CN108855093B - Nickel-copper hydrogenation catalyst and preparation method thereof - Google Patents

Nickel-copper hydrogenation catalyst and preparation method thereof Download PDF

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CN108855093B
CN108855093B CN201710338496.7A CN201710338496A CN108855093B CN 108855093 B CN108855093 B CN 108855093B CN 201710338496 A CN201710338496 A CN 201710338496A CN 108855093 B CN108855093 B CN 108855093B
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nickel
copper
solution
acidic
hydrogenation catalyst
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CN108855093A (en
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胡晓丽
郑云弟
潘曦竹
孙利民
马好文
王斌
展学成
钱颖
梁顺琴
常晓昕
谢培思
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Petrochina Co Ltd
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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
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth 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
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • B01J35/613—
    • B01J35/615—
    • B01J35/633—
    • B01J35/635—
    • 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
    • B01J37/0201—Impregnation
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Abstract

The invention relates to a nickel-copper series catalyst and a preparation method thereof, in particular to a preparation method of a nickel-copper series hydrogenation catalyst taking nickel-containing alumina as a carrier. The nickel-containing pseudo-boehmite preparation method comprises the following steps of containing active components of nickel and copper, taking nickel-containing alumina as a carrier, wherein a precursor of the nickel-containing alumina carrier is nickel-containing pseudo-boehmite, and the preparation process of the nickel-containing pseudo-boehmite comprises an acid-base neutralization gelling process. The catalyst of the invention uses a specific carrier, and has the advantages that the nickel and the pseudo-boehmite can be organically combined, so that the active component nickel is effectively dispersed in the pseudo-boehmite, and a nickel-containing alumina carrier with a specific crystal form is formed, and meanwhile, the pore structure and the acidity of the carrier are better regulated. The nickel-copper hydrogenation catalyst has high hydrogenation activity and selectivity.

Description

Nickel-copper hydrogenation catalyst and preparation method thereof
Technical Field
The invention relates to a nickel-copper series catalyst and a preparation method thereof, in particular to a preparation method of a nickel-copper series hydrogenation catalyst taking nickel-containing alumina as a carrier.
Background
In 2016, the operating rate of the worldwide ethylene cracking plant has continuously increased back to the fourth year. Pyrolysis gasoline is an important byproduct of ethylene pyrolysis, and accounts for about 50-80% of the ethylene production capacity. How to utilize the part of byproducts has great influence on improving the economic benefit of enterprises. Meanwhile, the pyrolysis gasoline also contains a large amount of various unsaturated hydrocarbons such as diolefin, alkyl alkenyl arene, indene and the like and impurities such as sulfur, nitrogen, oxygen and the like, so that the gasoline property is unstable. Two-stage hydrogenation is generally adopted for refining in industry, and chain conjugated olefin, cyclic conjugated olefin, styrene and the like are saturated through one-stage low-temperature liquid-phase hydrogenation; then two-stage high-temp. gas-phase hydrogenation is carried out to remove organic impurities containing sulfur, nitrogen and oxygen, mono-olefin is saturated by hydrogenation and then used as raw material for extracting aromatic hydrocarbon to prepare benzene, toluene and xylene. Therefore, the hydrogenation technology taking the pyrolysis gasoline hydrogenation catalyst as the core is an important branch in the hydrogenation field, and plays a significant role in the post-treatment of preparing ethylene by steam cracking. The currently adopted first-stage hydrogenation catalysts are roughly divided into two types, wherein one active component is a nickel non-noble metal catalyst; another class of active components are catalysts for noble metals. The non-noble metal catalyst has certain impurity resistance and water resistance due to factors such as structural difference, high metal content and the like, and the price advantage is obvious. Therefore, the industrial products of the non-noble metal catalysts are gradually replacing noble metal catalysts to be applied to cracking product hydrogenation series catalysts.
CN1218822A reports a Ni/Al2O3Is suitable forThe selective hydrogenation catalyst for cracking gasoline fraction is prepared with nickel supported on alumina carrier containing Li or alkali earth metal, and has poor hydrogenation load bearing and hydrogenation stability.
IT1312334 discloses a selective hydrogenation catalyst for selective hydrogenation of diolefins in distillate, comprising alumina, nickel oxide content of 5-25%, lithium or alkaline earth metal content of 0.1-2.0%, nickel is loaded on alumina containing lithium or alkaline earth metal.
CN101954282A relates to a hydrodesulfurization catalyst and a preparation method thereof, at least two composite metal oxides of molybdenum, nickel, zinc and copper are taken as active components, at least one of oxides of Si, Ti, Ca, Ce, Mg and P is added as an auxiliary agent, and the balance is alumina. Based on the mass of the catalyst, the mass percent of the active component is 5-15%, the mass percent of the auxiliary agent oxide is 0.2-25%, and the balance is aluminum oxide. The catalyst is used for hydrodesulfurization at high temperature, but the hydrodesulfurization effect is poor.
US3472763 reports a diene selective hydrogenation catalyst, the active component Ni content is 1-20%, and the auxiliary agent MoO31-5% of the catalyst, 1-5% of the auxiliary agent alkali metal and alkaline earth metal, more than 0.4ml/g of the catalyst pore volume and more than 30m of the specific surface2The catalyst is prepared by impregnating Al with aqueous solution of active component and auxiliary agent2O3And (3) preparing the carrier.
Hydrated aluminas such as pseudo-boehmite, and the like are widely used as raw materials for preparing alumina carriers, and although methods such as PH swing, addition of organic pore-expanding agents, hydrothermal treatment, and the like can be employed in the preparation of alumina carriers to improve the properties of alumina as a carrier, there is a limit to improving the properties of alumina as a carrier material of hydrogenation catalysts by these methods. The nature of the hydrated alumina feedstock used to prepare the alumina support is one of the most critical factors in producing an alumina support with superior performance.
CN1123392C describes a nickel-containing alumina carrier and a preparation method thereof, a mixture of an alkali-treated nickel-containing compound and carbon black is kneaded with aluminum hydroxide dry glue powder and is extruded into stripsMolding, drying and roasting to obtain the alumina carrier containing 2.0-14.0% of nickel, wherein the pore volume of the carrier is 0.4cm3/g～1.0cm3Per g, specific surface area of 160m2/g～420m2The specific area of the pores is 8.0-15.0 nm, the proportion of the pores larger than 6.0nm accounts for more than 85% of the total pores, the pore volume and the average pore diameter are larger, and the proportion of the macropores is more, so the catalyst is particularly suitable for being used as a carrier of a heavy oil hydrofining catalyst.
CN200710179630.X discloses a method for preparing nickel-coated alumina powder, which is characterized in that a mixed solution of nano alumina added with a dispersant is prepared into a suspension, a nickel salt solution is added under stirring, ammonia water is dropped into the mixed solution after uniform stirring, and distilled water is added to obtain a dark blue nickel-ammonia complex ([ Ni (NH)3)6]2+)-Carrying out hydrothermal aging, filtering, washing and drying on the alumina mixed solution C to obtain a green intermediate coating product; and then carrying out reduction roasting to obtain black nickel-coated alumina powder.
CN1102862C discloses a nickel-containing hydrogenation catalyst, which contains: 65-80% nickel, calculated as nickel oxide, 10-25% silicon, calculated as silica, 2-10% zirconium, calculated as zirconia, 0-10% aluminium, calculated as alumina, with the proviso that the sum of the contents of silica and alumina is at least 15% by weight, based on the total weight of the catalyst, which catalyst is obtainable by adding an acidic aqueous solution of a salt of nickel, zirconium and, if desired, aluminium to an alkaline aqueous solution or suspension of silicon and, if desired, a compound of aluminium, reducing the pH of the mixture thus obtained to at least 6.5, then adjusting the pH to 7-8 by further adding an alkaline solution, separating the solid thus deposited, drying, shaping and sintering. Also disclosed are methods of making the catalyst and its use in making medicinal white oils, high purity medicinal paraffins and low boiling, low aromatic content or aromatic-free hydrocarbon mixtures. The preparation method of the catalyst is usually used for preparing the catalyst with high active component content, but the catalyst prepared by the method has poor activity.
