CN102527390B - Preparation process of nickel-based supported catalyst and prepared catalyst - Google Patents
Preparation process of nickel-based supported catalyst and prepared catalyst Download PDFInfo
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Abstract
The invention discloses a preparation process of a nickel-based supported catalyst in which one or more of silicon dioxide, titanium dioxide, alumina, zirconium dioxide and rare earth oxide are taken as carriers. The preparation process comprises the following steps of: preparing a precursor with a sol-gel method; drying the precursor; smashing the precursor into powder of 200-400 meshes; adding a bonding agent and a pore structure adjusting agent, and kneading; performing extrusion molding; baking; and pre-reducing, wherein the bonding agent is preferably commercial SB (Styrene-Butadiene) powder; and the adding amount of the bonding agent is 3-25 percent, preferably 8-15 percent of the total weight of a precursor oxide; the pore structure adjusting agent is preferably a mixture of polyethylene glycol and oxalic acid or citric acid in the molar ratio of 1:(0.8-0.1); and the adding amount of the pore structure adjusting agent is 0.1-25 percent, preferably 0.5-15 percent of the total weight of the precursor oxide. The invention further provides a nickel-based supported catalyst which is prepared with the process and has high mechanical strength and high catalytic performance. Due to the adoption of a solidification technology, the bottle neck problems of easiness in agglomerating, easiness in collapse of a pore structure, strip explosion, strip breakage and the like existing in precursor superfine powder prepared with a sol-gel method are solved.
Description
Technical field
The invention belongs to chemical catalyst field, relate in particular to a kind of preparation technology of Supported Nickel Catalyst and the preformed catalyst of preparation thereof.
Background technology
Supported Nickel Catalyst is take nickel (Ni) as active component, silica (SiO
2), titanium dioxide (TiO
2), aluminium oxide (Al
2o
3) or rare earth oxide be carrier, it has deep hydrogenation, high arene saturating activity and cheap feature, be widely used in petrochemical industry and organic chemical industry's unifining process and organic products hydrogenation process, as be applied to producing cyclohexane by benzene hydrogenation, the Hydrogenation solvent naphtha of raffinating oil, aldehydes organic compound Hydrogenation alcohols organic compound, the technical fields such as fat compound hydrogenation.The preparation of Supported Nickel Catalyst is all generally first by distinct methods, to obtain nickel to be carried on the precursor in carrier with nickel oxide (NiO) form, then by precursor roasting, reduction.The precursor of domestic widely used Supported Nickel Catalyst, mainly prepares by infusion process and coprecipitation at present.As the Chinese invention patent prospectus of publication number 1146164A, 1546230A provides respectively a kind of Supported Nickel Catalyst of preparing by coprecipitation and method thereof; What publication number 1415413A, 1439456A Chinese invention patent prospectus were recorded prepares Supported Nickel Catalyst by infusion process.In recent years, due to preparation method, select equipment to there is good industrial operability, the catalyst making has unique architectural feature, good surface property and excellent catalytic performance, and sol-gel process is prepared ultra-fine nickel-base catalyst becomes the focus of research gradually.As the Chinese invention patent application prospectus of publication number CN 1210759A discloses low nickel content benzene hydrogenating catalyst prepared by a kind of sol-gel process, its preparation method is: the alkoxide of the alkoxide of silicon and titanium is dissolved in solvent, through hydrolysis, obtain silicon-titanium colloidal sol, then add nickel salt solution, polymerization obtains wet gel, obtains after drying the precursor of described catalyst.The specific area of this catalyst is high, active component (Ni) high degree of dispersion, and its particle diameter is less than 50nm, reaches nanoscale; Catalytic activity and selectively very high, and have good heat-resistant stability and anti-sulphur toxicity.
The catalyst that chemical engineering industry is used all needs to have suitable shape, size and mechanical strength, to be conducive to hydrodynamics, mass-and heat-transfer process, meets the requirement of catalytic reaction and reaction unit, make catalyst bring into play the premium properties that it has, the service life of extending catalyst.The precursor that sol-gel process obtains is irregular bulk, NiO, SiO wherein
2, TiO
2or rare earth oxide etc. is all lean property oxide, cementability is poor, and mechanical strength is low, therefore must be by after first precursor moulding, then roasting, reduction.The curing molding method of known catalyst, has oil ammonia column method, pressed disc method conventionally, extrusion method and rotational forming method.As the Chinese invention patent prospectus of publication number 1546230A, 1146164A, recorded coprecipitation and obtained precursor powder, then the method for compressing tablet or extruded moulding.Pressed disc method is applicable to the nickel-base catalyst moulding of aluminium oxide as carrier, the nickel-base catalyst moulding that is carrier for titanium oxide and silica, and process conditions are difficult to control.The precursor preparing by sol-gel process has higher specific area, and active component and carrier component are nano particle, in the process of mechanical crushing, easily causes subsiding and superfine powder reunion of part pore structure.Therefore the precursor curing molding technology that, prepared by sol-gel process must solve three problems: the mechanical strength of (1) catalyst will meet the needs of commercial Application; (2) in curing molding process, to prevent the reunion of superfine powder; (3) catalytic performance of curing molding rear catalyst can not decline.The forming process of the catalyst precursor that therefore, sol-gel process prepares is one of committed step of Industrial Catalysis production.
