CN108262047B - Nickel-molybdenum series hydrogenation catalyst and preparation method thereof - Google Patents

Nickel-molybdenum series hydrogenation catalyst and preparation method thereof Download PDF

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CN108262047B
CN108262047B CN201611263029.4A CN201611263029A CN108262047B CN 108262047 B CN108262047 B CN 108262047B CN 201611263029 A CN201611263029 A CN 201611263029A CN 108262047 B CN108262047 B CN 108262047B
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nickel
molybdenum
hydrogenation catalyst
aqueous solution
acidic
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CN108262047A (en
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胡晓丽
孙利民
马好文
郑云弟
王斌
展学成
钱颖
梁顺琴
李凤生
王博
常晓昕
潘曦竹
李平智
谢培思
蔡小霞
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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
    • B01J23/76—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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/883—Molybdenum and nickel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/18—Crystalline alumino-silicate carriers the catalyst containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a nickel-molybdenum series catalyst and a preparation method thereof, in particular to a preparation method of a nickel-molybdenum series hydrogenation catalyst taking nickel-containing alumina as a carrier. The nickel-containing alumina carrier is a precursor of 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-molybdenum hydrogenation catalyst has high hydrogenation activity and selectivity, and good chemical stability and thermal stability.

Description

Nickel-molybdenum series hydrogenation catalyst and preparation method thereof
Technical Field
The invention relates to a nickel-molybdenum series catalyst and a preparation method thereof, in particular to a preparation method of a nickel-molybdenum series hydrogenation catalyst taking nickel-containing alumina as a carrier.
Background
Many countries have ethylene production as a marker for the development level of petroleum chemical industry in that country. With the rapid development of economy in China, the ethylene yield increases year by 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 is catalysts for noble metals, using narrow cuts of the starting material. 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.
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.
CN200710179630.X discloses a molybdenum-nickel hydrogenation catalyst and a preparation method thereof, provides a molybdenum-nickel hydrogenation catalyst, and further provides a method for preparing a molybdenum-nickel hydrogenation catalyst with high active component loading and high reaction activity. The catalyst comprises MoO by weight320～40％，NiO 2.5～12％，TiO21-6％，P2O51.5-4.5%, and the balance of gamma-Al2O3. Ti, Mo and P are introduced between the carrier forming to prepare the hydrogenation catalyst with high desulfurization and denitrification activity.
CN1218822A reports a Ni/Al2O3The catalyst is prepared by loading nickel on an alumina carrier containing lithium or alkaline earth metal, and is poor in bearing hydrogenation load and hydrogenation stability.
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 may be employed in the preparation of alumina carriers to improve the properties of alumina as a carrier, there is a limit to the improvement of the properties of alumina of a hydrogenation catalyst support material 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 the mixture is extruded, formed, dried and roasted to obtain a nickel-containing alumina carrier2.0-14.0% of alumina carrier, 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 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 strength of the catalyst prepared by the method is poor.
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 ℃, 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 Phys Chem 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 key point of improving the comprehensive performance of the hydrogenation catalyst is to develop a novel carrier material suitable for the hydrogenation catalyst in the following three aspects of (1); (2) improving the content of active components of the hydrogenation catalyst; (3) and the utilization rate of the active component is improved by adding the auxiliary agent and the active component dispersing agent.
