CN104549427A - High-quality chemical raw material hydrocracking catalyst and preparation method thereof - Google Patents
High-quality chemical raw material hydrocracking catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a hydrocracking catalyst. The preparation method comprises the following steps: (1) pulping raw material powder of a hydrocracking catalyst carrier component, performing high-temperature and high-speed stirring treatment while pulping, filtering, and drying a filter cake, wherein the hydrocracking catalyst carrier component comprises a molecular sieve, and further comprises at least one of aluminum oxide, amorphous aluminium silicon, amorphous magnesium silicon and clay; (2) shaping the dried material, drying, roasting for activating, and preparing into a catalyst carrier; (3) loading a hydrogenating active component by an impregnation method to obtain the hydrocracking catalyst. Compared with the prior art, the preparation method of the hydrocracking catalyst has the advantage as follows: by the preparation method, a synergistic effect between different components can be further promoted, so that the using performance of the catalyst is improved.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst and preparation method thereof, especially production high-quality industrial chemicals hydrocracking catalyst and preparation method thereof.
Technical background
Enter 21st century, the consumption growth of petrochemicals has exceeded the growth of oil product, and large-scale ethene, large-scale aromatic device will become the important directions of petrochemical industry development.The principle of naphtha according to " suitable alkene is alkene, suitable Fang Zefang, suitable oil then oil then " produced by oil plant, should provide ethylene cracking material, provide the raw material of catalytic reforming again, in order to produce high-knock rating gasoline blend component and aroamtic hydrocarbon raw material.Hydrocracking technology is large with its feedstock oil strong adaptability, production chains, good product quality, can produce the advantages such as high-quality clean fuel oil and industrial chemicals, has become the core of oil-changes-fibre combination of refinery.
The hydrocracking catalyst of the core of hydrocracking technology, the raising of its level depends on the improvement of hydrocracking catalyst performance.Molecular sieve be the component of hydrocracking catalyst most critical, the performance of molecular sieve determines the performance of catalyst.And when the Nomenclature Composition and Structure of Complexes is certain, character and its preparation method of catalyst are closely related.Conventional preparation method's mainly infusion process, coprecipitation and kneading methods etc., are all widely used in hydrocracking catalyst preparation process.Wherein kneading method catalyst preparation process is the simplest, to material and technological requirement not high, but because preparation process is too extensive, each component is disperseed bad in the catalyst, part metals hydrogenation sites is wrapped, can not be played it well active, be generally the less demanding hydrocracking catalyst of Hydrogenation and adopted.The light oil type hydrogen cracking catalysts such as 3825 that the FC-14 catalyst of such as Uop Inc.'s early development and Fushun Petrochemical Research Institute (FRIPP) develop; Coprecipitation technology of preparing process is the most complicated, but uniform component distribution is good, between each component, matching relationship is good, and hydrogenation and cracking activity center evenly can be worked in coordination with and be played a role, ICR series hydrocracking catalyst many employings coprecipitation preparation of Chevron company exploitation; Infusion process is prepared hydrocracking and is most widely used, the method first prepares the carrier that high intensity, porous property has certain geometrical shape, then metal component is added by impregnation methods such as saturated or supersaturation, metal component is enriched in catalyst surface, its Hydrogenation can be given full play to, make catalyst have active and mechanical strength very well, most of trade mark hydrocracking catalyst of existing marketing all adopts infusion process to prepare.The preparation process of conventional catalyst preparation method is more extensive, and the machinery that the mutual mixing of each component adopts is dry mixed, and there is component secondary granularity after shaping large, the problem that micro Distribution is bad, is difficult to give full play of its catalytic activity.