Summary of the invention
The object of the present invention is to provide a kind of preparation technology of Supported Nickel Catalyst.The invention solves catalyst precursor superfine powder prepared by sol-gel process easily reunites, collapse of pore structure, fried bar, the problem of the bottleneck problem of the curing moldings such as disconnected bar and lean property oxide machinery intensity difference, the catalyst mechanical strength of utilizing this technique to prepare is high, meets the needs of commercial fixed bed reaction unit.Technique of the present invention is simple, does not need to prepare the special installation of superfine powder, and industry is workable, is suitable for large-scale industrial production.
It is high that another object of the present invention is to provide a kind of mechanical strength of utilizing above-mentioned preparation technology to prepare, the Supported Nickel Catalyst that catalytic performance is good.
In order to solve the problems of the technologies described above, the present invention has adopted following technical scheme:
A preparation technology for Supported Nickel Catalyst, comprises that sol-gel process is prepared precursor, precursor is dry, precursor is pulverized, adds binding agent kneading, extruded moulding, roasting and reduction; The active component of described precursor is nickel oxide, and carrier is one or more in silica, titanium dioxide, aluminium oxide, zirconium dioxide, rare earth oxide; Described precursor is ground into 200～400 order powders; The addition of described binding agent is 3～25% of described precursor oxide gross weight; In described kneading step, also to add the porosity agent of described precursor oxide gross weight 0.1～25%; Described porosity agent is selected from polyethylene glycol, polyethylene glycol alkyl ether, C
1~ C
3organic carboxyl acid in one or more.
In order to reduce production costs, improve the specific surface character of catalyst, the present invention is the catalyst precursor in a kind of pair of silicon source preferably, its carrier is silica and titanium dioxide, take oxide gross weight in described precursor as benchmark, the content of nickel oxide is 15～40%, and titanium dioxide and silica total content are 60 ~ 85%, and the mol ratio of titanium dioxide and silica is TiO
2﹕ SiO
2=0～0.5 ﹕ 1; The raw material of described precursor is the silicon dioxide gel of positive silicic acid aliphatic alcohol ester, fatty alcohol titanium, nickel salt and pH=5 ~ 6, wherein with SiO
2meter, the mol ratio of silicon dioxide gel and positive silicic acid aliphatic alcohol ester is the positive silicic acid aliphatic alcohol ester=0.1 ~ 0.4:1 of two silica sol ﹕; By following method, prepare:
(1) positive silicic acid aliphatic alcohol ester and the fatty alcohol titanium of amount of calculation are dissolved in to C
1~ C
3fatty alcohol and being selected from a kind of miscible system in water, 0.1 ~ 0.3M nitric acid, 0.5 ~ 1M acetic acid, wherein C
1~ C
3fatty alcohol accounts for 25 ~ 50% of described mixed solvent volume, stirs, and is mixed with concentration and with titanium oxide-silica weight, counts 0.15～0.30% Sol A;
(2) by water-soluble the nickel salt of amount of calculation and absolute ethyl alcohol, after stirring, add the silicon dioxide gel of amount of calculation, be mixed with sol B, wherein the concentration of nickel salt counts 10～25% with nickel oxide weight;
At (3) 30～80 ℃ of temperature, described solution glue A constant temperature is stirred 0.5～10 hour, then described sol B is added drop-wise in Sol A with wire, obtains colloidal sol C, continue at the temperature of 30～80 ℃, to stir 0.5～10 hour, the wet gel that obtains green transparent, obtains.
The above-mentioned preferred precursor of wet gel state, first at 25～200 ℃, preferably 50 ~ 150 ℃ are dried; After extruded moulding, at 200～650 ℃, carry out roasting; Finally, at 300～600 ℃, in the gaseous mixture of pure hydrogen or hydrogen/nitrogen, carry out prereduction.
Binding agent of the present invention can be selected from commodity silicon dioxide gel, commodity alumina sol, commodity SB powder, through being coated with 4 viscometer determining viscosity, be the one in described Sol A or the colloidal sol C of 8 ~ 50 seconds; Preferably commodity SB powder.
The chemical composition of above-mentioned Sol A is SiO
2-TiO
2, the chemical composition of colloidal sol C is NiO-SiO
2-TiO
2.
The preferred addition of binding agent of the present invention is 8～15% of described precursor oxide gross weight.
C of the present invention
1~ C
3organic carboxyl acid can be C
1~ C
3monocarboxylic acid, as formic acid, acetic acid, or C
1~ C
3polybasic carboxylic acid, as oxalic acid, citric acid; Preferably oxalic acid or citric acid.
Described porosity agent preferably mol ratio is polyethylene glycol: the mixture of oxalic acid or citric acid=1:0.8～0.1.
The preferred addition of porosity agent of the present invention is 0.5～15% of described precursor oxide gross weight.
In kneading process, for the ease of follow-up extrusion, can add if desired nitric acid, deionized water, field mountain valley with clumps of trees and bamboo powder or the sweet soil of sheep etc.The shape of extrudate is according to the needs of commercial plant, can be designed to trifolium-shaped, column type of certain diameter and length etc.
Utilize the inventive method to prepare the Supported Nickel Catalyst of moulding, for the ease of storing, can also, according to this area routine operation condition, use surface oxidation method, in dry nitrogen/oxygen mixture, carry out passivation, be then kept in airtight container.
