CN103285876A - Vinyl acetylene hydrogenation catalyst and preparation method and applications thereof - Google Patents

Abstract

The invention provides a vinyl acetylene hydrogenation catalyst and a preparation method and applications thereof, wherein the vinyl acetylene hydrogenation catalyst comprises the following compositions in parts by weight: 0.01-30 parts of active component, 40-99.989 parts of carriers and catalyst promoter, wherein the mole ratio of the catalyst promoter to the active component is (0.1-10):1. According to the vinyl acetylene hydrogenation catalyst, the acetylene hydrogenation activity and butadiene selectivity are high, the vinyl acetylene hydrogenation catalyst can be effectively used in vinyl acetylene hydrogenation reaction so as to further efficiently prepare butadiene.

Description

Vinyl acetylene hydrogenation catalyst and its preparation method and use

technical field

The invention relates to the technical field of catalyst preparation, in particular to the technical field of vinyl acetylene hydrogenation catalyst preparation. Specifically, the present invention relates to a vinyl acetylene hydrogenation catalyst and its preparation method and use. More specifically, the present invention provides a vinyl acetylene hydrogenation catalyst, a method for preparing a vinyl acetylene hydrogenation catalyst, a method for preparing butadiene, and a butadiene product.

Background technique

Butadiene is an important petrochemical basic organic raw material and high polymer monomer. Its position in petrochemical olefin raw materials is second only to ethylene and propylene, and it has a wide range of uses. It can not only be used to produce synthetic butadiene rubber (BR), styrene-butadiene rubber (SBR), nitrile rubber, styrene-butadiene-styrene elastomer (SBS), acrylonitrile-butadiene-styrene ( ABS) resin and other rubber and resin products can also be used to produce organic chemical products such as adiponitrile, 1,4-butanediol, anthraquinone, sulfolane, tetrahydrophthalic anhydride, higher alcohols and macrocyclic musk. Therefore, it is of great significance to efficiently produce butadiene.

At this stage, butadiene comes from the extraction of petroleum _C4 fraction. Due to the increasingly scarce oil resources in our country, the supply of butadiene is at risk. Butadiene is produced through the new technology of acetylene, specifically, acetylene is prepared into vinyl acetylene through dimerization reaction, and then vinyl acetylene is selectively hydrogenated to obtain butadiene, which can realize the production of butadiene from coal.

In the selective hydrogenation of alkynes, the monometallic catalyst tends to have a strong complexation with the alkyne bond, which gradually dissolves the adsorbed hydrocarbon into the reaction hydrocarbon medium, resulting in permanent deactivation of the catalyst. After the second or more metals are added, the interaction between the metals can prevent the loss of the active components of the catalyst, and at the same time, the dispersion of the active components on the carrier can be improved, thereby further improving the activity of the catalyst.

Based on the above background, the present invention proposes a multimetallic catalyst for preparing butadiene by hydrogenation of vinyl acetylene, which can be effectively applied in the process route of preparing butadiene from acetylene.

Contents of the invention

The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the invention provides a vinyl acetylene hydrogenation catalyst and a preparation method and use thereof.

According to one aspect of the present invention, the present invention provides a vinyl acetylene hydrogenation catalyst. According to an embodiment of the present invention, the catalyst comprises: an active component of 0.01-30 parts by weight; a carrier of 40-99.989 parts by weight; and a co-catalyst, wherein the molar ratio of the co-catalyst to the active component is (0.1-10 ): 1.

The inventors have found surprisingly that the vinyl acetylene hydrogenation catalyst according to the embodiment of the present invention has strong vinyl acetylene hydrogenation activity and high butadiene yne selectivity. According to a specific example of the present invention, the vinyl acetylene hydrogenation catalyst of the present invention can be effectively used in the hydrogenation reaction of vinyl acetylene, and further can efficiently prepare butadiene.

