CN1034276C - Solid acid catalyst for olefine hydrocarbons and phenyl alkylate - Google Patents
Solid acid catalyst for olefine hydrocarbons and phenyl alkylate Download PDFInfo
- Publication number
- CN1034276C CN1034276C CN91108244A CN91108244A CN1034276C CN 1034276 C CN1034276 C CN 1034276C CN 91108244 A CN91108244 A CN 91108244A CN 91108244 A CN91108244 A CN 91108244A CN 1034276 C CN1034276 C CN 1034276C
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- benzene
- degree
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- solid acid
- acid catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 19
- 239000011973 solid acid Substances 0.000 title claims abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 title description 2
- 150000002430 hydrocarbons Chemical class 0.000 title description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 150000001336 alkenes Chemical class 0.000 claims abstract description 15
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- -1 etc.) Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 3
- 229910052788 barium Inorganic materials 0.000 claims abstract 3
- 238000001035 drying Methods 0.000 claims description 10
- 230000008929 regeneration Effects 0.000 claims description 8
- 238000011069 regeneration method Methods 0.000 claims description 8
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical group 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 230000002262 irrigation Effects 0.000 claims 1
- 238000003973 irrigation Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 claims 1
- 238000005804 alkylation reaction Methods 0.000 abstract description 3
- 239000002808 molecular sieve Substances 0.000 abstract description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 2
- 230000001070 adhesive effect Effects 0.000 abstract 2
- 150000002500 ions Chemical class 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 238000005342 ion exchange Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 9
- 230000009466 transformation Effects 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000009418 renovation Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 description 1
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000000207 volumetry Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a solid acid catalyst for the alkylation reaction of straight chain olefins and benzene, which is prepared by modifying Y type molecular sieves in an ion exchange mode. Ions for modification are ions of alkaline earth metals (such as Ca, Sr, Ba, etc.), and rare earth elements (such as La, Ce) or misch metals. The solid acid catalyst is formed by using the no adhesive method and the adhesive Al2O3 method, and therefore, is high in conversion rate and selectivity. The washing method with benzene (organic solvent) regenerates the inactivated catalyst.
Description
The present invention relates to a kind of be used for normal olefine particularly carbon ten and be used for the method for this catalyst regeneration to the normal olefine of carbon 16 and the solid acid catalyst of benzene alkylation reaction.
Linear alkylbenzene is to produce the intermediate that biodegradable detergent is used, and all is at present to use linear olefin and benzene at HF or AlCl
3Katalysis under synthetic linear alkylbenzene.Because HF and AlCl
3All have very strong corrodibility, very high to the equipment requirements of producing, acid needs neutralizing treatment, is easy to environment and health of human body are worked the mischief.But not homogeneous solid acid catalyst non-corrosiveness, to the person and environment do not work the mischief, the facility investment expense is low.Be engaged at present a lot of of alkene and the development research of benzene alkylation reaction solid acid catalyst abroad, but majority is the research lower carbon number hydrocarbons.What United States Patent (USP) 4477585,4547605,4717780 reports adopted is ZSM series molecular sieve; What United States Patent (USP) 4075126 was reported is interlinkage polynite series; United States Patent (USP) 4335022,42586828,4368342,4524229 report be that tungstosilicic acid is immersed in synthetic composite catalyst on porous material such as silicon oxide, the pure aluminium silicate carrier, but the alkylated reaction that is used for normal olefine, transformation efficiency, selectivity, and life of catalyst all undesirable, up to the present big progress is not arranged.
The objective of the invention is to prepare a kind of particularly C of linear olefin that is used for
10-C
16Alkene and the benzene reaction solid acid catalyst that generates linear alkylbenzene, and the renovation process of this catalyzer is to substitute the HF or the AlCl of present industrial usefulness
3Catalyzer.This catalyzer has very high transformation efficiency, selectivity, and can repeatedly regenerate.
The present invention is to be matrix with zeolitic materials such as X type, Y type, mordenite, particularly y-type zeolite, carries out ion-exchanged, synthetic catalyst.Used Y zeolite SiO
2/ Al
2O
3In the 3.0-6.0 scope, under 75 ℃ of-95 ℃ of temperature with concentration 1-20Wt.% alkaline-earth metal Ca, Sr, the aqueous solution exchange of Ba compound 1-3 hour, 80 ℃-140 ℃ dry 4-20 hour, 200 ℃-600 ℃ roasting 2-10 hour.Repeated exchanged, drying, roasting once (condition is constant) then.With concentration is 0.1-20Wt.%NH
4Cl and 1-20Wt.% rare-earth elements La, Ce compound water solution be 75 ℃-95 ℃ down exchanges 1-3 hour, 80 ℃-140 ℃ dry 4-20 hour, 200 ℃-600 ℃ roasting 2-10 hour, repeated exchanged.Dry.Roasting is (condition is constant) once.
