WO2022213370A1 - 一种炔烃选择加氢催化剂及制备方法以及选择加氢方法 - Google Patents

一种炔烃选择加氢催化剂及制备方法以及选择加氢方法 Download PDF

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WO2022213370A1
WO2022213370A1 PCT/CN2021/086214 CN2021086214W WO2022213370A1 WO 2022213370 A1 WO2022213370 A1 WO 2022213370A1 CN 2021086214 W CN2021086214 W CN 2021086214W WO 2022213370 A1 WO2022213370 A1 WO 2022213370A1
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catalyst
microemulsion
content
prepared
semi
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PCT/CN2021/086214
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French (fr)
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谭都平
何盛宝
苟尕莲
谢元
王喆
车春霞
韩伟
吴伟
张峰
温翯
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中国石油天然气股份有限公司
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Priority to PCT/CN2021/086214 priority patent/WO2022213370A1/zh
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
    • C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond

Definitions

  • the invention relates to a selective hydrogenation catalyst, a preparation method and a selective hydrogenation method.
  • Ethylene is one of the most important basic raw materials in the petrochemical industry. As a monomer ethylene for synthesizing various polymers, most of them are cracked by steam cracking of petroleum hydrocarbons (such as ethane, propane, butane, naphtha and light diesel oil, etc.). be made of. The ethylene-based C2 fraction obtained by this method contains 0.5%-2.3% by mass of acetylene. When used in polymerization, acetylene in ethylene will complicate the polymerization process of ethylene, deteriorate the polymer properties, reduce the activity of the polymerization catalyst, and affect the physical properties of the polymer, so it must be removed.
  • petroleum hydrocarbons such as ethane, propane, butane, naphtha and light diesel oil, etc.
  • the catalysts used are mainly noble metal catalysts such as Pd, Pt, and Au.
  • Carbon two post-hydrogenation and pre-hydrogenation are based on the position of the acetylene hydrogenation reactor relative to the demethanizer.
  • the hydrogenation reactor is located before the demethanizer, and the hydrogenation reactor is located after the demethanizer. post hydrogenation.
  • the advantages of the post-hydrogenation process are that there are many control methods in the hydrogenation process, it is not easy to fly over temperature, and the operation is convenient, but the process is complex and requires separate hydrogen distribution.
  • the post-hydrogenation process of carbon 2 is prone to acetylene due to the low hydrogen content in the hydrogenation material.
  • Hydrogenation dimerization reaction produces carbon four fractions, which are further polymerized to form oligomers with wider molecular weights, commonly known as "green oil".
  • the green oil is adsorbed on the catalyst surface and further forms coke, which blocks the catalyst pores, so that the reactants cannot diffuse to the surface of the catalyst active center, resulting in a decrease in the catalyst activity.
  • Patent CN200810119385.8 discloses a non-precious metal supported selective hydrogenation catalyst and its preparation method and application, including a carrier and main active components and auxiliary active components supported on the carrier, wherein the main active group Divided into Ni, the auxiliary active component is selected from at least one of Mo, La, Ag, Bi, Cu, Nd, Cs, Ce, Zn and Zr, the main active component and auxiliary active component are both non- The crystalline form exists, the average particle size is less than 10 nm, the carrier is a porous material with no oxidizing property; and the catalyst is prepared by a micro-emulsion method.
  • the post-hydrogenation process of carbon 2 generally adopts a three-stage hydrogenation reactor.
  • the total conversion rate of acetylene in the first-stage reactor is 50-80%
  • the hydrogen/alkyne is 1.0-1.4
  • the total conversion rate of acetylene in the second-stage reactor is 40-20%.
  • Hydrogen/alkyne 1.4-2.0, residual acetylene is completely converted in the three-stage reactor, three-stage hydrogen/alkyne 2.5-4.0, and the acetylene content at the outlet of the three-stage reactor is generally below 1 ppm.
  • the hydrogenation dimerization of acetylene will occur to generate a series of oligomers with different molecular weights.
  • oligomers will adhere to the catalyst for a long time because they cannot flow with the gas phase material or have a very low moving speed. surface or into the pores, causing the catalyst pores to be blocked. Due to the slow moving speed, they will gradually aggregate. These oligomers themselves contain a large number of unsaturated bonds, and can be further polymerized, eventually forming coke, which greatly reduces the catalyst activity selectivity.
  • the amount of hydrogenation dimerization product is closely related to the hydrogenation conditions.
  • the hydrogen/alkyne is low, the hydrogenation dimerization reaction of acetylene is very violent due to insufficient hydrogen; the coking rate of the catalyst will be very rapid.
  • the amount of green oil generated in the first stage reactor is also the largest, the hydrodimerization reaction at the entrance of the first stage reactor is the most violent, and part of the green oil is polymerized at the entrance of the first stage reactor. , so that the activity of this part of the catalyst decreases rapidly.
  • the other part is the outlet of the first stage of the reactor, because as the hydrogenation reaction proceeds, the hydrogen/alkyne becomes lower and lower, so that the rate of the hydrogenation dimerization reaction increases again, and the increase of the temperature will intensify the polymerization of the green oil. .
  • Part of the C2 post-hydrogenation unit adopts a two-stage hydrogenation process.
  • the green oil generated by the first-stage reactor will enter the second-stage reactor, and will be formed by gathering at the entrance of the second-stage reactor, which makes the addition of the second-stage reactor.
  • the hydrogen effect deteriorates rapidly, the acetylene content at the outlet of the reactor will soon rise to above 1 ppm, and the purity of ethylene is not good, which affects the progress of olefin polymerization, so the catalyst has to be regenerated.
  • Part of the device adopts an isothermal reactor, which extends in the direction of material flow, and the temperature becomes lower and lower.
  • the green oil generated in the upper part of the reactor does not accumulate in the lower part of the reactor, and gradually forms coke, which makes the selectivity drop rapidly.
  • US5856262 reported a method for preparing a low-acid palladium catalyst with potassium hydroxide (or hydroxides of barium, strontium, rubidium, etc.) modified silicon oxide as a carrier. Under the condition of 0.71% mole fraction and 1.43 hydrogen-alkyne mole ratio, the outlet acetylene mole fraction is less than 1 ⁇ 10 -7 , and the ethylene selectivity reaches 56%.
  • US4404124 prepared a selective hydrogenation catalyst with shell distribution of active components by a step-by-step impregnation method, which can be applied to the selective hydrogenation of carbon two fractions to eliminate acetylene in ethylene.
  • US5587348 uses alumina as a carrier, adds cocatalyst silver and palladium to act, and adds fluorine chemically bonded with alkali metal to prepare a carbon dioxide hydrogenation catalyst with excellent performance.
  • the catalyst has the characteristics of reducing the generation of green oil, improving the selectivity of ethylene and reducing the generation of oxygenated compounds.
  • CN1736589A reported a Pd/ ⁇ -Al 2 O 3 selective hydrogenation catalyst prepared by a complete adsorption and impregnation method, and the catalyst produced a large amount of green oil during use.
  • CN200810114744.0 discloses a catalyst for selective hydrogenation of unsaturated hydrocarbons and a preparation method thereof.
  • the catalyst uses alumina as a carrier and palladium as an active component, and the anti-impurity and anti-coking properties of the catalyst are improved by adding rare earth, alkaline earth metal and fluorine, but the catalyst selectivity is not ideal.
  • the catalysts prepared by the above methods are all catalysts with a single distribution of pore size, and the selectivity of the catalyst is poor due to the influence of internal diffusion during the fixed-bed reaction process.
  • ZL971187339 discloses a hydrogenation catalyst
  • the carrier is a honeycomb-type carrier, which is a large-pore carrier, which effectively improves the selectivity of the catalyst.
  • CN1129606A discloses a hydrocarbon conversion catalyst
  • the carrier catalyst includes alumina, nickel oxide, iron oxide, etc.
  • the catalyst includes two kinds of pores, one is used to improve the catalytic reaction surface, and the other is conducive to diffusion.
  • CN101433842A discloses a hydrogenation catalyst, which is characterized in that the catalyst has a bimodal pore distribution, the most probable radius of the small pore part is 2-50 nm, and the most probable radius of the large pore part is 100-500 nm. Since the catalyst has a bimodal pore distribution , while having good hydrogenation activity, it also has good selectivity and large ethylene increment.
  • the formation of green oil and the coking of the catalyst are important factors affecting the service life of the catalyst.
  • the activity, selectivity and service life of the catalyst constitute the overall performance of the catalyst.
  • the methods listed above may provide a better way to improve the activity and selectivity of the catalyst, but they do not solve the problem that the catalyst is easy to coke, or solve the problem of the catalyst.
  • the problem of easy generation of green oil and coking is not solved, but the problem of selectivity is not solved.
  • the carrier with macroporous structure can improve the selectivity, the larger molecules generated by the polymerization and chain extension reactions are also easy to accumulate in the macropores of the carrier, resulting in coking and deactivation of the catalyst and affecting the service life of the catalyst.
  • CN201310114070.5 discloses a method for the selection of carbon distillate.
  • the hydrogenation method adopts a catalyst, and its active components Pd and Ag are supported by an aqueous solution impregnation method, and Ni is supported by a W/O microemulsion impregnation method.
  • CN201310114077.7 discloses a hydrogenation catalyst, the catalyst carrier has bimodal pore distribution, and the active components in the catalyst include Pd, Ag, and Ni, wherein Pd and Ag are located in small pores, and Ni is located in large pores.
  • CN 201310114079.6 discloses a catalyst preparation method. In the method, the catalyst carrier used has a bimodal pore distribution.
  • the microemulsion contains a metal salt of nickel. Since the dynamic volume of the microemulsion is larger than the small pore size, the microemulsion particles can only enter the macropores of the carrier. When Pd and Ag are loaded by solution method, the siphon effect of the small holes is stronger, and most of the Pd and Ag enter the macropores of the carrier. Therefore, Ni is mainly located in the macropores, and Pd and Ag are mainly located in the small holes.
  • the purpose of the present invention is to provide an alkyne selective hydrogenation catalyst and a preparation method, especially an alkyne selective hydrogenation catalyst and a preparation method which have good coking resistance and can reduce the reduction temperature of the catalyst.
  • the present invention provides a catalyst for selective hydrogenation of alkynes, wherein, the carrier of the catalyst is alumina or mainly alumina, and has a bimodal pore distribution structure; wherein the pore diameter of the small pores is 15-50nm , the pore size of the macropore is 80-500nm, and the catalyst contains at least Pd, Ni, and Cu. Based on the mass of the carrier as 100%, the content of Pd is 0.03-0.1%, and the content of Ni is 0.5-5%.
  • the weight ratio is 0.1-1.0:1.0, wherein Ni, Cu and part of Pd are supported by the microemulsion; the particle size of the microemulsion is not lower than the maximum pore size of small pores and not higher than the maximum pore size of macropores.
  • the catalyst carrier provided by the present invention is alumina or mainly alumina, and has a bimodal pore distribution structure; wherein the pore size of the small pores is 15-50 nm, and the pore size of the large pores is 80 nm.
  • the catalyst contains at least Pd, Ni and Cu, and the content of Pd is 0.035-0.08% (more preferably 0.035-0.07%), the content of Ni is 0.5-5%, and the content of Cu and
  • the weight ratio of Ni is 0.1-1.0:1, wherein Ni, Cu and part of Pd are supported in a microemulsion, and the particle size of the microemulsion is not lower than the maximum pore size of the small pores and not higher than the maximum pore size of the macropores (preferably Larger than the maximum pore size of small pores and smaller than the maximum pore size of large pores), the amount of Pd supported by the microemulsion is 1/100-1/200 of the sum of the Ni+Cu content; the remaining part of Pd is supported by solution.
  • the carrier of the catalyst provided by the present invention is alumina, which has bimodal pore size distribution characteristics, the pore size of small pores is 15-50 nm, and the pore size of large pores is 80-500 nm; the catalyst It contains at least active components Pd, Ni and Cu. Based on 100% of the mass of the carrier, the content of Pd is 0.03-0.09% (more preferably 0.035-0.075%), the content of Ni is 0.5-5%, and the content of Cu and Ni is 0.03-0.09%.
  • the weight ratio is 0.1-1.0:1.0, and Ni, Cu and part of Pd are supported by microemulsion. Further preferably, the amount of Pd supported by the microemulsion is 1/100-1/200 of the sum of Ni+Cu contents, and the remaining part of Pd is supported by solution.
  • the catalyst is preferably suitable for the hydrogenation of carbon distillates.
  • the support of the catalyst provided by the present invention is alumina or mainly alumina, alumina with a bimodal pore distribution structure, wherein the pore size of the small pores is 15-50 nm, and the large pores The pore size is 80-500nm, and the catalyst contains at least active components Pd, Ni and Cu. Based on the mass of the catalyst as 100%, the content of Pd is 0.06-0.1% (more preferably 0.07-0.1%), and the content of Ni is 0.5- 5%, the weight ratio of Cu to Ni is 0.1-1.0:1.0.
  • the amount of Pd supported by the microemulsion is 1/100-1/200 of the sum of Ni+Cu contents, and the remaining part of Pd is supported by solution.
  • the catalyst is preferably suitable for the selective hydrogenation method of the post-carbon two hydrogenation process using crude hydrogen as the hydrogen source.
  • the pore size of the small pores and the pore size of the macropores are respectively a size range, and the particle size of the microemulsion is not lower than (greater than) the maximum pore size of the small pores Not higher than (less than) the maximum pore size of macropores means that the particle size of the prepared microemulsion is not lower than (greater than) the upper limit of the pore size range of the small pores of a specific catalyst carrier, not higher than (less than (smaller) ) the upper limit of the pore size range of the macropores of the catalyst support.
  • the particle size of the microemulsion may be 50-500 nm or greater than 50 nm and less than 500 nm.
  • the carrier of the catalyst provided by the present invention is alumina or mainly alumina, and has a bimodal pore distribution structure; wherein the pore size of the small pores is 15-50 nm, and the pore size of the large pores is 15-50 nm.
  • the catalyst contains at least Pd, Ni, Cu, based on the mass of the carrier as 100%, the content of Pd is 0.06-0.08%, the content of Ni is 0.5-5%, and the weight ratio of Cu to Ni is 0.1-1.0 : 1.0, wherein Ni, Cu and part of Pd are supported by the microemulsion; the particle size of the microemulsion is not lower than the maximum pore size of the small pores and not higher than the maximum pore size of the macropores, and the amount of Pd supported by the microemulsion is Ni +1/100-1/200 of the sum of Cu content, and the remaining part of Pd is supported by solution.
  • the catalyst is suitable for both the hydrogenation reaction of carbon 2 fraction and the selective hydrogenation method of carbon 2 post-hydrogenation process using crude hydrogen as the hydrogen source.
  • the catalyst of the present invention further contains Ag, which is supported in solution, and its content is 0.03-0.5%, more preferably, the Ag content is 0.08-0.21%.
  • the role of Ag is to form an alloy with Pd, reduce the amount of green oil generated, and improve the selectivity of acetylene hydrogenation.
  • the carrier of the catalyst provided by the present invention is alumina or mainly alumina, and has a bimodal pore distribution structure; wherein the pore size of the small pores is 15-50 nm, and the pore size of the large pores is 15-50 nm.
  • the catalyst contains at least Pd, Ag, Ni, Cu, based on the mass of the carrier as 100%, the content of Pd is 0.035-0.07%, the content of Ag is 0.08-0.21%, and the content of Ni is 0.5-5% , the weight ratio of Cu to Ni is 0.1-1.0:1.0, in which Ni, Cu and part of Pd are supported in the form of microemulsion, mainly distributed in the macropores of the carrier, and the amount of Pd supported by the microemulsion method is the content of Ni+Cu 1/100-1/200 of the sum; Ag and part of Pd are loaded by solution method.
  • the support of the catalyst provided by the present invention is alumina or mainly alumina, alumina with a bimodal pore distribution structure, wherein the pore size of the small pores is 15-50 nm, and the large pores The pore size is 80-500nm, and the catalyst contains at least active components Pd, Ag, Ni, and Cu. Based on the mass of the catalyst as 100%, the content of Pd is 0.07-0.1%, the content of Ag is 0.03-0.5%, and the content of Ni is 0.07-0.1%. is 0.5-5%, the content of Cu is 0.5-5%, and the total content of Ni and Cu is 1-5.5%.
  • the catalyst is also preferably suitable for the selective hydrogenation process of the post-carbon two hydrogenation process using crude hydrogen as the hydrogen source.
  • the catalyst provided by the present invention has a specific surface area of 20-50 m 2 /g.
  • the microemulsion loading mentioned in the present invention refers to the impregnation method, wherein the impregnation liquid is a microemulsion, that is, the precursor of the active component (such as Pd, Ni, Cu, etc.) is not impregnated by forming a solution but impregnated by forming a microemulsion. load.
  • the solution load mentioned in the present invention refers to the impregnation method load, wherein the impregnation liquid is a solution.
  • a part of Pd is supported in the form of microemulsion, and the rest of Pd is supported in the form of impregnation, and the amount of Pd supported in the microemulsion is 1/100-1/200 of the sum of Ni+Cu content , more preferably 1/110-1/200.
  • the support is alumina or is mainly alumina; the crystal form of alumina is ⁇ , ⁇ crystal form or a mixed crystal form thereof; when the catalyst support is mainly alumina, the Alumina is above 80%.
  • the carrier with bimodal pore distribution adopted in the present invention ensures high catalyst activity, and the presence of macropores can reduce the influence of internal diffusion and improve catalyst selectivity.
  • the microemulsion loading process includes: dissolving the precursor salt in water, adding an oil phase, a surfactant and a co-surfactant, and fully stirring to form a microemulsion, wherein the oil phase is alkane or Cycloalkane, the surfactant is an ionic surfactant and/or a non-ionic surfactant, and the co-surfactant is an organic alcohol.
  • the microemulsion loading process satisfies the following conditions: the weight ratio of the water phase to the oil phase is 2-3, the weight ratio of the surfactant to the oil phase is 0.15-0.6, and the weight ratio of the surfactant to the oil phase is 0.15-0.6.
  • the weight ratio of the co-surfactant is 1-1.2, and the particle size of the microemulsion is greater than 50 nm and less than 500 nm.
  • the oil phase is C6-C8 saturated alkane or cycloalkane, preferably cyclohexane and n-hexane;
  • the surfactant is an ionic surfactant and/or Or non-ionic surfactant, preferably non-ionic surfactant, more preferably polyethylene glycol octyl phenyl ether or cetyl trimethyl ammonium bromide;
  • co-surfactant is C4-C6 alcohol species, preferably n-butanol and/or n-pentanol.
  • the order of loading of Pd in solution and loading of Ni and Cu in the microemulsion is not limited; after the Cu step.
  • the step of supporting Ag in solution is preferably after the step of supporting Pd in solution.
  • the selective hydrogenation reaction of acetylene occurs in the main active center composed of Pd, Ni and Cu are impregnated in the macropores of the carrier in the form of microemulsion, and the green oil generated by the reaction is composed of Cu and Ni. Saturated hydrogenation occurs on the active center.
  • the hydrogenation catalyst generally needs to be reduced before the catalyst is applied to ensure that the active components exist in the metal state, so that the catalyst has hydrogenation activity.
  • activation is a high-temperature calcination process, in which metal salts are generally decomposed into metal oxides, and the oxides will form clusters, which are generally nano-sized. Different oxides need to be reduced at different temperatures due to their different chemical properties.
  • the temperature around 200°C is an important critical temperature. Above this temperature, metal particles will aggregate significantly. Therefore, reducing the reduction temperature of active components to below 200°C is of great significance for hydrogenation catalysts.
  • the thought of solving catalyst coking in the present invention is:
  • the selective hydrogenation reaction of acetylene occurs in the main active center composed of Pd (when Ag is contained, it occurs in the main active center composed of Pd and Ag), and macromolecules such as green oil produced in the reaction easily enter the large pores of the catalyst. .
  • Ni/Cu components are supported, in which Ni has the function of saturated hydrogenation, and the green oil component will undergo saturated hydrogenation reaction at the active center composed of Ni/Cu. Because the double bond is saturated by hydrogenation, the green oil component can no longer undergo the polymerization reaction or the polymerization reaction rate is greatly reduced, the chain growth reaction of the green oil component is terminated or delayed, and the condensed ring compound with huge molecular weight cannot be formed, which is easily taken out of the reactor by the material. Therefore, the catalyst The degree of coking on the surface of the catalyst will be greatly reduced, and the operating life of the catalyst will be greatly extended.
  • the carrier of the present invention is required to have a bimodal pore distribution structure, in particular, large pores with a pore diameter of 80-500 nm and small pores with a pore diameter of 15-50 nm.
  • the method of the present invention to control the positioning of the Ni/Cu alloy in the catalyst macropores is that Ni/Cu is supported in the form of a microemulsion, and the particle size of the microemulsion is larger than the pore size of the small pores of the carrier, but smaller than the maximum pore size of the macropores.
  • Nickel and copper metal salts are contained in the microemulsion, and due to steric resistance, it is difficult to enter the pores of the carrier with smaller sizes, and mainly enter the macropores of the carrier. active center.
  • the macropores contain active centers composed of Ni/Cu and Pd, which have a good hydrogenation saturation effect on the green oil molecules, so that the green oil molecules entering the macropores are no longer polymerized, so they will gradually move out of the reactor, and it is not easy to Formation of coke.
  • the hydrogenation catalyst generally needs to be reduced before the catalyst is applied to ensure that the active components exist in the metal state, so that the catalyst has hydrogenation activity. Because during catalyst preparation, activation is a high-temperature calcination process, during which metal salts are decomposed into metal oxides, and the oxides form clusters, which are generally nano-sized. Different oxides need to be reduced at different temperatures due to their different chemical properties. However, for nano-sized metals, about 200 °C is an important critical temperature. Above this temperature, metal particles will aggregate significantly. Therefore, reducing the reduction temperature of active components is of great significance for hydrogenation catalysts.
  • the reduction temperature of Ni can be greatly lowered by supporting Cu together with Ni.
  • the reason is that the reduction temperature of NiO generally reaches more than 450 °C, and this temperature will cause the agglomeration of Pd.
  • a Cu/Ni alloy After adding Cu, a Cu/Ni alloy will be formed.
  • the reduction temperature can be reduced by more than 100 °C. reaching 350 °C, thereby alleviating the agglomeration of Pd.
  • the inventors also found that if part of Pd is loaded on the surface of the Ni/Cu alloy, the reduction temperature of the Ni/Cu alloy can be greatly reduced, which can reach below 200°C, even to 150°C, thereby avoiding the need for NiO Agglomeration of Pd active centers during high temperature reduction.
  • a better catalyst is that Pd mainly exists in the small pores of the catalyst, Ni/Cu is located in the macropores of the catalyst, and there is also some Pd in the Ni/Cu in the macropores, especially on its surface.
  • a better catalyst preparation process is that after Ni and Cu are loaded, a small amount of Pd is loaded in the macropores by a microemulsion method, and the amount of Pd loaded at this time is 1/100-1/200 of the sum of the Ni+Cu content.
  • the present invention also provides the preparation method of the above-mentioned catalyst, and the specific preparation process includes:
  • step (1) and step (2) can be interchanged, and step (3) follows step (1).
  • the carrier in the above step (1) is alumina or mainly alumina, and the crystal form of Al 2 O 3 is preferably ⁇ , ⁇ or a mixed crystal form thereof.
  • the alumina in the catalyst carrier is preferably more than 80%, and the carrier can also contain other metal oxides such as magnesium oxide, titanium oxide and the like.
  • the carrier in the above step (1) can be spherical, cylindrical, clover-shaped, four-leaf clover and the like.
  • the precursor salts of Ni, Cu and Pd described in the above steps (1) and (3) are soluble salts, which can be nitrates, chlorides or other soluble salts.
  • the weight ratio of Cu to Ni is 0.1-1:1, and the amount of Pd loaded by the emulsion method is 1/100-1/200 of the content of Ni+Cu.
  • Ag when Ag is also contained in the catalyst, Ag can form an alloy with the Pd supported in step (2), so as to improve the selectivity of acetylene hydrogenation.
  • the principle is: Ag and Pd form an alloy, and Ag atoms separate Pd atoms, which increases the spatial distance of the adsorbed acetylene molecules, and the corresponding reaction intermediates after acetylene hydrogenation have a larger distance between each other, which is not easy to occur. The coupling of the intermediates, Thus, the formation of green oil is reduced.
  • the preparation method of the catalyst of the present invention may include the following three:
  • the first, the preparation process of the catalyst comprises the following specific steps:
  • the second, the preparation process of the catalyst comprises the following specific steps:
  • the third, the preparation process of the catalyst includes the following specific steps:
  • the Ag is loaded by the saturated impregnation method, that is, the prepared Ag salt solution is 80-110% of the saturated water absorption of the carrier, and the pH is adjusted to 1-5.
  • the temperature is 500-550 ° C Roasting is carried out between 4-6 hours to obtain semi-finished catalyst B;
  • the surfactant in the above-mentioned steps (1) and (4) is an ionic surfactant or a nonionic surfactant, preferably a nonionic surfactant, more preferably polyethylene glycol octyl phenyl ether ( Triton X-100), cetyltrimethylammonium bromide (CTAB).
  • a nonionic surfactant more preferably polyethylene glycol octyl phenyl ether ( Triton X-100), cetyltrimethylammonium bromide (CTAB).
  • the oil phase in the above steps (1) and (4) is C 6 -C 8 saturated alkane or cycloalkane, preferably cyclohexane and n-hexane.
  • the co-surfactants in the above steps (1) and (4) are C 4 -C 6 alcohols, preferably n-butanol and n-pentanol.
  • the reduction temperature of the catalyst of the present invention is preferably 150-200°C.
  • the step of supporting Pd in the microemulsion is after the step of supporting Ni and Cu in the microemulsion.
  • the order of the solution loading of Pd and the microemulsion loading of Ni/Cu is not limited.
  • the step of loading Ag in solution is after the step of loading Pd in solution.
  • the preparation conditions of the microemulsion are: the weight ratio of the water phase to the oil phase is 2-3, the weight ratio of the surfactant to the oil phase is 0.15-0.6, and the ratio of the surfactant to the co-surfactant is 0.15-0.6.
  • the weight ratio is 1-1.2, the particle size of the formed microemulsion is larger than 50 nm and smaller than 500 nm.
  • the invention also provides a method for the selective hydrogenation of carbon distillate fractions of alkynes, wherein: the hydrogenated material is the carbon distillate fractions from the top of the front deethanizer column, and after entering the fixed bed reactor, gas phase hydrogenation is carried out to remove acetylene,
  • the process conditions of the selective hydrogenation reaction are: the inlet temperature of the reactor is 35-100°C, the pressure is 1.5-3.0MPa, and the gas volume space velocity is 2000-11000h -1 ; wherein, the catalyst is the catalyst provided by the present invention.
  • the catalyst used in the method for the selective hydrogenation of carbon distillate alkynes uses alumina as a carrier and has bimodal pore size distribution characteristics, and the pore sizes are 15-50 nm and 80-500 nm respectively; the The catalyst contains at least active components Pd, Ni and Cu. Based on 100% of the mass of the carrier, the content of Pd is 0.03-0.09%, the content of Ni is 0.5-5%, and the weight ratio of Cu to Ni is 0.1-1.0:1.0 , Ni, Cu and part of Pd are supported by microemulsion, the content of part of Pd is 1/100-1/200 of the content of Ni+Cu, and the particle size of the microemulsion is 50-500nm.
  • the catalyst preferably also contains 0.08-0.21% Ag, which is supported by solution. The preferred content of Pd is 0.035-0.075%.
  • the preferred solution of the catalyst provided by the present invention is: the loading of Pd adopts the method of two loadings by solution method, wherein the loading of Pd for the two loadings is distributed in different regions respectively.
  • a more preferred way is: the loading of Pd is carried out twice by the solution method, and the two times are the method of cation precursor and cation precursor respectively. It is easy to form the shell distribution of Pd when the anion is used as the precursor, which is mainly used for the selective hydrogenation of acetylene. With the cation as the precursor, the Pd can be distributed in a wider area, and it can form an alloy with Ni/Cu. The reduction temperature of /Cu is lowered to below 200°C.
  • a more preferred way of the present invention can also be as follows: the loading of Pd is carried out by means of a solution method and a microemulsion method; the Ni and Cu are loaded by a microemulsion method, and the particle size of the microemulsion is controlled to be between the maximum pore size of the small pores of the carrier and the Between the maximum pore diameters of the macropores, Ni and Cu are mainly distributed in the macropores of the carrier.
  • the amount of Pd supported by the microemulsion method is 1/100-1/200 of the total content of Ni and Cu.
  • the amount of Pd supported by the microemulsion method is after the Ni and Cu are supported by the microemulsion method. Most of the impregnation of Pd is by solution method.
  • a more preferred method of the present invention is to load the active component palladium in the small pores first, then load the active component nickel/copper and a small amount of palladium in the large pores of the catalyst, and load the active component palladium in the small pores.
  • Acetylene etc. mainly undergo selective hydrogenation reaction in small pores to generate ethylene.
  • the larger molecular size by-products generated in the reaction are mainly C4 to C16 fractions, which are more likely to enter the macropores, and undergo a saturated hydrogenation reaction under the action of active components such as nickel in the macropores. Since these molecules are saturated with hydrogen, their molecular chains no longer grow, so they are easily taken out of the reactor by the material.
  • Ni and Cu are impregnated at the same time, they will form an alloy. Due to the existence of Cu, the reduction temperature of Ni will be greatly reduced, and the minimum temperature will reach 350°C, but this temperature is still too high for Pd catalysts. . It is also found in the present invention that after a small amount of Pd is loaded on the Ni/Cu catalyst, the reduction temperature is greatly reduced and can be reduced to 150°C. This temperature is completely acceptable for the Pd catalyst, because the general Pd catalyst has a low temperature. The reduction temperature is 100-150 °C, and the catalyst can run for a long time at 120-130 °C in some cases, indicating that 100-150 °C will not cause aggregation of active components.
  • the conditions of the hydrogenation method of the present invention are: the fixed bed reactor is an adiabatic or isothermal reactor, and the reaction conditions are: the inlet temperature of the reactor is 35-100 DEG C, the reaction pressure is 1.5-3.0MPa, and the gas volume space velocity is 2000-11000h -1 .
  • the hydrogenation raw material is carbon two fractions, wherein ethylene is 65-93% (v/v); acetylene is 0.2-2.5% ( v/v), C3 fraction 0.01-0.8% (v/v); more preferably, 65-93% (v/v) of ethylene, followed by 5-35% (v/v) of ethane, acetylene 0.3-2.5% (v/v), C3 fraction 0.01-0.5% (v/v).
  • the above content is calculated based on the total volume of the hydrogenated feedstock as 100%.
  • the hydrogen-alkyne ratio at the reactor inlet is 1.3-2.2, preferably 1.3 -1.8.
  • the hydrogen-alkyne ratio refers to the molar ratio of hydrogen to alkyne.
  • the hydrogen-alkyne ratio at the inlet of the first-stage reactor is 1.0-1.4, and the two-stage reactor is hydrogenated.
  • the hydrogen-alkyne ratio at the inlet of the stage reactor was 1.5-2.5.
  • the hydrogen-alkyne ratio at the inlet of the first-stage reactor is 0.5-1.5
  • the inlet hydrogen-acetylene ratio of the second-stage reactor is 1.0-2.0
  • the inlet hydrogen-acetylene ratio of the three-stage reactor is 1.4-3.0.
  • the hydrogen-acetylene ratio at the inlet of the first-stage reactor is 0.8-1.5
  • the inlet hydrogen-acetylene ratio of the second-stage reactor is 0.8-1.5. It is 1.2-1.6
  • the inlet hydrogen-acetylene ratio of the three-stage reactor is 1.5-2.5.
  • the catalyst needs to be reduced before hydrogenation, and the reduction temperature is 150-200°C.
  • the present invention also provides a selective hydrogenation method for the post-carbon 2 hydrogenation process using crude hydrogen as the hydrogen source, wherein the hydrogenation material is the carbon 2 fraction from the top of the deethanizer column, and after entering the fixed bed reactor Carry out gas phase hydrogenation to remove acetylene, the hydrogen used in the hydrogenation reaction is crude hydrogen, the H content in the crude hydrogen is 20-50v/v%, the CO content is 0.1-1v/v%, and the reaction process conditions are: the reactor The inlet temperature is 55-130°C, the pressure is 1.5-3.0MPa, and the gas volume space velocity is 1500-6000h -1 ;
  • the catalyst is the catalyst of any one of claims 1-19.
  • the hydrogenation material is the carbon 2 fraction from the top of the deethanizer column , after entering the fixed-bed reactor, gas phase hydrogenation is carried out to remove acetylene, wherein the hydrogen used in the hydrogenation reaction is crude hydrogen, wherein the H content is 30-50v/v%, and the CO content is 0.1-1v/v%, The remaining part is methane; the reaction process conditions are: the inlet temperature of the reactor is 55-130° C., the pressure is 1.5-3.0 MPa, and the gas volume space velocity is 1500-4000 h ⁇ 1 ; wherein, the catalyst is the above-mentioned catalyst provided by the present invention.
  • the catalyst used in the above-mentioned selective hydrogenation method of the carbon 2 post-hydrogenation process using crude hydrogen as the hydrogen source is the carrier of alumina or mainly alumina, and has a bimodal pore distribution Structure of alumina, wherein the pore size of small pores is 15-50nm, the pore size of macropores is 80-500nm, the catalyst contains at least active components Pd, Ni, Cu, and the content of Pd is 0.06- 0.1%, the content of Ni is 0.5-5%, and the weight ratio of Cu to Ni is 0.1-1:1.
  • the specific surface area of the catalyst is preferably 20-50 m 2 /g.
  • the catalyst preferably also contains 0.03-0.5% Ag, which is supported by solution.
  • the preferred content of Pd is 0.07-0.1%, and the total content of Ni and Cu is preferably 1-5.5%.
  • the hydrogenation raw material is the material from the top of the deethanizer in the ethylene unit, Together with the metered crude hydrogen, it enters a fixed-bed carbon two hydrogenation reactor for selective hydrogenation to remove alkynes therein.
  • the reactor is a single-stage fixed-bed reactor.
  • the hydrogen-alkyne ratio in the reactor inlet material can be controlled to be 2-3 (molar ratio)
  • the reactor inlet temperature can be controlled to 65-130°C (preferably 65-125°C)
  • the reaction conditions can be controlled to: reaction pressure 1.5-3.0MPa
  • the gas volume air velocity is 1500-6000h -1 .
  • the CO content in the crude hydrogen is 0.1-1 v/v%, and the hydrogen content is 20-50v/v%.
  • the above content is calculated based on the total volume of crude hydrogen as 100%.
  • ethylene 60-93 v /v%, acetylene 0.2-1.0v/v%, carbon three fraction 1.0-7.0v/v% ethylene 60-93 v /v%, acetylene 0.2-1.0v/v%, carbon three fraction 1.0-7.0v/v%.
  • the above content is calculated based on the total volume of the hydrogenated feedstock as 100%.
  • the catalyst needs to be reduced before hydrogenation, and the reduction temperature is 150-200 °C °C.
  • the ratio of hydrogen to acetylene in the inlet material of the single-stage fixed bed reactor is 2-3 (The molar ratio of).
  • the content of C3 components in the material can reach up to 7.0%. Since the anti-coking ability of the catalyst of the present invention is significantly enhanced, it is far higher than the traditional hydrogenation method for C3 components. Due to the limitation of fraction content, even if the separation unit fluctuates greatly and the content of heavy components in the material exceeds the standard, the hydrogenation unit can still operate normally.
  • the catalyst of the present invention has the following characteristics: at the beginning of the hydrogenation reaction, since the hydrogenation activity of palladium is high and mainly distributed in the small pores, the selective hydrogenation reaction of acetylene mainly occurs in the small pores. With the prolongation of the running time of the catalyst, a part of by-products with larger molecular weight are formed on the surface of the catalyst. Due to the larger molecular size, more of these substances enter the macropores, and the residence time is longer. Under the action of the nickel catalyst, Hydrogenation of double bonds occurs to generate saturated hydrocarbons or aromatic hydrocarbons without isolated double bonds, and no longer generate substances with larger molecular weights.
  • the inventors also found that, after using the catalyst, even if the reactants contained more heavy fractions, the amount of green oil produced by the catalyst was greatly increased, and the activity and selectivity of the catalyst did not tend to decrease.
  • Figure 1 shows the particle size distribution of the Ni and Cu microemulsion prepared in Example 1-1.
  • FIG. 2 is a TPR graph of the catalyst of Example 1-1.
