned alkaline-earth metal be selected from magnesium (Mg), calcium (Ca) or barium (Ba) one or more.

The mol ratio of cobalt/manganese can be 0.1-0.2:1,0.2-0.5:1,0.5-1:1,1-2:1,2-5:1 or 5-10:1; The mol ratio of auxiliary agent/manganese can be 1:6-1:5,1:5-1:2,1:2-2:1 or 2:1-10:1.

A second aspect of the present invention provides a kind of preparation method of catalyst of the present invention, is selected from the arbitrary of following preparation method:

Preparation method one, when catalyst be cobalt and manganese time, comprise the following steps:

(1) according to the composition and ratio of catalyst, the salt of cobalt, manganese is mixed with mixing salt solution;

(2) precipitating reagent is mixed with precipitant solution;

(3) by described mixing salt solution and described precipitant solution co-precipitation;

(4) precipitation terminate rear aging, be separated, washing, dry and roasting, obtain the catalyst for synthesis gas mixed alcohol.

Preparation method two, when catalyst be cobalt and manganese time, comprise the following steps:

(1) according to the composition and ratio of catalyst, the salt of cobalt, manganese is mixed with salting liquid respectively;

(2) precipitating reagent is mixed with precipitant solution;

(3) by the described salting liquid that is mixed with respectively and described precipitant solution continuously and flow and precipitate respectively;

Preparation method three, when catalyst contains auxiliary agent, auxiliary agent be selected from transition metal, rare earth metal or alkaline-earth metal one or more, comprise the following steps:

(1) according to the composition and ratio of catalyst, the salt of cobalt, manganese and auxiliary agent is mixed with mixing salt solution;

(2) precipitating reagent is mixed with precipitant solution;

Preparation method four, when catalyst contains auxiliary agent, auxiliary agent be selected from transition metal, rare earth metal or alkaline-earth metal one or more, comprise the following steps:

(1) according to the composition and ratio of catalyst, the salt of cobalt, manganese and auxiliary agent is mixed with salting liquid respectively;

(2) precipitating reagent is mixed with precipitant solution;

Preparation method five, when auxiliary agent contains carrier component, comprise the following steps:

(1) according to the composition and ratio of catalyst, the salt of cobalt, manganese and the auxiliary agent except carrier component is mixed with mixing salt solution;

(2) precipitating reagent is mixed with precipitant solution;

(3) described carrier component is dispersed in jellyfish liquid, described mixing salt solution and described precipitant solution to be flow in described jellyfish liquid and co-precipitation;

Preparation method six, when auxiliary agent contains carrier component, comprise the following steps:

(1) according to the composition and ratio of catalyst, the salt of cobalt, manganese and the auxiliary agent except carrier component is mixed with salting liquid respectively;

(2) precipitating reagent is mixed with precipitant solution;

(3) described carrier component is dispersed in jellyfish liquid, the salting liquid be mixed with respectively and described precipitant solution is also flowed continuously in the jellyfish liquid of dispersible carrier component precipitate respectively in step (1);

Preferably, in preparation method one, preparation method three and preparation method five, total metal molar concentration range of the mixing salt solution of described step (1) is 0.01 ~ 5mol/L.

Preferably, in described step (2), the molar concentration scope of precipitant solution is 0.01 ~ 5mol/L.

Preferably, described precipitating reagent is selected from sodium carbonate, sodium acid carbonate, NaOH, potash, saleratus, potassium hydroxide, ammonium carbonate or NH ₃h ₂one or more in O; The salt of described cobalt, manganese and the auxiliary agent except carrier component is one or more in corresponding chlorate, nitrate, sulfate or acetate.Preferred, described precipitating reagent is sodium carbonate.

Preferably, in described step (3), precipitation temperature is 10 ~ 100 DEG C, and precipitation pH is 6 ~ 12.Preferred, precipitation temperature is 50 ~ 80 DEG C, and precipitation pH is 7 ~ 9.

Preferably, in described step (3), the volume ratio of mixing salt solution and precipitant solution is 1:5 ~ 5:1, is more preferably 1:2 ~ 2:1.

Preferably, in described step (4), aging temperature is 10 ~ 100 DEG C, and ageing time is 0.5 ~ 24h.Preferred, aging temperature is 50 ~ 80 DEG C, and ageing time is 1 ~ 5h.

Preferably, in described step (4), baking temperature is 50 ~ 150 DEG C, and drying time is 1 ~ 24h, and sintering temperature is 200 ~ 800 DEG C, and roasting time is 0.5 ~ 24h.Preferred, baking temperature is 100 ~ 120 DEG C, and drying time is 10 ~ 12h, and sintering temperature is 300 ~ 600 DEG C, and roasting time is 2 ~ 5h.

Catalyst of the present invention is a kind of cobalt manganese-based catalyst being applicable to synthesis gas mixed alcohol, is specially adapted to the mixed alcohol synthesis carrying out high carbon number alcohol in fixed bed reactors.

