CN108855128B - Selective hydrogenation catalyst and preparation method thereof - Google Patents

Selective hydrogenation catalyst and preparation method thereof Download PDF

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CN108855128B
CN108855128B CN201710339315.2A CN201710339315A CN108855128B CN 108855128 B CN108855128 B CN 108855128B CN 201710339315 A CN201710339315 A CN 201710339315A CN 108855128 B CN108855128 B CN 108855128B
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nickel
solution
acidic
hydrogenation catalyst
carrier
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CN108855128A (en
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胡晓丽
梁顺琴
王斌
展学成
郑云弟
孙利民
钱颖
马好文
刘肖飞
孙雪芹
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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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • 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

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Abstract

The invention relates to a selective hydrogenation catalyst and a preparation method thereof, in particular to a preparation method of a palladium-silver hydrogenation catalyst taking nickel-containing alumina as a carrier. Contains active components of palladium and silver, nickel-containing alumina is used as a carrier, the precursor of the nickel-containing alumina carrier is nickel-containing pseudo-boehmite, and the preparation process of the nickel-containing pseudo-boehmite comprises the acid-base neutralization and gelling process. The catalyst uses a specific carrier, has the advantages that nickel and pseudo-boehmite can be organically combined to form a nickel-containing alumina carrier with a specific crystal form, and simultaneously has a better regulation effect on the pore structure and acidity of the carrier, and the active components of the prepared catalyst are highly dispersed.

Description

Selective hydrogenation catalyst and preparation method thereof
Technical Field
The invention relates to a selective hydrogenation catalyst and a preparation method thereof, in particular to a palladium-silver catalyst taking nickel-containing alumina as a carrier and a preparation method thereof.
Background
The initial products in the catalytic cracking and steam cracking process contain more dienes and alkynes, and at a certain reaction temperature, the dienes and alkynes are easy to polymerize and possibly react with gas olefins in gasoline to produce coking precursors such as colloid and the like, and the coking precursors are selectively removed by adopting a hydrogenation method.
The selective hydrogenation catalyst used in the industry at present is mainly a supported metal catalyst, and the active components are mainly palladium or nickel. The two catalysts have own advantageous application range aiming at different raw oil properties due to the inherent characteristics of the two catalysts. Pd/Al2O3The catalyst has the advantages of simple pretreatment during starting, low starting temperature, high activity, large treatment capacity and the like; Ni/Al2O3The catalyst has certain advantages in the aspects of arsenic resistance, colloid resistance, water resistance and the like, so that the nickel-based catalyst has relatively stable performance under the condition of high impurity content. In order to increase the activity or selectivity of the catalyst, a certain amount of metal promoter is often added.
US4484015A provides a composition and method comprising palladium and silver, each in an amount sufficient to effect substantially selective hydrogenation of certain unsaturated hydrocarbons. For the selective hydrogenation of highly unsaturated hydrocarbons (e.g., alkynes or diolefins) to less unsaturated hydrocarbons (e.g., alkenes or monoolefins). The composition further includes an alkali metal-containing compound, such as potassium fluoride. However, the activity of the catalyst is to be further improved.
CN1181283B provides a catalyst and a preparation method thereof, which is used for selective hydrogenation of highly unsaturated hydrocarbons (such as alkyne or diene) into lower unsaturated hydrocarbons. The catalyst contains palladium, silver and spinel. Wherein the palladium and silver are each used in an amount sufficient to effect substantially selective hydrogenation of certain unsaturated hydrocarbons. Alternatively, palladium is present in the surface layer near the surface of the spinel. The catalyst comprises certain alkali metal-containing compounds.
CN102728351B relates to a selective hydrogenation catalyst for pyrolysis gasoline or fractions thereof, which comprises an alumina-titanium oxide compound as a carrier, and active components Pd and Ag loaded on the carrier, wherein the Pd content is 0.15-0.5 wt%, and the Ag content is 0.8-4.5 wt% based on 100% of the total weight of the catalyst. The catalyst can be used for hydrogenation of pyrolysis gasoline or fractions thereof, and has the characteristics of strong As impurity resistance and large gel capacity.
CN102430406B discloses a hydrogenation catalyst, which is characterized in that the active components are metallic palladium and rare earth oxide, the content of metallic palladium in the catalyst is 0.2-5 wt%, and the content of rare earth oxide is 0.1-2.5 wt%. The catalyst is prepared by preparing a palladium-rare earth aqueous solution from a water-soluble palladium-containing compound, a water-soluble rare earth-containing compound and water, and impregnating a carrier with the palladium-rare earth aqueous solution. The prepared catalyst is subjected to reduction treatment at 50-200 ℃ in a hydrogen atmosphere before use, so that oxidation state divalent palladium in a palladium compound is reduced into metal state palladium, and the catalyst is used for a refining process after caprolactam hydrogenation.