  • the catalyst of the present invention uses the following characterization methods in the preparation process: a dynamic light scattering particle size analyzer, which is used to analyze the microemulsion particle size distribution of Ni/Cu alloy on M286572 dynamic light scattering analyzer; The pore volume, specific surface area and pore size distribution of the carrier were analyzed on the company's 9510 mercury porosimeter. The contents of Pd, Ag, Ni and Cu in the catalyst were determined on an AA240FS atomic absorption spectrometer.
  • An Agilent 7890A gas chromatograph measures the reactor outlet and inlet hydrogen and acetylene content.
  • the catalyst weight was measured with a 0.1 mg electronic balance.
  • the initial acetylene conversion rate refers to the acetylene conversion rate measured within 24 hours from the start of feeding the reactor.
  • Acetylene conversion rate [(Acetylene content at reactor inlet - Acetylene content at reactor outlet)/Acetylene content at reactor outlet]*100%
  • Ethylene selectivity ⁇ 2-[(Hydrogen content at the reactor inlet-Hydrogen content at the reactor outlet)/(Acetylene content at the reactor inlet-Acetylene content at the reactor outlet)] ⁇ *100%
  • Coking amount [(catalyst weight after reaction - catalyst weight before reaction)/reactor catalyst weight]*100%
  • Catalyst carrier A commercially available bimodal pore distribution spherical alumina carrier with a diameter of 4 mm was used. After calcination at 1092°C for 4h, the bimodal pore size distribution ranges from 15-38nm and 80-350nm, the water absorption rate is 65%, and the specific surface area is 49.65m 2 /g. Weigh 100 g of the carrier.
  • the particle size of the microemulsion prepared in step (1) was determined to be 60.71 nm by dynamic light scattering, and the particle size of the microemulsion prepared in step (3) was 60.18 nm.
  • the prepared catalyst was measured by atomic absorption spectrometry, and it was found that in the catalyst prepared in Example 1-1, the content of Pd was 0.0575%, the content of Ni was 5%, and the content of Cu was 0.5%.
  • the TPR of this catalyst is shown in Figure 2. It can be seen from Fig. 2 that the reduction temperature of the Ni/Cu alloy is 350°C. After adding Pd to Ni/Cu, the reduction temperature is about 150°C.
  • Example 1-1 The same carrier as in Example 1-1 was used, and the catalyst preparation conditions were the same as those in Example 1-1, except that Cu was not supported.
  • step (2) Weigh 0.046g of palladium chloride and dissolve it in 60mL of deionized water, add 28.57g of cyclohexane, add 16.57g of Triton X-100, add 16g of n-butanol, fully stir to form a microemulsion, and prepare step (2)
  • the semi-finished catalyst B1-1 was placed in the prepared microemulsion, shaken for 30 min, filtered off the remaining liquid, dried at 40 °C, and calcined at 400 °C for 6 h to obtain the desired catalyst.
  • the particle size of the microemulsion emulsion prepared in (1) was 62.12 nm by dynamic light scattering, and the particle size of the microemulsion emulsion prepared in (3) was 60.18 nm.
  • the prepared catalyst was measured by atomic absorption spectrometry, and it was found that in Comparative Example 1-1, the Pd content was 0.0575%, and the Ni content was 5%.
  • Carrier A commercially available spherical alumina carrier with bimodal pore distribution was used, with a diameter of 3 mm. After calcination at 1111°C for 4h, the bimodal pore size distribution ranges from 20-40nm and 120-400nm, the water absorption rate is 62%, and the specific surface area is 39.71m 2 /g. Weigh 100 g of the carrier.
  • the particle size of the microemulsion prepared in step (1) was determined to be 55.48 nm by dynamic light scattering, and the particle size of the microemulsion prepared in step (3) was 54.40 nm.
  • the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.05%
  • the Ni content was 0.5%
  • the Cu content was 0.5%.
  • Example 1-2 The same carrier as in Example 1-2 was used, and the catalyst preparation conditions were the same as those in Example 1-2, except that Cu was supported by solution method.
  • Carrier A commercially available spherical alumina carrier with bimodal pore distribution was used, with a diameter of 3 mm. After calcination at 111°C for 4h, the bimodal pore size distribution ranges from 20-40nm and 120-400nm, the water absorption rate is 62%, and the specific surface area is 39.71m 2 /g. Weigh 100 g of the carrier.
  • step (2) -1 Weigh 0.0167g of palladium chloride, dissolve in 70mL of deionized water, add 34.14g of n-hexane, add 20g of CATB, add 19g of n-amyl alcohol, fully stir to form a microemulsion, and the semi-finished catalyst B2 prepared in step (2) -1 was immersed in the prepared microemulsion, shaken for 90 min, filtered off the remaining liquid, dried at 70 °C, and calcined at 600 °C for 4 h to obtain the desired catalyst.
  • the particle size of the microemulsion prepared in step (1) was determined to be 55.48 nm by dynamic light scattering, and the particle size of the microemulsion prepared in step (3) was 54.40 nm.
  • the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.05%
  • the Ni content was 0.5%
  • the Cu content was 0.5%.
  • Carrier A commercially available spherical alumina carrier with bimodal pore distribution was used, with a diameter of 4 mm. After calcination at 1128°C for 4h, the bimodal pore size distribution range is 25-50nm and 95-500nm, the water absorption rate is 62%, and the specific surface area is 20.19m 2 /g. Weigh 100 g of the carrier.
  • the particle size of the microemulsion prepared in step (1) was determined to be 403.65 nm by dynamic light scattering, and the particle size of the microemulsion prepared in step (4) was 401.83 nm.
  • the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.07%
  • the Ni content was 2%
  • the Cu content was 1%
  • the Ag content was 0.21%.
  • Example 1-3 The same carrier as in Example 1-3 was used, and the catalyst preparation conditions were the same as those in Example 1-3, except that the emulsion method did not support Pd.
  • step (3) take by weighing 0.33g of silver nitrate, dissolve it in 68.2mL deionized water, adjust the pH value to be 4, dissolve the semi-finished product catalyst B3-1 prepared in step (2) in the prepared silver nitrate solution containing silver, Shake, after the solution is completely absorbed, dry at 150°C for 2 hours, and calcinate at 500°C for 5 hours to obtain the desired catalyst.
  • the particle size of the microemulsion emulsion prepared in step (1) was determined by dynamic light scattering to be 403.65 nm.
  • the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.07%
  • the Ni content was 2%
  • the Cu content was 1%
  • the Ag content was 0.21%.
  • Carrier A commercially available spherical alumina-titanium oxide carrier with bimodal pore distribution is used, the titanium oxide content is 20%, and the diameter is 3 mm. After calcination at 1118°C for 4h, the bimodal pore size distribution ranges from 23-47nm and 90-450nm, the water absorption rate is 58%, and the specific surface area is 30.28m 2 /g. Weigh 100 g of the carrier.
  • the particle size of the microemulsion emulsion prepared in step (1) was determined to be 52.83 nm by dynamic light scattering, and the particle size of the microemulsion emulsion prepared in step (2) was 52.61 nm.
  • the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.064%
  • the Ni content was 1%
  • the Cu content was 1%
  • the Ag content was 0.08%.
  • the carrier and preparation conditions are the same as those in Examples 1-4, except that there is no Ni in the comparative example.
  • the particle size of the microemulsion emulsion prepared in step (1) was determined to be 52.87 nm by dynamic light scattering, and the particle size of the microemulsion emulsion prepared in step (2) was 52.65 nm.
  • the prepared catalysts were determined by atomic absorption spectrometry.
  • the Pd content was 0.064%
  • the Cu content was 1%
  • the Ag content was 0.08%.
  • Carrier A commercially available spherical alumina-magnesia carrier with bimodal pore distribution is used, the content of magnesia is 3%, and the diameter is 3mm. After calcination at 999°C for 4h, the bimodal pore size distribution range is 23-47nm and 80-380nm, the water absorption rate is 58%, and the specific surface area is 45.08m 2 /g. Weigh 100 g of the carrier.
  • step (3) Weigh 3.295 g of nickel chloride and 1.45 g of copper nitrate, dissolve them in 80 mL of deionized water, add 35.00 g of n-hexane, add 20.36 g of Triton X-100, add 19.39 g of n-hexanol, and stir well to form a microemulsion.
  • the semi-finished catalyst B5 prepared in step (2) is dipped into the prepared microemulsion, shaken for 180 minutes, filtered to remove residual liquid, dried at 70°C, and calcined at 500°C for 4 hours, which is called semi-finished catalyst C5.
  • the particle size of the microemulsion emulsion prepared in step (3) was determined to be 66.38 nm by dynamic light scattering, and the particle size of the microemulsion emulsion prepared in step (4) was 65.22 nm.
  • the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.055%
  • the Ni content was 1.5%
  • the Cu content was 0.5%
  • the Ag content was 0.10%.
  • the catalyst carrier and preparation conditions are the same as those in Examples 1-5, the difference is that the amount of Ni added is reduced to 0.3%.
  • the particle size of the microemulsion emulsion prepared in (3) was 66.32 nm by dynamic light scattering, and the particle size of the microemulsion emulsion prepared in (4) was 65.24 nm.
  • the prepared catalysts were determined by atomic absorption spectrometry.
  • the Pd content was 0.055%
  • the Ni content was 0.28%
  • the Cu content was 0.5%
  • the Ag content was 0.10%.
  • Carrier A commercially available spherical alumina-magnesia carrier with bimodal pore distribution is used, the content of magnesia is 10%, and the diameter is 3 mm. After calcination at 999°C for 4h, the bimodal pore size distribution range is 23-47nm and 80-380nm, the water absorption rate is 58%, and the specific surface area is 45.08m 2 /g. Weigh 100 g of the carrier.
  • the prepared catalysts were determined by atomic absorption spectrometry.
  • the Pd content was 0.055%
  • the Ni content was 1%
  • the Cu content was 1%
  • the Ag content was 0.10%.
  • the catalyst carrier and preparation conditions are the same as in Example 1-6, the difference is that the amount of Pd added during the preparation of the microemulsion in step (4) is reduced to 1/3 of that of Example 1-6, and less than 1/200 of the Ni+Cu content .
  • Carrier A commercially available spherical alumina-magnesia carrier with bimodal pore distribution is used, the content of magnesia is 10%, and the diameter is 3 mm. After calcination at 1000°C for 4h, the bimodal pore size distribution range is 23-47nm and 80-380nm, the water absorption rate is 58%, and the specific surface area is 45.08m 2 /g. Weigh 100 g of the carrier.
  • the particle size of the microemulsion emulsion prepared in step (3) was determined to be 66.32 nm by dynamic light scattering, and the particle size of the microemulsion emulsion prepared in step (4) was 65.36 nm.
  • the prepared catalysts were determined by atomic absorption spectrometry.
  • the Pd content was 0.0483%
  • the Ni content was 1%
  • the Cu content was 1%
  • the Ag content was 0.10%.
  • Carrier A commercially available spherical carrier with bimodal pore distribution is used, with an alumina content of 97%, a titanium oxide content of 3%, and a diameter of 3 mm. After calcination at 978°C for 4h, the bimodal pore size distribution ranges from 20-35nm and 90-200nm, the water absorption rate is 62%, and the specific surface area is 49.81m 2 /g. Weigh 100 g of the carrier.
  • the particle size of the microemulsion emulsion prepared in step (3) was determined by dynamic light scattering to be 100.60 nm, and the particle size of the microemulsion emulsion prepared in step (4) was 100.28 nm.
  • the prepared catalysts were determined by atomic absorption spectrometry.
  • the Pd content was 0.035%
  • the Ni content was 0.5%
  • the Cu content was 0.5%
  • the Ag content was 0.08%.
  • the carrier adopts the same commercially available spherical carrier with bimodal pore distribution as in Example 1-7, with an alumina content of 97% and a titanium oxide content of 3%.
  • the water absorption rate was 65%, and the specific surface area was 75.21 m 2 /g. Weigh 100 g of the carrier.
  • the particle size of the microemulsion emulsion prepared in step (3) was determined by dynamic light scattering to be 100.60 nm, and the particle size of the microemulsion emulsion prepared in step (4) was 100.23 nm.
  • the prepared catalysts were determined by atomic absorption spectrometry.
  • the Pd content was 0.035%
  • the Ni content was 0.5%
  • the Cu content was 0.5%
  • the Ag content was 0.08%.
  • the carriers of Examples 1-8 are the same as those of Examples 1-7, the preparation conditions are the same, and the difference is that the order of steps (1) and (2) is exchanged.
  • Carrier A commercially available spherical carrier with bimodal pore distribution is used, with an alumina content of 97%, a titanium oxide content of 3%, and a diameter of 3 mm. After calcination at 978°C for 4h, the bimodal pore size distribution ranges from 20-35nm and 90-200nm, the water absorption rate is 62%, and the specific surface area is 49.81m 2 /g. Weigh 100 g of the carrier.
  • step (2) is used to prepare a semi-finished product
  • Catalyst B8 was immersed in the prepared microemulsion, shaken for 90 minutes, filtered to remove residual liquid, dried at 80°C, and calcined at 600°C for 4 hours, which was called semi-finished catalyst C8.
  • the particle size of the microemulsion emulsion prepared in step (3) was determined by dynamic light scattering to be 100.60 nm, and the particle size of the microemulsion emulsion prepared in step (4) was 100.23 nm.
  • the prepared catalysts were determined by atomic absorption spectrometry.
  • the Pd content was 0.035%
  • the Ni content was 0.5%
  • the Cu content was 0.5%
  • the Ag content was 0.08%.
  • Steps 1-3 of the catalyst carrier and preparation conditions are the same as those of Example 1-8, except that the particle size of the microemulsion prepared in step (4) is larger than the maximum pore size of the carrier.
  • Carrier A commercially available spherical carrier with bimodal pore distribution is used, with an alumina content of 97%, a titanium oxide content of 3%, and a diameter of 3 mm. After calcination at 980°C for 4h, the bimodal pore size distribution ranges from 20-35nm and 90-200nm, the water absorption rate is 62%, and the specific surface area is 49.81m 2 /g. Weigh 100 g of the carrier.
  • the particle size of the microemulsion emulsion prepared in step (3) was determined by dynamic light scattering to be 100.60 nm, and the particle size of the microemulsion emulsion prepared in step (4) was 398.76 nm.
  • the prepared catalysts were determined by atomic absorption spectrometry.
  • the Pd content was 0.031%
  • the Ni content was 0.5%
  • the Cu content was 0.5%
  • the Ag content was 0.08%.
  • a commercially available bimodal pore distribution spherical alumina carrier with a diameter of 4 mm was weighed. After calcination at 1115°C for 4 hours, the pore size distribution ranges were 28-48nm and 102-499nm respectively, the water absorption was 50.35%, and the specific surface area was 20.73m 2 /g. Weigh 100g of the carrier.
  • the particle size of the microemulsion prepared in step (3) was determined to be 398.56 nm by dynamic light scattering, and the particle size of the microemulsion prepared in step (4) was 398.75 nm.
  • the element content was determined by atomic absorption spectrometry, and the catalysts prepared in Examples 1-9 were obtained.
  • the Pd content was 0.0675%
  • the Ni content was 5%
  • the Cu content was 0.5%
  • the Ag content was 0.21%.
  • Reduction gas hydrogen, reduction space velocity: 100h -1 , temperature 150°C, hold for 8h.
  • Comparative Example 1-9 Using the same carrier as Example 1-9, the preparation of Comparative Example 1-9 is the same as that of Example 1-9, the difference is that the particle size of the microemulsion when Ni/Cu is supported is 622.38 nm.
  • the particle size of the prepared microemulsion obtained in step (3) was determined to be 621.67 nm by dynamic light scattering, and the particle size of the prepared microemulsion obtained in step (4) was 399.62 nm.
  • the element content was determined by atomic absorption spectrometry, and the catalysts prepared in Comparative Examples 1-9 were obtained, wherein the Pd content was 0.0675%, the Ni content was 1.34%, the Cu content was 0.12%, and the Ag content was 0.21%.
  • Reduction gas hydrogen, reduction space velocity: 100h -1 , temperature 150°C, hold for 8h.
  • Catalyst preparation The carrier adopts a commercially available bimodal pore distribution spherical alumina carrier with a diameter of 3 mm. After calcination at 1118°C for 4h, the bimodal pore size distribution ranges from 30-43nm and 100-498nm, the water absorption rate is 62%, and the specific surface area is 20.35m 2 /g. Weigh 100 g of the carrier.
  • the particle size of the microemulsion emulsion prepared in step (1) was determined to be 497.65 nm by dynamic light scattering, and the particle size of the microemulsion emulsion prepared in step (2) was 495.32 nm.
  • the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.08%
  • the Ni content was 2.5%
  • the Cu content was 2.5%
  • the Ag content was 0.10%.
  • Reducing gas hydrogen, reducing space velocity: 100h -1 , temperature 200°C, hold for 4h.
  • the catalyst preparation conditions are the same as those of Examples 1-10, except that the specific surface area is less than 20 m 2 /g.
  • Catalyst preparation The carrier adopts a commercially available bimodal pore distribution spherical alumina carrier with a diameter of 3 mm. After calcination at 1155°C for 4h, the bimodal pore size distribution ranges from 41-76nm and 114-684nm, the water absorption rate is 60%, and the specific surface area is 14.29m 2 /g. Weigh 100 g of the carrier.
  • the particle size of the microemulsion emulsion prepared in step (1) was determined to be 497.61 nm by dynamic light scattering, and the particle size of the microemulsion emulsion prepared in step (2) was 495.33 nm.
  • the prepared catalysts were determined by atomic absorption spectrometry.
  • the Pd content was 0.08%
  • the Ni content was 2.5%
  • the Cu content was 2.5%
  • the Ag content was 0.10%.
  • Reducing gas hydrogen, reducing space velocity: 100h -1 , temperature 200°C, hold for 4h.
  • Carrier A commercially available spherical alumina carrier with bimodal pore distribution was used, with a diameter of 3 mm. After calcination at 1100°C for 4h, the bimodal pore size distribution ranges from 30-45nm and 300-450nm, the water absorption rate is 62%, and the specific surface area is 47m 2 /g. Weigh 100 g of the carrier.
  • the particle size of the microemulsion prepared in step (1) was determined to be 51.61 nm by dynamic light scattering, and the particle size of the microemulsion prepared in step (4) was 50.39 nm.
  • the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.05%
  • the Ni content was 0.5%
  • the Cu content was 0.5%
  • the Ag content was 0.08%.
  • the carrier and preparation steps are the same as those in Example 1-11, except that the particle size of the microemulsion in Comparative Example 1-11 is smaller than the maximum pore size of the pores of the carrier.
  • the particle size of the microemulsion prepared in step (1) was determined to be 30.87 nm by dynamic light scattering, and the particle size of the microemulsion prepared in step (4) was 30.24 nm.
  • the prepared catalysts were determined by atomic absorption spectrometry.
  • the Pd content was 0.05%
  • the Ni content was 0.5%
  • the Cu content was 0.5%
  • the Ag content was 0.08%.
  • a commercially available bimodal pore distribution spherical alumina carrier with a diameter of 4 mm was weighed. After calcination at 1088°C for 4 hours, the pore size distribution ranges were 20-46nm and 85-350nm respectively, the water absorption rate was 55%, and the specific surface area was 39.29m 2 /g. Weigh 100g of the carrier.
  • the particle size of the microemulsion prepared in step (2) was determined to be 98.78 nm by dynamic light scattering, and the particle size of the microemulsion prepared in step (3) was 99.31 nm.
  • the element content was measured by atomic absorption spectrometry, and the catalysts prepared in Examples 1-12 were obtained.
  • the Pd content was 0.057%
  • the Ni content was 1.57%
  • the Cu content was 0.5%
  • the Ag content was 0.18%.
  • Reducing gas hydrogen, reducing space velocity: 100h -1 , temperature 150°C, hold for 4h.
  • the catalyst carrier Examples 1-12 are the same, and the catalyst preparation conditions are also the same, except that the loading of Cu is lower than 1/10 of that of Ni.
  • a commercially available bimodal pore distribution spherical alumina carrier with a diameter of 4 mm was weighed. After calcination at 1090°C for 4 hours, the pore size distribution ranges were 20-46nm and 85-350nm respectively, the water absorption rate was 55%, and the specific surface area was 39.29m 2 /g. Weigh 100g of the carrier.
  • the particle size of the microemulsion prepared in step (2) was determined to be 98.78 nm by dynamic light scattering, and the particle size of the microemulsion prepared in step (3) was 99.31 nm.
  • the element content was determined by atomic absorption spectrometry, and the catalysts prepared in Comparative Examples 1-12 were obtained.
  • the Pd content was 0.057%
  • the Ni content was 1.57%
  • the Cu content was 0.1%
  • the Ag content was 0.18%.
  • Reducing gas hydrogen, reducing space velocity: 100h -1 , temperature 150°C, hold for 4h.
  • a commercially available bimodal pore distribution spherical alumina carrier with a diameter of 4 mm was weighed. After calcination at 1112°C for 4h, the pore size distribution ranges were 26-47nm and 95-450nm respectively, the water absorption rate was 55%, and the specific surface area was 25.45m 2 /g. Weigh 100g of the carrier.
  • the particle size of the microemulsion prepared in step (2) was 50.68 nm as determined by dynamic light scattering, and the particle size of the microemulsion prepared in step (3) was 50.32 nm,
  • the element content was measured by atomic absorption spectrometry, and the catalysts prepared in Examples 1-13 were obtained.
  • the Pd content was 0.054%
  • the Ni content was 4%
  • the Cu content was 1%
  • the Ag content was 0.13%.
  • Reduction gas hydrogen, reduction space velocity: 100h -1 , temperature 200°C, hold for 8h.
  • a commercially available bimodal pore distribution spherical alumina carrier with a diameter of 4 mm was weighed. After calcination at 1112°C for 4h, the pore size distribution ranges were 26-47nm and 95-450nm respectively, the water absorption rate was 55%, and the specific surface area was 25.45m 2 /g. Weigh 100g of the carrier.
  • the particle size of the microemulsion prepared in (1) was 50.68 nm as determined by dynamic light scattering, and the particle size of the microemulsion prepared in step (2) was 50.34 nm.
  • the element content was measured by atomic absorption spectrometry, and the catalysts prepared in Comparative Examples 1-13 were obtained.
  • the Pd content was 0.054%
  • the Ni content was 4%
  • the Cu content was 1%
  • the Ag content was 0.13%.
  • Reduction gas hydrogen, reduction space velocity: 100h -1 , temperature 200°C, hold for 8h.
  • a commercially available bimodal pore distribution spherical alumina carrier with a diameter of 4 mm was weighed. After calcination at 1088°C for 4 hours, the pore size distribution ranges were 20-46nm and 85-350nm respectively, the water absorption rate was 55%, and the specific surface area was 40.23m 2 /g. Weigh 100g of the carrier.
  • the particle size of the microemulsion prepared in step (1) was determined to be 80.28 nm by dynamic light scattering, and the particle size of the microemulsion prepared in step (3) was 80.56 nm.
  • the element content was determined by atomic absorption spectrometry, and the catalysts prepared in Examples 1-14 were obtained.
  • the Pd content was 0.043%, the Ni content was 1.57%, the Cu content was 0.5%, and the Ag content was 0.18%.
  • Reducing gas hydrogen, reducing space velocity: 100h -1 , temperature 150°C, hold for 4h.
  • Example 1-14 The same carrier as in Example 1-14 was used, and the preparation conditions were the same as those in Example 1-14, except that copper-nickel was supported by solution method.
  • the particle size of the microemulsion prepared in step (3) was determined to be 80.56 nm by dynamic light scattering.
  • the element content was measured by atomic absorption spectrometry, and the catalysts prepared in Comparative Examples 1-14 were obtained.
  • the Pd content was 0.043%
  • the Ni content was 1.57%
  • the Cu content was 0.5%
  • the Ag content was 0.18%.
  • Reducing gas hydrogen, reducing space velocity: 100h -1 , temperature 150°C, hold for 4h.
  • a commercially available bimodal pore distribution spherical alumina carrier with a diameter of 4 mm was weighed. After calcination at 1092°C for 4 hours, the pore size distribution ranges were 20-45nm and 85-350nm respectively, the water absorption rate was 55%, and the specific surface area was 39.47m 2 /g. Weigh 100g of the carrier.
  • the particle size of the microemulsion prepared in steps (1) and (3) was determined to be 101.39 nm by dynamic light scattering.
  • the element content was measured by atomic absorption spectrometry, and the catalysts prepared in Examples 1-15 were obtained, wherein the Pd content was 0.04%, the Ni content was 1.57%, the Cu content was 0.5%, and the Ag content was 0.18%.
  • Reducing gas hydrogen, reducing space velocity: 100h -1 , temperature 150°C, hold for 4h.
  • Catalyst preparation Weigh a commercially available spherical alumina carrier with unimodal pore distribution, with a diameter of 4 mm. After calcination at 1092°C for 4h, the pore size distribution range is 20-45nm, which is a single pore size distribution, the water absorption rate is 55%, and the specific surface area is 39.47m 2 /g. Weigh 100g of the carrier.
  • the particle size of the microemulsion prepared in steps (1) and (3) was determined to be 101.39 nm by dynamic light scattering.
  • the element content was measured by atomic absorption spectrometry, and the catalysts prepared in Comparative Examples 1-15 were obtained.
  • the Pd content was 0.034%
  • the Ni content was 0.32%
  • the Cu content was 0.11%
  • the Ag content was 0.18%.
  • Reducing gas hydrogen, reducing space velocity: 100h -1 , temperature 150°C, hold for 4h.
  • the filling amount of the catalyst in the fixed-bed reactor is 100 mL (record the weight), the packing is 50 mL, the space velocity of the reaction material: 5000/h, the operating pressure is 2.0 MPa, the hydrogen-acetylene ratio is 1.15, and the reactor inlet temperature is 50 °C.
  • the calculation method of the evaluation results is shown in Table 1-2.
  • the initial selectivity was the selectivity measured at 24 hours from the start of reactor feed.
  • the initial activity is the activity (acetylene conversion) measured at the beginning of the reactor feeding and 24 hours
  • composition of reaction materials is shown in Table 1-3.
  • reaction material C 2 H 2 C 2 H 4 C 2 H 6 C3 - C4 Content (v/v%) 1.5 86 12 3 ⁇ 10-3
  • Example 1-1 Comparative Example 1-1, without Cu supported, and the reduction temperature was 200°C, although the initial acetylene conversion and selectivity were substantially the same as those of the corresponding Examples. However, after 1000 hours, it is significantly lower than that of the examples, indicating that the Cu loading or catalyst reduction temperature is important to improve the anti-coking performance. Or maybe at the reduction temperature of 200 °C, the active center with saturated hydrogenation function did not play its due role.
  • Example 1-2 in Comparative Example 1-2 Compared with Example 1-2 in Comparative Example 1-2, the loading of Cu in Comparative Example 1-2 adopts the solution method, and Cu is highly uniformly dispersed in the carrier, which does not play a role in effectively reducing the reduction temperature of Ni. As the reaction proceeds, The coking amount of the catalyst increased obviously, and the difference from the catalyst of Example 1-2 became more and more obvious.
  • Comparative Example 1-4 does not support Ni, because the saturated hydrogenation of green oil is reduced, the coking amount of the catalyst is large after 1000 hours, and the performance is greatly reduced.
  • the catalysts of Comparative Examples 1-6 were prepared under the same preparation conditions as those of Examples 1-6, except that the content of Pd supported by the microemulsion method was significantly reduced. Due to the decrease of Pd content, it can no longer play the role of significantly reducing the reduction temperature of Ni, so that Ni has no obvious effect on the saturated hydrogenation of by-products, and the performance gap is also obvious after 1000 hours.
  • Comparative Example 1-7 has too large specific surface area and too small Pd active center scale on the catalyst. Although the initial selectivity is better, the initial activity is obviously insufficient. Also because the specific surface area is too large, the activity of the active center of Ni-Cu is insufficient, and the amount of coking after 1000 hours is also significantly higher than that of Examples 1-7.
  • Example 1-8 Ag was first loaded when preparing the catalyst, and Ag and Pd formed an alloy.
  • the content of Ag in the alloy structure was high, which reduced the activity of selective hydrogenation, so its initial activity was higher than that of Example 1-7. Difference.
  • Comparative Examples 1-8 when the microemulsion was loaded with Pd, the particle size of the microemulsion was larger than the maximum pore size of the carrier, so that Pd could not enter the pores of the carrier, and could only be partially supported on the outer surface of the catalyst, and part of it was lost with the solution.
  • the selectivity is good, but Pd cannot effectively form alloys with Ni-Cu, so it cannot effectively reduce the reduction temperature of Ni-Cu.
  • the green oil molecules cannot be effectively saturated hydrogenated, therefore, after 1000 hours, the performance of the catalysts in Comparative Examples 1-8 is significantly worse than that of the catalysts in Examples 1-8.
  • the particle size of the microemulsion when Pd is loaded is 398 nm
  • the particle size of the microemulsion when Ni-Cu is loaded is 621 nm, which is larger than the maximum pore size of the carrier, and the microemulsion containing Ni-Cu cannot enter the carrier.
  • the pores of the microemulsion it can only be partially adsorbed on the surface of the carrier with the microemulsion, and part of it is lost.
  • the adsorbed part cannot form an alloy with Ni-Cu.
  • the reduction temperature is 150 °C
  • part of the Ni-Cu cannot be effectively reduced, and the green oil molecules cannot be effectively saturated and hydrogenated. Therefore, after 1000 hours, Comparative Example 1
  • the catalyst reaction effect in -9 is worse than that of the embodiment.
  • Comparative Examples 1-10 the specific surface area of the catalyst is small, and at the same loading, the scale of the Pd active center is too large, resulting in high activity and poor selectivity, and the active center of Ni-Cu has a larger scale, which not only has a negative effect on by-products.
  • the saturated hydrogenation function of ethylene also has the hydrogenation effect on ethylene, resulting in poor ethylene hydrogenation selectivity.
  • the comparative examples 1-10 have less coke formation after 1000 hours, but the selectivity is significantly lower than that of the examples.
  • Ni and Cu are supported by solution method, which are uniformly distributed in the carrier, and it is difficult to form a catalytic reaction center with good activity.
  • Part of the Pd supported by solution method forms an active center in the outer layer of the carrier.
  • the existence of Ni and Cu is not conducive to improving the selectivity of Pd active centers, but has a negative impact. Therefore, the initial activity of the catalyst is acceptable, but the initial selectivity is poor. Since there is no active center for saturated hydrogenation of hydrogenation by-products, the amount of coking after 1000 hours is very large, and the performance declines very seriously.
  • Comparative Examples 1-15 a carrier with a single pore size distribution was used, and the particle size of the prepared microemulsion was larger than the maximum pore size of the carrier, so that the emulsion could not enter the carrier, and some active components could only be distributed in the outermost layer of the carrier, and some It can not be effectively loaded and lost. Although there is a certain saturation hydrogenation on the outer surface, the catalytic effect is still worse than that of Example 1-15.
  • the particle size of the microemulsion prepared in step (1) was determined to be 50.29 nm by dynamic light scattering, and the particle size of the microemulsion prepared in step (3) was 51.45 nm.
  • the element content was measured by atomic absorption spectrometry, and it was found that in the catalyst prepared in Example 2-1, the content of Pd was 0.08%, the content of Ni was 5.0%, and the content of Cu was 0.5%.
  • Reduction of the catalyst reduction gas: hydrogen, reduction space velocity: 100h -1 , temperature 150°C, and hold for 8h.
  • the particle size of the microemulsion prepared in step (1) was determined to be 50.31 nm by dynamic light scattering, and the particle size of the microemulsion prepared in step (3) was 51.38 nm.
  • the element content was measured by atomic absorption spectrometry, and it was found that in the catalyst prepared in Comparative Example 2-1A, the content of Pd was 0.08%, and the content of Ni was 5.2%.
  • Reduction of the catalyst reduction gas: hydrogen, reduction space velocity: 100h -1 , temperature 150°C, and hold for 8h.
  • the particle size of the microemulsion prepared in step (1) was determined to be 50.31 nm by dynamic light scattering, and the particle size of the microemulsion prepared in step (3) was 51.49 nm.
  • the element content was determined by atomic absorption spectrometry, and it was found that in the catalyst prepared in Comparative Example 2-1B, the content of Pd was 0.08%, and the content of Cu was 0.52%.
  • Reduction of the catalyst reduction gas: hydrogen, reduction space velocity: 100h -1 , temperature 150°C, and hold for 8h.
  • the two-stage reactor process the material space velocity is 4000/h, the operating pressure is 3.0MPa, and the catalyst loading is 200mL.
  • the reactor conditions are shown in Table 2-1.
  • the reaction results are shown in Table 2-2.
  • Material composition 1.8% (v/v) of acetylene at the inlet of the first-stage reactor, 80% (v/v) of ethylene.
  • a commercially available bimodal pore distribution spherical alumina carrier with a diameter of 4 mm was weighed. After calcination at 1115°C for 4 hours, the pore size distribution ranges were 30-43nm and 112-496nm respectively, the water absorption rate was 50%, and the specific surface area was 21.74m 2 /g. Weigh 100g of the carrier.
  • the particle size of the microemulsion prepared in step (1) is 487.63 nm
  • the particle size of the microemulsion prepared in step (2) is 486.19 nm.
  • the element content was determined by atomic absorption spectrometry, and the catalyst prepared in Example 2-2 was obtained, wherein the Pd content was 0.065%, the Ni content was 1.1%, and the Cu content was 1.1%.
  • Reduction of the catalyst reduction gas: hydrogen, reduction space velocity: 100h -1 , temperature 200°C, hold for 8h.
  • a commercially available spherical unimodal pore alumina carrier with a diameter of 4 mm was weighed. After calcination at 1115° C. for 4 hours, the pore size distribution range is 32-88 nm, the water absorption rate is 50%, and the specific surface area is 21.74 m 2 /g, and 100 g of the carrier is weighed.
  • the particle size of the microemulsion prepared in step (1) determined by dynamic light scattering was 487.65 nm, and the particle size of the microemulsion prepared in step (2) was 486.22 nm.
  • the element content was determined by atomic absorption spectrometry, and it was found that in the catalyst prepared in Comparative Example 2-2, the Pd content was 0.06%, the Ni content was 1.0%, and the Cu content was 1.1%.
  • Reduction of the catalyst reduction gas: hydrogen, reduction space velocity: 100h -1 , temperature 200°C, hold for 8h.
  • the material space velocity is 11000/h
  • the operating pressure is 1.5MPa
  • the catalyst loading volume is 300mL.
  • the reactor conditions are shown in Tables 2-3.
  • the reaction results are shown in Table 2-4.
  • Reactor inlet material acetylene 0.2% (v/v), ethylene 65% (v/v), C3 0.8% (v/v).
  • the reactor conditions are shown in Tables 2-5.
  • Comparative Example 2-2 is different from Example 2-2 in the early stage of the reaction.
  • the reason is that the carrier in Comparative Example 2-2 has a single pore size distribution without macropores, resulting in The active components cannot enter the pores of the carrier or semi-finished catalyst, and are completely on the outer surface of the carrier, and block the pores of the carrier, resulting in a decrease in catalyst activity.
  • Table 2-6 shows the results of the single-stage reactor.
  • the acetylene content at the inlet of the reactor is relatively low, the high content of C3 also promotes the formation of more by-products in the hydrogenation reaction.
  • the acetylene at the reactor outlet of the embodiment is The content is always 0, but in the comparative example, because only a small amount of Ni-Cu is adsorbed on the outer surface of the catalyst, most of the hydrogenation by-products cannot be saturated and hydrogenated, resulting in the accumulation of by-products and coking, the catalyst selectivity decreases and cannot be hydrogenated. Effectively remove acetylene. After 1000 hours, the reaction result was already unqualified.
  • a commercially available bimodal pore distribution spherical alumina carrier with a diameter of 4 mm was weighed. After calcination at 1092°C for 4 hours, the pore size distribution ranges were 20-46nm and 85-350nm respectively, the water absorption was 58%, and the specific surface area was 39.58m 2 /g. Weigh 100g of the carrier.
  • the particle size of the microemulsion prepared in step (2) was determined to be 78.38 nm by dynamic light scattering, and the particle size of the microemulsion prepared in step (3) was 77.64 nm.
  • the element content was measured by atomic absorption spectrometry, and it was found that the Pd content in the catalyst prepared in Example 2-3 was 0.035%, the Ni content was 0.5%, the Cu content was 0.5%, and the Ag content was 0.08%.
  • Reduction of the catalyst reduction gas: hydrogen, reduction space velocity: 100h -1 , temperature 150°C, hold for 4h.
  • a commercially available bimodal pore distribution spherical alumina carrier with a diameter of 4 mm was weighed. After calcination at 1092°C for 4 hours, the pore size distribution ranges were 20-46nm and 85-350nm respectively, the water absorption rate was 55%, and the specific surface area was 39.58m 2 /g. Weigh 100g of the carrier.
