CN1238239A - Catalyst for selective hydrogenation of diolefin as raw material for alkylation of C4 and preparing method thereof - Google Patents
Catalyst for selective hydrogenation of diolefin as raw material for alkylation of C4 and preparing method thereof Download PDFInfo
- Publication number
- CN1238239A CN1238239A CN 98110280 CN98110280A CN1238239A CN 1238239 A CN1238239 A CN 1238239A CN 98110280 CN98110280 CN 98110280 CN 98110280 A CN98110280 A CN 98110280A CN 1238239 A CN1238239 A CN 1238239A
- Authority
- CN
- China
- Prior art keywords
- carrier
- catalyst
- content
- palladium
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
A catalyst for selective hydrogenation of diolefin as raw material for C4 alkylation technically features that it is prepared by carrying Pd or Pd and Au on the delta-phase, theta-phase and alpha-phase mixed alumina carrier. The weight percentages of dela, theta and alpha phases are 85-95%, 4-10% and 1-5% respectively. The content of Pd as active component on carrier is 0.05-0.5% (m/m). The content of Au as promoter on carrier is 0.005-0.05% (m/m). The process for preparing carrier includes grinding diasporite, kneading, shaping, drying and sintering at 900-1100 deg.C for 2-8hr. Said catalyst has high S-poisoning resistance, high activity and selectivity.
Description
The present invention relates to a kind of C
4The catalyst of selective hydrogenation of diolefin as raw material for alkylation.
The isolated mixed c 4 of oil plant fluidized catalytic cracker is mainly as raw material for alkylation.Iso-butane wherein and alkene are produced the isoparaffin mixture under sulfuric acid or hydrofluoric acid catalyst effect, have the good volatility and the flammability of cleaning, are the desirable blend components of high-quality high-knock rating gasoline.Along with the raising of people's environmental consciousness, the demand of unleaded high-octane rating motor petrol is constantly increased, the importance of alkylation process becomes increasingly conspicuous.
Major impurity in the raw material for alkylation is water, sulfide and butadiene, and its main harm is the rising of doing that makes alkylate oil, and octane number descends, and sour consumption is increased, and causes environmental pollution.Below be the typical sulfuric acid consumption of different impurities:
The typical sulfur acid consumption of different impurities
The sulfur impurity acid consumption, kgH
2SO
4/ kg impurity
Water 10.6
H
2S,COS??????????????????????15～18
Butadiene 13.4
For the octane number that improves gasoline fraction will improve reaction temperature, this also can increase the content of the butadiene in the C-4-fraction in catalytic cracking unit, and Gao Shineng reaches 1.2% (m/m), therefore is necessary to remove these impurity.For sulphur in the raw material for alkylation and water, the existing way of oil plant solves, and is to select hydrogenation for butadiene the best way, promptly under the condition that a large amount of monoolefines exist, removes butadiene high-activity high-selectivity.The core of this way is to select hydrogenation catalyst.
As everyone knows, palladium is an optimum activity component of selecting hydrogenation, and palladium is loaded on the catalyst of making on the various porous oxides, has been widely used in the alkynes that removes in monoolefine or the diolefin cut and the diolefin in the monoolefine cut.At present most widely used on the Chemical Manufacture is Pd/Al
2O
3Series catalysts.This class catalyst is used for carbon tetraalkyl selective hydrogenation of diolefin as raw material, has two subject matters:
Though 1, raw material for alkylation is handled through desulfurization, but still contains the sulfide of about 20PPM, sulphur is the poisonous substance of palladium catalyst, can suppress activity of such catalysts greatly, guarantee that catalyst has enough activity, must improve reaction temperature.
2, selection of catalysts bad (yield of monoolefine is on the low side).
