CN1488718A - Hydroprocessing catalyst for heavy oil and preparing method thereof - Google Patents
Hydroprocessing catalyst for heavy oil and preparing method thereof Download PDFInfo
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- CN1488718A CN1488718A CNA021331251A CN02133125A CN1488718A CN 1488718 A CN1488718 A CN 1488718A CN A021331251 A CNA021331251 A CN A021331251A CN 02133125 A CN02133125 A CN 02133125A CN 1488718 A CN1488718 A CN 1488718A
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Abstract
The present invention relates to a preparation method of hydrogenation treatment catalyst. Said catalyst is prepared by loading molybdenum, nickel and phosphorus on a phosphorus and silicon contained alumina carrier prepared by adopting a special method, and said carrier prepared by special method is prepared by adding phosphorus adjuvant in the course of precipitation and ageing process and adding nano silicon-containing compound in the course of carrier forming process, for example, adding silicon dioxide. As compared with existent catalyst it has higher activity for hydro-desulfurization and hydro-denitrification of heavy oil, specially heavy fraction.
Description
1, technical field
The invention belongs to catalyst for hydroprocessing of heavy oil and preparation method thereof, it is applicable to the particularly hydrotreatment of heavy distillate of hydrotreatment of mink cell focus.
2, technical background
In general, the hydrotreating catalyst great majority of hydrocarbon feed are carrier with the aluminum oxide, with a certain active ingredient that is combined as of elements such as tungsten, molybdenum, nickel and cobalt.In order further to improve the activity and the activity stability of hydrotreating catalyst, take various methods, as improved preparation condition, carrier is carried out modification, add auxiliary agent etc.Wherein selected auxiliary agent has silicon, phosphorus, fluorine, boron, zirconium, titanium etc., and the method for adding auxiliary agent has coprecipitation method, mechanical mixing and pickling process.Chinese invention patent CN1075548C introduce to adopt even kneading method of a step, is about to prepare the preparation method of the hydrocarbon hydrogenizing treamtent catalyst that carrier and two steps of preparation catalyzer integrate.By pseudo-boehmite and contain the compound of fluorine element,,, prepare Mo-Ni-P (F)/Al through three sections constant temperature calcinings then through mixing, kneading, extruded moulding with Mo-Ni-P solution with high metal concentration
2O
3Hydrotreating catalyst.This catalyst preparation process is simple, and production cost is low, can obtain the higher catalyzer of metal component content; But because the intervention of metal component, the competition when each species interacts with pseudo-boehmite is inevitably, and this will weaken phosphate builder and/or fluorine auxiliary agent to the promoter action of catalyst performance, be unfavorable for improving catalyzer integral body hydrogenation performance.Chinese invention patent CN1048037C introduces is to be carrier with a kind of siliceous and macroporous aluminium oxide of phosphorus and the carrier that little porous aluminum oxide is mixed and made into, the hydrotreating catalyst of nickel-loaded, molybdenum, phosphorus active ingredient.Silicon additive in the catalyzer adds in preparation pseudo-boehmite process, and silicon source (water glass) is colloidalmaterial, this material and adding method thereof exist the influence of process to the character and/or the microtexture of aluminum oxide, cause the unhomogeneity of carrier character easily; Simultaneously because carrier had not only added silicon but also twice reaming that phosphorate brings pore distribution than disperse, thereby influence the surface properties and the use properties of carrier, be unfavorable for improving use properties accordingly such as catalyst activity.
3, summary of the invention
At the deficiencies in the prior art, the invention provides a kind of phosphorus and silicon additive in catalyst preparation process, introduced step by step, neither increase additional step, can obtain the preparation method of the more concentrated and active high catalyst for hydro-processing heavy distillate of large pore volume, high surface and pore distribution again.
Hydrotreating catalyst of the present invention is carrier with the aluminum oxide, with phosphorus and silicon is auxiliary agent, is active ingredient with vib metal and/or group VIII metal, and the pore volume of catalyzer is 0.30～0.40ml/g, be preferably 0.32～0.38ml/g, specific surface area is at 170～190m
2/ g is preferably 180～190m
2/ g, the pore size distribution of mean pore size 3-15nm accounts for more than 85% of total aperture, and is preferred more than 90%, is preferably 92%～96%, and tight tap density is preferably 0.94～0.97g/ml greater than 0.90～97g/ml.The TPD-NH of catalyzer
3Total acid content is 0.6～0.8mmol/g, is preferably 0.7～0.8mmol/g.