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-molybdenum 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-molybdenum hydrogenation catalyst is characterized in that: the catalyst contains active components of nickel and molybdenum, wherein the nickel-containing alumina is used as a carrier, and the catalyst contains 10-20 wt% (preferably 14.5-18.5 wt% of nickel oxide including nickel oxide in the nickel-containing alumina carrier), 0.1-5 wt% (preferably 0.3-2 wt%) of molybdenum oxide, 0-5 wt% (preferably 0.2-2 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 wt%; the specific surface area of the catalyst is 50-150 m2A pore volume of 0.30-0.55 cm/g3(ii) a bulk density of 0.6 to 1.1g/cm3. 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 carrier in the nickel-molybdenum 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 the carrier with a specific nickel and aluminum mixed crystal form is prepared finally. 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 preparation method of the nickel-containing pseudo-boehmite, the nickel source, the nickel content, the activation roasting temperature of the nickel-containing alumina carrier and the like can be different according to different use purposes of final catalysts. The nickel-containing alumina carrier of the present invention preferably contains nickel in an amount of 0.1 to 10wt%, 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 of nickel and molybdenum are added in the form of soluble salt, 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 molybdenum is preferably added in the form of ammonium molybdate. The preparation method of the catalyst is not limited in detail, and if the catalyst can be prepared by an isometric impregnation method, the catalyst is prepared by impregnating an aqueous solution containing nickel and molybdenum soluble salts on a carrier, drying the carrier and roasting the dried carrier at 300-500 ℃ for 3-8 hours. The nickel content in the catalyst is calculated by taking the total weight of the catalyst as 100wt%, and calculated by oxides: 10 to 20wt% (preferably 14.5 to 18.5 wt%) of nickel oxide, and 0.1 to 5wt% (preferably 0.3 to 2 wt%) of molybdenum 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 5wt%, preferably 0.2 to 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 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 6wt%, 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-molybdenum series 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 molybdenum, and then 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 60-80 ℃; the temperature in the step (2) is preferably 60-80 ℃, 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.
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 better less than 10wt% of the total mass of the nickel-containing pseudo-boehmite.
The roasting method and conditions are the common method and conditions for roasting the catalyst carrier, and can be carried out by adopting a vertical furnace, a converter and a mesh belt kiln, and the roasting conditions of the carrier are preferably as follows: roasting for 4-10 h at 800-1200 ℃, wherein the roasting temperature is preferably 850-1100 ℃.
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-molybdenum hydrogenation catalyst has high hydrogenation activity and selectivity, and good chemical stability and thermal stability.
Detailed Description
The content of active metal in the nickel-molybdenum 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-;
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
1L of Al with a concentration of 45g2O3The aluminum sulfate solution/L and the nickel nitrate solution 1L with the concentration of 8g NiO/L are mixed evenly and put into a container at a high position to prepare Al with the concentration of 145g2O3Putting 1L 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 a stirrer and is provided with 5L of bottom water, and the bottom of the stainless steel container can be filled with gas, controlling the pH value of a flow regulation reaction system (including gelling) to be 9.2 at the reaction and gelling temperature of 55 ℃, regulating the pH value of slurry to be 9.5 by dripping ammonia water after the reaction is finished, aging for 30min at the aging temperature of 55 ℃, filtering and separating mother liquor, washing, and drying at 120 ℃ for 2h 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. Preparing lanthanum nitrate, lithium carbonate and citric acid aqueous solution, dipping the solution on a nickel-containing carrier by adopting an equal-volume dipping method, drying the solution at 120 ℃ for 4h, and roasting the solution at 1000 ℃ for 4h to obtain the carrier containing nickel, lanthanum and lithium.
(3) Catalyst and process for preparing same
And (3) dissolving nickel nitrate and ammonium molybdate in water to prepare a steeping liquor, steeping the steeping liquor on 100g of the carrier prepared in the step (2) by an isometric steeping method, drying the carrier at 120 ℃, and roasting the carrier for 4 hours at 380 ℃ to obtain the catalyst C1.