The article "changes induced by calcinatio et alon temperature in hydrodesulfurization activity of NiCo-Mo/Al2O3Catalysis, Applied Catalysis, 1987,30:185-2O3Influence of the desulfurization activity of the catalyst thiophene. The results show that the desulfurization activity of the catalyst activated at 500 ℃ is significantly higher than that of the catalyst activated at 600 ℃, which is caused by the strong interaction of the metal in the catalyst and the alumina carrier to form a spinel structure when activated at 600 ℃, resulting in a significant decrease in the catalyst activity. The higher the activation temperature is, the higher the content of the generated nickel aluminate spinel phase is, and the more obvious the activity of the catalyst is reduced. "infection of support-interaction of the support latent developer and hydrolysis activity of Al2O3similar conclusions were also drawn for support W, CoW and NiW model catalysts, J PhysChem B, 2002, 106: 5897-. Because the nickel and the alumina carrier can generate strong interaction to generate a spinel structure in the high-temperature roasting process, the activity of the catalyst is obviously reduced, and the nickel and the alumina carrier are used as carefully as possible before the high-temperature roasting, so that the spinel structure is avoided. Unlike other metals, nickel-containing pseudo-boehmite has been reported only to a lesser extent because it is often calcined at high temperatures to prepare catalyst supports.
The catalyst with high hydrogenation activity is prepared, and the content of corresponding active metal components is also high. The single preparation of the hydrotreating catalyst by an impregnation method requires the preparation of a solution with high active metal component content to impregnate the carrier. Therefore, the following problems are involved in the impregnation process: (1) because the water absorption of the carrier is certain, the volume of the impregnation liquid adopting an equal-volume impregnation method is certain, and incomplete dissolution can be caused by excessively high addition of the active metal component; (2) in the process of preparing the catalyst, active components need to be impregnated for many times, and the active components with certain content can be impregnated on the carrier for two times, three times or even four times, so that the problems of complicated preparation procedures, long preparation period, loss of the active components and the like are caused; (3) in the process of multiple times of impregnation, organic or inorganic dispersing agents are often needed to be added into the impregnation liquid to increase the dispersion degree of the active metal components, but the problems of removal in the post-treatment process exist.
In the preparation process of the catalyst carrier, a compound containing an active metal component is introduced in a kneading mode, so that a certain amount of the compound containing the active metal component is contained in the formed carrier, and the problem of load difficulty in the preparation process of the catalyst with high content of the active metal component is solved. However, the active metal compound and the aluminum hydroxide dry glue powder or the alumina powder are directly mixed and molded by a mixing and kneading method in a mixing and kneading mode, the method has the problems of uneven mixing of crystal grains, poor catalyst strength and the like, and simultaneously, the components are not easy to combine to form a specific framework structure by simple mixing and kneading.
Disclosure of Invention
The invention aims to provide a novel nickel-copper hydrogenation catalyst and a preparation method thereof, which are suitable for the preparation requirement of a catalyst with higher active metal component content.
The nickel-copper hydrogenation catalyst comprises active components of nickel and copper, wherein nickel-containing alumina is used as a carrier, and the nickel-copper hydrogenation catalyst comprises 10-20 wt% (preferably 14.5-18.5 wt%) of nickel oxide, 0.01-5 wt% (preferably 0.05-3 wt%) of copper oxide, 0-5 wt% (preferably 0.2-1.8 wt%) of cerium oxide and/or lanthanum oxide, and 0-6 wt% (preferably 0.5-3 wt%) of alkali metal and/or alkaline earth metal oxide, based on the total weight of the catalyst being 100%; the specific surface area of the catalyst is 50-180 m2A pore volume of 0.30 to 0.60ml/g, a bulk density of 0.5 to 1.1g/cm3. The precursor of the nickel-containing alumina carrier is nickel-containing pseudo-boehmite, which can organically combine nickel and the pseudo-boehmite, and simultaneously the nickel-containing pseudo-boehmite and the carrier prepared from the nickel-containing pseudo-boehmite have proper pore size distribution.
The carrier in the nickel-copper hydrogenation catalyst is nickel-containing alumina, nickel-containing pseudo-boehmite needs to be prepared firstly, namely a precursor of the nickel-containing alumina carrier is the nickel-containing pseudo-boehmite, the simple physical mixing or coating of the pseudo-boehmite and a nickel-containing compound or a nickel salt solution is not performed, an acid-base reaction is performed, a gelling process is performed, and finally the carrier with a specific nickel and aluminum mixed crystal form is prepared. Only in this way can nickel and pseudoboehmite be organically combined, preferably the nickel-containing pseudoboehmite and the support prepared therefrom also have a suitable pore size distribution.
The nickel-containing alumina carrier is obtained by molding, drying and roasting the nickel-containing pseudo-boehmite. According to different use purposes of the final nickel-containing alumina carrier, the preparation method of the nickel-containing pseudo-boehmite, the nickel source, the nickel content, the preparation method of the nickel-containing alumina carrier, the activation roasting temperature and the like can be different.
The nickel-containing alumina carrier precursor, namely the nickel-containing pseudo-boehmite, is preferably (calculated by taking the total weight of the nickel-containing pseudo-boehmite as 100 wt%), and the nickel content is 0.1-10 wt%, preferably 0.5-5 wt%; the specific surface area is 300-420 m2A pore volume of 0.7-1.2 cm3The pore diameter is 5-10 nm; the nickel-containing pseudo-boehmite has the processes of acid-base neutralization and gel forming in the preparation process.
The nickel-containing alumina carrier used in the catalyst of the present invention is preferably prepared by molding and roasting nickel-containing pseudo-boehmite, and contains delta-Al2O3、δ-NiAl26O40And NiAl2O4The crystal form is a crystal form, wherein B1/B2 is more than or equal to 0.45 and less than or equal to 0.85 in an XRD spectrogram, B1 refers to the integral intensity of a peak with the 2 theta of 34.2-39.8 degrees in the XRD spectrogram, and B2 refers to the integral intensity of a peak with the 2 theta of 43.3-48.5 degrees in the XRD spectrogram.
The nickel-containing alumina carrier used in the catalyst of the invention contains delta-Al2O3、δ-NiAl26O40And NiAl2O4Mixed crystals of crystal forms, preferably delta-Al2O3、δ-NiAl26O40And NiAl2O4Accounting for 30-100 wt% of the total weight of the nickel-containing alumina carrier. Except for containing delta-Al2O3、δ-NiAl26O40And NiAl2O4Besides the mixed crystal of the crystal form, the carrier can also contain theta-Al2O3、α-Al2O3And/or gamma-Al2O3Preferably alpha-Al2O3The content is less than 30 wt%.
The invention depends on the purpose of the final catalyst, the preparation method of the nickel-containing pseudo-boehmite, the nickel source, the nickel content and the nickel-containing alumina carrierThe chemical calcination temperature and the like may be different. The nickel-containing alumina carrier of the present invention preferably contains nickel in an amount of 0.1 to 10 wt%, preferably 0.5 to 5 wt%. The specific surface area is 25-250 m2A pore volume of 0.15-0.85 cm3The pore diameter is 8-40 nm.