According to the embodiments of the present invention, in the catalyst of the present invention, the types of active components are not particularly limited. According to a specific example of the present invention, the active component may be at least one selected from metals Pd, Cu, Co, Ni, Pt, Au, Ir, Ru, Mo and Fe. Therefore, in the hydrogenation reaction of vinyl acetylene, the catalyst of the present invention can effectively perform its function, that is, catalyze the hydrogenation of vinyl acetylene to form butadiene.

According to the embodiment of the present invention, in the catalyst of the present invention, the type of carrier is not particularly limited. According to some embodiments of the present invention, the carrier can be oxides such as Al ₂ O ₃ , SiO ₂ , TiO _{2 ,} carbon materials such as graphene, carbon tubes, activated carbon, etc., or porous materials such as molecular sieves. According to a specific example of the present invention, the carrier may be at least one selected from Al ₂ O ₃ , SiO ₂ , TiO ₂ , ZnO, MgO, CaCO ₃ , molecular sieves, graphene, carbon tubes, and activated carbon. In the catalyst of the present invention, the carrier can not only play the role of skeleton, but also can disperse the active components of the catalyst to produce suitable active sites. Specifically, in the hydrogenation reaction of vinyl acetylene, the catalyst of the present invention can better The adsorption of vinyl acetylene and the desorption of product butadiene can be achieved efficiently, and the efficiency of producing butadiene can be significantly improved.

According to the embodiment of the present invention, in the catalyst of the present invention, the type of co-catalyst is not particularly limited. According to a specific example of the present invention, the promoter can be at least one metal selected from Cu, Co, Ni, Fe, Ga, Sn, Ag, Pt, Sn, Au, In, Sb, Ge, Bi, Fe, Mo and Pb. kind. In the catalyst of the present invention, metal-to-metal interactions can be produced between the co-catalyst and the active component metal, thereby effectively preventing the loss of the active component in the catalyst and simultaneously improving the dispersion of the active component on the carrier, thereby The activity of the catalyst and the selectivity of butadiene can be significantly improved.

According to still another aspect of the present invention, the present invention provides a method for preparing the vinyl acetylene hydrogenation catalyst according to the embodiment of the present invention. According to a specific example of the present invention, the method may include the following steps:

First, the soluble salt of the active component and the soluble salt of the co-catalyst are mixed with water so as to obtain a mixed metal salt solution, wherein the molar ratio of the co-catalyst to the active component is (0.1-10):1.

Secondly, the mixed metal salt solution is mixed with the carrier to carry out co-impregnation of the carrier, so as to obtain an impregnated product, wherein the weight ratio of the active component to the carrier is (0.01-30):(40-99.989).

Then, the impregnate is calcined in order to obtain a catalyst.

The inventors have surprisingly found that the vinyl acetylene hydrogenation catalyst of the present invention can be effectively prepared by using the method for preparing the catalyst according to the embodiment of the present invention, and the operation is simple, the efficiency is high, the time required is small, and the cost is low. The obtained catalyst ethylene The hydrogenation activity of acetylene is strong, and the selectivity of butadiene is high, so the catalyst can be effectively applied to large-scale industrial production of butadiene using acetylene as raw material.

The expression "a soluble salt of an active ingredient" as used herein refers to a salt that is soluble, and when the salt is dissolved in water, the metal ions produced by the metal elements contained therein can be used as the present The active component of the invention catalyst. According to the embodiments of the present invention, the type of the soluble salt of the active ingredient is not particularly limited. According to a specific example of the present invention, the soluble salt may be nitrate, chloride or organic metal salt. According to the embodiment of the present invention, the metal element contained in the soluble salt of the active component is not particularly limited. According to a specific example of the present invention, the metal element contained in the soluble salt of the active component may be at least one selected from Pd, Cu, Co, Ni, Pt, Au, Ir, Ru, Mo and Fe. Therefore, in the hydrogenation reaction of vinyl acetylene, the catalyst of the present invention can effectively perform its function, that is, catalyze the hydrogenation of vinyl acetylene to form butadiene.