The key point of improving the comprehensive performance of the palladium hydrogenation catalyst is to develop a novel carrier material suitable for the palladium hydrogenation catalyst in the following three aspects of (1); (2) adjusting the content of active components of the palladium hydrogenation catalyst; (3) and the addition of an auxiliary agent and an active component dispersing agent improves the comprehensive utilization rate of the active component.
Hydrated aluminas such as pseudo-boehmite, and the like are widely used as raw materials for preparing alumina carriers, and although methods such as a pH swing method, addition of an organic pore-expanding agent, 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 performance of alumina as a carrier material for 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, the mixture of nickel-containing compound and carbon black which are treated by alkali is mixed and kneaded with aluminum hydroxide dry glue powder, and the alumina carrier containing 2.0-14.0% of nickel is prepared by extrusion molding, drying and roasting, the pore volume of the carrier is 0.4cm3/g～1.0cm3Per g, specific surface area of 160m2/g～420m2The average pore diameter is 8.0-15.0 nm, the proportion of pores larger than 6.0nm accounts for more than 85 percent of the total pores, the pore volume and the average pore diameter are larger, and the catalyst is particularly suitable for being used as heavy oilA carrier of a 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, is obtained by adding an acidic aqueous solution of nickel, zirconium and, if necessary, aluminium salts to an alkaline aqueous solution or suspension of silicon and, if necessary, of compounds 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 commonly used for preparing the catalyst with high active component content. However, the catalyst prepared by this method has poor strength.
The article "changes induced by catalysis in the hydrolysis activity of NiCo-Mo/Al" by Agudo A L et 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 ℃ due to the activity at 600 ℃When the catalyst is used, metal in the catalyst and an alumina carrier have strong interaction to generate a spinel structure, so that the activity of the catalyst is obviously reduced. 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 active components of the conventional noble metal catalyst are easy to agglomerate and poison to deactivate in the reaction process, and the dispersity of palladium metal is the problem which many researchers try to solve.
Disclosure of Invention
The invention provides a palladium-silver selective hydrogenation catalyst and a preparation method thereof.
The content of palladium (calculated by simple substance) is 0.05-0.8 wt%, preferably 0.15-0.5 wt%, silver oxide is 0.05-5 wt%, preferably 0.2-3 wt%, nickel (calculated by simple substance) is 0.1-10 wt%, preferably 0.5-5 wt% calculated by 100% of the weight of the catalyst; the specific surface area of the catalyst is 20-150 m2/g, preferably 60-120 m2/g, and the pore volume is 0.12-0.6 ml/g, preferably 0.3-0.5 ml/g; 0.1 to 10 wt%, preferably 0.5 to 3 wt% of an alkali metal and/or alkaline earth metal oxide; cerium oxide and/or lanthanum oxide in an amount of 0 to 5 wt%, preferably 0.5 to 1.2 wt%.
A palladium-silver selective hydrogenation catalyst contains active components of palladium and silver, nickel-containing alumina is used as a carrier, and the catalyst contains 0.05-0.8 wt% of palladium (calculated by a simple substance) and 0.05-5 wt% of silver oxide, wherein the total weight of the catalyst is 100%; the specific surface area of the catalyst is 20-150 m2A pore volume of 0.12-0.6 cm3(ii) in terms of/g. 0.1-10 wt% of alkali metal and/or alkaline earth metal oxide; cerium oxide and/or oxygen0-5 wt% of lanthanum oxide; the precursor of the nickel-containing alumina carrier is nickel-containing pseudo-boehmite, and the preparation process of the nickel-containing pseudo-boehmite comprises the acid-base neutralization and gelling process; the hydrogenation catalyst is prepared by dipping a palladium-silver solution containing an active component into a nickel-containing alumina carrier, drying and roasting.
The palladium-silver hydrogenation catalyst of the invention comprises, by weight, 100% of the catalyst, 0.1-10 wt% of nickel, preferably 0.5-5 wt%, and 0.05-0.8 wt% of palladium, preferably 0.15-0.5 wt%; the content of the silver oxide is 0.05 to 5 weight percent, preferably 0.2 to 3 weight percent; the specific surface area is 20-150 m2A specific ratio of 60 to 120 m/g2(ii)/g; the pore volume is 0.12 to 0.6ml/g, preferably 0.3 to 0.5 ml/g.
The catalyst of the present invention contains alkali metal and/or alkaline earth metal (in the form of oxide) in an amount of 0.1 to 10 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 more of Li, K, Ca and Mg. When the catalyst is used for hydrogenation, alkyne and diene in an oil product are easy to polymerize to form colloid and are inactivated, the acidity and alkalinity of the surface of a catalyst carrier can be adjusted by adding alkali metal and/or alkaline earth metal, the hydrogenation activity and the hydrogenation stability can be improved by adjusting the acidity and alkalinity of the surface of the catalyst, the deposition of carbon and colloid in the hydrogenation process can be reduced, and the service life of the catalyst can be prolonged.