The preparation process of hydrotreating catalyst of the present invention is:
(1) phosphorous aluminium hydroxide and/or ratio adding kneading machine on demand such as aluminum oxide and extrusion aid are mixed;
(2) add mixed pinching such as nanometer silicon-containing compound (as nano silicon), peptization aqueous acid and become plastic;
(3) with gained plastic extruded moulding, gained wet bar drying, roasting;
(4) with steeping fluid the gained strip is flooded, the wet bar drying of dipping, roasting promptly make catalyzer of the present invention.
Above-mentioned phosphorated aluminium hydroxide is to contain aluminum salt solution to mix under agitation condition with precipitation agent, obtain aluminum hydroxide precipitation, wear out then, wash, filter the filter cake making beating that obtains, and add P contained compound, the filter cake of dry filter obtains phosphorated aluminium hydroxide again.Containing aluminum salt solution and precipitation agent can be aluminum chloride and ammoniacal liquor, Tai-Ace S 150 and ammoniacal liquor, aluminum nitrate and ammoniacal liquor, Tai-Ace S 150 and sodium metaaluminate, sodium metaaluminate and nitric acid, sodium metaaluminate and carbonic acid gas etc., does not preferably have the Tai-Ace S 150 and the sodium metaaluminate method of ammonia and nitrogen pollution and produces.Precipitation and condition such as aging can suitably be adjusted according to required aluminum oxide character.P contained compound is selected from the ammonium salt of phosphoric acid or phosphoric acid.The nanometer silicon-containing compound is a nano silicon, and particle diameter is 6～100nm.The peptization aqueous acid is the aqueous solution of nitric acid.The Mo-Ni-P solution of steeping fluid for adopting technical grade molybdenum oxide, basic nickel carbonate and phosphorous aqueous acid to be made into.
Catalyzer of the present invention has a series of performances that help the heavy distillate hydrotreatment: large pore volume can guarantee that reaction molecular passes in and out in the hole of catalyzer smoothly, high-specific surface area helps metal and disperses, provides more active centre, the pore size distribution of concentrating can increase the tight tap density of catalyzer, thereby increase catalyst volume pore volume and volumetric surface area, improve its active and stable corresponding to volume space velocity, the hydrogenation that higher acid amount helps heavy distillate takes off the impurity reactive activity.
The present invention about the advantage of method for preparing catalyst is:
(1) adopt the phosphorous aluminium hydroxide pore distribution concentration of the inventive method preparation, pore volume, specific surface area are bigger, and peptization is good, is easy to moulding, can reduce the consumption of peptization acid, reduces acid to alumina pore structural damage effect; In the extruded moulding process, introduce simultaneously the needed silicon additive of preparation catalyzer, can keep the characteristics of phosphorous aluminium hydroxide pore distribution concentration, solved with alumina supporter in the prior art and add the problem that phosphorus and silicon ribbon come the pore distribution disperse simultaneously.
(2) the silicon source of the silicon additive of the inventive method employing is nanometer silicon-containing compound such as nano silicon, this silicon source and adding method thereof can make the hole wall of catalyzer thin and closely knit, help increasing catalyzer pore volume, specific surface area and tight tap density, pore size distribution is more concentrated than the catalyzer of CN1048037C method preparation, catalyzer can obtain maximum volume pore volume and volumetric surface area, and hydrogenating desulfurization, denitrification activity are higher than the CN1048037C catalyzer far away.
(3) method for preparing catalyst of the present invention does not have the ammonia and nitrogen pollution problem, and production cost reduces.
4, embodiment
The group vib metal that catalyzer of the present invention uses is tungsten and/or molybdenum, and the group VIII metal is nickel and/or cobalt, is benchmark with final catalyst weight, catalyzer contains molybdenum oxide 18～28%, nickel oxide 2～6%, silicon-dioxide 0.5～7%, Vanadium Pentoxide in FLAKES 0.5～3%, all the other are aluminum oxide.