  • the particle size of the microemulsion prepared in step (2) was determined to be 78.45 nm by dynamic light scattering.
  • the element content was determined by atomic absorption spectrometry, and it was found that the Pd content of the catalyst prepared in Comparative Example 2-3A was 0.035%, the Ni content was 0.5%, the Cu content was 0.5%, and the Ag content was 0.08%.
  • Reduction of the catalyst reduction gas: hydrogen, reduction space velocity: 100h -1 , temperature 150°C, hold for 4h.
  • One-stage reactor process material space velocity 2000/h, operating pressure 3.0MPa, catalyst loading, 200mL.
  • the reactor conditions are shown in Tables 2-7.
  • the reaction results are shown in Tables 2-8.
  • First stage reactor inlet material acetylene 0.5% (v/v), ethylene 70% (v/v), carbon three 0.8% (v/v).
  • Carrier A commercially available spherical alumina carrier with bimodal pore distribution was used, with a diameter of 3 mm. After calcination at 1078°C for 4h, the bimodal pore size distribution ranges from 20-35nm and 90-250nm, the water absorption rate is 57%, and the specific surface area is 44.82m 2 /g. Weigh 100 g of the carrier.
  • the particle size of the microemulsion emulsion prepared in step (1) was determined to be 51.19 nm by dynamic light scattering, and the particle size of the microemulsion emulsion prepared in step (4) was 50.85 nm.
  • the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.05%
  • the Ni content was 1%
  • the Cu content was 0.25%
  • the Ag content was 0.14%.
  • Carrier A commercially available spherical alumina carrier with bimodal pore distribution was used, with a diameter of 3 mm. After calcination at 1078°C for 4h, the bimodal pore size distribution ranges from 20-35nm and 90-250nm, the water absorption rate is 62%, and the specific surface area is 44.82m 2 /g. Weigh 100 g of the carrier.
  • the particle size of the microemulsion emulsion prepared in step (1) was determined by dynamic light scattering to be 52.18 nm.
  • the particle size of the microemulsion emulsion prepared in step (4) was determined to be 26.58 nm by dynamic light scattering.
  • the element content of the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.05%
  • the Ni content was 1%
  • the Cu content was 0.25%
  • the Ag content was 0.15%.
  • Carrier A commercially available spherical alumina carrier with bimodal pore distribution was used, with a diameter of 3 mm. After calcination at 1078°C for 4h, the bimodal pore size distribution ranges from 20-35nm and 90-250nm, the water absorption rate is 57%, and the specific surface area is 44.82m 2 /g. Weigh 100 g of the carrier.
  • the particle size of the microemulsion emulsion prepared in step (1) was determined by dynamic light scattering to be 52.13 nm.
  • the particle size of the microemulsion emulsion prepared in step (4) was determined by dynamic light scattering to be 595.09 nm.
  • the element content of the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.05%
  • the Ni content was 1.0%
  • the Cu content was 0.25%
  • the Ag content was 0.15%.
  • Material composition inlet material of the first stage reactor: acetylene 1.4% (v/v), ethylene 85% (v/v), carbon three 0.5% (v/v).
  • the first and second stages are adiabatic reactors, the material space velocity is 5000/h, the third stage is an isothermal reactor, the material space velocity is 11000/h, the operating pressure is 2.5MPa, and the first and second stage catalyst loadings are 1000mL .
  • the reactor conditions are shown in Tables 2-11.
  • the reaction results are shown in Table 2-12.
  • Material composition 1.5% (v/v) of acetylene at the inlet of the first-stage reactor, 93% (v/v) of ethylene.
  • Carrier A commercially available spherical alumina-magnesia carrier with bimodal pore distribution is used, the content of magnesia is 3%, and the diameter is 3mm. After calcination at 1065°C for 4h, the bimodal pore size distribution ranges from 23-47nm and 80-380nm, the water absorption rate is 58%, and the specific surface area is 42.38m 2 /g. Weigh 100 g of the carrier.
  • microemulsion emulsion was 65.0 nm
  • particle size of the step (4) microemulsion emulsion was 65.24 nm by dynamic light scattering.
  • the element content of the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.04%
  • the Ni content was 0.75%
  • the Cu content was 0.75%
  • the Ag content was 0.21%.
  • the catalyst preparation conditions are the same as those in Example 2-5, except that the preparation step does not carry Pd by an emulsion method.
  • Carrier A commercially available spherical alumina-magnesia carrier with bimodal pore distribution is used, the content of magnesia is 3%, and the diameter is 3mm. After calcination at 1000°C for 4h, the bimodal pore size distribution range is 23-47nm and 80-380nm, the water absorption rate is 58%, and the specific surface area is 40m 2 /g. Weigh 100 g of the carrier.
  • step (3) Weigh 1.648 g of nickel chloride and 2.175 g of copper nitrate, dissolve them in 80 mL of deionized water, add 36.00 g of n-hexane, add 20.88 g of Triton X-100, add 19.4 g of n-hexanol, and stir well to form a microemulsion.
  • the semi-finished catalyst B5-1 prepared in step (2) was dipped into the prepared microemulsion, shaken for 180 minutes, filtered off the remaining liquid, dried at 70°C, and calcined at 500°C for 4 hours to obtain the desired catalyst.
  • the particle size of the microemulsion emulsion prepared in step (4) was determined by dynamic light scattering to be 65.20 nm.
  • the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.04%
  • the Ni content was 0.75%
  • the Cu content was 0.75%
  • the Ag content was 0.21%.
  • each stage is an adiabatic reactor, the material space velocity is 11000/h, the operating pressure is 2.3MPa, and the catalyst loading volume is 1000mL.
  • the reactor conditions are shown in Tables 2-13.
  • the reaction results are shown in Table 2-14.
  • Material composition 1.5% (v/v) of acetylene at the inlet of the first-stage reactor, 70% (v/v) of ethylene.
  • Carrier A commercially available spherical alumina carrier with bimodal pore distribution was used, with a diameter of 4 mm. After calcination at 1005°C for 4h, the bimodal pore size distribution ranges from 15-35nm and 80-203mm, the water absorption rate is 63%, and the specific surface area is 48.45m 2 /g. Weigh 100 g of the carrier.
  • the active component content of the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.07%
  • the Ni content was 5%
  • the Cu content was 0.50%.
  • Example 3-1 The same carrier as in Example 3-1 was used, and the catalyst preparation conditions and the contents of other components were the same as those in Example 3-1, except that Cu was not supported.
  • the active component content of the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.07%, and the Ni content was 0.5%.
  • reaction material C 2 H 2 H 2 C 2 H 4 C3 CO Content (v/v%) 0.3 0.6 93 0.5 0.03
  • Example 3-1 due to the large loading of Ni and Cu, it is easy to form a uniform distribution in the carrier, and the amount of Pd loaded after is much lower than that of the former, and its distribution is affected by the acidity of the solution. Therefore, part of the Pd forms a separate Part of the active center forms an alloy with Ni and Cu. Under the action of Pd, the reduction temperature of Ni-Cu alloy can be reduced to below 200 °C, and the by-products of selective hydrogenation can be saturated and hydrogenated, ensuring a good catalyst. performance.
  • Carrier A commercially available spherical alumina carrier with bimodal pore distribution was used, with a diameter of 4 mm. After calcination at 1005°C for 4h, the bimodal pore size distribution ranges from 15-35nm and 80-203mm, the water absorption rate is 63%, and the specific surface area is 48.45m 2 /g. Weigh 100 g of the carrier.
  • the active component content of the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.07%
  • the Ni content was 5%
  • the Cu content was 0.50%.
  • Example 3-2 The same carrier as in Example 3-2 was used, and the catalyst preparation conditions and the contents of other components were the same as those in Example 3-2, except that Cu was not supported.
  • the active component content of the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.07%, and the Ni content was 5%.
  • reaction material C 2 H 2 H 2 C 2 H 4 C3 CO Content (v/v%) 0.3 0.6 93 0.3 0.03
  • Example 3-2 due to the uniform distribution of Ni and Cu, when Pd is loaded for the first time, its acid content is low, and this part of Pd is distributed in the outer shell layer, forming a separate active center; the second loading The acidity of the solution is high.
  • This part of Pd forms an alloy with Ni-Cu, and the reduction temperature of the Ni-Cu alloy is reduced to below 200 °C, and the by-product of selective hydrogenation can be saturated and hydrogenated, ensuring a good catalyst. performance.
  • Example 3-2 since Pd is loaded twice, the loading area of Pd can be better controlled, more Ni-Cu-Pd alloys are formed, and the saturated hydrogenation effect of selective hydrogenation by-products is better, 1000 hours In terms of selectivity, Example 3-2 is better than Example 3-1.
  • Carrier A commercially available spherical alumina carrier with bimodal pore distribution was used, with a diameter of 4 mm. After calcination at 1005°C for 4h, the bimodal pore size distribution ranges from 15-35nm and 80-203mm, the water absorption rate is 63%, and the specific surface area is 48.45m 2 /g. Weigh 100 g of the carrier.
  • the active component content of the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.07%
  • the Ni content was 5%
  • the Cu content was 0.50%.
  • the preparation conditions of the carrier and catalyst are the same as those in Example 3-3, except that Cu is not supported.
  • the active component content of the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.07%, and the Ni content was 5%.
  • Hydrogenation reaction conditions the loading volume of the catalyst in the single-stage adiabatic fixed-bed reactor is 50 mL, the packing is 50 mL, the space velocity of the reaction material: 5000 h -1 , the operating pressure: 1.5 MPa, the hydrogen-alkyne ratio 2.0, and the reactor inlet temperature 85 °C.
  • the reaction material composition is shown in Table 3-5 below, and the operation result is shown in Table 3-6.
  • Crude hydrogen composition H 2 20%, CO content 1%.
  • reaction material C 2 H 2 H 2 C 2 H 4 C3 CO Content (v/v%) 0.3 0.6 93 1.0 0.03
  • Example 3-3 when Pd was loaded for the first time, an anion precursor was used, and Pd was more easily distributed in the outer shell layer to form a separate active center, which became the active center for the selective hydrogenation of acetylene; the second loaded part Pd, its solution acidity is high, the load time is long, it is easier to form alloys with Ni and Cu, and the reduction temperature of Ni-Cu alloy is reduced to below 200 °C. The better performance of the catalyst is ensured.
  • Example 3-3 Due to the loading of the anion precursor, it is easier to combine with the hydroxyl group of the carrier, and its distribution area is narrow, so the hydrogenation selectivity is higher. Therefore, the initial selectivity of Example 3-3 and the selectivity after 1000 hours are better than those of Example 3-2.
  • Carrier A commercially available bimodal pore distribution cylindrical alumina carrier with a diameter of 3 mm and a length of 3 mm is used. After calcination at 1018°C for 4 hours, the bimodal pore size distribution ranges from 18-38nm and 85-270mm, the water absorption rate is 61%, and the specific surface area is 43.62m 2 /g. Weigh 100g of the carrier.
  • step (3) take by weighing palladium nitrate 0.0108g, be dissolved in 61mL deionized water, adjust pH to be 1.8
  • the semi-finished product catalyst B2 prepared by step (2) is immersed in the prepared solution, shake for 10min, and leave standstill for more than 4 hours. Dry at 100°C and calcinate at 400°C for 6 h to obtain semi-finished catalyst C2.
  • step (3) The semi-finished catalyst C2 obtained in step (3) is placed in a fixed bed reaction device, and subjected to reduction treatment with hydrogen at a temperature of 150° C. for 7 hours to obtain the desired catalyst.
  • the active component content of the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.060%
  • the Ni content was 2.3%
  • the Cu content was 1.1%.
  • the catalyst carrier and preparation conditions are the same as those in Example 3-4, except that no nickel is supported.
  • step (3) The semi-finished catalyst C4-1 obtained in step (3) is placed in a fixed bed reaction device, and subjected to reduction treatment with hydrogen at a temperature of 150° C. for 7 hours to obtain the desired catalyst.
  • the active component content of the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.060%, and the Cu content was 1.1%.
  • Hydrogenation reaction conditions the loading volume of the catalyst in the single-stage adiabatic fixed-bed reactor is 50 mL, the packing is 50 mL, the space velocity of the reaction material: 1500/h, the operating pressure: 1.7 MPa, the hydrogen-alkyne ratio is 2.5, and the inlet temperature of the reactor is 55 °C.
  • the reaction material composition is shown in Table 3-7 below, and the operation result is shown in Table 3-8.
  • Crude hydrogen composition H2 50%, CO 0.5%.
  • reaction material C 2 H 2 H 2 C 2 H 4 C3 CO Content (v/v%) 0.2 0.5 60 7.0 0.01
  • Carrier A commercially available bimodal pore-distributed clover-shaped alumina carrier was used, with a diameter of 2 mm and a length of 4 mm. After calcination at 1118°C for 4h, the bimodal pore size distribution ranges from 30-49nm and 187-499mm, the water absorption rate is 55%, and the specific surface area is 20.80m 2 /g. Weigh 100 g of the carrier.
  • the active component content of the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.1%
  • the Ni content was 2.60%
  • the Cu content was 2.40%.
  • Carrier A commercially available monomodal pore-distributed clover-shaped alumina carrier is used, with a diameter of 2 mm and a length of 4 mm. After calcination at 1118°C for 4h, the bimodal pore size distribution range is 30-49nm, the water absorption rate is 55%, and the specific surface area is 20.80m 2 /g. Weigh 100 g of the carrier.
  • the active component content of the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.79%
  • the Ni content was 2.60%
  • the Cu content was 2.40%.
  • reaction material C 2 H 2 H 2 C 2 H 4 C3 CO Content (v/v%) 1.0 2.0 80 7.0 0.08
  • Comparative Examples 3-5 used supports with a unimodal pore distribution.
  • the size of the active center of the comparative example is large, and it is easy to adsorb multiple molecules at the same time, and the hydrogenation dimerization of acetylene is more likely to occur, resulting in a larger amount of green oil generated than the example, and the activity selectivity after 1000 hours is lower than that of the example.
  • a commercially available bimodal pore-distributed clover-shaped alumina carrier with a diameter of 2 mm and a length of 4 mm was used. After calcination at 1054°C for 4h, the bimodal pore size distribution range is 20-42nm and 90-360mm, the water absorption rate is 58%, and the specific surface area is 37.32m 2 /g. Weigh 100 g of the carrier.
  • step (3) take by weighing palladium nitrate 0.055g, dissolve in 65mL deionized water, add n-hexane 25g, add CATB 13.60g, add n-amyl alcohol 12.5g, fully stir to form a microemulsion, and the semi-finished product catalyst B6 prepared by step (2) Impregnated into the prepared microemulsion, shaken for 70 min, filtered off the remaining liquid, dried at 60 °C, and calcined at 500 °C for 4 h to obtain semi-finished catalyst C6.
  • the particle size of the microemulsion prepared in step (1) was determined to be 82.36 nm by dynamic light scattering, and the particle size of the microemulsion prepared in step (3) was 81.76 nm.
  • the active component content of the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.1%
  • the Ni content was 3.1%
  • the Ag content was 0.5%
  • the Cu content was 2.4%.
  • step (3) take by weighing palladium nitrate 0.055g, dissolve in 65mL deionized water, add n-hexane 25g, add CATB 13.60g, add n-amyl alcohol 12.5g, fully stir to form a microemulsion, the semi-finished product catalyst B6 prepared in step (3) -1 was immersed in the prepared microemulsion, shaken for 70 minutes, filtered off the remaining liquid, dried at 60°C, and calcined at 500°C for 4 hours to obtain semi-finished catalyst C6-1.
  • the particle size of the microemulsion prepared in step (1) was determined to be 82.36 nm by dynamic light scattering, and the particle size of the microemulsion prepared in step (3) was 81.76 nm.
  • the active component content of the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.10%
  • the Ni content was 3.1%
  • the Ag was 0.5%.
  • Hydrogenation reaction conditions the loading volume of the catalyst in the single-stage adiabatic fixed-bed reactor is 50 mL, the packing is 50 mL, the space velocity of the reaction material: 4000/h, the operating pressure: 3.0 MPa, the hydrogen-alkyne ratio is 2.5, and the inlet temperature of the reactor is 55 °C.
  • the composition of the reaction materials is shown in Table 3-11 below, and the operation results are shown in Table 3-12. Crude hydrogen composition: H2 50%, CO 0.1%.
  • reaction material C 2 H 2 H 2 C 2 H 4 C3 CO Content (v/v%) 1 3.0 83 1.0 0.006
  • Examples 3-6 a part of Pd was loaded by the solution method, and it was mainly loaded in the smaller pores of the carrier.
  • a microemulsion precursor Cu, Ni and part of Pd are successively loaded in the macropores of the carrier to form a Cu-Ni-Pd alloy.
  • Ni is the main active component, which has relatively The high saturation hydrogenation function can carry out saturated hydrogenation of the green oil formed in the selective hydrogenation process.
  • Ni and Pd also have a certain hydrogenation activity, the content of Pd is low. Therefore, the main function of these two components is to reduce the reduction temperature of Ni-containing alloys to below 200 °C.
  • There is no Cu in the comparative example so the active centers in the macropores do not play a role in the entire hydrogenation process. Due to the high acetylene content and the large amount of green oil produced, the coking of the comparative example was serious.
  • the initial selectivity of the catalyst is higher than that of the catalyst prepared by the solution method.
  • Carrier A commercially available four-leaf clover-shaped alumina carrier with bimodal pore distribution was used, with a diameter of 3 mm and a length of 3 mm. After calcination at 1092°C for 4h, the bimodal pore size distribution range is 22-45nm and 70-420mm, the water absorption rate is 56%, and the specific surface area is 29.67m 2 /g. Weigh 100 g of the carrier.
  • step (3) Weigh 0.084g of palladium chloride, dissolve in 70mL of deionized water, add 31.5g of n-hexane, add 17.50g of Triton X-100, add 16.8g of n-butanol, fully stir to form a microemulsion, and step (2)
  • the prepared semi-finished catalyst B7 was dipped into the prepared microemulsion, shaken for 90 min, filtered off the remaining liquid, dried at 80°C, and calcined at 600°C for 4 hours to obtain the semi-finished catalyst C7.
  • the particle size of the microemulsion emulsion prepared in step (1) was determined to be 66.68 nm by dynamic light scattering, and the particle size of the microemulsion emulsion prepared in step (3) was 67.49 nm.
  • the active component content of the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.07%
  • the Ni content was 0.5%
  • the Cu content was 0.5%.
  • the catalyst carrier and preparation conditions are the same as those in Example 3-7, except that Ni is not supported.
  • step (3) Weigh 0.084g of palladium chloride, dissolve in 70mL of deionized water, add 31.5g of n-hexane, add 17.50g of Triton X-100, add 16.8g of n-butanol, fully stir to form a microemulsion, and step (2)
  • the prepared semi-finished catalyst B7-1 was immersed in the prepared microemulsion, shaken for 90 minutes, filtered to remove residual liquid, dried at 80°C, and calcined at 600°C for 4 hours to obtain semi-finished catalyst C7-1.
  • the particle diameter of the microemulsion emulsion prepared in step (1) was 66.68 nm, and the particle diameter of the microemulsion emulsion prepared in step (3) was 67.49 nm.
  • the active component content of the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.07%, and the Cu content was 0.5%.
  • Hydrogenation reaction conditions the loading volume of the catalyst in the single-stage adiabatic fixed-bed reactor is 50 mL, the packing is 50 mL, the space velocity of the reaction material: 3000/h, the operating pressure: 3.0 MPa, the hydrogen-alkyne ratio is 3, and the inlet temperature of the reactor is 135 °C.
  • the composition of the reaction materials is shown in Table 3-13 below, and the operation results are shown in Table 3-14. Crude hydrogen composition: H2 30%, CO 1%.
  • reaction material C 2 H 2 H 2 C 2 H 4 C3 CO Content (v/v%) 0.6 1.8 83 7.0 0.06
  • the comparative example does not support Ni and the loading amount of Cu is low, the hydrogenation activity of effective reaction by-products cannot be formed despite the high reaction temperature, and the hydrogenation selectivity decreases to 10% after 1000 hours.
  • the initial selectivity of Examples 3-7 and Comparative Examples 3-7 is higher than that of the catalyst prepared by the solution method.
  • Carrier A commercially available spherical alumina carrier with bimodal pore distribution was used, with a diameter of 4 mm. After calcination at 1128°C for 4h, the bimodal pore size distribution range is 25-47nm and 300-498mm, the water absorption rate is 50%, and the specific surface area is 21.46m 2 /g. Weigh 100 g of the carrier.
  • step (3) weigh 0.0107g of palladium nitrate, dissolve in 70mL deionized water, add 23.3g of n-hexane, add 3.5g of CATB, add 2.95g of n-butanol, fully stir to form a microemulsion, and the semi-finished catalyst prepared by step (2) B8 was immersed in the prepared microemulsion, shaken for 100 min, the remaining liquid was filtered off, dried at 70 °C, and calcined at 450 °C for 5 h to obtain semi-finished catalyst C8.
  • the particle size of the microemulsion prepared in step (1) was determined to be 496.68 nm by dynamic light scattering, and the particle size of the microemulsion prepared in step (3) was 497.23 nm.
  • the active component content of the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.6%
  • the Ni content was 3.00%
  • the Cu content was 0.5%.
  • the catalyst carrier is the same as that of Examples 3-8, except that the loading of palladium is lower than 0.06%.
  • step (3) Weigh 0.0054g of palladium nitrate, dissolve in 70mL of deionized water, add 23.3g of n-hexane, add 3.5g of CATB, add 2.95g of n-butanol, fully stir to form a microemulsion, and the semi-finished catalyst prepared by step (2) B8 was immersed in the prepared microemulsion, shaken for 100 min, the remaining liquid was filtered off, dried at 70 °C, and calcined at 450 °C for 5 h to obtain semi-finished catalyst C8.
  • the particle size of the microemulsion prepared in step (1) was determined to be 496.68 nm by dynamic light scattering, and the particle size of the microemulsion prepared in step (3) was 497.23 nm.
  • the active component content of the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.3%
  • the Ni content was 3.00%
  • the Cu content was 0.5%.
  • Hydrogenation reaction conditions the filling amount of the catalyst in the single-stage isothermal bed reactor is 50 mL, and the packing is 50 mL.
  • Crude hydrogen composition hydrogen 40%, CO 0.3%.
  • the composition of the reaction materials is shown in Table 3-15 below, and the operation results are shown in Table 3-16.
  • reaction material C 2 H 2 H 2 C 2 H 4 C3 CO Content (v/v%) 0.2 0.4 70 3.0 0.003
  • a commercially available bimodal pore-distributed clover-shaped alumina carrier with a diameter of 2 mm and a length of 4 mm was used. After calcination at 1055°C for 4h, the bimodal pore size distribution ranges from 20-42nm and 90-360mm, the water absorption rate is 58%, and the specific surface area is 37.32m 2 /g. Weigh 100 g of the carrier.
  • step (3) (4) take by weighing palladium nitrate 0.055g, dissolve in 65mL deionized water, add n-hexane 25g, add CATB 13.50g, add n-amyl alcohol 12.5g, fully stir to form a microemulsion, the semi-finished product catalyst C9 prepared in step (3) Immerse into the prepared microemulsion, shake for 70 min, filter out the remaining liquid, dry at 60 °C, and calcinate at 500 °C for 4 h to obtain semi-finished catalyst D9.
  • the particle size of the microemulsion prepared in step (1) was determined to be 82.36 nm by dynamic light scattering, and the particle size of the microemulsion prepared in step (4) was 81.76 nm.
  • the active component content of the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.1%
  • the Ni content was 3.1%
  • the Ag content was 0.5%
  • the Cu content was 2.4%.
  • the catalyst preparation conditions were the same as those in Examples 3-9, except that a unimodal pore carrier was used.
  • a commercially available unimodal pore-distributed clover-shaped alumina carrier was used, with a diameter of 2 mm and a length of 4 mm. After calcination at 1060°C for 4h, the pore size distribution range is 59-113mm, the water absorption rate is 55%, and the specific surface area is 37.32m 2 /g. Weigh 100 g of the carrier.
  • step (3) take by weighing palladium nitrate 0.055g, dissolve in 65mL deionized water, add n-hexane 25g, add CATB 13.50g, add n-amyl alcohol 12.5g, fully stir to form a microemulsion, the semi-finished product catalyst B9 prepared by step (2) -1 was immersed in the prepared microemulsion, shaken for 70 min, filtered off the remaining liquid, dried at 60 °C, and calcined at 500 °C for 4 h to obtain semi-finished catalyst C9-1.
  • the particle size of the microemulsion prepared in step (1) was determined to be 82.36 nm by dynamic light scattering, and the particle size of the microemulsion prepared in step (3) was 81.76 nm.
  • the active component content of the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.10%
  • the Ni content was 3.1%
  • the Cu content was 2.4%.
  • Hydrogenation reaction conditions the loading volume of the catalyst in the single-stage adiabatic fixed-bed reactor is 50 mL, the packing is 50 mL, the space velocity of the reaction material: 1500/h, the operating pressure: 3.0 MPa, the hydrogen-alkyne ratio is 2.5, and the inlet temperature of the reactor is 55 °C.
  • the composition of the reaction materials is shown in Table 3-17 below, and the operation results are shown in Table 3-18. Crude hydrogen composition: H2 50%, CO 0.1%.
  • reaction material C 2 H 2 H 2 C 2 H 4 C3 CO Content (v/v%) 1 3.0 83 1.0 0.006
  • Carrier A commercially available spherical alumina carrier with bimodal pore distribution was used, with a diameter of 4 mm. After calcination at 1125°C for 4h, the bimodal pore size distribution ranges from 25-47nm and 300-498mm, the water absorption rate is 50%, and the specific surface area is 21.46m 2 /g. Weigh 100 g of the carrier.
  • the particle size of the microemulsion prepared in step (1) was determined to be 496.68 nm by dynamic light scattering, and the particle size of the microemulsion prepared in step (4) was 497.14 nm.
  • the active component content of the prepared catalyst was determined by atomic absorption spectrometry.
  • the Pd content was 0.10%
  • the Ni content was 3.00%
  • the Cu content was 0.5%
  • the Ag content was 0.06%.
  • the catalyst carrier and catalyst preparation conditions were the same as those in Example 3-10, except that the Ni loading was reduced to 1/10 of that in Example 3-10.
  • the particle size of the microemulsion prepared in step (1) was determined to be 496.68 nm by dynamic light scattering, and the particle size of the microemulsion prepared in step (4) was 497.14 nm.
  • the active component content of the prepared catalyst was determined by atomic absorption spectrometry. In the catalysts of Comparative Examples 3-10, the Pd content was 0.9%, the Ni content was 0.3%, the Cu content was 0.5%, and the Ag content was 0.06%.
  • Hydrogenation reaction conditions the filling amount of the catalyst in the single-stage isothermal bed reactor is 50 mL, and the packing is 50 mL.
  • Crude hydrogen composition hydrogen 40%, CO 0.3%.
  • the composition of the reaction materials is shown in Table 3-19 below, and the operation results are shown in Table 3-20.
  • reaction material C 2 H 2 H 2 C 2 H 4 C3 CO Content (v/v%) 0.2 0.4 70 3.0 0.003
  • Carrier A commercially available four-leaf clover-shaped alumina carrier with bimodal pore distribution was used, with a diameter of 3 mm and a length of 3 mm. After calcination at 1093°C for 4h, the bimodal pore size distribution ranges from 22-45nm and 70-420mm, the water absorption rate is 56%, and the specific surface area is 29.67m 2 /g. Weigh 100 g of the carrier.
  • step (3) Weigh 0.084g of palladium chloride, dissolve it in 70mL of deionized water, add 31.5g of n-hexane, add 17.50g of Triton X-100, add 16.8g of n-butanol, fully stir to form a microemulsion, and step (3)
  • the prepared semi-finished catalyst C11 was dipped into the prepared microemulsion, shaken for 90 min, filtered off the remaining liquid, dried at 80°C, and calcined at 600°C for 4 hours to obtain the semi-finished catalyst D11.
  • the particle size of the microemulsion emulsion prepared in step (1) was determined to be 66.68 nm by dynamic light scattering, and the particle size of the microemulsion emulsion prepared in step (4) was 67.49 nm.
  • the active component content of the prepared catalyst was determined by atomic absorption spectrometry. In the catalysts of Examples 3-11, the Pd content was 0.07%, the Ni content was 0.5%, and the Cu content was 0.5%. Ag content 0.16%.
  • the catalyst carrier and preparation conditions are the same as those in Example 3-11, except that the Pd content is low.
  • step (3) Weigh 0.0085g of palladium chloride, dissolve it in 70mL of deionized water, add 31.5g of n-hexane, add 17.50g of Triton X-100, add 16.8g of n-butanol, fully stir to form a microemulsion, and step (3)
  • the prepared semi-finished catalyst C11-1 was dipped into the prepared microemulsion, shaken for 90 minutes, filtered off the remaining liquid, dried at 80°C, and calcined at 600°C for 4 hours to obtain the semi-finished catalyst D11-1.
  • the particle size of the microemulsion emulsion prepared in step (1) was determined to be 66.68 nm by dynamic light scattering, and the particle size of the microemulsion emulsion prepared in step (4) was 67.49 nm.
  • the active component content of the prepared catalyst was determined by atomic absorption spectrometry. In the catalysts of Comparative Examples 3-11, the Pd content was 0.055%, the Ni content was 0.5%, the Cu content was 0.5%, and the Ag content was 0.16%.
  • Hydrogenation reaction conditions the loading volume of the catalyst in the single-stage adiabatic fixed-bed reactor is 50 mL, the packing is 50 mL, the space velocity of the reaction material: 4000/h, the operating pressure: 3.0 MPa, the hydrogen-alkyne ratio is 3, and the inlet temperature of the reactor is 135 °C.
  • the composition of the reaction materials is shown in Table 3-21 below, and the operation results are shown in Table 3-22. Crude hydrogen composition: H2 30%, CO 1%.