A third aspect of the present invention provides a kind of application of catalyst of the present invention, and it is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and catalytic reaction condition is: reaction temperature is 150 ~ 300 DEG C; Operating pressure is 0.1 ~ 15Mpa; Reaction velocity is 100 ~ 20000h ^-1; Synthesis gas is by H ₂form with CO, and H ₂the mol ratio of/CO is 0.1 ~ 10:1.

Preferably, catalytic reaction condition is: reaction temperature is 170 ~ 250 DEG C; Operating pressure is 2 ~ 6Mpa; Reaction velocity is 2000 ~ 6000h ^-1; Synthesis gas is by H ₂form with CO, and H ₂the mol ratio of/CO is 1 ~ 3:1.

Wherein, catalyst application of the present invention is in synthesis gas mixed alcohol, and reaction procatalyst need through overactivation, and activation condition is: in reducing gases atmosphere, gradient increased temperature to 150 ~ 600 DEG C, preferably 200 ~ 400 DEG C, activation 1 ~ 24h, preferably 6 ~ 12h.

Preferably, described reducing gases atmosphere is H ₂, CO, synthesis gas or above-mentioned gas and inert gas gaseous mixture, wherein, the air speed of reducing gases atmosphere is 1000 ~ 20000h ^-1.

Gained catalyst of the present invention has high activity, high total selective, high C of alcohol ₂₊selective and the high C of alcohol ₆₊alcohol is selective, can operate, have high Synthetic holography ability at lower temperature is as 200-250 DEG C, with low cost, prepare easy and be easy to advantage such as industry amplification etc.Below 250 DEG C, just can reach the one way CO conversion ratio of 36%, total oxygenatedchemicals is selective reaches 46wt%, C ₂₊selective (the C of alcohol ₂₊the total carbon number of alcohol accounts for the percentage of total oxygenatedchemicals carbon number) can 97wt% be reached, C ₆₊alcohol is selective reaches 65wt% (note: in this patent, unless specifically indicated, namely alcohol is selective refers to that oxygenatedchemicals is selective).

Detailed description of the invention

Below by way of specific instantiation, embodiments of the present invention are described, those skilled in the art the content disclosed by this description can understand other advantages of the present invention and effect easily.The present invention can also be implemented or be applied by detailed description of the invention different in addition, and the every details in this description also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.

Notice, in the following example, the concrete process equipment that indicates or device all adopt conventional equipment in this area or device; All force value and scope all refer to relative pressure.

In addition should be understood that the one or more method steps mentioned in the present invention do not repel and can also to there is additive method step or can also insert additive method step before and after described combination step between these steps clearly mentioned, except as otherwise noted; Will also be understood that, the relation that is connected between the one or more equipment/devices mentioned in the present invention is not repelled and can also to be there are other equipment/devices or can also insert other equipment/devices before and after described unit equipment/device between these two equipment/devices clearly mentioned, except as otherwise noted.And, except as otherwise noted, the numbering of various method steps is only the convenient tool differentiating various method steps, but not be ordering or the enforceable scope of restriction the present invention of restriction various method steps, the change of its relativeness or adjustment, when changing technology contents without essence, when being also considered as the enforceable category of the present invention.

[embodiment 1]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 0.05mol/L, controlling titration environment pH is 8, control titration temperature at 65 DEG C, after titration completely, aging 2h in 65 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 80 DEG C of oven dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is H ₂with N ₂gaseous mixture, H ₂/ gaseous mixture=10% (mol ratio), reduction air speed is 8000mlg ^-1h ^-1, reduction temperature is 300 DEG C, and the time is 5h.After reduction process terminates, be cooled to 180 DEG C; Then with synthesis gas (H ₂/ CO=2) and N ₂gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) by reactor pressure back pressure to 6.0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 250 DEG C, and reaction velocity is 6000mlg ^-1h ^-1, operating pressure is 6.0MPa, H ₂mol ratio=2 of/CO, reaction result is in table 1.

[embodiment 2]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 1mol/L, controlling titration environment pH is 8, control titration temperature at 65 DEG C, after titration completely, aging 2h in 65 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 80 DEG C of oven dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

[embodiment 3]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 4mol/L, controlling titration environment pH is 8, control titration temperature at 65 DEG C, after titration completely, aging 2h in 65 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 80 DEG C of oven dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

[embodiment 4]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L, controlling titration environment pH is 8, control titration temperature at 25 DEG C, after titration completely, aging 2h in 65 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 80 DEG C of oven dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

[embodiment 5]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L, controlling titration environment pH is 8, control titration temperature at 55 DEG C, after titration completely, aging 2h in 65 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 80 DEG C of oven dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

[embodiment 6]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L, controlling titration environment pH is 8, control titration temperature at 85 DEG C, after titration completely, aging 2h in 65 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 80 DEG C of oven dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

[embodiment 7]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L, controlling titration environment pH is 6, control titration temperature at 65 DEG C, after titration completely, aging 2h in 65 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 80 DEG C of oven dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

[embodiment 8]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L, controlling titration environment pH is 10, control titration temperature at 65 DEG C, after titration completely, aging 2h in 65 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 80 DEG C of oven dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