The present invention also provides a kind of mechanical strength high, the Supported Nickel Catalyst that catalytic performance is good, its intensity 90 ~ 170N/cm, specific area 300～450m
2/ g, pore volume 0.2～0.5mL/g, most probable pore-size distribution 2.0～5.0nm, an average grain diameter <15nm of active component nickel; The carrier of described catalyst is silica and titanium dioxide, the chemical composition of precursor is nickel oxide-titania-silica, take oxide gross weight in described precursor as benchmark, the content of nickel oxide is 15～40%, titanium dioxide and silica total content are 60 ~ 85%, and the mol ratio of titanium dioxide and silica is TiO
2﹕ SiO
2=0.1～0.15 ﹕ 1; The raw material of described precursor is the silicon dioxide gel of positive silicic acid aliphatic alcohol ester, fatty alcohol titanium, nickel salt and pH=5 ~ 6, wherein with SiO
2meter, the mol ratio of silicon dioxide gel and positive silicic acid aliphatic alcohol ester is the positive silicic acid aliphatic alcohol ester=0.1 ~ 0.4:1 of two silica sol ﹕; Preparation by the following method:
(1) positive silicic acid aliphatic alcohol ester and the fatty alcohol titanium of amount of calculation are dissolved in to C
1~ C
3fatty alcohol and being selected from a kind of miscible system in water, 0.1 ~ 0.3M nitric acid, 0.5 ~ 1M acetic acid, wherein C
1~ C
3fatty alcohol accounts for 25 ~ 50% of described mixed solvent volume, stirs, and is mixed with concentration and with titanium oxide-silica weight, counts 0.2～0.25% Sol A; By water-soluble the nickel salt of amount of calculation and absolute ethyl alcohol, after stirring, add the silicon dioxide gel of amount of calculation, be mixed with sol B, wherein the concentration of nickel salt counts 10～25% with nickel oxide weight; At 40～70 ℃ of temperature, described Sol A constant temperature is stirred 2～5 hours, then described sol B is added drop-wise in Sol A with wire, obtain colloidal sol C, continue at the temperature of 40～70 ℃, to stir 0.5～10 hour, the wet gel of the green transparent obtaining is described precursor;
(2) precursor of being prepared by step 1 dry, pulverize into 200～400 order powders at 50 ~ 150 ℃;
(3) in the powder of preparing to step 2, add commodity SB powder and porosity agent, fully stir, mix, mediate rear extruded moulding, obtain the catalyst precursor of moulding; The addition of described commodity SB powder is 8～15% of described precursor oxide gross weight, it is polyethylene glycol that described porosity agent is selected from mol ratio: the mixture of oxalic acid or citric acid=1:0.8～0.1, and the amount adding is 0.5～15% of described precursor oxide gross weight;
(4) precursor of the described moulding of being prepared by step 3 was 450～650 ℃ of roastings 4 ~ 8 hours;
(5) by the precursor of the moulding after step 4 roasting at 350 ~ 550 ℃, with hydrogen or the prereduction of hydrogen/nitrogen mist, obtain.
Conventional shaping of catalyst method has oil ammonia column method, pressed disc method, extrusion method, and inventor, take preferred precursor of the present invention as moulding basic material, has investigated the impact of above-mentioned three kinds of forming methods on catalyst performance.The results are shown in Table 1, wherein S
bETrepresent the specific surface area of catalyst that BET method is measured, V
prepresent pore volume, R
rrepresent most probable aperture; The reaction that generates cyclohexane with benzene hydrogenation is carried out the evaluation of catalyst reaction activity, reaction condition: P
h2=1.0Mpa, H
2﹕ C
6h
6(mol ratio)=3.5 ~ 4 ﹕ 1, liquid benzene air speed: 2.0h
-1.
The different forming method catalyst sample of table 1 specific surface character and catalyst property
a: unit (N/)
b: add nickel oxide-titanium oxide-silicon dioxide gel as binding agent, polyethylene glycol-citric acid is porosity agent.
Table 1 data show, catalyst curing molding method contrast table surface properties, mechanical strength impact are larger, but little on catalyst activity impact.Although the oil ammonia column method of forming does not need to add the auxiliary materials such as adhesive, and specific surface performance and the catalytic performance of the catalyst of moulding prepared by this method of forming are better, but for nickeliferous catalyst colloidal sol, in forming process, there is part active constituent stripping (ammonia is molten), the more difficult control of active constituent content, industrialization operating condition is harsher, therefore select extrusion method as curing molding method.
In the art, conventionally when extruded moulding, all to add suitable binding agent.Inventor finds in Study on Forming, do not add described pore structure to regulate whole dose, no matter adopt any binding agent, all easily there is the bar fracture of extruding, namely " fried bar " phenomenon, therefore,, for the moulding of Supported Nickel Catalyst precursor of the present invention, described porosity agent is important factor in order.By adding suitable porosity agent, curing molding technology of the present invention has solved superfine powder and has easily reunited, collapse of pore structure, fried bar, the problem of the bottleneck problem of the curing moldings such as disconnected bar and lean property oxide machinery intensity difference, prepared preformed catalyst mechanical strength reaches 90～170N/cm, can meet the needs of commercial fixed bed reaction unit.And preparation technology is simple, do not need to prepare the special installation of superfine powder, mature preparation process, industry is workable, is applicable to large-scale industrial production.
Supported Nickel Catalyst prepared by the present invention regulates whole dose owing to having added pore structure in extruded moulding process, makes loose structure feature more obvious, and increase in the aperture that is greater than 2nm, is more conducive to the mass-and heat-transfer of catalyst.
