CN1031072A - Process of ethylbenzene by alkylating low-density ethylene and relevant zeolite catalyst thereof - Google Patents
Process of ethylbenzene by alkylating low-density ethylene and relevant zeolite catalyst thereof Download PDFInfo
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- CN1031072A CN1031072A CN87105054A CN87105054A CN1031072A CN 1031072 A CN1031072 A CN 1031072A CN 87105054 A CN87105054 A CN 87105054A CN 87105054 A CN87105054 A CN 87105054A CN 1031072 A CN1031072 A CN 1031072A
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- Prior art keywords
- zeolite
- ethene
- catalyzer
- ammonium
- benzene
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- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 57
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000010457 zeolite Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 35
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 230000008569 process Effects 0.000 title claims description 10
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title abstract description 34
- 239000005977 Ethylene Substances 0.000 title description 16
- 230000002152 alkylating effect Effects 0.000 title description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 12
- 229910002796 Si–Al Inorganic materials 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000005864 Sulphur Substances 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 8
- 150000002910 rare earth metals Chemical class 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000005804 alkylation reaction Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- -1 rare earth halide Chemical class 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 14
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 150000004684 trihydrates Chemical class 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000003442 catalytic alkylation reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical class Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000004376 petroleum reforming Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N γ Benzene hexachloride Chemical compound ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind ofly being used for benzene and ethene carries out alkylated reaction, is the used Pentasil type Si-Al zeolite catalyzer that contains rare earth element of phenylating reaction process of raw material especially for low-concentration ethane.This catalyzer can directly be made raw material and benzene preparing ethylbenzene by reaction with the refinery exhaust (containing ethene 10～20%) that contains impurity such as hydrogen sulfide, water.Compare catalyzer of the present invention not only to have good reactivity worth and operation stability and production technique simple and easy with present industry similar catalyst.
Description
The present invention a kind ofly is used for benzene and ethene carries out alkylated reaction, particularly is applicable to benzene alkylation reaction process catalyst system therefor that direct employing low-concentration ethane is a raw material and preparation method thereof.
Ethylbenzene is the critical materials of producing polystyrene plastic.So far, the industrial making method of ethylbenzene mainly contains two kinds, and is a kind of for the carbon eight fraction fractionation by petroleum reforming oil get, and another kind of more main method is to be produced through catalytic alkylation reaction by benzene and ethene.A kind of method in back has developed multiple commercial run with different characteristics since the beginning industrialization of the '30s end.But the overwhelming majority in these methods all is that the ethene of employing high density (even polymerization-grade) is raw material, and certain limitation is arranged.
Along with the development of petroleum refining industry, discharge the refinery exhaust that contains low-concentration ethane (content 10～20%) in a large number day by day; For the utilization of ethene in these tail gas, from the fifties end, developed and severally produced the method for ethylbenzene by it, these methods are mainly as United States Patent (USP) U.S.2,939,890; U.S.3,691,245; U.S.3,702,886; U.S.3,848,012; U.S.4,107,224; U.S.4,459,426; English Patent B.P.827,830; B.P.1,162,481; Deutsches Reichs-Patent D.E.2,756,221; And Romanian patent RO.51, patents such as 253 are reported.Their catalyst system therefors roughly can be divided into three types: AlCl
3, BF
3Perhaps crystalline silico-alumino zeolite.Main with ZSM-5 type zeolite in Si-Al zeolite, this prepare zeolite is to do crystallization promotor with the tetrapropyl ammonium compound.But the H of these processes to being contained in the unstripped gas
2S, H
2O, CO, CO
2And O
2Deng foreign matter content strict requirement is arranged all, need be removed to the ppm level in advance, alkylation process is normally carried out.Because in these impurity, what have will make AlCl
3The catalyst consumption amount is order of magnitude ground to be increased so that inactivation, makes BF
3Poisoning of catalyst inactivation and hydrolysis produce hydrofluoric acid and cause the equipment heavy corrosion, perhaps can accelerate the aging speed of ZSM-5 type zeolite catalyst, shorten the operational cycle greatly.Therefore, these methods all will additionally be set up the refining plant that gives of unstripped gas, thereby bring shortcomings such as complex procedures, operational difficulty.
The objective of the invention is to prepare a kind of benzene alkylation with ethylene, particularly be applicable to the catalyzer that adopts the refinery exhaust (as catalytic cracked dry gas) contain low-concentration ethane to use for the benzene alkylation processes of reaction raw materials, this catalyzer not only has activity and selectivity preferably, and the H that exists in raw material
2S and H
2Under the condition that detrimental impurity such as O do not need to remove in advance, still have advantages of higher stability, the long operational cycle, thereby can improve the process economy benefit and improve its adaptability.
Catalyzer of the present invention is to be the primary activity component with Pentasil type Si-Al zeolite, the type zeolite system is synthesized during by crystallization promotor with ammonium hydroxide or diamine, and when synthetic the direct halogenation salt of interpolation rare earth element, in the crystalline silico-alumino zeolite that makes, add 30～70% binding agent kneading and compactings then, change Hydrogen into through ammonium salt exchange and roasting, handle making finished catalyst again through further upgrading.
The present invention adopts chemistry and physics upgrading treatment process, to regulate the intensity and the quantity of zeolite catalyst surface acid center.In addition, also adopt the super stabilizing means, to strengthen the operation stability of zeolite catalyst.For ease of to the control of zeolite surface tart, adopt conventional adsorb ammonia temperature programmed desorption(TPD) (TPD) method to detect and control device as main.At last catalyzer being carried out prevulcanized and handle, specifically is to adopt the wet method method for pre-sulphuration, introduces the sulphur component, with selectivity and the stability of improving zeolite catalyst.
