CN106732607B - Nickel-containing pseudo-boehmite and carrier prepared from same - Google Patents

Nickel-containing pseudo-boehmite and carrier prepared from same Download PDF

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CN106732607B
CN106732607B CN201510818869.1A CN201510818869A CN106732607B CN 106732607 B CN106732607 B CN 106732607B CN 201510818869 A CN201510818869 A CN 201510818869A CN 106732607 B CN106732607 B CN 106732607B
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nickel
solution
boehmite
acidic
pseudo
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CN106732607A (en
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胡晓丽
孙利民
梁顺琴
马好文
郑云弟
王斌
钱颖
彭蓉
李平智
印会鸣
潘曦竹
南洋
姚文君
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Petrochina Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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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  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention 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 pseudo-boehmite, so that an active component nickel is effectively dispersed in the pseudo-boehmite, a nickel-containing alumina carrier with a specific crystal form is formed, and meanwhile, the nickel-containing pseudo-boehmite has a good regulation effect on the pore structure and acidity of the carrier, and the finally prepared catalyst has high 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.

Description

Nickel-containing pseudo-boehmite and carrier prepared from same
Technical Field
The invention relates to a nickel-containing pseudo-boehmite and a carrier prepared by the same, in particular to a preparation method of the nickel-containing pseudo-boehmite which is particularly suitable for a hydrogenation catalyst carrier material.
Background
Hydrated aluminas such as pseudo-boehmite, and the like are widely used as raw materials for preparing alumina carriers, and although methods such as PH swing, addition of organic pore-expanding agents, hydrothermal treatment, and the like can be employed in the preparation of alumina carriers to improve the properties of alumina as a carrier, there is a limit to improving the properties of alumina as a carrier material of hydrogenation catalysts by these methods. The nature of the hydrated alumina feedstock used to prepare the alumina support is one of the most critical factors in producing an alumina support with superior performance.
CN102029192B discloses a method for preparing siliceous alumina, which comprises preparing modified clay, roasting clay raw soil at high temperature, and reacting with mixed acid, wherein the mixed acid is a mixture of strong acid and weak acid; and then carrying out gelling reaction on an aluminum-containing acidic solution and an alkaline solution in the modified clay slurry, carrying out aging, filtering, washing, drying, roasting and other steps after gelling to obtain the silicon-containing alumina, or drying and then roasting to obtain the silicon-containing alumina dry gel.
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 specific area of the pores is 8.0-15.0 nm, the proportion of the pores larger than 6.0nm accounts for more than 85% of the total pores, the pore volume and the average pore diameter are larger, and the proportion of the macropores is more, so the catalyst is particularly suitable for being used as a carrier of a heavy oil hydrofining catalyst.
CN200710179630.X discloses a method for preparing nickel-coated alumina powder, which is characterized in that a mixed solution of nano alumina added with a dispersant is prepared into a suspension, a nickel salt solution is added under stirring,after stirring evenly, ammonia water is dropped into the mixed solution, and distilled water is added to obtain the dark blue nickel-ammonia complex ([ Ni (NH) ]3)6]2+)-Carrying out hydrothermal aging, filtering, washing and drying on the alumina mixed solution C to obtain a green intermediate coating product; and then carrying out reduction roasting to obtain black nickel-coated alumina powder.
CN1102862C discloses a nickel-containing hydrogenation catalyst, which contains: 65-80% nickel, calculated as nickel oxide, 10-25% silicon, calculated as silica, 2-10% zirconium, calculated as zirconia, 0-10% aluminium, calculated as alumina, with the proviso that the sum of the contents of silica and alumina is at least 15% by weight, based on the total weight of the catalyst, which catalyst is obtainable by adding an acidic aqueous solution of a salt of nickel, zirconium and, if desired, aluminium to an alkaline aqueous solution or suspension of silicon and, if desired, a compound of aluminium, reducing the pH of the mixture thus obtained to at least 6.5, then adjusting the pH to 7-8 by further adding an alkaline solution, separating the solid thus deposited, drying, shaping and sintering. Also disclosed are methods of making the catalyst and its use in making medicinal white oils, high purity medicinal paraffins and low boiling, low aromatic content or aromatic-free hydrocarbon mixtures. The preparation method of the catalyst is usually used for preparing the catalyst with high active component content, but the catalyst prepared by the method has poor activity.