The present invention about the concrete way of hydrotreating catalyst preparation is:
(1) selecting Tai-Ace S 150 and sodium metaaluminate for use is raw material, under conditions such as stirring and suitable precipitation, mix, obtain aluminum hydroxide precipitation, wear out, wash, filter the filter cake making beating that obtains then, add phosphoric acid, and then the filter cake of dry filter, obtaining phosphorated aluminium hydroxide, slurry temperature is controlled to be 30～90 ℃.
(2) phosphorous aluminium hydroxide and commodity aluminium hydroxide and extrusion aid etc. are mixed in a certain amount of ratio adding kneading machine, mixed 5～20 minutes;
(3) peptizing agent that contains nano silicon (the silicon-dioxide add-on is 0.5～10%) of adding calculated amount, mixing to pinch became plastic in 20～40 minutes;
(4) with gained plastic extruded moulding, the wet bar of gained is 90～150 ℃ of dryings 4～10 hours, then 450～650 ℃ of roastings 1～6 hour, promptly get phosphorous and alumina supporter silicon.
The pore volume of above-mentioned phosphorus-containing alumina is 0.6～1.0ml/g, and average pore diameter is 6.0～10.0nm, and specific surface area is 380～450m
2/ g; The pore volume of commodity aluminum oxide is 0.2～0.6ml/g, and average pore diameter is 2.0～10.0nm, and specific surface area is 200～300m
2/ g; The weight ratio of mixture of phosphorous aluminium hydroxide and commodity aluminium hydroxide is 1: 1～1: 4.The adding method of nanometer silicon-containing compound can be in the following way: 1. the nanometer silicon-containing compound mixes and pinches with the above-mentioned aluminium source material that contains again after wetting with the peptization aqueous acid, 2. mix (making peptizing agent) with commodity aluminium hydroxide with peptization aqueous acid and nanometer silicon-containing compound, and then mix and to pinch with the above-mentioned aluminium source material that contains, 3. the nanometer silicon-containing compound mixes and pinches with wetting back of deionized water and the above-mentioned aluminium source material that contains, 4. substep adds, above-mentioned 1., wantonly two steps or two steps add respectively in above 2. and 3., and then contain with above-mentioned that aluminium source material is mixed to be pinched.Preferably with after phosphorous aluminium hydroxide and the mixing of part commodity aluminium hydroxide, add the peptizing agent made from another part commodity aluminium hydroxide and nano silicon, peptization aqueous acid (being generally nitric acid), wherein the part of sneaking into of commodity aluminium hydroxide is 1: 1～25: 1 with the weight ratio of doing the peptizing agent part.
(4) get certain amount of industrial level molybdenum oxide, basic nickel carbonate and phosphorous aqueous acid and make Mo-Ni-P solution;
(5) and alumina supporter silicon phosphorous to gained with Mo-Ni-P solution floods, and the wet bar of dipping after 0.5～6 hour, through 430～550 ℃ of roastings 1～4 hour, promptly makes catalyzer of the present invention 90～150 ℃ of dryings again.
The catalyzer of the inventive method preparation is used for the hydrotreatment process of mink cell focus, and the hydrotreatment process in particular for heavy distillate has higher hydrogenating desulfurization, denitrification activity.
Further specify technical solution of the present invention by the following examples.
Embodiment 1
(1) preparation of phosphorous aluminium hydroxide
In a clean container, add the 2500ml deionized water, be warming up to 65 ℃, under agitation condition, with proportion is that 1.14 aluminum sulfate aqueous solution and proportion are 1.37 the sodium metaaluminate aqueous solution, joins simultaneously in the deionized water of stirring, keeps 65 ℃ of temperature, pH is 8.5, and the reinforced time is 75 minutes.After stopping to feed in raw material, aging 60 minutes, the filter cake after the filtration added the deionized water pulp, and washing material 4 times makes Na in the material
+Content＜0.05m%, SO
4 2-Content＜1.2m%, Fe
3+Content＜0.08m%, then filtering aluminum hydroxide filter cake is joined in the solution of 2.0L deionized water and 45g 85m% phosphoric acid making beating evenly, control slurry temperature be 85 ℃, the filter cake of 40 minutes after-filtration of pulp directly 110 ℃ of dryings after 8 hours abrasive dust stand-by.