The catalyst of the invention can contain rare earth element cerium and/or lanthanum (existing in the form of oxide), and the content is 0-5 wt%, preferably 0.5-1.2 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 components is improved, and the hydrogenation selectivity and stability of the catalyst are improved.
The invention also provides a preparation method of the palladium-silver hydrogenation catalyst, which is prepared by adopting a conventional impregnation method, and the impregnation load of the metal palladium is the same as that of the common shell catalyst. The invention also provides a specific preparation method of the catalyst, which comprises the following steps: adding soluble salts of alkali metal and/or alkaline earth metal, lanthanum and/or cerium and active components into water for dissolving, then dipping the solution on a nickel-containing alumina carrier precursor, drying and roasting to obtain a nickel-containing carrier; and then, dipping the nickel-containing carrier by using a salt solution containing active components of palladium and silver, wherein the palladium and the silver can be dipped step by step or simultaneously, and then washing, drying and roasting are carried out to obtain the catalyst.
In the preparation method of the palladium-silver hydrogenation catalyst, the active component solution can be a soluble salt solution of palladium and silver. The palladium salt can be palladium nitrate, palladium chloride and palladium acetate, and is preferably palladium chloride. The silver salt is preferably silver nitrate. 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. In the present invention, cerium and/or lanthanum are preferably added in the form of soluble nitrates.
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 palladium-silver hydrogenation catalyst is different from the prior art in that nickel-containing alumina is used as a carrier, and a precursor of the nickel-containing alumina carrier is nickel-containing pseudo-boehmite.
The invention also provides a nickel-containing pseudo-boehmite and a carrier prepared from the nickel-containing pseudo-boehmite, wherein the nickel-containing pseudo-boehmite prepared by the method organically combines nickel and the pseudo-boehmite and has better regulation effect on the pore structure and the acidity of the nickel-containing pseudo-boehmite.
The precursor of the nickel-containing alumina carrier, namely the nickel-containing pseudo-boehmite, has the specific surface area of 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%, preferably 0.5-5 wt%, based on the total weight of the nickel-containing pseudo-boehmite as 100%.
Firstly, preparing nickel-containing pseudo-boehmite, wherein the preparation process of the nickel-containing pseudo-boehmite comprises the processes of acid-base neutralization and gelling. The nickel-containing pseudo-boehmite is subjected to at least the processes of forming, drying and roasting to obtain the nickel-containing alumina carrier.
The nickel-containing alumina carrier of the invention can be different in preparation method, nickel source, nickel content, preparation method of the nickel-containing alumina carrier, activation roasting temperature and the like according to different final use purposes.
The nickel-containing alumina carrier of the present invention preferably contains delta-Al2O3、δ-NiAl26O40、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 of the present invention preferably contains delta-Al2O3、δ-NiAl26O40、NiAl2O4Mixed crystals of crystal forms, preferably delta-Al2O3、δ-NiAl26O40And NiAl2O4Accounting for 30-100 percent of the total weight of the nickel-containing alumina carrier. The carrier may further contain theta-Al2O3、α-Al2O3And/or gamma-Al2O3Preferably alpha-Al2O3Less than 30 wt%.
The nickel-containing alumina carrier of the invention contains 0.1-10 wt%, preferably 0.75-7.5 wt% of nickel based on 100% of the total weight of the nickel-containing alumina carrier. The specific surface area is 20-180 m2G, pore volume 0.12cm3/g～0.65cm3/g。
The nickel-containing pseudo-boehmite is not simple physical blending or coating of the pseudo-boehmite and a nickel-containing compound or a nickel salt solution, but generates an acid-base reaction, has a gelling process, and finally prepares the nickel-containing alumina carrier with a specific nickel and aluminum mixed crystal form.
The invention also provides a preparation method of the more specific palladium-silver hydrogenation catalyst, which comprises the steps of dipping the nickel-containing alumina carrier by using a salt solution containing active components of palladium and silver, dipping the palladium and the silver step by step or simultaneously, washing, drying and roasting to obtain the catalyst; the nickel-containing alumina carrier is obtained by at least forming, 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 mixed solution containing aluminum salt and nickel salt, and adjusting the temperature of the acidic mixed solution to be 50-90 ℃, preferably 50-70 ℃, wherein the concentration of the acidic aluminum salt aqueous solution is 10-80 g of Al2O3The concentration of the acidic nickel salt aqueous solution is 3-50 gNiO/L;
(3) preparing alkali metal aluminate solution, wherein the concentration of the alkali metal aluminate solution is 50-300 g of Al2O3/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); the gelling temperature in the step (5) is preferably 50-70 ℃, and the pH value is preferably 7.5-9.5.