CN200910188113.8 gives a kind of twin crystal type Y molecular sieve that adopts as hydrocracking catalyst predominant cracking component, has prepared the hydrocracking catalyst can producing high-quality tail oil ethylene cracking material.But the method is only carried out the innovation of molecular sieve methods for the raising of tail oil quality, do not innovate to some extent in preparation method, catalyst performance improves limited.CN96109702.7 and CN97121663.0 all provides the method adopting infusion process to prepare high-activity hydrocracking catalyst, dipping solution is configured formed by ammonium metatungstate, nickel nitrate, for the carrier prepared catalyst of this immersion liquid dipping containing Y zeolite, refractory inorganic oxides, performance obtains obvious lifting.CN201010509144.1 gives and adopts the method for co-precipitation to prepare high activity, high intermediate oil selective hydrogenation Cracking catalyst, this catalyst take amorphous aluminum silicide as carrier, Y zeolite through special modification is acidic components, with VI B race metal and VIII race's metal for hydrogenation active component, with IV B race metal for co-catalyst, achieve good effect.CN88103069.4 gives the various powder of a kind of employing and carries out kneading and compacting hydrocracking catalyst preparation method, its carrier is by being cross-linked regularly interstratified mineral clay and aluminium oxide forms, active component is group vib and/or VIII non-noble metal j element in the periodic table of elements, is applicable to mild hydrocracking technical process.CN201010535641.9 gives a kind of special hydrocracking catalyst dipping method, and adopt Y zeolite as Cracking Component, the method first by metal impregnation on the carrier powder of aluminium oxide and/or amorphous aluminum silicide, and then with molecular sieve mixed-forming, then calcination activation is carried out, prepare hydrocracking catalyst, this catalyst has very high catalytic activity, has large specific area and pore volume can the product such as voluminous naphtha and liquefied gas simultaneously.
But in above-mentioned hydrocracking catalyst preparation process, only simple mechanical mixture between each carrier component of hydrocracking, often kind of component is all that the offspring form of reuniting exists in the catalyst, does not realize it and disperses in the catalyst uniformly, be difficult to give play to best performance.CN200610134152.6 discloses a kind of preparation method of hydrogenation catalyst.Adopt a kind of carrier material containing molecular sieve and amorphous aluminum silicide, adopt infusion process or coprecipitation to prepare final catalyst.Carrier material adopts the method preparation introducing molecular sieve pulp in amorphous aluminum silicide plastic process, improve molecular sieve distribution situation in silica-alumina supports, but both synergies fails to give full play to.
Summary of the invention
For the weak point of above-mentioned preparation method, the invention provides a kind of preparation method of hydrocracking catalyst, the synergy between different component can be promoted further, improve the serviceability of catalyst.
Hydrocracking catalyst preparation method of the present invention, comprises following content:
(1) material powder of carrier of hydrocracking catalyst component is pulled an oar, carry out High Temperature And Velocity stir process while making beating, then filter, filtration cakes torrefaction; Carrier of hydrocracking catalyst component comprises molecular sieve, comprises at least one in aluminium oxide, amorphous aluminum silicide, amorphous silicon magnesium and clay simultaneously;
(2) by material forming, drying, calcination activation after above-mentioned drying, catalyst carrier is prepared;
(3) adopt infusion process load hydrogenation active component, obtain hydrocracking catalyst.
In the inventive method, the molecular sieve for catalyst support component can be one or more in Y zeolite, beta-molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesopore molecular sieve etc.Required molecular sieve can require according to serviceability the modification carrying out being suitable for.In hydrocracking catalyst, carrier component material can also comprise acid more weak inorganic refractory oxide, is generally aluminium oxide (comprising the aluminium oxide containing auxiliary agent), during use generally with aluminum hydroxide solid elastomer powder for raw material.Acidic support material comprises molecular sieve and amorphous acidic components.Amorphous acidic components comprise amorphous aluminum silicide, amorphous silicon magnesium, clay etc.The raw material with large pore volume, bigger serface in the preferred this area such as amorphous acidic components and aluminium oxide.By weight content in final catalyst, the general content of acidic support material is 1% ~ 60%, and hydrogenation active component is generally 15% ~ 50% with oxide basis weight content in the catalyst, is preferably 20% ~ 40%, simultaneously can also salic less than 50%.Hydrogenation activity group is generally one or more in W, Mo, Ni, Co.The concrete consumption of often kind of carrier component is specifically determined according to the demand used.