Pertinent literature has: CN1071443A, a kind of catalyst that is used for one-stage selective hydrogenation of gasoline splitting.It is used for drippolene C
6-8The selection hydrogenation of cut, goal of the invention provides the diene selective height, and reaction temperature rising is low, has stronger anti-arsenic poisoning ability and operating condition catalyst stably.This activity of such catalysts component is a palladium, and carrier is δ, α mixed phase aluminium oxide, the preparation method of the not mentioned carrier of specification, and the composition of δ, α phase.This catalyst is used for C
4Selective hydrogenation of diolefin as raw material for alkylation activity and selectivity are not high enough.CN 85106117A, the catalysis selective hydrogenation of alkynes and alkadienes in the monoolefine.Catalyst wherein, active component are palladiums, and carrier is α-Al
2O
3The content of the raw material impurity sulphur that its require to use is less than 0.5PPM, otherwise, the very fast inactivation of catalyst, and the about 20PPM of sulphur in the raw material for alkylation.Therefore, it also is not suitable for C
4The selection hydrogenation of raw material for alkylation.French Patent (FRP) number is 4533779 " loading type Pd-Au Preparation of catalysts and the application in diolefin and/or selective acetylene hydrocarbon hydrogenation reaction ", catalyst carrier can be aluminium oxide or silica, active component has been used Pd and Au, the emphasis of its technical scheme is an active constituent loading in the method on the carrier: palladium compound is added on the inorganic carrier, roasting in oxygen-containing atmosphere, handle with reducing medium, add the chloride of gold again, handle with reducing medium, handle with the compound that can carry out fundamental reaction, make the content of halogen of catalyst be lower than 10PPM, roasting in oxygen-containing atmosphere.Thus, this technical scheme will be removed halogen.The purpose of this patent is to make catalyst have the poisoning capability of high anti-sulphur, and is highly stable to the elution of vinylacetylene, reduces the generation of oligomer.
The purpose of this invention is to provide C
4The catalyst of selective hydrogenation of diolefin as raw material for alkylation and method for making, catalyst have higher activity, selectivity and sulfur poisoning-resistant ability, and preparation technology is simple.
The C that is used for of the present invention
4The catalyst of selective hydrogenation of diolefin as raw material for alkylation, its major technique characteristics are to be principal phase mutually with δ, contain on the mixed phase alumina support of θ, α phase supported palladium or palladium and gold simultaneously and form.
δ, θ, α mixed phase alumina support, wherein δ accounts for 85～95% mutually.θ phase 4～10%, α phase 1～5% are by weight percentage.
The specific area of this carrier is 50～150m
2/ g, preferably 90～130m
2/ g; Specific pore volume 0.25～0.35ml/g, preferably 0.28～0.32ml/g.The pore radius of carrier preferably accounts for more than 50% of total pore volume at the volume in the hole of 5.0～10.0nm.Carrier can be bar shaped, sphere, compressing tablet shape etc.
The content of active component palladium on carrier is 0.05～0.5% (m/m), is preferably 0.1～0.3%; The content of promoter gold on carrier is 0.005～0.05% (m/m), is preferably 0.01～0.03%.
As the Preparation of catalysts method, at first be the preparation of carrier, carrier be by the boehmite powder after kneading, moulding, drying, formed in 2～8 hours at 900～1100 ℃ of following sintering.The carrier that obtains like this is the alumina support with δ, θ, α mixed phase crystal formation.
Said method, when 900～1100 ℃ of following sintering, preferably pass through following temperature-rise period:
(1) room temperature-110～130 ℃;
(2) 110～130 ℃ of following constant temperature 2 ± 0.5 hours;
(3)110～130℃-750～850℃；
(4) 750～850 ℃ of constant temperature 1 ± 0.5 hour;
(5)750～850℃-900～1100℃；
(6) 900～1100 ℃ of constant temperature 2～8 hours.
The boehmite powder is when moulding, and with common preparation method, used binding agent and expanding agent also can utilize known material, and expanding agent is 1～4% of a vehicle weight, and binding agent is 1～2% of a vehicle weight.
Palladium and gold are to adopt the mode of soaking of dividing, earlier with distilled water preimpregnation carrier, drop in after, flood with palladium compound solution, palladium compound can be a kind of in the known palladium compound, preferably the chlorate of palladium, nitrate.It is acid that solution preferably is, PH=1.5～2.5.Making the content of palladium on carrier behind the dipping is 0.05～0.5% (m/m).Then at 80～120 ℃
Under dried 2～6 hours, again 300～600 ℃ of following roastings 2～4 hours.