In the invention, the active components are nickel and copper, the nickel source is selected from one or more of nickel nitrate, nickel acetate, nickel chloride or nickel sulfate, and the nickel nitrate and the nickel acetate are preferred. The copper is preferably added in the form of copper nitrate or basic copper carbonate. The preparation method of the catalyst is not limited in detail, and for example, the catalyst can be prepared by an isometric impregnation method, wherein an aqueous solution containing nickel and copper soluble salts is impregnated on a carrier, dried and roasted at 300-500 ℃ for 3-8 hours. The nickel content in the catalyst is calculated by taking the total weight of the catalyst as 100 wt%, and calculated by oxides: 10 to 20 wt% (preferably 14.5 to 18.5 wt%) of nickel oxide, and 0.01 to 5 wt% (preferably 0.05 to 3 wt%) of copper oxide.
The catalyst of the present invention may contain cerium and/or lanthanum (in the form of oxides) as rare earth elements in an amount of 0 to 5 wt%, preferably 0.2 to 1.8 wt%. After cerium and/or lanthanum are added, the growth of catalyst carrier grains during high-temperature roasting can be inhibited, the dispersion degree of active component nickel is improved, and the hydrogenation selectivity and stability of the catalyst are improved. In the present invention, cerium and/or lanthanum are preferably added in the form of soluble nitrates.
The catalyst of the present invention may further contain an alkali metal and/or an alkaline earth metal (in the form of an oxide) in an amount of 0 to 6 wt%, preferably 0.5 to 3 wt%. The alkali metal and/or alkaline earth metal is one or more of Li, Na, K, Ca, Mg, Sr and Be, preferably one or two of Li and Mg. The addition of alkali metal and/or alkaline earth metal can regulate the acidity and alkalinity of the surface of the catalyst carrier, and the regulation of the acidity and alkalinity of the surface of the catalyst can improve the hydrogenation activity and the hydrogenation stability, thereby being beneficial to reducing the deposition of carbon and colloid in the hydrogenation process and prolonging the service life of the catalyst. In the present invention, the alkali metal and/or alkaline earth metal is preferably added in the form of a soluble nitrate, acetate or citrate.
The rare earth elements cerium and/or lanthanum and alkali metal and/or alkaline earth metal can be added in the carrier forming process; or the active components can be added into the carrier before being impregnated after the carrier is formed; it can also be added simultaneously with the active ingredient impregnation solution when the active ingredient is impregnated.
The invention also provides a preparation method of the more specific nickel-copper hydrogenation catalyst, which comprises the steps of dipping the nickel-containing alumina carrier by one step or multiple steps by using the solution containing nickel and copper, drying and roasting to obtain the catalyst; the nickel-containing alumina carrier is obtained by molding, drying and roasting nickel-containing pseudo-boehmite; the nickel-containing pseudo-boehmite is preferably obtained by the following method, and the specific process comprises the following steps:
(1) adding bottom water into the neutralization kettle, wherein the bottom water is deionized water, and heating to 50-90 ℃;
(2) respectively preparing an acidic aluminum salt aqueous solution and an acidic nickel salt aqueous solution, uniformly mixing the acidic aluminum salt aqueous solution and the acidic nickel salt aqueous solution to obtain an acidic aqueous solution containing aluminum salt and nickel salt, and adjusting the temperature of the mixed solution to be 50-90 ℃, wherein the concentration of the acidic aluminum salt aqueous solution is preferably 10-80 g of Al2O3The concentration of the acidic nickel salt aqueous solution is preferably 3-50 gNiO/L;
(3) preparing alkali metal aluminate solution, wherein the concentration of the alkali metal aluminate solution is preferably 50-300 gAl2O3/L；
(4) Adding the (2) and the (3) into the (1) in a concurrent flow manner, and continuously ventilating and stirring;
(5) controlling the gelling temperature of the step (4) to be 50-90 ℃, and controlling the gelling pH value to be 7-10;
(6) after the cementing, the nickel-containing pseudo-boehmite is prepared by aging, filtering, washing and drying.
In the preparation method, air can be introduced into the tank bottom in the step (1); and (5) the pH value of the gel is preferably 7-9.
The temperature in the step (1) in the preparation method is preferably 50-70 ℃; the temperature in the step (2) is preferably 50-70 ℃, and the stability is 3-5 min. The temperature difference between the positive temperature and the negative temperature of the mixed solution of the acid aluminum salt and the nickel salt, the alkali metal aluminate solution and the solution in the gel forming tank is preferably not more than 3 ℃, and the temperature of the mixed solution, the alkali metal aluminate solution and the solution in the gel forming tank is preferably the same.
In the preparation method, the pH value of the alkali metal aluminate solution in the step (3) is 9-14, and the preferable pH value is 12-14.
In the preparation method, in the step (5), the gelling temperature is preferably 50-70 ℃; the pH value of the gelling is preferably 7.5-9.5.
The aluminum salt and the nickel salt in the preparation method of the nickel-containing pseudo-boehmite can adopt industrial raw materials. The acidic aluminum salt aqueous solution can be one or a mixed solution of more of aluminum chloride, aluminum sulfate and aluminum nitrate, and is preferably an aluminum sulfate solution. The acidic nickel salt aqueous solution can be one or a mixture of nickel chloride, nickel sulfate, nickel bromide and nickel nitrate, and the nickel nitrate solution is preferred. And mixing the acidic aluminum salt solution and the acidic nickel salt solution to obtain an acidic aqueous solution containing aluminum salt and nickel salt, wherein the pH value is 2-5, and preferably 2-4. The alkali metal aluminate solution is sodium metaaluminate or potassium metaaluminate solution.
And (4) aging the material in the step (6) refers to keeping the gelatinized solution at a certain temperature and pH value for a certain time under the condition of continuous ventilation stirring or static state. Wherein the aging temperature is 50-80 ℃, and the aging time is 10-60 min.
The washing mode of the material in the step (6) is common knowledge of technicians in the field, and can adopt modes such as water adding washing during filtration, pulping washing, washing by using lower alcohols and the like, wherein the temperature is controlled to be 40-80 ℃, the pH value is 4-8, the washing time is 20-40 min, and the washing times are 2-5.
The drying mode in the step (6) can adopt oven drying, spray drying, mesh belt kiln drying, fluidized bed drying, natural drying, microwave drying and the like, the drying temperature is 70-150 ℃, the drying time is 2-24 hours, and preferably, segmented drying at different temperatures is adopted. Before the nickel-containing pseudo-boehmite is formed, one or more of peptizing agent, extrusion assistant and alumina dry glue powder can be added according to the requirement, and the specific adopted substances and the adding amount can be determined according to the knowledge in the field. For example, the peptizing agent can be one or more of nitric acid, phosphoric acid, hydrochloric acid and sulfuric acid, and the addition amount of the peptizing agent is 3-10 wt% of the total weight of the sample to be molded; the extrusion aid can be sesbania powder and the like, and the dosage of the extrusion aid is 2-6 wt% of the total weight of a sample to be molded; the alumina dry glue powder is prepared by a conventional method, but the adding amount is preferably less than 10 wt% of the total mass of the nickel-containing pseudo-boehmite.
The roasting method and conditions are common methods and conditions for roasting the catalyst carrier, and can adopt a vertical furnace, a converter and a mesh belt kiln for roasting, and the roasting conditions of the carrier are as follows: roasting for 4-10 h at 800-1200 ℃, wherein the roasting temperature is preferably 850-1100 ℃. This calcination temperature refers to the final shape calcination temperature of the support before the catalyst is impregnated with the active component. Before the calcination at this temperature, the carrier may be prepared by low-temperature calcination, but all the intermediate calcination steps are used.