The inventive method, can contain water soluble organic substance in the slurries of step (1).Water soluble organic substance comprises one or more in glycerine, acrylate, sucrose, phenol.By the liquid weight of preparation slurries, water soluble organic substance content is 0.5% ~ 10.0%.The water-miscible organic solvent contained in slurries, not only can increase viscosity and the surface tension of solution, the shearing force improved in the high-temperature process stirred destroys solid particle secondary particle structure, promote the interaction of each component, also can decompose in follow-up roasting process, carrier component is played to the effect of reaming, improve the pore structure of catalyst to a certain extent.In step (1) mixing speed be 400 turns/min ~ 1600 turn/min, preferably 600 ~ 1200 turns/min, controlling slurry system temperature is 65 ~ 95 DEG C, preferably 70 ~ 85 DEG C.Processing time is 2 ~ 6h, after process, slurries is carried out centrifugal filtration rapidly, by filter cake at 100 ~ 180 DEG C of drying 2 ~ 6h.
In the inventive method, shaping, the dry and roasting of catalyst carrier can adopt this area conventional method.Concrete as, material after drying is placed in roller, adds sour peptizing agent or binding agent, extrusion aid etc., through fully rolling aftershaping, then dry, calcination activation, prepares preformed catalyst carrier.Peptizing agent is generally acid solution in step (2), and can be inorganic acid, also can be organic acid, as one or the mixed acid of the organic acids such as nitric acid, hydrochloric acid, sulfuric acid, formic acid, acetic acid, ethanedioic acid, citric acid and/or phosphoric acid.The shape of extrusion carrier can be cylindrical, clover, bunge bedstraw herb, and irregular bar shaped.The sintering temperature of carrier is generally 300 ~ 600 DEG C, and roasting time is generally 2 ~ 10 hours.
In the inventive method, infusion process load hydrogenation active component is this area conventional method.Generally specific as follows: preparation is containing the metal compound solution of hydrogenation active component, hydrogenation active component is generally one or more of group vib and VIII metal, as W, Mo, Ni and Co, wherein VIB is ammonium salt or acidic oxide, concrete as at least one in molybdic acid, para-molybdic acid, molybdate, paramolybdate, wolframic acid, metatungstic acid, ethyl metatungstic acid, tungstates and metatungstate, wherein preferred ammonium paramolybdate and/or metatungstic acid ammonium salt.VIII metal adopts it to have water soluble salt, concrete as inorganic acid salts such as nitrate, halate, sulfate, phosphate, preferably nitrate; Also can be the acylates such as formates, acetate, oxalate, citrate and tartrate, preferred acetate.Suitable adjuvant component can be added as required, as contained the compound of one or more in P, F, B, Zr, Ti etc. in dipping solution in dipping solution.Be the ratio of 1:2 ~ 1:5 by carrier in solid-liquid volume ratio, carry out supersaturation dipping, dip time is 2 ~ 5h, filters redundant solution, and dry, roasting, obtains catalyst prod of the present invention.
Hydrocracking catalyst prepared by the inventive method has following character, and specific area is 120m
2/ g ~ 450m
2/ g, is preferably 160m
2/ g ~ 400m
2/ g; Pore volume is 0.20cm
3/ g ~ 0.50cm
3/ g, is preferably 0.30cm
3/ g ~ 0.45cm
3/ g, hydrogenation active component for 15% ~ 50%, is preferably 20% ~ 40% with oxide basis total content.
The inventive method adopts Precise control means, adopt in catalyst preparation process and the powder of each carrier component is carried out high frequency stirring under the high temperature conditions, under utilizing high temperature, the fast solid particle of molecular motion velocities is unstable, destroy solid particle secondary particle structure, the component particles of originally reuniting is tied poly-in the liquid phase, makes to exist in slurry system primary particle or nano level particle according to a certain ratio.Then, by slurry system by centrifugal filtration, Separation of Solid and Liquid is realized rapidly, and carry out drying, make the fine particle of each component according to proportioning from being newly combined into new offspring, thus each component better can play synergy, catalyst performance obtains and obviously promotes.
