Non-noble metal catalyst for ethylene deacetylation as well as preparation method and application of non-noble metal catalyst

Abstract

The invention belongs to the technical field of ethylene selective hydrofining, and particularly relates to a non-noble metal catalyst for ethylene deacetylation as well as a preparation method and application of the non-noble metal catalyst. In order to solve the problems of high catalyst price, low hydrogenation activity, poor ethylene selectivity, fast activity attenuation of the catalyst during long-term stable operation, easy carbon deposition and sulfur poisoning and the like, the invention creates a uniformly distributed non-noble metal nanoparticle catalyst, the active metal is highly dispersed nanoparticles, the particle size is 0.5-8nm, the ratio of 3-4.5 nm is not less than 50%, and the particle size is not less than 20%. The uniform and highly dispersed nanoparticles solve the contradictory problem of activity and selectivity. The specific surface area of the catalyst is 0.05-500m < 2 > / g, the pore volume is 0.001-0.5 cm < 3 > / g, and the pore structure of the catalyst can well improve the carbon capacity of the catalyst, so that the catalyst can have enough reaction channels after long-term operation, and the service life of the catalyst is greatly prolonged.

Description

Technical Field

[0001] The present invention belongs to the technical field of ethylene selective hydrogenation refining, and particularly relates to a non-noble metal catalyst for ethylene dealkyne removal, a preparation method and an application thereof. Background Art

[0002] Ethylene is one of the world's most produced chemical products. The ethylene industry is the core of the petrochemical industry, with ethylene products accounting for over 75% of petrochemical output and occupying a vital position in the national economy. Ethylene is an essential chemical raw material for synthetic fibers, synthetic rubber, synthetic plastics (polyethylene and polyvinyl chloride), and synthetic ethanol (alcohol). It is also used in the manufacture of vinyl chloride, styrene, ethylene oxide, acetic acid, acetaldehyde, ethanol, and explosives. Polyethylene, produced through ethylene polymerization, is one of the most widely used polymer materials. Current production processes typically contain small amounts of acetylene (~1%) and trace amounts of oxygen (ppm levels). These acetylene and oxygen can poison the Ziegler-Natta catalyst used in ethylene polymerization and reduce the quality of the resulting polyethylene. Therefore, acetylene and oxygen levels in the ethylene feed gas must be reduced to ppm levels before polymerization can be used.

[0003] Selective hydrogenation to remove acetylene is an ideal method for removing acetylene from ethylene feed gas. This method is commonly used in industry to remove acetylene and oxygen, achieving excellent results. This process generally uses a supported palladium catalyst, which requires the catalyst to be able to highly selectively hydrogenate acetylene from the ethylene / acetylene mixture to ethylene without over-hydrogenating it to ethane. Pure palladium nanocrystals generally have very poor selectivity for high acetylene conversion in the presence of ethylene. Therefore, CN104689816A discloses a Pd / ZnO single-atom catalyst and applies it to the selective hydrogenation reaction of acetylene. The noble metal content in this catalyst is still relatively high. Although the claims mention a noble metal content of 0.3%-4%, the examples thereof show that its noble metal Pd content is 1%, indicating that the catalyst cost is still relatively high. Patent CN115259985A proposes using a Pd-M / Al2O3 single-atom catalyst to improve the performance of the selective hydrogenation of acetylene to ethylene. M is one or more of Ni, Ag, Co, Zn, and Bi, with a Pd loading of 0.015-3.0 wt% and an M loading of 0-5 wt% based on the total catalyst weight. However, industrial raw materials contain trace amounts of organic sulfides, making single-atom catalysts susceptible to sulfur poisoning. Furthermore, carbon deposition is unavoidable during the reaction, and single-atom catalysts are also susceptible to this.

[0004] The use of surface modification, deposition of a second metal / metal oxide, and alloying methods to improve selectivity is also a commonly used method in the field. For example, CN102898266A obtains an AB / TiO2 type catalyst by continuous photodeposition of binary metals, wherein A is Pd, Pt, Au or Rh, and B is Ag, Cu or Ni. The selectivity of ethylene is 80-97%. This method is not easy to apply in large-scale industrial applications, and the selectivity of ethylene needs to be improved. CN109622000A loads nickel salts and zinc salts onto carbon materials by impregnation, first treating them under a hydrogen atmosphere to obtain a Ni3Zn catalyst, and then treating them under an acetylene atmosphere to obtain Ni3ZnC 0.7 Catalyst. Ni3ZnC is formed by introducing carbon atoms 0.7 The structure showed excellent selectivity in the reaction (about 82%). However, the industry requires that the acetylene in the ethylene / acetylene mixture be reduced to the ppm level, and this method obviously cannot meet the industrial requirements.

[0005] In summary, current technologies still suffer from issues such as high catalyst prices, low hydrogenation activity, poor ethylene selectivity, rapid catalyst activity decay during long-term stable operation, and susceptibility to carbon deposition and sulfur poisoning. These issues cannot meet the ethylene industry's demand for high-quality products, hindering its development. There is an urgent need to develop a catalyst that can effectively address these issues and promote the high-quality development of the ethylene industry. Summary of the Invention

[0006] In view of the above problems, the present invention provides a non-noble metal catalyst for ethylene dealkyne removal, a preparation method and application thereof.