  • reaction material C 2 H 2 H 2 C 2 H 4 C3 CO Content (v/v%) 0.6 1.8 83 7.0 0.06

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Abstract

一种炔烃选择加氢催化剂。催化剂载体为氧化铝或主要是氧化铝，并具有双峰孔分布结构，催化剂的比表面积为20-50m2/g；其中小孔的孔径为15-50nm，大孔的孔径为80-500nm，催化剂至少含有Pd、Ni、Cu，以载体的质量为100％计，Pd的含量为0.035-0.08％，Ni的含量为0.5-5％，Cu与Ni的重量比为0.1-1.0，其中微乳液负载Ni、Cu及部分Pd，微乳液的粒径大于小孔的最大孔径，小于大孔的最大孔径；微乳液负载的Pd的量是Ni+Cu含量之和的1/100-1/200；部分Pd采用溶液负载。本发明的催化剂，可用于碳二馏分的选择性加氢过程，具有良好的抗结焦性能，可在较长时间内，保持良好的加氢活性和优异的选择性。

Description

一种炔烃选择加氢催化剂及制备方法以及选择加氢方法 技术领域
本发明涉及一种选择加氢催化剂及制备方法以及选择加氢方法。
背景技术
乙烯是石油化学工业最重要的基础原料之一，作为合成各种聚合物的单体乙烯，绝大部分由石油烃(如乙烷、丙烷、丁烷、石脑油和轻柴油等)蒸汽裂解制得。经这种方法得到的以乙烯为主的C 2馏分中含有质量分数0.5％-2.3％的乙炔。在用于聚合时，乙烯中的乙炔会使乙烯的聚合过程复杂化，恶化聚合物性能，同时还会降低聚合催化剂的活性，并影响聚合物的物理性能，因此必须将其脱除。
目前工业上普遍采用选择加氢的方法脱除乙烯中的乙炔，采用的催化剂主要为Pd，Pt，Au等贵金属催化剂。碳二后加氢和前加氢是根据乙炔加氢反应器相对于脱甲烷塔的位置而言，加氢反应器位于脱甲烷塔之前为前加氢，加氢反应器位于脱甲烷塔之后为后加氢。
后加氢工艺的优点是加氢过程控制手段多，不易飞温，操作方便，但工艺较复杂，需要单独配氢，碳二后加氢工艺由于加氢物料中氢气含量少，容易发生乙炔的加氢二聚反应，生成碳四馏分，碳四馏分进一步聚合生成分子量较宽的低聚物，俗称“绿油”。绿油吸附在催化剂表面，并进一步形成结焦，阻塞催化剂孔道，使反应物不能扩散到催化剂活性中心表面，从而导致催化剂活性下降。
贵金属催化剂活性较高，但在使用过程中易生成绿油，使催化剂发生结焦失活，影响催化剂稳定性和使用寿命。专利CN200810119385.8公开了一种非贵金属负载型选择加氢催化剂及其制备方法和应用，包括载体以及负载在该载体上的主活性组分和助活性组分，其中，所述的主活性组分为Ni，所述的助活性组分选自Mo、La、Ag、Bi、Cu、Nd、Cs、Ce、Zn和Zr中的至少一种，主活性组分和助活性组分均以非晶态形式存在，平均粒径＜10nm，所述载体为不具氧化性的多孔材料；且所述的催化剂以微乳化法制备。
碳二后加氢工艺一般采用三段加氢反应器，一段反应器的乙炔总转化率在50-80％，氢/炔1.0-1.4，二段反应器的乙炔总转化率40-20％，氢/炔1.4-2.0，残余的乙炔在三段反应器完全转化，三段氢/炔2.5-4.0，三段反应器出口的乙炔含量一般在1ppm以下。碳二后加氢反应中，会发生乙炔的加氢二聚，生成一系列分子量不同的低聚物，这些低聚物由于不能随气相物料流动或移动速率很低，会较长时间附着在催化剂表面或进入孔道内，造成催化剂孔堵塞。由于移动速率慢，会逐步集聚，这些低聚物本身有含有大量不饱和键，还可以进一步聚合，最终形成结焦，使催化剂活性选择性大幅度下降。
加氢二聚产物的量与加氢条件密切相关，在低氢/炔时，由于氢气不足，乙炔的加氢二聚反应十分剧烈；催化剂结焦速率会十分迅速。
在反应过程中，由于一段反应器的除炔负荷大，一段反应器生成绿油的量也是最大的，一段反应器入口处的加氢二聚反应最剧烈，部分绿油在一段反应器入口聚合，使这部分催化剂活性迅速下降。另一个部位是一段反应器的出口，这是因为随加氢反应进行，氢/炔愈来愈低，使加氢二聚反应速率再上升，而且温度的升高又会使绿油的聚合加剧。
部分碳二后加氢装置采用了两段加氢工艺，一段反应器生成的绿油，部分会进入二段反应器，而且在二段反应器入口处聚集而形成，使二段反应器的加氢效果迅速恶化，反应器出口乙炔含量很快会上升到在1ppm以上，乙烯的纯度不好，影响烯烃聚合的进行，因此不得不对催化剂进行再生。
部分装置采用等温反应器，该反应器内延物料流动方向，温度愈来愈低，反应器上部生成的绿油在反应器下部不聚集，并逐渐形成结焦，使选择性下降很快。
部分乙烯装置，碳二馏分采用一段加氢，对催化剂稳定性的要求更高，一般催化剂在运行3个月后，由于绿油的影响，催化剂选择性会明显下降。
有些装置为了调节各反应器的加氢负荷，有时会人为地降低配入的氢气量，使某反应器入口氢/炔甚至低于1，会大大加速催化剂结焦，虽然调节了各反应器的负荷，却导致催化剂运行周期明显缩短。
结焦量一旦达到碳二加氢催化剂自身质量的10％以上，性能下降就很明显，绿油的生成如此严重的影响碳二后加氢催化剂的性能，但加氢二聚又不可避免，因此，使得如何降低绿油生成和延缓结焦成为催化剂设计中的永恒的课题之一。
US5856262报道了以氢氧化钾(或钡、锶、铷等的氢氧化物)改性的氧化硅为载体，制备低酸性钯催化剂的方法，在空速3000h -1，入口温度35℃，入口乙炔摩尔分数0.71％，氢炔摩尔比1.43的条件下，出口乙炔摩尔分数小于1×10 -7，乙烯选择性达56％。
US4404124通过分步浸渍法制备了活性组分壳层分布的选择加氢催化剂，可应用于碳二馏分的选择加氢，以消除乙烯中的乙炔。US5587348以氧化铝为载体，添加助催化剂银与钯作用，加入与碱金属化学键合的氟制备了性能优良的碳二加氢催化剂。该催化剂具有减少绿油生成，提高乙烯选择性，减少含氧化合物生成量的特点。
CN1736589A报道了一种采用完全吸附浸渍法制备的Pd/γ-Al 2O 3选择加氢催化剂，催化剂在使用过程中绿油生成量较大。CN200810114744.0公开了一种不饱和烃选择加氢催化剂及其制备方法。该催化剂以氧化铝为载体，以钯为活性组分，通过加入稀土和碱土金属和氟提高催化剂抗杂质和抗结焦性能，但其催化剂选择性并不理想。
以上方法制备的催化剂均采用孔径单一分布的催化剂，在固定床反应过程中，受到内扩散的影响，催化剂的选择性较差。ZL971187339公开了一种加氢催化剂，载体是一种蜂窝型载体，为大孔径载体，有效的提高了催化剂的选择性。CN1129606A公开了一种烃类转化催化剂，其载体催化剂包括氧化铝、氧化镍、氧化铁等，该催化剂中包括两种孔，一种用于提高催化反应表面，另一种有利于扩散。CN101433842A公开了一种加氢催化剂，其特征是催化剂具有双峰孔分布，小孔部分最可几半径为2-50nm，大孔部分最可几半径为100-500nm，由于催化剂为双峰孔分布，具有良好的加氢活性的同时，又有好的选择性，乙烯增量大。
在碳二加氢反应中，绿油的生成及催化剂的结焦是影响催化剂使用寿命的重要因素。催化剂的活性、选择性和使用寿命构成了催化剂的总体性能，以上所列出方法或对提高催化剂活性、选择性提出了较好的途径，却并没有解决催化剂容易结焦的问题，或者解决了催化剂易生成绿油和结焦的问题，却没有解决选择性的问题。具有大孔结构的载体虽然可以提高选择性，但是因聚合和链增长反应生成的较大分子也容易积留在载体大孔中，造成催化剂结焦失活，影响催化剂使用寿命。
CN201310114070.5公开了一种碳二馏分选择的方法，该加氢方法中采用了一种催化剂，其活性组分Pd，Ag采用水溶液浸渍法负载，Ni是采用W/O微乳液浸渍法负载的。CN201310114077.7公开了一种加氢催化剂，催化剂载体为双峰孔分布，该催化剂中所述的活性组分有Pd，Ag，Ni，其中Pd，Ag位于小孔中，Ni位于大孔中。CN 201310114079.6公开了一种催化剂制备方法，该方法中，所用的催化剂载体为双峰孔分布。通过制备一种粒径大于载体小孔的W/O型微乳，微乳中含有镍的金属盐，由于微乳的动力学体积大于小孔尺寸，微乳液粒 子只能进入载体的大孔。采用溶液法负载Pd，Ag，小孔的虹吸效应更强，大部分Pd，Ag进入载体大孔，因此形成了Ni主要位于大孔，Pd，Ag主要位于小孔。采用该方法后，Pd/Ag与Ni位于不同孔径的孔道中，反应生成的绿油在大孔中饱和加氢，催化剂结焦量降低。而且，在催化剂投运前，需要对催化剂进行还原。一般贵金属催化剂还原温度较低，但Ni的还原温度往往要达到500℃左右，在该温度下还原态的Pd原子极易聚集，使催化剂活性大幅度下降30％以上，需要大幅度增加活性组分等量以补偿活性损失，但又会引起选择性的下降。
发明内容
本发明的目的在于提供一种炔烃选择加氢催化剂及制备方法，特别是一种具有较好抗结焦性并且能够降低催化剂的还原温度的炔烃选择加氢催化剂及制备方法。
为达到上述目的，本发明提供了一种炔烃选择加氢催化剂，其中，该催化剂的载体为氧化铝或主要是氧化铝，并具有双峰孔分布结构；其中小孔的孔径为15-50nm，大孔的孔径为80-500nm，催化剂至少含有Pd、Ni、Cu，以载体的质量为100％计，Pd的含量为0.03-0.1％，Ni的含量为0.5-5％，Cu与Ni的重量比为0.1-1.0:1.0，其中，通过微乳液负载Ni、Cu及部分Pd；所述微乳液的粒径不低于小孔的最大孔径而且不高于大孔的最大孔径。
根据本发明的具体实施方案，优选地，本发明提供的催化剂载体为氧化铝或主要是氧化铝，并具有双峰孔分布结构；其中小孔的孔径为15-50nm，大孔的孔径为80-500nm，催化剂至少含有Pd、Ni、Cu，以载体的质量为100％计，Pd的含量为0.035-0.08％(更优选为0.035-0.07％)，Ni的含量为0.5-5％，Cu与Ni的重量比为0.1-1.0：1，其中，以微乳液负载Ni、Cu及部分Pd，所述微乳液的粒径不低于小孔的最大孔径而且不高于大孔的最大孔径(优选大于小孔的最大孔径、小于大孔的最大孔径)，微乳液负载的Pd的量是Ni+Cu含量之和的1/100-1/200；剩余部分Pd采用溶液负载。
根据本发明的具体实施方案，优选地，本发明提供的催化剂的载体为氧化铝，具有双峰孔径分布特征，小孔的孔径为15-50nm，大孔的孔径为80-500nm；所述催化剂至少含有活性组分Pd、Ni、Cu，以载体的质量100％计，Pd的含量为0.03-0.09％(更优选为0.035-0.075％)，Ni的含量为0.5-5％，Cu与Ni的重量比为0.1-1.0:1.0，通过微乳液负载Ni、Cu及部分Pd。进一步优选地，微乳液负载的Pd的量是Ni+Cu含量之和的1/100-1/200，剩余部分Pd采用溶液负载。该催化剂优选适用于碳二馏分的加氢反应。
根据本发明的具体实施方案，优选地，本发明提供的催化剂的载体为氧化铝或主要是氧化铝，具有双峰孔分布结构的氧化铝，其中小孔的孔径为15-50nm，大孔的孔径80-500nm，催化剂至少含有活性组分Pd，Ni、Cu，以催化剂的质量为100％计，Pd的含量为0.06-0.1％(更优选为0.07-0.1％)，Ni的含量为0.5-5％，Cu与Ni的重量比为0.1-1.0:1.0。进一步优选地，微乳液负载的Pd的量是Ni+Cu含量之和的1/100-1/200，剩余部分Pd采用溶液负载。该催化剂优选适用于采用粗氢为氢源的碳二后加氢工艺的选择加氢方法。
根据本发明的具体实施方案，对于一个具体的催化剂载体来说，其小孔的孔径、大孔的孔径分别是一个尺寸范围，而微乳液的粒径不低于(大于)小孔的最大孔径而不高于(小于)大孔的最大孔径是指负载时所配制的微乳液的粒径不低于(大于)某个具体的催化剂载体的小孔的孔径范围的上限、不高于(小于)催化剂载体的大孔的孔径范围的上限。根据本发明的具体实施方案，微乳液的粒径可以为50-500nm或者大于50nm、小于500nm。
根据本发明的具体实施方案，优选地，本发明提供的催化剂的载体为氧化铝或主要是氧化铝，并具有双峰孔分布结构；其中小孔的孔径为15-50nm，大孔的孔径为80-500nm，催化剂至 少含有Pd、Ni、Cu，以载体的质量为100％计，Pd的含量为0.06-0.08％，Ni的含量为0.5-5％，Cu与Ni的重量比为0.1-1.0:1.0，其中，通过微乳液负载Ni、Cu及部分Pd；所述微乳液的粒径不低于小孔的最大孔径而且不高于大孔的最大孔径，微乳液负载的Pd的量是Ni+Cu含量之和的1/100-1/200，剩余部分Pd采用溶液负载。该催化剂同时适用于碳二馏分的加氢反应，以及采用粗氢为氢源的碳二后加氢工艺的选择加氢方法。
根据本发明的具体实施方案，优选地，本发明的催化剂中还含有Ag，以溶液负载，其含量为0.03-0.5％，更优选地，Ag的含量为0.08-0.21％。Ag的作用是与Pd形成合金，减少绿油的生成量，以提高乙炔加氢的选择性。
根据本发明的具体实施方案，优选地，本发明提供的催化剂的载体为氧化铝或主要是氧化铝，并具有双峰孔分布结构；其中小孔的孔径为15-50nm，大孔的孔径为80-500nm，催化剂至少含有Pd、Ag、Ni、Cu，以载体的质量为100％计，Pd的含量为0.035-0.07％，Ag的含量为0.08-0.21％，Ni的含量为0.5-5％，Cu与Ni的重量比为0.1-1.0：1.0，其中Ni、Cu及部分Pd是以微乳液方式负载，主要分布在载体的大孔中，微乳液法负载的Pd的量是Ni+Cu含量之和的1/100-1/200；Ag及部分Pd以溶液法进行负载。
根据本发明的具体实施方案，优选地，本发明提供的催化剂的载体为氧化铝或主要是氧化铝，具有双峰孔分布结构的氧化铝，其中小孔的孔径为15-50nm，大孔的孔径为80-500nm，催化剂至少含有活性组分Pd、Ag、Ni、Cu，以催化剂的质量为100％计，Pd的含量为0.07-0.1％，Ag的含量为0.03-0.5％，Ni的含量为0.5-5％，Cu的含量为0.5-5％，Ni和Cu的总含量为1-5.5％。该催化剂也优选适用于采用粗氢为氢源的碳二后加氢工艺的选择加氢方法。
根据本发明的具体实施方案，优选地，本发明提供的催化剂的比表面积为20-50m 2/g。
本发明所述的微乳液负载是指浸渍法负载，其中浸渍液为微乳液，即活性组分(如Pd、Ni、Cu等)的前驱体不是通过形成溶液浸渍负载而是通过形成微乳液浸渍负载。本发明所述的溶液负载是指浸渍法负载，其中浸渍液为溶液。在本发明的催化剂中，一部分Pd以微乳液的形式负载，而其余的Pd以浸渍的方式负载，并且，微乳液负载的Pd的量是Ni+Cu含量之和的1/100-1/200，更优选为1/110-1/200。
根据本发明的具体实施方案，优选地，载体为氧化铝或主要是氧化铝；氧化铝的晶型为θ、α晶型或其混合晶型；当催化剂载体主要是氧化铝时，载体中的氧化铝在80％以上。本发明所采用的具有双峰孔分布的载体在保证催化剂高活性的同时，大孔的存在可以减少内扩散的影响，提高催化剂选择性。
根据本发明的具体实施方案，优选地，微乳液负载过程包括：将前驱体盐溶于水中，加入油相、表面活性剂和助表面活性剂，充分搅拌形成微乳液，其中油相为烷烃或环烷烃，表面活性剂为离子型表面活性剂和/或非离子型表面活性剂，助表面活性剂为有机醇。
根据本发明的具体实施方案，优选地，微乳液负载过程满足以下条件：水相与油相的重量比为2-3，表面活性剂与油相的重量比为0.15-0.6，表面活性剂与助表面活性剂的重量比为1-1.2，微乳液的粒径大于50nm、小于500nm。
根据本发明的具体实施方案，优选地，在微乳液负载过程中，油相为C6-C8饱和烷烃或环烷烃，优选为环己烷、正己烷；表面活性剂为离子型表面活性剂和/或非离子型表面活性剂，优选为非离子型表面活性剂，更优选为聚乙二醇辛基苯基醚或十六烷基三甲基溴化铵；助表面活性剂为C4-C6醇类，优选为正丁醇和/或正戊醇。
根据本发明的具体实施方案，优选地，催化剂在制备过程中，Pd的溶液负载与Ni、Cu的 微乳液负载先后次序不限定；优选地，微乳液负载Pd的步骤是在微乳液负载Ni和Cu步骤后。溶液负载Ag的步骤优选是在溶液负载Pd步骤后。
在本发明的催化剂中，乙炔的选择加氢反应发生在Pd组成的主活性中心，Ni和Cu以微乳液的形式将浸渍在载体的大孔中，反应生成的绿油在Cu与Ni组成的活性中心上发生饱和加氢。
对加氢反应而言，一般在催化剂应用前首先需要对加氢催化剂进行还原，保证活性组分以金属态存在，才能使催化剂具有加氢活性。因为催化剂制备过程中，活化是一个高温焙烧过程，在该过程中，金属盐一般分解为金属氧化物，氧化物会形成团簇，这种团簇一般是纳米尺寸的。不同的氧化物由于化学特性的不同，需要在不同的温度下进行还原。但对纳米尺寸的金属而言，200℃左右的温度是一个重要临界温度，超过该温度，金属粒子会十分显著的产生聚集。因此，降低活性组分的还原温度至200℃以下，对加氢催化剂而言，有十分重要的意义。
本发明解决催化剂结焦的思路是：
乙炔的选择加氢反应发生在Pd组成的主活性中心(当含有Ag时，则发生在Pd、Ag组成的主活性中心)，反应中生产的绿油等大分子，容易进入催化剂的大孔中。在催化剂的大孔中，负载了Ni/Cu组分，其中Ni具有饱和加氢功能，绿油组分会在Ni/Cu组成的活性中心发生饱和加氢反应。由于双键被加氢饱和，绿油组分不能再发生聚合反应或聚合反应速率大大降低，其链增长反应终止或延缓，不能形成巨大分子量稠环化合物，容易被物料带出反应器，因此催化剂的表面的结焦程度会大大降低，催化剂的运行寿命会大幅度延长。
本发明的载体要求具有双峰孔分布结构，特别是要有孔径在80-500nm的大孔，小孔的孔径为15-50nm。
本发明控制Ni/Cu合金定位于催化剂大孔的方法是，Ni/Cu以微乳液的形式负载，微乳液的粒径大于载体小孔孔径，而小于大孔的最大孔径。镍和铜金属盐包含在微乳液中，由于空间阻力的原因难于进入尺寸较小的载体孔道中，主要进入载体的大孔中，因此在催化剂的大小孔中，形成了具有不同加氢作用的活性中心。大孔中含有由Ni/Cu及Pd组成的活性中心，它对绿油分子有很好的加氢饱和作用，使进入大孔中的绿油分子不再聚合，因此会逐渐移出反应器，不易形成结焦。
对加氢反应而言，一般在催化剂应用前首先需要对加氢催化剂进行还原，保证活性组分以金属态存在，才能使催化剂具有加氢活性。因为催化剂制备过程中，活化是一个高温焙烧过程，在该过程中，金属盐分解为金属氧化物，氧化物会形成团簇，这种团簇一般是纳米尺寸的。不同的氧化物由于化学特性的不同，需要在不同的温度下进行还原。但对纳米尺寸的金属而言，200℃左右是一个重要临界温度，超过该温度，金属粒子会有十分显著的产生聚集。因此，降低活性组分的还原温度，对加氢催化剂而言，有十分重要的意义。
本发明人发现，将Cu与Ni一起负载后，可以大幅度降低Ni的还原温度。原因是NiO的还原温度一般要达到450℃以上，而这个温度会引起Pd的团聚，而加入Cu后将形成Cu/Ni合金，其还原温度与纯Ni的还原温度相比可以降低100℃以上，达到350℃，从而缓解Pd的团聚。
本发明人还发现，如果再将部分Pd负载在Ni/Cu合金的表面，则还可以大幅度的降低Ni/Cu合金的还原温度，可以达到200℃以下，甚至到150℃，从而避免在NiO在高温还原过程中，Pd活性中心的团聚。
因此，更佳的催化剂是Pd主要存在于催化剂小孔中，Ni/Cu位于催化剂的大孔中，在大孔中Ni/Cu的还有部分Pd，特别是在其表面。
更佳的催化剂制备过程是，在Ni和Cu负载后，以微乳液法将少量Pd负载在大孔中，该次 负载的Pd量是Ni+Cu含量之和的1/100-1/200。
本发明还提供了上述催化剂的制备方法，具体制备过程包括：
(1)将Ni和Cu的前驱体盐溶于水中，加入油相、表面活性剂和助表面活性剂，充分搅拌形成微乳液，将载体加入到制好的微乳液中浸渍0.5-4小时后，滤除余液，干燥后在400-600℃下焙烧4小时以上，得到半成品催化剂A；
(2)将Pd的前驱体盐溶于水，调pH为1.5-2.5，再将半成品催化剂A加入Pd的盐溶液中，浸渍吸附0.5-4h后，干燥后400-600℃条件下焙烧4-6h，得到半成品催化剂B；
(3)将Pd前驱体盐溶于水中，加入油相、表面活性剂和助表面活性剂，充分搅拌形成微乳液，将半成品催化剂B加入到制好的微乳液中浸渍0.5-4小时后，滤除余液，干燥后，在400-600℃下焙烧4小时以上，得到需要的催化剂。
在以上制备步骤中，步骤(1)和步骤(2)可以互换，步骤(3)在步骤(1)之后。
上述步骤(1)中的载体为氧化铝或主要是氧化铝，Al 2O 3晶型最好为θ、α或其混合晶型。催化剂载体中氧化铝最好在80％以上，载体中还可含有其它金属氧化物如氧化镁，氧化钛等。
上述步骤(1)中的载体可以是球形、圆柱形、三叶草形、四叶草形等。
上述步骤(1)、(3)中所述的Ni、Cu和Pd的前驱体盐为可溶性盐，可以是其硝酸盐、氯化盐或者其他可溶性盐。
根据本发明的具体实施方案，优选地，Cu与Ni的重量比为0.1-1:1，乳液法负载Pd量是Ni+Cu含量的1/100-1/200。
根据本发明的具体实施方案，当催化剂中还含有Ag时，Ag能够与步骤(2)负载的Pd形成合金，以提高乙炔加氢的选择性。其原理是：Ag与Pd形成合金，Ag原子分隔Pd原子，使吸附的乙炔分子的空间距离拉大，相应的乙炔加氢后的反应中间体的相互间距较大，不易发生中间体的耦合，因而减少了绿油的形成。
根据本发明的具体实施方案，优选地，当催化剂含有Ag时，本发明的催化剂的制备方法可以包括以下三种：
第一种，催化剂的制备过程包括以下具体步骤：
(1)将Ni和Cu的前驱体盐溶于水中，加入油相、表面活性剂和助表面活性剂，充分搅拌形成微乳液；将载体加入到制好的微乳液中浸渍0.5-4小时后，滤除余液；干燥后，在400-600℃下焙烧4-6h，得到半成品催化剂A；
(2)将Pd前驱体盐溶于水中，加入油相、表面活性剂和助表面活性剂，充分搅拌形成微乳液，将半成品催化剂A加入到制好的微乳液中浸渍0.5-4小时后，滤除余液；干燥后，在400-600℃下焙烧4-6h，得到半成品催化剂B；
(3)将Pd的前驱体盐溶于水，调pH为1.5-2.5，再将半成品催化剂B加入Pd的盐溶液中，浸渍吸附0.5-4h后，干燥后在400-600℃条件下焙烧4-6h，得到半成品催化剂C；
(4)将Ag盐的溶解在去离子中，调pH为1-5，将半成品催化剂C浸渍在已制备的溶液中，待溶液完全吸收后干燥，在400-600℃焙烧4-6h，得到所述催化剂；
第二种，催化剂的制备过程包括以下具体步骤：
(1)将Ni和Cu的前驱体盐溶于水中，加入油相、表面活性剂和助表面活性剂，充分搅拌形成微乳液；将载体加入到制好的微乳液中浸渍0.5-4小时后，滤除余液；干燥后，在400-600℃下焙烧4-6h，得到半成品催化剂A；
(2)将Pd的前驱体盐溶于水，调pH为1.5-2.5，再将半成品催化剂A加入Pd的盐溶液中， 浸渍吸附0.5-4h后，干燥后在400-600℃条件下焙烧4-6h，得到半成品催化剂B；
(3)Ag的负载以饱和浸渍方式进行，即配制的Ag盐的溶液是载体饱和吸水率的80-110％，调pH为1-5，浸渍后干燥，在400-600℃之间进行焙烧，得到半成品催化剂C；
(4)将Pd前驱体盐溶于水中，加入油相、表面活性剂和助表面活性剂，充分搅拌形成微乳液，将半成品催化剂C加入到制好的微乳液中浸渍0.5-4小时后，滤除余液；干燥后，在400-600℃下焙烧4-6h，得到所述催化剂；
第三种，催化剂的制备过程包括以下具体步骤：
(1)将Ni和Cu的前驱体盐溶于水中，加入油相、表面活性剂和助表面活性剂，充分搅拌形成微乳液；将载体加入到制好的微乳液中浸渍0.5-4小时后，滤除余液，在80-120℃下干燥1-6小时，在300-600℃下焙烧2-8h，得到半成品催化剂A；
(2)将Ag的负载以饱和浸渍法进行，即配制的Ag盐的溶液是载体饱和吸水率的80-110％，调pH为1-5，半成品催化剂A负载Ag之后在500-550℃之间进行焙烧，时间为4-6小时，得到半成品催化剂B；
(3)将Pd的前驱体盐溶于水，调pH为1.5-2.5，再将半成品催化剂B加入Pd的盐溶液中，浸渍吸附0.5-4h后，干燥1-4小时，400-550℃条件下焙烧2-6h，得到半成品催化剂C；
(4)将Pd前驱体盐溶于水中，加入油相、表面活性剂和助表面活性剂，充分搅拌形成微乳液；将半成品催化剂C加入到制好的微乳液中浸渍0.5-4小时后，滤除余液；在干燥后1-6小时，在300-600℃下焙烧2-8h，得到半成品催化剂D；
(5)将半成品催化剂D置于固定床反应装置中，用N 2：H 2＝1:1的混合气体，在150-200℃下，还原处理4-8h得到成品催化剂E。
上述步骤(1)、(4)中的表面活性剂为离子型表面活性剂或非离子型表面活性剂，优选非离子型表面活性剂，更优选的是聚乙二醇辛基苯基醚(Triton X-100)、十六烷基三甲基溴化铵(CTAB)。
上述步骤(1)、(4)中的油相为C 6-C 8饱和烷烃或环烷烃，优选环己烷、正己烷。
上述步骤(1)、(4)中的助表面活性剂为C 4-C 6醇类，优选正丁醇、正戊醇。
本发明催化剂的还原温度最好是150-200℃。
根据本发明的具体实施方案，在催化剂的制备过程中，优选地，微乳液负载Pd的步骤是在微乳液负载Ni和Cu步骤后。
根据本发明的具体实施方案，在催化剂的制备过程中，优选地，Pd的溶液负载与Ni/Cu的微乳液负载先后次序不限定。
根据本发明的具体实施方案，在催化剂的制备过程中，优选地，溶液负载Ag的步骤是在溶液负载Pd步骤后。
为防止Ni和Cu进入小孔，覆盖已负载的钯，最好将溶液法负载钯放在微乳液法负载Ni+Cu后进行。
本发明中，优选地，微乳液的制备条件是：水相与油相的重量比为2-3，表面活性剂与油相的重量比为0.15-0.6，表面活性剂与助表面活性剂的重量比为1-1.2，形成的微乳液粒径大于50nm、小于500nm。
本发明还提供了一种碳二馏分炔烃选择加氢方法，其中：加氢物料为来自前脱乙烷塔塔顶的碳二馏分，进入固定床反应器后进行气相加氢脱除乙炔，该选择性加氢反应的工艺条件为：反应器入口温度35-100℃，压力1.5-3.0MPa，气体体积空速2000-11000h -1；其中，所述催化剂 为本发明所提供上述的催化剂。
根据本发明的具体实施方案，优选地，碳二馏分炔烃选择加氢方法所使用的催化剂以氧化铝为载体，具有双峰孔径分布特征，孔径分别在15-50nm及80-500nm；所述催化剂至少含有活性组分Pd、Ni、Cu，以载体的质量100％计，Pd的含量为0.03-0.09％，Ni的含量为0.5-5％，Cu与Ni的重量比为0.1-1.0:1.0，Ni、Cu及部分Pd的负载采用微乳液负载，所述部分Pd的含量是所述Ni+Cu含量的1/100-1/200，所述的微乳液的粒径在50-500nm。该催化剂优选还含有0.08-0.21％的Ag，Ag通过溶液负载。Pd的优选含量为0.035-0.075％。
本发明提供的催化剂的优选方案是：Pd的负载采用溶液法两次负载的方法，其中，两次负载的Pd负载分别分布于不同的区域。更优选的方式为：Pd的负载采用溶液法两次负载的方法，两次分别是以阳离子前躯体和阳离子前躯体的方法。以阴离子为前躯体负载易形成Pd的壳层分布，主要用于乙炔的选择性加氢，以阳离子为前躯体，可以将Pd分布在更宽的区域，与Ni/Cu形成合金，可以将Ni/Cu的还原温度降低到200℃以下。
本发明的更优选的方式还可以为：Pd的负载采用溶液法、微乳液法分两次浸渍；Ni和Cu采用微乳液法负载，控制微乳液粒径介于载体的小孔的最大孔径和大孔的最大孔径之间，使得Ni、Cu主要分布在载体的大孔中。微乳液法负载的Pd的量是Ni、Cu总含量的1/100-1/200，微乳液法负载Pd是在微乳液法负载Ni、Cu之后。大部分Pd的浸渍采用溶液法。在用溶液法负载钯的过程中，由于小孔的虹吸作用，含有钯的溶液更快地进入小孔中，钯是以氯钯酸离子的形式存在，由于该离子可以与载体表面的羟基形成化学键，使钯被快速的靶定，因此溶液进入孔道的速率越快，负载的速度就越快。所以在以过饱和浸渍法浸渍Pd的过程中，更容易负载于小孔中。
本发明更优选的方式为先在小孔中先负载活性组分钯，而后在催化剂大孔中负载活性组分镍/铜及少量钯，在小孔中负载活性组分钯。乙炔等主要在小孔中发生选择性加氢反应，生成乙烯。而反应中生成的较大分子尺寸的副产物，主要为碳四至碳十六馏分，更容易进入大孔中，在大孔中的镍等活性组分的作用下发生饱和加氢反应。由于这些分子被加氢饱和，其分子链不再增长，因而容易被物料带出反应器。
本发明发现如果将Ni和Cu同时浸渍，二者会形成合金，由于Cu的存在，Ni的还原温度会有较大幅度的降低，最低达到350℃，但这个温度对Pd催化剂来讲仍然太高。本发明还发现，将少量在Pd负载在Ni/Cu催化剂上后，其还原温度有大幅度降低，可以降低到150℃，这个温度对Pd催化剂来讲是完全可以接受的，因为一般Pd催化剂的还原温度是100-150℃，催化剂在有些情况下在120-130℃可以较长时间运行，说明100℃-150℃不会引起活性组分的聚集。
本发明加氢方法的条件是：固定床反应器为绝热或等温反应器，反应条件为：反应器入口温度35-100℃，反应压力1.5-3.0MPa，气体体积空速2000-11000h -1。
根据本发明的具体实施方案，优选地，在上述碳二馏分炔烃选择加氢方法中，加氢原料为碳二馏分，其中乙烯65-93％(v/v)；乙炔0.2-2.5％(v/v)，碳三馏分0.01-0.8％(v/v)；更优选的是，乙烯占65-93％(v/v)，其次为乙烷5-35％(v/v)，乙炔0.3-2.5％(v/v)，碳三馏分0.01-0.5％(v/v)。上述含量以加氢原料的总体积为100％计算。
根据本发明的具体实施方案，优选地，在上述碳二馏分炔烃选择加氢方法中，使用固定床反应器单段反应器加氢时，反应器入口氢炔比为1.3-2.2，优选1.3-1.8。在本发明中，氢炔比均是指氢与炔的摩尔比。
根据本发明的具体实施方案，优选地，在上述碳二馏分炔烃选择加氢方法中，使用固定床 反应器两段反应器加氢时，一段反应器入口氢炔比为1.0-1.4，二段反应器入口氢炔比为1.5-2.5。
根据本发明的具体实施方案，优选地，在上述碳二馏分炔烃选择加氢方法中，使用固定床反应器三段反应器串联加氢时，一段反应器入口氢炔比为0.5-1.5，二段反应器入口氢炔比为1.0-2.0，三段反应器入口氢炔比为1.4-3.0，优选的是，一段反应器入口氢炔比为0.8-1.5，二段反应器入口氢炔比为1.2-1.6，三段反应器入口氢炔比为1.5-2.5。
根据本发明的具体实施方案，优选地，在上述碳二馏分炔烃选择加氢方法中，所述催化剂在加氢前，需要进行还原，还原温度为150-200℃。
本发明还提供了一种采用粗氢为氢源的碳二后加氢工艺的选择加氢方法，其中，加氢物料为来自脱乙烷塔塔顶的碳二馏分，进入固定床反应器后进行气相加氢脱除乙炔，加氢反应所使用的氢气为粗氢，粗氢中H 2含量为20-50v/v％，CO含量为0.1-1v/v％，反应工艺条件为：反应器入口温度55-130℃，压力1.5-3.0MPa，气体体积空速1500-6000h -1；
其中，所述催化剂为权利要求1-19任一项所述的催化剂。
根据本发明的具体实施方案，优选地，在上述采用粗氢为氢源的碳二后加氢工艺的选择加氢方法中，所述加氢物料为来自脱乙烷塔塔顶的碳二馏分，进入固定床反应器后进行气相加氢脱除乙炔，其中，加氢反应所使用的氢气为粗氢，其中H 2含量为30-50v/v％，CO含量为0.1-1v/v％，其余部分为甲烷；反应工艺条件为：反应器入口温度55-130℃，压力1.5-3.0MPa，气体体积空速1500-4000h -1；其中，所述催化剂为本发明所提供上述的催化剂。
根据本发明的具体实施方案，优选地，上述采用粗氢为氢源的碳二后加氢工艺的选择加氢方法所采用的催化剂的载体为氧化铝或主要是氧化铝，具有双峰孔分布结构的氧化铝，其中小孔的孔径为15-50nm，大孔的孔径80-500nm，催化剂至少含有活性组分Pd，Ni、Cu，以催化剂的质量为100％计，Pd的含量为0.06-0.1％，Ni的含量为0.5-5％，Cu与Ni的重量比为0.1-1:1。催化剂的比表面积优选为20-50m 2/g。该催化剂优选还含有0.03-0.5％的Ag，Ag通过溶液负载。在该催化剂中，Pd的优选含量为0.07-0.1％，Ni和Cu的总含量优选为1-5.5％。
根据本发明的具体实施方案，优选地，在上述采用粗氢为氢源的碳二后加氢工艺的选择加氢方法中，加氢原料为乙烯装置中来自脱乙烷塔塔顶的物料，与计量后的粗氢一起进入固定床碳二加氢反应器进行选择加氢，以脱除其中的炔烃。
根据本发明的具体实施方案，优选地，在上述采用粗氢为氢源的碳二后加氢工艺的选择加氢方法中，反应器是单段固定床反应器。反应器入口物料中氢炔比可以控制为2-3(摩尔比)，反应器入口温度可以控制为65-130℃(优选65-125℃)，反应条件可以控制为：反应压力1.5-3.0MPa，气体体积空速1500-6000h -1。
根据本发明的具体实施方案，优选地，在上述采用粗氢为氢源的碳二后加氢工艺的选择加氢方法中，粗氢中的CO含量为0.1-1v/v％，氢气含量为20-50v/v％。上述含量以粗氢的总体积为100％计算。
根据本发明的具体实施方案，优选地，在上述采用粗氢为氢源的碳二后加氢工艺的选择加氢方法中，进入单段固定床反应器的催化反应物料中，乙烯60-93v/v％，乙炔0.2-1.0v/v％，碳三馏分1.0-7.0v/v％。上述含量以加氢原料的总体积为100％计算。
根据本发明的具体实施方案，优选地，在上述采用粗氢为氢源的碳二后加氢工艺的选择加氢方法中，所述催化剂在加氢前需要进行还原，还原温度为150-200℃。
根据本发明的具体实施方案，优选地，在上述采用粗氢为氢源的碳二后加氢工艺的选择加氢方法中，单段固定床反应器入口物料中的氢炔比为2-3(摩尔比)。
采用粗氢为氢源的碳二后加氢工艺中，物料中碳三组分含量最高可达到7.0％，由于本发明的催化剂抗结焦能力显著增强，远远高于传统加氢方法对碳三馏分含量的限制，这就使得即使分离单元有较大幅度的波动，物料中重组分含量超标时，加氢单元仍然可以正常运行。
本发明的催化剂具有以下特性：在加氢反应开始时，由于钯的加氢活性高，而且主要分布在小孔中，因而乙炔的选择性加氢反应主要发生在小孔中。随着催化剂运行时间的延长，催化剂表面生成了一部分分子量较大的副产物，这些物质由于分子尺寸较大，较多的进入大孔中，而且停留时间较长，会在镍催化剂的作用下，发生双键的加氢反应，而生成饱和烃或不含孤立双键的芳香烃，不再生成分子量更大的物质。
本发明人发现，采用该方法制备的催化剂，其初始活性与不含钯的双峰孔分布催化剂相比，活性和选择性明显提高。
本发明人还发现，使用该催化剂后，即使反应物中含较多重馏分，催化剂绿油生成量大幅增加，催化剂活性及选择性仍没有下降的趋势。
附图说明
图1为实施例1-1中所配制Ni和Cu微乳液的粒径分布。
图2为实施例1-1的催化剂的TPR图。
具体实施方式
本发明催化剂在制备过程中用到以下表征方法：动态光散射粒径分析仪，在M286572动态光散射分析仪上分析Ni/Cu合金的微乳液粒径分布；全自动压汞仪，在美国麦克公司9510型压汞仪上分析载体的孔体积、比表面积和孔径分布。在AA240FS原子吸收光谱仪上，测定催化剂中Pd、Ag、Ni和Cu的含量。
安捷伦7890A气相色谱仪测量反应器出口、入口氢气及乙炔含量。
0.1mg电子天平测量催化剂重量。
初始乙炔转化率，指反应器从投料开始，24小时内测定的乙炔转化率。
乙炔转化率＝[(反应器入口乙炔含量-反应器出口乙炔含量)/反应器出口乙炔含量]*100％
乙烯选择性＝{2-[(反应器入口氢气含量-反应器出口氢气含量)/(反应器入口乙炔含量-反应器出口乙炔含量)]}*100％
结焦量＝[(反应后催化剂重量-反应前催化剂重量)/反应器催化剂重量]*100％
实施例1-1
催化剂载体：采用市售双峰孔分布球形氧化铝载体，直径为4mm。经过1092℃焙烧4h后，双峰孔径分布范围在15-38nm和80-350nm，吸水率65％，比表面积为49.65m 2/g。称取该载体100g。
催化剂制备：
(1)称取无水硝酸镍15.51g，氯化铜1.05g，溶于60mL去离子水中，加环己烷28.57g，加Triton X-100 16.57g，加正丁醇16g，充分搅拌形成微乳液(该Ni和Cu微乳液的粒径分布数据如表1-1、图1所示)，将称取的100g高温焙烧过的载体浸渍到所制备的微乳液中，摇动30min，滤除余液，用去离子水洗涤，在40℃下干燥，在400℃下焙烧6h，称为半成品催化剂A1。
(2)称取硝酸钯0.0651g，溶于110mL去离子水中，调pH为1.5，再将半成品催化剂A1浸渍到已配制的Pd盐溶液中，浸渍30min后，80℃干燥，400℃条件下焙烧6小时，得到半成品催化剂B1。