Example 2
(1) Nickel-containing pseudo-boehmite
1L of 50gAl2O3The aluminum sulfate solution of/L and the nickel nitrate solution of 0.5L with the concentration of 3g NiO/L are mixed evenly and put into a container at a high position to prepare Al with the concentration of 150g2O3And (4) putting 1L of sodium metaaluminate solution into a high-position container, controlling the flow rate of the sodium metaaluminate solution by connecting peristaltic pumps below the two containers to flow into a stainless steel container which is provided with a stirrer and is provided with 5L of bottom water, introducing gas into the bottom of the container, controlling the pH value of a flow regulation reaction system (including gelling) to be 9.0 at the reaction and gelling temperature of 60 ℃, regulating the pH value of slurry to be 9.6 by dripping ammonia water after the reaction is finished, aging for 25min at the aging temperature of 55 ℃, 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, citric acid, sesbania powder and water, kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 950 ℃ for 4h to obtain the nickel-containing carrier.
(3) Catalyst and process for preparing same
And (3) dissolving nickel acetate and ammonium molybdate in water to prepare a steeping liquid, steeping the steeping liquid on 100g of the carrier prepared in the step (2) by an isometric steeping method, drying the carrier at 120 ℃, and roasting the carrier for 4 hours at 380 ℃ to obtain the catalyst C2.
Example 3
(1) Nickel-containing pseudo-boehmite
1L of Al with a concentration of 45g2O3The aluminum sulfate solution of/L and the nickel nitrate solution of 1L with the concentration of 25g NiO/L are mixed evenly and filledPut into a high-level container to prepare Al with the concentration of 150g2O3Putting 1L 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 a stirrer and is provided with 5L of bottom water, introducing gas into the bottom of the container, controlling the pH value of a flow regulation reaction system (including gelling) to be 9.5 at the reaction and gelling temperature of 65 ℃, regulating the pH value of slurry to be 9.5 by dripping ammonia water after the reaction is finished, aging for 20min at the aging temperature of 60 ℃, 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 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 650 ℃ for 4h to obtain the nickel-containing carrier. Preparing lanthanum nitrate, lithium carbonate and citric acid aqueous solution, dipping the solution on a nickel-containing carrier by adopting an equal-volume dipping method, drying the solution at 120 ℃ for 4h, and roasting the solution at 900 ℃ for 4h to obtain the carrier containing nickel, magnesium, lanthanum and lithium.
(3) Catalyst and process for preparing same
And (3) dissolving nickel acetate and ammonium molybdate in water to prepare a steeping liquid, steeping the steeping liquid on 100g of the carrier prepared in the step (2) by an isometric steeping method, drying the carrier at 120 ℃, and roasting the carrier for 4 hours at 350 ℃ to obtain the catalyst C3.
Example 4
(1) Nickel-containing pseudo-boehmite
1L of Al with a concentration of 185g2O3Mixing the sodium metaaluminate solution and nickel nitrate solution with concentration of 15g NiO/L, placing the mixture in a stainless steel container with stirrer and gas-permeable bottom, introducing mixed gas of carbon dioxide and air, wherein the concentration of carbon dioxide in the mixed gas is 70 v%, and the flow rate is 3Nm3H is used as the reference value. Reacting at 35 deg.C, controlling flow rate to adjust pH value of reaction system (including gelatinizing) to 9.5, stopping introducing carbon dioxide, aging at 45 deg.C for 45min, filtering to separate mother liquor, and washing. 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. Preparing lithium carbonate and citric acid aqueous solution, dipping the lithium carbonate and citric acid aqueous solution on a nickel-containing carrier by adopting an equal-volume dipping method, drying the nickel-containing carrier for 4 hours at 120 ℃, and roasting the nickel-containing carrier for 4 hours at 1020 ℃ to obtain the nickel-and lithium-containing carrier.
(3) Catalyst and process for preparing same
And (3) dissolving nickel nitrate and ammonium molybdate in water to prepare a steeping liquor, steeping the steeping liquor on 100g of the carrier prepared in the step (2) by an isometric steeping method, drying the carrier at 120 ℃, and roasting the carrier for 4 hours at 400 ℃ to obtain the catalyst C4.
