CN110280270A

CN110280270A - A kind of Ru base catalyst and its preparation method and application directly preparing mixed alcohol for synthesis gas conversion

Info

Publication number: CN110280270A
Application number: CN201910661141.0A
Authority: CN
Inventors: 秦婷婷; 钟良枢; 孙予罕; 齐行振; 林铁军
Original assignee: Shanghai Advanced Research Institute of CAS
Current assignee: Shanghai Advanced Research Institute of CAS
Priority date: 2019-07-22
Filing date: 2019-07-22
Publication date: 2019-09-27
Anticipated expiration: 2039-07-22
Also published as: CN110280270B

Abstract

The invention discloses a kind of Ru base catalyst and its preparation method and application that mixed alcohol is directly prepared for synthesis gas conversion, the Ru base catalyst includes the oxide of Ru, at least one of oxide and carrier M3 of metal promoter M1 element, and the oxide of optional alkali metal M2 element.It is a kind of novel catalyst that the catalyst is directly prepared in mixed alcohol in synthesis gas conversion, while having high activity and total alcohol selectivity.

Description

A kind of Ru base catalyst and its preparation directly preparing mixed alcohol for synthesis gas conversion Methods and applications

Technical field

The present invention relates to catalyst technical fields, and in particular to a kind of Ru that mixed alcohol is directly prepared for synthesis gas conversion Base catalyst and its preparation method and application.

Background technique

With the increasingly scarcity of Global Oil resource, coal and natural gas will be as the main sources of future energy supply.And There is the energy resource structure of " rich coal, oil-poor, few gas " to carry out clearly while develop clean energy resource to existing fossil energy for China Clean conversion is also extremely important energy conversion approach.Wherein, turned using the synthesis gas that coal, natural gas and biomass are carried out as raw material Change is the energy conversion approach of a clean and effective in C1 chemical industry.By synthesis gas conversion can be made high-quality clean fuel and The chemicals of high added value, realized industrialized has methanol-fueled CLC, F- T synthesis, methanol-to-olefins and coal-ethylene glycol at present Deng, and synthesis gas converts mixed alcohol processed and its industrialization is not implemented.Mixed alcohol is a kind of chemicals of high added value, in gasoline There is important application in terms of additive, alternative oil product, industrial chemicals and solvent.Mixed alcohol can be used for liquid fuel and oil product addition Agent also acts as industrial chemicals after separation, has very extensive application prospect.When mixed alcohol is used for fuel oil additive, both The capability of antidetonance and octane number of oil product can be improved, and can be reduced NO in tail gas_x、SO_xThe discharge of equal pollutants, it is alternative have strive The methyl tertiary butyl ether(MTBE) (MTBE) of view has the advantages that improve fuel qualities, reduce environmental pollution.Synthesis gas reported at present The catalyst system for converting mixed alcohol processed has following four classes: (1) being representative exploitation by Italian Sanm company and Lugi company, Germany CuZnAl modified methanol synthetic catalyst；(2) it is catalyzed by the Cu-Co modified Fischer-Tropsch that French research institute (IFP) is representative exploitation Agent；It (3) is the molybdenum system sulfide catalyst of representative exploitation by DOW company, the U.S.；(4) noble metal Rh base catalyst.Current industrial There are mainly two types of the methods for preparing mixed alcohol: (1) chemical synthesis.The method not only depends on fossil resource unduly, and there is reaction The disadvantages of long flow path, technology are complicated, at high cost and by-product is more；(2) animal and plant fat adds hydrogen.It is deficient that the method is limited by raw material supply It is weary and be difficult to be mass produced.Therefore, based on the important application of mixed alcohol, the method that development replaces tradition to prepare mixed alcohol is extremely closed It is important.

Limitation the industrialized main cause of mixed alcohol be a lack of effective catalyst, cause activity, selectivity, stability and It is undesirable in terms of economy.Therefore, it is necessary to develop a kind of novel catalyst, make it in reactivity, total alcohol selectivity It is promoted in terms of stability, with further close to process of industrialization.

Summary of the invention

The object of the present invention is to provide a kind of Ru base catalyst and its system that mixed alcohol is directly prepared for synthesis gas conversion Preparation Method and application, it is a kind of novel catalyst that the catalyst is directly prepared in mixed alcohol in synthesis gas conversion, is had simultaneously There are high activity and total alcohol selectivity.

First aspect present invention provides a kind of Ru base catalyst that mixed alcohol is directly prepared for synthesis gas conversion, comprising:

The oxide of active component Ru；

At least one of oxide and carrier of metal promoter M1 element；

Wherein, M1 element is selected from transition metal element, third major element, alkali earth metal and group of the lanthanides in metal promoter At least one of element.

Preferably, further includes:

The oxide of alkali metal promoter M2 element.

It is highly preferred that M2 element is selected from least one of Li, Na, K, Rb, Cs in alkali metal promoter.

Preferably, further include in following technical characteristic at least one of:

1) transition metal element is selected from least one of Co, Mn, Cu, Zn and Zr in metal promoter；

2) third major element is Al in metal promoter；

3) alkali earth metal is selected from least one of Ca, Mg and Ba in metal promoter；

4) lanthanide series is Ce in metal promoter；

5) carrier is selected from oxide, the SiO of M1 element₂、TiO₂At least one of with carbon material, alternatively, the load Body is selected from oxide, the SiO of the M1 element of load M2 element₂、TiO₂At least one of with carbon material；When the Ru base is catalyzed Agent includes the oxide of metal promoter M1 element, when carrier includes the oxide of M1 element, as the M1 element of carrier and conduct The M1 element of metal promoter is not identical；When the Ru base catalyst includes the oxide of alkali metal promoter M2 element, carrier includes When loading the oxide of the M1 element of M2 element, the M2 element as carrier and the M2 element as alkali metal promoter be not identical；

6) Ru element accounts for the 0.1~8% of catalyst gross mass, such as 0.1~0.2%, 0.2~0.5%, 0.5~1%, 1~ 2%, 2~3.3%, 3.3~4%, 4~5% or 5~8%；

7) M1 element accounts for the 0~85% of catalyst gross mass in metal promoter, such as 0~20%, 20~34%, 34~ 58%, 58~60%, 60~61%, 61~62%, 62~63%, 63~64%, 64~68%, 68~69%, 69~70% Or 70~85%；

8) M2 element accounts for the 0~1.7% of catalyst gross mass in alkali metal promoter, such as 0~0.4%, 0.4~0.6%, 0.6~0.9%, 0.9~1%, 1~1.3% or 1.3~1.7%；

9) carrier account for the 99.9% of catalyst gross mass hereinafter, such as 0~67.6%, 67.6~73.1%, 73.1~ 73.3%, 73.3~73.9%, 73.9~74.3%, 74.3~93.4%, 93.4~98.7%, 98.7~99.3% or 99.3 ~99.9%.When the oxide of the element containing M2 in carrier, carrier is with the oxide of M1 element, SiO₂、TiO₂, in carbon material At least one and M2 element oxide gross mass meter.

It is highly preferred that feature 5) in, in terms of carrier gross mass, in carrier M2 element account for carrier mass percent be 0~ 0.6%.

Second aspect of the present invention provides the preparation method of above-mentioned Ru base catalyst, and the preparation method is in following method One kind:

Preparation method one, includes the following steps:

1a) according to Ru base catalyst composition and ratio, the salt of Ru salt and metal promoter M1 element is dissolved in water, obtains mixing gold Belong to salting liquid；

The precipitating reagent of alkali metal promoter M2 element 1b) is dissolved in water, obtains precipitant solution；

1c) by the obtained precipitant solution of the obtained mixed salt solution of step 1a) and step 1b) while instilling mother liquor Middle co-precipitation obtains co-precipitation solution；

1d) co-precipitation solution age, centrifugation, washing, drying and roasting that step 1c) is obtained are urged to get the Ru base Agent；

Preparation method two, includes the following steps:

2a) according to Ru base catalyst composition and ratio, the salt of Ru salt and metal promoter M1 element is dissolved in water, obtains mixing gold Belong to salting liquid；

The precipitating reagent of not alkali metal containing M2 element 2b) is dissolved in water, obtains precipitant solution；

2c) by the obtained precipitant solution of the obtained mixed salt solution of step 2a) and step 2b) while instilling mother liquor In, it stirs and evenly mixs, forms co-precipitation solution；

2d) co-precipitation solution age, centrifugation, washing, drying and roasting that step 2c) is obtained are urged to get the Ru base Agent；

Preparation method three, includes the following steps:

3a) according to Ru base catalyst composition and ratio, Ru salt is dissolved in water, obtains dipping solution；Alternatively, by Ru salt, and, The salt of metal promoter M1 element and at least one of the salt of alkali metal M2 element, are dissolved in water, obtain dipping solution；

3b) dipping solution for obtaining step 3a) uses one step of equi-volume impregnating dipping or step impregnation to the load On body, wherein the carrier after step dipping or in step impregnation after every step dipping is stood, dry and roasting is to get the Ru base Catalyst；

Step 3b) in, when the Ru base catalyst includes the oxide of alkali metal M2 element, the step dipping are as follows: Ru salt dipping solution and the salt dipping solution of alkali metal M2 element impregnate simultaneously, alternatively, Ru salt dipping solution, metal promoter M1 member The salt dipping solution and the salt dipping solution of alkali metal M2 element of element impregnate simultaneously；