[0007] In order to achieve the above-mentioned purpose, the present invention adopts the following technical solutions:

[0008] The present invention provides a non-precious metal catalyst for ethylene dealkyning, comprising three parts: an active component, an auxiliary agent, and a carrier. The active component is at least one of the non-precious metals Ni, Co, Fe, Mo, and Cu; the auxiliary agent is one or two of the non-precious metals Na, K, Mg, Ca, Cr, Zr, Zn, Mn, and Ti; and the carrier is at least one of kaolin, acid clay, montmorillonite, SiC, SiO2, and Al2O3.

[0009] Furthermore, the content of the active component is 0.05-30wt%, the content of the auxiliary agent is 0.5-30wt%, and the rest is the carrier.

[0010] Furthermore, the active component exists in the form of an alloy or a metal complex on the carrier. The active component is a highly dispersed nanoparticle with a particle size of 0.5-8 nm, of which 3-4.5 nm accounts for ≮50%.

[0011] Furthermore, the specific surface area of ​​the catalyst is 0.05-500m 2 / g, pore volume of 0.001-0.5cm 3 / g, and the bulk density is 0.3-1.5g / mL.

[0012] The present invention also provides a method for preparing a non-noble metal catalyst for ethylene dealkyne removal, comprising the following steps:

[0013] Step 1: preparing a mixed solution of an active component soluble precursor and an auxiliary agent soluble precursor, and heating the mixed solution;

[0014] Step 2, adjusting the pH of the mixed solution obtained in step 1;

[0015] Step 3, impregnating the carrier in the solution obtained in step 2, stirring continuously during the impregnation process so that the active ingredients and auxiliary agents are distributed on the carrier with specific structural characteristics;

[0016] Step 4: drying and calcining the catalyst obtained in step 3 to obtain the catalyst.

[0017] Furthermore, in step 1, the soluble precursor of the active component is sulfate, nitrate, chloride, oxalate, formate, or acetate, and the soluble precursor of the auxiliary agent is nitrate, sulfate, or chloride. If the auxiliary agent is Na or K, its soluble precursor may also be carbonate or bicarbonate.

[0018] The total concentration of the mixed solution is 0.01-1 mol / L, and the mixed solution is heated to between 15-80°C.

[0019] Furthermore, in step 2, an organic acid or an inorganic acid is used to adjust the pH of the mixed solution obtained in step 1 to between 1.0 and 4.0;

[0020] The organic or inorganic acid is hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, acetic acid, or citric acid.

[0021] Furthermore, in step 3, the immersion time is 0.5-24 hours.

[0022] Furthermore, in step 4, during drying, the temperature is increased from room temperature to 100-150°C at a heating rate of 20-60°C / h, and dried at this temperature for 6-24 hours; during calcination, the temperature is increased to 200-800°C at a heating rate of 20-60°C / h, and calcined for 2-12 hours.

[0023] The present invention also provides an application of a non-noble metal catalyst for ethylene dealkyne removal, which is used for selective hydrogenation of ethylene to remove acetylene and oxygen.

[0024] Furthermore, the specific conditions of the application are:

[0025] The catalyst is reduced and activated in a hydrogen atmosphere before use. The required activation temperature is 150-650°C, the pressure is 0.1-5.0 MPa, and the hydrogen volume space velocity is 200-20000 h -1 After activation, the catalyst is directly fed into the ethylene feedstock for reaction. The reaction conditions are: temperature 50-350°C, pressure 0.1-5.0 MPa, mass space velocity 5-50000 h -1 .

[0026] Compared with the prior art, the present invention has the following advantages:

[0027] In response to the existing problems of high catalyst prices, low hydrogenation activity, poor ethylene selectivity, rapid catalyst activity decay during long-term stable operation, easy carbon deposition and sulfur poisoning, the present invention has created a uniformly distributed non-precious metal nanoparticle catalyst. The active metal is a highly dispersed nanoparticle with a particle size of 0.5-8nm, of which 3-4.5nm accounts for ≮50%. The uniform and highly dispersed nanoparticles solve the contradiction between activity and selectivity. The specific surface area of ​​the catalyst is 0.05-500m 2 / g, pore volume of 0.001-0.5cm 3 / g. The catalyst's pore structure significantly improves its carbon capacity, ensuring sufficient reaction channels for long-term operation and significantly extending its lifespan. Consequently, the catalyst of this invention exhibits advantages such as high acetylene and oxygen hydrogenation activity, high ethylene selectivity, excellent long-term stability, strong sulfur tolerance, and resistance to carbon deposition. It meets the stringent requirements of industrial operation and has great potential for industrialization. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 TEM characterization and particle size distribution diagram, where (A) and (D) are Example 1; (B) and (E) are Comparative Example 1; (C) and (F) are Comparative Example 2. DETAILED DESCRIPTION

[0029] In order to further illustrate the technical solution of the present invention, the present invention is further described below through examples. Example 1

[0030] The method for preparing a non-precious metal catalyst for ethylene dealkyning of the present embodiment comprises the following steps: Step 1: prepare a 0.5 mol / L mixed solution of the active component soluble precursors CuCl2 and FeSO4 and the auxiliary agent soluble precursor NaCO3, and heat the mixed solution to 50°C; Step 2, adjusting the pH of the mixed solution obtained in step 1 to 2.0 using hydrochloric acid; Step 3: Immerse the carrier Al2O3 in the solution obtained in step 2 for 12 hours, stirring continuously during the immersion process to allow the active components and additives to be distributed on the carrier with specific structural characteristics; Step 4, drying and calcining the catalyst obtained in step 3 to obtain the catalyst, wherein the temperature is increased from room temperature to 120°C at a heating rate of 20°C / h during drying, and dried at this temperature for 12 hours; and the temperature is increased to 600°C at a heating rate of 30°C / h during calcination, and calcined for 8 hours.