Example 5
(1) Nickel-containing pseudo-boehmite
1L of 190gAl2O3Mixing the sodium metaaluminate solution and nickel nitrate solution with concentration of 8gNiO/L in the amount of 1L, placing the mixture in a stainless steel container with stirrer and bottom capable of being filled with gas, and filling mixed gas of carbon dioxide and air, wherein the concentration of carbon dioxide in the mixed gas is 60 v%, and the flow rate is 5Nm3H is used as the reference value. Reacting at 40 deg.C, controlling flow rate to adjust pH value of reaction system (including gelatinizing) to 10.0, stopping introducing carbon dioxide, aging for 35min at 40 deg.C, filtering to separate mother liquor, and washing. Drying at 110 ℃ for 3h to obtain 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 970 ℃ for 4h to obtain the nickel-containing carrier.
(3) Catalyst and process for preparing same
And (3) dissolving nickel acetate, ammonium molybdate and lanthanum nitrate into water to prepare impregnation liquid, impregnating the impregnation liquid onto 100g of the carrier prepared in the step (2), drying the impregnation liquid at 120 ℃, and roasting the impregnation liquid for 3 hours at 480 ℃ to obtain the catalyst C5.
Example 6
(1) Nickel-containing pseudo-boehmite
1L of Al with a concentration of 197g2O3the/L sodium metaaluminate solution and the 1L nickel nitrate solution with the concentration of 2.5gNiO/L are evenly mixed and are placed in a non-gas tank with a stirrer and the bottom of the tank can be filled with gasIntroducing a mixed gas of carbon dioxide and air into a steel container, wherein the concentration of carbon dioxide in the mixed gas is 70 v%, and the flow rate is 4Nm3H is used as the reference value. Reacting and gelatinizing at 30 deg.C, controlling flow rate to adjust pH value of reaction system (including gelatinizing) to 9.5, stopping introducing carbon dioxide, aging for 30min at 40 deg.C, filtering to separate mother liquor, washing, drying at 100 deg.C for 2 hr, and drying at 120 deg.C for 2 hr to obtain nickel-containing pseudoboehmite.
(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 920 ℃ for 4h to obtain the carrier containing nickel, magnesium and lithium.
(3) Catalyst and process for preparing same
And (3) dissolving nickel nitrate and ammonium molybdate in water to prepare a steeping liquor, steeping the steeping liquor on 100g of the carrier prepared in the step (2) by an isometric steeping method, drying the carrier at 120 ℃, and roasting the carrier for 4 hours at 380 ℃ to obtain the catalyst C6.
Example 7
(1) Nickel-containing pseudo-boehmite
1L of Al with a concentration of 195g2O3The method comprises the following steps of uniformly mixing an aluminum nitrate solution/L and a nickel nitrate solution 0.5L with the concentration of 7gNiO/L, putting the mixture into a container at a high position, putting 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 to flow into a stainless steel container which is provided with a stirrer and is provided with 5L of bottom water and can be filled with gas at the bottom of the container, controlling the reaction and gelling temperature to be 50 ℃, controlling the pH value of a flow regulation reaction system (including gelling) to be 7.5, adding ammonia water to regulate the pH value of slurry to be 8.5 after the reaction is finished, aging for 60min, filtering and separating mother liquor at the aging temperature. 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, sesbania powder and water, kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 350 ℃ for 4h to obtain the nickel-containing carrier. Preparing lanthanum nitrate, lithium carbonate and citric acid aqueous solution, dipping the solution on a nickel-containing carrier 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 ammonium molybdate in water to prepare a steeping liquor, steeping the steeping liquor on 100g of the carrier prepared in the step (2) by an isometric steeping method, drying the carrier at 120 ℃, and roasting the carrier for 4 hours at 380 ℃ to obtain the catalyst C7.