(2) preparation of support of the catalyst
Get above-mentioned phosphorous aluminium hydrate powder 157g, commodity aluminium hydrate powder 188g, add the rolling machine mixed grind, mixed grind 20 minutes, add the peptizing agent made from 28g nano silicon (the analytical pure nano silicon that chemical industry company limited in Tianjin produces), 80g commodity aluminium hydroxide and 360g peptization acid (2.5% nitric acid) aqueous solution, mixing to pinch became plastic in 30 minutes; With gained plastic extruded moulding, the wet bar of gained is 110 ℃ of dryings 6 hours, then under airflow, and 500 ℃ of roastings 4 hours.
(3) preparation of Mo-Ni-P dipping solution
Get the technical grade molybdenum oxide respectively and (contain MoO
399%), basic nickel carbonate (containing Ni＞40%), phosphoric acid (contain H
3PO
485%) and deionized water 245g, 65g, 27g and 400g, according to the method configuration MoO of the configuration Mo-Ni-P solution of routine
3Content is 45g/100ml, and NiO content is 10.0g/100ml, and P content is the solution of 3.3g/100ml.
(4) Preparation of catalysts
Placing clean container by (2) gained carrier, add solution by (3) preparation, liquor capacity/vehicle weight=2.5 are soaked after 2 hours and are taken out, and gained wets bar 110 ℃ of dryings 2 hours, then under airflow, 480 ℃ of roastings 4 hours.
Embodiment 2
In embodiment 1, the add-on of 85m% phosphoric acid is changed into 58g by 45g, the charging capacity of other each material and operational condition are all identical with embodiment 1, i.e. the cost example.
Embodiment 3
In embodiment 1, the add-on of 85m% phosphoric acid is changed into 70g by 45g, the nanometer silicon-containing compound use half with the wetting back of the aqueous nitric acid of 30ml 2.5% add, half adds by embodiment 1 adding method, and material mixed pinch, the charging capacity of other each material and operational condition are all identical with embodiment 1, i.e. the cost example.
Embodiment 4
In embodiment 1, the add-on of nano silicon is changed into 21g by 28g, the nanometer silicon-containing compound mixes and pinches with containing aluminium source material with the wetting back of 50ml deionized water, and the charging capacity of other each material and operational condition are all identical with embodiment 1, i.e. the cost example.
Embodiment 5
In embodiment 1, the add-on of nano silicon is changed into 15g by 28g, the nanometer silicon-containing compound mixes and pinches with containing aluminium source material with the wetting back of the aqueous nitric acid of 40ml 2.5%, and the charging capacity of other each material and operational condition are all identical with embodiment 1, i.e. the cost example.
Embodiment 6
In embodiment 1, the add-on of nano silicon is changed into 7g by 28g, the charging capacity of other each material and operational condition are all identical with embodiment 1, i.e. the cost example.
Comparative example 1
This example prepares the process of catalyzer by Chinese patent CN1048037C.
Get the phosphorous and aluminium hydrate powder (physico-chemical property sees Table 1) of silicon of the macropore of 210g Chinese patent CN1048037C preparation, moisture SB aluminum oxide powder 170g, 7g sesbania powder and the 5g citric acid that Germany produces, adding premixed device mixes, premix 15 minutes, add and contain the peptizing agent that nitric acid 2.75m% makes with moisture SB aluminum oxide powder of 45g and 410g, mixing to pinch became plastic in 25 minutes; With gained plastic extruded moulding, the gained strip is 115 ℃ of dryings 6 hours, then under airflow, 500 ℃ of roastings 4 hours, phosphorous and silicon.Get above-mentioned carrier 100g, contain the ammonium hydroxide aqueous solution preimpregnation of 10m% earlier with 250ml, wore out 1 hour under the room temperature, discharge presoak, the wet bar of gained flooded 2.0 hours with isopyknic nickel-molybdenum-phosphorus solution then 110 ℃ of dryings 8 hours, discharge mother liquor, 110 ℃ of dryings 4 hours, under airflow, 500 ± 10 ℃ of roastings 4 hours.Final consisting of of catalyzer: the MoO that gets
3M%25.7, NiOm%3.83, SiO
2M%1.52, P
2O
5Pm%5.29.