The present invention is not only applicable to multi-component hydrocracking catalyst preparation process, is also applicable to the preparation of other load class multicomponent catalyst.
In the preparation process of hydrocracking catalyst of the present invention, the making beating aqueous solution and metal impregnation liquid all can recycle.Preparation method is simple, and be easy to operation, the prices of raw and semifnished materials are cheap, are suitable for the preparation of various extruded moulding catalyst or carrier, and without particular/special requirement, existing equipment just can realize.
Detailed description of the invention
The inventive method adopts the mixed processing mode of high-temperature liquid-phase and high-speed stirred to substitute conventional machinery and is dry mixed, and changing viscosity and the surface tension of solution, improving the depolymerization effect of agglomerated particles by adding water-miscible organic solvent.Increase high-speed stirred and improve the means such as system temperature, increase applying shearing force and improve Particles Moving speed, each carrier component powdered granule of reuniting is made to tie poly-in the liquid phase, form nanoscale or primary particle particle, then through centrifugal filtration fast, dry, each component is made to regroup into new offspring according to special ratios, thus make each carrier component can realize the dispersed of microcosmic according to macroscopical proportioning, each component can better play collaborative effect, and catalyst performance obtains and promotes further.
A kind of concrete preparation process of hydrocracking catalyst of the present invention is as follows:
(1) contents on dry basis that hydrogenation splits catalyst carrier material is measured, as the contents on dry basis of the materials such as Modified Zeolite Y, aluminum hydroxide solid elastomer and contained amorphous silica-alumina dry glue.A certain amount of said components is taken in ratio needed for catalyst carrier, be placed in the solution (also can be pure water solution) containing water-miscible organic solvent that high temperature and high speed stirs, solid-to-liquid ratio is 1:5 ~ 1:20, beating time is 2 ~ 5h, then centrifugal filtration is carried out, realize Separation of Solid and Liquid, by filter cake under 100 ~ 180 DEG C of conditions dry 2 ~ 6 hours.
(2) filter cake of above-mentioned drying is placed in roller, add sour peptizing agent or binding agent, the extrusion aids etc. such as nitric acid, after fully rolling, form the paste shape that can squeeze, then extruded moulding, orifice plate can be cylinder, clover, bunge bedstraw herb or other irregular strip, cut to lengthen 3 ~ 8mm.Wet bar to be carried out under 120 ~ 200 DEG C of conditions dry 2 ~ 6 hours, calcination activation, activation temperature 300 ~ 600 DEG C, time 2 ~ 6h, prepares preformed catalyst carrier, then measures its water absorption rate.
(3) for tungstenic nickel hydrogenation metal catalyst, the preparation of non-noble hydrogenation metal salting liquid: get a certain amount of deionized water under stirring, add nickel nitrate crystal gradually, treat solution clear, add ammonium metatungstate crystal, after all dissolving, static, filter, obtain metal impregnation solution, wherein WO
3content 30.0 ~ 60.0gWO
3/ 100mL, NiO content 8.0 ~ 15.0gNiO/100mL.
(4) step (2) obtains and contains carrier strip in the ratio of solid-to-liquid ratio 1:2 ~ 1:5, carries out supersaturation dipping, time 2 ~ 5h, filter redundant solution, under 120 ~ 200 DEG C of conditions, drying 2 ~ 6 hours, then carries out calcination process, temperature 250 ~ 550 DEG C, time 2 ~ 6h, obtains catalyst prod of the present invention.Cut to lengthen 3 ~ 8mm.
In carrier of hydrocracking catalyst of the present invention, the method for modifying of molecular sieve used can be hydrothermal treatment consists or EDTA, SiCl
4, (NH
4)
2siF
6, the chemical dealuminization modification method such as phosgene or oxalic acid, and use acid, alkali, the hydro-thermal of salt formula complexing agent and the molecular sieve of the method for modifying process such as chemical dealuminization combines.The character of modified molecular screen used is: silica alumina ratio is 3 ~ 100, is preferably 10 ~ 60, Na
2o content≤0.5wt%, meleic acid amount is 0.1 ~ 1.2mmol/g, preferably 0.2 ~ 0.6mmol/g.