The article "changes induced by catalysis in hydrogenation 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. "influx of support-interaction on the sulfidation behavior andhydrodesulfurization activity of Al2O3similar conclusions were also drawn for support W, CoW and NiW model catalysts, JPhys 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. Because high-temperature calcination is often required when the catalyst carrier is used for preparing the catalyst carrier, people worry about the high temperature calcination, and therefore, unlike other metals, nickel-containing pseudo-boehmite is rarely reported.
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
Aiming at the defects of the prior art, the traditional method and the prejudice are broken through the improvement of the technology, and the nickel-containing pseudo-boehmite is prepared by loading the metal nickel in a new way.
The invention provides a nickel-containing pseudo-boehmite and a carrier prepared from the same, 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 invention provides a nickel-containing pseudo-boehmite, wherein the content of nickel is 0.1-10 wt%, preferably 0.5-5 wt%, based on 100 wt% of alumina in the nickel-containing pseudo-boehmite; the specific surface area is 300-420 m2Per g, pore volume of 0.7cm3/g～1.2cm3Per gram, the aperture is 5nm to 10 nm; the nickel-containing pseudo-boehmite has the processes of acid-base neutralization and gel forming in the preparation process.
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 acid-base reaction, has a gelling process, and finally prepares a carrier with a specific nickel and aluminum mixed crystal form.
The carrier is preferably obtained by a method comprising the 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 mixed solution to be 50-90 ℃, 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 and alkali goldThe concentration of the aluminate solution is 50-300 g 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); 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. 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 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. 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.
The invention also provides a nickel-containing alumina carrier obtained by molding and roasting the nickel-containing pseudo-boehmite.
A nickel-containing alumina carrier is prepared from nickel-containing pseudo-boehmite through shaping and calcining, and 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 prepared by the invention 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 α -Al2O3Less than 30 wt%.
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 of the present invention preferably contains nickel in an amount of 0.1 wt% to 10 wt%, preferably 0.5wt% to 7.5 wt%. Specific surface area 20m2/g～230m2Per g, pore volume of 0.10cm3/g～0.65cm3The pore diameter is 7nm to 30 nm.
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 better less than 10 percent 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 at 800-1200 ℃ for 4-10 h.
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-containing pseudo-boehmite and the carrier prepared by the nickel-containing pseudo-boehmite provided by the invention have the advantages that 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 regulated, and the finally prepared catalyst has high 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.
Detailed Description
The content of nickel in the pseudo-boehmite is measured by an atomic absorption method, the infrared acidity is measured by pyridine-infrared, and the crystal form of the carrier is measured by a D8 advanced X-ray powder diffractometer (XRD) produced by Bruker Germany under the specific conditions of CuK α radiation, 40 kilovolts and 40 milliamperes, the scanning speed is 0.02 DEG/step and 0.5 second/step, B1 is the integral intensity of a peak with the 2 theta of 34.2-39.8 DEG in an XRD spectrogram, and B2 is 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 50g2O3The aluminum sulfate solution of/L and the nickel nitrate solution of 1L with the concentration of 13g NiO/L are mixed evenly and put into a container at a high position to prepare Al with the concentration of 140g2O3Putting 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 5L 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 55 ℃, controlling the pH value of a flow regulation reaction system to be 9, regulating the pH value of slurry to be 9.5 by dripping ammonia water, aging for 30 minutes after the reaction is finished, filtering and separating mother liquor, and washing. Drying at 90 deg.C for 3h, and drying at 120 deg.C for 2h to obtain nickel-containing pseudoboehmite N1.