Step 3b) in, when the Ru base catalyst includes the oxide of alkali metal M2 element, the step impregnation are as follows: Ru salt dipping solution dipping, elder generation's Ru salt dipping solution impregnate alkali metal M2 again to the salt dipping solution dipping of first alkali metal M2 element again Salt dipping solution dipping, the elder generation's Ru salt dipping solution of element impregnate again the salt dipping solution and metal promoter M1 of alkali metal M2 element The mixed solution dipping of the salt dipping solution of element, the salt dipping solution of elder generation Ru salt dipping solution and metal promoter M1 element mix Close the salt dipping that solution impregnates again the salt dipping solution dipping of alkali metal M2 element, elder generation's Ru salt dipping solution and alkali metal M2 element The salt dipping solution dipping of metal promoter M1 element, the salt dipping of first metal promoter M1 element are molten again for the mixed solution dipping of solution Liquid dipping the mixed solution dipping of the salt dipping solution of Ru salt dipping solution and alkali metal M2 element, first alkali metal M2 element again Salt dipping solution impregnates again the mixed solution dipping of the salt dipping solution of Ru salt dipping solution and metal promoter M1 element, first metal The mixed solution of the salt dipping solution of the salt dipping solution and alkali metal M2 element of auxiliary agent M1 element impregnates Ru salt dipping solution again Dipping；

Step 3b) in, when the Ru base catalyst does not include the oxide of alkali metal M2 element, the step dipping Are as follows: Ru salt dipping solution direct impregnation, alternatively, the salt dipping solution of Ru salt dipping solution and metal promoter M1 element soaks simultaneously Stain；

Step 3b) in, when the Ru base catalyst does not include the oxide of alkali metal M2 element, the step impregnation Are as follows: first Ru salt dipping solution impregnates again the salt dipping solution dipping of metal promoter M1 element, alternatively, first metal promoter M1 element Ru salt dipping solution impregnates salt dipping solution dipping again；

Preparation method four, includes the following steps:

4a) according to catalyst composition and ratio, the salt of metal promoter M1 element is dissolved in water, obtains metal promoter M1 element Salting liquid；

It is 4b) that the precipitating reagent of alkali metal M2 element is soluble in water, precipitant solution is obtained, alternatively, will not alkali metal containing M2 The precipitating reagent of element is soluble in water, obtains precipitant solution；

4c) by the salting liquid and step 4b of the metal promoter M1 element that step 4a) is obtained) obtained precipitant solution is simultaneously It instills in mother liquor and is co-precipitated, obtain co-precipitation solution；

4d) co-precipitation solution age, centrifugation, washing, drying and the roasting for obtaining step 4c) obtains metal promoter M1 The oxide of alkali metal containing M2 element or the not oxide of alkali metal containing M2 element, i.e., the described carrier in element；

4e) according to Ru base catalyst composition and ratio, Ru salt is dissolved in water, obtains dipping solution；Alternatively, by Ru salt, and, The salt of metal promoter M1 element and at least one of the salt of alkali metal M2 element, are dissolved in water, obtain dipping solution；

4f) dipping solution for obtaining step 4e) uses one step of equi-volume impregnating dipping or step impregnation to step 4d) The oxide of alkali metal containing M2 element or not on the oxide of alkali metal containing M2 element in obtained metal promoter M1 element, In, in the metal promoter M1 element after step dipping or in step impregnation after every step dipping the oxide of alkali metal containing M2 element or The oxide of person's not alkali metal containing M2 element stands, dry and roast to get the Ru base catalyst；

Step 4f) in, when the Ru base catalyst includes the oxide of alkali metal M2 element, the step dipping are as follows: Ru salt dipping solution and the salt dipping solution of alkali metal M2 element impregnate simultaneously, alternatively, Ru salt dipping solution, metal promoter M1 member The salt dipping solution and the salt dipping solution of alkali metal M2 element of element impregnate simultaneously；

Step 4f) in, when the Ru base catalyst includes the oxide of alkali metal M2 element, the step impregnation are as follows: Ru salt dipping solution dipping, elder generation's Ru salt dipping solution impregnate alkali metal M2 again to the salt dipping solution dipping of first alkali metal M2 element again Salt dipping solution dipping, the elder generation's Ru salt dipping solution of element impregnate again the salt dipping solution and metal promoter M1 of alkali metal M2 element The mixed solution dipping of the salt dipping solution of element, the salt dipping solution of elder generation Ru salt dipping solution and metal promoter M1 element mix Close the salt dipping that solution impregnates again the salt dipping solution dipping of alkali metal M2 element, elder generation's Ru salt dipping solution and alkali metal M2 element The salt dipping solution dipping of metal promoter M1 element, the salt dipping of first metal promoter M1 element are molten again for the mixed solution dipping of solution Liquid dipping the mixed solution dipping of the salt dipping solution of Ru salt dipping solution and alkali metal M2 element, first alkali metal M2 element again Salt dipping solution impregnates again the mixed solution dipping of the salt dipping solution of Ru salt dipping solution and metal promoter M1 element, first metal The mixed solution of the salt dipping solution of the salt dipping solution and alkali metal M2 element of auxiliary agent M1 element impregnates Ru salt dipping solution again Dipping；

Step 4f) in, when the Ru base catalyst does not include the oxide of alkali metal M2 element, the step dipping Are as follows: Ru salt dipping solution direct impregnation, alternatively, the salt dipping solution of Ru salt dipping solution and metal promoter M1 element soaks simultaneously Stain；

Step 4f) in, when the Ru base catalyst does not include the oxide of alkali metal M2 element, the step impregnation Are as follows: first Ru salt dipping solution impregnates again the salt dipping solution dipping of metal promoter M1 element, alternatively, first metal promoter M1 element Ru salt dipping solution impregnates salt dipping solution dipping again.

1) the Ru salt be selected from ruthenic chloride, iodate ruthenium, acetic acid ruthenium, ruthenium hydrochloride potassium, acetylacetone,2,4-pentanedione ruthenium, nitrosyl nitric acid ruthenium, At least one of carbonyl ruthenic chloride and ruthenium hydrochloride ammonium；

2) salt of the metal promoter M1 element is selected from the nitre of the chlorate of metal promoter M1 element, metal promoter M1 element Hydrochlorate, the sulfate of metal promoter M1 element, the carbonate of metal promoter M1 element and metal promoter M1 element acetate in At least one；

3) salt of the alkali metal M2 element be selected from the carbonate of alkali metal M2 element, alkali metal M2 element nitrate, The chlorate of alkali metal M2 element, the ammonium salt of alkali metal M2 element, the sulfate of alkali metal M2 element and alkali metal M2 element At least one of acetate.

1) step 1b) in, the precipitating reagent of the alkali metal M2 element is selected from Na₂CO₃、K₂CO₃、Rb₂CO₃、Cs₂CO₃、LiOH、 At least one of NaOH, KOH, RbOH and CsOH；

2) step 2b) in, the precipitating reagent of the not alkali metal containing M2 element is selected from (NH₄)₂CO₃And NH₃·H₂In O at least It is a kind of；

3) step 1a) and step 2a) in, the total mol concentration of the mixed salt solution is 0.5~4mol/L, more excellent It is selected as 1~2mol/L, such as 0.5~1mol/L, 1~2mol/L or 2~4mol/L；

4) step 1b) and step 2b) in, the precipitant solution molar concentration be 0.5~4mol/L, more preferably 1~ 2mol/L, such as 0.5~1mol/L, 1~2mol/L or 2~4mol/L；

5) step 1c) and step 2c) in, the mother liquor is water；

6) step 1c) and step 2c) in, co-precipitation temperature is 10~80 DEG C, more preferably 20~50 DEG C, such as 10~20 DEG C, 20~23 DEG C, 23~25 DEG C, 25~50 DEG C or 50~80 DEG C；

7) step 1c) and step 2c) in, co-precipitation pH is 6~12, more preferably 7~10, such as 6~7,7~8,8~10 Or 10~12；

8) step 1d) and step 2d) in, aging temperature be 20~80 DEG C, more preferably 20~50 DEG C, such as 20~20 DEG C, 20~23 DEG C, 23~25 DEG C, 25~50 DEG C or 50~80 DEG C；

9) step 1d) and step 2d) in, ageing time be 0.5~for 24 hours, more preferably 1~12h, such as 0.5~1h, 1~ 2h, 2~12h, 12~for 24 hours；

10) step 1d) and step 2d) in, centrifugation, washing 0~10 time, more preferably 3~8 times；

11) step 1d) and step 2d) in, drying temperature be 80~150 DEG C, more preferably 100~120 DEG C, such as 80~ 100 DEG C, 100~120 DEG C or 120~150 DEG C；

12) step 1d) and step 2d) in, drying time is 6~48h, more preferably 12~for 24 hours, such as 6~12h, 12~ For 24 hours or 24~48h；

13) step 1d) and step 2d) in, maturing temperature be 250~400 DEG C, more preferably 300~400 DEG C, such as 250~ 300 DEG C, 300~330 DEG C or 330~400 DEG C；

14) step 1d) and step 2d) in, calcining time be 0.5~for 24 hours, more preferably 2~12h, such as 0.5~2h, 2~ 3h, 3~12h or 12~for 24 hours；

15) step 1d) and step 2d) in, dry atmosphere in air atmosphere, nitrogen atmosphere, argon atmosphere at least It is a kind of；

16) step 1d) and step 2d) in, calcination atmosphere in air atmosphere, nitrogen atmosphere, argon atmosphere at least It is a kind of.