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 acid aluminum salt and nickel salt mixed solution and the alkali metal aluminate solution and the solution in the gel forming tank is not more than 3 ℃, and the temperature of the acid aluminum salt and nickel salt mixed solution and the temperature of the alkali metal aluminate solution are preferably the same. In the step (3), an aqueous alkaline precipitant solution may be added to the alkali metal aluminate solution. The pH value of the alkali metal aluminate solution (or the mixed solution of the alkali metal aluminate solution and the alkaline precipitant aqueous solution) is 9-14, and the pH value is preferably 12-14.
The aluminum salt, the nickel salt and the alkaline precipitant in the preparation method of the nickel-containing pseudo-boehmite can all 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 waterThe solution can be one or a mixture of nickel chloride, nickel sulfate, nickel bromide and nickel nitrate, and is preferably a nickel nitrate solution. The pH value of the mixed solution of the acidic aluminum salt and the acidic nickel salt is 2-5, and the pH value is preferably 2-4. The alkali metal aluminate solution is sodium metaaluminate or potassium metaaluminate solution; the alkaline precipitant is ammonium bicarbonate solution, sodium bicarbonate solution, ammonia water solution, sodium hydroxide solution or calcium hydroxide solution, preferably ammonia water solution, NH3The content is 50-120 g/L.
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% of the total weight of a sample to be molded; the extrusion aid can be sesbania powder, and the dosage of the extrusion aid is 2-6% 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 percent of the total mass of the nickel-containing pseudo-boehmite.
The method and the conditions for roasting the catalyst carrier are the common method and the conditions for roasting the catalyst carrier, and can be roasted by adopting a vertical furnace, a converter and a mesh belt kiln, wherein the roasting conditions of the carrier are as follows: roasting for 3-8 h at 800-1200 ℃, wherein the roasting temperature is preferably 900-1100 ℃. The roasting temperature of the carrier is the roasting temperature of the carrier before active components of palladium and silver are impregnated so as to ensure the specific surface and pore volume required by the catalyst and finally prepare the carrier with a specific nickel and aluminum mixed crystal form. Before roasting at the temperature, the carrier can be prepared by low-temperature roasting, but intermediate transition roasting steps are adopted, and the roasting temperature is preferably 500-700 ℃ for 3-8 hours. The roasting temperature of the catalyst is 300-550 ℃, and the roasting time is 3-8 h.
In the method, rare earth elements cerium and/or lanthanum and alkali metal and/or alkaline earth metal are added in the carrier forming process; or after the carrier is formed, the active components are firstly added into the carrier before being impregnated; or when the active component is impregnated, the active component and the active component impregnation solution are added simultaneously.
Before the catalyst is used, hydrogen is preferably used for reduction for 4-24 hours at the temperature of 20-120 ℃, and the hydrogenation catalyst is suitable for selective hydrogenation of diene and alkyne.
The nickel-containing pseudo-boehmite and the carrier prepared from the nickel-containing pseudo-boehmite have the advantages that nickel and the pseudo-boehmite can be organically combined to form a nickel-containing alumina carrier with a specific crystal form, and meanwhile, the nickel-containing pseudo-boehmite has a good adjusting effect on the pore structure and the acidity of the carrier. The catalyst prepared by the nickel-containing alumina carrier has a good dispersing effect on the loaded noble metal active component, and has good selectivity and stability.
Detailed Description
The analysis method comprises the following steps:
the method for measuring the composition content of the catalyst comprises the following steps: analyzing by using national standard GB/T15337 of atomic absorption Spectroscopy rules and GB19723 of chemical reagent GB/T15337 of flame atomic absorption Spectroscopy rules;
specific surface area: measured by GB/T19587 standard;
pore volume: GB/T21650.2-2008 standard determination;
and (3) crystal form analysis: 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: CuKa 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;
diene value: measured by the method of UOP 326-2008;
bromine number: the SH/T0236-92 standard is adopted for determination.
Water content: measuring by using GB/T11133-89 standard;
sulfur content: measuring by adopting a WK-2B micro coulometer;
the invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto.
Example 1
(1) Preparation of a Nickel-containing support
2L of Al with a concentration of 25g2O3The aluminum sulfate solution of/L and the nickel nitrate solution of 1L with the concentration of 3.2gNiO/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 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 9.2 by dripping ammonia water, aging for 35 minutes after the reaction is finished, filtering and separating mother liquor, washing and drying to obtain the nickel-containing pseudo-boehmite. Weighing the prepared nickel-containing pseudo-boehmite, kneading into a plastic body, extruding into strips, forming, drying, and roasting at 600 ℃ to obtain the nickel-containing carrier. Preparing cerium nitrate and magnesium nitrate solution, impregnating the nickel-containing carrier by adopting an isometric impregnation method, drying at 120 ℃ for 4h, and roasting at 980 ℃ for 4h to obtain the cerium, magnesium and nickel-containing carrier.