The expression "a soluble salt of a cocatalyst" used herein refers to a salt that is soluble, and after the salt is dissolved in water, the metal ions produced by the metal elements contained therein can be used as the present invention. Catalyst co-catalyst. According to the embodiment of the present invention, the type of the soluble salt of the co-catalyst is not particularly limited. According to a specific example of the present invention, the soluble salt may be nitrate, chloride or organic metal salt. According to the embodiment of the present invention, the metal element contained in the soluble salt of the co-catalyst is not particularly limited. According to a specific example of the present invention, the metal element contained in the soluble salt of the cocatalyst can be selected from metals Cu, Co, Ni, Fe, Ga, Sn, Ag, Pt, Sn, Au, In, Sb, Ge, Bi, At least one of Fe, Mo and Pb. In order to achieve the co-catalysis of two or more metals, the soluble salt of the active component and the soluble salt of the co-catalyst must be soluble salts containing different metal ions. Thus, the catalyst of the present invention can effectively prevent the loss of the active components in the catalyst due to the metal-to-metal interaction between the cocatalyst and the active components, and at the same time improve the dispersion of the active components on the carrier, thereby significantly Improve catalyst activity and butadiene selectivity.

In addition, according to an embodiment of the present invention, when the soluble salt of the active component and the soluble salt of the cocatalyst are mixed with water, the water used is deionized water, thus, the obtained mixed metal salt solution can be avoided from being affected by other ions. interference.

According to the embodiment of the present invention, in the catalyst of the present invention, the type of carrier is not particularly limited. According to some embodiments of the present invention, the carrier can be oxides such as Al ₂ O ₃ , SiO ₂ , TiO _{2 ,} carbon materials such as graphene, carbon tubes, activated carbon, etc., or porous materials such as molecular sieves. According to a specific example of the present invention, the carrier may be at least one selected from Al ₂ O ₃ , SiO ₂ , TiO ₂ , ZnO, MgO, CaCO ₃ , molecular sieves, graphene, carbon tubes, and activated carbon. The carrier can not only act as a skeleton, but also disperse the active components of the catalyst to generate suitable active sites. Specifically, in the hydrogenation reaction of vinyl acetylene, the catalyst of the present invention can better realize the adsorption of vinyl acetylene And the desorption of the product butadiene can significantly improve the efficiency of producing butadiene.

According to an embodiment of the present invention, the method for co-impregnating the support by mixing the mixed metal salt solution and the support is not particularly limited, and may be performed by stepwise co-impregnation or simultaneous co-impregnation. According to a specific example of the present invention, the simultaneous co-impregnation method is used to mix the mixed metal salt solution and the carrier for co-impregnation, which may include: impregnating a certain concentration of the mixed metal salt solution with the carrier according to the loading capacity of the active component and the cocatalyst, Calcination is then carried out in order to obtain the catalyst of the invention. According to some embodiments of the present invention, the mixed metal salt solution and the carrier are mixed for co-impregnation of the carrier by a step-by-step co-impregnation method, which may include: according to the loading capacity of the active component and the co-catalyst, the carrier is first impregnated with a certain concentration of active The soluble salt solution of the components is calcined, then impregnated with a certain concentration of the soluble salt solution of the co-catalyst, and then calcined again, so as to obtain the catalyst of the present invention. According to the embodiments of the present invention, the equipment for calcination is not particularly limited. According to a specific example of the present invention, the calcination may be performed using a muffle furnace. According to the embodiments of the present invention, the temperature and time of calcination are not particularly limited. According to a specific example of the present invention, the temperature of calcination is 200-800°C, and the time is 0.5-24h. Thus, the catalyst of the present invention can be effectively prepared

Specifically, according to an embodiment of the present invention, the method for preparing a catalyst of the present invention may include the following steps:

Using deionized water, the soluble salt of the active component and the soluble salt of the co-catalyst are prepared in a molar ratio of (0.1-10): 1 to form a mixed metal salt solution. Then, measure a certain volume of mixed solution and slowly add it into a ceramic element dish with a certain amount of carrier, and stir it with a glass rod while adding, so as to obtain a paste precursor, wherein the weight ratio of the active component to the carrier is (0.01 -30): (40-99.989). Next, the obtained paste precursor was left to stand for 3 hours to carry out carrier co-impregnation, and then it was put into a muffle furnace for calcination, so as to obtain the catalyst of the present invention.