The preferred carrier of the present invention is the Supported Nickel Catalyst (Ni/TiO of titanium dioxide and silica
2-SiO
2), owing to using the positive silicic acid aliphatic alcohol ester of silicon dioxide gel Substitute For Partial, having kept the good specific area performance of its precursor, the specific area of the catalyst after prereduction is at 300～400m
2/ g, pore volume 0.2～0.5mL/g, most probable pore-size distribution 2.0～5.0nm; An average grain diameter <30nm of active component nickel, that definite is <15nm.It can be used for benzene hydrogenation, toluene hydrogenation, the raffinate oil organic chemical industries such as hydrogenation, petrochemical industry, and in hydrotreatment process, there is high heat endurance, carbon deposit recyclability, there is reactivity temperature wide (120 ~ 280 ℃) high-speed, the low catalytic performance that waits of hydrogen-consuming volume.
Accompanying drawing explanation
Fig. 1 is the Adsorption and desorption isotherms of the Ni-based type catalyst of strip prepared of embodiment 6, and wherein 1 represents adsorption isotherm, and 2 represent desorption isotherms.
Fig. 2 is the Adsorption and desorption isotherms of the Ni-based type catalyst of strip prepared of comparative example 2, and wherein 1 represents adsorption isotherm, and 2 represent desorption isotherms.
Fig. 3 is strip nickel-base catalyst transmission electron microscope (TEM) photo prepared by embodiment 7.
The specific embodiment
Below by embodiment, the invention will be further described.Should be appreciated that, these embodiment only, for the present invention is described, limit the scope of the invention and be not used in.The experimental technique of the unreceipted actual conditions of the following example, conventionally according to normal condition, or the condition that provides or advise according to manufacturer.Unless otherwise indicated, the familiar meaning of all specialties used herein and scientific terminology and those skilled in the art is identical.In addition any method similar or impartial to this method and material all can be used in the inventive method.
Main raw material(s) used in embodiment and comparative example is as follows:
Ethyl orthosilicate, methyl silicate: chemical pure, 5-linked chemical plant, Shanghai
Butyl titanate: chemical pure, Xing Ta chemical plant, Shanghai Jinshan county
Ludox: technical grade, Nanjing, Nanjing petrochemical industry research institute, pH=5 ~ 11.5, SiO
2solid content 20.6%, the used time is adjusted pH=5 ~ 6.
Nickel nitrate, nickel formate, nickelous carbonate: chemical pure, Chinese medicine (group) Solution on Chemical Reagents in Shanghai Co., Ltd
Polyethylene glycol (PEG): chemical pure, Gao Nan chemical plant, PVG
Formic acid, acetic acid: chemical pure, Chinese medicine (group) Solution on Chemical Reagents in Shanghai Co., Ltd
Polyethylene glycol monomethyl ether, analyze pure, Belgian ACIOS
Oxalic acid: analyze pure, Shishewei Chemical Co., Ltd., Shanghai
Citric acid: analyze pure, Shanghai reagent one factory
SB powder: technical grade, Chalco Shandong Aluminium Industrial Corp
Zirconyl nitrate: chemical pure, Liu Lidian chemical plant, Beijing
Ammonium ceric nitrate zirconium: analyze pure, Chinese medicine (group) Solution on Chemical Reagents in Shanghai Co., Ltd
JEM-2010 type high score rate transmission electron microscope, Japanese JEOL company
ASAP2020 type automatic absorbing instrument, U.S. Merck & Co., Inc
ZQJ-II type intelligence granule strength experimental machine, connection intelligent experimental machine factory greatly
Embodiment 1:
With commercially available ethyl orthosilicate, Ludox, butyl titanate, nickel nitrate is raw material.First get 185.8 grams of ethyl orthosilicates, 51.1 grams of butyl titanates in beaker, add deionized water and absolute ethyl alcohol, be mixed with 0.22m% (with TiO
2-SiO
2calculate) TiO
2-SiO
2sol A
1, 40 ℃～70 ℃ are stirred 4 hours.With deionized water and 70 grams of nickel nitrates of anhydrous alcohol solution, after stirring, add 80 grams of Ludox, be mixed with sol B
1, sol B
1middle nickel nitrate concentration is that 11m%(calculates with NiO).Then by sol B
1with wire, be added drop-wise to Sol A
1in, obtain colloidal sol C
1, continue stir about 3 hours at the temperature of 40 ℃～70 ℃, obtain the wet gel of the thick green transparent of poor fluidity.After drying, (chemical composition is NiO-TiO to wet gel to obtain dry bulk catalyst precursor
2-SiO
2ternary compound oxides).
According to table 2, change the consumption of ethyl orthosilicate, Ludox, all the other operating procedures, with embodiment 1, obtain different block presomas.
Comparative example 1:
Get 242.6 grams of ethyl orthosilicates, 51.1 grams of butyl titanates in beaker, add deionized water and absolute ethyl alcohol, be mixed with 0.22m% (with TiO
2-SiO
2calculate) TiO
2-SiO
2sol A
2, 40 ℃～70 ℃ are stirred 4 hours.With deionized water and 70 grams of nickel nitrates of anhydrous alcohol solution, be mixed with sol B
2, sol B
2middle nickel nitrate concentration is that 11m%(calculates with NiO).Then by sol B
2with wire, be added drop-wise to Sol A
2in, continue stir about 3 hours at the temperature of 40 ℃～70 ℃, obtain the wet gel of the thick green transparent of poor fluidity.After drying, (chemical composition is NiO-TiO to wet gel to obtain bulk catalyst precursor
2-SiO
2ternary compound oxides).