1) step 3b) in, dipping temperature is 5~25 DEG C, more preferably 22 DEG C, such as 5~22 DEG C, 22~23 DEG C or 23~25 ℃；

2) step 3b) in, time of repose is 4~48h, more preferably 12~for 24 hours, such as 4~12h, 12~for 24 hours or 24~ 48h；

3) step 3b) in, drying temperature be 80~150 DEG C, more preferably 100~120 DEG C, such as 80~100 DEG C, 100~ 120 DEG C or 120~150 DEG C；

4) step 3b) in, drying time is 6~48h, more preferably 12~for 24 hours, such as 6~12h, 12~for 24 hours or 24~ 48h；

5) step 3b) in, maturing temperature is 250~400 DEG C, more preferably 300~400 DEG C, such as 250~300 DEG C, 300 ~350 DEG C or 350~400 DEG C；

6) step 3b) in, calcining time be 0.5~for 24 hours, more preferably 2~12h, such as 0.5~2h, 2~4h, 4~12h Or 12~for 24 hours；

7) step 3b) in, it stands atmosphere and is selected from one of air atmosphere, nitrogen atmosphere and argon atmosphere or a variety of；

8) step 3b) in, dry atmosphere is selected from one of air atmosphere, nitrogen atmosphere and argon atmosphere or a variety of；

9) step 3b) in, calcination atmosphere is selected from one of air atmosphere, nitrogen atmosphere and argon atmosphere or a variety of.

1) step 4b) in, the precipitating reagent of the alkali metal M2 element is selected from Na₂CO₃、K₂CO₃、Rb₂CO₃、Cs₂CO₃、LiOH、 One of NaOH, KOH, RbOH and CsOH or a variety of；

2) step 4b) in, the precipitating reagent of the not alkali metal containing M2 element is selected from (NH₄)₂CO₃And NH₃·H₂One of O Or two kinds；

3) step 4a) in, the molar concentration of the metal promoter M1 element salting liquid is 0.5~4mol/L, more preferably 1 ~2mol/L, such as 0.5~1mol/L, 1~2mol/L or 2~4mol/L；

4) step 4b) in, the molar concentration of the precipitant solution is 0.5~4mol/L, more preferably 1~2mol/L, Such as 0.5~1mol/L, 1~2mol/L or 2~4mol/L；

5) step 4c) in, the mother liquor is water；

6) step 4c) in, co-precipitation temperature is 10~80 DEG C, more preferably 20~50 DEG C, such as 10~20 DEG C, 20~25 DEG C, 25~50 DEG C or 50~80 DEG C；

7) step 4c) in, co-precipitation pH is 6~12, more preferably 7~10, such as 6~7,7~8,8~10 or 10~12；

8) step 4d) in, aging temperature be 20~80 DEG C, more preferably 20~50 DEG C, such as 20~20 DEG C, 20~25 DEG C, 25~50 DEG C or 50~80 DEG C；

9) step 4d) in, ageing time be 0.5~for 24 hours, more preferably 1~12h, such as 0.5~1h, 1~2h, 2~12h, 12~for 24 hours；

10) step 4d) in, centrifugation, washing 0~10 time, more preferably 3~8 times；

11) step 4d) in, drying temperature be 80~150 DEG C, more preferably 100~120 DEG C, such as 80~100 DEG C, 100~ 120 DEG C or 120~150 DEG C；

12) step 4d) in, drying time is 6~48h, more preferably 12~for 24 hours, such as 6~12h, 12~for 24 hours or 24~ 48h；

13) step 4d) in, maturing temperature is 250~400 DEG C, more preferably 300~400 DEG C, such as 250~300 DEG C, 300 ~330 DEG C or 330~400 DEG C；

14) step 4d) in, calcining time be 0.5~for 24 hours, more preferably 2~12h, such as 0.5~2h, 2~3h, 3~12h Or 12~for 24 hours；

15) step 4d) in, dry atmosphere is selected from one of air atmosphere, nitrogen atmosphere and argon atmosphere or a variety of；

16) step 4d) in, calcination atmosphere is selected from one of air atmosphere, nitrogen atmosphere, argon atmosphere or a variety of；

17) step 4f) in, dwell temperature is 5~25 DEG C, more preferably 22 DEG C, such as 5~22 DEG C, 22~23 DEG C or 23~ 25℃；

18) step 4f) in, time of repose is 4~48h, more preferably 12~for 24 hours, such as 4~12h, 12~for 24 hours or 24~ 48h；

19) step 4f) in, drying temperature be 80~150 DEG C, more preferably 100~120 DEG C, such as 80~100 DEG C, 100~ 120 DEG C or 120~150 DEG C；

20) step 4f) in, drying time is 6~48h, more preferably 12~for 24 hours, such as 6~12h, 12~for 24 hours or 24~ 48h；

21) step 4f) in, maturing temperature is 250~400 DEG C, more preferably 300~400 DEG C, such as 250~300 DEG C, 300 ~330 DEG C or 330~400 DEG C；

22) step 4f) in, calcining time be 0.5~for 24 hours, more preferably 2~12h, such as 0.5~2h, 2~3h, 3~12h Or 12~for 24 hours；

23) step 4f) in, dry atmosphere is selected from one of air atmosphere, nitrogen atmosphere and argon atmosphere or a variety of；

24) step 4f) in, calcination atmosphere is selected from one of air atmosphere, nitrogen atmosphere and argon atmosphere or a variety of.

Third aspect present invention provides the purposes of above-mentioned Ru base catalyst, for the synthesis gas conversion directly system in fixed bed Standby mixed alcohol.

Heretofore described mixed alcohol is the straight chain alcohol of methanol and methanol or more, general formula C_nH_2n+1OH。

1) compression molding is carried out to the Ru base catalyst, chooses the catalyst of 40~60 mesh and the quartz sand of 40~60 mesh Loaded in fixed bed after particle mixing；

2) for before synthesis gas conversion directly prepares mixed alcohol in fixed bed, to the Ru base catalyst 0.1~ It is restored under 0.5Mpa；

3) synthesis gas conversion directly prepares the reaction condition of mixed alcohol are as follows: unstripped gas is selected from H₂/ CO=0.5, H₂/ CO=1, H₂One of synthesis gas of/CO=2 is a variety of, air speed WHSV=1000~4000ml/ (g_catH), such as 1000~ 2000ml/(g_catOr 2000~4000ml/ (g h)_catH), reaction temperature is 210~250 DEG C, such as 210~220 DEG C, 220 ~240 DEG C or 240~250 DEG C, reaction pressure is 0.5~6MPa, such as 0.5~2MPa or 2~6MPa.

It is highly preferred that feature 2) in, further include at least one in following technical characteristic:

A) reducing atmosphere is selected from hydrogen, carbon monoxide, synthesis gas, dilution synthesis gas, dilution hydrogen and dilution carbon monoxide One of or it is a variety of, diluent gas is inert gas, and diluent gas volume fraction is below 90%；

B) reducing condition: reduction temperature is 200~400 DEG C, such as 200~300 DEG C or 300~400 DEG C, the recovery time It is 8000ml/ (g for 0.5~12h, such as 0.5~5h or 5~12h, air speed WHSV_cat·h)；

C) 160~220 DEG C are cooled to after the Ru base catalyst reduction, such as 160~200 DEG C or 200~220 DEG C, It is activated under 0.1~0.5MPa.

Even more preferably, in feature c), activation phenomenon is selected from H₂/ CO=0.5, H₂/ CO=1 and H₂The conjunction of/CO=2 At one of gas or a variety of, air speed WHSV is 1000~4000ml/ (g_catH), such as 1000~2000ml/ (g_catH) or 2000~4000ml/ (g_catH), activation time is 12~48h, such as 12~24 or 24~48h.

Ru base catalyst of the invention directly prepares the reaction of mixed alcohol for synthesis gas conversion, and CO conversion ratio reaches as high as 33.3%, total alcohol selectively reaches as high as 29.9%.The Ru base catalyst has high activity and total alcohol selectivity, preparation side Method is simple, easy to operate, and stability is good, is easy to repeat and industry is amplified, have potential prospects for commercial application.

Specific embodiment

Illustrate technical solution of the present invention below by way of specific specific example.It should be understood that mention one of the present invention or Multiple method and steps do not repel before and after the combination step that there is also other methods step or the steps specifically mentioned at these Other methods step can also be inserted between rapid；It should also be understood that these embodiments are merely to illustrate the present invention rather than limitation The scope of the present invention.Moreover, unless otherwise indicated, the number of various method steps is only to identify the convenient tool of various method steps, Rather than it for the arrangement order of limitation various method steps or limits the scope of the invention, the change of relativeness or tune It is whole, without material changes in technical content, when being also considered as the enforceable scope of the present invention.

The technology of the present invention details is subject to detailed description by following embodiments.It should be noted that for embodiment, make With only further illustrating technical characteristic of the invention, rather than limit the present invention.

[embodiment 1]

Cobalt nitrate and 50% manganese nitrate solution are weighed according to Co/Mn=1 (molar ratio), wherein Co and Mn element point The 33% and 35% of catalyst gross mass is not accounted for；It is carried out by 0.1% pair of hydrate ruthenium trichloride that Ru element accounts for catalyst gross mass It weighs, and the metal mixed salting liquid of 1mol/L is made in deionized water in above-mentioned three kinds of metal salt co-dissolves；By alkali gold Belong to Na and account for the 0.6% of catalyst gross mass natrium carbonicum calcinatum is weighed and is dissolved in deionized water and 2mol/L is made sinks Shallow lake agent solution.