(2) Nickel-containing alumina
Weighing the prepared nickel-containing pseudo-boehmite N1100 g, adding 5ml of nitric acid, 2ml of phosphoric acid, 7g of sesbania powder and water, mixing and kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 950 ℃ for 4h to obtain a carrier Z1.
Example 2
(1) Nickel-containing pseudo-boehmite
1L of Al with a concentration of 50g2O3The aluminum sulfate solution of/L and the nickel nitrate solution of 0.5L with the concentration of 5.2g NiO/L are mixed evenly and put into a container at a high position 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 5L 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, adjusting the pH value of slurry to be 9.5 by dripping ammonia water, aging for 20 minutes after the reaction is finished, filtering and separating mother liquor, and washing. Drying at 90 ℃ for 3h and at 120 ℃ for 2h to obtain sample N2.
(2) Nickel-containing alumina
Weighing the prepared nickel-containing pseudo-boehmite N2100 g, adding 5.5ml of nitric acid, 1.8ml of phosphoric acid, 7.5g of sesbania powder and water, mixing and kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 1000 ℃ for 4h to obtain a carrier Z2.
Example 3
(1) Nickel-containing pseudo-boehmite
1L of Al with a concentration of 30g2O3The aluminum sulfate solution/L and the nickel nitrate solution 2L with the concentration of 10g NiO/L are mixed evenly and put into a container at a high position to prepare Al with the concentration of 150g2O3Putting 1L 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 5L of bottom water and is provided with a stirrer, introducing gas into the bottom of the container, controlling the reaction temperature to be 65 ℃, controlling the pH value of a flow regulation reaction system to be 9, regulating the pH value of slurry to be 9.5 by dripping ammonia water, aging for 40 minutes after the reaction is finished, filtering and separating mother liquor, and washing. Drying at 90 ℃ for 3h and at 120 ℃ for 2h to obtain sample N3.
(2) Nickel-containing alumina
Weighing the prepared nickel-containing pseudo-boehmite N3100 g, adding 6ml of nitric acid, 1.5ml of phosphoric acid, 7.2g of sesbania powder and water, mixing and kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 850 ℃ for 4h to obtain a carrier Z3.
Comparative example 1
(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/L sodium metaaluminate solution into high-position containers, controlling the flow rate of the solution by connecting peristaltic pumps below the two containers to flow into a stainless steel container which is provided with a stirrer and is provided with 5L of bottom water, introducing gas into the bottom of the container, controlling the reaction temperature to be 55 ℃, controlling the pH value of a flow regulation reaction system to be 9, regulating the pH value of slurry to be 9.5 by dripping ammonia water, aging for 30 minutes after the reaction is finished, filtering and separating mother liquor, and washing. Drying at 90 deg.C for 3h, and drying at 120 deg.C for 2h to obtain pseudoboehmite A1.
(2) Alumina oxide
Weighing the prepared pseudoboehmite A1100 g, adding 5.5ml of nitric acid, 2.2ml of phosphoric acid, 7.5g of sesbania powder and water, mixing and kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 900 ℃ for 4h to obtain the carrier D1.
Example 4
(1) Nickel-containing pseudo-boehmite
1L of Al with a concentration of 190g2O3The sodium metaaluminate solution/L and the nickel nitrate solution 1L with the concentration of 8g NiO/L are evenly mixed and are placed in a stainless steel container which is provided with a stirrer and can be filled with gas at the bottom of the tank, the mixed gas of carbon dioxide and air is filled, the concentration of the carbon dioxide in the mixed gas is 60 v%, and the flow rate is 5Nm3H is used as the reference value. The reaction temperature is 40 ℃, the pH value is 10 at the end of the reaction, the introduction of carbon dioxide is stopped, the aging is carried out for 25 minutes, and mother liquor is filtered and separated and washed. Drying at 90 ℃ for 3h and at 120 ℃ for 2h to obtain sample N4.