[0031] The catalyst prepared in this embodiment includes three parts: active components Cu and Fe, auxiliary agent Na, and carrier Al2O3, wherein the content of the active components is 30wt%, the content of the auxiliary agent is 30wt%, and the rest is the carrier; the active components Cu and Fe exist on the carrier in the form of alloy or metal composite, and the active components Cu and Fe are highly dispersed nanoparticles with a particle size of 0.5-8nm, of which 3-4.5nm accounts for 60%, and the specific surface area is 300m 2 / g, pore volume 0.1cm 3 / g, and the bulk density is 0.3g / mL.

[0032] The catalyst was reduced and activated in a hydrogen atmosphere before use. The required activation temperature was 500°C, the pressure was 0.2 MPa, and the hydrogen volume space velocity was 200 h -1 After activation, the catalyst was directly fed into the ethylene feedstock for reaction under the following reaction conditions: temperature 200°C, pressure 0.1 MPa, mass space velocity 800 h -1 . Example 2

[0033] The method for preparing a non-precious metal catalyst for ethylene dealkyning of the present embodiment comprises the following steps: Step 1: prepare a 0.5 mol / L mixed solution of the active component soluble precursor CuCl2 and the auxiliary agent soluble precursor NaCO3, and heat the mixed solution to 50°C; Step 2, adjusting the pH of the mixed solution obtained in step 1 to 2.0 using hydrochloric acid; Step 3: Immerse the SiO2 carrier in the solution obtained in step 2 for 12 hours, stirring continuously during the immersion process to allow the active components and additives to be distributed on the carrier with specific structural characteristics; Step 4, drying and calcining the catalyst obtained in step 3 to obtain the catalyst, wherein the temperature is increased from room temperature to 120°C at a heating rate of 30°C / h during drying, and dried at this temperature for 12 hours; and the temperature is increased to 600°C at a heating rate of 40°C / h during calcination, and calcined for 8 hours.

[0034] The catalyst prepared in this embodiment includes three parts: active component Cu, auxiliary agent Na, and carrier Al2O3, wherein the content of the active component is 20wt%, the content of the auxiliary agent is 30wt%, and the rest is the carrier; the active component Cu exists in the form of an alloy or a metal composite on the carrier, and the active component Cu is a highly dispersed nanoparticle with a particle size of 0.5-8nm, of which 3-4.5nm accounts for 52%, and the specific surface area is 30m 2 / g, pore volume 0.2cm 3 / g, and the bulk density is 0.8g / mL.

[0035] The catalyst was reduced and activated in a hydrogen atmosphere before use. The required activation temperature was 300°C, the pressure was 1 MPa, and the hydrogen volume space velocity was 1000 h -1 After activation, the catalyst was directly fed into the ethylene feedstock for reaction under the following conditions: temperature 100°C, pressure 0.5 MPa, mass space velocity 300 h -1 . Example 3

[0036] The method for preparing a non-precious metal catalyst for ethylene dealkyning of the present embodiment comprises the following steps: Step 1: prepare a 1 mol / L mixed solution of the active component soluble precursors Ni(NO3)2 and Mo2(SO4)3 and the additive soluble precursor CaCl2, and heat the mixed solution to 80°C; Step 2, adjusting the pH of the mixed solution obtained in step 1 to 4.0 using hydrochloric acid; Step 3: Immerse the composite support Al2O3-SiO2 in the solution obtained in step 2 for 24 hours, stirring continuously during the immersion process to allow the active components and additives to be distributed on the support with specific structural characteristics; Step 4, drying and calcining the catalyst obtained in step 3 to obtain the catalyst, wherein the temperature is increased from room temperature to 150°C at a heating rate of 50°C / h during drying, and dried at this temperature for 6 hours; the temperature is increased to 800°C at a heating rate of 60°C / h during calcination, and calcined for 2 hours.

[0037] The catalyst prepared in this embodiment includes three parts: active components Ni and Mo, additive Ca, and composite carrier Al2O3-SiO2, wherein the content of the active components is 5wt%, the content of the additive is 10wt%, and the rest is the composite carrier; the active components Ni and Mo exist in the form of alloy or metal composite on the composite carrier, and the active components Ni and Mo are highly dispersed nanoparticles with a particle size of 0.5-8nm, of which 3-4.5nm accounts for 80%, and the specific surface area is 500m 2 / g, pore volume 0.5cm 3 / g, and the bulk density is 0.5g / mL.