Example 8
(1) Nickel-containing pseudo-boehmite
2L of Al with a concentration of 100gAl2O3Putting 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 and gelling temperature is 35 ℃, the flow is controlled to adjust the pH value of the reaction system (including gelling) to 10.0, 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 30min, adjusting the pH value of the slurry to 9.5 by dropwise adding ammonia water, aging for 30min after the reaction is finished, wherein the aging temperature is 40 ℃, 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 990 ℃ for 4h to obtain the nickel-containing carrier.
(3) Catalyst and process for preparing same
Dissolving nickel nitrate and ammonium molybdate 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 steeping liquid at 120 ℃, roasting the steeping liquid at 350 ℃ for 4h, steeping 35% of the total amount of the nickel nitrate and the ammonium molybdate by adopting the isometric steeping method in two steps, drying the steeping liquid at 120 ℃, and roasting the steeping liquid at 380 ℃ for 4h to obtain the catalyst C8.
Example 9
(1) Nickel-containing pseudo-boehmite
2L of 92gAl2O3L placing sodium metaaluminate solutionIntroducing a mixed gas of carbon dioxide and air into a stainless steel container with a stirrer and a gas-introducing tank bottom, wherein the concentration of carbon dioxide in the mixed gas is 60 v%, and the flow rate is 3Nm3H is used as the reference value. The reaction and gelling temperature is 35 ℃, the flow is controlled to adjust the pH value of the reaction system (including gelling) to 10.0, and the introduction of carbon dioxide is stopped. Adding 1L of nickel nitrate solution with the concentration of 7gNiO/L under the condition of air stirring, stabilizing for 20min, adjusting the pH value of the slurry to 9.5 by dropwise adding ammonia water, aging for 40min after the reaction is finished at the aging temperature of 45 ℃, 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 ammonium molybdate in water to prepare a steeping liquor, steeping the steeping liquor on 100g of the carrier prepared in the step (2) by an isometric steeping method, drying the carrier at 120 ℃, and roasting the carrier for 4 hours at 400 ℃ to obtain the catalyst C9.
Comparative example 1
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 10.0g of sesbania powder, uniformly mixing, weighing 40g of carbon black and 18.5g 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%) 76ml, stirring with a glass rod to make tetrabutyl ammonium hydroxide solution fully contact with the mixture, standing for 20min, adding into aluminum hydroxide dry glue powder mixed with sesbania powder, and mixing 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 pasty plastic, extruding into clover-shaped strips on a strip extruder, drying at 120 ℃ for 3.5h, and roasting at 950 ℃ for 4h to obtain the nickel-containing alumina carrier.
Dissolving nickel nitrate, ammonium molybdate and lithium carbonate in water together to prepare a steeping liquor, steeping the steeping liquor on 100g of the prepared nickel-containing carrier, drying the steeping liquor at 120 ℃, and roasting the steeping liquor for 4 hours at 420 ℃ to obtain the catalyst D1.
Comparative example 2
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 6.0g of sesbania powder, uniformly mixing, weighing 30g of carbon black and 8.4g 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%) 40ml, stirring with a glass rod to make tetrabutyl ammonium hydroxide solution fully contact with the mixture, standing for 30min, adding into aluminum hydroxide dry glue powder mixed with sesbania powder, and mixing 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 pasty plastic, extruding into clover-shaped strips on a strip extruder, and drying at 110 ℃ for 4 hours to obtain the nickel-containing alumina carrier. Preparing a lithium carbonate aqueous solution, dipping the lithium carbonate aqueous solution on a nickel-containing carrier by adopting an equal-volume dipping method, drying the lithium carbonate aqueous solution for 4h at 120 ℃, and roasting the lithium carbonate aqueous solution for 4h at 900 ℃ to obtain the nickel-and lanthanum-containing carrier.
Dissolving nickel nitrate and ammonium molybdate into water 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 D2.