(2) Preparation of the catalyst
Preparing an active component impregnation liquid from palladium nitrate and silver nitrate, adjusting the pH value of the solution to be 2.4, impregnating the prepared impregnation liquid on 100g of a carrier, removing residual liquid after 20 minutes, washing with distilled water, aging, drying, and roasting at 420 ℃ for 4 hours to obtain the catalyst C1.
Example 2
(1) Preparation of a Nickel-containing support
2L of Al with a concentration of 25g2O3The aluminum sulfate solution of/L and the nickel nitrate solution of 1L with the concentration of 10.5g NiO/L are mixed evenly and put into a container at a high position to prepare Al with the concentration of 75g2O3And putting 2L of sodium metaaluminate solution into a high-position container, connecting peristaltic pumps below the two containers to control the flow rate 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 60 ℃, controlling the flow to adjust the pH value of a reaction system to be 9.2, adjusting the pH value of slurry to be 9.4 by dripping 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. Weighing the prepared nickel-containing pseudo-boehmite, 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. Preparing a calcium nitrate solution, impregnating the nickel-containing carrier by adopting an isometric impregnation method, drying at 120 ℃ for 4h, and roasting at 1000 ℃ for 4h to obtain the calcium-containing and nickel-containing carrier.
(2) Preparation of the catalyst
Preparing palladium chloride into an active component impregnation liquid, adjusting the pH value of the solution to be 2.5, impregnating the prepared impregnation liquid on 100g of a carrier, removing residual liquid after 15 minutes, washing with distilled water, aging, drying, and roasting at 420 ℃ for 4 hours to obtain a palladium-containing catalyst; preparing active component impregnation liquid from silver nitrate, impregnating the prepared impregnation liquid on a palladium-containing catalyst, aging, drying, and roasting at 450 ℃ for 4 hours to obtain the catalyst C2.
Example 3
(1) Preparation of a Nickel-containing support
5L of Al with a concentration of 40g2O3Putting 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 4.5g 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 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 30 ℃, the pH value at the end of the reaction is 10, and the introduction of carbon dioxide is stoppedAging for 35 minutes, filtering and separating mother liquor, washing and drying to obtain the nickel-containing pseudo-boehmite. Weighing the prepared nickel-containing pseudo-boehmite, kneading into a plastic body, extruding into strips, forming, drying at 110 ℃ for 6h, and roasting at 580 ℃ for 4h to obtain the nickel-containing carrier. Preparing lanthanum nitrate solution, impregnating the nickel-containing carrier by adopting an isometric impregnation method, drying at 120 ℃ for 4h, and roasting at 1020 ℃ for 4h to obtain the lanthanum-and nickel-containing carrier.
(2) Preparation of the catalyst
Preparing active component impregnation liquid from palladium nitrate and silver nitrate, adjusting the pH value of the solution to be 2.3, impregnating the prepared impregnation liquid on 100g of nickel-containing carrier, removing residual liquid after 20 minutes, washing with distilled water, aging, drying, and roasting at 450 ℃ for 4 hours to obtain the catalyst C3.
Example 4
(1) Preparation of a Nickel-containing support
5L of Al with a concentration of 40g2O3Putting the/L sodium metaaluminate solution into a stainless steel container with a stirrer and a gas-permeable tank bottom, putting 2L nickel nitrate solution with the concentration of 7.9gNiO/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 70 v%, and the flow rate is 3Nm3H is used as the reference value. The reaction temperature is 35 ℃, 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, the mother liquor is filtered and separated, and the nickel-containing pseudo-boehmite is prepared by washing and drying. Weighing the prepared nickel-containing pseudo-boehmite, mixing with lithium carbonate, nitric acid, citric acid, sesbania powder and water, kneading into a plastic body, extruding into strips, forming, drying at 110 ℃ for 6h, and roasting at 960 ℃ for 4h to obtain the lithium-containing and nickel-containing carrier.
(2) Preparation of the catalyst
Preparing active component impregnation liquid from palladium nitrate and silver nitrate, adjusting the pH value of the solution to be 2.6, impregnating the prepared impregnation liquid on 100g of nickel-containing carrier, removing residual liquid after 25 minutes, washing with distilled water, aging, drying, and roasting at 480 ℃ for 4 hours to obtain the catalyst C4.