[embodiment 9]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L, controlling titration environment pH is 12, control titration temperature at 65 DEG C, after titration completely, aging 2h in 65 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 80 DEG C of oven dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

[embodiment 10]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L, controlling titration environment pH is 8, control titration temperature at 65 DEG C, after titration completely, aging 24h in 20 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 80 DEG C of oven dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

[embodiment 11]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L, controlling titration environment pH is 8, control titration temperature at 65 DEG C, after titration completely, aging 12h in 50 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 80 DEG C of oven dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

[embodiment 12]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L, controlling titration environment pH is 8, control titration temperature at 65 DEG C, after titration completely, aging 1h in 80 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 80 DEG C of oven dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

[embodiment 13]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L, controlling titration environment pH is 8, control titration temperature at 65 DEG C, after titration completely, aging 0.5h in 100 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 80 DEG C of oven dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

[embodiment 14]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L, controlling titration environment pH is 8, control titration temperature at 65 DEG C, after titration completely, aging 2h in 65 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 50 DEG C of oven dry 24h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

[embodiment 15]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L, controlling titration environment pH is 8, control titration temperature at 65 DEG C, after titration completely, aging 2h in 65 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 100 DEG C of oven dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

[embodiment 16]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L, controlling titration environment pH is 8, control titration temperature at 65 DEG C, after titration completely, aging 2h in 65 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 150 DEG C of oven dry 6h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

[embodiment 17]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L, controlling titration environment pH is 8, control titration temperature at 65 DEG C, after titration completely, aging 2h in 65 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 80 DEG C of oven dry 12h, after grinding evenly, with temperature programming to 200 DEG C roasting 24h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

[embodiment 18]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L, controlling titration environment pH is 8, control titration temperature at 65 DEG C, after titration completely, aging 2h in 65 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 80 DEG C of oven dry 12h, after grinding evenly, with temperature programming to 300 DEG C roasting 16h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is H ₂with N ₂gaseous mixture, H ₂/ gaseous mixture=10% (mol ratio), reduction air speed is 8000mlg ^-1h ^-1, reduction temperature is 350 DEG C, and the time is 5h.After reduction process terminates, be cooled to 180 DEG C; Then with synthesis gas (H ₂/ CO=2) and N ₂gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) by reactor pressure back pressure to 6.0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 250 DEG C, and reaction velocity is 6000mlg ^-1h ^-1, operating pressure is 6.0MPa, H ₂mol ratio=2 of/CO, reaction result is in table 1.

[embodiment 19]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L, controlling titration environment pH is 8, control titration temperature at 65 DEG C, after titration completely, aging 2h in 65 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 80 DEG C of oven dry 12h, after grinding evenly, with temperature programming to 500 DEG C roasting 10h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

[embodiment 20]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L, controlling titration environment pH is 8, control titration temperature at 65 DEG C, after titration completely, aging 2h in 65 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 80 DEG C of oven dry 12h, after grinding evenly, with temperature programming to 800 DEG C roasting 2h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

[embodiment 21]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L, controlling titration environment pH is 8, control titration temperature at 65 DEG C, after titration completely, aging 2h in 65 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 80 DEG C of oven dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is H ₂with N ₂gaseous mixture, H ₂/ gaseous mixture=10% (mol ratio), reduction air speed is 8000mlg ^-1h ^-1, reduction temperature is 300 DEG C, and the time is 5h.After reduction process terminates, be cooled to 180 DEG C; Then with synthesis gas (H ₂/ CO=2) and N ₂gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) by reactor pressure back pressure to .0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 250 DEG C, and reaction velocity is 300mlg ^-1h ^-1, operating pressure is 0.5MPa, H ₂mol ratio=2 of/CO, reaction result is in table 1.

[embodiment 22]

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is H ₂with N ₂gaseous mixture, H ₂/ gaseous mixture=10% (mol ratio), reduction air speed is 8000mlg ^-1h ^-1, reduction temperature is 300 DEG C, and the time is 5h.After reduction process terminates, be cooled to 180 DEG C; Then with synthesis gas (H ₂/ CO=2) and N ₂gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) by reactor pressure back pressure to .0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 250 DEG C, and reaction velocity is 10000mlg ^-1h ^-1, operating pressure is 9MPa, H ₂mol ratio=2 of/CO, reaction result is in table 1.

[embodiment 23]

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is H ₂with N ₂gaseous mixture, H ₂/ gaseous mixture=10% (mol ratio), reduction air speed is 8000mlg ^-1h ^-1, reduction temperature is 300 DEG C, and the time is 5h.After reduction process terminates, be cooled to 180 DEG C; Then with synthesis gas (H ₂/ CO=2) and N ₂gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) by reactor pressure back pressure to .0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 250 DEG C, and reaction velocity is 20000mlg ^-1h ^-1, operating pressure is 15MPa, H ₂mol ratio=2 of/CO, reaction result is in table 1.