(2) Nickel-containing alumina
Weighing the prepared nickel-containing pseudo-boehmite N4100 g, adding 5.8ml of nitric acid, 1.6ml of phosphoric acid, 6.8g of sesbania powder and water, mixing and kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 1050 ℃ for 4h to obtain the carrier Z4.
Example 5
(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. The reaction temperature is 35 ℃, the pH value at the end of the reaction is 9.5, the introduction of carbon dioxide is stopped, the aging is carried out for 45 minutes, and mother liquor is filtered and separated and washed. Drying at 120 ℃ for 2h to obtain a sample N5.
(2) Nickel-containing alumina
Weighing the prepared nickel-containing pseudo-boehmite N5100 g, adding 6.4ml of nitric acid, 1.5ml of phosphoric acid, 7.2g of sesbania powder and water, mixing and kneading into a plastic body, extruding into strips, forming, drying at 110 ℃ for 4h, and roasting at 950 ℃ for 4h to obtain a carrier Z5.
Comparative example 2
(1) Pseudo-boehmite
2L of Al with a concentration of 120g2O3Putting the/L sodium metaaluminate solution into a stainless steel container which is provided with a stirrer and can be filled with gas at the bottom of the tank, filling mixed gas of carbon dioxide and air, wherein the concentration of the carbon dioxide in the mixed gas is 60 v%, and the flow rate is 4Nm3H is used as the reference value. The reaction temperature is 40 ℃, the pH value is 10 at the end of the reaction, the introduction of carbon dioxide is stopped, the aging is carried out for 30 minutes, and the mother liquor is filtered and separated and washed. Drying at 90 ℃ for 3h and 120 ℃ for 2h to obtain sample A2.
(2) Alumina oxide
Weighing the prepared pseudoboehmite A2100g, adding 7.2ml of nitric acid, 1.8ml of phosphoric acid, 7.8g of sesbania powder and water, mixing and kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 920 ℃ for 4h to obtain a carrier D2.
Example 6
(1) Nickel-containing pseudo-boehmite
1L of Al with a concentration of 180g2O3The aluminum nitrate solution of/L and the nickel nitrate solution of 0.5L with the concentration of 36g NiO/L are mixed evenly and put into a container at a high position, and the ammonia water solution with the concentration of 10wt percent is prepared and put into the container at the high positionAnd the lower parts of the two containers are connected with a peristaltic pump for controlling the flow rate to flow into a stainless steel container which is filled with 3L bottom water, is provided with a stirrer and can be filled with gas at the bottom of the tank, the reaction temperature is 45 ℃, the PH value of a flow regulation reaction system is controlled to be 8, after the reaction is finished, ammonia water is added to regulate the PH value of the slurry to be 8.5, the aging is carried out for 30 minutes, and mother liquor is filtered and separated and washed. Drying at 90 ℃ for 3h and at 120 ℃ for 2h to obtain sample N6.
(2) Nickel-containing alumina
Weighing the prepared nickel-containing pseudo-boehmite N6100 g, adding 5.5ml nitric acid, 2.2ml phosphoric acid, 7.5g sesbania powder and water, mixing and kneading into plastic body, extruding and molding, then drying for 4h at 120 ℃, and roasting for 4h at 890 ℃ to obtain the carrier Z6.
Example 7
(1) Nickel-containing pseudo-boehmite
1L of Al with a concentration of 195g2O3The preparation method comprises the following steps of uniformly mixing an aluminum nitrate solution and a nickel nitrate solution, wherein the aluminum nitrate solution and the nickel nitrate solution are mixed, the mixture is placed in a container at a high position, an ammonia water solution with the concentration of 8 wt% is prepared and placed in the container at the high position, a peristaltic pump is connected below the two containers, the ammonia water solution is controlled to flow into a stainless steel container which is provided with a stirrer and 5L of bottom water, gas can be introduced into the bottom of the stainless steel container, the reaction temperature is 50 ℃, the PH value of a flow regulation reaction system is controlled to be 7.5, after the reaction is finished, ammonia water is added to regulate the PH value of slurry to be 8.5, aging is carried out for 60 minutes, mother. Drying at 90 ℃ for 3h and at 120 ℃ for 2h to obtain sample N7.