Example 5
(1) Preparation of a Nickel-containing support
2.5L of Al with a concentration of 80g2O3Putting 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 3Nm3H is used as the reference value. The reaction temperature is 35 ℃, the pH value at the end of the reaction is 10, and the introduction of carbon dioxide is stopped. Adding 0.5L of nickel nitrate solution with the concentration of 14.5g NiO/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, washing and drying to obtain the nickel-containing pseudo-boehmite. Weighing the prepared nickel-containing pseudo-boehmite, kneading into a plastic body, extruding into strips, forming, drying at 110 ℃ for 6h, and roasting at 650 ℃ for 4h to obtain the nickel-containing carrier. Preparing a cerium nitrate solution, impregnating the nickel-containing carrier by adopting an isometric impregnation method, drying at 120 ℃ for 5h, and roasting at 920 ℃ for 4h to obtain the cerium-and nickel-containing carrier.
(2) Preparation of the catalyst
Preparing active component impregnation liquid from palladium nitrate and silver nitrate, adjusting the pH value of the solution to be 2.7, impregnating the prepared impregnation liquid on 100g of nickel-containing carrier, removing residual liquid after 20 minutes, washing with distilled water, aging, drying, and roasting at 460 ℃ for 4 hours to obtain the catalyst C5.
Comparative example 1
(1) Preparation of the support
1L of Al with a concentration of 50g2O3Aluminum sulfate solution/L and 1.5L of Al with a concentration of 150g2O3Respectively filling/L sodium metaaluminate solution into high-position containers, controlling the flow rate by connecting peristaltic pumps below the two containers to flow into a stainless steel container which is filled with 5L bottom water and is provided with a stirrer, and can be filled with gas at the bottom of the container, 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 9.2 by dripping ammonia water, aging for 35 minutes after the reaction is finished, filtering and separating mother liquor, washing and drying to obtain the pseudoboehmite. Weighing the prepared pseudo-boehmite, kneading into a plastic body, extruding into strips, forming, drying, roasting at 600 ℃ and preparing the nickel-containing carrier. Preparing cerium nitrate and magnesium nitrate solution, impregnating the nickel-containing carrier by adopting an isovolumetric impregnation method, drying at 120 ℃ for 4h, and roasting at 970 ℃ for 4h to obtain the cerium nitrate and magnesium nitrate solutionTo cerium and magnesium containing supports.
(2) Preparation of the catalyst
Preparing an active component impregnation liquid from palladium nitrate and silver nitrate, adjusting the pH value of the solution to be 2.4, impregnating the prepared impregnation liquid on 100g of a carrier, removing residual liquid after 20 minutes, washing with distilled water, aging, drying, and roasting at 420 ℃ for 4 hours to obtain the catalyst D1.
Comparative example 2
(1) Preparation of the support
2L of Al with a concentration of 110g2O3Putting 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. And (3) stopping introducing carbon dioxide at the reaction temperature of 30 ℃ and the pH value of the reaction end point of 10, aging for 35 minutes, filtering and separating mother liquor, washing and drying to obtain the pseudo-boehmite. Weighing the prepared pseudo-boehmite, kneading into a plastic body, extruding into strips, forming, drying at 110 ℃ for 6h, and roasting at 580 ℃ for 4h to obtain the carrier. Preparing lanthanum nitrate solution, impregnating the carrier by adopting an isometric impregnation method, drying at 120 ℃ for 4h, and roasting at 1000 ℃ for 4h to obtain the lanthanum-containing carrier.
(2) Preparation of the catalyst
Preparing an active component impregnation liquid from palladium nitrate and silver nitrate, adjusting the pH value of the solution to be 2.3, impregnating the prepared impregnation liquid on 100g of a carrier, removing residual liquid after 20 minutes, washing with distilled water, aging, drying, and roasting at 450 ℃ for 4 hours to obtain the catalyst D2.
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 4.0g of sesbania powder, uniformly mixing, weighing 15g of carbon black and 17.62g of basic nickel carbonate, uniformly mixing, and adding tetrabutyl ammonium hydroxide (wherein C is the tetrabutyl ammonium hydroxide measured in a cylinder previously16H37NO content about 10 w%) 55ml, and tetrabutylammonium hydroxide solution was brought into full contact with the mixture by stirring with a glass rod, left for 20 minutes and added theretoMixing the aluminum hydroxide dry glue powder mixed with the sesbania powder uniformly 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 paste plastic, extruding into clover-shaped strips on a strip extruder, drying at 120 ℃, and roasting to obtain the nickel-containing aluminum oxide. Preparing magnesium nitrate aqueous solution, impregnating the nickel-containing carrier by adopting an isometric impregnation method, drying the nickel-containing carrier at 110 ℃ for 6h, and roasting the nickel-containing carrier at 1000 ℃ for 4h to obtain the nickel-containing carrier.