According to yet another aspect of the present invention, the present invention provides a method for preparing butadiene. According to an embodiment of the present invention, the method may include the following steps: using the vinyl acetylene hydrogenation catalyst according to the embodiment of the present invention to hydrogenate vinyl acetylene.

According to a specific example of the present invention, using the method for preparing butadiene of the present invention, butadiene can be effectively prepared, and the process is simple, efficient, less time-consuming, and low in cost, and can be effectively applied to the production of synthetic cis-butadiene Butadiene rubber (BR), styrene-butadiene rubber (SBR), nitrile rubber, styrene-butadiene-styrene elastomer (SBS), acrylonitrile-butadiene-styrene (ABS) resin and other rubber and Resin products, and organic chemical products such as adiponitrile, 1,4-butanediol, anthraquinone, sulfolane, tetrahydrophthalic anhydride, higher alcohols and macrocyclic musk, so that the method for preparing butadiene of the present invention can be effectively popularized and applied in large-scale industrial production.

According to an embodiment of the present invention, in the method for preparing butadiene of the present invention, the form of vinyl acetylene is not particularly limited. According to a particular example of the invention, vinylacetylene may be provided in the form of pure vinylacetylene or a mixture of vinylacetylene and a second gas. Wherein, according to some embodiments of the present invention, when vinyl acetylene is provided in the form of a mixture of vinyl acetylene and the second gas, in the mixture of vinyl acetylene and the second gas, the volume percentage of vinyl acetylene may be 20 -100%. The function of the "second gas" used in this article is to dilute vinyl acetylene to ensure production safety. The meaning of the term "second" used in this article refers to the type of gas that is different from vinyl acetylene. It should be noted that the use of the term "second" is only for the convenience of description, and cannot be understood as indicating or implying relative importance sex. According to the embodiment of the present invention, the type of the "second gas" is not particularly limited, as long as it can dilute vinyl acetylene to ensure production safety. Those skilled in the art can understand that the second gas can be a single gas, or a mixture of multiple gases in any proportion. According to a specific example of the present invention, the second gas may be at least one selected from nitrogen, argon, butene and butane. In addition, according to some specific examples of the present invention, in the method for preparing butadiene of the present invention, the reaction conditions for the hydrogenation reaction of vinyl acetylene may be: reaction temperature 30°C, normal pressure, vinyl acetylene space velocity 100ml·gcat ^-1 ·h ^-1 , the alkyne hydrogen ratio is 1.2. Wherein, the term "space velocity" used herein refers to the ratio of the volume flow rate of vinyl acetylene at normal temperature and pressure to the mass of the catalyst.

According to another aspect of the present invention, the present invention provides butadiene. According to an embodiment of the present invention, the butadiene is prepared by the method for preparing butadiene of the present invention. According to a specific example of the present invention, the butadiene of the present invention has low cost and stable supply, and can be effectively applied to butadiene rubber (BR), styrene-butadiene rubber (SBR), nitrile rubber, styrene-butadiene-benzene Various rubber and resin products such as ethylene elastomer (SBS), acrylonitrile-butadiene-styrene (ABS) resin, and adiponitrile, 1,4-butanediol, anthraquinone, sulfolane, tetrahydrophthalic anhydride, Production of organic chemical products such as higher alcohols and macrocyclic musks.

It should be noted that the vinyl acetylene hydrogenation catalyst and its preparation method of the present invention were completed by the inventors of the present application through arduous creative work and optimization work.

Additional aspects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.

Detailed ways

Embodiments of the present invention are described in detail below, and it should be noted that the embodiments described below are exemplary, and are only used to explain the present invention, and should not be construed as limiting the present invention.