[embodiment 24]

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is H ₂with N ₂gaseous mixture, H ₂/ gaseous mixture=10% (mol ratio), reduction air speed is 8000mlg ^-1h ^-1, reduction temperature is 300 DEG C, and the time is 5h.After reduction process terminates, be cooled to 180 DEG C; Then with synthesis gas (H ₂/ CO=2) and N ₂gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) by reactor pressure back pressure to 6.0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 250 DEG C, and reaction velocity is 6000mlg ^-1h ^-1, operating pressure is 6.0MPa, H ₂mol ratio=0.1 of/CO, reaction result is in table 1.

[embodiment 25]

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is H ₂with N ₂gaseous mixture, H ₂/ gaseous mixture=10% (mol ratio), reduction air speed is 8000mlg ^-1h ^-1, reduction temperature is 300 DEG C, and the time is 5h.After reduction process terminates, be cooled to 180 DEG C; Then with synthesis gas (H ₂/ CO=2) and N ₂gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) by reactor pressure back pressure to 6.0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 250 DEG C, and reaction velocity is 6000mlg ^-1h ^-1, operating pressure is 6.0MPa, H ₂mol ratio=1 of/CO, reaction result is in table 1.

[embodiment 26]

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is H ₂with N ₂gaseous mixture, H ₂/ gaseous mixture=10% (mol ratio), reduction air speed is 8000mlg ^-1h ^-1, reduction temperature is 300 DEG C, and the time is 5h.After reduction process terminates, be cooled to 180 DEG C; Then with synthesis gas (H ₂/ CO=2) and N ₂gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) by reactor pressure back pressure to 6.0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 250 DEG C, and reaction velocity is 6000mlg ^-1h ^-1, operating pressure is 6.0MPa, H ₂mol ratio=10 of/CO, reaction result is in table 1.

[embodiment 27]

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is H ₂with N ₂gaseous mixture, H ₂/ gaseous mixture=10% (mol ratio), reduction air speed is 8000mlg ^-1h ^-1, reduction temperature is 150 DEG C, and the time is 24h.After reduction process terminates, be cooled to 180 DEG C; Then with synthesis gas (H ₂/ CO=2) and N ₂gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) by reactor pressure back pressure to 6.0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 250 DEG C, and reaction velocity is 6000mlg ^-1h ^-1, operating pressure is 6.0MPa, H ₂mol ratio=2 of/CO, reaction result is in table 1.

[embodiment 28]

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is H ₂with N ₂gaseous mixture, H ₂/ gaseous mixture=10% (mol ratio), reduction air speed is 8000mlg ^-1h ^-1, reduction temperature is 350 DEG C, and the time is 10h.After reduction process terminates, be cooled to 180 DEG C; Then with synthesis gas (H ₂/ CO=2) and N ₂gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) by reactor pressure back pressure to 6.0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 250 DEG C, and reaction velocity is 6000mlg ^-1h ^-1, operating pressure is 6.0MPa, H ₂mol ratio=2 of/CO, reaction result is in table 1.

[embodiment 29]

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is H ₂with N ₂gaseous mixture, H ₂/ gaseous mixture=10% (mol ratio), reduction air speed is 8000mlg ^-1h ^-1, reduction temperature is 600 DEG C, and the time is 3h.After reduction process terminates, be cooled to 180 DEG C; Then with synthesis gas (H ₂/ CO=2) and N ₂gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) by reactor pressure back pressure to 6.0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 250 DEG C, and reaction velocity is 6000mlg ^-1h ^-1, operating pressure is 6.0MPa, H ₂mol ratio=2 of/CO, reaction result is in table 1.

[embodiment 30]

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is H ₂with N ₂gaseous mixture, H ₂/ gaseous mixture=10% (mol ratio), reduction air speed is 1000mlg ^-1h ^-1, reduction temperature is 300 DEG C, and the time is 5h.After reduction process terminates, be cooled to 180 DEG C; Then with synthesis gas (H ₂/ CO=2) and N ₂gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) by reactor pressure back pressure to 6.0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 250 DEG C, and reaction velocity is 6000mlg ^-1h ^-1, operating pressure is 6.0MPa, H ₂mol ratio=2 of/CO, reaction result is in table 1.

[embodiment 31]

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is synthesis gas and N ₂gaseous mixture, synthesis gas/gaseous mixture=10% (mol ratio), reduction air speed is 10000mlg ^-1h ^-1, reduction temperature is 300 DEG C, and the time is 5h.After reduction process terminates, be cooled to 180 DEG C; Then with synthesis gas (H ₂/ CO=2) and N ₂gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) by reactor pressure back pressure to 6.0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 250 DEG C, and reaction velocity is 6000mlg ^-1h ^-1, operating pressure is 6.0MPa, H ₂mol ratio=2 of/CO, reaction result is in table 1.

[embodiment 32]

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is CO and N ₂gaseous mixture, H ₂/ gaseous mixture=10% (mol ratio), reduction air speed is 20000mlg ^-1h ^-1, reduction temperature is 300 DEG C, and the time is 5h.After reduction process terminates, be cooled to 180 DEG C; Then with synthesis gas (H ₂/ CO=2) and N ₂gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) by reactor pressure back pressure to 6.0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 250 DEG C, and reaction velocity is 6000mlg ^-1h ^-1, operating pressure is 6.0MPa, H ₂mol ratio=2 of/CO, reaction result is in table 1.