By embodiment 1～3, comparative example 1 gained catalyst precursor after drying, in 200 ℃～550 ℃ roastings 5～10 hours, by the screening of bulk catalyst presoma, be 40～60 particle diameters, after self-control fixed bed continuous-flow micro-reactor in-situ reducing, take benzene hydrogenation, generate cyclohexane as hydrogenation reaction model.Catalyst respectively reacts after 100 hours at 220 ℃ (benzene conversion ratio 100%, cyclohexanes selective 100%), relatively the impact of Ludox addition contrast table surface properties.Specific surface character before and after embodiment 1～3, comparative example 1 raw materials, producing cyclohexane by benzene hydrogenation reaction is listed in table 2(BET mensuration and is adopted the U.S. ASAP2020 of Merck & Co., Inc type automatic absorbing instrument nitrogen to be adsorbed gas, as follows).
Table 2
Note: benzene hydrogenation generates cyclohexane reaction evaluating condition: liquid benzene air speed=2.0h
-1, hydrogen benzene ratio=3.5:1, P
h2=0.9Mpa,
Reaction temperature=220 ℃.
Embodiment 4: with NiO-TiO
2-SiO
2colloidal sol is gelling agent extruded moulding
100 grams of the catalyst precursors (in institute's oxycompound gross weight) of preparing in embodiment 1 same recipe ratio and method, are milled to 250～350 object powders, and it is the colloidal sol C of 15～20 seconds that painting 4 viscosimeters prepared by embodiment 1 record viscosity
1(NiO-TiO
2-SiO
2colloidal sol) 20 grams as binding agent, and Ratio of filler bitumen (mass ratio)=8 ﹕ 1, by described colloidal sol C
1add in described powder, then add 6 grams of porosity agent polyethylene glycol monomethyl ethers, 1.3 grams of citric acids, mediate, and extrusion makes the column type bar of φ 3mm.By dry 25～150 ℃ of the strip catalyst presomas of moulding, 550 ℃ of roastings 6 hours.Intensity (catalyst length 5mm measures 50-80 grain) and the specific surface character of measuring strip catalyst, data are listed in table 3.ZQJ-II type intelligence granule strength experimental machine (connection intelligent experimental machine factory produces greatly) for the mensuration of catalyst strength.
Embodiment 5: with TiO
2-SiO
2colloidal sol is gelling agent extruded moulding
100 grams of the catalyst precursors (in institute's oxycompound gross weight) of preparing in embodiment 1 same recipe ratio and method, it is the Sol A of 15～20 seconds that painting 4 viscosimeters prepared by comparative example 1 record viscosity
2(TiO
2-SiO
2colloidal sol) 19 as binding agent, Ratio of filler bitumen (mass ratio)=8.4 ﹕ 1; 5 grams of polyethylene glycol, 1 gram of oxalic acid is as porosity agent; Press the step extruded moulding that embodiment 4 is identical, dry, roasting, intensity (catalyst length 5mm measures 50-80 grain) and the specific surface character of strip catalyst, data are listed in table 3.
Embodiment 6: take SB powder as gelling agent extruded moulding
Get 927 grams of ethyl orthosilicates, 276 grams of butyl titanates in beaker, add deionized water and absolute ethyl alcohol, be mixed with 0.22m% (with TiO
2-SiO
2calculate) TiO
2-SiO
2sol A
3, 40 ℃～70 ℃ are stirred 4 hours.With deionized water and 655 grams of nickel nitrates of anhydrous alcohol solution, then add 568 grams of SiO
2colloidal sol, is mixed with sol B
3, sol B
3middle nickel nitrate concentration is that 14.2m%(calculates with NiO).Then by sol B
3with wire, be added drop-wise to solution A
3in, continue stir about 3 hours at the temperature of 40 ℃～70 ℃, obtain the wet gel of the thick green transparent of poor fluidity.After drying, (chemical composition is NiO-TiO to wet gel to obtain bulk catalyst precursor
2-SiO
2ternary compound oxides).Above-mentioned bulk catalyst presoma is milled to 200～400 orders, adds 60 grams of SB powder, 3% nitric acid 300mL, 6 grams, field mountain valley with clumps of trees and bamboo powder, 80 grams of pore structure conditioning agent polyethylene glycol, 8 grams of stubborn lemon acid, mix, mediate, extruded moulding, the strip catalyst presoma bar diameter of moulding is 3mm.By dry the strip catalyst presoma of moulding, 550 ℃ of roastings 6 hours.The ZQJ-II type intelligence granule strength experimental machine of producing with large connection intelligent experimental machine factory is measured intensity (catalyst length 5mm measures 50-80 grain) and the specific surface character of strip catalyst, and data are listed in table 3.Adsorption and desorption isotherms as shown in Figure 1.
Comparative example 2: take SB powder as gelling agent extruded moulding.
In extruded moulding process, do not add pore structure conditioning agent polyethylene glycol and citric acid, other steps are with embodiment 6, and its specific surface character data is listed in table 3.Adsorption and desorption isotherms is as shown in Fig. 2.