The deionized water of 100ml is added in beaker, above-mentioned mixed metal salt and precipitant solution are instilled into the burning simultaneously In cup, stir and evenly mix.Co-precipitation temperature is 23 DEG C, and co-precipitation pH is 8.Aging 2h, aging terminate at 23 DEG C after titration Centrifuge washing 6 times afterwards are subsequently placed in 100 DEG C of baking ovens dry 12h, finally 330 DEG C of roasting 3h in Muffle furnace, dry and roasting It is carried out in air atmosphere.

Catalytic performance test is carried out in fixed bed to above-mentioned catalyst.Weigh the above-mentioned catalyst of 1.5g and 3.0g quartz sand Particle mixing, catalyst and quartz sand are 40~60 mesh.Logical 10% synthesis gas/nitrogen (H₂/ CO=0.5) it is restored, it is empty Fast WHSV=8000ml/ (g_catH), reduction temperature is 300 DEG C and keeps 5h.H is switched to after being cooled to 200 DEG C after reduction₂/ The synthesis gas of CO=1 is activated, air speed WHSV=2000ml/ (g_catH), activation time is for 24 hours.Lead to H after activation₂/ The synthesis gas of CO=1 is reacted, air speed WHSV=2000ml/ (g_catH), back pressure is warming up to 220 DEG C and is commented to 6MPa Valence, results of property are shown in Table 1.

[embodiment 2]

Cobalt nitrate and 50% manganese nitrate solution are weighed according to Co/Mn=1 (molar ratio), wherein Co and Mn element point The 34% and 35% of catalyst gross mass is not accounted for；It is carried out by 0.2% pair of hydrate ruthenium trichloride that Ru element accounts for catalyst gross mass It weighs, and the metal mixed salting liquid of 1mol/L is made in deionized water in above-mentioned three kinds of metal salt co-dissolves；By alkali gold Belong to Na and account for the 0.6% of catalyst gross mass natrium carbonicum calcinatum is weighed and is dissolved in deionized water and 2mol/L is made sinks Shallow lake agent solution.

[embodiment 3]

Cobalt nitrate and 50% manganese nitrate solution are weighed according to Co/Mn=1 (molar ratio), wherein Co and Mn element point The 33% and 35% of catalyst gross mass is not accounted for；0.5% pair of nitrosyl nitric acid ruthenium solution of catalyst gross mass is accounted for by Ru element It is weighed, and the metal mixed salting liquid of 1mol/L is made in deionized water in above-mentioned three kinds of metal salt co-dissolves；It presses 0.4% pair of natrium carbonicum calcinatum that Alkali-Metal Na accounts for catalyst gross mass, which is weighed and is dissolved in deionized water, is made 2mol/L Precipitant solution.

[embodiment 4]

Cobalt nitrate and 50% manganese nitrate solution are weighed according to Co/Mn=1 (molar ratio), wherein Co and Mn element point The 31% and 32% of catalyst gross mass is not accounted for；By Ru element account for 1% pair of nitrosyl nitric acid ruthenium solution of catalyst gross mass into Row weighs, and the metal mixed salting liquid of 1mol/L is made in deionized water in above-mentioned three kinds of metal salt co-dissolves；By alkali 0.9% pair of natrium carbonicum calcinatum that metal Na accounts for catalyst gross mass, which is weighed and is dissolved in deionized water, is made 2mol/L's Precipitant solution.

Catalytic performance test is carried out in fixed bed to above-mentioned catalyst.Weigh the above-mentioned catalyst of 1.5g and 3.0g quartz sand Particle mixing, catalyst and quartz sand are 40~60 mesh.Logical 10% synthesis gas/nitrogen (H₂/ CO=0.5) it is restored, it is empty Fast WHSV=8000ml/ (g_catH), reduction temperature is 300 DEG C and keeps 5h.H is switched to after being cooled to 200 DEG C after reduction₂/ The synthesis gas of CO=1 is activated, air speed WHSV=2000ml/ (g_catH), activation time is for 24 hours.Lead to H after activation₂/ The synthesis gas of CO=1 is reacted, air speed WHSV=2000ml/ (g_catH), back pressure is warming up to 210 DEG C and is commented to 6MPa Valence, results of property are shown in Table 1.

[embodiment 5]

Cobalt nitrate and 50% manganese nitrate solution are weighed according to Co/Mn=1 (molar ratio), wherein Co and Mn element point The 31% and 33% of catalyst gross mass is not accounted for；Claim by 2% pair of hydrate ruthenium trichloride that Ru element accounts for catalyst gross mass Amount, and the metal mixed salting liquid of 1mol/L is made in deionized water in above-mentioned three kinds of metal salt co-dissolves；By alkali metal 1% pair of natrium carbonicum calcinatum that Na accounts for catalyst gross mass is weighed and is dissolved in the precipitating reagent that 2mol/L is made in deionized water Solution.

[embodiment 6]

Cobalt nitrate and 50% manganese nitrate solution are weighed according to Co/Mn=1 (molar ratio), wherein Co and Mn element point The 30% and 32% of catalyst gross mass is not accounted for；Claim by 4% pair of hydrate ruthenium trichloride that Ru element accounts for catalyst gross mass Amount, and the metal mixed salting liquid of 1mol/L is made in deionized water in above-mentioned three kinds of metal salt co-dissolves；By alkali metal 0.9% pair of natrium carbonicum calcinatum that Na accounts for catalyst gross mass is weighed and is dissolved in the precipitating that 2mol/L is made in deionized water Agent solution.

[embodiment 7]

Cobalt nitrate and 50% manganese nitrate solution are weighed according to Co/Mn=1 (molar ratio), wherein Co and Mn element point The 30% and 31% of catalyst gross mass is not accounted for；Claim by 8% pair of hydrate ruthenium trichloride that Ru element accounts for catalyst gross mass Amount, and the metal mixed salting liquid of 1mol/L is made in deionized water in above-mentioned three kinds of metal salt co-dissolves；By alkali metal 1.3% pair of anhydrous carbon number sodium that Na accounts for catalyst gross mass is weighed and is dissolved in the precipitating that 2mol/L is made in deionized water Agent solution.

[embodiment 8]

The 4% of the catalyst gross mass weighing for carrying out hydrate ruthenium trichloride is accounted for by Ru element, it is total to account for catalyst by Mn element 60% pair of 50% manganese nitrate solution of quality weighs, and above two dissolving metal salts are made in deionized water The metal mixed salting liquid of 1mol/L；It is weighed simultaneously by 1.7% pair of natrium carbonicum calcinatum that Alkali-Metal Na accounts for catalyst gross mass It is dissolved in the precipitant solution that 2mol/L is made in certain deionized water.

The deionized water of 100ml is added in beaker, above-mentioned mixed metal salt and precipitant solution are instilled into the beaker simultaneously In, it stirs and evenly mixs.Co-precipitation temperature is 23 DEG C, and co-precipitation pH is 8.After titration at 23 DEG C aging 2h, after aging Centrifuge washing 6 times, dry 12h is subsequently placed in 100 DEG C of baking ovens, finally 330 DEG C of roasting 3h in Muffle furnace, dry and roasting is equal It is carried out in air atmosphere.

Catalytic performance test is carried out in fixed bed to above-mentioned catalyst.Weigh the above-mentioned catalyst of 1.5g and 3.0g quartz sand Particle mixing, catalyst and quartz sand are 40~60 mesh.Logical 10% synthesis gas/nitrogen (H₂/ CO=0.5) it is restored, it is empty Fast WHSV=8000ml/ (g_catH), reduction temperature is 300 DEG C and keeps 5h.H is switched to after being cooled to 200 DEG C after reduction₂/ The synthesis gas of CO=1 is activated, air speed WHSV=2000ml/ (g_catH), activation time is for 24 hours.Lead to H after activation₂/ The synthesis gas of CO=1 is reacted, air speed WHSV=2000ml/ (g_catH), back pressure is warming up to 240 DEG C and is commented to 6MPa Valence, results of property are shown in Table 1.

[embodiment 9]

The 4% of the catalyst gross mass weighing for carrying out hydrate ruthenium trichloride is accounted for by Ru element, it is total to account for catalyst by Co element 60% pair of cobalt nitrate of quality weighs, and 1mol/L is made in deionized water in above two metal salt co-dissolve Metal mixed salting liquid；It is weighed and is dissolved in by 0.4% pair of natrium carbonicum calcinatum that Alkali-Metal Na accounts for catalyst gross mass The precipitant solution of 2mol/L is made in deionized water.

[embodiment 10]

Nitrosyl nitric acid ruthenium and cobalt nitrate are weighed by Co/Ru=10 (molar ratio), and by the metal salt of Ru and Co Co-dissolve obtains mixing salt solution in deionized water, and 20%, the Ru element that wherein Co element accounts for catalyst gross mass, which accounts for, urges The 3.3% of agent gross mass.It is weighed by 0.6% pair of sodium nitrate that Na element accounts for catalyst gross mass and is dissolved in deionization Base agent solution is obtained in water.10g absorbent charcoal carrier (account for catalyst gross mass 67.6%) is weighed, measuring its water absorption is 1.2ml/g first impregnates the mixing salt solution of Ru and Co on the activated carbon, after standing, drying, roasting, then impregnates Na on it, Through standing, drying, roasting.Wherein all static conditions in air atmosphere (about 23 DEG C) standing 12h of room temperature；It is dry Condition is 120 DEG C of holding 12h in the vacuum oven of air atmosphere；Roasting condition is the lower 60 DEG C of holdings 2h of nitrogen atmosphere, then 350 DEG C of roasting 4h after 120 DEG C of holding 2h.