[embodiment 33]

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is H ₂with N ₂gaseous mixture, H ₂/ gaseous mixture=10% (mol ratio), reduction air speed is 8000mlg ^-1h ^-1, reduction temperature is 200 DEG C, and the time is 5h.After reduction process terminates, be cooled to 180 DEG C DEG C; Then with synthesis gas (H ₂/ CO=2) and N ₂gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) by reactor pressure back pressure to 6.0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 250 DEG C, and reaction velocity is 6000mlg ^-1h ^-1, operating pressure is 6.0MPa, H ₂mol ratio=2 of/CO, reaction result is in table 1.

[embodiment 34]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L.

Adopt two coprecipitations, above-mentioned mixing salt solution and precipitant solution are carried out co-precipitation, wherein, mother liquor selects deionized water (200ml), and controlling titration environment pH is 8, controls titration temperature at 65 DEG C, after titration completely, aging 2h in 65 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program be warming up to 80 DEG C dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is H ₂with N ₂gaseous mixture, H ₂/ gaseous mixture=10% (mol ratio), reduction air speed is 8000mlg ^-1h ^-1, reduction temperature is 250 DEG C, and the time is 5h.After reduction process terminates, be cooled to 180 DEG C; Then with synthesis gas (H ₂/ CO=2) and N ₂gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) by reactor pressure back pressure to 6.0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 250 DEG C, and reaction velocity is 6000mlg ^-1h ^-1, operating pressure is 6.0MPa, H ₂mol ratio=2 of/CO, reaction result is in table 1.

[embodiment 35]

[embodiment 36]

[embodiment 37]

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is H ₂with N ₂gaseous mixture, H ₂/ gaseous mixture=10% (mol ratio), reduction air speed is 8000mlg ^-1h ^-1, reduction temperature is 400 DEG C, and the time is 5h.After reduction process terminates, be cooled to 180 DEG C; Then with synthesis gas (H ₂/ CO=2) and N ₂gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) by reactor pressure back pressure to 6.0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 250 DEG C, and reaction velocity is 6000mlg ^-1h ^-1, operating pressure is 6.0MPa, H ₂mol ratio=2 of/CO, reaction result is in table 1.

[embodiment 38]

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is H ₂with N ₂gaseous mixture, H ₂/ gaseous mixture=10% (mol ratio), reduction air speed is 8000mlg ^-1h ^-1, reduction temperature is 300 DEG C, and the time is 5h.After reduction process terminates, be cooled to 180 DEG C; Then with synthesis gas (H ₂/ CO=2) and N ₂gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) by reactor pressure back pressure to 2.0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 250 DEG C, and reaction velocity is 6000mlg ^-1h ^-1, operating pressure is 2.0MPa, H ₂mol ratio=2 of/CO, reaction result is in table 1.

[embodiment 39]

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is H ₂with N ₂gaseous mixture, H ₂/ gaseous mixture=10% (mol ratio), reduction air speed is 8000mlg ^-1h ^-1, reduction temperature is 300 DEG C, and the time is 5h.After reduction process terminates, be cooled to 180 DEG C; Then with synthesis gas (H ₂/ CO=2) and N ₂gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) by reactor pressure back pressure to 4.0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 250 DEG C, and reaction velocity is 6000mlg ^-1h ^-1, operating pressure is 4.0MPa, H ₂mol ratio=2 of/CO, reaction result is in table 1.

[embodiment 40]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/10 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L.

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is H ₂with N ₂gaseous mixture, H ₂/ gaseous mixture=10% (mol ratio), reduction air speed is 8000mlg ^-1h ^-1, reduction temperature is 300 DEG C, and the time is 5h.After reduction process terminates, be cooled to 180 DEG C; Then with synthesis gas (H ₂/ CO=2) and N ₂gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) by reactor pressure back pressure to 6.0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 300 DEG C, and reaction velocity is 6000mlg ^-1h ^-1, operating pressure is 6.0MPa, H ₂mol ratio=2 of/CO, reaction result is in table 1.

[embodiment 41]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/5 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L.

[embodiment 42]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/2 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L.

[embodiment 43]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=2/1 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L.

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is H ₂with N ₂gaseous mixture, H ₂/ gaseous mixture=10% (mol ratio), reduction air speed is 8000mlg ^-1h ^-1, reduction temperature is 300 DEG C, and the time is 5h.After reduction process terminates, be cooled to 180 DEG C; Then with synthesis gas (H ₂/ CO=2) and N ₂gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) by reactor pressure back pressure to 6.0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 250 DEG C, and reaction velocity is 6000mlg ^-1h ^-1, operating pressure is mol ratio=2 of 6.0MPa, H2/CO, and reaction result is in table 1.

[embodiment 44]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=5/1 is dissolved in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L.

[embodiment 45]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=10/1 is dissolved in respectively in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L.