[0038] The catalyst was reduced and activated in a hydrogen atmosphere before use. The required activation temperature was 150°C, the pressure was 2 MPa, and the hydrogen volume space velocity was 2000 h -1 After activation, the catalyst was directly fed into the ethylene feedstock for reaction under the following conditions: temperature 50°C, pressure 5 MPa, mass space velocity 100 h -1 . Example 4

[0039] The method for preparing a non-precious metal catalyst for ethylene dealkyning of the present embodiment comprises the following steps: Step 1: prepare a 0.01 mol / L mixed solution of the active component soluble precursors CuCl2, Ni(NO3)2 and CoSO4 and the additive soluble precursor ZnCl2, and heat the mixed solution to 15°C; Step 2, adjusting the pH of the mixed solution obtained in step 1 to 2.0 using sulfuric acid; Step 3: immerse the SiC carrier in the solution obtained in step 2 for 0.5 h, stirring continuously during the immersion process to allow the active components and additives to be distributed on the carrier with specific structural characteristics; Step 4: drying and calcining the catalyst obtained in step 3 to obtain the catalyst, wherein the temperature is increased from room temperature to 100°C at a heating rate of 25°C / h during drying and dried at this temperature for 24 hours; and the temperature is increased to 200°C at a heating rate of 35°C / h during calcination and calcined for 12 hours.

[0040] The catalyst prepared in this embodiment includes three parts: active components Cu, Ni and Co, auxiliary agent Zn, and carrier SiC, wherein the content of the active components is 0.5wt%, the content of the auxiliary agent is 15wt%, and the rest is the carrier; the active components Cu, Ni and Co exist on the carrier in the form of alloy or metal composite, and the active components Cu, Ni and Co are highly dispersed nanoparticles with a particle size of 0.5-8nm, of which 3-4.5nm accounts for 65%, and the specific surface area is 0.05m 2 / g, pore volume 0.001cm 3 / g, and the bulk density is 1.5g / mL.

[0041] The catalyst was reduced and activated in a hydrogen atmosphere before use. The required activation temperature was 150°C, the pressure was 1 MPa, and the hydrogen volume space velocity was 2000 h -1 After activation, the catalyst was directly fed into the ethylene feedstock for reaction. The reaction conditions were: temperature 350°C, pressure 0.5 MPa, mass space velocity 5 h -1 . Example 5

[0042] The method for preparing a non-precious metal catalyst for ethylene dealkyning of the present embodiment comprises the following steps: Step 1: prepare a 0.6 mol / L mixed solution of NiCl2 and FeSO4, which are soluble precursors of the active components, and TiCl2, which is a soluble precursor of the auxiliary agent, and heat the mixed solution to 60°C; Step 2, adjusting the pH of the mixed solution obtained in step 1 to 3.0 using oxalic acid; Step 3: Immerse the composite carrier of kaolin, acid clay, and montmorillonite in the solution obtained in step 2 for 10 hours, stirring continuously during the immersion process to allow the active components and additives to be distributed on the carrier with specific structural characteristics; Step 4, drying the catalyst obtained in step 3 and calcining to obtain the catalyst, wherein the temperature is increased from room temperature to 110°C at a heating rate of 38°C / h during drying and dried at this temperature for 10 hours; the temperature is increased to 400°C at a heating rate of 45°C / h during calcination and calcined for 10 hours.

[0043] The catalyst prepared in this embodiment includes three parts: active components Ni and Fe, auxiliary agent Na, and composite carriers kaolin, acid clay, and montmorillonite. The content of the active components is 10wt%, the content of the auxiliary agent is 15wt%, and the rest is the composite carrier; the active components Ni and Fe exist in the form of alloy or metal composite on the composite carrier, and the active components Ni and Fe are highly dispersed nanoparticles with a particle size of 0.5-8nm, of which 3-4.5nm accounts for 70%, and the specific surface area is 200m 2 / g, pore volume 0.3cm 3 / g, and the bulk density is 1.1g / mL.

[0044] The catalyst was reduced and activated in a hydrogen atmosphere before use. The required activation temperature was 650°C, the pressure was 0.1 MPa, and the hydrogen volume space velocity was 15000 h -1 After activation, the catalyst was directly fed into the ethylene feedstock for reaction under the following conditions: temperature 120°C, pressure 1 MPa, mass space velocity 50,000 h -1 . Example 6

[0045] The method for preparing a non-precious metal catalyst for ethylene dealkyning of the present embodiment comprises the following steps: Step 1: prepare a 0.2 mol / L mixed solution of the active component soluble precursors Cu(HCO2)2 and CoSO4 and the auxiliary agent soluble precursor MgCl2, and heat the mixed solution to 80°C; Step 2, adjusting the pH of the mixed solution obtained in step 1 to 1.0 using acetic acid; Step 3: Immerse the composite carrier of kaolin, acid clay, and montmorillonite in the solution obtained in step 2 for 5 hours, stirring continuously during the immersion process to allow the active components and additives to be distributed on the carrier with specific structural characteristics; Step 4, drying the catalyst obtained in step 3 and calcining to obtain the catalyst, wherein the temperature is increased from room temperature to 100°C at a heating rate of 55°C / h during drying and dried at this temperature for 24 hours; the temperature is increased to 200°C at a heating rate of 52°C / h during calcination and calcined for 5 hours.