The preparation method comprises the steps of dipping a nickel-containing alumina carrier by using a nickel-copper-containing solution through one step or multiple steps, and then drying and roasting to prepare the catalyst; the roasting conditions are as follows: roasting for 3-8 h at 300-500 ℃.
Before the catalyst is used, hydrogen is preferably used for reduction for 6-16 h at 380-450 ℃, and the hydrogenation catalyst is particularly suitable for the reaction of selective hydrogenation of diolefin into monoolefin.
The catalyst of the invention uses a specific carrier, and has the advantages that the nickel and the pseudo-boehmite can be organically combined, so that the active component nickel is effectively dispersed in the pseudo-boehmite, a nickel-containing alumina carrier with a specific crystal form is formed, the pore structure and the acidity of the carrier are well adjusted, and the finally prepared catalyst has higher hydrogenation activity. Compared with the catalyst prepared by adopting the impregnation method, the method has the advantages of simple process, easy modulation of the performance of the carrier material and the like.
In the preparation process of the carrier precursor used by the catalyst, the compound containing the active component is introduced firstly, so that the prepared carrier contains a certain amount of the compound containing the active metal component, and the preparation difficulty of the catalyst with higher active metal component content can be greatly reduced. On the basis of ensuring the performance of the catalyst, the purposes of simplifying the preparation process of the catalyst and optimizing the preparation process are achieved. The nickel-copper hydrogenation catalyst has high hydrogenation activity and selectivity.
Detailed Description
The nickel and copper content in the nickel-copper hydrogenation catalyst is measured by adopting an atomic absorption method; the crystal form of the carrier is determined by an X-ray powder diffractometer (XRD) of D8Advance model produced by Bruker company in Germany, and the specific conditions are as follows: CuKalpha radiation, 40 kilovolts, 40 milliamperes, a scanning speed of 0.02 DEG/step and 0.5 seconds/step, wherein B1 refers to the integral intensity of a peak with the 2 theta of 34.2-39.8 DEG in an XRD spectrogram, and B2 refers to the integral intensity of a peak with the 2 theta of 43.3-48.5 DEG in the XRD spectrogram.
The analysis method comprises the following steps:
oil product distillation range: the petroleum product test method SYB-2110-60 is adopted for determination;
bromine number: measuring by using SH/T0236-92 standard;
diene: measuring by adopting SH/T0714-2002 standard;
specific surface area: measured by GB/T19587 standard;
pore volume, pore size and pore size distribution: GB/T21650.2-2008 standard determination;
water content: measuring by using GB/T11133-89 standard;
sulfur content: measuring by adopting a WK-2B micro coulometer;
nitrogen content: measuring by using a KY-3000N chemiluminescence azotometer;
arsenic content: measured by DV-4300 atomic emission spectrometer.
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto.
Example 1
(1) Nickel-containing pseudo-boehmite
4L of Al with a concentration of 50g2O3Putting the/L sodium metaaluminate solution into a stainless steel container with a stirrer and a gas-permeable tank bottom, putting 1L nickel nitrate solution with the concentration of 8.95g NiO/L into a container at a high position, and controlling the flow rate by connecting a peristaltic pump. Introducing mixed gas of carbon dioxide and air, and simultaneously dropwise adding the prepared nickel nitrate solution, wherein the concentration of the carbon dioxide in the mixed gas is 65 v%, and the flow rate is 4Nm3H is used as the reference value. The reaction temperature is 40 ℃, the pH value at the end of the reaction is 9.8, the introduction of carbon dioxide is stopped, the aging is carried out for 30 minutes, and mother liquor is filtered and separated and washed. Drying at 110 deg.C5h, preparing the nickel-containing pseudo-boehmite.
(2) Nickel-containing support
Weighing the prepared nickel-containing pseudo-boehmite, mixing with nitric acid, phosphoric acid, sesbania powder and water, kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 960 ℃ for 4h to obtain the nickel-containing carrier.
(3) Catalyst and process for preparing same
And (3) dissolving nickel acetate, copper nitrate and cerium nitrate into water to prepare an impregnation solution, impregnating the impregnation solution on 100g of the carrier prepared in the step (2), drying at 120 ℃, and roasting at 480 ℃ for 3 hours to obtain the catalyst C1.
Comparative example 1
(1) Pseudo-boehmite
4L of Al with a concentration of 50g2O3Putting the/L sodium metaaluminate solution into a stainless steel container which is provided with a stirrer and can be filled with gas at the bottom of the tank, filling mixed gas of carbon dioxide and air, wherein the concentration of the carbon dioxide in the mixed gas is 60 v%, and the flow rate is 4Nm3H is used as the reference value. The reaction temperature is 35 ℃, the pH value at the end of the reaction is 10, the introduction of carbon dioxide is stopped, the aging is carried out for 35 minutes, and mother liquor is filtered and separated and washed. Drying at 120 deg.C for 4h to obtain pseudo-boehmite.
(2) Carrier
Weighing the prepared pseudoboehmite, mixing with nitric acid, phosphoric acid, sesbania powder and water, kneading into a plastic body, extruding into strips, molding, drying at 120 ℃ for 4h, and roasting at 970 ℃ for 4h to obtain the carrier.
(3) Catalyst and process for preparing same
And (3) dissolving nickel nitrate, copper nitrate and cerium nitrate into water to prepare impregnation liquid, impregnating the impregnation liquid on 100g of the carrier prepared in the step (2), drying the impregnation liquid at 120 ℃, and roasting the impregnation liquid for 3 hours at 410 ℃ to obtain the catalyst D1.
Example 2
(1) Nickel-containing pseudo-boehmite
4L of Al with a concentration of 50g2O3Putting the/L sodium metaaluminate solution into a stainless steel container with a stirrer and a gas-permeable tank bottom, putting 1L nickel nitrate solution with the concentration of 10g NiO/L into a container at a high position, and controlling the flow rate by connecting a peristaltic pump. Introducing mixed gas of carbon dioxide and air, and dripping prepared nitric acidNickel solution, carbon dioxide concentration in mixed gas 70 v%, flow 3Nm3H is used as the reference value. The reaction temperature is 35 ℃, the pH value at the end of the reaction is 9.5, the introduction of carbon dioxide is stopped, the aging is carried out for 45 minutes, and mother liquor is filtered and separated and washed. Drying at 110 ℃ for 3h to prepare the nickel-containing pseudo-boehmite.
(2) Nickel-containing support
Weighing the prepared nickel-containing pseudo-boehmite, mixing with nitric acid, phosphoric acid, citric acid, sesbania powder and water, kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 620 ℃ for 4h to obtain the nickel-containing carrier precursor. Preparing lithium carbonate and citric acid aqueous solution, dipping the lithium carbonate and citric acid aqueous solution on the nickel-containing carrier precursor by adopting an equal-volume dipping method, drying the nickel-containing carrier precursor for 4 hours at 120 ℃, and roasting the nickel-containing carrier precursor for 4 hours at 1000 ℃ to obtain the nickel-and lithium-containing carrier.
(3) Catalyst and process for preparing same
The catalyst is prepared by a two-step impregnation method. Firstly, dissolving nickel nitrate, basic copper carbonate and ammonia water in water to prepare impregnation liquid, and impregnating 100g of the carrier prepared in the step (2) by adopting an isometric impregnation method to obtain 60% of the total amount of the nickel nitrate. Drying at 120 ℃, roasting at 350 ℃ for 4h, impregnating 35 percent of the total amount of the nickel nitrate by adopting an isometric impregnation method in the second step, drying at 120 ℃, and roasting at 380 ℃ for 4h to obtain the catalyst C2.