Preparing active component impregnation liquid from palladium nitrate and silver nitrate, adjusting the pH value of the solution to be 2.7, impregnating the prepared impregnation liquid on 100g of nickel-containing carrier, removing residual liquid after 20 minutes, washing with distilled water, aging, drying, and roasting at 460 ℃ for 4 hours to obtain the catalyst D3.
Example 6
(1) Preparation of a Nickel-containing support
4L of Al with a concentration of 50g2O3Mixing aluminum nitrate solution/L and nickel nitrate solution 1L with the concentration of 2gNiO/L uniformly, putting the mixture into a container at a high position, preparing 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 connecting a peristaltic pump, flowing into a stainless steel container which is provided with a stirrer and is provided with 2L of bottom water, introducing gas into the bottom of the container, controlling the reaction temperature to be 45 ℃, controlling the flow to adjust the pH value of a reaction system to be 7.8, adding ammonia water to adjust the pH value of slurry to be 8.2 after the reaction is finished, aging for 35 minutes, filtering and separating mother liquor, washing, and drying to obtain the nickel-containing pseudo-boehmite. Weighing the prepared nickel-containing pseudo-boehmite, kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 1060 ℃ for 4h to obtain the nickel-containing carrier.
(2) Preparation of the catalyst
Preparing palladium chloride into an active component impregnation liquid, adjusting the pH value of the solution to be 2.2, impregnating the prepared impregnation liquid on 100g of a carrier, removing residual liquid after 35 minutes, washing with distilled water, aging, drying, and roasting at 430 ℃ for 4 hours to obtain a palladium-containing catalyst; preparing active component impregnation liquid from silver nitrate, impregnating the prepared impregnation liquid on a palladium-containing catalyst, aging, drying, and roasting at 450 ℃ for 4 hours to obtain the catalyst C6.
Comparative example 4
(1) Preparation of the support
4L of Al with a concentration of 50g is prepared2O3Respectively filling aluminum nitrate solution and ammonia water solution with the concentration of 8 wt% into a high-position container, connecting peristaltic pumps below the two containers for controlling the flow rate to flow into a stainless steel container which is filled with 2L of bottom water and is provided with a stirrer, introducing gas into the bottom of the container, controlling the reaction temperature to be 45 ℃, controlling the flow to adjust the pH value of a reaction system to be 7.8, adding ammonia water to adjust the pH value of slurry to be 8.25 after the reaction is finished, aging for 35 minutes, filtering and separating mother liquor, washing and drying to obtain the pseudo-boehmite. Weighing the prepared pseudo-boehmite, kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 1030 ℃ for 4h to obtain the carrier.
(2) Preparation of the catalyst
Preparing palladium chloride into an active component impregnation liquid, adjusting the pH value of the solution to be 2.2, impregnating the prepared impregnation liquid on 100g of a carrier, removing residual liquid after 35 minutes, washing with distilled water, aging, drying, and roasting at 430 ℃ for 4 hours to obtain a palladium-containing catalyst; preparing active component impregnation liquid from silver nitrate, impregnating the prepared impregnation liquid on a palladium-containing catalyst, aging, drying, and roasting at 450 ℃ for 4 hours to obtain the catalyst D4.
The physical properties and compositions of the catalysts C1-C6 in examples 1-6 and the catalysts D1-D4 in comparative examples 1-4 are shown in Table 1.
TABLE 1 physical Properties and compositions of catalysts of examples and comparative examples
Figure BDA0001294793710000141
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-C6 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 evaluation of the catalyst was carried out on a 100ml adiabatic bed hydrogenation reactor, the catalyst first being still under hydrogen at 90 ℃The reaction solution is cooled to 45 ℃ after 8 hours. Evaluating process conditions: reaction pressure: 2.8MPa, inlet temperature: 45 ℃, space velocity of fresh raw oil: 3.5h-1Hydrogen to oil volume ratio: 200: 1 (volume ratio based on fresh oil).
TABLE 2 Hydrofeed oil Properties
Figure BDA0001294793710000151
Table 3 catalyst evaluation average data
Figure BDA0001294793710000152
It can be seen from the above examples and comparative examples that the hydrogenation catalyst of nickel-molybdenum 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 activity and selectivity.
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 (22)

1. A selective hydrogenation catalyst characterized by: the catalyst contains active components of palladium and silver, nickel-containing alumina is used as a carrier, the total weight of the catalyst is 100%, the content of palladium is 0.05-0.8 wt% of a simple substance, the content of silver oxide is 0.05-5 wt%, and the content of nickel is 0.1-10 wt% of the simple substance; the specific surface area of the catalyst is 20-150 m2The pore volume is 0.12-0.6 ml/g; 0.1-10 wt% of alkali metal and/or alkaline earth metal oxide; 0-5 wt% of cerium oxide and/or lanthanum oxide; the precursor of the nickel-containing alumina carrier is nickel-containing pseudo-boehmite; dipping a nickel-containing alumina carrier in a palladium-silver solution containing an active component, drying and roasting to prepare a 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 (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.