(3)称取氯化钯0.046g溶于60mL去离子水中，加环己烷28.57g，加Triton X-100 16.57g，加正丁醇16g，充分搅拌形成微乳液，将称取的100g半成品催化剂B1放置在制备的微乳液中，摇动30min，滤除余液，在40℃下干燥，在400℃下焙烧6h，得到所要的催化剂。
动态光散射测定步骤(1)制备的微乳液乳液的粒径是60.71nm，步骤(3)制备的微乳液的粒径是60.18nm。
由原子吸收光谱法测定制备的催化剂，得到实施例1-1制备的催化剂中，Pd的含量为0.0575％，Ni含量为5％，Cu含量为0.5％。
表1-1实施例1-1中微乳液的粒径分布数据
Figure PCTCN2021086214-appb-000001
催化剂的还原：
使用前放置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在200℃温度，还原处理8h。
该催化剂的TPR如图2所示。从图2中看出，Ni/Cu合金的还原温度是350℃。Ni/Cu再增加Pd后，还原温度是150℃左右。
对比例1-1
使用与实施例1-1相同的载体，催化剂制备条件与实施例1-1相同，区别是不负载Cu。
催化剂制备：
(1)称取无水硝酸镍15.61g溶于60mL去离子水中，加环己烷28.57g，加Triton X-100 16.57g，加正丁醇16g充分搅拌形成微乳液，将称取的100g高温焙烧过的载体浸渍到所制备的微乳液中，摇动30min，滤除余液，在40℃下干燥，在400℃下焙烧6h，称为半成品催化剂A1-1。
(2)称取硝酸钯0.0651g，溶于110mL去离子水中，调pH为1.5，再将半成品催化剂A1-1浸渍到已配制的Pd盐溶液中，浸渍30min后，80℃干燥6小时，400℃条件下焙烧6小时，得到半成品催化剂B1-1。
(3)称取氯化钯0.046g溶于60mL去离子水中，加环己烷28.57g，加Triton X-100 16.57g，加正丁醇16g，充分搅拌形成微乳液，将步骤(2)制备的半成品催化剂B1-1放置在制备的微乳液中，摇动30min，滤除余液，在40℃下干燥，在400℃下焙烧6h，得到所要的催化剂。
动态光散射测定(1)制备的微乳液乳液的粒径是62.12nm，(3)制备的微乳液乳液的粒径是60.18nm。
由原子吸收光谱法测定制备的催化剂，得到对比例1-1中，Pd含量为0.0575％，Ni含量为5％。
催化剂的还原：
使用前放置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在200℃还原处理8h。
实施例1-2
载体：采用市售双峰孔分布球形氧化铝载体，直径为3mm。经过1111℃焙烧4h后，双峰孔径分布范围在20-40nm和120-400nm，吸水率62％，比表面积为39.71m 2/g。称取该载体100g。
催化剂制备：
(1)称取氯化镍1.098g，硝酸铜1.47g，溶于70mL去离子水中，加正己烷34.14g，加CATB20g，加正戊醇19g，充分搅拌形成微乳液，将称取的100g高温焙烧过的载体浸渍到所制备的微乳液中，摇动90min，滤除余液，在80℃下干燥，在600℃下焙烧4h，称为半成品催化剂A2。
(2)称取氯化钯0.068g，溶于100mL去离子水中，调pH为1.8，再将半成品催化剂A2浸渍到已配制的Pd盐溶液中，浸渍60min后，100℃干燥，600℃条件下焙烧4小时，得到半成品催化剂B2。
(3)称取0.0167g氯化钯，溶于70mL去离子水中，加正己烷34.14g，加CATB 20g，加正戊醇19g，充分搅拌形成微乳液，将步骤(2)制备的半成品催化剂B2浸渍到所制备的微乳液中，摇动90min，滤除余液，在70℃下干燥，在600℃下焙烧4h，得到所要的催化剂。
动态光散射测定步骤(1)制备的微乳液的粒径是55.48nm，步骤(3)制备的微乳液的粒径是54.40nm。
由原子吸收光谱法测定制备的催化剂，实施例1-2的催化剂中，Pd含量为0.05％，Ni含量为0.5％，Cu含量为0.5％。
催化剂的还原：
使用前放置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在150℃还原处理8h。
对比例1-2
使用与实施例1-2相同的载体，催化剂制备条件与实施例1-2相同，区别是Cu是溶液法负载的。
载体：采用市售双峰孔分布球形氧化铝载体，直径为3mm。经过111℃焙烧4h后，双峰孔径分布范围在20-40nm和120-400nm，吸水率62％，比表面积为39.71m 2/g。称取该载体100g。
催化剂制备：
(1)称取氯化镍1.098g，溶于70mL去离子水中，加正己烷34.14g，加CATB 20g，加正戊醇19g，充分搅拌形成微乳液，将称取的100g高温焙烧过的载体浸渍到所制备的微乳液中，摇动90min，滤除余液，在80℃下干燥，在600℃下焙烧4h，称为半成品催化剂A2-1。
(2)称取氯化钯0.068g，硝酸铜1.47g，溶于100mL去离子水中，调pH为1.8，再将半成品催化剂A2-1浸渍到已配制的Pd盐溶液中，浸渍60min后，100℃干燥，600℃条件下焙烧4小时，得到半成品催化剂B2-1。
(3)称取0.0167g氯化钯，溶于70mL去离子水中，加正己烷34.14g，加CATB 20g，加正戊醇19g，充分搅拌形成微乳液，将步骤(2)制备的半成品催化剂B2-1浸渍到所制备的微乳液中，摇动90min，滤除余液，在70℃下干燥，在600℃下焙烧4h，得到所要的催化剂。
动态光散射测定步骤(1)制备的微乳液的粒径是55.48nm，步骤(3)制备的微乳液的粒径是54.40nm。
由原子吸收光谱法测定制备的催化剂，实施例1-2中，Pd含量为0.05％，Ni含量为0.5％，Cu含量为0.5％。
催化剂的还原：
使用前放置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在150℃温度，还原处理8h。
实施例1-3
载体：采用市售双峰孔分布球形氧化铝载体，直径为4mm。经过1128℃焙烧4h后，双峰孔径分布范围在25-50nm和95-500nm，吸水率62％，比表面积为20.19m 2/g。称取该载体100g。
催化剂制备：
(1)称取无水硝酸镍6.203g，氯化铜2.11g，溶于76mL去离子水中，加环己烷26g，加Triton X-100 4.9g，加正丁醇4.49g，充分搅拌形成微乳液，将称取的100g高温焙烧过的载体浸渍到所制备的微乳液中，摇动240min，滤除余液，在80℃下干燥，在500℃下焙烧5h，称为半成品催化剂A3。
(2)称取硝酸钯0.108g，溶于90mL去离子水中，调pH为2，再将半成品催化剂A3浸渍到已配制的Pd盐溶液中，浸渍90min后，120℃干燥，500℃条件下焙烧5小时，得到半成品催化剂B3。
(3)称取硝酸银0.33g，溶于68.2mL去离子水中，调pH值为4，将步骤(2)制备的半成品催化剂B3溶解于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，150℃干燥，在500℃焙烧5小时，得到半成品催化剂C3。
(4)称取0.043g硝酸钯，溶于76mL去离子水中，加环己烷26g，加Triton X-100 4.9g，加正丁醇4.49g，充分搅拌形成微乳液，将步骤(3)制备的半成品催化剂C3浸渍到所制备的微乳液中，摇动240min，滤除余液，在80℃下干燥，在500℃下焙烧5h，得到所要的催化剂。
动态光散射测定步骤(1)制备的微乳液的粒径是403.65nm，步骤(4)制备的微乳液的粒径是401.83nm。
由原子吸收光谱法测定制备的催化剂，实施例1-3中，Pd含量为0.07％，Ni含量为2％，Cu含量为1％，Ag含量为0.21％。
催化剂的还原：
使用前放置于固定床反应装置中，用纯氢在150℃温度，还原处理8h。
对比例1-3
使用与实施例1-3相同的载体，催化剂制备条件与实施例1-3相同，区别是乳液法不负载Pd。
催化剂制备：
(1)称取无水硝酸镍6.203g，氯化铜2.11g溶于76mL去离子水中，加环己烷26g，加Triton X-100 4.9g，加正丁醇4.49g，充分搅拌形成微乳液，将称取的100g载体浸渍到所制备的微乳液中，摇动100min，滤除余液，在80℃下干燥，在500℃下焙烧5h，称为半成品催化剂A3-1。
(2)称取硝酸钯0.151g，溶于90mL去离子水中，调pH为2，再将半成品催化剂A3-1浸渍到已配制的Pd盐溶液中，浸渍90min后，120℃干燥4小时，500℃条件下焙烧5小时，得到半成品催化剂B3-1。
(3)称取硝酸银0.33g，溶于68.2mL去离子水中，调pH值为4，将步骤(2)制备的半成品催化剂B3-1溶解于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，150℃干燥2小时，在500℃焙烧5小时，得到所要的催化剂。
动态光散射测定步骤(1)制备的微乳液乳液的粒径是403.65nm。
由原子吸收光谱法测定制备的催化剂，对比例1-3中，Pd含量为0.07％，Ni含量为2％，Cu含量为1％，Ag含量为0.21％。
催化剂的还原：
使用前放置于固定床反应装置中，用纯氢在150℃温度，还原处理8h。
实施例1-4
载体：采用市售双峰孔分布球形氧化铝-氧化钛载体，氧化钛含量为20％，直径为3mm。经过1118℃焙烧4h后，双峰孔径分布范围在23-47nm和90-450nm，吸水率58％，比表面积为30.28m 2/g。称取该载体100g。
催化剂制备：
(1)称取氯化镍2.21g，硝酸铜2.94g，溶于80mL去离子水中，加正己烷40.00g，加CATB24g，加正戊醇23g，充分搅拌形成微乳液，将称取的100g高温焙烧过的载体浸渍到所制备的微乳液中，摇动180min，滤除余液，在80℃下干燥，在550℃下焙烧5h，称为半成品催化剂A4。
(2)称取氯化钯0.033g，溶于80mL去离子水中，加正己烷40.00g，加CATB 24g，加正戊醇23g，充分搅拌形成微乳液，将半成品催化剂A4浸渍到所制备的微乳液中，摇动180min，滤除余液，在80℃下干燥，在550℃下焙烧5h，称为半成品催化剂B4。
(3)称取氯化钯0.075g，溶于80mL去离子水中，调pH为2.5，再将半成品催化剂B4浸渍到已配制的Pd盐溶液中，浸渍120min后，130℃干燥，550℃条件下焙烧5小时，得到半成品催化剂C4。
(4)称取硝酸银0.126g，溶于58mL去离子水中，调pH值为5，将步骤(3)制备的半成品催化剂C4溶解于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，100℃干燥，在500℃焙烧5小时，得到所要的催化剂。
动态光散射测定步骤(1)制备的微乳液乳液的粒径是52.83nm，步骤(2)制备的微乳液乳液的粒径是52.61nm。
由原子吸收光谱法测定制备的催化剂，实施例1-4中，Pd含量为0.064％，Ni含量为1％，Cu含量为1％，Ag含量为0.08％。
催化剂的还原：
使用前放置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在200℃温度，还原处理8h。
对比例1-4
载体及制备条件与实施例1-4相同，区别是对比例中无Ni。
(1)称取硝酸铜2.94g，溶于80mL去离子水中，加正己烷40.00g，加CATB 24g，加正戊醇23g，充分搅拌形成微乳液，将称取的100g高温焙烧过的载体浸渍到所制备的微乳液中，摇动180min，滤除余液，在80℃下干燥，550℃下焙烧5h，称为半成品催化剂A4-1。
(2)称取氯化钯0.033g，溶于80mL去离子水中，加正己烷40.00g，加CATB 24g，加正戊醇23g，充分搅拌形成微乳液，将半成品催化剂A4-1浸渍到所制备的微乳液中，摇动180min，滤除余液，在80℃干燥，在550℃下焙烧5h，称为半成品催化剂B4-1。
(3)称取氯化钯0.075g，溶于80mL去离子水中，调pH为2.5，再将半成品催化剂B4-1浸渍到已配制的Pd盐溶液中，浸渍120min后，130℃干燥，500℃条件下焙烧5小时，得到半成品催化剂C4-1。
(4)称取硝酸银0.126g，溶于58mL去离子水中，调pH值为5，将步骤(3)制备的半成 品催化剂N溶解于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，100℃干燥，在550℃焙烧5小时，得到所要的催化剂。
动态光散射测定步骤(1)制备的微乳液乳液的粒径是52.87nm，步骤(2)制备的微乳液乳液的粒径是52.65nm。
由原子吸收光谱法测定制备的催化剂，对比例1-4中，Pd含量为0.064％，Cu含量为1％，Ag含量为0.08％。
催化剂的还原：
使用前放置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在200℃温度，还原处理8h。
实施例1-5
载体：采用市售双峰孔分布球形氧化铝-氧化镁载体，氧化镁含量为3％，直径为3mm。经过999℃焙烧4h后，双峰孔径分布范围在23-47nm和80-380nm，吸水率58％，比表面积为45.08m 2/g。称取该载体100g。
催化剂制备：
(1)称取氯化钯0.076g，溶于80mL去离子水中，调pH为2，再将载体浸渍到已配制的Pd盐溶液中，浸渍120min后，130℃干燥，500℃条件下焙烧4小时，得到半成品催化剂A5。
(2)称取硝酸银0.158g，溶于58mL去离子水中，调pH值为5，将步骤(1)制备的半成品催化剂A5溶解于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，100℃干燥，在500℃焙烧4小时，得到半成品催化剂B5。
(3)称取氯化镍3.295g，硝酸铜1.45g，溶于80mL去离子水中，加正己烷35.00g，加Triton X-100 20.36g，加正己醇19.39g，充分搅拌形成微乳液，将步骤(2)制备的半成品催化剂B5浸渍到所制备的微乳液中，摇动180min，滤除余液，在70℃下干燥，在500℃下焙烧4h，称为半成品催化剂C5。
(4)称取氯化钯0.017g，溶于80mL去离子水中，加正己烷35.00g，加Triton X-100 20.36g，加正己醇19.39g，充分搅拌形成微乳液，将制备的半成品催化剂C5浸渍到所制备的微乳液中，摇动180min，滤除余液，在70℃下干燥，在500℃下焙烧4h，得到所要的催化剂。
动态光散射测定步骤(3)制备的微乳液乳液的粒径是66.38nm，步骤(4)制备的微乳液乳液的粒径是65.22nm。
由原子吸收光谱法测定制备的催化剂，实施例1-5中，Pd含量为0.055％，Ni含量为1.5％，Cu含量为0.5％，Ag含量为0.10％。
催化剂的还原：
使用前放置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在180℃温度，还原处理8h。
对比例1-5
催化剂载体及制备条件与实施例1-5相同，区别是Ni加入量降低到0.3％。
催化剂制备：
(1)称取氯化钯0.076g，溶于80mL去离子水中，调pH为2，再将载体浸渍到已配制的Pd盐溶液中，浸渍120min后，130℃干燥，500℃条件下焙烧4小时，得到半成品催化剂A5-1。
(2)称取硝酸银0.157g，溶于58mL去离子水中，调pH值为5，将步骤(1)制备的半成品催化剂A5-1溶解于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，100℃干燥， 在500℃焙烧4小时，得到半成品催化剂B5-1。
(3)称取氯化镍0.659g，硝酸铜1.45g，溶于80mL去离子水中，加正己烷35.00g，加Triton X-100 20.36g，加正己醇19.39g，充分搅拌形成微乳液，将步骤(2)制备的半成品催化剂B5-1浸渍到所制备的微乳液中，摇动180min，滤除余液，在70℃下干燥，在500℃下焙烧4h，称为半成品催化剂C5-1。
(4)称取氯化钯0.017g，溶于80mL去离子水中，加正己烷35.00g，加Triton X-100 20.36g，加正己醇19.39g，充分搅拌形成微乳液，将制备的半成品催化剂C5-1浸渍到所制备的微乳液中，摇动180min，滤除余液，在70℃下干燥，在500℃下焙烧4h，得到所要的催化剂。
动态光散射测定(3)制备的微乳液乳液的粒径是66.32nm，(4)制备的微乳液乳液的粒径是65.24nm。
由原子吸收光谱法测定制备的催化剂，对比例1-5中，Pd含量为0.055％，Ni含量为0.28％，Cu含量为0.5％，Ag含量为0.10％。
实施例1-6
载体：采用市售双峰孔分布球形氧化铝-氧化镁载体，氧化镁含量为10％，直径为3mm。经过999℃焙烧4h后，双峰孔径分布范围在23-47nm和80-380nm，吸水率58％，比表面积为45.08m 2/g。称取该载体100g。
催化剂制备：
(1)称取氯化镍2.20g，硝酸铜2.93g，溶于80mL去离子水中，加正己烷36.00g，加Triton X-100 20.36g，加正己醇19.50g，充分搅拌形成微乳液，将称取的100g高温焙烧过的载体浸渍到所制备的微乳液中，摇动180min，滤除余液，在70℃下干燥，在600℃下焙烧4h，称为半成品催化剂A6。
(2)称取氯化钯0.076g，溶于80mL去离子水中，调pH为2.5，再将半成品催化剂A6浸渍到已配制的Pd盐溶液中，浸渍120min后，130℃干燥，600℃条件下焙烧4小时，得到半成品催化剂B6。
(3)称取硝酸银0.157g，溶于58mL去离子水中，调pH值为5，将步骤(2)制备的半成品催化剂B6溶解于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，100℃干燥，550℃焙烧6小时，得到半成品催化剂C6。
(4)称取氯化钯0.017g，溶于80mL去离子水中，加正己烷36.00g，加Triton X-100 20.36g，加正己醇19g，充分搅拌形成微乳液，将步骤(3)制备的半成品催化剂C6浸渍到所制备的微乳液中，摇动180min，滤除余液，在70℃下干燥，在400℃下焙烧6h，得到所要的催化剂。动态光散射测定步骤(3)制备的微乳液乳液的粒径是66.32nm，步骤(4)制备的微乳液乳液的粒径是65.36nm。
由原子吸收光谱法测定制备的催化剂，实施例1-6中，Pd含量为0.055％，Ni含量为1％，Cu含量为1％，Ag含量为0.10％。
催化剂的还原：
使用前放置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在200℃温度，还原处理8h。
对比例1-6
催化剂载体与制备条件与实施例1-6相同，不同的是步骤(4)制备微乳液时加入的Pd的量降低为实施例1-6的1/3，小于Ni+Cu含量的1/200。
载体：采用市售双峰孔分布球形氧化铝-氧化镁载体，氧化镁含量为10％，直径为3mm。经过1000℃焙烧4h后，双峰孔径分布范围在23-47nm和80-380nm，吸水率58％，比表面积为45.08m 2/g。称取该载体100g。
催化剂制备：
(1)称取氯化镍2.20g，硝酸铜2.93g，溶于80mL去离子水中，加正己烷36.00g，加Triton X-100 20.36g，加正己醇19.50g，充分搅拌形成微乳液，将称取的100g高温焙烧过的载体浸渍到所制备的微乳液中，摇动180min，滤除余液，在70℃下干燥，在600℃下焙烧4h，称为半成品催化剂A6-1。
(2)称取氯化钯0.076g，溶于80mL去离子水中，调pH为2.5，再将半成品催化剂A6-1浸渍到已配制的Pd盐溶液中，浸渍120min后，130℃干燥，600℃条件下焙烧4小时，得到半成品催化剂B6-1。
(3)称取硝酸银0.157g，溶于58mL去离子水中，调pH值为5，将步骤(2)制备的半成品催化剂B6-1溶解于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，100℃干燥，550℃焙烧6小时，得到半成品催化剂C6-1。
(4)称取氯化钯0.0057g，溶于80mL去离子水中，加正己烷36.00g，加Triton X-100 20.36g，加正己醇19g，充分搅拌形成微乳液，将步骤(3)制备的半成品催化剂C6-1浸渍到所制备的微乳液中，摇动180min，滤除余液，在70℃下干燥，在400℃下焙烧6h，得到所要的催化剂。
动态光散射测定步骤(3)制备的微乳液乳液的粒径是66.32nm，步骤(4)制备的微乳液乳液的粒径是65.36nm。
由原子吸收光谱法测定制备的催化剂，对比例1-6中，Pd含量为0.0483％，Ni含量为1％，Cu含量为1％，Ag含量为0.10％。
实施例1-7
载体：采用市售双峰孔分布球形载体，氧化铝97％，氧化钛含量3％，直径为3mm。经过978℃焙烧4h后，双峰孔径分布范围在20-35nm和90-200nm，吸水率62％，比表面积为49.81m 2/g。称取该载体100g。
催化剂制备：
(1)称取氯化钯0.05g，溶于100mL去离子水中，调pH为1.8，再将载体浸渍到已配制的Pd盐溶液中，浸渍60min后，100℃干燥，400℃条件下焙烧6小时，得到半成品催化剂A7。
(2)称取硝酸银0.126g，溶于57mL去离子水中，调pH值为3，将步骤(1)制备的半成品催化剂A7溶解于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，140℃干燥，在600℃焙烧6小时，得到半成品催化剂B7。
(3)称取硝酸镍1.56g，氯化铜1.06g，溶于71.5g水中，加入27.0g正己烷，13.75g CTAB，12.73g正戊醇充分搅拌形成微乳液，将半成品催化剂B7加入到制好的微乳液中浸渍80min后，滤除余液，用去离子水洗剂至中性。在80℃下干燥，在600℃下焙烧4h，得到半成品催化剂C7。
(4)称取氯化钯0.009g，溶于71.5g水中，加入27.50g正己烷，13.75g CTAB，12.50g正戊醇充分搅拌形成微乳液，将半成品催化剂C7加入到制好的微乳液中浸渍80min后，滤除余液，用去离子水洗剂至中性。在80℃下干燥，在600℃下焙烧4h，得到所要的催化剂。
动态光散射测定步骤(3)制备的微乳液乳液的粒径是100.60nm，步骤(4)制备的微乳液乳液的粒径100.28nm。
由原子吸收光谱法测定制备的催化剂，实施例1-7中，Pd含量为0.035％，Ni含量为0.5％， Cu含量为0.5％，Ag含量为0.08％。
催化剂的还原：
使用前放置于固定床反应装置中，用摩尔比为N2:H2＝1:1的混合气体，在150℃温度，还原处理8h。
对比例1-7
载体采用与实施例1-7相同的市售双峰孔分布球形载体，氧化铝97％，氧化钛含量3％，在940℃焙烧，载体双峰孔径分布范围在10-20nm和30-97nm，吸水率65％，比表面积为75.21m 2/g。称取该载体100g。
催化剂制备：
(1)称取氯化钯0.05g，溶于100mL去离子水中，调pH为1.8，再将载体浸渍到已配制的Pd盐溶液中，浸渍60min后，100℃干燥，400℃条件下焙烧6小时，得到半成品催化剂A7-1。
(2)称取硝酸银0.126g，溶于57mL去离子水中，调pH值为3，将步骤(1)制备的半成品催化剂A7-1溶解于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，140℃干燥，在600℃焙烧6小时，得到半成品催化剂B7-1。
(3)称取硝酸镍1.56g，氯化铜1.06g，溶于71.5g水中，加入27.0g正己烷，13.75g CTAB，12.73g正戊醇充分搅拌形成微乳液，将半成品催化剂B7-1加入到制好的微乳液中浸渍80min后，滤除余液，用去离子水洗剂至中性。在80℃下干燥，在600℃下焙烧4h，得到半成品催化剂C7-1。
(4)称取氯化钯0.009g，溶于71.5g水中，加入27.5g正己烷，13.75g CTAB，12.50g正戊醇充分搅拌形成微乳液，将半成品催化剂C7-1加入到制好的微乳液中浸渍80min后，滤除余液，用去离子水洗剂至中性。在80℃下干燥，在600℃下焙烧4h，得到所要的催化剂。
动态光散射测定步骤(3)制备的微乳液乳液的粒径是100.60nm，步骤(4)制备的微乳液乳液的粒径100.23nm。
由原子吸收光谱法测定制备的催化剂，对比例1-7中，Pd含量为0.035％，Ni含量为0.5％，Cu含量为0.5％，Ag含量为0.08％。
催化剂的还原：使用前放置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在150℃温度，还原处理8h。
实施例1-8
实施例1-8的载体与实施例1-7相同，制备条件相同，区别是步骤(1)和(2)的次序调换。
载体：采用市售双峰孔分布球形载体，氧化铝97％，氧化钛含量3％，直径为3mm。经过978℃焙烧4h后，双峰孔径分布范围在20-35nm和90-200nm，吸水率62％，比表面积为49.81m 2/g。称取该载体100g。
催化剂制备：
(1)称取硝酸银0.126g，溶于57mL去离子水中，调pH值为3，将已焙烧的载体100g溶解于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，140℃干燥，在400℃焙烧6小时得到半成品催化剂A8。
(2)称取氯化钯0.05g，溶于100mL去离子水中，调pH为1.8，再将步骤(1)制备的半成品催化剂A8载体浸渍到已配制的Pd盐溶液中，浸渍60min后，100℃干燥，600℃条件下焙烧6小时，得到半成品催化剂B8。
(3)称取硝酸镍1.56g，氯化铜1.06g，溶于71.5g水中，加入27.0g正己烷，13.75g CTAB，12.73g正戊醇充分搅拌形成微乳液，将步骤(2)制备半成品催化剂B8浸渍到所制备的微乳液 中，摇动90min，滤除余液，在80℃下干燥，在600℃下焙烧4h，称为半成品催化剂C8。
(4)称取氯化钯0.009g，溶于71.5g水中，加入27.5g正己烷，13.75g CTAB，12.45g正戊醇充分搅拌形成微乳液，将(3)制备的半成品催化剂C8浸渍到所制备的微乳液中，摇动90min，滤除余液，在80℃下干燥，在600℃下焙烧4h，得到所要的催化剂。
动态光散射测定步骤(3)制备的微乳液乳液的粒径是100.60nm，步骤(4)制备的微乳液乳液的粒径100.23nm。
由原子吸收光谱法测定制备的催化剂，实施例1-8中，Pd含量为0.035％，Ni含量为0.5％，Cu含量为0.5％，Ag含量为0.08％。
催化剂的还原：
使用前放置于固定床反应装置中，用摩尔比为N2:H2＝1:1的混合气体，在150℃温度，还原处理8h。
对比例1-8
催化剂载体及制备条件的1-3步与实施例1-8相同，不同的是步骤(4)制备的微乳液粒径，大于载体的最大孔径。
载体：采用市售双峰孔分布球形载体，氧化铝97％，氧化钛含量3％，直径为3mm。经过980℃焙烧4h后，双峰孔径分布范围在20-35nm和90-200nm，吸水率62％，比表面积为49.81m 2/g。称取该载体100g。
催化剂制备：
(1)称取硝酸银0.126g，溶于57mL去离子水中，调pH值为3，将已焙烧的载体100g溶解于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，140℃干燥，在400℃焙烧6小时得到半成品催化剂A8-1。
(2)称取氯化钯0.05g，溶于100mL去离子水中，调pH为1.8，再将步骤(1)制备的半成品催化剂A8-1载体浸渍到已配制的Pd盐溶液中，浸渍60min后，100℃干燥，600℃条件下焙烧6小时，得到半成品催化剂B8-1。
(3)称取硝酸镍1.56g，氯化铜1.06g，溶于71.5g水中，加入27.10g正己烷，13.75g CTAB，12.73g正戊醇充分搅拌形成微乳液，将步骤(2)制备半成品催化剂B8-1浸渍到所制备的微乳液中，摇动90min，滤除余液，在80℃下干燥，在600℃下焙烧4h，称为半成品催化剂C8-1。
(4)称取氯化钯0.009g，溶于65g水中，加入22.26g环己烷，4.22g TritonX-100，3.70g正丁醇充分搅拌形成微乳液，将(3)制备的半成品催化剂C8-1浸渍到所制备的微乳液中，摇动90min，滤除余液，在80℃下干燥，在600℃下焙烧4h，得到所要的催化剂。
动态光散射测定步骤(3)制备的微乳液乳液的粒径是100.60nm，步骤(4)制备的微乳液乳液的粒径398.76nm。
由原子吸收光谱法测定制备的催化剂，对比例1-8中，Pd含量为0.031％，Ni含量为0.5％，Cu含量为0.5％，Ag含量为0.08％。
实施例1-9
催化剂制备：
称取市售双峰孔分布球形氧化铝载体，直径为4mm。经过1115℃焙烧4h后，孔径分布范围分别是28-48nm和102-499nm，吸水率为50.35％，比表面积为20.73m 2/g，称取该载体100g。
(1)称取0.068g氯化钯盐溶于120mL去离子水中，调pH为2.5，再将载体加入Pd的盐溶液中，浸渍吸附1小时后，120℃干燥，600℃条件下焙烧4h，得到所需的半成品催化剂A9。
(2)取50mL去离子水，加入0.33g硝酸银使其完全溶解，调pH为3，将半成品催化剂A9浸渍在所制备的溶液中，摇动15min，在120℃干燥，600℃焙烧4小时，制得半成品催化剂B9。
(3)称取无水硝酸镍15.58g，硝酸铜1.471g溶于65g水中，加入22.40g环己烷，4.25g TritonX-100，3.80g正丁醇充分搅拌形成微乳液。将步骤(2)制备的半成品催化剂B9加入到制好的微乳液中浸渍4小时后，滤除余液，在60℃下干燥，在600℃下焙烧4h，得到半成品催化剂C9。
(4)称取硝酸钯0.059g，溶于65g水中，加入22.40g环己烷，4.25g TritonX-100，3.80g正丁醇充分搅拌形成微乳液。将步骤(3)制备的半成品C9浸渍到制备的微乳液中浸渍4小时后，滤除余液，用去离子水洗涤至中性。在60℃下干燥，在600℃下焙烧4h，得到所要的催化剂。
动态光散射法测定步骤(3)制备的微乳液的粒径为398.56nm，步骤(4)制备的微乳液的粒径为398.75nm。
用原子吸收光谱法测定元素含量，得到实施例1-9所制备的催化剂，Pd含量为0.0675％，Ni含量为5％，Cu含量为0.5％，Ag含量0.21％。
催化剂的还原：
还原气体：氢气，还原空速：100h -1，温度150℃，保持8h。
对比例1-9
催化剂制备：
使用与实施例1-9相同的载体，对比例1-9制备与实施例1-9步骤相同，区别是负载Ni/Cu时的微乳液粒径622.38nm。
(1)称取0.068g氯化钯盐溶于120mL去离子水中，调pH为2.5，再将载体加入Pd的盐溶液中，浸渍吸附70min后，120℃干燥，600℃条件下焙烧4h，得到所需的半成品催化剂A9-1。
(2)取50mL去离子水，加入0.33g硝酸银使其完全溶解，调pH为3，将半成品催化剂A9-1浸渍在所制备的溶液中，摇动15min，在120℃干燥，600℃焙烧4小时，制得半成品催化剂B9-1。
(3)称取无水硝酸镍15.58g，硝酸铜1.471g溶于65g水中，加入22.40g环己烷，2.75g TritonX-100，2.75g正丁醇充分搅拌形成微乳液，将步骤2制备的半成品催化剂B9-1加入到制好的微乳液中浸渍4小时后，滤除余液，在60℃下干燥，在600℃下焙烧4h，得到半成品催化剂C9-1。
(4)称取硝酸钯0.059g，溶于65g水中，加入22.26g环己烷，4.25g TritonX-100，3.80g正丁醇，充分搅拌形成微乳液。将步骤(3)制备的半成品C9-1浸渍到制备的微乳液中浸渍4小时后，滤除余液，在60℃下干燥，在600℃下焙烧4h。得到所要的催化剂。
动态光散射法测定步骤(3)中得到的制备的微乳液的粒径为621.67nm，步骤(4)中得到的制备的微乳液的粒径为399.62nm。
用原子吸收光谱法测定元素含量，得到对比例1-9所制备的催化剂，其中Pd含量为0.0675％，Ni含量为1.34％，Cu含量为0.12％，Ag含量0.21％。
催化剂的还原：
还原气体：氢气，还原空速：100h -1，温度150℃，保持8h。
实施例1-10
催化剂制备：载体采用市售双峰孔分布球形氧化铝载体，直径为3mm。经过1118℃焙烧4h后，双峰孔径分布范围在30-43nm和100-498nm，吸水率62％，比表面积为20.35m 2/g。称取该载体100g。
(1)称取氯化镍5.52g，硝酸铜7.38g，溶于69mL去离子水中，加正戊烷23.2g，加CATB 3.45g，加正辛醇2.88g，充分搅拌形成微乳液，将称取的100g高温焙烧过的载体浸渍到所制备的微乳液中，摇动90min，滤除余液，在60℃下干燥，在400℃下焙烧6h，得到半成品催化剂A10。
(2)称取氯化钯0.051g，溶于69mL去离子水中，加正戊烷23.2g，加CATB 3.50g，加正辛醇2.91g，充分搅拌形成微乳液，将半成品催化剂A10浸渍到所制备的微乳液中，摇动90min，滤除余液，在70℃下干燥，在400℃下焙烧6h，称为半成品催化剂B10。
(3)称取氯化钯0.084g，溶于100mL去离子水中，调pH为1.8，再将半成品催化剂B10浸渍到已配制的Pd盐溶液中，浸渍60min后，100℃干燥，400℃条件下焙烧6小时，得到半成品催化剂C10。
(4)称取硝酸银0.158g，溶于57mL去离子水中，调pH值为3，将步骤(3)制备的半成品催化剂C10溶解于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，140℃干燥，在500℃焙烧6小时，得到所要的催化剂。
动态光散射测定步骤(1)制备的微乳液乳液的粒径是497.65nm，步骤(2)制备的微乳液乳液的粒径是495.32nm。
由原子吸收光谱法测定制备的催化剂，实施例1-10中，Pd含量为0.08％，Ni含量为2.5％，Cu含量为2.5％，Ag含量为0.10％。
催化剂的还原：
还原气体：氢气，还原空速：100h -1，温度200℃，保持4h。
对比例1-10
与实施例1-10的催化剂制备条件相同，只是比表面积小于20m 2/g。
催化剂制备：载体采用市售双峰孔分布球形氧化铝载体，直径为3mm。经过1155℃焙烧4h后，双峰孔径分布范围在41-76nm和114-684nm，吸水率60％，比表面积为14.29m 2/g。称取该载体100g。
(1)称取氯化镍5.52g，硝酸铜7.38g，溶于69mL去离子水中，加正戊烷23.2g，加CATB3.45g，加正辛醇2.88g，充分搅拌形成微乳液，将称取的100g高温焙烧过的载体浸渍到所制备的微乳液中，摇动90min，滤除余液，在60℃下干燥，在400℃下焙烧6h，得到半成品催化剂A10-1。
(2)称取氯化钯0.051g，溶于69mL去离子水中，加正戊烷23g，加CATB 3.50g，加正辛醇2.91g，充分搅拌形成微乳液，将半成品催化剂A10-1浸渍到所制备的微乳液中，摇动90min，滤除余液，在70℃下干燥，在400℃下焙烧6h，称为半成品催化剂B10-1。
(3)称取氯化钯0.084g，溶于100mL去离子水中，调pH为1.8，再将半成品催化剂B10-1浸渍到已配制的Pd盐溶液中，浸渍60min后，100℃干燥，400℃条件下焙烧6小时，得到半成品催化剂C10-1。
(4)称取硝酸银0.158g，溶于57mL去离子水中，调pH值为3，将步骤(3)制备的半成品催化剂C10-1溶解于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，140℃干燥，在500℃焙烧6小时，得到所要的催化剂。
动态光散射测定步骤(1)制备的微乳液乳液的粒径是497.61nm，步骤(2)制备的微乳液乳液的粒径是495.33nm。
由原子吸收光谱法测定制备的催化剂，对比例1-10中，Pd含量为0.08％，Ni含量为2.5％，Cu含量为2.5％，Ag含量为0.10％。
催化剂的还原：
还原气体：氢气，还原空速：100h -1，温度200℃，保持4h。
实施例1-11