The moulding of catalyzer is divided into two kinds of methods, and a kind of is the binder free type, and catalyst fines is got the 8-30 order in the pressure lower sheeting moulding of 5-30 ton; Another kind is the adding additives type, and used binding agent is Al
2O
3, kaolin, polynite, silica gel etc., consumption accounts for the 10-50% of gross weight, extruded moulding.
These catalyzer fixed-bed reactor, 100 ℃-300 ℃ of temperature of reaction, pressure 0.5-5MPa, liquid hourly space velocity=0.5-20Hr
-1, benzene/alkene (mol ratio)=5-30, transformation efficiency is 99-100%, selectivity is 90-100%.
Renovation process of the present invention is at 100 ℃-300 ℃ of temperature, pressure 1.0-5.0MPa, liquid hourly space velocity=0.1-5.0Hr
-1With the benzene flushing, flush away is the polymeric colloid on catalyst surface under the condition.Regeneration rear catalyst transformation efficiency returns to 99-100%.
Product analysis is measured with gas-chromatography and standard potential volumetry.
The following examples are to explanation of the present invention, are not limiting the scope of the invention.
The former powder of embodiment one 100 gram NaY, SiO
2/ AL
2O
3=4.5, add 800 milliliters of 10Wt.%Ca (NO
3)
2Solution exchange 2 hours, temperature is 90 ± 5 ℃, exchanges back 120 ℃ of dryings 3 hours, 550 ℃ of roastings 4 hours, repeated exchanged, drying, roasting once, condition is constant.Use the NH of 5Wt.% again
4La (the NO of Cl and 5Wt.%
3)
3800 milliliters of the aqueous solution exchange 2 hours, and 90 ± 5 ℃ of temperature exchange back 120 ℃ of dryings 3 hours, and 550 ℃ of roastings are 4 hours then.Repeated exchanged, drying, roasting be (condition is constant) once.The powder that synthesizes is in 10 tons forming under the pressure, and fragmentation is beaten sheet and got the 10-16 order, activates 3 hours down in 350 ℃.
The raw material of reaction is the mixture of benzene and alkane alkene, benzene/alkene (C
10-C
13) (mol ratio)=20,150 ℃ of temperature of reaction degree, pressure 1.5MPa, liquid hourly space velocity=2.5Hr
-1From reaction result, successive reaction 24 hours, transformation efficiency is more than 99%, and selectivity is more than 99%.
The bearing reaction time of table 1 catalyzed reaction (hour) 048 12 16 20 24 olefin conversion %, 0 99.9 99.8 99.7 99.8 99.9 99.9 selectivity % 0 99.3 99.8 99.7 99.4 99.6 99.9
Synthesizing of embodiment two catalyzer, but forming method difference with example one.The forming method of this catalyzer is as follows: get 10 gram catalyst powder, add 3 gram Al
2O
3, add water furnishing paste, be squeezed into 1.2 * 3mm bar.In air air-dry 12 hours, 120 ℃ dry 4 hours down, 550 ℃ of following roastings 4 hours.Intensity 〉=0.15MPa/ particle.The condition of reaction and raw material are with example one
The bearing reaction time of table 2 catalyzed reaction, (hour) 043 12 16 20 24 olefin conversion % 0 99.1 99.0 99.2 99.7 99.0 99.3 reaction times of 0 99.8 99.8 99.7 99.6 99.8 99.8 selectivity %, (hour) 28 32 36 40 44 olefin conversion %, 99.4 98.8 98.6 96.7 95.2 selectivity % 99.0 99.3 99.6 99.2 99.2
React regeneration later in 40 hours 24 hours.Renovation process is: 230 ℃ of temperature, under the pressure 3.5MPa condition, with benzene flushing 24 hours, liquid hourly space velocity=0.5Hr
-1
The table 3 regeneration back catalyzed reaction bearing reaction time (hour) 048 12 16 20 24 olefin conversion %, 0 99.7 99.6 99.6 99.4 99.3 99.4 selectivity % 0 99.1 99.2 99.2 99.3 99.7 99.6
The former powder of embodiment 3 100 gram NaY, SiO
2/ Al
2O
3=4.5, add 800 milliliters of 10Wt.%SrCl
2Aqueous solution exchange 2 hours, temperature is 90 ± 5 ℃, exchanges back 120 ℃ of dryings 3 hours, 550 ℃ of roastings 4 hours, repeated exchanged.Dry.Roasting is (condition is constant) once.Use 5Wt.%La (NO again
3)
3800 milliliters of the aqueous solution exchange 2 hours, and 90 ± 5 ℃ of temperature exchange back 120 ℃ of dryings 3 hours, and 550 ℃ of roastings are 4 hours then.Repeated exchanged, drying, roasting be (condition is constant) once.Forming method is with example two. and the raw material of reaction is the mixture of benzene and alkane alkene, benzene/alkene (C
10-C
13) (mol ratio)=15.