Adopt the precipitation method, above-mentioned salting liquid precipitant solution is precipitated out respectively continuously in same container, wherein, mother liquor selects deionized water (200ml), and controlling titration environment pH is 8, controls titration temperature at 65 DEG C, after titration completely, aging 2h in 65 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program be warming up to 80 DEG C dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is H ₂with N ₂gaseous mixture, H2/ gaseous mixture=10% (mol ratio), reduction air speed is 8000mlg ^-1h ^-1, reduction temperature is 300 DEG C, and the time is 5h.After reduction process terminates, be cooled to 180 DEG C; Then with synthesis gas (H ₂/ CO=2) and N ₂gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) by reactor pressure back pressure to 6.0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 250 DEG C, and reaction velocity is 6000mlg ^-1h ^-1, operating pressure is 6.0MPa, H ₂mol ratio=2 of/CO, reaction result is in table 1.

[embodiment 46]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in respectively in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by NaHCO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L.

[embodiment 47]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in respectively in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, is dissolved in a certain amount of deionized water by NaOH and forms Na ⁺concentration is the precipitant solution of 2mol/L.

[embodiment 48]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in respectively in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by K ₂cO ₃be dissolved in a certain amount of deionized water and form K ⁺concentration is the precipitant solution of 2mol/L.

[embodiment 49]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in respectively in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by KHCO ₃be dissolved in a certain amount of deionized water and form K ⁺concentration is the precipitant solution of 2mol/L.

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is H ₂with N ₂gaseous mixture, H ₂/ gaseous mixture=10% (mol ratio), reduction air speed is 8000mLg ^-1h ^-1, reduction temperature is 300 DEG C, and the time is 5h.After reduction process terminates, be cooled to 180 DEG C; Then with the gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) of synthesis gas (H2/CO=2) and N2 by reactor pressure back pressure to 6.0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 230 DEG C, and reaction velocity is 6000mLg ^-1h ^-1, operating pressure is 6.0MPa, H ₂mol ratio=2 of/CO, reaction result is in table 1.

[embodiment 50]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in respectively in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, is dissolved in a certain amount of deionized water by KOH and forms K ⁺concentration is the precipitant solution of 2mol/L.

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is H ₂with N ₂gaseous mixture, H ₂/ gaseous mixture=10% (mol ratio), reduction air speed is 8000mLg ^-1h ^-1, reduction temperature is 300 DEG C, and the time is 5h.After reduction process terminates, be cooled to 180 DEG C; Then with synthesis gas (H ₂/ CO=2) with the gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) of N2 by reactor pressure back pressure to 6.0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 250 DEG C, and reaction velocity is 6000mLg ^-1h ^-1, operating pressure is 6.0MPa, H ₂mol ratio=2 of/CO, reaction result is in table 1.

[embodiment 51]

By Mn (NO ₃) ₂the aqueous solution and Co (NO ₃) ₂6H ₂o in molar ratio Co/Mn=1/1 is dissolved in respectively in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L.

Adopt the precipitation method, above-mentioned salting liquid precipitant solution be precipitated out respectively continuously in same container, wherein, mother liquor selects deionized water (200ml), in advance a certain amount of SiO of dispersion ₂pressed powder (Si/Co=2, mol ratio), controlling titration environment pH is 8, controls titration temperature at 65 DEG C, after titration completely, aging 2h in 65 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program be warming up to 80 DEG C dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

[embodiment 52]

Adopt the precipitation method, above-mentioned salting liquid precipitant solution be precipitated out respectively continuously in same container, wherein, mother liquor selects deionized water (200ml), in advance a certain amount of TiO of dispersion ₂pressed powder (Ti/Co=2, mol ratio), controlling titration environment pH is 8, controls titration temperature at 65 DEG C, after titration completely, aging 2h in 65 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program be warming up to 80 DEG C dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

[embodiment 53]

Adopt the precipitation method, above-mentioned salting liquid precipitant solution be precipitated out respectively continuously in same container, wherein, mother liquor selects deionized water (200ml), in advance a certain amount of Al of dispersion ₂o ₃pressed powder (Al/Co=2, mol ratio), controlling titration environment pH is 8, controls titration temperature at 65 DEG C, after titration completely, aging 2h in 65 DEG C of mother liquors, through centrifugal, washing 6 times after, be placed in baking oven Program be warming up to 80 DEG C dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, then compressing tablet be crushed to 40 ~ 60 orders, obtains catalyst.

[embodiment 54]

Adopt the precipitation method, above-mentioned salting liquid precipitant solution is precipitated out respectively continuously in same container, wherein, mother liquor selects deionized water (200ml), a certain amount of active carbon powder (C/Co=2 of prior dispersion, mol ratio), controlling titration environment pH is 8, control titration temperature at 65 DEG C, after titration completely, aging 2h in 65 DEG C of mother liquors, through centrifugal, after washing 6 times, be placed in baking oven Program and be warming up to 80 DEG C of oven dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, then compressing tablet be crushed to 40 ~ 60 orders, obtain catalyst.

[embodiment 55]

By Co (NO ₃) ₂6H ₂o, Mn (NO ₃) ₂, Fe (NO ₃) ₂9H ₂o in molar ratio Co/Mn/Fe=1/2/1 is dissolved in respectively in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L.