载体：采用市售双峰孔分布球形氧化铝载体，直径为3mm。经过1100℃焙烧4h后，双峰孔径分布范围在30-45nm和300-450nm，吸水率62％，比表面积为47m 2/g。称取该载体100g。
催化剂制备：
(1)称取氯化镍1.10g，硝酸铜1.47g，溶于70mL去离子水中，加正己烷35g，加CATB 21g，加正戊醇20g，充分搅拌形成微乳液，将称取的100g高温焙烧过的载体浸渍到所制备的微乳液中，摇动90min，滤除余液，在80℃下干燥，在500℃下焙烧5h，称为半成品催化剂A11。
(2)称取氯化钯0.067g，溶于100mL去离子水中，调pH为1.8，再将半成品催化剂A11浸渍到已配制的Pd盐溶液中，浸渍60min后，100℃干燥，500℃条件下焙烧5小时，得到半成品催化剂B11。
(3)称取硝酸银0.126g，溶于57mL去离子水中，调pH值为3，将步骤(2)制备的半成品催化剂B11溶解于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，140℃干燥，在500℃焙烧5小时，得到半成品催化剂C11。
(4)称取氯化钯0.018g，溶于70mL去离子水中，加正己烷35g，加CATB 21g，加正戊醇20g，充分搅拌形成微乳液，将称取的半成品催化剂C11浸渍到所制备的微乳液中，摇动90min，滤除余液，在80℃下干燥，在500℃下焙烧5h得到所要的催化剂。
动态光散射测定步骤(1)制备的微乳液的粒径是51.61nm，步骤(4)制备的微乳液的粒径是50.39nm。
由原子吸收光谱法测定制备的催化剂，实施例1-11中，Pd含量为0.05％，Ni含量为0.5％，Cu含量为0.5％，Ag含量为0.08％。
催化剂的还原：
使用前放置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在200℃温度，还原处理8h。
对比例1-11
载体及制备步骤与实施例1-11相同，区别是对比例1-11中微乳液粒径小于载体小孔的最大孔径。
催化剂制备：
(1)称取氯化镍1.10g，硝酸铜1.47g，溶于70mL去离子水中，加正己烷37g，加CATB 30g，加正戊醇30g，充分搅拌形成微乳液，将称取的100g高温焙烧过的载体浸渍到所制备的微乳液中，摇动90min，滤除余液，在80℃下干燥，在500℃下焙烧5h，称为半成品催化剂A11-1。
(2)称取氯化钯0.067g，溶于100mL去离子水中，调pH为1.8，再将半成品催化剂A11-1浸渍到已配制的Pd盐溶液中，浸渍60min后，100℃干燥，500℃条件下焙烧5小时，得到半成品催化剂B11-1。
(3)称取硝酸银0.126g，溶于57mL去离子水中，调pH值为3，将步骤(2)制备的半成 品催化剂B11-1溶解于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，140℃干燥，在500℃焙烧5小时，得到半成品催化剂C11-1。
(4)称取氯化钯0.018g，溶于70mL去离子水中，加正己烷37g，加CATB 30g，加正戊醇30g，充分搅拌形成微乳液，将得到半成品催化剂C11-1浸渍到所制备的微乳液中，摇动90min，滤除余液，在80℃下干燥，在500℃下焙烧5h，得到所要的催化剂。
动态光散射测定步骤(1)制备的微乳液的粒径是30.87nm，步骤(4)制备的微乳液的粒径是30.24nm。
由原子吸收光谱法测定制备的催化剂，对比例1-11中，Pd含量为0.05％，Ni含量为0.5％，Cu含量为0.5％，Ag含量为0.08％。
催化剂的还原：
使用前放置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在200℃温度，还原处理8h。
实施例1-12
催化剂制备：
称取市售双峰孔分布球形氧化铝载体，直径为4mm。经过1088℃焙烧4h后，孔径分布范围分别是20-46nm和85-350nm，吸水率为55％，比表面积为39.29m 2/g，称取该载体100g。
(1)称取0.08g氯化钯盐溶于140mL去离子水中，调pH为2，再将已制备的载体加入Pd的盐溶液中，浸渍吸附50min后，110℃干燥，550℃条件下焙烧5h，得到所需的半成品催化剂A12。
(2)称取硝酸镍4.93g，硝酸铜1.47g，溶于71.5g水中，加入27.5g正己烷，13.80g CTAB，12.73g正戊醇充分搅拌形成微乳液，将半成品催化剂A12加入到制好的微乳液中浸渍80min后，滤除余液，用去离子水洗剂至中性。在80℃下干燥，在550℃下焙烧5小时。得到半成品催化剂B12。
(3)称取硝酸钯0.021g，溶于71.5g水中，加入27.5g正己烷，13.80g CTAB，12.73g正戊醇充分搅拌形成微乳液，将半成品催化剂B12加入到制好的微乳液中浸渍80min后，滤除余液，用去离子水洗剂至中性。在80℃下干燥，在450℃下焙烧6小时，得到半成品催化剂C12。
(4)取49.5mL去离子水，加入0.291g硝酸银使其完全溶解，调pH为2，将半成品催化剂C12浸渍在所制备的溶液中，摇动10min，在100℃干燥，550℃焙烧6小时，即制得所要的催化剂。
动态光散射法测定步骤(2)制备的微乳液的粒径为98.78nm，步骤(3)制备的微乳液的粒径为99.31nm。
用原子吸收光谱法测定元素含量，得到实施例1-12所制备的催化剂，Pd含量为0.057％，Ni含量为1.57％，Cu含量为0.5％，Ag含量为0.18％。
催化剂的还原：
还原气体：氢气，还原空速：100h -1，温度150℃，保持4h。
对比例1-12
催化剂载体实施例1-12相同，催化剂制备条件也相同，差别是Cu的负载量低于Ni的1/10。
称取市售双峰孔分布球形氧化铝载体，直径为4mm。经过1090℃焙烧4h后，孔径分布范围分别是20-46nm和85-350nm，吸水率为55％，比表面积为39.29m 2/g，称取该载体100g。
(1)称取0.08g氯化钯盐溶于140mL去离子水中，调pH为2，再将已制备的载体加入Pd 的盐溶液中，浸渍吸附50min后，110℃干燥，550℃条件下焙烧5h，得到所需的半成品催化剂A12-1。
(2)称取硝酸镍4.93g，硝酸铜0.294g，溶于71.5g水中，加入27.5g正己烷，13.80g CTAB，12.73g正戊醇充分搅拌形成微乳液，将半成品催化剂A12-1加入到制好的微乳液中浸渍80min后，滤除余液，用去离子水洗剂至中性。在80℃下干燥，在550℃下焙烧5小时。得到半成品催化剂B12-1。
(3)称取硝酸钯0.021g，溶于71.5g水中，加入27.5g正己烷，13.80g CTAB，12.73g正戊醇充分搅拌形成微乳液，将半成品催化剂B12-1加入到制好的微乳液中浸渍80min后，滤除余液，用去离子水洗剂至中性。在80℃下干燥，在450℃下焙烧6小时，得到半成品催化剂C12-1。
(4)取49.5mL去离子水，加入0.291g硝酸银使其完全溶解，调pH为2，将半成品催化剂C12-1浸渍在所制备的溶液中，摇动10min，在100℃干燥，550℃焙烧6小时，即制得所要的催化剂。
动态光散射法测定步骤(2)制备的微乳液的粒径为98.78nm，步骤(3)制备的微乳液的粒径为99.31nm。
用原子吸收光谱法测定元素含量，得到对比例1-12所制备的催化剂，Pd含量为0.057％，Ni含量为1.57％，Cu含量为0.1％，Ag含量为0.18％。
催化剂的还原：
还原气体：氢气，还原空速：100h -1，温度150℃，保持4h。
实施例1-13
催化剂制备：
称取市售双峰孔分布球形氧化铝载体，直径为4mm。经过1112℃焙烧4h后，孔径分布范围分别是26-47nm和95-450nm，吸水率为55％，比表面积为25.45m 2/g，称取该载体100g。
(1)称取0.075g硝酸钯盐溶于44mL去离子水中，调pH为2，将配制的溶液喷淋在已制备的载体上，待溶液全部吸收后，100℃干燥，500℃条件下焙烧4h，得到半成品催化剂A13。
(2)称取无水硝酸镍12.46g，硝酸铜2.94g溶于70.00g水中，加入35.00g环己烷，21.00g TritonX-100，20.80g正丁醇充分搅拌形成微乳液。将半成品催化剂A13加入到制好的微乳液中浸渍3小时后，滤除余液，在60℃下干燥，在500℃下焙烧4h。得到半成品催化剂B13。
(3)称取硝酸钯0.0416g溶于70.00g水中，加入35.00g环己烷，21.00g TritonX-100，20.80g正丁醇充分搅拌形成微乳液。将半成品催化剂B13加入到制好的微乳液中浸渍3小时后，滤除余液，在60℃下干燥，在550℃下焙烧4小时，得到半成品催化剂C13。
(4)取60mL去离子水，加入0.21g硝酸银使其完全溶解，调pH为4，将制备的溶液喷淋在半成品催化剂C13上，待溶液全部吸收后，在110℃干燥，550℃焙烧4小时以上。制得所要的催化剂。
动态光散射法测定(2)制备的微乳液的粒径为50.68nm，步骤(3)制备的微乳液的粒径为50.32nm，
用原子吸收光谱法测定元素含量，得到实施例1-13所制备的催化剂，Pd含量为0.054％，Ni含量为4％，Cu含量为1％，Ag含量0.13％。
催化剂的还原：
还原气体：氢气，还原空速：100h -1，温度200℃，保持8h。
对比例1-13
采用与实施例1-13相同的载体，活性组分加入量含量相同，不同的是，Pd全部采用乳液法负载。
催化剂制备：
称取市售双峰孔分布球形氧化铝载体，直径为4mm。经过1112℃焙烧4h后，孔径分布范围分别是26-47nm和95-450nm，吸水率为55％，比表面积为25.45m 2/g，称取该载体100g。
(1)称取无水硝酸镍12.46g，硝酸铜2.94g溶于70.00g水中，加入35.00g环己烷，21.00g TritonX-100，20.80g正丁醇充分搅拌形成微乳液。将半成品催化剂A13加入到制好的微乳液中浸渍3小时后，滤除余液，在60℃下干燥，在500℃下焙烧4h。得到半成品催化剂A13-1。
(2)称取硝酸钯0.1166g溶于70.00g水中，加入35.00g环己烷，21.00g TritonX-100，20.80g正丁醇充分搅拌形成微乳液。将半成品催化剂A13-1加入到制好的微乳液中浸渍3小时后，滤除余液，在60℃下干燥，在550℃下焙烧4小时，得到半成品催化剂B13-1。
(3)取60mL去离子水，加入0.21g硝酸银使其完全溶解，调pH为4，将制备的溶液喷淋在半成品催化剂C13-1上，待溶液全部吸收后，在110℃干燥，550℃焙烧4小时以上。制得所要的催化剂。
动态光散射法测定(1)制备的微乳液的粒径为50.68nm，步骤(2)制备的微乳液的粒径为50.34nm。
用原子吸收光谱法测定元素含量，得到对比例1-13所制备的催化剂，Pd含量为0.054％，Ni含量为4％，Cu含量为1％，Ag含量0.13％。
催化剂的还原：
还原气体：氢气，还原空速：100h -1，温度200℃，保持8h。
实施例1-14
催化剂制备：
称取市售双峰孔分布球形氧化铝载体，直径为4mm。经过1088℃焙烧4h后，孔径分布范围分别是20-46nm和85-350nm，吸水率为55％，比表面积为40.23m 2/g，称取该载体100g。
(1)称取无水硝酸镍4.93g，硝酸铜1.47g，溶于70mL去离子水中，加正己烷26.92g，加CATB 16.16g，加正戊醇16.00g，充分搅拌形成微乳液，将已制备的载体加入到制好的微乳液中浸渍80min后，滤除余液，在70℃下干燥，在500℃下焙烧4小时。得到半成品催化剂A14。
(2)称取0.07g硝酸钯溶于140mL去离子水中，调pH为2，再将已制备的半成品催化剂A14加入Pd的盐溶液中，浸渍吸附50min后，110℃干燥，550℃条件下焙烧4h，得到所需的半成品催化剂B14。
(3)称取硝酸钯0.023g，溶于70mL去离子水中，加正己烷26.92g，加CATB 16.16g，加正戊醇16.00g，充分搅拌形成微乳液，将半成品催化剂B14加入到制好的微乳液中浸渍80min后，滤除余液，在70℃下干燥，在550℃下焙烧4小时，得到半成品催化剂C14。
(4)取49.5mL去离子水，加入0.291g硝酸银使其完全溶解，调pH为2，将半成品催化剂C14浸渍在所制备的溶液中，摇动10min，在100℃干燥，550℃焙烧4小时，即制得所要的催化剂。
动态光散射法测定步骤(1)制备的微乳液的粒径为80.28nm，步骤(3)制备的微乳液的粒径为80.56nm。
用原子吸收光谱法测定元素含量，得到实施例1-14所制备的催化剂，Pd含量为0.043％，Ni含量为1.57％，Cu含量为0.5％，Ag含量为0.18％。
催化剂的还原：
还原气体：氢气，还原空速：100h -1，温度150℃，保持4h。
对比例1-14
催化剂制备：
使用与实施例1-14相同的载体，制备条件与实施例1-14相同，区别是溶液法负载铜镍。
(1)称取无水硝酸镍4.93g，硝酸铜1.47g，溶于71.5g水中，充分搅拌，将已制备的载体加入到制好的溶液中浸渍80min后，滤除余液，在70℃下干燥，在500℃下焙烧4小时。得到半成品催化剂A14-1。
(2)称取0.07g硝酸钯溶于140mL去离子水中，调pH为2，再将已制备的半成品催化剂A14-1加入Pd的盐溶液中，浸渍吸附50min后，110℃干燥，550℃条件下焙烧4h，得到所需的半成品催化剂B14-1。
(3)称取硝酸钯0.023g，溶于70mL去离子水中，加正己烷26.92g，加CATB 16.16g，加正戊醇16.00g，充分搅拌形成微乳液，将半成品催化剂B14-1加入到制好的微乳液中浸渍80min后，滤除余液，在70℃下干燥，在550℃下焙烧4小时，得到半成品催化剂C14-1。
(4)取49.5mL去离子水，加入0.291g硝酸银使其完全溶解，调pH为2，将半成品催化剂C14-1浸渍在所制备的溶液中，摇动10min，在100℃干燥，550℃焙烧4小时，即制得所要的催化剂。
动态光散射法测定步骤(3)制备的微乳液的粒径为80.56nm。
用原子吸收光谱法测定元素含量，得到对比例1-14所制备的催化剂，Pd含量为0.043％，Ni含量为1.57％，Cu含量为0.5％，Ag含量为0.18％。
催化剂的还原：
还原气体：氢气，还原空速：100h -1，温度150℃，保持4h。
实施例1-15
催化剂制备：
称取市售双峰孔分布球形氧化铝载体，直径为4mm。经过1092℃焙烧4h后，孔径分布范围分别是20-45nm和85-350nm，吸水率为55％，比表面积为39.47m 2/g，称取该载体100g。
(1)称取无水硝酸镍4.93g，硝酸铜1.47g，溶于71.5g水中，加入27.5g异戊烷，13.75g CTAB，12.60g正己醇充分搅拌形成微乳液，将已制备的载体加入到制好的微乳液中浸渍80min后，滤除余液，在70℃下干燥，在500℃下焙烧4小时。得到半成品催化剂A15。
(2)称取0.064g硝酸钯溶于140mL去离子水中，调pH为2，再将已制备的半成品催化剂A15加入Pd的盐溶液中，浸渍吸附50min后，110℃干燥，550℃条件下焙烧6h，得到所需的半成品催化剂B15。
(3)称取硝酸钯0.022g，溶于71.5g水中，加入27.5g异戊烷，13.75g CTAB，12.60g正己醇充分搅拌形成微乳液，将半成品催化剂B15加入到制好的微乳液中浸渍80min后，滤除余液，在70℃下干燥，在550℃下焙烧4小时，得到半成品催化剂C15。
(4)取49.5mL去离子水，加入0.291g硝酸银使其完全溶解，调pH为2，将半成品催化剂C15浸渍在所制备的溶液中，摇动10min，在100℃干燥，500℃焙烧6小时，即制得所要的催化剂。
动态光散射法测定步骤(1)、(3)制备的微乳液的粒径为101.39nm。
用原子吸收光谱法测定元素含量，得到实施例1-15所制备的催化剂，其中Pd含量为0.04％， Ni含量为1.57％，Cu含量为0.5％，Ag含量为0.18％。
催化剂的还原：
还原气体：氢气，还原空速：100h -1，温度150℃，保持4h。
对比例1-15
采用单峰孔径分布载体
催化剂制备：称取市售单峰孔分布球形氧化铝载体，直径为4mm。经过1092℃焙烧4h后，孔径分布范围是20-45nm，为单孔径分布，吸水率为55％，比表面积为39.47m 2/g，称取该载体100g。
(1)称取无水硝酸镍4.93g，硝酸铜1.47g，溶于71.5g水中，加入27.5g异戊烷，13.75g CTAB，12.60g正己醇充分搅拌形成微乳液，将已制备的载体加入到制好的微乳液中浸渍80min后，滤除余液，用去离子水洗剂至中性。在70℃下干燥，在500℃下焙烧4小时。得到半成品催化剂A15-1。
(2)称取0.064g硝酸钯溶于140mL去离子水中，调pH为2，再将已制备的半成品催化剂A15-1加入Pd的盐溶液中，浸渍吸附50min后，110℃干燥，550℃条件下焙烧6h，得到所需的半成品催化剂B15-1。
(3)称取硝酸钯0.022g，溶于71.5g水中，加入27.5g异戊烷，13.75g CTAB，12.60g正己醇充分搅拌形成微乳液，将半成品催化剂B15-1加入到制好的微乳液中浸渍80min后，滤除余液，用去离子水洗剂至中性。在70℃下干燥，在550℃焙烧4小时，得到半成品催化剂C15-1。
(4)取49.5mL去离子水，加入0.291g硝酸银使其完全溶解，调pH为2，将半成品催化剂C15-1浸渍在所制备的溶液中，摇动10min，在100℃干燥，500℃焙烧6小时，即制得所要的催化剂。
动态光散射法测定步骤(1)、(3)制备的微乳液的粒径为101.39nm。
用原子吸收光谱法测定元素含量，得到对比例1-15所制备的催化剂，Pd含量为0.034％，Ni含量为0.32％，Cu含量为0.11％，Ag含量为0.18％。
催化剂的还原：
还原气体：氢气，还原空速：100h -1，温度150℃，保持4h。
催化剂应用于碳二后加氢反应的性能
评价方式：催化剂在固定床单段反应器的装填量为100mL(记录重量)，填料50mL，反应物料空速：5000/h，操作压力2.0MPa，氢炔比1.15，反应器入口温度50℃。评价结果的计算方法如表1-2所示。
表1-2评价结果的计算方法
Figure PCTCN2021086214-appb-000002
初始选择性为反应器投料开始，24小时测量得到的选择性。
初始活性为反应器投料开始，24小时测量得到的活性(乙炔转化率)
反应物料组成见表1-3。
表1-3反应物料组成
反应物料 C 2H 2 C 2H 4 C 2H 6 C 3-C 4
含量(v/v％) 1.5 86 12 3×10 -3
催化剂评价结果见表1-4。
表1-4催化剂评价结果
Figure PCTCN2021086214-appb-000003
由表1-2和表1-3催化剂评价结果对比可以看出：
与实施例1-1相比，对比例1-1，没有负载Cu，还原温度为200℃，虽然初始乙炔转化率及 选择性与相应的实施例相比基本相同。但1000小时后，则明显低于实施例，表明Cu的负载或催化剂还原温度对提高抗结焦性能是重要的。或可能在200℃的还原温度下，具有饱和加氢功能的活性中心，没有发挥应有的作用。
对比例1-2与实施例1-2相比，对比例1-2中Cu的负载采用溶液法，Cu在载体呈高度均匀分散，没有起到有效降低Ni还原温度的作用，随反应进行，催化剂结焦量明显增加，与实施例1-2催化剂的差别也愈来愈明显。
对比例1-3与实施例1-3相比，Pd采用的是溶液法负载，Pd进入了小孔，其活性很高，对比例1-3初期乙炔转化率达到100％。在大孔中没有Pd的情况下，对比例1-3在150℃下，Ni-Cu没有还原，1000小时后结焦量很大，催化剂性能下降幅度大；
对比例1-4与实施例1-4相比，是不负载Ni，由于对绿油的饱和加氢作用降低，1000小时后催化剂的结焦量大，性能下降幅度大。
对比例1-5中，Ni含量降低到0.3％，在该含量和反应条件下，Ni-Cu活性中心的加氢活性已经不足，不能对选择加氢副产物进行饱和加氢，1000小时后，与实施例1-5相比，催化剂性能下降较多。
对比例1-6的催化剂与实施例1-6制备条件相同，只是微乳液法负载的Pd含量明显降低。由于Pd含量降低，已经不能起到将显著降低Ni还原温度的作用，致使Ni不具有明显的对副产物饱和加氢的作用，1000小时后性能差距也较明显。
对比例1-7与实施例1-7相比，比表面积过大，催化剂上的Pd活性中心尺度过小，虽然初始选择性较好，初活性明显不足。同样由于比表面积过大，Ni-Cu的活性中心活性不足，1000小时后结焦量也明显高于实施例1-7。
在实施例1-8中，制备催化剂时先负载Ag，Ag与Pd形成了合金，该合金结构中Ag的含量较高，降低了选择加氢的活性，因此其初始活性较实施例1-7差。
对比例1-8中，微乳液负载Pd时，微乳液的粒径大于载体的最大孔径，使Pd不能进入载体的孔中，只能部分负载在催化剂的外表面，部分随溶液流失，虽然初始选择性较好，但Pd不能有效的与Ni-Cu形成时合金，因此也不能有效降低Ni-Cu的还原温度。不能对绿油分子进行有效的饱和加氢，因此，1000小时后，对比例1-8中催化剂性能明显较实施例1-8中催化剂性能差。
在实施例1-9中，负载Pd时的微乳液粒径是398nm，负载Ni-Cu时微乳液粒径是621nm，该粒径大于载体的最大孔径，含Ni-Cu的微乳液不能进入载体的孔中，只能随微乳液部分吸附在载体的表面，部分流失。吸附的部分因不能与Ni-Cu形成合金，在还原温度为150℃时，部分Ni-Cu不能得到有效还原，不能对绿油分子进行有效的饱和加氢，因此，1000小时后，对比例1-9中催化剂反应效果较实施例差。
对比例1-10中，催化剂的比表面面积小，相同负载量时，Pd活性中心的尺度过大，导致活性高而选择性差，而且Ni-Cu的活性中心尺度更大，不仅具有对副产物的饱和加氢功能，也具有了对乙烯的加氢作用，导致乙烯加氢选择性变差。从结焦量来看，对比例1-10在1000小时后虽然结焦量更少，但选择性明显低于实施例。
在对比例1-11中，微乳液负载各组分时，其乳液的孔径小于载体小孔的最大孔径，使各组分均负载在小孔中。这些组分均具有加氢活性，集中聚焦在小孔中，使小孔中加氢活性中心活性过高，初始选择性很差，而且副产物的生成加剧。由于Ni-Cu活性中心的分布位置不合理，导致生成的副产物不能被加氢饱和，1000小时后结焦较大，活性、乙烯选择性均较实施例差。
对比例1-12中，Cu的负载量过少，虽然在大孔中Pd、Ni、Cu形成了合金，由于Cu较Ni易还原，可以起到促进Ni还原的作用。但该对比例中Cu含量过低，不能起到促进Ni还原的作用，1000小时后催化剂结焦也较严重。
对比例1-13中，Pd全部采用微乳液法负载，使Pd没有负载在20-30nm的最佳孔径内，而且全部Pd与Ni、Cu形成的合金，其活性中心位于较大的孔中，单个活性中心的活性好，本征选择性差，受扩散影响，大孔中的活性中心不易与乙炔分子相遇，故初活性不好，选择性也差。
在对比例1-14中，Ni、Cu采用溶液法负载，其在载体中呈均匀分布，难以形成具有较好活性的催化反应中心，部分与溶液法负载的Pd在载体外层形成活性中心，但Ni、Cu的存在，并不利于提高Pd活性中心的选择性，反而起到负面影响。因此，该催化剂初活性尚可，初期选择性较差。由于没有了对加氢副产物饱和加氢的活性中心，1000小时后结焦量很大，性能下降很严重。
对比例1-15中用采用的是单孔径分布的载体，制备的微乳液粒径大于载体的最大孔径，导致乳液不能进入载体中，部分活性组分只能分布于载体的最外层，部分不能有效负载而流失，虽在外表面具有一定的饱和加氢作用，但催化效果仍较实施例1-15差。
实施例2-1：
催化剂制备：
市售双峰孔分布球形氧化铝载体，直径为4mm。经过1058℃焙烧4h后，孔径分布范围分别是15-32nm和80-204nm，吸水率60％，比表面积为47.28m 2/g，称取该载体100g。
(1)称取无水硝酸镍15.94g，硝酸铜1.47g溶于72mL去离子水中，加正己烷36g，加CATB 21.6g，加正戊醇21.50g，充分搅拌形成微乳液。将载体加入到制好的微乳液中浸渍30min后，滤除余液，在40℃下干燥，在400℃下焙烧6h。得到半成品催化剂A。
(2)称取0.079g氯化钯溶于120mL去离子水中，调pH为1.5，再将半成品催化剂A加入Pd的盐溶液中，浸渍吸附30min后，100℃干燥，400℃条件下焙烧6h，得到半成品催化剂B。
(3)称取硝酸钯0.071g溶于72mL去离子水中，加正己烷36g，加CATB 21.6g，加正戊醇21.50g，充分搅拌形成微乳液，将半成品催化剂B加入到制好的微乳液中浸渍30min后，滤除余液，在40℃下干燥，在400℃下焙烧6h，即制得所要的催化剂。
动态光散射法测定步骤(1)制备的微乳液的粒径为50.29nm，步骤(3)制备的微乳液的粒径为51.45nm。
用原子吸收光谱法测定元素含量，得到实施例2-1所制备的催化剂中，Pd的含量为0.08％，Ni含量为5.0％，Cu含量为0.5％。
催化剂的还原：还原气体：氢气，还原空速：100h -1，温度150℃，保持8h。
对比例2-1A：
市售双峰孔分布球形氧化铝载体，直径为4mm。经过1058℃焙烧4h后，孔径分布范围分别是15-32nm和80-204nm，吸水率60％，比表面积为47.28m 2/g，称取该载体100g。
(1)称取无水硝酸镍15.94g，溶于72mL去离子水中，加正己烷36g，加CATB 21.6g，加正戊醇21.50g，充分搅拌形成微乳液。将载体加入到制好的微乳液中浸渍30min后，滤除余液，在40℃下干燥，在400℃下焙烧6h。得到半成品催化剂A1-1。
(2)称取0.079g氯化钯溶于120mL去离子水中，调pH为1.5，再将半成品催化剂A1-1加入Pd的盐溶液中，浸渍吸附30min后，100℃干燥，400℃条件下焙烧6h，得到半成品催化剂B1-1。
(3)称取硝酸钯0.071g溶于72mL去离子水中，加正己烷36g，加CATB 21.6g，加正戊醇 21.50g，充分搅拌形成微乳液，将半成品催化剂B1-1加入到制好的微乳液中浸渍30min后，滤除余液，在40℃下干燥，在400℃下焙烧6h，即制得所要的催化剂。
动态光散射法测定步骤(1)制备的微乳液的粒径为50.31nm，步骤(3)制备的微乳液的粒径为51.38nm。
用原子吸收光谱法测定元素含量，得到对比例2-1A所制备的催化剂中，Pd的含量为0.08％，Ni含量为5.2％。
催化剂的还原：还原气体：氢气，还原空速：100h -1，温度150℃，保持8h。
对比例2-1B
市售双峰孔分布球形氧化铝载体，直径为4mm。经过1058℃焙烧4h后，孔径分布范围分别是15-32nm和80-204nm，吸水率60％，比表面积为47.28m 2/g，称取该载体100g。
(1)称取硝酸铜1.47g溶于72mL去离子水中，加正己烷36g，加CATB 21.6g，加正戊醇21.50g，充分搅拌形成微乳液。将载体加入到制好的微乳液中浸渍30min后，滤除余液，在40℃下干燥，在400℃下焙烧6h，得到半成品催化剂A1-2。
(2)称取0.079g氯化钯溶于120mL去离子水中，调pH为1.5，再将半成品催化剂A1-2加入Pd的盐溶液中，浸渍吸附30min后，100℃干燥，400℃条件下焙烧6h，得到半成品催化剂B1-2。
(3)称取硝酸钯0.071g溶于72mL去离子水中，加正己烷36g，加CATB 21.6g，加正戊醇21.50g，充分搅拌形成微乳液，将半成品催化剂B1-2加入到制好的微乳液中浸渍30min后，滤除余液，在40℃下干燥，在400℃下焙烧6h，即制得所要的催化剂。
动态光散射法测定步骤(1)制备的微乳液的粒径为50.31nm，步骤(3)制备的微乳液的粒径为51.49nm。
用原子吸收光谱法测定元素含量，得到对比例2-1B所制备的催化剂中，Pd的含量为0.08％，Cu含量为0.52％。
催化剂的还原：还原气体：氢气，还原空速：100h -1，温度150℃，保持8h。
实施效果 加氢反应条件
二段反应器工艺，物料空速4000/h，操作压力3.0MPa，催化剂装填量200mL。反应器条件如表2-1所示。反应结果如表2-2所示。
物料组成：一段反应器入口乙炔：1.8％(v/v)，乙烯80％(v/v)。
表2-1各段反应器条件
Figure PCTCN2021086214-appb-000004
表2-2反应结果
Figure PCTCN2021086214-appb-000005
Figure PCTCN2021086214-appb-000006
从表2-2的评价结果看，在24小时内，对比例2-1A和1B中反应的活性选择性与实施例2-1相同，但500小时和1000小时后，对比例2-1A和1B中反应的活性选择性与实施例2-1差距逐渐拉大，原因是Ni和Cu缺失后，对加氢副产物饱和加氢活性不足，导致催化剂结焦严重。活性选择性下降。反应器出口乙炔超过要求值，乙烯质量不合格。
实施例2-2
催化剂制备：
称取市售双峰孔分布球形氧化铝载体，直径为4mm。经过1115℃焙烧4h后，孔径分布范围分别是30-43nm和112-496nm，吸水率为50％，比表面积为21.74m 2/g，称取该载体100g。
(1)称取无水硝酸镍3.19g，硝酸铜2.95g溶于80g水中，加入26.67g环己烷，4.0g TritonX-100，3.50g正丁醇充分搅拌形成微乳液。将载体加入到制好的微乳液中浸渍4小时后，滤除余液，在80℃下干燥，在600℃下焙烧4h得到所需的半成品催化剂A2。
(2)称取硝酸钯0.043g，溶于80g水中，加入26.67g环己烷，4.0g TritonX-100，3.50g正丁醇，充分搅拌形成微乳液。将步骤(1)制备的半成品A2浸渍到制备的微乳液中浸渍4小时后，滤除余液，在80℃下干燥，在600℃焙烧4h，制得半成品催化B2。
(3)称取0.067g氯化钯盐溶于120mL去离子水中，调pH为2.5，再将半成品催化剂B2加入Pd的盐溶液中，浸渍吸附1小时后，120℃干燥，600℃条件下焙烧4h，得到成品催化剂。
用动态光散射法(激光光散射法)测定，步骤(1)制备的微乳液的粒径为487.63nm，步骤(2)制备的微乳液的粒径为486.19nm。
用原子吸收光谱法测定元素含量，得到实施例2-2所制备的催化剂中，其中Pd含量为0.065％，Ni含量为1.1％，Cu含量为1.1％。
催化剂的还原：还原气体：氢气，还原空速：100h -1，温度200℃，保持8h。
对比例2-2
催化剂制备：
称取市售球形单峰孔氧化铝载体，直径为4mm。经过1115℃焙烧4h后，孔径分布范围是32-88nm，吸水率为50％，比表面积为21.74m 2/g，称取该载体100g。
(1)称取无水硝酸镍3.19g，硝酸铜2.95g溶于80g水中，加入26.67g环己烷，4.0g TritonX-100，3.50g正丁醇充分搅拌形成微乳液。将制备的载体加入到制好的微乳液中浸渍4小时后，滤除余液，在80℃干燥，在600℃焙烧4h得到所需的半成品催化剂A2-1。
(2)称取硝酸钯0.043g，溶于80g水中，加入26.67g环己烷，4.0g TritonX-100，3.50g正丁醇，充分搅拌形成微乳液。将步骤(1)制备的半成品A2-1浸渍到制备的微乳液中浸渍4小时后，滤除余液，用去离子水洗涤至中性。在80℃下干燥，在600℃下焙烧4h，制得半成品催 化剂B2-1。
(3)称取0.067g氯化钯盐溶于120mL去离子水中，调pH为2.5，再将半成品催化剂B2-1加入Pd的盐溶液中，浸渍吸附1小时后，120℃干燥，600℃条件下焙烧4h，得到成品催化剂。
动态光散射法测定步骤(1)制备的微乳液的粒径为487.65nm，步骤(2)制备的微乳液的粒径为486.22nm。
用原子吸收光谱法测定元素含量，得到对比例2-2所制备的催化剂中，Pd含量为0.06％，Ni含量为1.0％，Cu含量为1.1％。
催化剂的还原：还原气体：氢气，还原空速：100h -1，温度200℃，保持8h。
实施效果
加氢反应条件1
三段反应器工艺，物料空速11000/h，操作压力1.5MPa，催化剂装填量300mL。反应器条件如表2-3所示。反应结果如表2-4所示。
物料组成：一段反应器入口乙炔：2.5％(v/v)，乙烯93％(v/v)。
表2-3各段反应器条件
Figure PCTCN2021086214-appb-000007
表2-4反应结果
Figure PCTCN2021086214-appb-000008
加氢反应条件2
单段反应器工艺，物料空速4000/h，操作压力1.6MPa，催化剂装填量200mL。
反应器入口物料：乙炔0.2％(v/v)，乙烯65％(v/v)，C3 0.8％(v/v)。反应器条件如表2-5所示。
表2-5反应器条件
  500小时前 500-1000小时 1000-2000小时
氢/炔 1.5 1.8 2.0
入口温度 40 55 65
表2-6反应结果
Figure PCTCN2021086214-appb-000009
从表2-4的结果看，反应初期对比例2-2与实施例2-2已经有区别，原因是对比例2-2中的载体为单孔径分布，没有大孔，导致微乳液中的活性组分不能进入载体或半成品催化剂的孔中，完全在载体的外表面，并堵塞载体的孔道，导致催化剂活性的下降。
随反应进行，生成的副产物在催化剂壳层内累积，并形成结焦，对比例2-2中的催化剂性能逐渐下降。位于催化剂表面的活性组分虽然有一定的对副产物饱和加氢的功能，但只能使部分加氢副产物饱和加氢，孔的堵塞现象愈来愈严重，催化剂性能下降明显。
表2-6为单段反应器结果，虽然反应器入口乙炔含量较低，但碳三含量很高也促使加氢反应中形成较多的副产物，直至2000小时，实施例的反应器出口乙炔含量始终为0，而对比例中，由于仅少量Ni-Cu吸附在催化剂外表面，不能对大部分地加氢副产物进行饱和加氢，致使副产物不断累积而结焦，催化剂选择性下降而不能有效脱除乙炔。1000小时后反应结果已经不合格。
实施例2-3
催化剂制备：
称取市售双峰孔分布球形氧化铝载体，直径为4mm。经过1092℃焙烧4h后，孔径分布范围分别是20-46nm和85-350nm，吸水率为58％，比表面积为39.58m 2/g，称取该载体100g。
(1)称取0.051g氯化钯盐溶于140mL去离子水中，调pH为2，再将载体加入Pd的盐溶液中，浸渍吸附50min后，110℃干燥，550℃条件下焙烧5h，得到所需的半成品催化剂A3。
(2)称取无水硝酸镍1.59g，硝酸铜1.47g，溶于71.5g水中，加入28.80g正己烷，17.16g CTAB，15.6g正戊醇充分搅拌形成微乳液，将半成品催化剂A3加入到制好的微乳液中浸渍80min后，滤除余液，用去离子水洗剂至中性。在80℃下干燥，在550℃下焙烧5小时，得到半成品催化剂B3。
(3)称取硝酸钯0.0107g，溶于71.5g水中，加入28.80g正己烷，17.16g CTAB，15.6g正戊醇充分搅拌形成微乳液，将半成品催化剂B3加入到制好的微乳液中浸渍80min后，滤除余液，在80℃下干燥，在550℃下焙烧5小时，得到半成品催化剂C3。
(4)取49.5mL去离子水，加入0.126g硝酸银使其完全溶解，调pH为2，将半成品催化剂C3浸渍在所制备的溶液中，摇动10min，在100℃干燥，500℃焙烧5小时，即制得所要的催化剂。
动态光散射法测定步骤(2)制备的微乳液的粒径为78.38nm，步骤(3)制备的微乳液的粒径为77.64nm。
用原子吸收光谱法测定元素含量，得到实施例2-3所制备的催化剂中Pd含量为0.035％，Ni含量为0.5％，Cu含量为0.5％，Ag含量为0.08％。
催化剂的还原：还原气体：氢气，还原空速：100h -1，温度150℃，保持4h。
对比例2-3
催化剂制备：
称取市售双峰孔分布球形氧化铝载体，直径为4mm。经过1092℃焙烧4h后，孔径分布范围分别是20-46nm和85-350nm，吸水率为55％，比表面积为39.58m 2/g，称取该载体100g。
(1)称取0.059g氯化钯盐溶于140mL去离子水中，调pH为2，再将载体加入Pd的盐溶液中，浸渍吸附50min后，110℃干燥，550℃条件下焙烧5h，得到所需的半成品催化剂A3-1。
(2)称取无水硝酸镍1.59g，硝酸铜1.47g，溶于71.5g水中，加入28.80g正己烷，17.16g CTAB，15.6g正戊醇充分搅拌形成微乳液，将半成品催化剂A3-1加入到制好的微乳液中浸渍80min后，滤除余液，用去离子水洗剂至中性。在80℃下干燥，在550℃下焙烧5小时，得到半成品催化剂B3-1。