2. The selective hydrogenation catalyst of claim 1, wherein: 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%.
3. The selective hydrogenation catalyst of claim 1, wherein: the nickel-containing alumina carrier is prepared from nickel-containing pseudo-boehmite by at least forming, drying and roasting processes, 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.
4. The selective hydrogenation catalyst of claim 1, wherein: Delta-Al in nickel-containing alumina carrier2O3、δ-NiAl26O40And NiAl2O4Accounting for 30-100 wt% of the total weight of the nickel-containing alumina carrier.
5. The selective hydrogenation catalyst of claim 1, wherein: the nickel-containing alumina carrier contains theta-Al2O3、α-Al2O3And/or gamma-Al2O3。
6. The selective hydrogenation catalyst of claim 3, wherein: the roasting conditions of the nickel-containing alumina carrier are as follows: roasting at 800-1200 ℃ for 4-10 h.
7. The selective hydrogenation catalyst of claim 1, wherein: the roasting temperature of the catalyst is 300-550 ℃, and the roasting time is 3-8 h.
8. The selective hydrogenation catalyst according to claim 1, wherein the palladium content is 0.15-0.5 wt% by simple substance, the silver oxide is 0.2-3 wt%, and the nickel content is 0.5-5 wt% by simple substance, based on 100% by total weight of the catalyst; the specific surface area of the catalyst is 60-120 m2The pore volume is 0.3-0.5 ml/g; 0.5-3 wt% of an alkali metal and/or alkaline earth metal oxide; 0.5-1.2 wt% of cerium oxide and/or lanthanum oxide.
9. The selective hydrogenation catalyst of claim 2, wherein the nickel content is 0.5 wt% to 5 wt% based on 100 wt% of the total weight of the nickel-containing pseudoboehmite.
10. The selective hydrogenation catalyst of claim 5, wherein the nickel-containing alumina support contains α -Al2O3The content is less than 30 wt%.
11. The selective hydrogenation catalyst according to claim 6, wherein the calcination temperature of the nickel-containing alumina support is 900 to 1100 ℃.
12. A method of preparing a selective hydrogenation catalyst as claimed in claim 1, characterized in that: dipping a nickel-containing alumina carrier by using a salt solution containing active components of palladium and silver, wherein the palladium and the silver are dipped step by step or simultaneously, and then washed, dried and roasted to obtain a catalyst; the nickel-containing alumina carrier is obtained by at least forming, drying 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 (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.
13. The method for preparing a selective hydrogenation catalyst according to claim 12, characterized in that: and (2) introducing air into the kettle bottom of the neutralization kettle in the step (1).
14. The method for preparing a selective hydrogenation catalyst according to claim 12, characterized in that: and (4) the pH value of the alkali metal aluminate solution in the step (3) is 9-14.
15. The method for preparing a selective hydrogenation catalyst according to claim 12, 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.
16. The method for preparing a selective hydrogenation catalyst according to claim 12, 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.
17. The method for preparing a selective hydrogenation catalyst according to claim 12, characterized in that: in the step (6), the aging temperature is 50-80 ℃, and the aging time is 10-60 min.
18. The method for preparing a selective hydrogenation catalyst according to claim 12, characterized in that: the rare earth elements cerium and/or lanthanum and alkali metal and/or alkaline earth metal are added in the carrier forming process; or after the carrier is formed, the active components are firstly added into the carrier before being impregnated; or when the active component is impregnated, the active component and the active component impregnation solution are added simultaneously.
19. The method for preparing a selective hydrogenation catalyst according to claim 12, wherein the temperature of the aqueous acidic solution containing aluminum salt and nickel salt is adjusted to 50 to 70 ℃, and the concentration of the aqueous acidic aluminum salt solution is adjusted to 10 to 80g of Al2O3The concentration of the acidic nickel salt aqueous solution is 3-50 g NiO/L; the concentration of the alkali metal aluminate solution is 50-300 g Al2O3L; and (3) controlling the gelling temperature of the step (4) to be 50-70 ℃, and controlling the gelling pH value to be 7.5-9.5.
20. The method for preparing a selective hydrogenation catalyst according to claim 14, wherein the pH of the alkali metal aluminate solution in the step (3) is 12 to 14.
21. The method of claim 15, wherein the aqueous acidic aluminum salt solution is an aluminum sulfate solution; the aqueous acidic nickel salt solution is a nickel nitrate solution.
22. The method according to claim 16, wherein the acidic aqueous solution containing an aluminum salt and a nickel salt has a pH of 2 to 4.
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