(2) Nickel-containing alumina
Weighing the prepared nickel-containing pseudo-boehmite N7100 g, adding 6.4ml of nitric acid, 1.8ml of phosphoric acid, 7.2g of sesbania powder and water, mixing and kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 940 ℃ for 4h to obtain the carrier Z7.
Comparative example 3
(1) Pseudo-boehmite
2L of Al with a concentration of 100g2O3Respectively placing aluminum nitrate solution and ammonia water solution with concentration of 8 wt% into high-position containers, controlling flow rate by connecting peristaltic pump under the two containers, flowing into stainless steel container with 3L bottom water, stirrer, and gas at 45 deg.CControlling the flow to adjust the pH value of the reaction system to be 7.5, adding ammonia water to adjust the pH value of the slurry to be 8.5 after the reaction is finished, aging for 30 minutes, filtering and separating mother liquor, and washing. Drying at 90 ℃ for 3h and 120 ℃ for 2h to obtain sample A3.
(2) Alumina oxide
Weighing the prepared pseudoboehmite A3100 g, adding 6.2ml nitric acid, 2.2ml phosphoric acid, 7.8g sesbania powder and water, mixing and kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 880 ℃ for 4h to obtain the carrier D3.
Example 8
(1) Nickel-containing pseudo-boehmite
2L of Al with a concentration of 100g2O3Putting 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 is 10 at the end of the reaction, and the introduction of carbon dioxide is stopped. And (3) adding 0.5L of nickel nitrate solution with the concentration of 24g NiO/L under the condition of air stirring, stabilizing for 20 minutes, then dropwise adding ammonia water to adjust the pH value of the slurry to 9.5, aging for 40 minutes after the reaction is finished, filtering and separating mother liquor, and washing. Drying at 90 ℃ for 3h and at 120 ℃ for 2h to obtain sample N8.
(2) Nickel-containing alumina
Weighing the prepared nickel-containing pseudo-boehmite N8100 g, adding 7ml of nitric acid, 1.5ml of phosphoric acid, 8g of sesbania powder and water, mixing and kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 950 ℃ for 4h to obtain a carrier Z8.
Example 9
(1) Nickel-containing pseudo-boehmite
2L of Al with a concentration of 92g2O3Putting 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 filling mixed gas of carbon dioxide and air, wherein the concentration of the carbon dioxide in the mixed gas is 80 v%, and the flow rate is 2Nm3H is used as the reference value. The reaction temperature was 30 ℃ and the pH at the end of the reaction was 10.5, and the introduction of carbon dioxide was stopped. Adding 1L of nickel nitrate solution with the concentration of 7g NiO/L under the condition of air stirring, stabilizing for 30 minutes, and then drippingAnd adding ammonia water to adjust the pH value of the slurry to 9.5, aging for 30 minutes after the reaction is finished, filtering and separating mother liquor, and washing. Drying at 90 ℃ for 3h and at 120 ℃ for 2h to obtain sample N8.
(2) Nickel-containing alumina
Weighing the prepared nickel-containing pseudo-boehmite N8100 g, adding 6ml of nitric acid, 2.8ml of phosphoric acid, 8g of sesbania powder and water, mixing and kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 980 ℃ for 4h to obtain a carrier Z8.