Comparative example 3
(1) Pseudo-boehmite
1L of Al with a concentration of 50g2O3Aluminum sulfate solution/L and 1.5L of Al with a concentration of 150g2O3Respectively loading the 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 filled with 5L of bottom water, is provided with a stirrer and can be filled with gas at the bottom of the container, controlling the pH value of a flow regulation reaction system (including gelling) to be 9.0 at the reaction and gelling temperature of 50 ℃, and regulating the pH value by adding ammonia water dropwise after the reaction is finishedAging the slurry at pH 9.5 for 30min at 50 deg.C, filtering to separate mother liquor, and washing. Drying at 90 deg.C for 3h, and drying at 120 deg.C for 2h to obtain pseudo-boehmite.
(2) Carrier
Weighing the prepared pseudoboehmite, mixing with lithium carbonate, 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 950 ℃ for 4h to obtain the carrier.
(3) Catalyst and process for preparing same
And (3) dissolving nickel nitrate, ammonium molybdate and lanthanum nitrate into water together to prepare impregnation liquid, impregnating the impregnation liquid onto 100g of the carrier prepared in the step (2), drying the impregnation liquid at 120 ℃, and roasting the impregnation liquid for 3 hours at 390 ℃ to obtain the catalyst D3.
Comparative example 4
(1) Pseudo-boehmite
2L of Al with a concentration of 150g2O3Putting 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. Reacting at 35 deg.C, controlling flow rate to adjust pH value of reaction system (including gelatinizing) to 10.0, stopping introducing carbon dioxide, aging at 45 deg.C for 30min, filtering to separate mother liquor, and washing. 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, forming, drying at 120 ℃ for 4h, and roasting at 1000 ℃ for 4h to obtain the carrier.
(3) Catalyst and process for preparing same
And (3) dissolving nickel nitrate, ammonium molybdate, cerium nitrate and lanthanum nitrate in 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 D4.
Comparative example 5
(1) Pseudo-boehmite
2L of 150gAl2O3Putting 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, and introducingIntroducing a mixed gas of carbon dioxide and air, wherein the concentration of carbon dioxide in the mixed gas is 70 v%, and the flow rate is 3Nm3H is used as the reference value. Reacting at 35 deg.C, controlling flow rate to adjust pH value of reaction system (including gelatinizing) to 9.5, stopping introducing carbon dioxide, aging at 45 deg.C for 20min, filtering to separate mother liquor, and washing. Drying at 90 deg.C for 3h, and drying at 120 deg.C for 2h to obtain pseudo-boehmite.
(2) Carrier
Weighing the prepared pseudoboehmite, 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 carrier. Preparing magnesium nitrate and lithium carbonate aqueous solution, impregnating the carrier by adopting an equal-volume impregnation method, drying the carrier at 120 ℃ for 4 hours, and roasting the carrier at 980 ℃ for 4 hours to obtain the carrier containing magnesium and lithium.
(3) Catalyst and process for preparing same
And (3) dissolving nickel acetate and ammonium molybdate in 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 400 ℃ for 3h to obtain the catalyst D5.
Comparative example 6
(1) Pseudo-boehmite
2L of 100gAl is prepared2O3Respectively filling an aluminum nitrate solution and an ammonia water solution with the concentration of 8 wt% into a high-position container, controlling the flow rate of the aluminum nitrate solution and the ammonia water solution under the two containers by a peristaltic pump, flowing into a stainless steel container which is filled with 3L of bottom water and is provided with a stirrer, introducing gas into the bottom of the container, controlling the reaction and gelling temperature to be 45 ℃, controlling the pH value of a flow regulation reaction system (including gelling) to be 8.0, after the reaction is finished, adding ammonia water to regulate the pH value of slurry to be 8.5, aging for 30min, controlling the aging temperature to be 50 ℃, filtering and separating mother liquor, and washing. Drying at 120 deg.C for 2h to obtain pseudo-boehmite.
(2) Carrier
Weighing the prepared pseudoboehmite, mixing with nitric acid, citric acid, sesbania powder and water, kneading into a plastic body, extruding into strips, forming, drying at 120 ℃, and roasting at 880 ℃ for 4 hours to obtain the carrier.