[0046] The catalyst prepared in this embodiment includes active components Cu and Co, an auxiliary agent Mg, and a carrier of SiC, wherein the content of the active components is 30wt%, the content of the auxiliary agent is 0.5wt%, and the rest is the carrier; the active components Cu and Co exist on the carrier in the form of an alloy or a metal composite, and the active components Cu and Co are highly dispersed nanoparticles with a particle size of 0.5-8nm, of which 3-4.5nm accounts for 70%, and the specific surface area is 0.1m 2 / g, pore volume 0.04cm 3 / g, and the bulk density is 1.3g / mL.

[0047] The catalyst was reduced and activated in a hydrogen atmosphere before use. The required activation temperature was 200°C, the pressure was 3 MPa, and the hydrogen volume space velocity was 10,000 h -1 After activation, the catalyst was directly fed into the ethylene feedstock for reaction under the following conditions: temperature 150°C, pressure 5 MPa, mass space velocity 1000 h -1 . Example 7

[0048] The method for preparing a non-precious metal catalyst for ethylene dealkyning of the present embodiment comprises the following steps: Step 1: prepare a 0.1 mol / L mixed solution of the active component soluble precursors Ni(CH3COO)2 and Mo(NO3)4 and the auxiliary agent soluble precursor Mn(NO3)2, and heat the mixed solution to 20°C; Step 2, adjusting the pH of the mixed solution obtained in step 1 to 2.0 using nitric acid; Step 3: placing the composite carrier of acid clay and montmorillonite in the solution obtained in step 2 and immersing it for 1 hour, stirring continuously during the immersion process so that the active components and additives are distributed on the carrier with specific structural characteristics; Step 4, drying and calcining the catalyst obtained in step 3 to obtain the catalyst, wherein the temperature is increased from room temperature to 150°C at a heating rate of 20°C / h during drying, and dried at this temperature for 6 hours; the temperature is increased to 800°C at a heating rate of 60°C / h during calcination, and calcined for 2 hours.

[0049] The catalyst prepared in this embodiment includes active components Ni and Mo, an additive Mn, and a composite carrier of acid clay and montmorillonite, wherein the content of the active component is 0.05wt%, the content of the additive is 20wt%, and the rest is the carrier; the active components Ni and Mo exist on the carrier in the form of an alloy or a metal composite, and the active components Ni and Mo are highly dispersed nanoparticles with a particle size of 0.5-8nm, of which 3-4.5nm accounts for 55%, and the specific surface area is 1m 2 / g, pore volume 0.06cm 3 / g, and the bulk density is 1.5g / mL.

[0050] The catalyst was reduced and activated in a hydrogen atmosphere before use. The required activation temperature was 250°C, the pressure was 5 MPa, and the hydrogen volume space velocity was 8000 h -1 After activation, the catalyst was directly fed into the ethylene feedstock for reaction under the following conditions: temperature 200°C, pressure 3 MPa, mass space velocity 500 h -1 . Example 8

[0051] The method for preparing a non-precious metal catalyst for ethylene dealkyning of the present embodiment comprises the following steps: Step 1: prepare a 1 mol / L mixed solution of the active component soluble precursors Fe(HCO2)2 and CuSO4, and the auxiliary agent soluble precursors NaHCO3 and MgCl2, and heat the mixed solution to 40°C; Step 2, adjusting the pH of the mixed solution obtained in step 1 to 4.0 using citric acid; Step 3: Impregnate the SiO2 carrier in the solution obtained in step 2 for 0.5 h, stirring continuously during the impregnation process to allow the active components and additives to be distributed on the carrier with specific structural characteristics; Step 4, drying the catalyst obtained in step 3 and calcining to obtain the catalyst, wherein the temperature is increased from room temperature to 130°C at a heating rate of 35°C / h during drying and dried at this temperature for 8 hours; the temperature is increased to 500°C at a heating rate of 30°C / h during calcination and calcined for 10 hours.

[0052] The catalyst prepared in this embodiment includes active components Fe and Cu, additives Na and Mg, and a carrier SiO2, wherein the content of the active components is 0.1wt%, the content of the additives is 20wt%, and the rest is the carrier; the active components Fe and Cu exist on the carrier in the form of an alloy or a metal composite, and the active components Fe and Cu are highly dispersed nanoparticles with a particle size of 0.5-8nm, of which 3-4.5nm accounts for 50%, and the specific surface area is 50m 2 / g, pore volume 0.1cm 3 / g, and the bulk density is 1.0g / mL.