Comparative example 4
This comparative example a nickel-containing support was prepared according to the method described in the example in CN1123392C, with the following specific steps:
100g of aluminum hydroxide dry glue powder A5 and 5.0g of sesbania powder are weighed and mixed uniformly, 20g of carbon black and 9.3g of basic nickel carbonate are weighed and mixed uniformly, and tetrabutylammonium hydroxide (wherein C is tetrabutyl ammonium hydroxide measured in a cylinder previously16H37NO content of about 10 w%) 38ml, stirring with a glass rod to make the tetrabutylammonium hydroxide solution fully contact with the mixture, standing for 15 minutes, adding the tetrabutylammonium hydroxide solution into aluminum hydroxide dry glue powder mixed with sesbania powder, and uniformly mixing again;
6.3ml of acetic acid and 2.0g of citric acid are measured and dissolved in 95ml of deionized water, then the mixture is added into aluminum hydroxide dry glue powder mixed with basic nickel carbonate, carbon black and sesbania powder, after the mixture is kneaded into uniform pasty plastic, the mixture is extruded into clover-shaped strips with the thickness of 2.0mm on a strip extruder, after the drying is carried out for 3.5 hours at the temperature of 120 ℃, the drying is carried out for 4 hours at the temperature of 900 ℃, and the nickel-containing alumina carrier D4 is prepared.
Preparing a catalyst:
13 carriers are respectively impregnated with nickel oxide as an active component and cerium oxide as an auxiliary agent in equal volume, and the carriers are dried and roasted under the same condition to prepare catalysts, wherein the catalysts prepared by the nickel-containing alumina carriers N1-N9 in the examples are respectively named as C1-C9, and the catalysts prepared by the carriers D1-D4 in the comparative examples are respectively named as C10-C13. The content of nickel and the content of the auxiliary agent cerium oxide in the finally prepared catalyst are the same. Wherein, calculated by simple substance nickel, the nickel content in the catalyst is 12.8 wt%, and the cerium oxide content is 3.0 wt%.
Catalyst evaluation
The cracked gasoline is used as a raw material, the properties of the raw material are shown in Table 3, and the C1-C13 catalysts are evaluated. The evaluation was carried out for 300h, and samples were taken every 24h for analysis of bromine number and diene, and the average data are shown in Table 4 below.
The evaluation of the catalyst is carried out on a 100ml adiabatic bed hydrogenation reaction device, the catalyst is firstly reduced for 10 hours under hydrogen at 350-450 ℃, then the temperature is reduced to 35 ℃, and the raw oil is passivated for 2 hours by cyclohexane containing 1000ppm of dimethyl disulfide. Evaluating process conditions: reaction pressure: 2.8MPa, inlet temperature: 50 ℃, space velocity of fresh raw oil: 3.0h-1Hydrogen to oil volume ratio: 200: 1 (volume ratio based on fresh oil).
TABLE 1 Nickel containing pseudo-boehmite/pseudo-boehmite Properties
Figure BDA0000855035310000121
Figure BDA0000855035310000131
TABLE 2 Nickel containing alumina Carrier/alumina Carrier Properties
Figure BDA0000855035310000132
TABLE 3 Hydrofeed oil Properties
Figure BDA0000855035310000133
Table 4 catalyst evaluation average data
As can be seen from table 4: under the same evaluation process conditions, the catalyst prepared by the nickel-containing alumina carrier has relatively low diene and bromine number of the hydrogenation product, which fully shows that the catalyst prepared in the embodiment has higher hydrogenation activity and stability.

Claims (19)

1. The nickel-containing pseudo-boehmite is characterized in that the nickel content is 0.5-5 wt% based on 100 wt% of the alumina in the nickel-containing pseudo-boehmite; the specific surface area of the nickel-containing pseudo-boehmite is 300 m2/g～420m2Per g, pore volume of 0.7cm3/g～1.2cm3Per gram, the aperture is 5nm to 10 nm; the preparation process of the nickel-containing pseudo-boehmite comprises the processes of acid-base neutralization and gel forming.