Table 1 macropore aluminium hydrate powder physico-chemical property
| Pore volume ml/g | Specific surface area m 2/g | Mean pore size nm | The 3-15nm aperture accounts for total aperture, v% | ??SiO 2??m％ | ????P 2O 5????m％ |
| ??0.998 | ??375 | ??1.05 | ????72.8 | ??3.85 | ????3.67 |
Embodiment 7
Present embodiment is the physico-chemical property and the activity rating result of above each routine catalyzer.
The physico-chemical property of each routine catalyzer sees Table 2.
Adopt density (20 ℃) 0.9084g/cm
3, 332～526 ℃ of boiling ranges, sulphur content 1.05%, nitrogen 0.11%, the Iranian VGO oil of aromatic hydrocarbons 44.2% is stock oil, the comparative evaluation activity of the hydrodenitrification of catalyzer, hydrogenating desulfurization.Be reflected on the 100ml hydrogenation unit and carry out.Catalyzer is packed into behind the reactor, and prevulcanized under hydrogen sulfide atmosphere earlier makes it be converted into sulphided state, and carry out hydrogenation reaction, reaction process condition then: reactive hydrogen power is 14.7MPa, and volume space velocity is 1.0h
-1, hydrogen-oil ratio (v) is 1000: 1.Compare the catalyst reaction activity with control hydrogenated oil nitrogen content＜10 μ g/g, the comparative evaluation the results are shown in Table 3.
By this example as can be known, adopt the catalyzer of the inventive method preparation to have superior physico-chemical property, pore volume is 0.33～0.36ml/g, and specific surface area is 180～190m
2/ g, tight tap density 0.94～97g/ml, especially pore size distribution is more concentrated, and the pore size distribution of mean pore size 3-15nm accounts for 92～96% of total aperture, and the acidity of surperficial solid acid obviously increases, TPD-NH
3Total acid content is 0.7～0.8mmol/g, and 150～400 ℃ weak acid amount and/or middle strong acid amount distribute and account for 90%～95% of total acid content, and strength of acid distributes suitable.Identical in other operational condition, when reaching the identical denitrogenation degree of depth, catalyzer of the present invention is than the desulfurization of CN1048037C catalyst hydrogenation, denitrification activity height, temperature of reaction is low more than 5 ℃.
Table 2 catalyzer physico-chemical property
| Embodiment | Comparative example | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Physico-chemical property | ||||||||
| Pore volume, cm 3/g | ??0.305 | ??0.355 | ??0.337 | ??0.345 | ??0.349 | ??0.350 | ??0.341 | |
| Specific surface area, m 2/g | ??162 | ??187 | ??179 | ??180 | ??185 | ??183 | ??187 | |
| Mean pore size, nm | ??8.1 | ??7.6 | ??7.8 | ??7.6 | ??7.5 | ??7.9 | ??7.7 | |
| 3～15nm aperture accounts for total aperture branch rate, % | ??90.8 | ??95.8 | ??95.2 | ??95.1 | ??95.5 | ??92.8 | ??95.9 | |
| Tap density, g/cm 3 | ??0.910 | ??0.957 | ??0.954 | ??0.945 | ??0.968 | ??0.942 | ??0.949 | |
| Crushing strength, N/mm | ??18.2 | ??20.3 | ??19.6 | ??19.1 | ??20.9 | ??21.7 | ??20.5 | |
| Total acid content (TPD-NH 3)，mmol/g | ??0.580 | ??0.756 | ??0.747 | ??0.741 | ??0.744 | ??0.732 | ??0.705 | |
| Acidity distribution (TPD-NH 3) mmol/g | ?150～250℃ | ??0.210 | ??0.367 | ??0.355 | ??0.323 | ??0.369 | ??0.323 | ??0.337 |
| ?250～400℃ | ??0.198 | ??0.329 | ??0.327 | ??0.357 | ??0.316 | ??0.347 | ??0.305 | |
| MoO 3，m％ | ??25.7 | ??24.9 | ??25.3 | ??25.8 | ??25.1 | ??25.4 | ??25.6 | |
| NiO，??m％ | ??3.83 | ??3.99 | ??4.01 | ??3.86 | ??3.98 | ??4.10 | ??3.98 | |
| P 2O 5，m％ | ??5.29 | ??4.17 | ??4.98 | ??5.19 | ??4.32 | ??3.99 | ??4.01 | |
| SiO 2，m％ | ??1.52 | ??5.9 | ??5.6 | ??5.7 | ??4.5 | ??3.3 | ??1.56 | |
| The silicon source | Water glass | Nano-silicon | Nano-silicon | Nano-silicon | Nano-silicon | Nano-silicon | Nano-silicon | |
Table 3 catalyst activity comparative evaluation result
| Embodiment | Comparative example | Embodiment 1 | Embodiment 3 | Embodiment 4 | Embodiment 6 |
| Temperature of reaction, ℃, | ??378 | ??372 | ??372 | ??371 | ??373 |
| Generate oily sulphur content, μ g/g | ??159 | ??68 | ??49 | ??44 | ??51 |
| Generate oily nitrogen content, μ g/g | ??9.0 | ??8.8 | ??8.3 | ??9.6 | ??7.9 |
Claims (10)
1, a kind of catalyst for hydroprocessing of heavy oil, with the aluminum oxide is carrier, is auxiliary agent with phosphorus and silicon, is active ingredient with vib metal and/or group VIII metal, the pore size distribution that it is characterized in that mean pore size 3-15nm accounts for more than 85% of total aperture, the TPD-NH of catalyzer
3Total acid content is 0.6～0.8mmol/g.