Flood the carrier of the above-mentioned supported palladium compound that obtains again with gold compound solution, gold compound mainly is halide, particularly chloride, with the aqueous solution of its formation, acid solution etc.Making the content of gold on carrier behind the dipping is 0.005～0.05% (m/m).Dried 2～6 hours down at 80～120 ℃ then, again 300～600 ℃ of following roastings 2～4 hours.
Advantage of the present invention:
Catalyst of the present invention is used for carbon tetraalkyl selective hydrogenation of diolefin as raw material, has the sulfur poisoning-resistant ability, and active high, the selectivity height does not need higher reaction temperature.The intensity of catalyst is more than 200N/cm.
Illustrate with example below:
Example 1 (according to the present invention)
(1) preparation of carrier
With the 1.0kg boehmite, behind the mountain valley with clumps of trees and bamboo powder mixing of 0.04kg field, add the solution that 0.5L contains citric acid 0.02kg.After kneading, extrusion molding,, make carrier by following temperature sintering.
1, room temperature-120 ℃
2,120 ℃ of constant temperature 2h
3、120-800℃
4,800 ℃ of constant temperature 1h
5、800-1000℃
6,1000 ℃ of constant temperature 4h
7, cooling naturally.
The carrier that makes has following physical property:
Specific pore volume: 0.30ml/g; Specific surface: 120m
2/ g.
Crystalline phase: based on δ mutually, account for 88～92%, θ phase 5～8%, α phase 3～4%.
(2) Preparation of catalysts
1, takes by weighing the PdCl that 1.7 gram palladium content are no less than 59% (m/m)
2Powder is dissolved in the 312.5ml distilled water, adds appropriate hydrochloric acid, regulates PH=1.5～2.5, makes PdCl
2Solution;
2, take by weighing the gold chloride that 0.209 gram gold content is no less than 47.8% (m/m), be dissolved in the 200ml distilled water, make chlorauric acid solution;
3, get the carrier 500g that step (1) makes, place distilled water, after 20 minutes, drain carrier, be dipped in above-mentioned PdCl
2In the solution.After 2 hours, surplus liquid substantially transparent is analyzed wherein palladium content, and not enough 20ppm illustrates that palladium almost completely is adsorbed onto on the carrier.Taking-up drains, through 120 ℃ 3 hours, again 400 ℃ of following roastings 3 hours;
4, sample is placed above-mentioned chlorauric acid solution, gold content is wherein analyzed in upper strata stillness of night color complete obiteration after 1 hour again, not enough 10ppm, it is dry to drain the back, roasting, method with soak palladium after identical.
So just made catalyst A, the content of its palladium on carrier is 0.2% (m/m), gold content 0.02% (m/m).
Example 2 (comparative sample)
(1) preparing carriers
The batching of carrier is identical with example 1 with extrusion molding, and just sintering carries out (different with example 1 is last sintering temperature height) by following temperature:
1, room temperature-120 ℃
2,120 ℃ of constant temperature 2h
3、120-800℃
4,800 ℃ of constant temperature 1h
5、800-1200℃
6,1200 ℃ of constant temperature 4h
7, cooling naturally.
The carrier that makes has following physical property:
Specific pore volume: 0.22ml/g; Specific surface: 30m
2/ g.
Crystalline phase: α phase
(2) Preparation of Catalyst is with example 1.
So just made catalyst B, the content of its palladium on carrier is 0.2% (m/m), and gold content is 0.02% (m/m).
Example 3 (comparative sample)
(1) preparation of carrier
Method preparation by example 1.
(2) Preparation of Catalyst
Preparation of catalysts was undertaken by 1,3 step in (2) of example 1, did not promptly contain gold.
So just made catalyst C, its palladium content is 0.2% (m/m).
Example 4 (according to the present invention)
Carrier and Preparation of catalysts be with example 1, palladium content 0.15% (m/m), and gold content 0.02% (m/m) makes catalyst F.