[embodiment 56]

By Co (NO ₃) ₂6H ₂o, Mn (NO ₃) ₂, Zr (NO ₃) ₄5H ₂o in molar ratio Co/Mn/Zr=1/2/1 is dissolved in respectively in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L.

[embodiment 57]

By Co (NO ₃) ₂6H ₂o, Mn (NO ₃) ₂, Zn (NO ₃) ₂6H ₂o in molar ratio Co/Mn/Zn=1/2/1 is dissolved in respectively in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L.

[embodiment 58]

By Co (NO ₃) ₂6H ₂o, Mn (NO ₃) ₂, Ca (NO ₃) ₂co/Mn/Ca=6/6/1 is dissolved in respectively in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na in molar ratio ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L.

[embodiment 59]

By Co (NO ₃) ₂6H ₂o, Mn (NO ₃) ₂, Mg (NO ₃) ₂co/Mn/Mg=6/6/1 is dissolved in respectively in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na in molar ratio ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L.

[embodiment 60]

By Co (NO ₃) ₂6H ₂o, Mn (NO ₃) ₂, Ba (NO ₃) ₂co/Mn/Ba=6/6/1 is dissolved in respectively in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na in molar ratio ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L.

[embodiment 61]

By Co (NO ₃) ₂6H ₂o, Mn (NO ₃) ₂, Ce (NO ₃) ₃6H ₂o in molar ratio Co/Mn/Ce=5/5/1 is dissolved in respectively in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L.

[embodiment 62]

By Co (NO ₃) ₂6H ₂o, Mn (NO ₃) ₂, La (NO ₃) ₃6H ₂o in molar ratio Co/Mn/La=5/5/1 is dissolved in respectively in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L.

[embodiment 63]

By Co (NO ₃) ₂6H ₂o, Mn (NO ₃) ₂, La (NO ₃) ₃6H ₂o in molar ratio Co/Mn/La=1/1/10 is dissolved in respectively in a certain amount of deionized water and forms the mixed solution that total metal concentration is 2mol/L, by Na ₂cO ₃be dissolved in a certain amount of deionized water and form Na ⁺concentration is the precipitant solution of 2mol/L.

[embodiment 64]

This catalyst is for the synthesis of in the reaction of gas mixed alcohol, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5g, and with the dilution of 3g fine quartz sand, reducing atmosphere is H ₂with N ₂gaseous mixture, H ₂/ gaseous mixture=10% (mol ratio), reduction air speed is 8000mlg ^-1h ^-1, reduction temperature is 300 DEG C, and the time is 5h.After reduction process terminates, be cooled to 180 DEG C; Then with synthesis gas (H ₂/ CO=2) and N ₂gaseous mixture (synthesis gas/gaseous mixture=10% (mol ratio)) by reactor pressure back pressure to 6.0MPa, then after reaction temperature being risen to target temperature point, use synthesis gas instead and displace 10% synthesis gas in reactor, emptying after about 24h gradually.Reaction temperature is 200 DEG C, and reaction velocity is 6000mlg ^-1h ^-1, operating pressure is 6.0MPa, H ₂mol ratio=2 of/CO, reaction result is in table 1.

Table 1 embodiment catalyst reaction result

In above-mentioned experiment, meet following condition and all can use: total metal molar concentration range of mixing salt solution is 0.01 ~ 5mol/L; The molar concentration scope of precipitant solution is 0.01 ~ 5mol/L; Precipitation temperature is 10 ~ 100 DEG C, and precipitation pH is 6 ~ 12; The volume ratio of mixing salt solution and precipitant solution is 1:5 ~ 5:1; Aging temperature is 10 ~ 100 DEG C, and ageing time is 0.5 ~ 24h; Baking temperature is 50 ~ 150 DEG C, and drying time is 1 ~ 24h; Sintering temperature is 200 ~ 800 DEG C, and roasting time is 0.5 ~ 24h; For the synthesis of in the reaction of gas mixed alcohol, catalytic reaction condition is: reaction temperature is 150 ~ 300 DEG C; Operating pressure is 0.1 ~ 15Mpa; Reaction velocity is 100 ~ 20000h ^-1; Synthesis gas is by H ₂form with CO, and H ₂the mol ratio of/CO is 0.1 ~ 10:1; Catalyst activates for the synthesis of before gas mixed alcohol, and activation condition is: in reducing gases atmosphere, gradient increased temperature to 150 ~ 600 DEG C, activation 1 ~ 24h; Reducing gases atmosphere is H ₂, CO, synthesis gas or above-mentioned gas and inert gas gaseous mixture, wherein, the air speed of reducing gases atmosphere is 1000 ~ 20000h ^-1, those skilled in the art can carry out selection optimization according to routine techniques.

As can be seen from Table 1, this catalyst is in mixed alcohol synthetic reaction process, and can operate at lower temperature is as 200-250 DEG C, Synthetic holography ability is higher, simultaneously selective the and C of total alcohol ₂₊alcohol (and C ₆₊alcohol) selective higher.