[embodiment 11]

It weighs a certain amount of cobalt nitrate and is dissolved in the Co salting liquid for obtaining 1mol/L in deionized water, weigh a certain amount of Natrium carbonicum calcinatum is simultaneously dissolved in the precipitant solution that 2mol/L is obtained in deionized water, with the oxidation of M1 oxide and Alkali-Metal Na Object gross mass meter, the mass percent of Alkali-Metal Na are 0.6%.The deionized water of 100ml is added in beaker, by above-mentioned Co salt Solution and precipitant solution instill in the beaker simultaneously, stir and evenly mix.Co-precipitation temperature is 25 DEG C, and co-precipitation pH is 8.Titration knot Aging 2h, centrifuge washing 6 times after aging at 25 DEG C after beam are subsequently placed in 100 DEG C of baking ovens dry 12h, finally in horse Not 330 DEG C of roasting 3h in furnace, dry and roasting carry out in air atmosphere, and the Co of alkali metal containing Na can be made in the above method₃O₄ Oxide (i.e. the M1 oxide of alkali metal containing).

It is accounted for the weighing of 1% progress hydrate ruthenium trichloride of catalyst gross mass by Ru element and is dissolved in deionized water and obtained To Ru salting liquid.Weigh the Co of the alkali metal containing Na of 10g₃O₄Oxide as the carrier (oxide and Co of Alkali-Metal Na₃O₄ Gross mass account for the 98.7% of catalyst gross mass), measure its water absorption be 0.6ml/g, Ru salt is impregnated in Co₃O₄On, through quiet It sets, dry, roast.Wherein static conditions (about 23 DEG C) standing 12h of room temperature in air atmosphere；Drying condition is air gas 100 DEG C of holding 12h in the baking oven of atmosphere；Roasting condition is the lower 60 DEG C of holdings 2h of air atmosphere, then 330 DEG C after 120 DEG C of holding 2h Roast 3h.

[embodiment 12]

[embodiment 13]

It weighs a certain amount of manganese nitrate and is dissolved in the Mn salting liquid for obtaining 1mol/L in deionized water, weigh a certain amount of Natrium carbonicum calcinatum is simultaneously dissolved in the precipitant solution that 2mol/L is obtained in deionized water, with the oxidation of M1 oxide and Alkali-Metal Na Object gross mass meter, the mass percent of Alkali-Metal Na are 0.6%.The deionized water of 100ml is added in beaker, by above-mentioned Mn salt Solution and precipitant solution instill in the beaker simultaneously, stir and evenly mix.Co-precipitation temperature is 25 DEG C, and co-precipitation pH is 8.Titration knot Aging 2h, centrifuge washing 6 times after aging at 25 DEG C after beam are subsequently placed in 100 DEG C of baking ovens dry 12h, finally in horse Not 330 DEG C of roasting 3h in furnace, dry and roasting carry out in air atmosphere, and the MnO of alkali metal containing Na can be made in the above method₂ Oxide (i.e. the M1 oxide of alkali metal containing).

The weighing of 0.5% progress hydrate ruthenium trichloride of catalyst gross mass is accounted for by Ru element and is dissolved in deionized water Obtain Ru salting liquid.Weigh the MnO of 20g alkali metal containing Na₂Oxide as the carrier (oxide and MnO of Alkali-Metal Na₂'s Gross mass accounts for the 99.3% of catalyst gross mass), measuring its water absorption is 0.14ml/g, and Ru salt is impregnated in MnO₂On, through quiet It sets, dry, roast.Wherein static conditions (about 23 DEG C) standing 12h of room temperature in air atmosphere；Drying condition is air gas In 120 DEG C of holding 12h in the vacuum oven of atmosphere；Roasting condition is the lower 60 DEG C of holdings 2h of air atmosphere, then in 120 DEG C of holding 2h 330 DEG C of roasting 3h afterwards.

[embodiment 14]

It weighs a certain amount of cerous nitrate and is dissolved in the Ce salting liquid for obtaining 1mol/L in deionized water, weigh a certain amount of Natrium carbonicum calcinatum is simultaneously dissolved in the precipitant solution that 2mol/L is obtained in deionized water, with the oxidation of M1 oxide and Alkali-Metal Na Object gross mass meter, the mass percent of Alkali-Metal Na are 0.6%.The deionized water of 100ml is added in beaker, by above-mentioned Ce salt Solution and precipitant solution instill in the beaker simultaneously, stir and evenly mix.Co-precipitation temperature is 25 DEG C, and co-precipitation pH is 8.Titration knot Aging 2h, centrifuge washing 6 times after aging at 25 DEG C after beam are subsequently placed in 100 DEG C of baking ovens dry 12h, finally in horse Not 330 DEG C of roasting 3h in furnace, dry and roasting carry out in air atmosphere, and the CeO of alkali metal containing Na can be made in the above method₂ Oxide (i.e. the M1 oxide of alkali metal containing).

The weighing of 0.5% progress hydrate ruthenium trichloride of catalyst gross mass is accounted for by Ru element and is dissolved in deionized water Obtain Ru salting liquid.Weigh the CeO of 20g alkali metal containing Na₂Oxide as the carrier (oxide and CeO of Alkali-Metal Na₂'s Gross mass accounts for the 99.3% of catalyst gross mass), measuring its water absorption is 0.21ml/g, and Ru salt is impregnated in CeO₂On, through quiet It sets, dry, roast.Wherein static conditions (about 23 DEG C) standing 12h of room temperature in air atmosphere；Drying condition is air gas In 120 DEG C of holding 12h in the vacuum oven of atmosphere；Roasting condition is the lower 60 DEG C of holdings 2h of air atmosphere, then in 120 DEG C of holding 2h 330 DEG C of roasting 3h afterwards.

[embodiment 15]

The weighing of 0.5% progress hydrate ruthenium trichloride of catalyst gross mass is accounted for by Ru element and is dissolved in deionized water Obtain Ru salting liquid.Weigh 20g TiO₂Powder is as carrier (TiO₂Account for the 99.3% of catalyst gross mass), measure its water absorption For 0.33ml/g, Ru salt is impregnated in TiO₂On, through standing, drying, roasting.Wherein static conditions room in air atmosphere (about 23 DEG C) standing 12h of temperature；Drying condition is in the vacuum oven of air atmosphere in 120 DEG C of holding 12h；Roasting condition is sky The lower 60 DEG C of holdings 2h of gas atmosphere, then 330 DEG C of roasting 3h after 120 DEG C of holding 2h.

[embodiment 16]

The weighing of 0.5% progress hydrate ruthenium trichloride of catalyst gross mass is accounted for by Ru element and is dissolved in deionized water Obtain Ru salting liquid.Weigh 10g SiO₂Aerosol is as carrier (SiO₂Account for the 99.3% of catalyst gross mass), measure its water suction Amount is 2.0ml/g, and Ru salt is impregnated in SiO₂On aerosol, through standing, drying, roasting.Wherein static conditions are in air (about 25 DEG C) standing 12h of room temperature under atmosphere；Drying condition is in the vacuum oven of air atmosphere in 120 DEG C of holding 12h；Roasting Condition is the lower 60 DEG C of holdings 2h of air atmosphere, then 330 DEG C of roasting 3h after 120 DEG C of holding 2h.

Catalytic performance test is carried out in fixed bed to above-mentioned catalyst.Weigh the above-mentioned catalyst of 1.5g and 3.0g quartz sand Particle mixing, catalyst and quartz sand are 40~60 mesh.Logical 10% synthesis gas/nitrogen (H₂/ CO=0.5) it is restored, it is empty Fast WHSV=8000ml/ (g_catH), reduction temperature is 300 DEG C and keeps 5h.H is switched to after being cooled to 200 DEG C after reduction₂/ The synthesis gas of CO=1 is activated, air speed WHSV=2000ml/ (g_catH), activation time is for 24 hours.Lead to H after activation₂/ The synthesis gas of CO=1 is reacted, air speed WHSV=2000ml/ (g_catH), back pressure is warming up to 250 DEG C and is commented to 6MPa Valence, results of property are shown in Table 1.

[embodiment 17]

It is weighed by 0.2% pair of nitrosyl nitric acid ruthenium that Ru element accounts for catalyst gross mass, accounts for catalyst by Co element 20% pair of cobalt nitrate of gross mass weighs, and the metal salt co-dissolve of Ru and Co is obtained salt-mixture in deionized water Solution.10g coconut palm board active carbon is weighed as carrier (coconut palm board active carbon accounts for the 74.3% of catalyst gross mass), measures its water absorption For 2.34ml/g, the mixing salt solution of Ru and Co is impregnated on the activated carbon, after standing, drying, roasting.Wherein stand item Part in air atmosphere (about 23 DEG C) standing 12h of room temperature；Drying condition is 120 DEG C of holdings in the vacuum oven of air atmosphere 12h；Roasting condition is the lower 60 DEG C of holdings 2h of nitrogen atmosphere, then 350 DEG C of roasting 4h after 120 DEG C of holding 2h.

[embodiment 18]

It is weighed by 0.5% pair of nitrosyl nitric acid ruthenium that Ru element accounts for catalyst gross mass, accounts for catalyst by Co element 20% pair of cobalt nitrate of gross mass weighs, and the metal salt co-dissolve of Ru and Co is obtained salt-mixture in deionized water Solution.10g coconut palm board active carbon is weighed as carrier (coconut palm board active carbon accounts for the 73.9% of catalyst gross mass), measures its water absorption For 2.34ml/g, the mixing salt solution of Ru and Co is impregnated on the activated carbon, after standing, drying, roasting.Wherein stand item Part in air atmosphere (about 23 DEG C) standing 12h of room temperature；Drying condition is 120 DEG C of holdings in the vacuum oven of air atmosphere 12h；Roasting condition is the lower 60 DEG C of holdings 2h of nitrogen atmosphere, then 350 DEG C of roasting 4h after 120 DEG C of holding 2h.