[0053] The catalyst was reduced and activated in a hydrogen atmosphere before use. The required activation temperature was 300°C, the pressure was 2 MPa, and the hydrogen volume space velocity was 50,000 h -1 After activation, the catalyst was directly fed into the ethylene feedstock for reaction under the following conditions: temperature 150°C, pressure 2 MPa, mass space velocity 10,000 h -1 . Example 9

[0054] The method for preparing a non-precious metal catalyst for ethylene dealkyning of the present embodiment comprises the following steps: Step 1: prepare a 0.05 mol / L mixed solution of the active component soluble precursors CuCl2 and Co(CH3COO)2 and the auxiliary agent soluble precursor K2SO4, and heat the mixed solution to 60°C; Step 2, adjusting the pH of the mixed solution obtained in step 1 to 3.0 using oxalic acid; Step 3, placing the composite support of Al2O3 and kaolin in the solution obtained in step 2 and immersing it for 15 hours, stirring continuously during the immersion process, so that the active components and additives are distributed on the support with specific structural characteristics; Step 4, drying the catalyst obtained in step 3 and calcining to obtain the catalyst, wherein the temperature is increased from room temperature to 100°C at a heating rate of 25°C / h during drying, and dried at this temperature for 10 hours; the temperature is increased to 400°C at a heating rate of 25°C / h during calcination, and calcined for 7 hours.

[0055] The catalyst prepared in this embodiment includes active components Co and Cu, an additive K, and a composite carrier of Al2O3 and kaolin, wherein the content of the active components is 0.05wt%, the content of the additive is 10wt%, and the rest is the carrier; the active components Co and Cu exist on the carrier in the form of an alloy or a metal composite, and the active components Co and Cu are highly dispersed nanoparticles with a particle size of 0.5-8nm, of which 3-4.5nm accounts for 65%, and the specific surface area is 240m 2 / g, pore volume 0.4cm 3 / g, and the bulk density is 0.5g / mL.

[0056] The catalyst was reduced and activated in a hydrogen atmosphere before use. The required activation temperature was 600°C, the pressure was 1 MPa, and the hydrogen volume space velocity was 20,000 h -1 After activation, the catalyst was directly fed into the ethylene feedstock for reaction under the following conditions: temperature 130°C, pressure 2 MPa, mass space velocity 2000 h -1 . Example 10

[0057] The method for preparing a non-precious metal catalyst for ethylene dealkyning of the present embodiment comprises the following steps: Step 1: prepare a 0.01 mol / L mixed solution of the active component soluble precursors C2H2NiO4 and CoSO4, and the auxiliary agent soluble precursors CrCl3 and Zn(NO3)2, and heat the mixed solution to 15°C; Step 2, adjusting the pH of the mixed solution obtained in step 1 to 1.0 using sulfuric acid; Step 3: Immerse the SiO2 carrier in the solution obtained in step 2 for 20 hours, stirring continuously during the immersion process to allow the active components and additives to be distributed on the carrier with specific structural characteristics; Step 4, drying and calcining the catalyst obtained in step 3 to obtain the catalyst, wherein the temperature is increased from room temperature to 120°C at a heating rate of 40°C / h during drying, and dried at this temperature for 20 hours; and the temperature is increased to 300°C at a heating rate of 40°C / h during calcination, and calcined for 5 hours.

[0058] The catalyst prepared in this embodiment includes active components Ni and Co, additives Cr and Zn, and a SiO2 carrier, wherein the content of the active components is 1wt%, the content of the additives is 11wt%, and the rest is the carrier; the active components Ni and Co exist on the carrier in the form of an alloy or a metal composite, and the active components Ni and Co are highly dispersed nanoparticles with a particle size of 0.5-8nm, of which 3-4.5nm accounts for 70%, and the specific surface area is 180m 2 / g, pore volume 0.4cm 3 / g, and the bulk density is 0.7g / mL.

[0059] The catalyst was reduced and activated in a hydrogen atmosphere before use. The required activation temperature was 200°C, the pressure was 0.7 MPa, and the hydrogen volume space velocity was 4000 h -1 After activation, the catalyst was directly fed into the ethylene feedstock for reaction under the following reaction conditions: temperature 100°C, pressure 1 MPa, mass space velocity 3500 h -1 . Example 11

[0060] The method for preparing a non-precious metal catalyst for ethylene dealkyning of the present embodiment comprises the following steps: Step 1: prepare a 0.8 mol / L mixed solution of the active component soluble precursors Cu(NO3)2, C2H2NiO4 and FeCl2 and the auxiliary agent soluble precursor KHCO3, and heat the mixed solution to 80°C; Step 2, adjusting the pH of the mixed solution obtained in step 1 to 2.0 using citric acid; Step 3: Immerse the Al2O3-SiO2 composite support in the solution obtained in step 2 for 10 hours, stirring continuously during the immersion process to allow the active components and additives to be distributed on the support with specific structural characteristics; Step 4, drying the catalyst obtained in step 3 and calcining to obtain the catalyst, wherein the temperature is increased from room temperature to 100°C at a heating rate of 50°C / h during drying, and dried at this temperature for 10 hours; and the temperature is increased to 600°C at a heating rate of 50°C / h during calcination, and calcined for 12 hours.

[0061] The catalyst prepared in this embodiment includes active components Ni, Cu and Fe, a promoter K, and a carrier that is an Al2O3-SiO2 composite carrier, wherein the content of the active components is 15wt%, the content of the promoter is 15wt%, and the rest is the carrier; the active components Ni, Cu and Fe exist on the carrier in the form of an alloy or a metal composite, and the active components Ni, Cu and Fe are highly dispersed nanoparticles with a particle size of 0.5-8nm, of which 3-4.5nm accounts for 55%, and the specific surface area is 370m 2 / g, pore volume 0.2cm 3 / g, and the bulk density is 0.9g / mL.