Example 3
(1) Nickel-containing pseudo-boehmite
4L of Al with a concentration of 50g2O3Putting the/L sodium metaaluminate solution into a stainless steel container with a stirrer and a gas-permeable tank bottom, putting 1L nickel nitrate solution with the concentration of 3g NiO/L into a container at a high position, and controlling the flow rate by connecting a peristaltic pump. Introducing mixed gas of carbon dioxide and air, and simultaneously dropwise adding the prepared nickel nitrate solution, wherein the concentration of the carbon dioxide in the mixed gas is 60 v%, and the flow rate is 5Nm3H is used as the reference value. And (3) stopping introducing carbon dioxide at the reaction temperature of 30 ℃ and the pH value of 10 at the end of the reaction, aging for 40 minutes, filtering and separating mother liquor, washing, drying at 100 ℃ for 2 hours, and drying at 120 ℃ for 2 hours to obtain the nickel-containing pseudo-boehmite.
(2) Nickel-containing support
Weighing the prepared nickel-containing pseudo-boehmite, mixing with magnesium nitrate, lithium carbonate, nitric acid, citric acid, sesbania powder and water, kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 910 ℃ for 4h to obtain the carrier containing nickel, magnesium and lithium.
(3) Catalyst and process for preparing same
And (2) dissolving nickel nitrate and nickel nitrate in water to prepare a steeping liquid, steeping the steeping liquid onto 100g of the carrier prepared in the step (2) by adopting a two-step isometric steeping method, steeping 65% of the total amount of the nickel nitrate by adopting the isometric steeping method in one step, drying the soaked nickel nitrate at 120 ℃, roasting the soaked nickel nitrate at 350 ℃ for 4 hours, steeping 35% of the total amount of the nickel nitrate by adopting the isometric steeping method in a second step, drying the soaked nickel nitrate at 120 ℃, and roasting the roasted nickel nitrate at 380 ℃ for 4 hours to obtain the catalyst C.
Example 4
(1) Nickel-containing pseudo-boehmite
2L of Al with a concentration of 30g2O3The aluminum sulfate solution of/L and the nickel nitrate solution of 1L with the concentration of 12gNiO/L are mixed evenly and put into a container at a high position to prepare Al with the concentration of 50g2O3Putting 3L of sodium metaaluminate solution into a high-position container, controlling the flow rate of the solution by connecting peristaltic pumps below the two containers to flow into a stainless steel container which is provided with 2L of bottom water and is provided with a stirrer, and the bottom of the stainless steel container can be filled with gas, controlling the reaction temperature to be 56 ℃, controlling the pH value of a flow regulation reaction system to be 9.3, regulating the pH value of slurry to be 9.5 by dripping ammonia water, aging for 30 minutes after the reaction is finished, filtering and separating mother liquor, washing, and drying for 2 hours at 120 ℃ to prepare the nickel-containing pseudo-boehmite.
(2) Nickel-containing support
Weighing the prepared nickel-containing pseudo-boehmite, mixing with nitric acid, citric acid, sesbania powder and water, kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 600 ℃ for 4h to obtain the nickel-containing alumina carrier precursor. Preparing lanthanum nitrate, lithium carbonate and citric acid aqueous solution, dipping the solution on a nickel-containing carrier precursor by adopting an equal-volume dipping method, drying the solution at 120 ℃ for 4h, and roasting the solution at 980 ℃ for 4h to obtain the carrier containing nickel, lanthanum and lithium.
(3) Catalyst and process for preparing same
And (3) dissolving nickel nitrate and copper nitrate in water to prepare impregnation liquid, impregnating the impregnation liquid on 100g of the carrier prepared in the step (2) by an isometric impregnation method, drying the carrier at 120 ℃, and roasting the carrier at 380 ℃ for 4 hours to obtain the catalyst C4.
Example 5
(1) Nickel-containing pseudo-boehmite
2L of Al with a concentration of 30g2O3The aluminum sulfate solution of/L and the nickel nitrate solution of 1L with the concentration of 6g NiO/L are mixed evenly and put into a container at a high position to prepare Al with the concentration of 50g2O3And putting 3L of sodium metaaluminate solution into a high-position container, controlling the flow rate of the sodium metaaluminate solution under the two containers by connecting peristaltic pumps, flowing into a stainless steel container which is provided with 2L of bottom water and is provided with a stirrer, and the bottom of the stainless steel container can be filled with gas, controlling the reaction temperature to be 60 ℃, controlling the pH value of a flow regulation reaction system to be 9, regulating the pH value of slurry to be 9.8 by dripping ammonia water, aging for 25 minutes after the reaction is finished, filtering and separating mother liquor, and washing. Drying at 120 ℃ for 4h to prepare the nickel-containing pseudo-boehmite.
(2) Nickel-containing support
Weighing the prepared nickel-containing pseudo-boehmite, mixing with nitric acid, phosphoric acid, citric acid, sesbania powder and water, kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 1020 ℃ for 4h to obtain the nickel-containing carrier.
(3) Catalyst and process for preparing same
Dipping the carrier prepared in the step (2) on 100g by adopting a two-step isometric dipping method to prepare a nickel nitrate solution dipping carrier with 50 percent of total nickel content in one step, drying the carrier at 120 ℃, roasting the carrier at 350 ℃ for 4 hours, dissolving nickel acetate, basic copper carbonate and ammonia water in water to prepare dipping solution in the second step, adding the rest 50 percent of nickel content, drying the carrier at 120 ℃, and roasting the carrier at 380 ℃ for 4 hours to obtain the catalyst C5.
Example 6
(1) Nickel-containing pseudo-boehmite
2L of Al with a concentration of 25g2O3The aluminum sulfate solution of/L and the nickel nitrate solution of 1L with the concentration of 25gNiO/L are mixed evenly and put into a container at a high position to prepare Al with the concentration of 50g2O3Putting 3L of sodium metaaluminate solution into a high-position container, controlling the flow rate of the solution by connecting peristaltic pumps below the two containers to flow into a stainless steel container which is provided with 2L of bottom water and is provided with a stirrer, and the bottom of the stainless steel container can be filled with gas, controlling the reaction temperature to be 65 ℃, controlling the flow to adjust the pH value of a reaction system to be 9.0, adjusting the pH value of slurry to be 9.5 by dripping ammonia water, aging for 20 minutes after the reaction is finished, filtering and separating mother liquor, and washing. In thatDrying at 120 ℃ for 4h to prepare the nickel-containing pseudo-boehmite.
(2) Nickel-containing support
Weighing the prepared nickel-containing pseudo-boehmite, mixing with magnesium nitrate, nitric acid, citric acid, sesbania powder and water, kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 550 ℃ for 4h to obtain the nickel-containing carrier precursor. Preparing lanthanum nitrate, lithium carbonate and citric acid aqueous solution, dipping the solution on a nickel-containing carrier precursor by adopting an equal-volume dipping method, drying the solution for 4h at 120 ℃, and roasting the solution for 4h at 950 ℃ to obtain the carrier containing nickel, magnesium, lanthanum and lithium.
(3) Catalyst and process for preparing same
The catalyst is prepared by a two-step impregnation method. Firstly, dissolving nickel acetate, basic copper carbonate and ammonia water in water to prepare impregnation liquid, and impregnating 100g of the carrier prepared in the step (2) by adopting an isometric impregnation method to obtain 40% of the total amount of the nickel nitrate. Drying at 120 ℃, roasting at 360 ℃ for 4h, impregnating 60 percent of the total amount of the nickel nitrate by adopting an isometric impregnation method in the second step, drying at 120 ℃, and roasting at 400 ℃ for 4h to obtain the catalyst C6.