Example 1:

Use deionized water to make palladium nitrate and copper nitrate into 3.73×10 ^-3 mol/L solutions, and then mix the two solutions into mixed metal salts according to the ratio of pd%=50% and Cu%=50%. solution. Measure 30ml of mixed metal salt solution, slowly add 10g of carrier α-Al ₂ O ₃ into the ceramic element dish, stir with glass rod while adding, so as to obtain paste precursor. Next, the resulting paste precursor was left to stand for 3 hours to carry out co-impregnation of the carrier, and then it was put into a muffle furnace for roasting so as to prepare a vinyl acetylene catalyst, wherein the temperature control program of the muffle furnace was: use 30min The temperature was raised to 100°C, held at this temperature for 1 h, then raised to 500°C over 1 h and held for 4 h, and finally lowered to 30°C over 3 h.

Example 2:

According to the preparation method of Example 1, a vinyl acetylene hydrogenation catalyst was prepared. Wherein, the difference from Example 1 is that the mixed metal salt used in the catalyst preparation is palladium, silver and copper nitrate, and its composition is pd%=60%, Cu%=20%, Ag%=20%.

Example 3:

According to the preparation method of Example 1, a vinyl acetylene hydrogenation catalyst was prepared. Wherein, the difference from Example 1 lies in that the mixed metal salt solution used in the preparation of the catalyst is a nitrate solution of palladium and silver, and its composition is pd%=60%, Ag%=40%.

Example 4:

According to the preparation method of Example 1, a vinyl acetylene hydrogenation catalyst was prepared. Wherein, the difference from Example 1 is that the carrier used is SiO ₂ .

Example 5:

According to the preparation method of Example 1, a vinyl acetylene hydrogenation catalyst was prepared. Wherein, the difference from Example 1 is that the carrier used is ZnO.

Embodiment 6:

According to the preparation method of Example 1, a vinyl acetylene hydrogenation catalyst was prepared. Wherein, the difference from Example 1 is that the mixed metal salt solution used in the preparation of the catalyst is a mixed solution of palladium chloride and copper chloride.

Embodiment 7:

According to the preparation method of Example 1, a vinyl acetylene hydrogenation catalyst was prepared. Wherein, the difference from Example 1 lies in that the mixed metal salt solution used for catalyst preparation is nickel and copper nitrate solution, and its composition is Ni%=70%, Cu%=30%.

Embodiment 8:

According to the preparation method of Example 1, a vinyl acetylene hydrogenation catalyst was prepared. Wherein, the difference from Example 1 lies in that the mixed metal salt solution used for catalyst preparation is a nitrate solution of cobalt and copper, and its composition is Co%=60%, Cu%=40%.

Embodiment 9:

According to the preparation method of Example 1, a vinyl acetylene hydrogenation catalyst was prepared. Wherein, the difference from Example 1 is: the mixed metal salt solution used for catalyst preparation is a nitrate solution of nickel, silver and copper, and its composition is Ni%=60%, Cu%=20%, Ag%=20% .

Example 10:

According to the preparation method of Example 1, a vinyl acetylene hydrogenation catalyst was prepared. Wherein, the difference from Example 1 is that the mixed metal salt solution used for catalyst preparation is a nitrate solution of iron, cobalt and copper, and its composition is Fe%=40%, Co%=30%, Cu%=30%.

Example 11:

According to the preparation method of Example 1, a vinyl acetylene hydrogenation catalyst was prepared. Among them, the difference from Example 1: the co-impregnation of the carrier is carried out by a step-by-step co-impregnation method. Specifically, first use the carrier to impregnate the same amount of palladium nitrate solution as in Example 1, and after roasting, grind the roasted product finely, then impregnate with the same amount of copper nitrate solution, and roast again to obtain the obtained catalyst needed.