[0062] The catalyst was reduced and activated in a hydrogen atmosphere before use. The required activation temperature was 400°C, the pressure was 5 MPa, and the hydrogen volume space velocity was 12000 h -1 After activation, the catalyst was directly fed into the ethylene feedstock for reaction under the following conditions: temperature 100°C, pressure 5 MPa, mass space velocity 10 h -1 .

[0063] Comparative Example 1 The catalyst composition of this comparative example is the same as that of Example 11, except that: Step 1, the temperature of the mixed solution is 25°C; In step 2, hydrochloric acid is not used to adjust the pH of the mixed solution obtained in step 1; Step 3: insufficient stirring during the dipping process; Step 4: During drying, the temperature is increased from room temperature to 150°C at a heating rate of 10°C / h, and dried at this temperature for 6 hours; during roasting, the temperature is increased to 800°C at a heating rate of 100°C / h, and roasted for 2 hours.

[0064] The particle size of the active component is 0.6-2.4nm, of which 1.2-1.8nm accounts for 65%, and the specific surface area is 500m 2 / g, pore volume 0.5cm 3 / g, and the bulk density is 0.5g / mL.

[0065] The catalyst was reduced and activated in a hydrogen atmosphere before use. The required activation temperature was 150°C, the pressure was 2 MPa, and the hydrogen volume space velocity was 2000 h -1 After activation, the catalyst was directly fed into the ethylene feedstock for reaction under the following conditions: temperature 50°C, pressure 5 MPa, mass space velocity 100 h -1 .

[0066] Comparative Example 2 The catalyst used in this comparative example is industrial catalyst Ni / Al2O3, in which the active component content is 40wt%, the particle size is 7-18nm, of which 11-13nm accounts for 50%, and the specific surface area is 183m 2 / g, pore volume is 0. 4cm 3 / g, and the bulk density is 0.5g / mL.

[0067] The hydrogenation activity and selectivity results of the catalysts of Examples 1-11 and Comparative Examples 1-2 are shown in Table 1 below.

[0068] Table 1 Hydrogenation activity and selectivity results Example Active ingredient Particle size Pore ​​structure Hydrogenation activity Hydrogenation selectivity life Example 1 Cu and Fe, content 30wt% 0.5-8nm, of which 3-4.5nm accounts for 60% <![CDATA[The specific surface area is 300 m 2 / g, the pore volume is 0.1 cm 3 / g, and the bulk density is 0.3 g / mL]]> 99.5% 99.7% 8000h Example 2 Cu, content 20wt% 0.5-8nm, of which 3-4.5nm accounts for 52% <![CDATA[The specific surface area is 30 m 2 / g, the pore volume is 0.2 cm 3 / g, and the bulk density is 0.8 g / mL]]> 99.1% 99.0% 8000h Example 3 Ni and Mo, content 5wt% 0.5-8nm, of which 3-4.5nm accounts for 80% <![CDATA[Specific surface area is 500 m 2 / g, pore volume is 0.5 cm 3 / g, bulk density is 0.5 g / mL]]> 99.3% 99.8% 10000h Example 4 Cu, Ni and Co, content 0.5wt% 0.5-8nm, of which 3-4.5nm accounts for 65% <![CDATA[The specific surface area is 0.05 m 2 / g, the pore volume is 0.001 cm 3 / g, and the bulk density is 1.5 g / mL]]> 99.2% 99.4% 5000h Example 5 Ni and Fe, content 10wt% 0.5-8nm, of which 3-4.5nm accounts for 70% <![CDATA[The specific surface area is 200 m 2 / g, the pore volume is 0.3 cm 3 / g, and the bulk density is 1.1 g / mL]]> 99.4% 99.3% 6000h Example 6 Cu and Co, content 30wt% 0.5-8nm, of which 3-4.5nm accounts for 70% <![CDATA[The specific surface area is 0.1 2 / g, the pore volume is 0.04 cm 3 / g, and the bulk density is 1.3 g / mL]]> 99.2% 98.9% 5000h Example 7 Ni and Mo, content 0.05wt% 0.5-8nm, of which 3-4.5nm accounts for 55% <![CDATA[The specific surface area is 1 m 2 / g, the pore volume is 0.06 cm 3 / g, and the bulk density is 1.5 g / mL]]> 98.2% 98.7% 6000h Example 8 Cu and Fe, content 0.1wt% 0.5-8nm, of which 3-4.5nm accounts for 50% <![CDATA[The specific surface area is 50 m 2 / g, the pore volume is 0.1 cm 3 / g, and the bulk density is 1 g / mL]]> 98.5% 98.8% 5000h Example 9 Cu and Co, content 0.05wt% 0.5-8nm, of which 3-4.5nm accounts for 65% <![CDATA[The specific surface area is 240 m 2 / g, the pore volume is 0.4 cm 3 / g, and the bulk density is 0.5 g / mL]]> 98.2% 98.5% 6000h Example 10 Ni and Co, content 1wt% 0.5-8nm, of which 3-4.5nm accounts for 70% <![CDATA[The specific surface area is 180 m 2 / g, the pore volume is 0.4 cm 3 / g, and the bulk density is 0.7 g / mL]]> 99.2% 99.6% 8000h Example 11 Cu, Ni and Fe, content 15wt% 0.5-8nm, of which 3-4.5nm accounts for 55% <![CDATA[The specific surface area is 370 m 2 / g, the pore volume is 0.2 cm 3 / g, and the bulk density is 0.9 g / mL]]> 99.5% 99.6% 6000h Comparative Example 1 Cu, Ni and Fe, content 15wt% 0.6-2.4nm, of which 1.2-1.8nm accounts for 65% <![CDATA[The specific surface area is 500 m 2 / g, the pore volume is 0.5 cm 3 / g, and the bulk density is 0.5 g / mL]]> 82.6% 92.5% Comparative Example 2 Ni content: 40wt% 7-18nm, of which 11-13nm accounts for 50% <![CDATA[The specific surface area is 183 m 2 / g, the pore volume is 0.4 cm 3 / g, and the bulk density is 0.5 g / mL]]> 100% 58.9% The catalysts prepared in Examples 1-11 have sulfur-resistant hydrogenation stability and a sulfur content of 10-300 ppm; whereas the catalysts in Comparative Examples 1 and 2 are easily sulfur poisoned and their stability is greatly reduced.