Comparative example 2
(1) Pseudo-boehmite
2L of Al with a concentration of 30g2O3Al sulfate solution/L and 3L of Al with a concentration of 60g2O3Respectively loading the/L sodium metaaluminate solution into high-position containers, controlling the flow rate of the solution by connecting peristaltic pumps below the two containers to flow into a stainless steel container which is provided with a stirrer and 2L of bottom water and can be filled with gas at the bottom of the container, controlling the reaction temperature to be 50 ℃, controlling the flow to adjust the pH value of a reaction system to be 9, adjusting the pH value of slurry to be 9.5 by dripping ammonia water, aging for 30 minutes after the reaction is finished, filtering and separating mother liquor, and washing. Drying at 120 deg.C for 5h to obtain pseudo-boehmite.
(2) Carrier
Weighing the prepared pseudoboehmite, mixing with magnesium nitrate, nitric acid, citric acid, sesbania powder and water, kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 550 ℃ for 4h to obtain the carrier precursor. Preparing lanthanum nitrate, lithium carbonate and citric acid aqueous solution, impregnating the carrier precursor by adopting an isometric impregnation method, drying the carrier precursor for 4 hours at 120 ℃, and roasting the carrier precursor for 4 hours at 920 ℃ to obtain the carrier containing magnesium, lanthanum and lithium.
(3) Catalyst and process for preparing same
The catalyst is prepared by a two-step impregnation method. Firstly, dissolving nickel acetate, basic copper carbonate and ammonia water in water to prepare impregnation liquid, and impregnating 100g of the carrier prepared in the step (2) by adopting an isometric impregnation method to obtain 40% of the total amount of the nickel nitrate. Drying at 120 ℃, roasting at 350 ℃ for 4h, soaking 60 percent of the total amount of the nickel nitrate in two steps by adopting an equal-volume impregnation method, drying at 120 ℃, and roasting at 420 ℃ for 4h to obtain the catalyst D2.
Example 7
(1) Nickel-containing pseudo-boehmite
4L of Al with a concentration of 50g2O3Putting the/L sodium metaaluminate solution into a stainless steel container which is provided with a stirrer and can be filled with gas at the bottom of the tank, filling mixed gas of carbon dioxide and air, wherein the concentration of the carbon dioxide in the mixed gas is 60 v%, and the flow rate is 4Nm3H is used as the reference value. The reaction temperature is 35 ℃, the pH value is 10 at the end of the reaction, and the introduction of carbon dioxide is stopped. Adding 0.5L of nickel nitrate solution with the concentration of 24gNiO/L under the condition of air stirring, stabilizing for 30 minutes, then adjusting the pH value of the slurry to 9.5 by dropwise adding ammonia water, aging for 30 minutes after the reaction is finished, filtering and separating mother liquor, and washing. Drying at 90 deg.C for 3h, and drying at 120 deg.C for 2h to obtain nickel-containing pseudoboehmite.
(2) Nickel-containing support
Weighing the prepared nickel-containing pseudo-boehmite, mixing with nitric acid, phosphoric acid, citric acid, sesbania powder and water, kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 600 ℃ for 4h to obtain the nickel-containing carrier precursor. Preparing lithium carbonate and citric acid aqueous solution, dipping the lithium carbonate and citric acid aqueous solution on the nickel-containing carrier precursor by adopting an equal-volume dipping method, drying the nickel-containing carrier precursor at 120 ℃ for 4 hours, and roasting the nickel-containing carrier precursor at 990 ℃ for 4 hours to obtain the nickel-and lithium-containing carrier.
(3) Catalyst and process for preparing same
And (3) dissolving nickel nitrate and basic copper carbonate in ammonia water and water to prepare a steeping liquor, steeping the steeping liquor on 50g of the carrier prepared in the step (2) by an isometric steeping method, drying the carrier at 120 ℃, and roasting the carrier at 380 ℃ for 4 hours to obtain the catalyst C7.
Comparative example 3
This comparative example a nickel-containing support was prepared according to the method described in the example in CN1123392C, with the following specific steps:
weighing 200g of aluminum hydroxide dry glue powder and 7.5g of sesbania powder, uniformly mixing, weighing 35g of carbon black and 16g of basic nickel carbonate, uniformly mixing, and adding tetrabutylammonium hydroxide (wherein C is the tetrabutylammonium hydroxide measured in a previous measuring cylinder)16H37NO content about 10 w%) 68ml, stirring with a glass rod to make the tetrabutylammonium hydroxide solution fully contact with the mixture, standing for 30 minutes, adding the tetrabutylammonium hydroxide solution into aluminum hydroxide dry glue powder mixed with sesbania powder, and uniformly mixing again;
adding a mixed solution of acetic acid, citric acid and deionized water into aluminum hydroxide dry glue powder mixed with basic nickel carbonate, carbon black and sesbania powder, kneading into uniform pasty plastic, extruding into clover-shaped strips on a strip extruder, drying at 120 ℃ for 4 hours, and roasting at 920 ℃ for 4 hours to obtain the nickel-containing alumina carrier.
Dissolving nickel nitrate, copper nitrate and lithium carbonate in water together to prepare impregnation liquid, impregnating the impregnation liquid on 100g of the prepared nickel-containing carrier, drying the impregnation liquid at 120 ℃, and roasting the impregnation liquid for 4 hours at 420 ℃ to obtain the catalyst D4.
Example 8
(1) Nickel-containing pseudo-boehmite
4L of Al with a concentration of 50g2O3Putting the/L sodium metaaluminate solution into a stainless steel container which is provided with a stirrer and can be filled with gas at the bottom of the tank, filling mixed gas of carbon dioxide and air, wherein the concentration of the carbon dioxide in the mixed gas is 70 v%, and the flow rate is 3Nm3H is used as the reference value. The reaction temperature is 35 ℃, the pH value is 10 at the end of the reaction, and the introduction of carbon dioxide is stopped. Adding 1L of nickel nitrate solution with the concentration of 5g NiO/L under the condition of air stirring, stabilizing for 20 minutes, then adjusting the pH value of the slurry to 9.5 by dropwise adding ammonia water, aging for 40 minutes after the reaction is finished, filtering and separating mother liquor, and washing. Drying at 120 deg.c for 4 hr to obtain nickel containing pseudoboehmite.
(2) Nickel-containing support
Weighing the prepared nickel-containing pseudo-boehmite, mixing with nitric acid, citric acid, sesbania powder and water, kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 1050 ℃ for 4h to obtain the nickel-containing carrier.
(3) Catalyst and process for preparing same
And (3) dissolving nickel nitrate and copper nitrate in water to prepare a steeping liquor, steeping the steeping liquor on 50g of the carrier prepared in the step (2) by an isometric steeping method, drying the carrier at 120 ℃, and roasting the carrier at 400 ℃ for 4 hours to obtain the catalyst C8.
Example 9
(1) Nickel-containing pseudo-boehmite
4L of Al with a concentration of 50g2O3The preparation method comprises the following steps of uniformly mixing an aluminum nitrate solution/L and a nickel nitrate solution 1L with the concentration of 8gNiO/L, putting the mixture into a container at a high position, preparing an ammonia water solution with the concentration of 8 wt% into the container at the high position, controlling the flow rate of the ammonia water solution under the two containers by a peristaltic pump, flowing the ammonia water solution into a stainless steel container which is provided with 5L of bottom water, is provided with a stirrer, and can be filled with gas at the bottom of the container, controlling the reaction temperature to be 50 ℃, controlling the flow to adjust the pH value of a reaction system to be 7.5, adding ammonia water to adjust the pH value of slurry after the reaction is finished, aging for 60 minutes. Drying at 90 deg.C for 3h, and drying at 120 deg.C for 2h to obtain nickel-containing pseudoboehmite.