The aluminium oxide that the present invention uses or amorphous aluminum silicide are generally selected and can be selected existing goods, pore volume 0.5 mL/g ~ 1.8mL/g, and specific area is 220m
2/ g ~ 550m
2/ g, meleic acid amount is 0.05 ~ 0.70mmol/g.
The present invention selects metal salt solution, is generally group vib and group VIII metal salt, and as one or more of the saline solution of the metals such as W, Mo, Ni, Co, VIII slaine is water-soluble organic acid salt, and solution concentration is generally 8.0 ~ 20.0g metal/100mL.
The following examples are for illustrating in greater detail the preparation method of carrier of the present invention, but scope of the present invention is not only limited to the scope of these embodiments.
The large pore molecular sieve used in embodiment for Modified Zeolite Y be that commercially available H type Y molecular sieve is through the Modified Zeolite Y of 500 DEG C of hydrothermal treatment consists after 2 hours.Mesoporous molecular sieve is that modified ZSM-5 H type molecular sieve is through the modified ZSM-5 type molecular sieve of 500 DEG C of hydrothermal treatment consists after 2 hours.
The aluminum hydroxide solid elastomer powder used in embodiment produces 3824 macroporous aluminium oxides for Tianjin Tian Jiu company, 400 DEG C of roastings after 3 hours character be pore volume 0.82mL/g, specific area 323m
2/ g.
The contained amorphous silica-alumina dry glue powder used in embodiment produces 3903 amorphous aluminum silicides for Tianjin Tian Jiu company, 400 DEG C of roastings after 3 hours character be pore volume 0.76mL/g, specific area 286m
2/ g, meleic acid 0.744mmol/g.
Embodiment 1
By final hydrocracking catalyst weighing scale containing Y molecular sieve 30%, containing nickel oxide 5.0%, containing tungsten oxide 22.0%, surplus is aluminium oxide.Select Above-mentioned catalytic agent raw materials: modified Y molecular sieve and aluminum hydroxide solid elastomer powder.
Catalyst preparation process is as follows: Modified Zeolite Y and aluminum hydroxide solid elastomer powder are inserted, in 5% glycerin solution that the weight content that temperature is 80 DEG C is 900 turns/min with mixing speed is, stir 3h, centrifugal filtration, Separation of Solid and Liquid, drying 4 hours at 120 DEG C.Mixed with extrusion aid, sesbania powder by dry cake and put into roller and roll, adding concentration is 4gHNO
3/ 100mL dilute nitric acid solution carries out peptization, and being extruded into diameter is 1.5mm column type, and wet bar at 120 DEG C dry 4 hours, 550 DEG C of roastings 3 hours, prepares catalyst carrier.Then adopt supersaturation mode to flood W-Ni solution, Separation of Solid and Liquid, at 120 DEG C, drying 4 hours, 500 DEG C of roastings 3 hours, prepares finished catalyst.
Catalyst numbering is respectively HC-1.
Embodiment 2
By final hydrocracking catalyst weighing scale containing Y molecular sieve 30%, containing nickel oxide 5.0%, containing molybdenum oxide 15.0%, surplus is aluminium oxide.Select Above-mentioned catalytic agent raw materials: modified Y molecular sieve and aluminum hydroxide solid elastomer powder.
Preparation method is with embodiment 1, and difference is: raw material to be placed in temperature be 80 DEG C and mixing speed is the aqueous solution of 800 turns/min.Obtain catalyst and be numbered HC-2.
Embodiment 3
By final hydrocracking catalyst weighing scale containing modified Y molecular sieve 10%, amorphous aluminum silicide 50%, containing nickel oxide 5.0%, containing tungsten oxide 22.0%, surplus is aluminium oxide.Select Above-mentioned catalytic agent raw materials: modified Y molecular sieve, amorphous aluminum silicide and aluminum hydroxide solid elastomer powder.