Adsorption and desorption isotherms in Fig. 1 and Fig. 2 is all IV type, but the shape difference of their adsorption desorption hysteresis loop.Because the shape of adsorption desorption hysteresis loop has reflected certain pore structure situation, therefore, can be by the situation of change of the pore structure before and after adsorption desorption loop line research curing molding.In Fig. 1, in extruded moulding process, add porosity agent to carry out the strip NiO-TiO after kneading, extrusion
2-SiO
2the adsorption desorption hysteresis loop of catalyst precursor goes out the atypical loop line of H3 type, it is the stack of several typical loop lines, this situation may be because part hole in this type of material is the parallel-plate compared with homogeneous, and the larger tabular pore of size variation scope that part hole is one end almost to be sealed, can infer thus, through the hole shape of ball milling and the formation of extrusion kneading, be the original thin neck of block xerogel, the wide hole shape of body tubular type ink bottle shape and the hole shape that mixes in the slit-shaped hole being formed by tabular particle, there is double-pore structure feature.And the strip NiO-TiO that does not add porosity agent in Fig. 2
2-SiO
2the adsorption desorption hysteresis loop of catalyst precursor shows, the pore structure in this system is without definite shape.
Embodiment 7: take SB powder as gelling agent extruded moulding
Get 927 grams of ethyl orthosilicates, 276 grams of butyl titanates in beaker, add deionized water and absolute ethyl alcohol, be mixed with 0.22m% (with TiO
2-SiO
2calculate) TiO
2-SiO
2sol A
4, 40 ℃～70 ℃ are stirred 4 hours.With deionized water and 520 grams of nickel nitrates of anhydrous alcohol solution, then add 568 grams of SiO
2colloidal sol, is mixed with sol B
4, sol B
4middle nickel nitrate concentration is that 12.6m%(calculates with NiO).Then by sol B
4with wire, be added drop-wise to Sol A
4in, continue stir about 3 hours at the temperature of 40 ℃～70 ℃, obtain the wet gel of the thick green transparent of poor fluidity.After drying, (chemical composition is NiO-TiO to wet gel to obtain bulk catalyst precursor
2-SiO
2ternary compound oxides).Above-mentioned bulk catalyst presoma is milled to 200～400 orders, adds 60 grams of SB powder, 3% nitric acid 300mL, 6 grams, field mountain valley with clumps of trees and bamboo powder, 80 grams of pore structure conditioning agent polyethylene glycol, 8 grams of citric acids, mix, mediate, extruded moulding, the strip catalyst presoma bar diameter of moulding is 3mm.After the strip catalyst presoma of moulding is dry, control suitable heating rate, pass into appropriate air in 550 ℃ of roastings 6 hours.And carry out prereduction outside device in 550 ℃, hydrogen atmosphere, after reduction finishes, carry out passivation with nitrogen/air, until all pass into air, strip catalyst face shaping after passivation is the column type bar of about φ 2.8 × 6mm, is kept in dry closed container.The intensity of oxidation state strip catalyst and reduction-state strip catalyst and specific surface character, data are listed in table 3.The TEM figure of reduction-state strip catalyst is shown in Fig. 3, as can see from Figure 3, and through curing molding, carrier component and active component are nanometer system, active component nickel is high degree of dispersion in catalyst, and the particle diameter of active component nickel is less than 10nm, and at catalyst surface without obvious packing phenomenon.
Table 3
Embodiment 8: the heat endurance of strip nickel-base catalyst and urge old test
On 100ml pilot evaluating device, it is pressure 1.0Mpa, liquid volume air speed 2.0h that the pre-reduction type catalyst of embodiment 7 and a domestic commercially available industrial catalyst (as reference agent) are under equal conditions urged to old contrast test, appreciation condition
-1, hydrogen benzene mole is than for 3.3:1.Result of the test is in Table 4.
Table 4 is urged old comparative test result
Embodiment 9: catalyst regeneration test
Table 5 embodiment 7 before and after pre-reduction type catalyst regenerations with fresh dose of physico-chemical property and Performance Ratio
Compared with fresh dose, urge catalyst specific surface and pore volume after old running to decline seldom, have a certain amount of carbon distribution, regeneration rear catalyst benzene conversion ratio activity and cyclohexane have selectively reached respectively 100m% and 99.99m%, with fresh dose there is no difference, this explanation catalyst there is good regenerability.
Catalyst prepared by embodiment 10: embodiment 7 Hydrogenation of raffinating oil
The catalyst that test raw material 1 and test raw material 2 prepared with experimental example 7 respectively of raffinating oil carries out hydrogenation reaction, and before hydrogenation reaction, the character of raw material and hydrogenation reaction afterproduct is listed in table 6.On micro-reactor, carry out activity rating.
Testing result before and after table 6 test raw material hydrogenation reaction
In test raw material 2: W benzene=4.6502% W toluene=0.9740%
Hydrogenation reaction process conditions: T=160 ℃, P
h2=0.4MPa, hydrogen-oil ratio 20, feedstock oil liquid hourly space velocity (LHSV) are 5h
-1.
Embodiment 11
Get 687 grams of ethyl orthosilicates, 73 grams of zirconyl nitrates and 269 grams of nickel nitrates, prepare NiO-ZrO by sol-gel process
2-SiO
2the wet gel of ternary compound oxides green transparent.After drying, (chemical composition is NiO-ZrO to wet gel to obtain bulk catalyst precursor
2-SiO
2ternary compound oxides).Above-mentioned block presoma is milled to 200～400 orders, adds 45 grams of SB powder, 3% nitric acid 100mL, 3 grams, field mountain valley with clumps of trees and bamboo powder, 45 grams of pore structure conditioning agent polyethylene glycol monomethyl ethers, 3 grams of citric acids, mix, mediate extruded moulding, the trifolium-shaped that strip catalyst presoma bar diameter is 1.2mm.After trifolium-shaped catalyst precursor is dry, control suitable heating rate, pass into appropriate air in 550 ℃ of roastings 6 hours.The intensity of oxidation state strip catalyst and specific surface character, data are listed in table 3.