2, according to the described catalyzer of claim 1, the pore volume that it is characterized in that described catalyzer is 0.30～0.40ml/g, and specific surface area is 170～190m
2/ g, the pore size distribution of mean pore size 3-15nm accounts for more than 90% of total aperture.
3, according to the described catalyzer of claim 1, the pore volume that it is characterized in that described catalyzer is 0.32～0.38ml/g, and specific surface area is 180～190m
2/ g, the pore size distribution of mean pore size 3-15nm accounts for 92%～96% of total aperture.
4,, it is characterized in that the TPD-NH of described catalyzer according to the described catalyzer of claim 1
3Total acid content is 0.7～0.8mmol/g.
5, according to the described catalyzer of claim 1, it is characterized in that the group vib metal that described catalyzer uses is tungsten and/or molybdenum, the group VIII metal is nickel and/or cobalt, with final catalyst weight is benchmark, catalyzer contains molybdenum oxide 18～28%, nickel oxide 2～6%, silicon-dioxide 0.5～7%, Vanadium Pentoxide in FLAKES 0.5～3%.
6, according to the described catalyzer of claim 1, it is 92%～96% that the pore size distribution that it is characterized in that described mean pore size 3-15nm accounts for total aperture.
7, the preparation method of the described catalyst for hydroprocessing of heavy oil of a kind of claim 1 is characterized in that adopting following process:
(1) phosphorous aluminium hydroxide and/or aluminum oxide and extrusion aid are mixed;
(2) adding nanometer silicon-containing compound, mixed the pinching of peptization aqueous acid become plastic;
(3) with the moulding of gained plastic, gained wet bar drying, roasting;
(4) with steeping fluid the gained forming composition is flooded, dry, roasting promptly make final catalyzer.
8, in accordance with the method for claim 7, it is characterized in that described nanometer silicon-containing compound is that particle diameter is the nano silicon of 6～100nm.
9, in accordance with the method for claim 7, the preparation process that it is characterized in that described phosphorous aluminium hydroxide and/or aluminum oxide is: contain aluminum salt solution and mix under agitation condition with precipitation agent, obtain aluminum hydroxide precipitation, wear out, wash, filter the filter cake making beating that obtains then, and adding P contained compound, the filter cake of dry filter obtains phosphorated aluminium hydroxide or aluminum oxide again.