(3) Catalyst and process for preparing same
Dissolving nickel nitrate and ammonium molybdate in water to prepare a steeping liquor, steeping the steeping liquor on 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 dipped nickel nitrate at 120 ℃, roasting the dipped nickel nitrate at 350 ℃ for 4h, steeping 35% of the total amount of the nickel nitrate and the ammonium molybdate by adopting the isometric steeping method in two steps, drying the dipped nickel nitrate and the ammonium molybdate at 120 ℃, and roasting the dipped nickel molybdate at 420 ℃ for 4h to obtain the catalyst.
The physical properties and compositions of the catalysts C1-C9 in examples 1-9 and the catalysts D1-D6 in comparative examples 1-6 are shown in Table 1.
TABLE 1 physical Properties and compositions of catalysts of examples and comparative examples
Figure BDA0001200146510000151
Figure BDA0001200146510000161
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-D6 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 70 ℃, and raw oil is passivated for 4 hours by cyclohexane containing 1000ppm of dimethyl disulfide. Evaluating process conditions: the reaction pressure is 2.8MPa, the inlet temperature is 50 ℃, and the airspeed of fresh raw oil is 3.0h-1The volume ratio of hydrogen to oil was 200: 1 (volume ratio based on fresh oil).
TABLE 2 Hydrofeed oil Properties
Figure BDA0001200146510000162
Table 3 catalyst evaluation average data
Catalyst numbering C1 C2 C3 C4 C5 C6 C7 C8
Hydrogenated product diene/(gI/100 g) 1.71 2.01 1.64 1.42 1.54 1.65 2.14 1.12
Hydrogenated product bromine number gBr/100g 21.7 22.6 20.7 24.5 25.8 24.1 22.5 26.2
Catalyst numbering C9 D1 D2 D3 D4 D5 D6
Hydrogenated product diene/(gI/100 g) 2.54 2.65 2.38 2.84 2.98 2.11 1.87
Hydrogenated product bromine number gBr/100g 19.8 25.5 28.4 23.4 23.5 25.6 27.0
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 stability.
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 (28)

1. A nickel-molybdenum series hydrogenation catalyst contains active components of nickel and molybdenum, and takes alumina containing nickel as a carrier, and is characterized in that: the catalyst comprises, by weight, 100wt% of nickel oxide, 0.1-5 wt% of molybdenum 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 50-150 m2A pore volume of 0.30-0.55 cm/g3(ii) a bulk density of 0.6 to 1.1g/cm3(ii) a 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; dipping the nickel-containing alumina carrier in the solution containing the active components, drying and roasting to prepare the nickel-molybdenum hydrogenation catalyst;
wherein the nickel-containing pseudo-boehmite is obtained by the following method, comprising the following steps of:
(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-molybdenum-based hydrogenation catalyst according to claim 1, characterized in that: the catalyst comprises 14.5-18.5 wt% of nickel oxide, 0.3-2 wt% of molybdenum oxide, 0.2-2 wt% of cerium oxide and/or lanthanum oxide, and 0.5-3 wt% of alkali metal and/or alkaline earth metal oxide, wherein the weight of the catalyst is 100 wt%.
3. The nickel-molybdenum-based hydrogenation catalyst according to claim 1, characterized in that: in the step (2), the concentration of the acidic aluminum salt aqueous solution is 10-80 gAl2O3and/L, wherein the concentration of the acidic nickel salt aqueous solution is 3-50 gNiO/L.
4. The nickel-molybdenum-based hydrogenation catalyst according to claim 1, characterized in that: in the step (3), the concentration of the alkali metal aluminate solution is 50-300 gAl2O3/L。
5. The nickel-molybdenum-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%.
6. The nickel-molybdenum-based hydrogenation catalyst according to claim 5, characterized in that: the nickel content in the nickel-containing pseudo-boehmite is 0.5-5 wt%.