The above; be only preferred embodiment of the present invention; not to any formal and substantial restriction of the present invention; should be understood that; for those skilled in the art; under the prerequisite not departing from the inventive method, also can make some improvement and supplement, these improve and supplement and also should be considered as protection scope of the present invention.All those skilled in the art, without departing from the spirit and scope of the present invention, a little change made when utilizing disclosed above technology contents, the equivalent variations of modifying and developing, be Equivalent embodiments of the present invention; Meanwhile, all according to substantial technological of the present invention to the change of any equivalent variations that above-described embodiment is done, modify and differentiation, all still belong in the scope of technical scheme of the present invention.

Claims

1. for the synthesis of a catalyst for gas mixed alcohol, it is characterized in that, described catalyst comprises following component: cobalt and manganese, and the mol ratio of cobalt/manganese is 0.1-10:1.

2. as claimed in claim 1 for the synthesis of the catalyst of gas mixed alcohol, it is characterized in that, the mol ratio of cobalt/manganese is 1-10:1, is preferably 0.2-5:1.

3. as claimed in claim 1 or 2 for the synthesis of the catalyst of gas mixed alcohol, it is characterized in that, described catalyst also comprises auxiliary agent, the mol ratio of auxiliary agent/manganese not higher than 10:1, described auxiliary agent be selected from carrier component, transition metal, rare earth metal or alkaline-earth metal one or more.

4., as claimed in claim 3 for the synthesis of the catalyst of gas mixed alcohol, it is characterized in that,

Described carrier component is selected from Al ₂o ₃, SiO ₂, TiO ₂or one or more in active carbon;

Described transition metal be selected from Fe, Zr or Zn one or more;

Described rare earth metal be selected from La or Ce one or more;

Described alkaline-earth metal be selected from Mg, Ca or Ba one or more.

5. a preparation method for the catalyst for the synthesis of gas mixed alcohol as described in as arbitrary in Claims 1-4, is characterized in that, be selected from the arbitrary of following preparation method:

(2) precipitating reagent is mixed with precipitant solution;

6. as claimed in claim 5 for the synthesis of the preparation method of the catalyst of gas mixed alcohol, it is characterized in that, in preparation method one, preparation method three and preparation method five, total metal molar concentration range of the mixing salt solution of described step (1) is 0.01 ~ 5mol/L.

7., as claimed in claim 5 for the synthesis of the preparation method of the catalyst of gas mixed alcohol, it is characterized in that, in described step (2), the molar concentration scope of precipitant solution is 0.01 ~ 5mol/L.

8., as claimed in claim 5 for the synthesis of the preparation method of the catalyst of gas mixed alcohol, it is characterized in that, described precipitating reagent is selected from sodium carbonate, sodium acid carbonate, NaOH, potash, saleratus, potassium hydroxide, ammonium carbonate or NH ₃h ₂one or more in O; The salt of described cobalt, manganese and the auxiliary agent except carrier component is one or more in corresponding chlorate, nitrate, sulfate or acetate.

9. as claimed in claim 5 for the synthesis of the preparation method of the catalyst of gas mixed alcohol, it is characterized in that, in described step (3), precipitation temperature is 10 ~ 100 DEG C, and precipitation pH is 6 ~ 12.

10., as claimed in claim 5 for the synthesis of the preparation method of the catalyst of gas mixed alcohol, it is characterized in that, in described step (3), the volume ratio of mixing salt solution and precipitant solution is 1:5 ~ 5:1.

11. as claimed in claim 5 for the synthesis of the preparation method of the catalyst of gas mixed alcohol, and it is characterized in that, in described step (4), aging temperature is 10 ~ 100 DEG C, and ageing time is 0.5 ~ 24h.

12., as claimed in claim 5 for the synthesis of the preparation method of the catalyst of gas mixed alcohol, is characterized in that, in described step (4), baking temperature is 50 ~ 150 DEG C, drying time is 1 ~ 24h, and sintering temperature is 200 ~ 800 DEG C, and roasting time is 0.5 ~ 24h.

13. 1 kinds as arbitrary in Claims 1 to 4 as described in the application of the catalyst for the synthesis of gas mixed alcohol, it is characterized in that, for the synthesis of in the reaction of gas mixed alcohol, catalytic reaction condition is: reaction temperature is 150 ~ 300 DEG C; Operating pressure is 0.1 ~ 15Mpa; Reaction velocity is 100 ~ 20000h ^-1; Synthesis gas is by H ₂form with CO, and H ₂the mol ratio of/CO is 0.1 ~ 10:1.

14. as claimed in claim 13 for the synthesis of the application of the catalyst of gas mixed alcohol, it is characterized in that, described catalyst activates for the synthesis of before gas mixed alcohol, and activation condition is: in reducing gases atmosphere, gradient increased temperature to 150 ~ 600 DEG C, activation 1 ~ 24h.

15. as claimed in claim 14 for the synthesis of the application of the catalyst of gas mixed alcohol, and it is characterized in that, described reducing gases atmosphere is H ₂, CO, synthesis gas or above-mentioned gas and inert gas gaseous mixture, wherein, the air speed of reducing gases atmosphere is 1000 ~ 20000h ^-1.