Example 5 (according to the present invention)
Carrier and Preparation of catalysts be with example 1, palladium content 0.2% (m/m), and gold content 0.03% (m/m) makes catalyst G.
With example 1,2,3,4,5 catalyst A that make, B, C, F, G and present industrial use pyrolysis gasoline hydrogenation catalyst D (homemade), E (external product) pressurize to turn round by following experimental condition together and estimate result such as table 1:
Test method: adopt the continuous evaluating apparatus of pressurization, simulation industrial operation condition is investigated original catalyst particle size (activity of φ 2.2 * 3～5mm), selectivity etc.
Carbon four raw materials: take from the raw material for alkylation of triumph oil plant alkyl plant, its table composed as follows:
Constituent content, % (m/m)
Iso-butane 55.28
Normal butane 1.87
Isobutene+butene-1 40.11
Anti-butene-2 1.96
Maleic-2 0.38
Butadiene 0.393
Monoolefine total amount 42.47
Total sulfur, ppm 25.0
Hydrogen: take from the reformer hydrogen of triumph oil plant, H
2Content 85% the rest is C
1-C
4Alkane.
Appreciation condition:
C
4Air speed: 10h
-1
Pressure: 1.50Mpa
Temperature: 50 ℃
H
2/C
4 --:2.0mol/mo1
Represent activity with butadiene conversion:
Yield with monoolefine is represented selectivity:
Table 1 pressurization running evaluation result
| Project | Raw material | Product | ||||||
| ????A | ???B | ???C | ???D | ???E | ????F | ????G | ||
| Total C 4 -Contain and put % butadiene % X receipts % Y receipts % | ?42.47 ?0.393 | 42.82 0.0035 99.11 100.82 | 42.50 0.0269 93.16 100.07 | 42.61 0.0183 95.34 100.33 | 42.55 0.0246 93.74 100.19 | 42.73 0.0165 95.80 100.61 | ?42.84 ?0.0083 ?97.89 ?100.87 | ?42.85 ?0.0123 ?96.87 ?100.89 |
Last table shows, catalyst A of the present invention, and F, no matter G is the conversion ratio of butadiene, or the yield of monoolefine, all obviously is better than comparative sample B, C and present industrial catalyst D, E has reached purpose of the present invention.
Claims (10)
1, a kind of C that is used for
4The catalyst of selective hydrogenation of diolefin as raw material for alkylation is characterized in that being is being principal phase with δ mutually, contains on the mixed phase alumina support of θ, α phase the load active component palladium simultaneously and forms.
2, catalyst according to claim 1 is characterised in that and also contains the promoter gold on the carrier.
3, according to claim 1,2 described catalyst, be characterised in that δ, θ, α mixed phase alumina support, wherein δ account for 85～95% mutually, θ mutually 4～10%, α mutually 1～5% by weight percentage.
4, according to claim 1,2 described catalyst, the specific area that is characterised in that carrier is 50～150m
2/ g, specific pore volume 0.25～0.35ml/g.
5, catalyst according to claim 4, the specific area that is characterised in that carrier is 90～130m
2/ g, specific pore volume 0.28～0.32ml/g.
6, catalyst according to claim 4 is characterised in that the volume of pore radius in the hole of 5.0～10.0nm of carrier accounts for more than 50% of total pore volume.
7, according to claim 1,2 described catalyst, be characterised in that the content of palladium on carrier is 0.05～0.5% (m/m), be preferably 0.1～0.3%, the content of gold on carrier is 0.005～0.05% (m/m), is preferably 0.01-0.03%.
8, a kind of method for preparing claim 1 or 2 described catalyst, comprise the preparation of carrier and load active component on carrier, it is characterized in that carrier be by the boehmite powder after kneading, moulding, drying, formed in 2～8 hours at 900～1100 ℃ of following sintering.