(2) Nickel-containing support
Weighing the prepared nickel-containing pseudo-boehmite, mixing with lanthanum nitrate, nitric acid, citric acid, sesbania powder and water, kneading into a plastic body, extruding into strips, forming, and drying at 120 ℃ for 4 hours. Roasting for 4h at 350 ℃ to obtain the carrier precursor containing lanthanum and nickel. Preparing magnesium nitrate aqueous solution, dipping the magnesium nitrate aqueous solution on a nickel-containing carrier by adopting an isometric dipping method, drying the magnesium nitrate aqueous solution for 4h at 120 ℃, and roasting the magnesium nitrate aqueous solution for 4h at 850 ℃ to obtain the carrier containing lanthanum, magnesium and nickel.
(3) Catalyst and process for preparing same
And (3) dissolving nickel nitrate and copper nitrate in water to prepare a steeping liquor, steeping the steeping liquor on 50g of the carrier prepared in the step (2) by an isometric steeping method, drying the carrier at 120 ℃, and roasting the carrier at 380 ℃ for 4 hours to obtain the catalyst C9.
Comparative example 4
(1) Pseudo-boehmite
4L of Al with a concentration of 50g is prepared2O3Respectively placing Al nitrate solution and 8 wt% ammonia water solution in high-position containers, controlling flow rate by peristaltic pump under the two containers, flowing into stainless steel container with 3L bottom water, stirrer, and gas at 45 deg.CAdjusting the pH value of the reaction system to be 8.0, adding ammonia water to adjust the pH value of the slurry to be 8.5 after the reaction is finished, aging for 30 minutes, filtering and separating mother liquor, and washing. Drying at 120 deg.C for 6h to obtain pseudo-boehmite.
(2) Carrier
Weighing the prepared pseudoboehmite, mixing with lanthanum nitrate, nitric acid, citric acid, sesbania powder and water, kneading into a plastic body, extruding into strips, forming, and drying at 120 ℃ for 4 hours. A lanthanum containing support precursor is obtained. Preparing magnesium nitrate aqueous solution, dipping the magnesium nitrate aqueous solution on a nickel-containing carrier by adopting an isometric dipping method, drying the carrier at 120 ℃ for 4h, and roasting the carrier at 880 ℃ for 4h to obtain the carrier containing lanthanum and magnesium.
(3) Catalyst and process for preparing same
Dissolving nickel nitrate in water to prepare impregnation liquid, impregnating the impregnation liquid on 100g of carrier, drying the impregnation liquid at 120 ℃, and roasting the impregnation liquid for 4 hours at 450 ℃ to obtain the catalyst D3.
TABLE 1 physical Properties and compositions of catalysts of examples and comparative examples
Figure BDA0001294593860000161
Evaluation of catalyst:
the pyrolysis gasoline is used as a raw material, the properties of the raw material are shown in table 2, and the catalysts of C1-C9 and D1-D4 are evaluated. The evaluation was carried out for 300h, and samples were taken every 12h for analysis of bromine number and diene, and the average data are shown in Table 3 below.
The catalyst evaluation is carried out on a 100ml adiabatic bed hydrogenation reaction device, the catalyst is firstly reduced for 10 hours under hydrogen at 380-450 ℃, then the temperature is reduced to 50 ℃, and the raw oil is passivated for 5 hours by cyclohexane containing 1000ppm of dimethyl disulfide. Evaluating process conditions: reaction pressure: 2.8MPa, inlet temperature: 55 ℃, space velocity of fresh raw oil: 3.0h-1Hydrogen to oil volume ratio: 200: 1 (volume ratio based on fresh oil).
TABLE 2 Hydrofeed oil Properties
Figure BDA0001294593860000171
Table 3 catalyst evaluation average data
Figure BDA0001294593860000172
It can be seen from the above examples and comparative examples that the hydrogenation catalyst of nickel-copper series prepared by using the nickel-containing alumina of the present invention has relatively low diene and bromine number of the hydrogenation product under the same evaluation process conditions, which fully indicates that the catalyst prepared in the examples has higher hydrogenation performance.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (25)

1. A nickel-copper hydrogenation catalyst contains active components of nickel and copper, and takes alumina containing nickel as a carrier, and is characterized in that: the catalyst comprises, by weight, 100 wt% of nickel oxide, 0.01-5 wt% of copper oxide, 0-5 wt% of cerium oxide and/or lanthanum oxide, and 0-6 wt% of alkali metal and/or alkaline earth metal oxide; the specific surface area of the catalyst is 50-180 m2A pore volume of 0.30-0.60 cm3(ii) a bulk density of 0.5 to 1.1g/cm3(ii) a The precursor of the nickel-containing alumina carrier is nickel-containing pseudo-boehmite; dipping the nickel-containing alumina carrier in the solution containing the active components, drying and roasting to prepare the nickel-copper hydrogenation catalyst;
wherein, the preparation process of the nickel-containing pseudo-boehmite comprises the following steps:
(1) adding bottom water into the neutralization kettle, wherein the bottom water is deionized water, and heating to 50-90 ℃;
(2) respectively preparing an acidic aluminum salt aqueous solution and an acidic nickel salt aqueous solution, uniformly mixing the acidic aluminum salt aqueous solution and the acidic nickel salt aqueous solution to obtain an acidic aqueous solution containing aluminum salt and nickel salt, and adjusting the temperature of the acidic aqueous solution to 50-90 ℃;
(3) preparing alkali metal aluminate solution;
(4) adding the acidic aqueous solution obtained in the step (2) and the alkali metal aluminate solution obtained in the step (3) into the neutralization kettle in the step (1) in a concurrent flow manner, and continuously ventilating and stirring until gelling;
(5) controlling the gelling temperature of the step (4) to be 50-90 ℃, and controlling the gelling pH value to be 7-10;
(6) after the cementing, the nickel-containing pseudo-boehmite is prepared by aging, filtering, washing and drying.
2. The nickel-copper based hydrogenation catalyst according to claim 1, characterized in that: the specific surface area of the nickel-containing pseudo-boehmite is 300-420 m2A pore volume of 0.7 to 1.2 cm/g3(ii)/g, the pore diameter is 5-10 nm; the nickel content is 0.1-10 wt% based on the total weight of the nickel-containing pseudo-boehmite as 100 wt%.
3. The nickel-copper based hydrogenation catalyst according to claim 1, characterized in that: the nickel content of the nickel-containing alumina carrier is 0.1-10 wt% and the specific surface area is 25-250 m based on the total weight of the nickel-containing alumina carrier being 100%2A pore volume of 0.15-0.85 cm3The pore diameter is 8-40 nm.
4. The nickel-copper based hydrogenation catalyst according to claim 1, characterized in that: the nickel-containing alumina carrier is obtained by molding and roasting nickel-containing pseudo-boehmite and contains delta-Al2O3、δ-NiAl26O40And NiAl2O4The crystal form is a crystal form, wherein B1/B2 is more than or equal to 0.45 and less than or equal to 0.85 in an XRD spectrogram, B1 refers to the integral intensity of a peak with the 2 theta of 34.2-39.8 degrees in the XRD spectrogram, and B2 refers to the integral intensity of a peak with the 2 theta of 43.3-48.5 degrees in the XRD spectrogram.
5. The nickel-copper based hydrogenation catalyst according to claim 1, characterized in that: Delta-Al in nickel-containing alumina carrier2O3、δ-NiAl26O40And NiAl2O4Accounting for 30-100 wt% of the total weight of the nickel-containing alumina carrier.