10, in accordance with the method for claim 7, the adding method that it is characterized in that described nanometer silicon-containing compound is one of in the following way: 1. the nanometer silicon-containing compound mixes and pinches with the above-mentioned aluminium source material that contains again after wetting with the peptization aqueous acid, 2. mix with peptization aqueous acid and nanometer silicon-containing compound with commodity aluminium hydroxide, and then mix and to pinch with the above-mentioned aluminium source material that contains, 3. the nanometer silicon-containing compound mixes and pinches with wetting back of deionized water and the above-mentioned aluminium source material that contains, 4. substep adds, 1. above-mentioned, 2. wantonly two steps or two steps add respectively in above and 3., and then mix and pinch with the above-mentioned aluminium source material that contains.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02133125 CN1282732C (en) | 2002-10-10 | 2002-10-10 | Hydroprocessing catalyst for heavy oil and preparing method thereof |
| PCT/CN2003/000839 WO2004037408A1 (en) | 2002-10-10 | 2003-09-29 | A silicon-containing alumina support, preparation thereof and a catalyst comprising the alumina support |
| KR1020057006163A KR100884595B1 (en) | 2002-10-10 | 2003-09-29 | A silicon-containing alumina support, preparation thereof and a catalyst comprising the alumina support |
| JP2004545680A JP5006516B2 (en) | 2002-10-10 | 2003-09-29 | Silicon-containing alumina support, method for preparing the same, and catalyst containing the alumina support |
| EP03753239.7A EP1552880B1 (en) | 2002-10-10 | 2003-09-29 | A silicon-containing alumina support, preparation thereof and a catalyst comprising the alumina support |
| CA2501973A CA2501973C (en) | 2002-10-10 | 2003-09-29 | A silicon-containing alumina support, preparation thereof and a catalyst comprising the alumina support |
| AU2003272858A AU2003272858A1 (en) | 2002-10-10 | 2003-09-29 | A silicon-containing alumina support, preparation thereof and a catalyst comprising the alumina support |
| US10/682,221 US6875722B2 (en) | 2002-10-10 | 2003-10-09 | Silicon-containing alumina support, a process for preparing the support and a catalyst containing the support |
| US11/069,034 US7253135B2 (en) | 2002-10-10 | 2005-02-28 | Silicon-containing alumina support, a process for preparing the support and a catalyst containing the support |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02133125 CN1282732C (en) | 2002-10-10 | 2002-10-10 | Hydroprocessing catalyst for heavy oil and preparing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1488718A true CN1488718A (en) | 2004-04-14 |
| CN1282732C CN1282732C (en) | 2006-11-01 |
Family
ID=34145459
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02133125 Expired - Lifetime CN1282732C (en) | 2002-10-10 | 2002-10-10 | Hydroprocessing catalyst for heavy oil and preparing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100435950C (en) * | 2006-09-30 | 2008-11-26 | 厦门大学 | Preparing method for hydrodesulphurization catalyst and start working method thereof |
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| CN101376830B (en) * | 2007-08-27 | 2012-06-27 | 中国石油化工股份有限公司 | Hydrotreating catalyst carrier and preparation thereof |
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| CN101376829B (en) * | 2007-08-27 | 2012-11-21 | 中国石油化工股份有限公司 | Bubbling bed hydrotreating catalyst and preparation thereof |
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2002
- 2002-10-10 CN CN 02133125 patent/CN1282732C/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100435950C (en) * | 2006-09-30 | 2008-11-26 | 厦门大学 | Preparing method for hydrodesulphurization catalyst and start working method thereof |
| CN101376830B (en) * | 2007-08-27 | 2012-06-27 | 中国石油化工股份有限公司 | Hydrotreating catalyst carrier and preparation thereof |
| CN101376832B (en) * | 2007-08-27 | 2012-09-12 | 中国石油化工股份有限公司 | Preparation of bubbling bed hydrotreating catalyst |
| CN101376829B (en) * | 2007-08-27 | 2012-11-21 | 中国石油化工股份有限公司 | Bubbling bed hydrotreating catalyst and preparation thereof |
| CN101942334A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Production method of molecular sieve dewaxing raw material |
| CN101942334B (en) * | 2009-07-09 | 2013-10-09 | 中国石油化工股份有限公司 | Production method of molecular sieve dewaxing raw material |
| CN104667960A (en) * | 2013-11-26 | 2015-06-03 | 中国石油化工股份有限公司 | A catalyst for diesel oil hydrogenation modification and a preparing method thereof |
| CN104667960B (en) * | 2013-11-26 | 2017-04-12 | 中国石油化工股份有限公司 | A catalyst for diesel oil hydrogenation modification and a preparing method thereof |
| CN105983445A (en) * | 2015-02-03 | 2016-10-05 | 中国石油天然气股份有限公司 | Hydrogenation catalyst carrier and preparation method therefor |
| CN105983445B (en) * | 2015-02-03 | 2019-08-02 | 中国石油天然气股份有限公司 | A kind of catalyst carrier for hydrgenating and preparation method thereof |
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