[embodiment 19]

It is weighed by 1% pair of nitrosyl nitric acid ruthenium that Ru element accounts for catalyst gross mass, it is total to account for catalyst by Co element 20% pair of cobalt nitrate of quality weighs, and it is molten that the metal salt co-dissolve of Ru and Co obtained salt-mixture in deionized water Liquid.The coconut shell activated high-area carbon of 10g (coconut palm board active carbon accounts for the 73.3% of catalyst gross mass) is weighed, measuring its water absorption is 2.34ml/g impregnates the mixing salt solution of Ru and Co, after standing, drying, roasting on the activated carbon.Wherein static conditions In air atmosphere (about 23 DEG C) standing 12h of room temperature；Drying condition is 120 DEG C of holdings in the vacuum oven of air atmosphere 12h；Roasting condition is the lower 60 DEG C of holdings 2h of nitrogen atmosphere, then 350 DEG C of roasting 4h after 120 DEG C of holding 2h.

[embodiment 20]

Catalytic performance test is carried out in fixed bed to above-mentioned catalyst.Weigh the above-mentioned catalyst of 1.5g and 3.0g quartz sand Particle mixing, catalyst and quartz sand are 40~60 mesh.Logical 10% synthesis gas/nitrogen (H₂/ CO=0.5) it is restored, it is empty Fast WHSV=8000ml/ (g_catH), reduction temperature is 300 DEG C and keeps 5h.H is switched to after being cooled to 200 DEG C after reduction₂/ The synthesis gas of CO=1 is activated, air speed WHSV=2000ml/ (g_catH), activation time is for 24 hours.Lead to H after activation₂/ The synthesis gas of CO=1 is reacted, air speed WHSV=2000ml/ (g_catH), back pressure is warming up to 220 DEG C of progress to 0.5MPa Evaluation, results of property are shown in Table 1.

[embodiment 21]

Catalytic performance test is carried out in fixed bed to above-mentioned catalyst.Weigh the above-mentioned catalyst of 1.5g and 3.0g quartz sand Particle mixing, catalyst and quartz sand are 40~60 mesh.Logical 10% synthesis gas/nitrogen (H₂/ CO=0.5) it is restored, it is empty Fast WHSV=8000ml/ (g_catH), reduction temperature is 300 DEG C and keeps 5h.H is switched to after being cooled to 200 DEG C after reduction₂/ The synthesis gas of CO=1 is activated, air speed WHSV=2000ml/ (g_catH), activation time is for 24 hours.Lead to H after activation₂/ The synthesis gas of CO=1 is reacted, air speed WHSV=2000ml/ (g_catH), back pressure is warming up to 220 DEG C and is commented to 2MPa Valence, results of property are shown in Table 1.

[embodiment 22]

Catalytic performance test is carried out in fixed bed to above-mentioned catalyst.Weigh the above-mentioned catalyst of 1.5g and 3.0g quartz sand Particle mixing, catalyst and quartz sand are 40~60 mesh.Logical 10% synthesis gas/nitrogen (H₂/ CO=0.5) it is restored, it is empty Fast WHSV=8000ml/ (g_catH), reduction temperature is 300 DEG C and keeps 5h.H is switched to after being cooled to 200 DEG C after reduction₂/ The synthesis gas of CO=1 is activated, air speed WHSV=2000ml/ (g_catH), activation time is for 24 hours.Lead to H after activation₂/ The synthesis gas of CO=1 is reacted, air speed WHSV=1000ml/ (g_catH), back pressure is warming up to 220 DEG C and is commented to 6MPa Valence, results of property are shown in Table 1.

[embodiment 23]

Catalytic performance test is carried out in fixed bed to above-mentioned catalyst.Weigh the above-mentioned catalyst of 1.5g and 3.0g quartz sand Particle mixing, catalyst and quartz sand are 40~60 mesh.Logical 10% synthesis gas/nitrogen (H₂/ CO=0.5) it is restored, it is empty Fast WHSV=8000ml/ (g_catH), reduction temperature is 300 DEG C and keeps 5h.H is switched to after being cooled to 200 DEG C after reduction₂/ The synthesis gas of CO=1 is activated, air speed WHSV=2000ml/ (g_catH), activation time is for 24 hours.Lead to H after activation₂/ The synthesis gas of CO=1 is reacted, air speed WHSV=4000ml/ (g_catH), back pressure is warming up to 220 DEG C and is commented to 6MPa Valence, results of property are shown in Table 1.

[embodiment 24]

It weighs a certain amount of copper nitrate, zinc nitrate and aluminum nitrate and is dissolved in the mixing gold for obtaining 1mol/L in deionized water Belong to salting liquid；It weighs a certain amount of natrium carbonicum calcinatum and is dissolved in the precipitant solution for obtaining 2mol/L in deionized water.With M1 The oxide gross mass meter of oxide (i.e. the oxide of Cu element, Zn element and Al element) and Alkali-Metal Na, the matter of Cu element Measuring the mass percent that the mass percent that percentage is 47%, Zn element is 24%, Al element is 3%, the matter of Alkali-Metal Na Measuring percentage is 0.6%.

The deionized water of 100ml is added in beaker, above-mentioned mixed salt solution and precipitant solution are instilled simultaneously In the beaker, stir and evenly mix.Co-precipitation temperature is 25 DEG C, and co-precipitation pH is 8.Aging 2h, aging at 25 DEG C after titration After centrifuge washing 6 times, be subsequently placed in 100 DEG C of baking ovens dry 12h, finally 330 DEG C of roasting 3h in Muffle furnace, it is dry with Roasting carries out in air atmosphere, and oxide (the i.e. alkali metal containing of the CuZnAl of alkali metal containing Na can be made in the above method M1 oxide).

It is accounted for the weighing of 5% progress hydrate ruthenium trichloride of catalyst gross mass by Ru element and is dissolved in deionized water and obtained To Ru salting liquid.Weigh the 10g above method preparation alkali metal containing Na CuZnAl oxide as carrier (Alkali-Metal Na The oxide of oxide and CuZnAl account for the 93.4% of catalyst gross mass), measuring its water absorption is 2.0ml/g, and Ru salt is soaked Stain is on CuZnAl, through standing, drying, roasting.Wherein static conditions are the lower 25 DEG C of standings 12h of air atmosphere；Dried strip Part be air atmosphere under in baking oven 120 DEG C of holding 12h；Roasting condition is the lower 330 DEG C of roastings 3h of air atmosphere.

[embodiment 25]

It weighs a certain amount of magnesium nitrate and hydrate ruthenium trichloride and is dissolved in the mixing gold for obtaining 1mol/L in deionized water Belong to salting liquid, wherein Mg and Ru element accounts for the 58% and 4% of catalyst gross mass respectively；Weigh a certain amount of natrium carbonicum calcinatum simultaneously It is dissolved in the precipitant solution that 2mol/L is obtained in deionized water, wherein Alkali-Metal Na accounts for the 0.6% of catalyst gross mass.

The deionized water of 100ml is added in beaker, above-mentioned mixed salt solution and precipitant solution are instilled simultaneously In the beaker, stir and evenly mix.Co-precipitation temperature is 25 DEG C, and co-precipitation pH is 8.Aging 2h, aging at 25 DEG C after titration After centrifuge washing 6 times, be subsequently placed in 100 DEG C of baking ovens dry 12h, finally 330 DEG C of roasting 3h in Muffle furnace, it is dry with Roasting carries out in air atmosphere.

[embodiment 26]

It weighs a certain amount of zirconium nitrate and hydrate ruthenium trichloride and is dissolved in the mixing gold for obtaining 1mol/L in deionized water Belong to salting liquid, wherein Zr and Ru element accounts for the 70% and 4% of catalyst gross mass respectively, weighs a certain amount of natrium carbonicum calcinatum simultaneously It is dissolved in the precipitant solution that 2mol/L is obtained in deionized water, wherein Alkali-Metal Na accounts for the 0.6% of catalyst gross mass.

[embodiment 27]

It weighs a certain amount of barium nitrate and hydrate ruthenium trichloride and is dissolved in the mixing gold for obtaining 1mol/L in deionized water Belong to salting liquid, wherein Ba and Ru element accounts for the 85% and 4% of catalyst gross mass respectively, weighs a certain amount of natrium carbonicum calcinatum simultaneously It is dissolved in the precipitant solution that 2mol/L is obtained in deionized water, wherein Alkali-Metal Na accounts for the 0.6% of catalyst gross mass.

[embodiment 28]

It weighs a certain amount of calcium chloride and hydrate ruthenium trichloride and is dissolved in the mixing gold for obtaining 1mol/L in deionized water Belong to salting liquid, wherein Ca and Ru element accounts for the 34% and 4% of catalyst gross mass respectively, weighs a certain amount of natrium carbonicum calcinatum simultaneously It is dissolved in the precipitant solution that 2mol/L is obtained in deionized water, wherein Alkali-Metal Na accounts for the 0.6% of catalyst gross mass.