Example 12:

According to the preparation method of Example 1, a vinyl acetylene hydrogenation catalyst was prepared. Wherein, the difference from Example 1 is that the mixed metal salt solution used for catalyst preparation is a nitrate solution of nickel and copper, which consists of Ni%=70%, Cu%=30%, and the carrier used is carbon tube .

Example 13:

According to the preparation method of Example 1, a vinyl acetylene hydrogenation catalyst was prepared. Wherein, the difference from Example 1 is that the mixed metal salt solution used for the preparation of the catalyst is a nitrate solution of nickel and copper, and its composition is Ni%=70%, Cu%=30%, and the carrier used is CaCO ₃ .

Example 14:

According to the preparation method of Example 1, a vinyl acetylene hydrogenation catalyst was prepared. Wherein, the difference from Example 1 lies in that the mixed metal salt solution used for catalyst preparation is a nitrate solution of cobalt and copper, its composition is Co%=60%, Cu%=40%, and the carrier is MgO.

Example 15:

According to the preparation method of Example 1, a vinyl acetylene hydrogenation catalyst was prepared. Wherein, the difference from Example 1 lies in that the mixed metal salt solution used for catalyst preparation is a nitrate solution of cobalt and copper, its composition is Co%=60%, Cu%=40%, and the calcination temperature is 1000°C.

Example 16:

According to the preparation method of Example 1, a vinyl acetylene hydrogenation catalyst was prepared. Wherein, the difference from Example 1 is that the metal salt solution used in the preparation of the catalyst is a single palladium nitrate solution, and its concentration is equal to the concentration of palladium ions in the mixed solution.

Example 17:

According to the preparation method of Example 1, a vinyl acetylene hydrogenation catalyst was prepared. Wherein, the difference from Example 1 is that the palladium salt used for catalyst preparation is palladium acetate.

Example 18:

According to the preparation method of Example 7, a vinyl acetylene hydrogenation catalyst was prepared. Wherein, the difference from Example 7 lies in that the metal salt solution used in the preparation of the catalyst is a single nickel nitrate solution, and its concentration is equal to the concentration of nickel ions in the mixed solution.

Embodiment 19: catalyst effect evaluation

The catalyst prepared by embodiment 1-18 is evaluated according to the following methods:

First, the catalysts prepared in Examples 1-18 were respectively reduced in hydrogen for 8 hours. Next, in the miniature fixed-bed reaction device, the aforementioned catalysts were used to carry out the hydrogenation reaction of vinyl acetylene, and then the gas obtained by the reaction was collected, wherein the reaction conditions were: reaction temperature 30°C, normal pressure, vinyl acetylene space velocity 100ml· gcat ^-1 ·h ^-1 , the alkyne hydrogen ratio is 1.2. Next, Agilent 1790 gas chromatography was used to analyze the composition of the collected gas samples, so as to obtain the amounts of vinyl acetylene and butadiene in the collected gas samples. Then, calculate the vinyl acetylene conversion and butadiene selectivity of each of the above-mentioned catalysts in the vinyl acetylene hydrogenation reaction it participated in, and the results are shown in Table 1 below, wherein the vinyl acetylene conversion and butadiene selectivity The calculation formula of is as follows:

Table 1 Catalyst evaluation results

Example Conversion rate of vinyl acetylene (%) Butadiene selectivity (%) Example 1 55.6 81.5 Example 2 52.8 84.4 Example 3 56.2 81.8 Example 4 58.0 78.0 Example 5 58.8 77.7 Example 6 56.9 81.9 Example 7 28.5 67.8 Example 8 43.1 77.2 Example 9 35.9 72.6 Example 10 36.2 75.8 Example 11 56.5 82.4 Example 12 32.8 70.9 Example 13 28.8 79.3

Example 14 41.5 78.8 Example 15 37.5 79.8 Example 16 45.1 80.1 Example 17 59.9 83.2 Example 18 22.9 63.2