(3)取49.5mL去离子水，加入0.126g硝酸银使其完全溶解，调pH为2，将半成品催化剂B3-1浸渍在所制备的溶液中，摇动10min，在100℃干燥，500℃焙烧5小时，即制得所要的催化剂。
动态光散射法测定步骤(2)制备的微乳液的粒径为78.45nm。
用原子吸收光谱法测定元素含量，得到对比例2-3A所制备的催化剂中Pd含量为0.035％，Ni含量为0.5％，Cu含量为0.5％，Ag含量为0.08％。
催化剂的还原：还原气体：氢气，还原空速：100h -1，温度150℃，保持4h。
加氢反应条件：
一段反应器工艺，物料空速2000/h，操作压力3.0MPa，催化剂装填量，200mL。反应器条件如表2-7所示。反应结果如表2-8所示。
物料组成：
一段反应器入口物料：乙炔0.5％(v/v)，乙烯70％(v/v)，碳三0.8％(v/v)。
表2-7反应器条件
  500小时前 500小时后
氢/炔 1.5 1.8
入口温度 55 65
表2-8反应结果
Figure PCTCN2021086214-appb-000010
从表2-8可以看出，在对比例2-3A中，1000小时后反应器出口乙炔严重超标，表明催化剂性能已经完全不合格。主要是由于乳液法未负载钯，镍和铜的氧化物在150℃没有还原为金属态，因而没有对副产物的重馏分饱和加氢的作用，导致催化剂结焦较快。
实施例2-4
载体：采用市售双峰孔分布球形氧化铝载体，直径为3mm。经过1078℃焙烧4h后，双峰 孔径分布范围在20-35nm和90-250nm，吸水率57％，比表面积为44.82m 2/g。称取该载体100g。
催化剂制备：
(1)称取无水硝酸镍3.18g，无硝酸铜0.74g，溶于70mL去离子水中，加正己烷35g，加CATB 21g，加正戊醇20g，充分搅拌形成微乳液，将称取的100g高温焙烧过的载体浸渍到所制备的微乳液中，摇动90min，滤除余液，在60℃下干燥，在500℃下焙烧6h，称为半成品催化剂A4。
(2)称取氯化钯0.069g，溶于100mL去离子水中，调pH为1.8，再将半成品催化剂A4浸渍到已配制的Pd盐溶液中，浸渍60min后，100℃干燥，500℃条件下焙烧6小时，得到半成品催化剂B4。
(3)称取硝酸银0.236g，溶于57mL去离子水中，调pH值为3，将步骤(2)制备的半成品催化剂B4溶解于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，140℃干燥，在550℃焙烧6小时，得到半成品催化剂C4。
(4)称取氯化钯0.016g，溶于70mL去离子水中，加正己烷35g，加CATB 21g，加正戊醇20g，充分搅拌形成微乳液，将半成品催化剂C4浸渍到所制备的微乳液中，摇动90min，滤除余液，在60℃下干燥，在500℃下焙烧6h得到所要的催化剂。
动态光散射测定步骤(1)制备的微乳液乳液的粒径是51.19nm，步骤(4)制备的微乳液乳液的粒径是50.85nm。
由原子吸收光谱法测定制备的催化剂，实施例2-4中，Pd含量为0.05％，Ni含量为1％，Cu含量为0.25％，Ag含量为0.14％。
催化剂的还原：使用前放置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在190℃温度，还原处理8h。
对比例2-4A
催化剂制备：
载体：采用市售双峰孔分布球形氧化铝载体，直径为3mm。经过1078℃焙烧4h后，双峰孔径分布范围在20-35nm和90-250nm，吸水率62％，比表面积为44.82m 2/g。称取该载体100g。
(1)称取称取无水硝酸镍3.18g，无硝酸铜0.74g，溶于70mL去离子水中，加正己烷35g，加CATB 21g，加正戊醇20g，充分搅拌形成微乳液，将称取的100g高温焙烧过的载体浸渍到所制备的微乳液中，摇动90min，滤除余液，在60℃下干燥，在500℃下焙烧6h，称为半成品催化剂A4-1。
(2)称取氯化钯0.069g，溶于100mL去离子水中，调pH为1.8，再将半成品催化剂A4-1浸渍到已配制的Pd盐溶液中，浸渍60min后，100℃干燥，500℃条件下焙烧6小时，得到半成品催化剂B4-1。
(3)称取硝酸银0.236g，溶于57mL去离子水中，调pH值为3，将步骤(2)制备的半成品催化剂B4-1溶解于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，140℃干燥，在550℃焙烧6小时，得到半成品催化剂C4-1。
(4)称取氯化钯0.016g，溶于70mL去离子水中，加正己烷38g，加CATB 24g，加正戊醇24g，充分搅拌形成微乳液，将半成品催化剂C4-1浸渍到所制备的微乳液中，摇动90min，滤除余液，在60℃下干燥，在500℃下焙烧6h得到所要的催化剂。
动态光散射测定步骤(1)制备的微乳液乳液的粒径是52.18nm。
动态光散射测定步骤(4)制备的微乳液乳液的粒径是26.58nm。
由原子吸收光谱法测定制备的催化剂的元素含量，对比例2-4A的催化剂中，Pd含量为0.05％，Ni含量为1％，Cu含量为0.25％，Ag含量为0.15％。
催化剂的还原：使用前放置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在190℃温度，还原处理8h。
对比例2-4B
载体：采用市售双峰孔分布球形氧化铝载体，直径为3mm。经过1078℃焙烧4h后，双峰孔径分布范围在20-35nm和90-250nm，吸水率57％，比表面积为44.82m 2/g。称取该载体100g。
(1)称取称取无水硝酸镍3.18g，无硝酸铜0.74g，溶于70mL去离子水中，加正己烷35g，加CATB 21g，加正戊醇20g，充分搅拌形成微乳液，将称取的100g高温焙烧过的载体浸渍到所制备的微乳液中，摇动90min，滤除余液，在60℃下干燥，在500℃下焙烧6h，称为半成品催化剂A4-2。
(2)称取氯化钯0.069g，溶于100mL去离子水中，调pH为1.8，再将半成品催化剂A4-2浸渍到已配制的Pd盐溶液中，浸渍60min后，100℃干燥，500℃条件下焙烧6小时，得到半成品催化剂B4-2。
(3)称取硝酸银0.236g，溶于57mL去离子水中，调pH值为3，将步骤(2)制备的半成品催化剂B4-2溶解于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，140℃干燥，在550℃焙烧6小时，得到半成品催化剂C4-2。
(4)称取氯化钯0.016g，溶于65mL去离子水中，加22.15g正己烷，2.79g CATB，2.75g正丁醇，充分搅拌形成微乳液，将半成品催化剂C4-2浸渍到所制备的微乳液中，摇动90min，滤除余液，在60℃下干燥，在500℃下焙烧6h得到所要的催化剂。
动态光散射测定步骤(1)制备的微乳液乳液的粒径是52.13nm。
动态光散射测定步骤(4)制备的微乳液乳液的粒径是595.09nm。
由原子吸收光谱法测定制备的催化剂元素含量，对比例2-4B的催化剂中，Pd含量为0.05％，Ni含量为1.0％，Cu含量为0.25％，Ag含量为0.15％。
催化剂的还原：使用前放置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在190℃温度，还原处理8h。
实施效果
加氢反应条件1二段反应器工艺，物料空速5000/h，操作压力2.2MPa，催化剂装填量200mL。反应器条件如表2-9所示。反应结果如表2-10所示。
物料组成：一段反应器入口物料：乙炔1.4％(v/v)，乙烯85％(v/v)，碳三0.5％(v/v)。
表2-9各段反应器条件
Figure PCTCN2021086214-appb-000011
表2-10反应结果
Figure PCTCN2021086214-appb-000012
Figure PCTCN2021086214-appb-000013
加氢反应条件2
三段反应器工艺：一、二段为绝热反应器，物料空速5000/h，第三段为等温反应器，物料空速11000/h，操作压力2.5MPa，一、二段催化剂装填量1000mL。反应器条件如表2-11所示。反应结果如表2-12所示。
物料组成：一段反应器入口乙炔1.5％(v/v)，乙烯93(v/v)。
表2-11各段反应器条件
  一段 二段 三段
氢/炔 0.8 1.2-1.5 2.0-2.5
各段入口温度 45 55 70
表2-12反应结果
Figure PCTCN2021086214-appb-000014
从表2-10及表2-12中可以看出，对比例2-4A及4B在反应初期的活性略高于实施例2-4，表明独立存在的钯具有加氢活性，可以与乙炔反应形成乙烯等，但随反应进行，对比例2-4A及4B催化剂的活性选择性逐渐较实施例2-4差，到1000小时后，反应器出口乙炔含量已经不合格。从表2-12中的结焦量看，其一段反应器的催化剂结焦量很大，表明低氢/炔更易导致催化剂结焦。也表明本催化剂具有更优异的抗结焦性能。
实施例2-5
载体：采用市售双峰孔分布球形氧化铝-氧化镁载体，氧化镁含量为3％，直径为3mm。经 过1065℃焙烧4h后，双峰孔径分布范围在23-47nm和80-380nm，吸水率58％，比表面积为42.38m 2/g。称取该载体100g。
催化剂制备：
(1)称取氯化钯0.051g，溶于80mL去离子水中，调pH为3，再将载体浸渍到已配制的Pd盐溶液中，浸渍120min后，130℃干燥，500℃条件下焙烧4小时，得到半成品催化剂A5。
(2)称取硝酸银0.33g，溶于58mL去离子水中，调pH值为5，将步骤(1)制备的半成品催化剂A5溶解于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，100℃干燥，在600℃焙烧4小时，得到半成品催化剂B5。
(3)称取氯化钯0.017g，溶于80mL去离子水中，加正己烷36.00g，加Triton X-100 20.88g，加正己醇19.4g，充分搅拌形成微乳液，将制备的半成品催化剂B5浸渍到所制备的微乳液中，摇动180min，滤除余液，在70℃下干燥，在500℃下焙烧4h，称为半成品催化剂C5。
(4)称取氯化镍1.648g，硝酸铜2.175g，溶于80mL去离子水中，加正己烷36.00g，加Triton X-100 20.88g，加正己醇19.60g，充分搅拌形成微乳液，将步骤(2)制备的半成品催化剂C5浸渍到所制备的微乳液中，摇动180min，滤除余液，在70℃下干燥，在500℃下焙烧4h，得到所要的催化剂。
动态光散射测定制备的步骤(1)微乳液乳液的粒径是65.0nm，步骤(4)微乳液乳液的粒径是65.24nm。
由原子吸收光谱法测定制备的催化剂元素含量，实施例2-5的催化剂中，Pd含量为0.04％，Ni含量为0.75％，Cu含量为0.75％，Ag含量为0.21％。
催化剂的还原：使用前放置于固定床反应装置中，用摩尔比为N2:H2＝1:1的混合气体，在180℃温度，还原处理8h。
对比例2-5
催化剂制备条件与实施例2-5相同，不同的是制备步骤无乳液法负载Pd。
载体：采用市售双峰孔分布球形氧化铝-氧化镁载体，氧化镁含量为3％，直径为3mm。经过1000℃焙烧4h后，双峰孔径分布范围在23-47nm和80-380nm，吸水率58％，比表面积为40m 2/g。称取该载体100g。
(2)称取氯化钯0.069g，溶于80mL去离子水中，调pH为3，再将载体浸渍到已配制的Pd盐溶液中，浸渍120min后，130℃干燥，500℃条件下焙烧4小时，得到半成品催化剂A5-1。
(2)称取硝酸银0.33g，溶于58mL去离子水中，调pH值为5，将步骤(1)制备的半成品催化剂A5-1溶解于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，100℃干燥，在600℃焙烧4小时，得到半成品催化剂B5-1。
(3)称取氯化镍1.648g，硝酸铜2.175g，溶于80mL去离子水中，加正己烷36.00g，加Triton X-100 20.88g，加正己醇19.4g，充分搅拌形成微乳液，将步骤(2)制备的半成品催化剂B5-1浸渍到所制备的微乳液中，摇动180min，滤除余液，在70℃下干燥，在500℃下焙烧4h，得到所要的催化剂。
动态光散射测定步骤(4)制备的微乳液乳液的粒径是65.20nm。
由原子吸收光谱法测定制备的催化剂，对比例2-5中，Pd含量为0.04％，Ni含量为0.75％，Cu含量为0.75％，Ag含量为0.21％。
催化剂的还原：使用前放置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在180℃温度，还原处理8h。
实施效果
加氢反应条件
三段反应器工艺：各段为绝热反应器，物料空速11000/h，操作压力2.3MPa，催化剂装填量1000mL。反应器条件如表2-13所示。反应结果如表2-14所示。
物料组成：一段反应器入口乙炔：1.5％(v/v)，乙烯70％(v/v)。
表2-13各段反应器条件
  一段 二段 三段
氢/炔 1.5 1.4 1.5
各段入口温度 45 55 70
表2-14反应结果
Figure PCTCN2021086214-appb-000015
表2-14中，对比例2-5的催化剂1000小时后，尽管三段反应器入口乙炔含量仅0.12％，反应器出口乙炔含量达到40ppm。表明三段低氢/炔对脱除乙炔不利，但实施例2-5的催化剂，仍然能够将乙炔完全转化，表明本发明的催化剂，在经过1000小时运行后，性能衰减很小。而对比例2-5的催化剂要差的多，原因是未用乳液法负载Pd，导致镍和铜不能在180℃被还原。
实施例3-1
载体：采用市售双峰孔分布球形氧化铝载体，直径为4mm。经过1005℃焙烧4h后，双峰孔径分布范围在15-35nm和80-203mm，吸水率63％，比表面积为48.45m 2/g。称取该载体100g。
催化剂制备：
(1)称取无水硝酸镍15.6g，硝酸铜1.48g，溶于63mL去离子水中，将称取的载体浸渍到所制备的溶液中，摇动10min，100℃干燥后400℃下焙烧8h，称为半成品催化剂A1。
(2)称取硝酸钯0.151g，溶于70mL去离子水中，调pH为1.3，再将半成品催化剂A1浸渍到已配制的硝酸Pd盐溶液中，浸渍60min后，120℃干燥后再400℃条件下焙烧6小时，得到半成品催化剂B1。
(3)将步骤(2)得到的半成品催化剂C放置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在190℃温度，还原处理5h，得到所要的催化剂。
由原子吸收光谱法测定制备的催化剂的活性组分含量，实施例3-1的催化剂中，Pd含量为0.07％，Ni含量为5％，Cu含量为0.50％。
对比例3-1
使用与实施例3-1相同的载体，催化剂制备条件及其它组分的含量相同与实施例3-1相同，区别是未负载Cu。
(1)称取无水硝酸镍1.59g，溶于63mL去离子水中，将称取的载体浸渍到所制备的溶液中，摇动10min，100℃干燥后400℃下焙烧8h，称为半成品催化剂A1-1。
(2)称取硝酸钯0.151g，溶于70mL去离子水中，调pH为1.3，再将半成品催化剂A1-1浸渍到已配制的硝酸Pd盐溶液中，浸渍60min后，120℃干燥后再400℃条件下焙烧6小时，得到半成品催化剂B1-1。
(3)将步骤(2)得到的半成品催化剂B1-1放置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在190℃温度，还原处理5h，得到所要的催化剂。
由原子吸收光谱法测定制备的催化剂的活性组分含量，对比例3-1的催化剂中，Pd含量为0.07％，Ni含量为0.5％。
实施效果 加氢反应条件：催化剂在单段绝热固定床反应器的装填量为50mL，填料50mL，反应物料空速：6000h -1，操作压力：1.5MPa，氢炔比2.0，反应器入口温度70℃。反应物料组成见下表3-1，运行结果见表3-2。粗氢组成：H 220％，CO含量1％。
表3-1物料组成
反应物料 C 2H 2 H 2 C 2H 4 C 3 CO
含量(v/v％) 0.3 0.6 93 0.5 0.03
表3-2运行结果
Figure PCTCN2021086214-appb-000016
与实施例3-1相比，对比例3-1中没有负载Cu。
实施例3-1中，由于Ni和Cu的负载量较大，在载体中易形成均匀分布，后负载的Pd量远低于前者，其分布受溶液酸度的影响，因此，部分Pd形成单独的活性中心，部分与Ni和Cu形成合金，Ni-Cu合金在Pd的作用下，其还原温度可以降低到200℃以下，可以对选择性加氢的副产物进行饱和加氢，保证了催化剂较好的性能。
对比例3-1中没有Cu，仅靠Pd不足以将Ni的还原温度降低到200℃以下，因此，该催化剂不具有对选择性加氢副产物饱和加氢的功能，催化剂结焦较快。1000小时后选择性与活性明显低于实施例3-1。
实施例3-2
载体：采用市售双峰孔分布球形氧化铝载体，直径为4mm。经过1005℃焙烧4h后，双峰孔径分布范围在15-35nm和80-203mm，吸水率63％，比表面积为48.45m 2/g。称取该载体100g。
催化剂制备：
(1)称取无水硝酸镍15.6g，硝酸铜1.48g，溶于63mL去离子水中，将称取的载体浸渍到所制备的溶液中，摇动10min，100℃干燥后400℃下焙烧8h，称为半成品催化剂A2。
(2)称取硝酸钯0.140g，溶于70mL去离子水中，调pH为2.5，再将半成品催化剂A2浸渍到已配制的硝酸Pd盐溶液中，浸渍60min后，120℃干燥后再400℃条件下焙烧6小时，得到半成品催化剂B2。
(3)称取硝酸钯0.011g，溶于70mL去离子水中，调pH为1.0，再将半成品催化剂B2浸渍到已配制的硝酸Pd盐溶液中，浸渍20min后，静置4小时以上，120℃干燥后再400℃条件下焙烧6小时，得到半成品催化剂C2。
(4)将步骤(3)得到的半成品催化剂C2放置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在190℃温度，还原处理5h，得到所要的催化剂。
由原子吸收光谱法测定制备的催化剂的活性组分含量，实施例3-2的催化剂中，Pd含量为0.07％，Ni含量为5％，Cu含量为0.50％。
对比例3-2
使用与实施例3-2相同的载体，催化剂制备条件及其它组分的含量相同与实施例3-2相同，区别是未负载Cu。
催化剂制备：
(1)称取无水硝酸镍15.6g，溶于63mL去离子水中，将称取的载体浸渍到所制备的溶液中，摇动10min，100℃干燥后400℃下焙烧8h，称为半成品催化剂A2-1。
(2)称取硝酸钯0.140g，溶于70mL去离子水中，调pH为2.5，再将半成品催化剂A2-1浸渍到已配制的硝酸Pd盐溶液中，浸渍20min后，120℃干燥后再400℃条件下焙烧6小时，得到半成品催化剂B2-1。
(3)称取硝酸钯0.011g，溶于70mL去离子水中，调pH为1.0，再将半成品催化剂B2-1浸渍到已配制的硝酸Pd盐溶液中，浸渍20min后，静置4小时以上，120℃干燥后再400℃条件下焙烧6小时，得到半成品催化剂C2-1。
(4)将步骤(3)得到的半成品催化剂C2-1放置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在190℃温度，还原处理5h，得到所要的催化剂。
由原子吸收光谱法测定制备的催化剂的活性组分含量，对比例3-2的催化剂中，Pd含量为0.07％，Ni含量为5％。
实施效果 加氢反应条件：催化剂在单段绝热固定床反应器的装填量为50mL，填料50mL，反应物料空速：4000h -1，操作压力：1.5MPa，氢炔比2.0，反应器入口温度65℃。反应物料组成见下表3-3，运行结果见表3-4。粗氢组成：H 2 20％，CO含量1％。
表3-3物料组成
反应物料 C 2H 2 H 2 C 2H 4 C 3 CO
含量(v/v％) 0.3 0.6 93 0.3 0.03
表3-4运行结果
Figure PCTCN2021086214-appb-000017
与实施例3-2相比，对比例3-2中没有负载Cu。
实施例3-2中，由于Ni和Cu的形成均匀分布，第一次负载Pd时，其酸量较低，该部分Pd分布于较外的壳层，形成单独的活性中心；第二次负载的部分Pd，溶液酸度高，该部分Pd与Ni-Cu形成合金，将Ni-Cu合金还原温度降低到200℃以下，可以对选择性加氢的副产物进行饱和加氢，保证了催化剂较好的性能。
对比例3-2中没有Cu，仅靠Pd不足以将Ni的还原温度降低到200℃以下，因此，该催化 剂不具有对选择性加氢副产物饱和加氢的功能，催化剂结焦较快。1000小时后选择性与活性明显低于实施例3-2。
实施例3-2中，由于Pd是2次负载，可以较好的控制Pd的负载区域，形成较多Ni-Cu-Pd合金，对选择加氢副产物的饱和加氢效果更好，1000小时后的选择性，实施例3-2优于实施例3-1。
实施例3-3
载体：采用市售双峰孔分布球形氧化铝载体，直径为4mm。经过1005℃焙烧4h后，双峰孔径分布范围在15-35nm和80-203mm，吸水率63％，比表面积为48.45m 2/g。称取该载体100g。
催化剂制备：
(1)称取无水硝酸镍15.6g，硝酸铜1.48g，溶于63mL去离子水中，将称取的载体浸渍到所制备的溶液中，摇动10min，100℃干燥后400℃下焙烧8h，称为半成品催化剂A3。
(2)称取氯化钯0.140g，溶于70mL去离子水中，调pH为2.0，再将半成品催化剂A3浸渍到已配制的氯化钯盐溶液中，浸渍60min后，120℃干燥后再400℃条件下焙烧6小时，得到半成品催化剂B3。
(3)称取硝酸钯0.011g，溶于70mL去离子水中，调pH为1.0，再将半成品催化剂B3浸渍到已配制的硝酸Pd盐溶液中，浸渍20min后，静置4小时以上，120℃干燥后再400℃条件下焙烧6小时，得到半成品催化剂C3。
(4)将步骤(3)得到的半成品催化剂C3放置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在190℃温度，还原处理5h，得到所要的催化剂。
由原子吸收光谱法测定制备的催化剂的活性组分含量，实施例3-3的催化剂中，Pd含量为0.07％，Ni含量为5％，Cu含量为0.50％。
对比例3-3
载体及催化剂制备条件与实施例3-3相同，区别是未负载Cu。
催化剂制备：
(1)称取无水硝酸镍15.6g，溶于63mL去离子水中，将称取的载体浸渍到所制备的溶液中，摇动10min，100℃干燥后400℃下焙烧8h，称为半成品催化剂A3-1。
(2)称取氯化钯0.140g，溶于70mL去离子水中，调pH为2.0，再将半成品催化剂A3-1浸渍到已配制的硝酸Pd盐溶液中，浸渍20min后，120℃干燥后再400℃条件下焙烧6小时，得到半成品催化剂B3-1。
(3)称取硝酸钯0.011g，溶于70mL去离子水中，调pH为1.0，再将半成品催化剂B3-1浸渍到已配制的硝酸Pd盐溶液中，浸渍20min后，静置4小时以上，120℃干燥后再400℃条件下焙烧6小时，得到半成品催化剂C3-1。
(4)将步骤(3)得到的半成品催化剂C3-1放置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在190℃温度，还原处理5h，得到所要的催化剂。
由原子吸收光谱法测定制备的催化剂的活性组分含量，对比例3-3的催化剂中，Pd含量为0.07％，Ni含量为5％。
实施效果
加氢反应条件：催化剂在单段绝热固定床反应器的装填量为50mL，填料50mL，反应物料空速：5000h -1，操作压力：1.5MPa，氢炔比2.0，反应器入口温度85℃。反应物料组成见下表3-5，运行结果见表3-6。粗氢组成：H 220％，CO含量1％。
表3-5物料组成
反应物料 C 2H 2 H 2 C 2H 4 C 3 CO
含量(v/v％) 0.3 0.6 93 1.0 0.03
表3-6运行结果
Figure PCTCN2021086214-appb-000018
与实施例3-3相比，对比例3-3中没有负载Cu。
实施例3-3中，第一次负载Pd时，采用的是阴离子前驱体，Pd更易分布在外壳层，形成单独的活性中心，成为乙炔选择性加氢的活性中心；第二次负载的部分Pd，其溶液酸度高，负载时间长，更易与Ni和Cu形成合金，将Ni-Cu合金还原温度降低到200℃以下，该部分活性中心，对选择性加氢的副产物进行饱和加氢，保证了催化剂较好的性能。
对比例3-3中没有Cu，仅靠Pd不足以将Ni的还原温度降低到200℃以下，因此，该催化剂不具有对选择性加氢副产物饱和加氢的功能，催化剂结焦较快。1000小时后选择性与活性明显低于实施例3-3。
由于阴离子前驱体的负载，更易与载体的羟基结合，其分布区域跟窄，所以加氢选择性更高。因此，实施例3-3的初始选择性及1000小时后的选择性，均优于实施例3-2。
实施例3-4
载体：采用市售双峰孔分布圆柱形氧化铝载体，直径为3mm，长度为3mm。经过1018℃焙烧4h后，双峰孔径分布范围在18-38nm和85-270mm，吸水率61％，比表面积为43.62m 2/g，称取该载体100g。
催化剂制备：
(1)称取氯化镍4.41g，氯化铜2.12g，溶于61mL去离子水中，将称取的载体浸渍到所制备的溶液中，摇动20min，120℃下干燥，在600℃下焙烧4h，称为半成品催化剂A4。
(2)称取氯化钯0.093g，溶于100mL去离子水中，调pH为1.8，再将半成品催化剂A4浸渍到已配制的Pd盐溶液中，浸渍60min后，100℃干燥，450℃条件下焙烧5小时，得到半成品催化剂B2。
(3)称取硝酸钯0.0108g，溶于61mL去离子水中，调节PH为1.8将步骤(2)制备的半成品催化剂B2浸渍到所制备的溶液中，摇动10min，静置4小时以上。在100℃下干燥，在400℃下焙烧6h得到半成品催化剂C2。
(4)将步骤(3)得到的半成品催化剂C2放置于固定床反应装置中，用氢气在150℃温度，还原处理7h，得到所要的催化剂。
由原子吸收光谱法测定制备的催化剂的活性组分含量，实施例3-4的催化剂中，Pd含量为0.060％，Ni含量为2.3％，Cu含量为1.1％。
对比例3-4
催化剂载体及制备条件与实施例3-4相同，不同的是不负载镍。
催化剂制备：
(1)称取氯化铜2.12g，溶于61mL去离子水中，将称取的载体浸渍到所制备的溶液中，摇动20min，120℃下干燥，在600℃下焙烧4h，称为半成品催化剂A4-1。
(2)称取氯化钯0.093g，溶于100mL去离子水中，调pH为1.8，再将半成品催化剂A4-1浸渍到已配制的Pd盐溶液中，浸渍60min后，100℃干燥，450℃条件下焙烧5小时，得到半成品催化剂B4-1。
(3)称取硝酸钯0.0108g，溶于61mL去离子水中，调节PH为1.8将步骤(2)制备的半成品催化剂B4-1浸渍到所制备的溶液中，摇动10min，静置4小时以上。在100℃下干燥，在400℃下焙烧6h得到半成品催化剂C4-1。
(4)将步骤(3)得到的半成品催化剂C4-1放置于固定床反应装置中，用氢气在150℃温度，还原处理7h，得到所要的催化剂。
由原子吸收光谱法测定制备的催化剂的活性组分含量，对比例3-4的催化剂中，Pd含量为0.060％，Cu含量为1.1％。
实施效果
加氢反应条件：催化剂在单段绝热固定床反应器的装填量为50mL，填料50mL，反应物料空速：1500/h，操作压力：1.7MPa，氢炔比2.5，反应器入口温度55℃。反应物料组成见下表3-7，运行结果见表3-8。粗氢组成：H 2 50％，CO 0.5％。
表3-7物料组成
反应物料 C 2H 2 H 2 C 2H 4 C 3 CO
含量(v/v％) 0.2 0.5 60 7.0 0.01
表3-8运行结果
Figure PCTCN2021086214-appb-000019
与实施例3-4相比，对比例3-4中没有负载Ni。
由于镍的缺少，对比例3-4中Cu与Pd虽然形成合金，而且较Ni更易还原，但其形成的活性中心加氢活性不足，不能有效的对选择性加氢的副产物进行饱和加氢。导致催化剂结焦较多，1000小时乙炔转化率不达标，选择性也较差。
实施例3-5
载体：采用市售双峰孔分布三叶草形氧化铝载体，直径为2mm，长度为4mm。经过1118℃焙烧4h后，双峰孔径分布范围在30-49nm和187-499mm，吸水率55％，比表面积为20.80m 2/g。称取该载体100g。
催化剂制备：
(1)称取无水硝酸镍8.29g，氯化铜5.08g，溶55mL去离子水中，将称取的载体浸渍到所制备的溶液中，摇动20min，在80℃下干燥，在500℃下焙烧4h，称为半成品催化剂A5。
(2)称取氯化钯0.124g，溶于100mL去离子水中，调pH为1.8，再将半成品催化剂A5浸渍到已配制的Pd盐溶液中，浸渍60min后，110℃干燥，500℃条件下焙烧4小时，得到半成品催化剂B5。
(3)称取硝酸钯0.057g，溶于55mL去离子水中，调节溶液PH为1.3，将步骤(2)制备的半成品催化剂B5浸渍到所制备的溶液中，摇动30min，静置4小时以上，在80℃下干燥，在500℃下焙烧4h得到半成品催化剂C5。
(4)将步骤(3)得到的半成品催化剂C4置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1 的混合气体，在200℃温度，还原处理6h，得到所要的成品催化剂。
由原子吸收光谱法测定制备的催化剂的活性组分含量，实施例3-5的催化剂中，Pd含量为0.1％，Ni含量为2.60％，Cu含量为2.40％。
对比例3-5
载体：采用市售单峰孔分布三叶草形氧化铝载体，直径2mm，长度4mm。经过1118℃焙烧4h后，双峰孔径分布范围在30-49nm，吸水率55％，比表面积为20.80m 2/g。称取该载体100g。
催化剂制备：
(1)称取无水硝酸镍8.29g，氯化铜5.08g，溶55mL去离子水中，将称取的载体浸渍到所制备的溶液中，摇动20min，在80℃下干燥，在500℃下焙烧4h，称为半成品催化剂A5-1。
(2)称取氯化钯0.124g，溶于100mL去离子水中，调pH为1.8，再将半成品催化剂A5-1浸渍到已配制的Pd盐溶液中，浸渍60min后，110℃干燥，500℃条件下焙烧4小时，得到半成品催化剂B5-1。
(3)称取硝酸钯0.057g，溶于55mL去离子水中，调节溶液PH为1.3，将步骤(2)制备的半成品催化剂B5-1浸渍到所制备的溶液中，摇动30min，静置4小时以上，在80℃下干燥，在500℃下焙烧4h得到半成品催化剂C5-1。
(4)将步骤(3)得到的半成品催化剂C5-1置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在200℃温度，还原处理6h，得到所要的成品催化剂。
由原子吸收光谱法测定制备的催化剂的活性组分含量，对比例3-5的催化剂中，Pd含量为0.79％，Ni含量为2.60％，Cu含量为2.40％。
实施效果
加氢反应条件：催化剂在单段绝热固定床反应器的装填量为100mL，填料50mL，反应物料空速：4000/h，操作压力：2.0MPa，氢炔比2，反应器入口温度75℃。反应物料组成及运行结果见下表3-9和表3-10。
粗氢组成：H 2 30％，CO 0.8％。
表3-9物料组成
反应物料 C 2H 2 H 2 C 2H 4 C 3 CO
含量(v/v％) 1.0 2.0 80 7.0 0.08
表3-10运行结果
Figure PCTCN2021086214-appb-000020
对比例3-5使用的是单峰孔分布的载体。
在碳二馏分的选择性加氢过程中，由于主活性组分分布在靠外的壳层，较50nm以下范围的孔有利乙炔分子与活性中心接触，并发生反应。本对比例中，由于采用的单峰孔径分布的载体，绝大部分孔径在50nm以下，Ni-Cu-Pd形成的合金，由于活性组分含量高，在该孔径范围也具有乙炔和乙烯的加氢活性，但Ni-Cu的本征选择性较差，导致部分乙烯也发生加氢，故初始选择性，对比例低于实施例。对比例的活性中心尺寸大，容易同时吸附多个分子，更容易发生乙炔的加氢二聚，导致其绿油生成量大于实施例，1000小时后活性选择性均低于实施例。
实施例3-6
采用市售双峰孔分布三叶草形氧化铝载体，直径为2mm，长度为4mm。经过1054℃焙烧4h后，双峰孔径分布范围在20-42nm和90-360mm，吸水率58％，比表面积为37.32m 2/g。称取该载体100g。
催化剂制备：
(1)称取无水硝酸镍9.64g，氯化铜5.08g溶于65mL去离子水中，加正己烷25g，加CATB13.60g，加正戊醇12.5g，充分搅拌形成微乳液，将称取的载体浸渍到所制备的微乳液中，摇动70min，滤除余液，在60℃下干燥，在500℃下焙烧4h，称为半成品催化剂A6。
(2)称取氯化钯0.126g，溶于100mL去离子水中，调pH为1.8，再将半成品催化剂A6浸渍到已配制的Pd盐溶液中，浸渍60min后，110℃干燥，500℃条件下焙烧4小时，得到半成品催化剂B6。
(3)称取硝酸钯0.055g，溶于65mL去离子水中，加正己烷25g，加CATB 13.60g，加正戊醇12.5g，充分搅拌形成微乳液，将步骤(2)制备的半成品催化剂B6浸渍到所制备的微乳液中，摇动70min，滤除余液，在60℃下干燥，在500℃下焙烧4h得到半成品催化剂C6。
(4)将步骤(3)得到的半成品催化剂C6置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在200℃温度，还原处理6h，得到所要的成品催化剂。
动态光散射测定步骤(1)制备的微乳液的粒径是82.36nm，步骤(3)制备的微乳液的粒径是81.76nm。
由原子吸收光谱法测定制备的催化剂的活性组分含量，实施例3-6的催化剂中，Pd含量为0.1％，Ni含量为3.1％，Ag 0.5％，Cu含量为2.4％。
对比例3-6
载体及催化剂制备条件于实施例3-6相同，区别是不加铜
催化剂制备：
(1)称取无水硝酸镍9.64g，溶于65mL去离子水中，加正己烷25g，加CATB 13.60g，加正戊醇12.5g，充分搅拌形成微乳液，将称取的载体浸渍到所制备的微乳液中，摇动70min，滤除余液，在60℃下干燥，在500℃下焙烧4h，称为半成品催化剂A6-1。
(2)称取氯化钯0.126g，溶于100mL去离子水中，调pH为1.8，再将半成品催化剂A6-1浸渍到已配制的Pd盐溶液中，浸渍60min后，110℃干燥，500℃条件下焙烧4小时，得到半成品催化剂B6-1。
(3)称取硝酸钯0.055g，溶于65mL去离子水中，加正己烷25g，加CATB 13.60g，加正戊醇12.5g，充分搅拌形成微乳液，将步骤(3)制备的半成品催化剂B6-1浸渍到所制备的微乳液中，摇动70min，滤除余液，在60℃下干燥，在500℃下焙烧4h得到半成品催化剂C6-1。
(4)将步骤(3)得到的半成品催化剂C6-1置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在200℃温度，还原处理6h，得到所要的成品催化剂。
动态光散射测定步骤(1)制备的微乳液的粒径是82.36nm，步骤(3)制备的微乳液的粒径是81.76nm。
由原子吸收光谱法测定制备的催化剂的活性组分含量，对比例3-6的催化剂中，Pd含量为0.10％，Ni含量为3.1％，Ag 0.5％。
实施效果
加氢反应条件：催化剂在单段绝热固定床反应器的装填量为50mL，填料50mL，反应物料 空速：4000/h，操作压力：3.0MPa，氢炔比2.5，反应器入口温度55℃。反应物料组成见下表3-11，运行结果见表3-12。粗氢组成：H 2 50％，CO 0.1％。
表3-11物料组成
反应物料 C 2H 2 H 2 C 2H 4 C 3 CO
含量(v/v％) 1 3.0 83 1.0 0.006
表3-12运行结果
Figure PCTCN2021086214-appb-000021