[0069] After the catalyst prepared in Example 1-11 is run for a long period of time, the carbon deposition amount can reach 5-15%, while still maintaining a relatively high activity selectivity.

Claims

1. A non-precious metal catalyst for ethylene dealkyne removal, characterized in that: The invention comprises three parts: an active component, an auxiliary agent, and a carrier. The active component is at least one of non-precious metals Ni, Co, Fe, Mo, and Cu; the auxiliary agent is one or two of Na, K, Mg, Ca, Cr, Zr, Zn, Mn, and Ti; and the carrier is at least one of kaolin, acid clay, montmorillonite, SiC, SiO2, and Al2O3. The active component exists on the carrier in the form of an alloy or a metal complex. The active component is highly dispersed nanoparticles with a particle size of 0.5-8 nm, of which 3-4.5 nm accounts for ≮50%.

2. The non-noble metal catalyst for ethylene dealynylation according to claim 1, characterized in that: The content of the active component is 0.05-30wt%, the content of the auxiliary agent is 0.5-30wt%, and the rest is carrier.

3. A non-noble metal catalyst for ethylene dealynylation according to claim 1 or 2, characterized in that: The specific surface area of ​​the catalyst is 0.05-500m 2 / g, pore volume of 0.001-0.5cm 3 / g, and the bulk density is 0.3-1.5g / mL.

4. The method for preparing a non-noble metal catalyst for ethylene dealynylation according to any one of claims 1 to 3, characterized in that: The following steps are involved: Step 1: preparing a mixed solution of an active component soluble precursor and an auxiliary agent soluble precursor, and heating the mixed solution; Step 2, adjusting the pH of the mixed solution obtained in step 1; Step 3, impregnating the carrier in the solution obtained in step 2, stirring continuously during the impregnation process so that the active ingredients and auxiliary agents are distributed on the carrier with specific structural characteristics; Step 4: drying and calcining the catalyst obtained in step 3 to obtain the catalyst.

5. The method for preparing a non-noble metal catalyst for ethylene dealynylization according to claim 4, characterized in that: In step 1, the soluble precursor of the active component is sulfate, nitrate, chloride, oxalate, formate, or acetate, and the soluble precursor of the auxiliary agent is nitrate, sulfate, or chloride. If the auxiliary agent is Na or K, its soluble precursor may also be carbonate or bicarbonate. The total concentration of the mixed solution is 0.01-1 mol / L, and the mixed solution is heated to between 15-80°C.

6. The method for preparing a non-noble metal catalyst for ethylene dealynylization according to claim 4, characterized in that: In step 2, an organic acid or an inorganic acid is used to adjust the pH of the mixed solution obtained in step 1 to between 1.0 and 4.0; The organic or inorganic acid is hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, acetic acid, or citric acid.

7. The method for preparing a non-noble metal catalyst for ethylene dealynylization according to claim 4, characterized in that: In step 3, the immersion time is 0.5-24 hours.

8. The method for preparing a non-noble metal catalyst for ethylene dealynylization according to claim 4, characterized in that: In step 4, during drying, the temperature is raised from room temperature to 100-150° C. at a heating rate of 2-20° C. / min, and dried at this temperature for 6-24 hours; during calcination, the temperature is raised to 200-800° C. at a heating rate of 2-20° C. / min, and calcined for 2-12 hours.

9. Use of a non-noble metal catalyst for ethylene dealynylation according to any one of claims 1 to 3, characterized in that: Used for selective hydrogenation of ethylene to remove acetylene and oxygen.

10. The use of a non-noble metal catalyst for ethylene dealynylation according to claim 9, characterized in that: The specific conditions of the application are: The catalyst is reduced and activated in a hydrogen atmosphere before use. The required activation temperature is 150-650°C, the pressure is 0.1-5.0 MPa, and the hydrogen volume space velocity is 200-20000 h -1 After activation, the catalyst is directly fed into the ethylene feedstock for reaction. The reaction conditions are: temperature 50-350°C, pressure 0.1-5.0 MPa, mass space velocity 5-50000 h -1 .

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