As can be seen from Table 1, when metal palladium is the active component, higher catalyst activity and product selectivity can be obtained (embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, implementation Example 6, embodiment 11, embodiment 16), this is mainly because metal palladium has strong adsorption capacity to alkyne and the adsorption capacity difference of alkyne and alkene on metal palladium is larger. Simultaneously it can be seen that the selectivity of the product butadiene is higher when α-Al ₂ O ₃ is used as a carrier (comparative example 1, example 4 and example 5), and the effect of the distributed co-impregnation method is better than that of the synchronous co-impregnation method Method (comparative embodiment 1 and embodiment 11). Comparing Example 1 and Example 16, Example 7 and Example 16, it can be seen that the catalytic effect of the bimetallic catalyst is significantly better than the single metal catalyst of the same load, if this is due to the formation of an alloy phase in the bimetallic catalyst, or The dilution effect of co-catalyst atoms on active metal atoms (see Goetz J, Voipe M A.Low-loadedPd-Pb/α-Al ₂ O ₃ Catalysts.Journal of Catalysis, 2001, 199: 338-345, by reference to incorporated herein in its entirety).

In the description of this specification, descriptions with reference to the terms "one embodiment", "some embodiments", "example", "specific examples", or "some examples" mean that specific features described in connection with the embodiment or example , structure, material or characteristic is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

Although the embodiments of the present invention have been shown and described, those skilled in the art can understand that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principle and spirit of the present invention. The scope of the invention is defined by the claims and their equivalents.

Claims (10)

1. a vinylacetylene hydrogenation catalyst is characterized in that, comprises:

0.01-30 the active component of weight portion;

40-99.989 the carrier of weight portion; And

Co-catalyst, wherein, the mol ratio of described co-catalyst and described active component is (0.1-10): 1.

2. catalyst according to claim 1 is characterized in that, described active component is be selected from metal Pd, Cu, Co, Ni, Pt, Au, Ir, Ru, Mo and Fe at least a.

3. catalyst according to claim 1 is characterized in that, described carrier is to be selected from Al ₂O ₃, SiO ₂, TiO ₂, ZnO, MgO, CaCO ₃, molecular sieve, Graphene, carbon pipe and active carbon at least a.

4. catalyst according to claim 1 is characterized in that, described co-catalyst is be selected from metal Cu, Co, Ni, Fe, Ga, Sn, Ag, Pt, Sn, Au, In, Sb, Ge, Bi, Fe, Mo and Pb at least a.

5. a method for preparing each described vinylacetylene hydrogenation catalyst of claim 1-4 is characterized in that, may further comprise the steps:

The soluble-salt of described soluble salts of active components and described co-catalyst is soluble in water, in order to obtain mixed salt solution, the mol ratio of wherein said co-catalyst and described active component is (0.1-10): 1;

Described mixed salt solution mixed with described carrier carry out carrier and flood altogether, in order to obtain macerate, wherein, the weight ratio of described active component and described carrier is (0.01-30): (40-99.989); And

Described macerate is calcined, in order to obtain described catalyst,

Randomly, described soluble salts of active components is nitrate, chloride or organic metal salt,

Randomly, the soluble-salt of described co-catalyst is nitrate, chloride or organic metal salt,

Randomly, described dipping altogether is for being total to dipping step by step or flooding altogether synchronously.

6. method according to claim 5 is characterized in that, the temperature of described calcining is 200-800 ℃, and the time is 0.5-24h.

7. a method for preparing butadiene is characterized in that, may further comprise the steps:

Right to use requires each described catalyst of 1-4, and vinylacetylene is carried out hydrogenation reaction.

8. method according to claim 7 is characterized in that, described vinylacetylene provides with the form of the mixture of pure ethylene ethyl-acetylene or vinylacetylene and second gas.

9. method according to claim 8 is characterized in that, in the mixture of described vinylacetylene and second gas, the percent by volume of described vinylacetylene is 20-100%,

Randomly, described second gas is be selected from nitrogen, argon gas, butylene and butane at least a.

10. butadiene goods is characterized in that, it is by each described method preparation of claim 7-9.