Preparation method is with embodiment 1, and difference is: the 10% acrylate aqueous solution that to be the weight content of 800 turns/min be that raw material to be placed in temperature be 70 DEG C and mixing speed.Obtain catalyst and be numbered HC-3.
Embodiment 4
By final hydrocracking catalyst weighing scale containing Modified Zeolite Y 40%, containing ZSM-5 molecular sieve 20%, amorphous aluminum silicide 10%, containing nickel oxide 5%, select Above-mentioned catalytic agent raw materials containing tungsten oxide 22.0%: modified Y molecular sieve, modified zsm-5 zeolite, 3824 aluminum hydroxide solid elastomer powder and 3903 contained amorphous silica-alumina dry glue powder.
Preparation method is with embodiment 1, and difference is: raw material to be placed in temperature be 100 DEG C and mixing speed 5% phenol solution that to be the weight content of 700 turns/min be.Obtain catalyst and be numbered HC-4.
Comparative example 1
According to catalyst composition and the raw material of embodiment 1, first support material is made catalyst carrier, carrier shaping use 4.0gHNO
3/ 100mL dilute nitric acid solution, as sour peptizing agent, adopts conventional infusion process load hydrogenation active component, and metallic solution is the high concentration metal mixed solution that nickel nitrate and ammonium metatungstate are prepared, and obtains catalyst and is numbered HC-B1.
Comparative example 2
According to catalyst composition and raw material and the preparation method of embodiment 2, unlike adopting conventional speed of agitator of pulling an oar and temperature, being respectively 300 turns/min and 40 DEG C, obtaining catalyst and be numbered HC-B1.
Comparative example 3
By the catalyst composition of embodiment 3 and the method for raw material and CN200610134152.6, in the process of amorphous aluminum silicide plastic, introduce molecular sieve and aluminum hydroxide solid elastomer powder slurries, gelling temperature and mixing speed are with embodiment 3, and catalyst is numbered HC-B3.
Instrumental analysis and activity rating are carried out to above each routine catalyst.Each routine catalyst physico-chemical property is shown in Table 1.Table 1. catalyst physico-chemical property
Note: R
bETfor the average pore diameter that BET method measures.
Evaluating apparatus adopts on 200mL small hydrogenation device and carries out, and carries out presulfurization before activity rating to catalyst.The raw materials used oil nature of evaluation of catalyst activity is in table 2, and catalyst reaction performance comparison the results are shown in Table 3.Evaluate HC-1, HC-2, HC-B1 and HC-B3 and carry out comparative evaluation, then feedstock oil first directly enter hydrocracking catalyst bed through Hydrobon catalyst bed, through Hydrobon catalyst bed control organic nitrogen content in feedstock oil lower than 20 micrograms/gram.
Table 2. feedstock oil character
Table 3. catalyst reaction performance comparison evaluation result
* industrial chemicals total recovery=heavy naphtha yield+tail oil yield
As can be seen from above experimental data, catalyst prepared by the inventive method has higher Hydrogenation and cracking performance, and product quality is better, and reaction temperature is lower.
Claims (14)
1. a hydrocracking catalyst preparation method, is characterized in that: comprise following content:
(1) material powder of carrier of hydrocracking catalyst component is pulled an oar, carry out High Temperature And Velocity stir process while making beating, then filter, filtration cakes torrefaction; Carrier of hydrocracking catalyst component comprises molecular sieve, comprises at least one in aluminium oxide, amorphous aluminum silicide, amorphous silicon magnesium and clay simultaneously;
(2) by material forming, drying, calcination activation after above-mentioned drying, catalyst carrier is prepared;
(3) adopt infusion process load hydrogenation active component, obtain hydrocracking catalyst.
2. method according to claim 1, is characterized in that: the molecular sieve for catalyst support component is one or more in Y zeolite, beta-molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesopore molecular sieve.