9, method according to claim 8 is characterised in that when 900～1100 ℃ of following sintering, has passed through following temperature-rise period:
(1) room temperature-110～130 ℃;
(2) 110～130 ℃ of following constant temperature 2 ± 0.5 hours;
(3)110～130℃-750～850℃；
(4) 750～850 ℃ of constant temperature 1 ± 0.5 hour;
(5)750～850℃-900～1100℃；
(6) 900～1100 ℃ of constant temperature 2～8 hours.
10, method according to claim 8, be characterised in that active component be substep successively with palladium compound and the proofing of gold compound solution on the carrier of distilled water preimpregnation, making the content of palladium on carrier is 0.05-0.5% (m/m), the content of gold on carrier is 0.005～0.05% (m/m), dried 2～6 hours down at 80～120 ℃ each dipping back, again 300～600 ℃ of following roastings 2～4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110280A CN1084222C (en) | 1998-06-10 | 1998-06-10 | Catalyst for selective hydrogenation of diolefin as raw material for alkylation of C4 and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110280A CN1084222C (en) | 1998-06-10 | 1998-06-10 | Catalyst for selective hydrogenation of diolefin as raw material for alkylation of C4 and preparing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1238239A true CN1238239A (en) | 1999-12-15 |
| CN1084222C CN1084222C (en) | 2002-05-08 |
Family
ID=5220342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98110280A Expired - Lifetime CN1084222C (en) | 1998-06-10 | 1998-06-10 | Catalyst for selective hydrogenation of diolefin as raw material for alkylation of C4 and preparing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1084222C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313205C (en) * | 2004-04-02 | 2007-05-02 | 中国石油天然气股份有限公司 | Selective hydrogenation and mono-olefin isomerism catalyst, and its preparing method and use |
| CN100389874C (en) * | 2006-07-14 | 2008-05-28 | 谷育英 | Catalyst and its preparing process and usage method and use |
| CN104437498A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Catalyst and method for preparing butene-2 through butene-1 hydroisomerization |
| CN106552621A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | 2-butylene hydro-isomerization prepares the catalyst used by 1-butylene and prepares the method for 1-butylene |
| CN108865243A (en) * | 2017-05-15 | 2018-11-23 | 中国石油天然气股份有限公司 | A kind of pre-hydrotreating method of carbon tetra-alkylation raw material |
| CN111375395A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Alumina carrier and carbon dioxide three-fraction selective hydrogenation catalyst and application thereof |
| CN111375451A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Alumina carrier and carbon dioxide three-fraction selective hydrogenation catalyst |
| CN112675837A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Carbon four selective hydrogenation catalyst, preparation method and application thereof |
| CN114436751A (en) * | 2020-10-16 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of methylcyclopentene |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2523149A1 (en) * | 1982-03-15 | 1983-09-16 | Catalyse Soc Prod Francais | NEW CATALYST SUPPORTING PALLADIUM-OR, ITS PREPARATION AND USE IN SELECTIVE HYDROGENATION REACTIONS OF DIOLEFINIC AND / OR ACETYLENE HYDROCARBONS |
| JPS5959634A (en) * | 1982-09-27 | 1984-04-05 | Mitsui Petrochem Ind Ltd | Selective hydrogenation of acetylene |
| CN1005268B (en) * | 1985-08-16 | 1989-09-27 | 化学工业部北京化工研究院 | Catalytic selective hydrogenation of alkynes and dialkenes in mono-alkenes |
| CN1026494C (en) * | 1991-10-04 | 1994-11-09 | 兰州化学工业公司化工研究院 | Catalyst for one-stage selective hydrogenation of gasoline splitting |
-
1998
- 1998-06-10 CN CN98110280A patent/CN1084222C/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313205C (en) * | 2004-04-02 | 2007-05-02 | 中国石油天然气股份有限公司 | Selective hydrogenation and mono-olefin isomerism catalyst, and its preparing method and use |
| CN100389874C (en) * | 2006-07-14 | 2008-05-28 | 谷育英 | Catalyst and its preparing process and usage method and use |
| CN104437498A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Catalyst and method for preparing butene-2 through butene-1 hydroisomerization |