2. The nickel-containing pseudoboehmite according to claim 1, characterized in that the process for preparing the nickel-containing pseudoboehmite comprises the 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 mixed solution containing aluminum salt and nickel salt, and adjusting the temperature of the acidic mixed solution to be 50-90 ℃, 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 acidic mixed 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 colloid is formed;
(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.
3. The nickel-containing pseudoboehmite according to claim 2, characterized in that air is introduced into the bottom of the neutralization tank in the step (1).
4. The nickel-containing pseudoboehmite according to claim 2, characterized in that the temperature of the acidic mixed solution in step (2) is adjusted to 60 to 80 ℃.
5. The nickel-containing pseudoboehmite according to claim 2, characterized in that an alkaline precipitant aqueous solution is added to the alkali metal aluminate solution in step (3).
6. The nickel-containing pseudoboehmite according to claim 2, characterized in that in step (5), the gelling temperature is 60-80 ℃; and the pH value of the formed gel is 7-9.
7. The nickel-containing pseudo-boehmite according to claim 2 or 5, characterized in that the pH value of the alkali metal aluminate solution or a mixed solution thereof with an aqueous alkaline precipitant solution is 9 to 14.
8. The nickel-containing pseudo-boehmite according to claim 7, characterized in that the pH value of the alkali metal aluminate solution or a mixed solution thereof with an aqueous alkaline precipitant solution is 12 to 14.
9. The nickel-containing pseudoboehmite according to claim 2, 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.
10. The nickel-containing pseudoboehmite according to claim 9, characterized in that the acidic aluminum salt aqueous solution is an aluminum sulfate solution; the aqueous acidic nickel salt solution is a nickel nitrate solution.
11. The nickel-containing pseudoboehmite according to claim 2, characterized in that the pH of the mixed solution of the acidic aluminum salt and the acidic nickel salt is 2 to 5.
12. The nickel-containing pseudoboehmite according to claim 11, characterized in that the pH of the mixed solution of acidic aluminum salt and acidic nickel salt is 2 to 4.
13. The nickel-containing pseudoboehmite according to claim 5, characterized in that the basic precipitant is an ammonium bicarbonate solution, a sodium bicarbonate solution, an aqueous ammonia solution, a sodium hydroxide solution or a calcium hydroxide solution.
14. The nickel-containing pseudoboehmite according to claim 13, characterized in that said alkaline precipitant is an aqueous ammonia solution, NH3The content is 50-120 g/L.
15. The nickel-containing pseudoboehmite according to claim 2, characterized in that in the step (6), the aging temperature is 50 to 80 ℃ and the aging time is 10 to 60 min.
16. A nickel-containing alumina carrier is prepared from nickel-containing pseudo-boehmite through shaping and calcining, and 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;
wherein, the nickel content is 0.5wt percent to 7.5wt percent, and the specific surface area of the nickel-containing alumina carrier is 20m2/g～230m2Per g, pore volume of 0.10cm3/g～0.65cm3The pore diameter is 7nm to 30 nm.
17. The nickel-containing alumina carrier according to claim 16, wherein the nickel-containing alumina carrier contains delta-Al2O3、δ-NiAl26O40And NiAl2O4The nickel-containing alumina carrier accounts for 30-100% of the total weight of the nickel-containing alumina carrier.
18. The nickel-containing alumina carrier according to claim 16, wherein the nickel-containing alumina carrier contains θ -Al2O3、α-Al2O3And/or gamma-Al2O3；α-Al2O3Less than 30 wt%.
19. The nickel-containing alumina support according to claim 16, wherein: the roasting conditions are as follows: roasting at 800-1200 ℃ for 4-10 h.
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CN103055922A (en) * 2011-10-21 2013-04-24 中国石油化工股份有限公司 Preparation method of bulk phase hydrocracking catalyst
CN103055876A (en) * 2013-01-22 2013-04-24 新地能源工程技术有限公司 Preparation method of wide-temperature methanation catalyst
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