7. The nickel-molybdenum-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.
8. The nickel-molybdenum-based hydrogenation catalyst according to claim 7, characterized in that: the nickel content of the nickel-containing alumina carrier is 0.5-5 wt%.
9. The nickel-molybdenum-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.
10. The nickel-molybdenum-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.
11. The nickel-molybdenum-based hydrogenation catalyst according to claim 1, characterized in that: the nickel-containing alumina carrier also contains theta-Al2O3、α- Al2O3And/or gamma-Al2O3。
12. The nickel-molybdenum-based hydrogenation catalyst according to claim 11, wherein: when the nickel-containing alumina carrier contains alpha-Al2O3When the content is less than 30 wt%.
13. The nickel-molybdenum-based hydrogenation catalyst according to claim 9, characterized in that: the roasting conditions of the nickel-containing alumina carrier are as follows: roasting at 800-1200 ℃ for 4-10 h.
14. The nickel-molybdenum-based hydrogenation catalyst according to claim 13, wherein: the roasting temperature of the nickel-containing alumina carrier is 850-1100 ℃.
15. A method for preparing the nickel-molybdenum-based hydrogenation catalyst according to claim 1, wherein: dipping a nickel-containing alumina carrier by using a solution containing nickel and molybdenum 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.
16. The method for producing a nickel-molybdenum-based hydrogenation catalyst according to claim 15, wherein: and (2) introducing air into the kettle bottom of the neutralization kettle in the step (1).
17. The method for producing a nickel-molybdenum-based hydrogenation catalyst according to claim 15, wherein: and (3) adjusting the temperature of the acidic aqueous solution to 50-70 ℃ in the step (2).
18. The method for producing a nickel-molybdenum-based hydrogenation catalyst according to claim 15, wherein: in the step (5), the gelling temperature is 50-70 ℃; the pH value of the gelling is 7.5-9.5.
19. The method for producing a nickel-molybdenum-based hydrogenation catalyst according to claim 15, wherein: the pH value of the alkali metal aluminate solution in the step (3) is 9-14.
20. The method for preparing a nickel-molybdenum-based hydrogenation catalyst according to claim 19, wherein: the pH value of the alkali metal aluminate solution in the step (3) is 12-14.
21. The method for producing a nickel-molybdenum-based hydrogenation catalyst according to claim 15, wherein: 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.
22. The method for preparing a nickel-molybdenum-based hydrogenation catalyst according to claim 21, wherein: the acidic aluminum salt aqueous solution is an aluminum sulfate solution, and the acidic nickel salt aqueous solution is a nickel nitrate solution.
23. The method for producing a nickel-molybdenum-based hydrogenation catalyst according to claim 15, 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 aluminum salt and nickel salt, wherein the pH value is 2-5.
24. The method for preparing a nickel-molybdenum-based hydrogenation catalyst according to claim 23, wherein: the pH value of the acidic aqueous solution containing the aluminum salt and the nickel salt is 2-4.
25. The method for producing a nickel-molybdenum-based hydrogenation catalyst according to claim 15, wherein: in the step (6), the aging temperature is 50-80 ℃, and the aging time is 10-60 min.
26. The method for producing a nickel-molybdenum-based hydrogenation catalyst according to claim 15, wherein: dipping a nickel-containing alumina carrier by using a solution containing nickel and molybdenum 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 ℃.
27. The method for producing a nickel-molybdenum-based hydrogenation catalyst according to claim 15, wherein: in the step (2), the concentration of the acidic aluminum salt aqueous solution is 10-80 gAl2O3and/L, wherein the concentration of the acidic nickel salt aqueous solution is 3-50 gNiO/L.
28. The method for producing a nickel-molybdenum-based hydrogenation catalyst according to claim 15, wherein: in the step (3), the concentration of the alkali metal aluminate solution is 50-300 gAl2O3/L。
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