The bearing reaction time of table 4 catalyzed reaction, (hour) 08 16 32 38 44 50 olefin conversion % 0 99.3 99.3 99.7 99.6 99.5 99.6 reaction times of 0 99.7 99.8 99.8 99.7 99.7 99.7 selectivity %, (hour) 56 60 64 olefin conversion %, 99.3 98.0 94.8 selectivity % 99.3 99.4 99.5
React after 64 hours and regenerated 24 hours, renovation process is with example two.The bearing reaction time of table 5 regeneration back catalyzed reaction (hour) 048 12 16 20 24 olefin conversion %, 0 99.7 99.8 99.4 99.4 99.3 99.3 selectivity % 0 99.0 99.3 99.7 99.2 99.3 99.7
La (NO in the catalyzer in embodiment four examples three
3)
3With Ce (NO
3)
3Replace, remaining component, give-and-take conditions, exchange concentration and Preparation of Catalyst, forming method are with example three.
Reacted 48 hours, transformation efficiency 〉=99%, a transformation efficiency reduces to 96% after selectivity 〉=99%, 56 hour, and after 24 hours, transformation efficiency returns to more than 99% as the regeneration of example two methods, and sustained reaction 24 hours, transformation efficiency 〉=99%.
Claims (3)
1. one kind prepares C
10-C
16The method of linear alkylbenzene is characterized in that used raw material is C
10-C
16Normal olefine and benzene, the mol ratio of benzene and alkene is 5-30, temperature of reaction is the 100-300 degree, pressure is 0.5-5MPa, liquid hourly space velocity is 0.5-20Hr
-1, be reflected under the conditions of non-hydrogen and carry out, adopt solid acid to make catalyzer, this catalyzer be Y zeolite with the aqueous solution of alkaline-earth metal Ca, Sr, Ba compound exchange under the 75-95 degree, drying roasting under the 200-600 degree; And then use NH
4Cl and rare-earth elements La, Ce compound water solution exchange under the 75-95 degree, drying, and roasting under the 200-600 degree, adding additives are made, and this catalyzer is to wash regeneration with organic solvent-benzene under the 100-300 degree.
2. according to the described preparation of claim 1. C
10-C
16The method of linear alkylbenzene is characterized in that the used Y zeolite SiO of preparation of used solid acid catalyst
2/ Al
2O
3In the 3.0-6.0 scope, the exchange concentration of alkaline earth element Ca, Sr, Ba is 1-20wt%, and the exchange concentration of rare-earth elements La, Ce is 1-20wt%, NH
4The exchange concentration of Cl is 0.1-20wt%, and added binding agent is Al
2O
3, kaolin, polynite, silica gel, content is the 10-50% of gross weight.