[embodiment 29]

Cobalt nitrate and 50% manganese nitrate solution are weighed according to Co/Mn=1 (molar ratio), wherein Co and Mn element point The 30% and 32% of catalyst gross mass is not accounted for；Claim by 4% pair of hydrate ruthenium trichloride that Ru element accounts for catalyst gross mass Amount, and the metal mixed salting liquid of 1mol/L is made in deionized water in above-mentioned three kinds of metal salt co-dissolves；By alkali metal 0.9% pair of lithium hydroxide that Li accounts for catalyst gross mass is weighed and is dissolved in the precipitating reagent that 1mol/L is made in deionized water Solution.

[embodiment 30]

Cobalt nitrate and 50% manganese nitrate solution are weighed according to Co/Mn=1 (molar ratio), wherein Co and Mn element point The 30% and 32% of catalyst gross mass is not accounted for；Claim by 4% pair of hydrate ruthenium trichloride that Ru element accounts for catalyst gross mass Amount, and the metal mixed salting liquid of 1mol/L is made in deionized water in above-mentioned three kinds of metal salt co-dissolves；By alkali metal 0.9% pair of potassium carbonate that K accounts for catalyst gross mass weighed and be dissolved in be made in deionized water 2mol/L precipitating reagent it is molten Liquid.

[embodiment 31]

Cobalt nitrate and 50% manganese nitrate solution are weighed according to Co/Mn=1 (molar ratio), wherein Co and Mn element point The 30% and 32% of catalyst gross mass is not accounted for；Claim by 4% pair of hydrate ruthenium trichloride that Ru element accounts for catalyst gross mass Amount, and the metal mixed salting liquid of 1mol/L is made in deionized water in above-mentioned three kinds of metal salt co-dissolves；By alkali metal 0.9% pair of rubidium carbonate that Rb accounts for catalyst gross mass weighed and be dissolved in be made in deionized water 1mol/L precipitating reagent it is molten Liquid.

[embodiment 32]

Cobalt nitrate and 50% manganese nitrate solution are weighed according to Co/Mn=1 (molar ratio), wherein Co and Mn element point The 30% and 32% of catalyst gross mass is not accounted for；Claim by 4% pair of hydrate ruthenium trichloride that Ru element accounts for catalyst gross mass Amount, and the metal mixed salting liquid of 1mol/L is made in deionized water in above-mentioned three kinds of metal salt co-dissolves；By alkali metal 0.9% pair of cesium carbonate that Cs accounts for catalyst gross mass weighed and be dissolved in be made in deionized water 1mol/L precipitating reagent it is molten Liquid.

[embodiment 33]

Account for the 0.5% and 20% pair of hydrate ruthenium trichloride and cobalt nitrate of catalyst gross mass respectively by Ru element and Co element Weighing, both salt are dissolved in deionized water and obtain mixing salt solution.Weigh the MnO of 20g alkali metal containing Na₂Oxidation Object is as the carrier (oxide and MnO of Alkali-Metal Na₂Gross mass account for the 73.9% of catalyst gross mass), measure its water absorption For 0.14ml/g, salt-mixture is impregnated in MnO₂On, through standing, drying, roasting.Wherein static conditions are in air atmosphere (about 23 DEG C) standing 12h of room temperature；Drying condition is in the vacuum oven of air atmosphere in 120 DEG C of holding 12h；Roasting condition is The lower 60 DEG C of holdings 2h of air atmosphere, then 330 DEG C of roasting 3h after 120 DEG C of holding 2h.

[embodiment 34]

It weighs a certain amount of manganese nitrate and is dissolved in the Mn salting liquid for obtaining 1mol/L in deionized water, weigh a certain amount of Ammonium carbonate is simultaneously dissolved in the precipitant solution that 2mol/L is obtained in deionized water.The deionized water of 100ml is added in beaker, it will Above-mentioned Mn salting liquid and precipitant solution instill in the beaker simultaneously, stir and evenly mix.Co-precipitation temperature is 25 DEG C, and co-precipitation pH is 8.Aging 2h, centrifuge washing 6 times after aging at 25 DEG C after titration are subsequently placed in 100 DEG C of baking ovens dry 12h, Finally 330 DEG C of roasting 3h in Muffle furnace, dry and roasting carry out in air atmosphere, and MnO can be made in the above method₂Oxygen Compound (i.e. the not M1 oxide of alkali metal containing).

0.5%, 20% and 0.6wt% of catalyst gross mass is accounted for respectively to hydration by Ru element, Co element and Na element Ruthenium trichloride, cobalt nitrate and sodium nitrate are weighed, these three salt are dissolved in deionized water and obtain mixing salt solution.It weighs 20g MnO₂As carrier (MnO₂Account for the 73.1% of catalyst gross mass), measuring its water absorption is 0.14ml/g, and salt-mixture is soaked Stain is in MnO₂On, through standing, drying, roasting.Wherein static conditions (about 23 DEG C) standing 12h of room temperature in air atmosphere； Drying condition is in the vacuum oven of air atmosphere in 120 DEG C of holding 12h；Roasting condition is the lower 60 DEG C of holdings of air atmosphere 2h, then 330 DEG C of roasting 3h after 120 DEG C of holding 2h.

1 embodiment catalyst reaction performance result of table

As seen from Table 1, synthesis gas conversion is carried out in fixed bed using catalyst prepared by this patent directly to prepare Mixed alcohol shows higher catalytic performance.As described in Example 1, when Ru content is only 0.1wt%, CO high conversion rate reaches 30.3%.Even embodiment 8 shows to be reacted at 240 DEG C, CO conversion ratio and lower, the explanation of total alcohol selectivity Individual RuMn is more difficult for the activation and insertion of CO, and the introducing of Co can be improved Ru base catalyst and convert directly for synthesis gas Connect the activity for preparing mixed alcohol and total alcohol selectivity.Embodiment 9 shows that total alcohol is selectively 14.8%, is lower than Examples 1 to 7, Illustrate that Mn can promote Ru base catalyst and directly prepare mixed alcohol for synthesis gas conversion.Embodiment 11 to 16 shows different carriers Upper dipping Ru can obtain certain alcohol product.Embodiment 17 to 19 shows on active carbon while impregnating Ru, Co to obtain Higher activity, and activity increases when Ru increase, but total alcohol selective difference is little.Embodiment 20 to 23 shows reaction pressure Change with air speed selectively has a certain impact to reactivity and total alcohol.Embodiment 25 to 28 shows Ru and other gold A certain amount of alcohol can be obtained by belonging to coprecipitation.Embodiment 29 to 32 shows that different alkali metal precipitating reagents is precipitated, equal energy Obtain preferable total alcohol selectivity.Embodiment 33 to 34 shows influence difference of the different incorporation ways of alkali metal to mixed alcohol It is less big.CO conversion ratio in embodiment reaches as high as 35.5%, and total alcohol selectively reaches as high as 37.0%.In addition, embodiment In catalyst performance stabilised, preparation method is simple, easy to operate, is easy to repeat and industry amplification, and there is potential industry to answer Use prospect.

The above, only presently preferred embodiments of the present invention, not to the present invention in any form with substantial limitation, It should be pointed out that under the premise of not departing from the method for the present invention, can also be made for those skilled in the art Several improvement and supplement, these are improved and supplement also should be regarded as protection scope of the present invention.All those skilled in the art, Without departing from the spirit and scope of the present invention, when made using disclosed above technology contents it is a little more Dynamic, modification and the equivalent variations developed, are equivalent embodiment of the invention；Meanwhile all substantial technologicals pair according to the present invention The variation, modification and evolution of any equivalent variations made by above-described embodiment, still fall within the range of technical solution of the present invention It is interior.

Claims

1. a kind of Ru base catalyst for directly preparing mixed alcohol for synthesis gas conversion characterized by comprising

The oxide of active component Ru；

At least one of oxide and carrier of metal promoter M1 element；

Wherein, M1 element is selected from transition metal element, third major element, alkali earth metal and lanthanide series in metal promoter At least one of.

2. Ru base catalyst as described in claim 1, which is characterized in that further include:

The oxide of alkali metal promoter M2 element.

3. Ru base catalyst as claimed in claim 2, which is characterized in that in alkali metal promoter M2 element be selected from Li, Na, K, At least one of Rb, Cs.

4. Ru base catalyst as described in any one of claims 1 to 3, which is characterized in that further include in following technical characteristic At least one of:

2) third major element is Al in metal promoter；

4) lanthanide series is Ce in metal promoter；

5) carrier is selected from oxide, the SiO of M1 element₂、TiO₂At least one of with carbon material, alternatively, the carrier selects Oxide, the SiO of the M1 element of self-supported M2 element₂、TiO₂At least one of with carbon material；As the Ru Ji Cuihuajibao The oxide of metal promoter M1 element is included, when carrier includes the oxide of M1 element, as the M1 element of carrier and as metal The M1 element of auxiliary agent is not identical；When the Ru base catalyst includes the oxide of alkali metal promoter M2 element, carrier includes load When the oxide of the M1 element of M2 element, the M2 element as carrier and the M2 element as alkali metal promoter be not identical；

6) Ru element accounts for the 0.1~8% of catalyst gross mass；

7) M1 element accounts for the 0~85% of catalyst gross mass in metal promoter；

8) M2 element accounts for the 0~1.7% of catalyst gross mass in alkali metal promoter；

9) carrier accounts for 99.9% or less catalyst gross mass.

5. Ru base catalyst as claimed in claim 4, which is characterized in that feature 5) in, in terms of carrier gross mass, M2 in carrier The mass percent that element accounts for carrier is 0~0.6%.