实施例3-6中采用溶液法负载了部分Pd，其主要负载在载体的较小的孔中。采用了微乳液前驱体，将Cu，Ni和部分Pd先后负载在载体的大孔中，形成Cu-Ni-Pd的合金，在这种合金结构中，Ni是主要的活性组分，其具有较高的饱和加氢功能，可以将选择性加氢过程中形成的绿油，进行饱和加氢。Ni与Pd虽然也有一定的加氢活性，但Pd含量低，因此，这2种组分的主要作用是将含Ni合金的还原温度降低到200℃以下。对比例中无Cu，因此，大孔中的活性中心，在整个加氢过程中没有发挥作用。由于乙炔含量高，绿油生成量大，对比例的结焦很严重。
本实施例与溶液法负载的催化剂相比，由于Cu，Ni只位于大孔中，不参与乙烯的加氢，因此其初始选择性高于溶液法制备的催化剂。
实施例3-7
载体：采用市售双峰孔分布四叶草形氧化铝载体，直径为3mm，长度为3mm。经过1092℃焙烧4h后，双峰孔径分布范围在22-45nm和70-420mm，吸水率56％，比表面积为29.67m 2/g。称取该载体100g。
催化剂制备：
(1)氯化镍1.11g，硝酸铜1.49g，溶于60mL去离子水中，加正己烷27g，加Triton X-100 15.00g，加正丁醇14.4g，充分搅拌形成微乳液，将称取的载体浸渍到所制备的微乳液中，摇动90min，滤除余液，在80℃下干燥，在600℃下焙烧4h，称为半成品催化剂A7。
(2)称取氯化钯0.11g，溶于100mL去离子水中，调pH为1.8，再将半成品催化剂A7浸渍到已配制的Pd盐溶液中，浸渍60min后，90℃干燥，550℃条件下焙烧4小时，得到半成品催化剂B7。
(3)称取氯化钯0.084g，溶于70mL去离子水中，加正己烷31.5g，加Triton X-100 17.50g，加正丁醇16.8g，充分搅拌形成微乳液，将步骤(2)制备的半成品催化剂B7浸渍到所制备的微乳液中，摇动90min，滤除余液，在80℃下干燥，在600℃下焙烧4h得到半成品催化剂C7。
(4)将步骤(3)得到的半成品催化剂C7置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在150℃温度，还原处理8h，得到所要的成品催化剂。
动态光散射测定步骤(1)制备的微乳液乳液的粒径是66.68nm，步骤(3)制备的微乳液乳液的粒径是67.49nm。
由原子吸收光谱法测定制备的催化剂的活性组分含量，实施例3-7的催化剂中，Pd含量为0.07％，Ni含量为0.5％，Cu含量为0.5％。
对比例3-7
催化剂载体及制备条件与实施例3-7相同，区别是不负载Ni。
催化剂制备：
(1)称取硝酸铜1.49g，溶于60mL去离子水中，加正己烷27g，加Triton X-100 15.00g，加正丁醇14.4g，充分搅拌形成微乳液，将称取的载体浸渍到所制备的微乳液中，摇动90min，滤除余液，在80℃下干燥，在600℃下焙烧4h，称为半成品催化剂A7-1。
(2)称取氯化钯0.11g，溶于100mL去离子水中，调pH为1.8，再将半成品催化剂A7-1浸渍到已配制的Pd盐溶液中，浸渍60min后，90℃干燥，550℃条件下焙烧4小时，得到半成品催化剂B7-1。
(3)称取氯化钯0.084g，溶于70mL去离子水中，加正己烷31.5g，加Triton X-100 17.50g，加正丁醇16.8g，充分搅拌形成微乳液，将步骤(2)制备的半成品催化剂B7-1浸渍到所制备的微乳液中，摇动90min，滤除余液，在80℃下干燥，在600℃下焙烧4h得到半成品催化剂C7-1。
(4)将步骤(3)得到的半成品催化剂C7-1置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在150℃温度，还原处理8h，得到所要的成品催化剂。
动态光散射测定步骤(1)制备的微乳液乳液的粒径是66.68nm，(3)制备的微乳液乳液的粒径是67.49nm。
由原子吸收光谱法测定制备的催化剂的活性组分含量，对比例3-7的催化剂中，Pd含量为0.07％，Cu含量为0.5％。
实施效果
加氢反应条件：催化剂在单段绝热固定床反应器的装填量为50mL，填料50mL，反应物料空速：3000/h，操作压力：3.0MPa，氢炔比3，反应器入口温度135℃。反应物料组成见下表3-13，运行结果见表3-14。粗氢组成：H 2 30％，CO 1％。
表3-13物料组成
反应物料 C 2H 2 H 2 C 2H 4 C 3 CO
含量(v/v％) 0.6 1.8 83 7.0 0.06
表3-14运行结果
Figure PCTCN2021086214-appb-000022
由于对比例没有负载Ni，且Cu的负载量较低，尽管反应温度高，也不能形成有效的反应副产物的加氢活性中，1000小时后，加氢选择性降低到10％。但实施例3-7和对比例3-7的初始选择性，高于溶液法制备的催化剂的初始选择性。
实施例3-8
载体：采用市售双峰孔分布球形氧化铝载体，直径为4mm。经过1128℃焙烧4h后，双峰孔径分布范围在25-47nm和300-498mm，吸水率50％，比表面积为21.46m 2/g。称取该载体100g。
催化剂制备：
(1)称取无水硝酸镍9.34g，氯化铜1.06g，溶于70mL去离子水中，加正己烷23.3g，加CATB 3.5g，加正丁醇2.95g，充分搅拌形成微乳液，将称取的载体浸渍到所制备的微乳液中，摇动100min，滤除余液，在70℃下干燥，在450℃下焙烧5h，称为半成品催化剂A8。
(2)称取氯化钯0.093g，溶于50mL去离子水中，调pH为1.8，将步骤(1)制备的半成品催化剂B8浸渍于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，90℃干燥， 在550℃焙烧4小时，得到半成品催化剂B8。
(3)称取硝酸钯0.0107g，溶于70mL去离子水中，加正己烷23.3g，加CATB 3.5g，加正丁醇2.95g，充分搅拌形成微乳液，将步骤(2)制备的半成品催化剂B8浸渍到所制备的微乳液中，摇动100min，滤除余液，在70℃下干燥，在450℃下焙烧5h得到半成品催化剂C8。
(4)将步骤(3)得到的半成品催化剂C8置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在180℃温度，还原处理4h，得到所要的成品催化剂。
动态光散射测定步骤(1)制备的微乳液的粒径是496.68nm，步骤(3)制备的微乳液的粒径是497.23nm。
由原子吸收光谱法测定制备的催化剂的活性组分含量，实施例3-8的催化剂中，Pd含量为0.6％，Ni含量为3.00％，Cu含量为0.5％。
对比例3-8
催化剂载体与实施例3-8相同，不同的是钯的负载量低于0.06％。
催化剂制备：
(1)称取无水硝酸镍9.34g，氯化铜1.06g，溶于70mL去离子水中，加正己烷23.3g，加CATB 3.5g，加正丁醇2.95g，充分搅拌形成微乳液，将称取的载体浸渍到所制备的微乳液中，摇动100min，滤除余液，在70℃下干燥，在450℃下焙烧5h，称为半成品催化剂A8。
(2)称取氯化钯0.0465g，溶于50mL去离子水中，调pH为1.8，将步骤(1)制备的半成品催化剂B8浸渍于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，90℃干燥，在550℃焙烧4小时，得到半成品催化剂B8。
(3)称取硝酸钯0.0054g，溶于70mL去离子水中，加正己烷23.3g，加CATB 3.5g，加正丁醇2.95g，充分搅拌形成微乳液，将步骤(2)制备的半成品催化剂B8浸渍到所制备的微乳液中，摇动100min，滤除余液，在70℃下干燥，在450℃下焙烧5h得到半成品催化剂C8。
(4)将步骤(3)得到的半成品催化剂C8置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在180℃温度，还原处理4h，得到所要的成品催化剂。
动态光散射测定步骤(1)制备的微乳液的粒径是496.68nm，步骤(3)制备的微乳液的粒径是497.23nm。
由原子吸收光谱法测定制备的催化剂的活性组分含量，对比例3-8的催化剂中，Pd含量为0.3％，Ni含量为3.00％，Cu含量为0.5％。
实施效果
加氢反应条件：催化剂在单段等温床反应器的装填量为50mL，填料50mL。粗氢组成：氢气40％，CO 0.3％。反应物料空速：3000/h，操作压力：3.0MPa，氢炔比2，反应器入口温度85℃。反应物料组成见下表3-15，运行结果见表3-16。
表3-15物料组成
反应物料 C 2H 2 H 2 C 2H 4 C 3 CO
含量(v/v％) 0.2 0.4 70 3.0 0.003
表3-16运行结果
Figure PCTCN2021086214-appb-000023
对比例3-8中，由于钯含量不足，加氢活性差，无法满足除炔要求。
实施例3-9
采用市售双峰孔分布三叶草形氧化铝载体，直径为2mm，长度为4mm。经过1055℃焙烧4h后，双峰孔径分布范围在20-42nm和90-360mm，吸水率58％，比表面积为37.32m 2/g。称取该载体100g。
催化剂制备：
(1)称取无水硝酸镍9.64g，氯化铜5.08g溶于65mL去离子水中，加正己烷25g，加CATB 13.50g，加正戊醇12.5g，充分搅拌形成微乳液，将称取的载体浸渍到所制备的微乳液中，摇动70min，滤除余液，在60℃下干燥，在500℃下焙烧4h，称为半成品催化剂A9。
(2)称取硝酸银0.79g溶解于64g去离子水中，用硝酸条件溶液PH为1.0，将半成品催化剂A6浸渍在制备的溶液中，浸渍30min，500℃下焙烧6h，称为半成品催化剂B9。
(3)称取氯化钯0.126g，溶于100mL去离子水中，调pH为1.8，再将半成品催化剂A9浸渍到已配制的Pd盐溶液中，浸渍60min后，110℃干燥，500℃条件下焙烧4小时，得到半成品催化剂C9。
(4)称取硝酸钯0.055g，溶于65mL去离子水中，加正己烷25g，加CATB 13.50g，加正戊醇12.5g，充分搅拌形成微乳液，将步骤(3)制备的半成品催化剂C9浸渍到所制备的微乳液中，摇动70min，滤除余液，在60℃下干燥，在500℃下焙烧4h得到半成品催化剂D9。
(5)将步骤(4)得到的半成品催化剂D9置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在200℃温度，还原处理6h，得到所要的成品催化剂。
动态光散射测定步骤(1)制备的微乳液的粒径是82.36nm，步骤(4)制备的微乳液的粒径是81.76nm。
由原子吸收光谱法测定制备的催化剂的活性组分含量，实施例3-9的催化剂中，Pd含量为0.1％，Ni含量为3.1％，Ag 0.5％，Cu含量为2.4％。
对比例3-9
催化剂制备条件与实施例3-9相同，区别是采用单峰孔载体。
采用市售单峰孔分布三叶草形氧化铝载体，直径为2mm，长度为4mm。经过1060℃焙烧4h后，孔径分布范围在59-113mm，吸水率55％，比表面积为37.32m 2/g。称取该载体100g。
催化剂制备：
(1)称取无水硝酸镍9.64g，氯化铜5.08g溶于65mL去离子水中，加正己烷25g，加CATB 13.50g，加正戊醇12.5g，充分搅拌形成微乳液，将称取的载体浸渍到所制备的微乳液中，摇动70min，滤除余液，在60℃下干燥，在500℃下焙烧4h，称为半成品催化剂A9-1。
(2)称取氯化钯0.126g，溶于100mL去离子水中，调pH为1.8，再将半成品催化剂A9-1浸渍到已配制的Pd盐溶液中，浸渍60min后，110℃干燥，500℃条件下焙烧4小时，得到半成品催化剂B9-1。
(3)称取硝酸钯0.055g，溶于65mL去离子水中，加正己烷25g，加CATB 13.50g，加正戊醇12.5g，充分搅拌形成微乳液，将步骤(2)制备的半成品催化剂B9-1浸渍到所制备的微乳液中，摇动70min，滤除余液，在60℃下干燥，在500℃下焙烧4h得到半成品催化剂C9-1。
(5)将步骤(4)得到的半成品催化剂C9-1置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在200℃温度，还原处理6h，得到所要的成品催化剂。
动态光散射测定步骤(1)制备的微乳液的粒径是82.36nm，步骤(3)制备的微乳液的粒 径是81.76nm。
由原子吸收光谱法测定制备的催化剂的活性组分含量，对比例3-9的催化剂中，Pd含量为0.10％，Ni含量为3.1％，Cu含量为2.4％。
实施效果
加氢反应条件：催化剂在单段绝热固定床反应器的装填量为50mL，填料50mL，反应物料空速：1500/h，操作压力：3.0MPa，氢炔比2.5，反应器入口温度55℃。反应物料组成见下表3-17，运行结果见表3-18。粗氢组成：H 2 50％，CO 0.1％。
表3-17物料组成
反应物料 C 2H 2 H 2 C 2H 4 C 3 CO
含量(v/v％) 1 3.0 83 1.0 0.006
表3-18运行结果
Figure PCTCN2021086214-appb-000024
实施例3-10
载体：采用市售双峰孔分布球形氧化铝载体，直径为4mm。经过1125℃焙烧4h后，双峰孔径分布范围在25-47nm和300-498mm，吸水率50％，比表面积为21.46m 2/g。称取该载体100g。
催化剂制备：
(1)称取无水硝酸镍9.34g，氯化铜1.06g，溶于70mL去离子水中，加正己烷23.3g，加CATB 3.5g，加正丁醇3.0g，充分搅拌形成微乳液，将称取的载体浸渍到所制备的微乳液中，摇动100min，滤除余液，在70℃下干燥，在450℃下焙烧5h，称为半成品催化剂A10。
(2)称取硝酸银0.095g，溶于55mL去离子水中，调pH值为3，再将半成品催化剂A10浸渍到已配制的Pd盐溶液中，浸渍60min后，80℃干燥，530℃条件下焙烧5小时，得到半成品催化剂B10。
(3)称取硝酸钯0.129g，溶于50mL去离子水中，调pH为1.8，将步骤(2)制备的半成品催化剂B10浸渍于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，90℃干燥，在550℃焙烧4小时，得到半成品催化剂C10。
(4)称取硝酸钯0.0645g，溶于70mL去离子水中，加正己烷23.3g，加CATB 3.5g，加正丁醇3.0g，充分搅拌形成微乳液，将步骤(3)制备的半成品催化剂C10浸渍到所制备的微乳液中，摇动100min，滤除余液，在70℃下干燥，在450℃下焙烧5h得到半成品催化剂D10。
(5)将步骤(4)得到的半成品催化剂D10置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在180℃温度，还原处理4h，得到所要的成品催化剂。
动态光散射测定步骤(1)制备的微乳液的粒径是496.68nm，步骤(4)制备的微乳液的粒径是497.14nm。
由原子吸收光谱法测定制备的催化剂的活性组分含量，实施例3-10的催化剂中，Pd含量为0.10％，Ni含量为3.00％，Cu含量为0.5％，Ag含量为0.06％。
对比例3-10
催化剂载体与催化剂制备条件与实施例3-10相同，不同的是Ni负载量降低至实施例3-10的1/10。
催化剂制备：
(1)称取无水硝酸镍0.934g，氯化铜1.06g，溶于70mL去离子水中，加正己烷23.3g，加CATB 3.5g，加正丁醇3.0g，充分搅拌形成微乳液，将称取的载体浸渍到所制备的微乳液中，摇动100min，滤除余液，在70℃下干燥，在450℃下焙烧5h，称为半成品催化剂A10-1。
(2)称取硝酸银0.095g，溶于55mL去离子水中，调pH值为3，将步骤(1)制备的半成品催化剂A10-1浸渍于所配制的配制含银的硝酸银溶液中，摇动，待溶液全部吸收后，浸渍60min后，80℃干燥，530℃条件下焙烧5小时，得到半成品催化剂B10-1。
(3)称取硝酸钯0.129g，溶离子水中，调pH为1.8，再将半成品催化剂B10-1浸渍到已配制的Pd盐溶液中，90℃干燥，在550℃焙烧4小时，得到半成品催化剂C10-1。
(4)称取硝酸钯0.0645g，溶于70mL去离子水中，加正己烷23.3g，加CATB 3.5g，加正丁醇3.0g，充分搅拌形成微乳液，将步骤(3)制备的半成品催化剂C10-1浸渍到所制备的微乳液中，摇动100min，滤除余液，在70℃下干燥，在450℃下焙烧5h得到半成品催化剂D10。
(5)将步骤(4)得到的半成品催化剂D10置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在180℃温度，还原处理4h，得到所要的成品催化剂。
动态光散射测定步骤(1)制备的微乳液的粒径是496.68nm，步骤(4)制备的微乳液的粒径是497.14nm。由原子吸收光谱法测定制备的催化剂的活性组分含量，对比例3-10的催化剂中，Pd含量为0.9％，Ni含量为0.3％，Cu含量为0.5％，Ag含量为0.06％。
实施效果
加氢反应条件：催化剂在单段等温床反应器的装填量为50mL，填料50mL。粗氢组成：氢气40％，CO 0.3％。反应物料空速：3000/h，操作压力：3.0MPa，氢炔比2，反应器入口温度65℃。反应物料组成见下表3-19，运行结果见表3-20。
表3-19物料组成
反应物料 C 2H 2 H 2 C 2H 4 C 3 CO
含量(v/v％) 0.2 0.4 70 3.0 0.003
表3-20运行结果
Figure PCTCN2021086214-appb-000025
对比例3-10中，负载的Ni含量降低，使得Ni与Cu的活性中心，其活性已不能对加氢副产物具有饱和加氢的作用，因此，虽然反应器初始活性与选择性较好，但随反应的进行，加氢副产物不断累积，形成的结焦使对比例中催化剂性能不断下降，以致1000小时后乙炔转化率降低到95％，选择性也降低到初始值的一半。
实施例3-11
载体：采用市售双峰孔分布四叶草形氧化铝载体，直径为3mm，长度为3mm。经过1093℃焙烧4h后，双峰孔径分布范围在22-45nm和70-420mm，吸水率56％，比表面积为29.67m 2/g。称取该载体100g。
催化剂制备：
(1)称取氯化镍1.11g，硝酸铜1.49g，溶于60mL去离子水中，加正己烷27g，加Triton X-100 15.00g，加正丁醇14.4g，充分搅拌形成微乳液，将称取的载体浸渍到所制备的微乳液中，摇动 90min，滤除余液，在80℃下干燥，在600℃下焙烧4h，称为半成品催化剂A11。
(2)称取硝酸银0.26g，溶解于45g去离子水中，用硝酸条件溶液PH为5.0，将半成品催化剂A11浸渍到配制的Ag溶液中，浸渍60in后，120℃干燥，500℃下焙烧6h，称为半成品催化剂B11
(3)称取氯化钯0.11g，溶于100mL去离子水中，调pH为1.8，再将半成品催化剂B11浸渍到已配制的Pd盐溶液中，浸渍60min后，90℃干燥，550℃条件下焙烧4小时，得到半成品催化剂C11。
(4)称取氯化钯0.084g，溶于70mL去离子水中，加正己烷31.5g，加Triton X-100 17.50g，加正丁醇16.8g，充分搅拌形成微乳液，将步骤(3)制备的半成品催化剂C11浸渍到所制备的微乳液中，摇动90min，滤除余液，在80℃下干燥，在600℃下焙烧4h得到半成品催化剂D11。
(5)将步骤(4)得到的半成品催化剂D11置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在150℃温度，还原处理8h，得到所要的成品催化剂。
动态光散射测定步骤(1)制备的微乳液乳液的粒径是66.68nm，步骤(4)制备的微乳液乳液的粒径是67.49nm。由原子吸收光谱法测定制备的催化剂的活性组分含量，实施例3-11的催化剂中，Pd含量为0.07％，Ni含量为0.5％，Cu含量为0.5％。Ag含量0.16％。
对比例3-11
催化剂载体及制备条件与实施例3-11相同，区别是Pd含量低。
催化剂制备：
(1)称取氯化镍1.11g，硝酸铜1.49g，溶于60mL去离子水中，加正己烷27g，加Triton X-100 15.00g，加正丁醇14.4g，充分搅拌形成微乳液，将称取的载体浸渍到所制备的微乳液中，摇动90min，滤除余液，在80℃下干燥，在600℃下焙烧4h，称为半成品催化剂A11-1。
(2)称取硝酸银0.26g，溶解于45g去离子水中，用硝酸条件溶液PH为5.0，将(1)制备的A11-1催化剂，浸渍在已配制的银溶液中，浸渍60in后，120℃干燥，500℃下焙烧6h，称为半成品催化剂B11-1
(3)称取氯化钯0.084g，溶于100mL去离子水中，调pH为1.8，再将半成品催化剂B11-1浸渍到已配制的Pd盐溶液中，浸渍60min后，90℃干燥，550℃条件下焙烧4小时，得到半成品催化剂C11-1。
(4)称取氯化钯0.0085g，溶于70mL去离子水中，加正己烷31.5g，加Triton X-100 17.50g，加正丁醇16.8g，充分搅拌形成微乳液，将步骤(3)制备的半成品催化剂C11-1浸渍到所制备的微乳液中，摇动90min，滤除余液，在80℃下干燥，在600℃焙烧4h得到半成品催化剂D11-1。
(5)将步骤(4)得到的半成品催化剂D11-1置于固定床反应装置中，用摩尔比为N 2:H 2＝1:1的混合气体，在150℃温度，还原处理8h，得到所要的成品催化剂。
动态光散射测定步骤(1)制备的微乳液乳液的粒径是66.68nm，步骤(4)制备的微乳液乳液的粒径是67.49nm。由原子吸收光谱法测定制备的催化剂的活性组分含量，对比例3-11的催化剂中，Pd含量为0.055％，Ni含量为0.5％，Cu含量为0.5％，Ag含量0.16％。
实施效果
加氢反应条件：催化剂在单段绝热固定床反应器的装填量为50mL，填料50mL，反应物料空速：4000/h，操作压力：3.0MPa，氢炔比3，反应器入口温度135℃。反应物料组成见下表3-21，运行结果见表3-22。粗氢组成：H 2 30％，CO 1％。
表3-21物料组成
反应物料 C 2H 2 H 2 C 2H 4 C 3 CO
含量(v/v％) 0.6 1.8 83 7.0 0.06
表3-22运行结果
Figure PCTCN2021086214-appb-000026
本反应工况中，尽管物料中乙炔含量并非最高，物料中CO含量也高达600ppm，对催化剂的活性有十分明显的抑制作用，对比例中溶液法负载的Pd含量低于极限值后，仅靠提高反应器入口温度也不能有效的脱除乙炔，因此，在将反应器入口温度提高至135℃，也不能把乙炔完全转化。

Claims (37)

  1. 一种炔烃选择加氢催化剂，其中，该催化剂的载体为氧化铝或主要是氧化铝，并具有双峰孔分布结构；其中小孔的孔径为15-50nm，大孔的孔径为80-500nm，催化剂至少含有Pd、Ni、Cu，以载体的质量为100％计，Pd的含量为0.03-0.1％，Ni的含量为0.5-5％，Cu与Ni的重量比为0.1-1.0:1.0，其中，通过微乳液负载Ni、Cu及部分Pd；所述微乳液的粒径不低于小孔的最大孔径而且不高于大孔的最大孔径。
  2. 根据权利要求1所述的炔烃选择加氢催化剂，其中，该催化剂的载体为氧化铝或主要是氧化铝，并具有双峰孔分布结构；其中小孔的孔径为15-50nm，大孔的孔径为80-500nm，催化剂至少含有Pd、Ni、Cu，以载体的质量为100％计，Pd的含量为0.035-0.08％，Ni的含量为0.5-5％，Cu与Ni的重量比为0.1-1.0：1.0，其中微乳液负载Ni、Cu及部分Pd，所述微乳液的粒径不低于小孔的最大孔径而不高于大孔的最大孔径，微乳液负载的Pd的量是Ni+Cu含量之和的1/100-1/200；剩余部分Pd采用溶液负载。
  3. 根据权利要求1所述的炔烃选择加氢催化剂，其中，该催化剂以氧化铝为载体，具有双峰孔径分布特征，小孔的孔径为15-50nm，大孔的孔径为80-500nm；所述催化剂至少含有活性组分Pd、Ni、Cu，以载体的质量100％计，Pd的含量为0.03-0.09％，Ni的含量为0.5-5％，Cu与Ni的重量比为0.1-1.0:1.0，通过微乳液负载Ni、Cu及部分Pd。
  4. 根据权利要求1所述的炔烃选择加氢催化剂，其中，该催化剂载体为氧化铝或主要是氧化铝，具有双峰孔分布结构的氧化铝，其中小孔的孔径为15-50nm，大孔的孔径为80-500nm，催化剂至少含有活性组分Pd，Ni、Cu，以催化剂的质量为100％计，Pd的含量为0.06-0.1％，Ni的含量为0.5-5％，Cu与Ni的重量比为0.1-1.0:1.0。
  5. 根据权利要求1所述的催化剂，其中，该催化剂载体为氧化铝或主要是氧化铝，并具有双峰分布结构；其中小孔的孔径为15-50nm，大孔的孔径为80-500nm，催化剂至少含有Pd、Ni、Cu，以载体的质量为100％计，Pd的含量为0.06-0.08％，Ni的含量为0.5-5％，Cu与Ni的重量比为0.1-1.0：1.0，其中通过微乳液负载Ni、Cu及部分Pd并且主要分布在载体的大孔中，微乳液法负载的Pd的量是Ni+Cu含量之和的1/100-1/200。
  6. 根据权利要求1-5任一项所述的催化剂，其中，该催化剂中还含有Ag，以溶液负载，其含量为0.03-0.5％，优选为0.08-0.21％。
  7. 根据权利要求6所述的催化剂，其中，催化剂载体为氧化铝或主要是氧化铝，并具有双峰孔分布结构；其中小孔的孔径为15-50nm，大孔的孔径为80-500nm，催化剂至少含有Pd、Ag、Ni、Cu，以载体的质量为100％计，Pd的含量为0.035-0.07％，Ag的含量为0.08-0.21％，Ni的含量为0.5-5％，Cu与Ni的重量比为0.1-1.0：1，其中通过微乳液负载Ni、Cu及部分Pd并且主要分布在载体的大孔中，微乳液法负载的Pd的量是Ni+Cu含量之和的1/100-1/200；Ag及部分Pd以溶液法进行负载。
  8. 根据权利要求1所述的催化剂，其中，载体为氧化铝或主要是氧化铝；氧化铝的晶型为θ、α晶型或其混合晶型；当载体主要是氧化铝时，载体中的氧化铝在80％以上。
  9. 根据权利要求3所述的炔烃选择加氢催化剂，其中，所述Pd的含量为0.035-0.075％，微乳液负载的部分Pd的含量是所述的Ni+Cu含量之和的1/110-1/200。
  10. 根据权利要求1所述的炔烃选择加氢催化剂，其中，所述催化剂载体为氧化铝或主要是氧化铝，具有双峰孔分布结构的氧化铝，其中小孔的孔径为15-50nm，大孔的孔径为80-500nm，催化剂至少含有活性组分Pd、Ag、Ni、Cu，以催化剂的质量为100％计，Pd的含量为0.07-0.1％，Ag的含量为0.03-0.5％，Ni含量为0.5-5％，Cu含量为0.5-5％，Ni和Cu的总含量为1-5.5％。
  11. 根据权利要求1-10任一项所述的炔烃选择加氢催化剂，其中，所述催化剂的比表面积为20-50m 2/g。
  12. 根据权利要求1所述的炔烃选择加氢催化剂，其中，通过微乳液负载的Pd的量是Ni+Cu含量之和的1/100-1/200。
  13. 根据权利要求1所述的催化剂，其中，微乳液负载过程包括：将前驱体盐溶于水中，加入油相、表面活性剂和助表面活性剂，充分搅拌形成微乳液，其中油相为烷烃或环烷烃，表面活性剂为离子型表面活性剂和/或非离子型表面活性剂，助表面活性剂为有机醇。
  14. 根据权利要求13所述的催化剂，其中，其中，微乳液负载过程满足以下条件：水相与油相的重量比为2-3，表面活性剂与油相的重量比为0.15-0.6，表面活性剂与助表面活性剂的重量比为1-1.2，微乳液的粒径大于50nm、小于500nm。
  15. 根据权利要求13或14所述的催化剂，其中，在微乳液负载过程中，油相为C6-C8饱和烷烃或环烷烃；表面活性剂为离子型表面活性剂和/或非离子型表面活性剂；助表面活性剂为C4-C6的醇类。
  16. 根据权利要求13-15任一项所述的催化剂，其中，所述油相为环己烷或正己烷。
  17. 根据权利要求13-15任一项所述的催化剂，其中，所述表面活性剂为聚乙二醇辛基苯基醚或十六烷基三甲基溴化铵。
  18. 根据权利要求13-15任一项所述的催化剂，其中，所述助表面活性剂为正丁醇和/或正戊醇。
  19. 根据权利要求1所述的催化剂，其中，催化剂在制备过程中，微乳液负载Pd的步骤是在微乳液负载Ni和Cu步骤后。
  20. 根据权利要求1所述的催化剂，其中，催化剂在制备过程中，Pd的溶液负载与Ni、Cu的微乳液负载先后次序不限定。
  21. 根据权利要求6或10所述的催化剂，其中，催化剂在制备过程中，溶液负载Ag的步骤是在溶液负载Pd步骤后。
  22. 根据权利要求1-21任一项所述的催化剂的制备方法，其包含以下步骤：
    (1)将Ni和Cu的前驱体盐溶于水中，加入油相、表面活性剂和助表面活性剂，充分搅拌 形成微乳液，将载体加入到制好的微乳液中浸渍0.5-4小时后，滤除余液，干燥后在400-600℃下焙烧4小时以上，得到半成品催化剂A；
    (2)将Pd的前驱体盐溶于水，调pH为1.5-2.5，再将半成品催化剂A加入Pd的盐溶液中，浸渍吸附0.5-4h后，干燥后400-600℃条件下焙烧4-6h，得到半成品催化剂B；
    (3)将Pd前驱体盐溶于水中，加入油相、表面活性剂和助表面活性剂，充分搅拌形成微乳液，将半成品催化剂B加入到制好的微乳液中浸渍0.5-4小时后，滤除余液，干燥后，在400-600℃下焙烧4小时以上，得到所述催化剂。
  23. 根据权利要求22所述的催化剂的制备方法，其中，当催化剂含有Ag时，该制备方法的制备过程具体包含以下步骤：
    (1)将Ni和Cu的前驱体盐溶于水中，加入油相、表面活性剂和助表面活性剂，充分搅拌形成微乳液；将载体加入到制好的微乳液中浸渍0.5-4小时后，滤除余液；干燥后，在400-600℃下焙烧4-6h，得到半成品催化剂A；
    (2)将Pd前驱体盐溶于水中，加入油相、表面活性剂和助表面活性剂，充分搅拌形成微乳液，将半成品催化剂A加入到制好的微乳液中浸渍0.5-4小时后，滤除余液；干燥后，在400-600℃下焙烧4-6h，得到半成品催化剂B；
    (3)将Pd的前驱体盐溶于水，调pH为1.5-2.5，再将半成品催化剂B加入Pd的盐溶液中，浸渍吸附0.5-4h后，干燥后在400-600℃条件下焙烧4-6h，得到半成品催化剂C；
    (4)将Ag盐的溶解在去离子中，调pH为1-5，将半成品催化剂C浸渍在已制备的溶液中，待溶液完全吸收后干燥，在400-600℃焙烧4-6h，得到所述催化剂；
    优选地，所述制备方法包括以下具体步骤：
    (1)将Ni和Cu的前驱体盐溶于水中，加入油相、表面活性剂和助表面活性剂，充分搅拌形成微乳液；将载体加入到制好的微乳液中浸渍0.5-4小时后，滤除余液；干燥后，在400-600℃下焙烧4-6h，得到半成品催化剂A；
    (2)将Pd的前驱体盐溶于水，调pH为1.5-2.5，再将半成品催化剂A加入Pd的盐溶液中，浸渍吸附0.5-4h后，干燥后在400-600℃条件下焙烧4-6h，得到半成品催化剂B；
    (3)Ag的负载以饱和浸渍方式进行，即配制的Ag盐的溶液是载体饱和吸水率的80-110％，调pH为1-5，浸渍后干燥，在400-600℃之间进行焙烧，得到半成品催化剂C；
    (4)将Pd前驱体盐溶于水中，加入油相、表面活性剂和助表面活性剂，充分搅拌形成微乳液，将半成品催化剂C加入到制好的微乳液中浸渍0.5-4小时后，滤除余液；干燥后，在400-600℃下焙烧4-6h，得到所述催化剂；
    或者，所述催化剂的制备步骤包括：
    (1)将Ni和Cu的前驱体盐溶于水中，加入油相、表面活性剂和助表面活性剂，充分搅拌形成微乳液；将载体加入到制好的微乳液中浸渍0.5-4小时后，滤除余液，在80-120℃下干燥1-6小时，在300-600℃下焙烧2-8h，得到半成品催化剂A；
    (2)将Ag的负载以饱和浸渍法进行，即配制的Ag盐的溶液是载体饱和吸水率的80-110％，调pH为1-5，半成品催化剂A负载Ag之后在500-550℃之间进行焙烧，时间为4-6小时，得到半成品催化剂B；
    (3)将Pd的前驱体盐溶于水，调pH为1.5-2.5，再将半成品催化剂B加入Pd的盐溶液中，浸渍吸附0.5-4h后，干燥1-4小时，400-550℃条件下焙烧2-6h，得到半成品催化剂C；
    (4)将Pd前驱体盐溶于水中，加入油相、表面活性剂和助表面活性剂，充分搅拌形成微乳液；将半成品催化剂C加入到制好的微乳液中浸渍0.5-4小时后，滤除余液；在干燥后1-6小时，在300-600℃下焙烧2-8h，得到半成品催化剂D；
    (5)将半成品催化剂D置于固定床反应装置中，用N 2：H 2＝1:1的混合气体，在150-200℃下，还原处理4-8h得到成品催化剂E。
  24. 根据权利要求22或23所述的制备方法，其中，微乳液满足以下条件：水相与油相的重量比为2-3，表面活性剂与油相的重量比为0.15-0.6，表面活性剂与助表面活性剂的重量比为1-1.2，微乳液粒径大于50nm、小于500nm。
  25. 一种碳二馏分炔烃选择加氢方法，其中：加氢物料为来自前脱乙烷塔塔顶的碳二馏分，进入固定床反应器后进行气相加氢脱除乙炔，该选择性加氢反应的工艺条件为：反应器入口温度35-100℃，压力1.5-3.0MPa，气体体积空速2000-11000h -1；
    其中，所述催化剂为权利要求1-21任一项所述的催化剂。
  26. 根据权利要求25所述的碳二馏分炔烃选择加氢方法，其中，所述催化反应物料中乙烯占65-93％(v/v)，乙炔0.2-2.5％(v/v)。
  27. 根据权利要求25所述的碳二馏分炔烃选择加氢方法，其中，所述催化反应物料中乙烯占65-93％(v/v)，其次为乙烷5-35％(v/v)，乙炔0.3-2.5％(v/v)，碳三馏分0.01-0.8％(v/v)。
  28. 根据权利要求25-27任一项所述的碳二馏分炔烃选择加氢方法，其中，使用固定床反应器单段反应器加氢时，反应器入口氢炔比为1.3-2.2，优选1.3-1.8。
  29. 根据权利要求25-28任一项所述的碳二馏分炔烃选择加氢方法，其中，使用固定床反应器两段反应器加氢时，一段反应器入口氢炔比为1.0-1.4，二段反应器入口氢炔比为1.5-2.5。
  30. 根据权利要求25-29任一项所述的碳二馏分炔烃选择加氢方法，其中，使用固定床反应器三段反应器串联加氢时，一段反应器入口氢炔比为0.5-1.5，二段反应器入口氢炔比为1.0-2.0，三段反应器入口氢炔比为1.4-3.0，优选的是，一段反应器入口氢炔比为0.8-1.5，二段反应器入口氢炔比为1.2-1.6，三段反应器入口氢炔比为1.5-2.5。
  31. 根据权利要求25所述的碳二馏分炔烃选择加氢方法，其中，所述催化剂在加氢前，需要进行还原，还原温度为150-200℃。
  32. 一种采用粗氢为氢源的碳二后加氢工艺的选择加氢方法，其中，加氢物料为来自脱乙烷塔塔顶的碳二馏分，进入固定床反应器后进行气相加氢脱除乙炔，加氢反应所使用的氢气为 粗氢，粗氢中H 2含量为20-50v/v％，CO含量为0.1-1v/v％，反应工艺条件为：反应器入口温度55-130℃，压力1.5-3.0MPa，气体体积空速1500-6000h -1；
    其中，所述催化剂为权利要求1-21任一项所述的催化剂。
  33. 根据权利要求32所述的选择加氢方法，其中，所述加氢物料为来自脱乙烷塔塔顶的碳二馏分，进入固定床反应器后进行气相加氢脱除乙炔，其中，加氢反应所使用的氢气为粗氢，其中H 2含量为30-50v/v％，CO含量为0.1-1v/v％，其余部分为甲烷；反应工艺条件为：反应器入口温度55-130℃，压力1.5-3.0MPa，气体体积空速1500-4000h -1；
    其中，所述催化剂为权利要求4所述的催化剂。
  34. 根据权利要求32所述的选择加氢方法，其中，反应器是单段固定床反应器。
  35. 根据权利要求32所述的选择加氢方法，其中，进入单段固定床反应器的催化反应物料中，乙烯60-93v/v％，乙炔0.2-1.0v/v％，碳三馏分1.0-7.0v/v％。
  36. 根据权利要求32所述的选择加氢方法，其中，所述催化剂在加氢前需要进行还原，还原温度为150-200℃。
  37. 根据权利要求32所述的选择加氢方法，其中，单段固定床反应器入口物料中的氢炔比为2-3。
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