Embodiment 12
Get 687 grams of ethyl orthosilicates, 105 grams of ammonium ceric nitrate zirconiums and 269 grams of nickel nitrates, prepare NiO-CeO by sol-gel process
2-SiO
2the wet gel of ternary compound oxides green transparent.After drying, (chemical composition is NiO-CeO to wet gel to obtain bulk catalyst precursor
2-SiO
2ternary compound oxides).Above-mentioned bulk catalyst presoma is milled to 200～400 orders, adds 30 grams of SB powder, 3% nitric acid 100mL, 3 grams, field mountain valley with clumps of trees and bamboo powder, 45 grams of pore structure conditioning agent polyethylene glycol, 5 grams of citric acids, mix, mediate extruded moulding, strip catalyst presoma bar diameter 2mm.After strip catalyst presoma is dry, control suitable heating rate, pass into appropriate air in 550 ℃ of roastings 6 hours.The intensity of oxidation state strip catalyst and specific surface character, data are listed in table 3.
Claims (2)
1. a preparation technology for Supported Nickel Catalyst, comprises that colloidal sol-gel method is prepared precursor, precursor is dry, precursor is pulverized, adds binding agent kneading, extruded moulding, roasting and prereduction; The active component of described precursor is nickel oxide, and carrier is one or more in silica, titanium dioxide, aluminium oxide, zirconium dioxide, rare earth oxide; It is characterized in that: described precursor is ground into 200～400 order powders; The addition of described binding agent is 3～25% of described precursor oxide gross weight; The porosity agent that also will add described precursor oxide gross weight 0.1～25% in described kneading step, described porosity agent is selected from polyethylene glycol, polyethylene glycol alkyl ether, C
1~ C
3organic carboxyl acid in one or more.
2. according to the preparation technology described in claim 1, it is characterized in that: in described precursor, carrier is silica and titanium dioxide, take oxide gross weight in described precursor as benchmark, the content of nickel oxide is 15～40%, titanium dioxide and silica total content are 60 ~ 85%, and the mol ratio of titanium dioxide and silica is TiO
2: SiO
2=>0～0.5:1; The raw material of described precursor is the silicon dioxide gel of positive silicic acid aliphatic alcohol ester, fatty alcohol titanium, nickel salt and pH=5 ~ 6, wherein with SiO
2meter, the mol ratio of silicon dioxide gel and positive silicic acid aliphatic alcohol ester is silicon dioxide gel: positive silicic acid aliphatic alcohol ester=0.1 ~ 0.4:1; By following method, prepare:
(1) positive silicic acid aliphatic alcohol ester and the fatty alcohol titanium of amount of calculation are dissolved in to C
1~ C
3fatty alcohol and being selected from a kind of miscible system in water, 0.1 ~ 0.3M nitric acid, 0.5 ~ 1M acetic acid, wherein C
1~ C
3fatty alcohol accounts for 25 ~ 50% of described mixed solvent volume, stirs, and is mixed with concentration and with titanium dioxide-silica weight, counts 0.15～0.30% Sol A;
(2) by water-soluble the nickel salt of amount of calculation and absolute ethyl alcohol, after stirring, add the silicon dioxide gel of amount of calculation, be mixed with sol B, wherein the concentration of nickel salt counts 10～25% with nickel oxide weight;
At (3) 30～80 ℃ of temperature, described Sol A constant temperature is stirred 0.5～10 hour, then described sol B is added drop-wise in Sol A with wire, obtains colloidal sol C, continue at the temperature of 30～80 ℃, to stir 0.5～10 hour, the wet gel that obtains green transparent, obtains.
3. according to the preparation technology described in claim 1 or 2, it is characterized in that: described binding agent is selected from commodity silicon dioxide gel, commodity alumina sol, commodity SB powder, through being coated with 4 viscometer determining viscosity, is the one in described Sol A or the colloidal sol C of 8 ~ 50 seconds.
4. according to the preparation technology described in claim 3, it is characterized in that: described binding agent is commodity SB powder.
5. according to the preparation technology described in claim 1,2 or 4, it is characterized in that: the addition of described binding agent is that described catalyst precursor oxide gross weight is benchmark 8～15%.
6. according to the preparation technology described in claim 3, it is characterized in that: the addition of described binding agent is that described catalyst precursor oxide gross weight is benchmark 8～15%.
7. according to the preparation technology described in claim 1 or 2, it is characterized in that: described C
1~ C
3organic carboxyl acid be selected from oxalic acid.
8. according to the preparation technology described in claim 1 or 2, it is characterized in that: described porosity agent is that mol ratio is polyethylene glycol: the mixture of oxalic acid=1:0.8～0.1.
9. according to the preparation technology described in claim 1 or 2, it is characterized in that: the addition of described porosity agent is 0.5～15% of described precursor oxide gross weight.
10. according to the preparation technology described in claim 7, it is characterized in that: the addition of described porosity agent is 0.5～15% of described precursor oxide gross weight.
11. described preparation technologies according to Claim 8, is characterized in that: the addition of described porosity agent is 0.5～15% of described precursor oxide gross weight.
12. according to the preparation technology described in claim 2, it is characterized in that: the baking temperature of described precursor is 25～200 ℃.