3. according to the described preparation of claim 1. C
10-C
16The method of linear alkylbenzene, the regeneration that it is characterized in that used solid acid catalyst are to make irrigation at the 100-300 degree with organic solvent-benzene, under the 1.0-5.0MPa pressure, and the liquid hourly space velocity 0.1-5.0Hr of benzene
-1, the recovery time is 1-48 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91108244A CN1034276C (en) | 1991-11-20 | 1991-11-20 | Solid acid catalyst for olefine hydrocarbons and phenyl alkylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91108244A CN1034276C (en) | 1991-11-20 | 1991-11-20 | Solid acid catalyst for olefine hydrocarbons and phenyl alkylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1072353A CN1072353A (en) | 1993-05-26 |
| CN1034276C true CN1034276C (en) | 1997-03-19 |
Family
ID=4909159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91108244A Expired - Fee Related CN1034276C (en) | 1991-11-20 | 1991-11-20 | Solid acid catalyst for olefine hydrocarbons and phenyl alkylate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1034276C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100478705C (en) * | 2006-03-06 | 2009-04-15 | 中南大学 | Signal magnifying multiple circuit with digital control |
| CN100483152C (en) * | 2006-09-01 | 2009-04-29 | 中南大学 | Multifunctional sender and controller for electrical surveying signal |
| US7812208B2 (en) | 2008-09-22 | 2010-10-12 | Uop Llc | Binderless adsorbents with improved mass transfer properties and their use in the adsorptive separation of para-xylene |
| US7820869B2 (en) | 2008-06-30 | 2010-10-26 | Uop Llc | Binderless adsorbents and their use in the adsorptive separation of para-xylene |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055876C (en) * | 1996-01-25 | 2000-08-30 | 中国石油化工总公司 | Alkylated catalyst for preparation of alkylbenzene |
| CN1077808C (en) * | 1996-07-05 | 2002-01-16 | 中国科学院大连化学物理研究所 | Catalyst of alkyl benzene with straight chain made by alkylation from benzene and straight chain olefin and its application |
| CN1079285C (en) * | 1997-06-06 | 2002-02-20 | 中国石油化工总公司 | Catalyst for alkylation of benzene and ethylbenzene manufactured from ethylene |
| CN106179486B (en) * | 2015-04-29 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of regeneration method containing noble metal and EUO type molecular sieve catalyst |
| CN110562995B (en) * | 2018-06-06 | 2021-05-28 | 中国石油化工股份有限公司 | Synthesis method of nano Y zeolite, synthesized nano Y zeolite and application |
| CN111203287A (en) * | 2018-11-21 | 2020-05-29 | 内蒙古伊泰煤基新材料研究院有限公司 | Regeneration method of benzene alkylation solid acid catalyst |
| CN113304771B (en) * | 2021-06-11 | 2022-09-09 | 上海巽田科技股份有限公司 | Catalyst for preparing glycol ether and method for preparing glycol ether by using same |
| CN117680188A (en) * | 2022-08-26 | 2024-03-12 | 中国石油化工股份有限公司 | Alkylation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3565964A (en) * | 1968-08-05 | 1971-02-23 | Sun Oil Co | Alumino-silicate catalyzed reactions of polycyclic aromatic hydrocarbons in the presence of hydrogen |
| SU973510A1 (en) * | 1979-08-27 | 1982-11-15 | Институт теплофизики СО АН СССР | Composition for making protective refractory daubing |
-
1991
- 1991-11-20 CN CN91108244A patent/CN1034276C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3565964A (en) * | 1968-08-05 | 1971-02-23 | Sun Oil Co | Alumino-silicate catalyzed reactions of polycyclic aromatic hydrocarbons in the presence of hydrogen |
| SU973510A1 (en) * | 1979-08-27 | 1982-11-15 | Институт теплофизики СО АН СССР | Composition for making protective refractory daubing |
Non-Patent Citations (1)
| Title |
|---|
| 《沸石分子筛》 科学出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100478705C (en) * | 2006-03-06 | 2009-04-15 | 中南大学 | Signal magnifying multiple circuit with digital control |
| CN100483152C (en) * | 2006-09-01 | 2009-04-29 | 中南大学 | Multifunctional sender and controller for electrical surveying signal |
| US7820869B2 (en) | 2008-06-30 | 2010-10-26 | Uop Llc | Binderless adsorbents and their use in the adsorptive separation of para-xylene |
| US7812208B2 (en) | 2008-09-22 | 2010-10-12 | Uop Llc | Binderless adsorbents with improved mass transfer properties and their use in the adsorptive separation of para-xylene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1072353A (en) | 1993-05-26 |
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Owner name: CHINA PETROCHEMICAL CORPORATION Free format text: FORMER OWNER: ALKYLBENZENE PLANT, JINLING PETROCHEMICAL CORPORATION, SINOPEC Effective date: 20080118 |
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Effective date of registration: 20080118 Address after: 6, Yi Xin East Street, Beijing, Chaoyang District Patentee after: China Petrochemical Group Corp. Address before: Suojin village in Nanjing city of Jiangsu Province, No. seventy-eight Patentee before: Alkyl Benzene Plant Jinling Petro-Chemical Corp SINOPEC |
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Granted publication date: 19970319 Termination date: 20101120 |