6. such as the preparation method of Ru base catalyst described in any one of claim 1 to 5, which is characterized in that the preparation method Selected from one of following method:

Preparation method one, includes the following steps:

1a) according to Ru base catalyst composition and ratio, the salt of Ru salt and metal promoter M1 element is dissolved in water, obtains mixed metal salt Solution；

1c) by the obtained precipitant solution of the obtained mixed salt solution of step 1a) and step 1b) while instilling in mother liquor altogether Precipitating obtains co-precipitation solution；

1d) co-precipitation solution age, centrifugation, washing, drying and the roasting for obtaining step 1c) are to get the Ru base catalyst；

Preparation method two, includes the following steps:

2a) according to Ru base catalyst composition and ratio, the salt of Ru salt and metal promoter M1 element is dissolved in water, obtains mixed metal salt Solution；

2c) by the obtained precipitant solution of the obtained mixed salt solution of step 2a) and step 2b) while instilling in mother liquor, It stirs and evenly mixs, forms co-precipitation solution；

2d) co-precipitation solution age, centrifugation, washing, drying and the roasting for obtaining step 2c) are to get the Ru base catalyst；

Preparation method three, includes the following steps:

3a) according to Ru base catalyst composition and ratio, Ru salt is dissolved in water, obtains dipping solution；Alternatively, by Ru salt, and, metal The salt of auxiliary agent M1 element and at least one of the salt of alkali metal M2 element, are dissolved in water, obtain dipping solution；

3b) dipping solution for obtaining step 3a) uses on one step of equi-volume impregnating dipping or step impregnation to the carrier, Wherein, the carrier after step dipping or in step impregnation after every step dipping is stood, dry and roasting is to get Ru base catalysis Agent；

Preparation method four, includes the following steps:

4a) according to catalyst composition and ratio, the salt of metal promoter M1 element is dissolved in water, the salt for obtaining metal promoter M1 element is molten Liquid；

It is 4b) that the precipitating reagent of alkali metal M2 element is soluble in water, precipitant solution is obtained, alternatively, will not alkali metal containing M2 element Precipitating reagent it is soluble in water, obtain precipitant solution；

4c) by the salting liquid and step 4b of the metal promoter M1 element that step 4a) is obtained) it obtained precipitant solution while instilling It is co-precipitated in mother liquor, obtains co-precipitation solution；

4d) co-precipitation solution age, centrifugation, washing, drying and the roasting for obtaining step 4c) obtains metal promoter M1 element The oxide of middle alkali metal containing M2 element or the not oxide of alkali metal containing M2 element, i.e., the described carrier；

4e) according to Ru base catalyst composition and ratio, Ru salt is dissolved in water, obtains dipping solution；Alternatively, by Ru salt, and, metal The salt of auxiliary agent M1 element and at least one of the salt of alkali metal M2 element, are dissolved in water, obtain dipping solution；

4f) dipping solution that step 4e) is obtained is obtained using one step of equi-volume impregnating dipping or step impregnation to step 4d) Metal promoter M1 element in alkali metal containing M2 element oxide or not on the oxide of alkali metal containing M2 element, wherein In metal promoter M1 element after one step dipping or in step impregnation after every step dipping the oxide of alkali metal containing M2 element or The oxide of alkali metal containing M2 element is not stood, dry and roasting is to get the Ru base catalyst.

7. the preparation method of Ru base catalyst as claimed in claim 6, which is characterized in that further include in following technical characteristic At least one of:

1) the Ru salt is selected from ruthenic chloride, iodate ruthenium, acetic acid ruthenium, ruthenium hydrochloride potassium, acetylacetone,2,4-pentanedione ruthenium, nitrosyl nitric acid ruthenium, carbonyl At least one of ruthenic chloride and ruthenium hydrochloride ammonium；

2) salt of the metal promoter M1 element is selected from the nitric acid of the chlorate of metal promoter M1 element, metal promoter M1 element Salt, the sulfate of metal promoter M1 element, the carbonate of metal promoter M1 element and metal promoter M1 element acetate in It is at least one；

3) salt of the alkali metal M2 element is selected from the carbonate of alkali metal M2 element, the nitrate of alkali metal M2 element, alkali gold Belong to the acetic acid of the chlorate of M2 element, the ammonium salt of alkali metal M2 element, the sulfate of alkali metal M2 element and alkali metal M2 element At least one of salt.

8. the preparation method of Ru base catalyst as claimed in claim 6, which is characterized in that further include in following technical characteristic At least one of:

2) step 2b) in, the precipitating reagent of the not alkali metal containing M2 element is selected from (NH₄)₂CO₃And NH₃·H₂At least one in O Kind；

3) step 1a) and step 2a) in, the total mol concentration of the mixed salt solution is 0.5~4mol/L；

4) step 1b) and step 2b) in, the precipitant solution molar concentration is 0.5~4mol/L；

5) step 1c) and step 2c) in, the mother liquor is water；

6) step 1c) and step 2c) in, co-precipitation temperature is 10~80 DEG C；

7) step 1c) and step 2c) in, co-precipitation pH is 6~12；

8) step 1d) and step 2d) in, aging temperature is 20~80 DEG C；

9) step 1d) and step 2d) in, ageing time be 0.5~for 24 hours；

10) step 1d) and step 2d) in, centrifugation, washing 0~10 time；

11) step 1d) and step 2d) in, drying temperature is 80~150 DEG C；

12) step 1d) and step 2d) in, drying time is 6~48h；

13) step 1d) and step 2d) in, maturing temperature is 250~400 DEG C；

14) step 1d) and step 2d) in, calcining time be 0.5~for 24 hours；

15) step 1d) and step 2d) in, dry atmosphere is selected from least one of air atmosphere, nitrogen atmosphere, argon atmosphere；

16) step 1d) and step 2d) in, calcination atmosphere is selected from least one of air atmosphere, nitrogen atmosphere, argon atmosphere.

9. the preparation method of Ru base catalyst as claimed in claim 6, which is characterized in that further include in following technical characteristic At least one of:

1) step 3b) in, dipping temperature is 5~25 DEG C；

2) step 3b) in, time of repose is 4~48h；

3) step 3b) in, drying temperature is 80~150 DEG C；

4) step 3b) in, drying time is 6~48h；

5) step 3b) in, maturing temperature is 250~400 DEG C；

6) step 3b) in, calcining time be 0.5~for 24 hours；

10. the preparation method of Ru base catalyst as claimed in claim 6, which is characterized in that further include in following technical characteristic At least one of:

2) step 4b) in, the precipitating reagent of the not alkali metal containing M2 element is selected from (NH₄)₂CO₃And NH₃·H₂One of O or two Kind；

3) step 4a) in, the molar concentration of the metal promoter M1 element salting liquid is 0.5~4mol/L；

4) step 4b) in, the molar concentration of the precipitant solution is 0.5~4mol/L；

5) step 4c) in, the mother liquor is water；

6) step 4c) in, co-precipitation temperature is 10~80 DEG C；

7) step 4c) in, co-precipitation pH is 6~12；

8) step 4d) in, aging temperature is 20~80 DEG C；

9) step 4d) in, ageing time be 0.5~for 24 hours；

10) step 4d) in, centrifugation, washing 0~10 time；

11) step 4d) in, drying temperature is 80~150 DEG C；

12) step 4d) in, drying time is 6~48h；

13) step 4d) in, maturing temperature is 250~400 DEG C；

14) step 4d) in, calcining time be 0.5~for 24 hours；

17) step 4f) in, dwell temperature is 5~25 DEG C；

18) step 4f) in, time of repose is 4~48h；

19) step 4f) in, drying temperature is 80~150 DEG C；

20) step 4f) in, drying time is 6~48h；

21) step 4f) in, maturing temperature is 250~400 DEG C；

22) step 4f) in, calcining time be 0.5~for 24 hours；

11. such as the purposes of Ru base catalyst described in any one of claim 1 to 5, which is characterized in that for being closed in fixed bed Mixed alcohol is directly prepared at gas conversion.

12. the purposes of Ru base catalyst as claimed in claim 11, which is characterized in that further include in following technical characteristic extremely One item missing:

1) compression molding is carried out to the Ru base catalyst, chooses the catalyst of 40~60 mesh and the quartz sand particle of 40~60 mesh Loaded in fixed bed after mixing；

3) synthesis gas conversion directly prepares the reaction condition of mixed alcohol are as follows: unstripped gas is selected from H₂/ CO=0.5, H₂/ CO=1, H₂/CO One of=2 synthesis gas is a variety of, air speed WHSV=1000~4000ml/ (g_catH), reaction temperature is 210~250 DEG C, reaction pressure is 0.5~6MPa.

13. the purposes of Ru base catalyst as claimed in claim 12, which is characterized in that feature 2) in, it further include following technology At least one of in feature:

A) reducing atmosphere is in hydrogen, carbon monoxide, synthesis gas, dilution synthesis gas, dilution hydrogen and dilution carbon monoxide One or more, diluent gas is inert gas, and diluent gas volume fraction is below 90%；

B) reducing condition: reduction temperature is 200~400 DEG C, and the recovery time is 0.5~12h, and air speed WHSV is 8000ml/ (g_cat·h)；

C) 160~220 DEG C are cooled to after the Ru base catalyst reduction, are activated under 0.1~0.5MPa.

14. the purposes of Ru base catalyst as claimed in claim 13, which is characterized in that in feature c), activation phenomenon is selected from H₂/ CO=0.5, H₂/ CO=1 and H₂One of synthesis gas of/CO=2 is a variety of, and air speed WHSV is 1000~4000ml/ (g_cat· H), activation time is 12~48h.