6. The nickel-copper based hydrogenation catalyst according to claim 1, characterized in that: the nickel-containing alumina carrier also contains theta-Al2O3、α-Al2O3And/or gamma-Al2O3。
7. The nickel-copper-based hydrogenation catalyst according to claim 4, characterized in that: the roasting conditions of the nickel-containing alumina carrier are as follows: roasting at 800-1200 ℃ for 4-10 h.
8. The nickel-copper-based hydrogenation catalyst according to claim 1, comprising 14.5 to 18.5 wt% of nickel oxide, 0.05 to 3 wt% of copper oxide, 0.2 to 1.8 wt% of cerium oxide and/or lanthanum oxide, and 0.5 to 3 wt% of an alkali metal oxide and/or an alkaline earth metal oxide, based on 100 wt% of the catalyst.
9. The nickel-copper based hydrogenation catalyst according to claim 2, wherein the nickel content is 0.5 to 5 wt% based on 100 wt% of the total weight of the nickel-containing pseudo-boehmite.
10. The nickel-copper-based hydrogenation catalyst according to claim 3, wherein the nickel content of the nickel-containing alumina support is 0.5 to 5 wt% based on 100 wt% of the total weight of the nickel-containing alumina support.
11. The nickel-copper-based hydrogenation catalyst according to claim 6, wherein the alpha-Al in the nickel-containing alumina support2O3The content is less than 30 wt%.
12. The nickel-copper-based hydrogenation catalyst according to claim 7, wherein the calcination temperature of the nickel-containing alumina support is 850 to 1100 ℃.
13. A method for preparing the nickel-copper based hydrogenation catalyst according to claim 1, characterized in that: impregnating a nickel-containing alumina carrier by using a nickel-and-copper-containing solution through one step or multiple steps, and then drying and roasting to obtain a catalyst; the nickel-containing alumina carrier is obtained by molding and roasting nickel-containing pseudo-boehmite; the nickel-containing pseudo-boehmite is obtained by the following method, and the specific process comprises the following steps:
(1) adding bottom water into the neutralization kettle, wherein the bottom water is deionized water, and heating to 50-90 ℃;
(2) respectively preparing an acidic aluminum salt aqueous solution and an acidic nickel salt aqueous solution, uniformly mixing the acidic aluminum salt aqueous solution and the acidic nickel salt aqueous solution to obtain an acidic aqueous solution containing aluminum salt and nickel salt, and adjusting the temperature of the acidic aqueous solution to 50-90 ℃;
(3) preparing alkali metal aluminate solution;
(4) adding the acidic aqueous solution obtained in the step (2) and the alkali metal aluminate solution obtained in the step (3) into the neutralization kettle in the step (1) in a concurrent flow manner, and continuously ventilating and stirring until gelling;
(5) controlling the gelling temperature of the step (4) to be 50-90 ℃, and controlling the gelling pH value to be 7-10;
(6) after the cementing, the nickel-containing pseudo-boehmite is prepared by aging, filtering, washing and drying.
14. The method for producing a nickel-copper-based hydrogenation catalyst according to claim 13, characterized in that: and (2) introducing air into the kettle bottom of the neutralization kettle in the step (1).
15. The method for producing a nickel-copper-based hydrogenation catalyst according to claim 13, characterized in that: and (3) adjusting the temperature of the acidic aqueous solution to 50-70 ℃ in the step (2).
16. The method for producing a nickel-copper-based hydrogenation catalyst according to claim 13, characterized in that: in the step (5), the gelling temperature is 50-70 ℃; the pH value of the gelling is 7.5-9.5.
17. The method for producing a nickel-copper-based hydrogenation catalyst according to claim 13, characterized in that: and (4) the pH value of the alkali metal aluminate solution in the step (3) is 9-14.
18. The method for producing a nickel-copper-based hydrogenation catalyst according to claim 13, characterized in that: the acidic aluminum salt aqueous solution is a mixed solution of one or more of aluminum chloride, aluminum sulfate and aluminum nitrate; the acidic nickel salt aqueous solution is a mixed solution of one or more of nickel chloride, nickel sulfate, nickel bromide and nickel nitrate; the alkali metal aluminate solution is sodium metaaluminate or potassium metaaluminate solution.
19. The method for producing a nickel-copper-based hydrogenation catalyst according to claim 13, characterized in that: in the step (2), the acidic aluminum salt and the acidic nickel salt aqueous solution are mixed to obtain an acidic aqueous solution containing aluminum salt and nickel salt, wherein the pH value is 2-5.
20. The method for producing a nickel-copper-based hydrogenation catalyst according to claim 13, characterized in that: in the step (6), the aging temperature is 50-80 ℃, and the aging time is 10-60 min.
21. The method for producing a nickel-copper-based hydrogenation catalyst according to claim 13, characterized in that: impregnating a nickel-containing alumina carrier by using a nickel-and-copper-containing solution through one step or multiple steps, and then drying and roasting to prepare a catalyst; the roasting conditions are as follows: roasting for 3-8 h at 300-500 ℃.
22. The method of claim 13, wherein the concentration of the aqueous acidic aluminum salt solution is 10-80 gAl2O3The concentration of the acidic nickel salt aqueous solution is 3-50 gNiO/L; the concentration of the alkali metal aluminate solution is 50-300 gAl2O3/L。
23. The method for preparing a nickel-copper based hydrogenation catalyst according to claim 17, wherein the pH of the alkali metal aluminate solution in the step (3) is 12 to 14.
24. The method of claim 18, wherein the aqueous acidic aluminum salt solution is an aluminum sulfate solution; the aqueous acidic nickel salt solution is a nickel nitrate solution.
25. The method according to claim 19, wherein in the step (2), the acidic aluminum salt and the acidic nickel salt aqueous solution are mixed to obtain an acidic aqueous solution containing an aluminum salt and a nickel salt, and the pH value is 2 to 4.
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CN112547067B (en) * 2019-09-10 2023-06-20 中国石油化工股份有限公司 Preparation method of catalyst for slurry bed methane synthesis reaction
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1428298A (en) * 1998-01-30 2003-07-09 日本能源株式会社 Method for preparing artificial boehmite
CN101147866A (en) * 2006-09-20 2008-03-26 中国石油化工股份有限公司 Paraffin hydrogenation refined catalyst and its preparing process and application
CN102268283A (en) * 2011-07-08 2011-12-07 中国石油天然气股份有限公司 Hydrorefining method of distillate oil
RU2496574C1 (en) * 2012-07-20 2013-10-27 Федеральное государственное бюджетное учреждение науки Институт химии нефти Сибирского отделения Российской академии наук (ИХН СО РАН) Catalyst for hydrofining diesel fractions
CN105712840A (en) * 2014-12-02 2016-06-29 中国科学院大连化学物理研究所 Method for producing high-carbon primary alcohols by catalytic conversion of ethanol

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1428298A (en) * 1998-01-30 2003-07-09 日本能源株式会社 Method for preparing artificial boehmite
CN101147866A (en) * 2006-09-20 2008-03-26 中国石油化工股份有限公司 Paraffin hydrogenation refined catalyst and its preparing process and application
CN102268283A (en) * 2011-07-08 2011-12-07 中国石油天然气股份有限公司 Hydrorefining method of distillate oil
RU2496574C1 (en) * 2012-07-20 2013-10-27 Федеральное государственное бюджетное учреждение науки Институт химии нефти Сибирского отделения Российской академии наук (ИХН СО РАН) Catalyst for hydrofining diesel fractions
CN105712840A (en) * 2014-12-02 2016-06-29 中国科学院大连化学物理研究所 Method for producing high-carbon primary alcohols by catalytic conversion of ethanol

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