| CN106552621A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | 2-butylene hydro-isomerization prepares the catalyst used by 1-butylene and prepares the method for 1-butylene |
| CN108865243A (en) * | 2017-05-15 | 2018-11-23 | 中国石油天然气股份有限公司 | A kind of pre-hydrotreating method of carbon tetra-alkylation raw material |
| CN108865243B (en) * | 2017-05-15 | 2021-03-30 | 中国石油天然气股份有限公司 | Pre-hydrogenation treatment method of carbon tetra-alkylation raw material |
| CN111375395A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Alumina carrier and carbon dioxide three-fraction selective hydrogenation catalyst and application thereof |
| CN111375451A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Alumina carrier and carbon dioxide three-fraction selective hydrogenation catalyst |
| CN111375451B (en) * | 2018-12-29 | 2022-12-13 | 中国石油化工股份有限公司 | Alumina carrier and carbon dioxide three-fraction selective hydrogenation catalyst |
| CN112675837A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Carbon four selective hydrogenation catalyst, preparation method and application thereof |
| CN114436751A (en) * | 2020-10-16 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of methylcyclopentene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1084222C (en) | 2002-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1231559C (en) | Catalytic reforming process for producing aromatic hydrocarbon-rich products using three catalyst zone | |
| CN1021409C (en) | Process for eliminating mercury from hydrocarbons | |
| CN1041386A (en) | Produce the method for white oil by heavy alkylate by-product | |
| CN1382199A (en) | Desulfurization process and bimetallic sorbent systems for same | |
| CN1009804B (en) | Trimetallic catalyst for hydrocarbon coversion | |
| CN1049512A (en) | Hydrocracking catalyst and method for hydrogen cracking | |
| CN105080578B (en) | N-alkane low-temperature isomerization catalyst as well as preparation method and application thereof | |
| CN1290974C (en) | Catalyst combination for improving the grade of hydrocarbons with boiling point in the range of naphtha | |
| CN1856359A (en) | Desulfurization and novel process for same | |
| CN1084222C (en) | Catalyst for selective hydrogenation of diolefin as raw material for alkylation of C4 and preparing method thereof | |
| CN1233531A (en) | Catalyst containing zeolite EUO and use of catalyst in process for isomerizing aromatic compounds containing 8 carbon atoms per molecule | |
| CN1113830A (en) | Multimetallic and multigradient reforming catalyst for converting paraffins to aromatics | |
| CN104549376A (en) | Preparation method of alkane isomerization catalysts | |
| CN1097480C (en) | Catalyst for selective hydrogenation of acetylene hydrocarbon | |
| CN108940354B (en) | C10+Heavy aromatics selective hydrogenation ring-opening catalyst and preparation method thereof | |
| CN1030329C (en) | Catalyst for dehydroaromatization of alkane and its preparing process | |
| CN1488723A (en) | Aromatization catalyst and clean gasoline producing process | |
| CN1191331C (en) | Dual-function reforming catalyst containing Pt and Sn and its preparing process | |
| CN1188495C (en) | Selective hydrogenization catalyst and its preparing method and use | |
| CN1140333C (en) | Method for removing halogen-contd. compound in gas or liquid using composite catalyst contg. at least one metallic element | |
| CN1175089C (en) | Reforming catalyst containing molecular sieve | |
| CN1030328C (en) | Method for preparing hydrogenation catalyst | |
| CN1488722A (en) | Isomerization catalyst and preparation thereof | |
| JP3512317B2 (en) | Catalyst for hydrotreating hydrocarbon oil and method for hydrotreating light oil | |
| JP3537979B2 (en) | Catalyst for hydrotreating hydrocarbon oil and method for hydrotreating light oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: CHINA PETROCHEMICAL CORPORATION Free format text: FORMER OWNER: SINOPEC QILU PETRO-CHEMICAL CORP. Effective date: 20071228 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20071228 Address after: Linzi Zibo District, Shandong province Sinopec Qilu Branch of science and technology Patentee after: China Petrochemical Group Corp. Address before: 124 mailbox, Linzi District, Zibo, Shandong Patentee before: Qilu Petrochemical Company of China Petrochemical Corp. |
|
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20020508 |