3. method according to claim 1 and 2, it is characterized in that: in hydrocracking catalyst, carrier component material comprises acidic support material, acidic support material comprises molecular sieve and amorphous acidic components, by weight content in final catalyst, acidic support material content is 1% ~ 60%, hydrogenation active component for 15% ~ 50%, is preferably 20% ~ 40% with oxide basis weight content in the catalyst, simultaneously can also salic less than 50%.
4. method according to claim 3, is characterized in that: hydrogenation activity group is one or more in W, Mo, Ni, Co.
5. method according to claim 1, is characterized in that: containing water soluble organic substance in the slurries of step (1).
6. method according to claim 5, is characterized in that: by the liquid weight of preparation slurries, water soluble organic substance content is 0.5% ~ 10.0%.
7. method according to claim 5, is characterized in that: water soluble organic substance comprises one or more in glycerine, acrylate, sucrose, phenol.
8. method according to claim 1, is characterized in that: in step (1) mixing speed be 400 turns/min ~ 1600 turn/min, preferably 600 ~ 1200 turns/min, controlling slurry system temperature is 65 ~ 95 DEG C, preferably 70 ~ 85 DEG C.
9. method according to claim 1, is characterized in that: in step (1), the processing time is 2 ~ 6h.
10. method according to claim 1, is characterized in that: after process terminates, slurries are carried out centrifugal filtration rapidly.
11. methods according to claim 1, is characterized in that: the filter cake after filtering in step (1) is at 100 ~ 180 DEG C of drying 2 ~ 6h.
12. methods according to claim 1, is characterized in that: in step (2), the sintering temperature of carrier is 300 ~ 600 DEG C, and roasting time is 2 ~ 10 hours.
13. methods according to claim 1, it is characterized in that: infusion process load hydrogenation active component process is as follows: preparation is containing the metal compound solution of hydrogenation active component, hydrogenation active component is one or more of group vib and VIII metallic element, be the ratio of 1:2 ~ 1:5 by carrier in solid-liquid volume ratio, carry out supersaturation dipping, dip time is 2 ~ 5h, filter redundant solution, drying, roasting, obtains catalyst.
The hydrocracking catalyst that described in the arbitrary claim of 14. claim 1 to 13 prepared by method, is characterized in that: hydrocracking catalyst has following character, specific area is 120m
2/ g ~ 450m
2/ g, is preferably 160m
2/ g ~ 400m
2/ g; Pore volume is 0.20cm
3/ g ~ 0.50cm
3/ g, is preferably 0.30cm
3/ g ~ 0.45cm
3/ g; Hydrogenation active component for 15% ~ 50%, is preferably 20% ~ 40% with oxide basis total content.
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| CN106944126A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | hydrocracking catalyst intermediate, hydrocracking catalyst and preparation method thereof |
| CN108714433A (en) * | 2018-05-11 | 2018-10-30 | 北京高新利华科技股份有限公司 | A kind of hydrocracking catalyst and its preparation method and application |
| CN113731385A (en) * | 2021-08-20 | 2021-12-03 | 宜昌苏鹏科技有限公司 | Catalyst carrier for preparing hydrogen peroxide by fixed bed anthraquinone process and preparation method of catalyst |
| CN114100681A (en) * | 2020-08-26 | 2022-03-01 | 中国石油天然气股份有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
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| CN108714433A (en) * | 2018-05-11 | 2018-10-30 | 北京高新利华科技股份有限公司 | A kind of hydrocracking catalyst and its preparation method and application |
| CN108714433B (en) * | 2018-05-11 | 2020-10-30 | 北京高新利华科技股份有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
| CN114100681A (en) * | 2020-08-26 | 2022-03-01 | 中国石油天然气股份有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
| CN113731385A (en) * | 2021-08-20 | 2021-12-03 | 宜昌苏鹏科技有限公司 | Catalyst carrier for preparing hydrogen peroxide by fixed bed anthraquinone process and preparation method of catalyst |
| CN113731385B (en) * | 2021-08-20 | 2023-11-28 | 宜昌苏鹏科技有限公司 | Catalyst carrier for preparing hydrogen peroxide by fixed bed anthraquinone method and preparation method of catalyst |
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