13. according to the preparation technology described in claim 12, it is characterized in that: the baking temperature of described precursor is 50～150 ℃.
14. according to the preparation technology described in claim 2, it is characterized in that: the temperature of described roasting is 200～650 ℃.
15. according to the preparation technology described in claim 2, it is characterized in that: described prereduction temperature is 300～600 ℃, and prereduction gas is the gaseous mixture of pure hydrogen or hydrogen/nitrogen.
16. Supported Nickel Catalysts of preparing according to the preparation technology described in claim 2, is characterized in that: the intensity 90 ~ 170N/cm of described Supported Nickel Catalyst, specific area 300～450m
2/ g, pore volume 0.2～0.5mL/g, most probable pore-size distribution 2.0～5.0nm, an average grain diameter <15nm of active component nickel; The carrier of described Supported Nickel Catalyst is silica and titanium dioxide, the chemical composition of precursor is nickel oxide-titanium dioxide-silica, take oxide gross weight in described precursor as benchmark, the content of nickel oxide is 15～40%, titanium dioxide and silica total content are 60 ~ 85%, and the mol ratio of titanium dioxide and silica is TiO
2: SiO
2=0.1～0.15:1; The raw material of described precursor is the silicon dioxide gel of positive silicic acid aliphatic alcohol ester, fatty alcohol titanium, nickel salt and pH=5 ~ 6, wherein with SiO
2meter, the mol ratio of silicon dioxide gel and positive silicic acid aliphatic alcohol ester is SiO
2: positive silicic acid aliphatic alcohol ester=0.1 ~ 0.4:1; Preparation by the following method:
(1) positive silicic acid aliphatic alcohol ester and the fatty alcohol titanium of amount of calculation are dissolved in to C
1~ C
3fatty alcohol and being selected from a kind of miscible system in water, 0.1 ~ 0.3M nitric acid, 0.5 ~ 1M acetic acid, wherein C
1~ C
3fatty alcohol accounts for 25 ~ 50% of described mixed solvent volume, stirs, and is mixed with concentration and with titanium dioxide-silica weight, counts 0.2～0.25% Sol A; By water-soluble the nickel salt of amount of calculation and absolute ethyl alcohol, after stirring, add the silicon dioxide gel of amount of calculation, be mixed with sol B, wherein the concentration of nickel salt counts 10～25% with nickel oxide weight; At 40～70 ℃ of temperature, described Sol A constant temperature is stirred 2～5 hours, then described sol B is added drop-wise in Sol A with wire, obtain colloidal sol C, continue at the temperature of 40～70 ℃, to stir 0.5～10 hour, the wet gel of the green transparent obtaining is described precursor;
(2) precursor of being prepared by step 1 dry, pulverize into 200～400 order powders at 50 ~ 150 ℃;
(3) in the powder of preparing in step 2, add commodity SB powder and porosity agent, fully stir, mix, mediate rear extruded moulding, obtain the precursor of moulding; The addition of described commodity SB powder is 8～15% of precursor oxide gross weight, it is polyethylene glycol that described porosity agent is selected from mol ratio: the mixture of oxalic acid=1:0.8～0.1, and the amount adding is 0.5～15% of described precursor oxide gross weight;
(4) precursor of the described moulding of being prepared by step 3 was 450～650 ℃ of roastings 4 ~ 8 hours;
(5) by the precursor of the moulding after step 4 roasting at 350 ~ 550 ℃, with hydrogen or the prereduction of hydrogen/nitrogen mist, obtain.
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| CN105195208A (en) * | 2015-09-24 | 2015-12-30 | 神华集团有限责任公司 | Monolithic catalyst, preparation method thereof and desulphurization method utilizing monolithic catalyst |
| CN109569680B (en) * | 2017-09-29 | 2021-12-17 | 中国石油化工股份有限公司 | Catalyst with hydrogenation catalysis effect, preparation method and application thereof, and heavy oil hydrogenation asphaltene removal method |
| CN111250091A (en) * | 2020-03-03 | 2020-06-09 | 广东工业大学 | Supported catalyst and preparation method thereof |
| CN113385175B (en) * | 2020-03-13 | 2023-09-05 | 中国石油化工股份有限公司 | Hydrogenation saturation catalyst and preparation method and application thereof |
| CN113527028B (en) * | 2020-04-14 | 2023-10-10 | 中国石油化工股份有限公司 | Preparation method of tetrahydrodicyclopentadiene |
| US11951457B2 (en) * | 2021-01-04 | 2024-04-09 | Qatar University | Metal-silica nanocomposites prepared through a single step solution combustion synthesis (SCS) |
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| US4880524A (en) * | 1987-11-20 | 1989-11-14 | Shell Oil Company | Process for hydrotreating hydrocarbon feeds |
| CN1210759A (en) * | 1997-09-05 | 1999-03-17 | 中国石油化工总公司 | Low nickel content benzene hydrogenating catalyst and its preparing process |
| CN1613557A (en) * | 2004-09-29 | 2005-05-11 | 江苏工业学院 | Carrier superfine alloy hydrogenation catalyst for dearomatization and its preparation |
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| US4880524A (en) * | 1987-11-20 | 1989-11-14 | Shell Oil Company | Process for hydrotreating hydrocarbon feeds |
| CN1210759A (en) * | 1997-09-05 | 1999-03-17 | 中国石油化工总公司 | Low nickel content benzene hydrogenating catalyst and its preparing process |
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| CN101172235A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Nano hydrogenation catalysts composition and method of producing the same |
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