The weight percent that zeolite catalyst of the present invention is formed is: mishmetal 0.3～6%, or lanthanum 0.2～3%, sulphur 0.05～0.2%, zeolite (its SiO
2/ Al
2O
3Ratio 40～100) content 30～70%, and Al
2O
3Content 70～30%.
The preparation process of zeolite catalyst is:
One, zeolite is synthetic
With water glass (or water glass) and ammonium hydroxide (or diamine); Tai-Ace S 150 (or sodium metaaluminate), sulfuric acid and rare earth halide, be hybridly prepared into solution respectively, under violent stirring, two solution are mixed into glue, colloid moves into crystallization in the autoclave, crystallization condition is a crystallization 10 hours to 7 days under 100～200 ℃ of conditions, is preferably in 110-170 ℃ of following crystallization 3～4 days.After crystallization is finished, filter, wash and drying, can obtain containing the Pentasil Si-Al zeolite of rare earth.The physico-chemical property of this zeolite is: SiO
2/ Al
2O
3(molecular ratio) 40～100, content of rare earth 0.3～6%Wt or lanthanum 0.2～3%Wt, surface-area 340～380m
2/ g.The loading capacity of normal hexane, hexanaphthene and water is respectively: 9～11.5%Wt, 4～5%Wt and 7～9%Wt.
Two, Preparation of catalysts
1. with above-mentioned synthetic zeolite and a certain amount of aluminum oxide, it is kneaded and formed to add an amount of diluted nitric acid aqueous solution again, oven dry, roasting under the condition of inert gas and progressively intensification;
2. with above-mentioned zeolite product ammonium salt (the most handy ammonium nitrate and the ammonium hydroxide mix) aqueous solution, exchange becomes the ammonium type, and 80～90 ℃ of ion-exchange temperatures are so that this half-finished sodium content is brought down below 0.05～0.02%Wt;
With above-mentioned ammonium type zeolite product at inert gas and changing into again under the full air, in 450～540 ℃, roasting is more than 6 hours;
4. above-mentioned h-type zeolite product is then carried out hydrothermal treatment consists, condition is flooding quantity 2～20ml/g sample hour, and 500～650 ℃ of temperature and time are more than 2～10 hours;
5. the Pentasil type zeolite catalyst after above-mentioned processing is again with sulfidizing, dry method or wet method all can, vulcanizing agent such as H
2S, SO
2And ammonium sulfide all can, but preferably adopt the wet method sulfidizing, the employing ammonium sulfide is a vulcanizing agent, uses hydrogen treat subsequently again, get final product finished product Pentasil type zeolite catalyst.
Embodiment 1: prepare zeolite
Get 2889 milliliters and contain Na
2O 62.58mg/ml and SiO
2193.21mg/ml water glass solution, 1980 ml pure waters and 244 the gram concentration 98% quadrols mix; Other gets content is 99% Al
2(SO
4)
318H
2O 69.3 grams, 482 milliliters in 4M sulfuric acid, content are 99% LaCl
36H
22000 milliliters of O29.9 gram and pure water, and mix; Under violent stirring, two solution are mixed into glue, present and continue again behind the glue to stir 30 minutes, gelatigenous object is transferred in rotary (or stirring-type) stainless steel autoclave that volume is 10 liters.At first under 110 ℃ of conditions, left standstill aging 12 hours, crystallization 50 hours under 165 ℃ of conditions again, the rotation of crystallization process mesohigh still (or stirring) speed is 13 cels.After crystallization process was finished, product was cooled off rapidly, and inclining mother liquor, again with pure water washing for several times, was 8～9 until the pH value of solution, filter, 120 ℃ dry 10 hours down, promptly get and contain lanthanum Pentasil type Si-Al zeolite.The SiO of this finished product
2/ Al
2O
3(molecular ratio) is 50, contains lanthanum 2.01%Wt, 25 ℃ of normal hexane loading capacity 10.20%Wt(adsorption conditionses, normal hexane dividing potential drop 20mmHg).
Embodiment 2: the preparation of zeolite catalyst
With alumina trihydrate and concentration is 33% aqueous nitric acid and example 1 dry good zeolite product, mixes also to mix and pinches evenly, and the consumption of alumina trihydrate is so that butt Al
2O
3With the weight ratio of zeolite be 35%/65%, the consumption of aqueous nitric acid is looked to mix and is pinched thing and do wet appropriateness and be advisable, it is rectangular to be extruded into φ 2m/m then, dry more than 24 hours under 110～120 ℃ of conditions, again that drying is good bar is cut into garden cylindricality particle.This garden cylindricality material slowly rises to 450 ℃ with 3～4 ℃/minute of heat-up rates in nitrogen gas stream, 450 ℃ of roastings 1 hour, 500 ℃ of roastings 1 hour, and 540 ℃ of roastings 2 hours, then under airflow 540 ℃ continue roasting 3 hours.Take out after being chilled to room temperature, use 1N NH
4NO
3With 0.5N NH
4The OH mixing solutions carries out the ammonium ion exchange operation; After finishing, exchange washs to there not being NO with pure water
- 3, filter and 110 ℃ of dryings more than 24 hours.The sodium of products therefrom contains＜0.05%Wt.
Will be exsiccant ammonium type zeolite sample pack in the tube furnace, (so that the oxygen level of mixed gas is about 1%) slowly heats up in nitrogen and Air mixing air-flow, 540 ℃ of roastings 4 hours, cut off source of the gas subsequently, improve pure water and intensification simultaneously, flooding quantity is 5～10 a milliliters/gram sample hour, keeps 4 hours under 580～600 ℃ of temperature condition.After hydrothermal treatment consists operation is finished, change again with dry air and purge cooling, take out to room temperature.
Embodiment 3: the sulfuration of catalyzer
Get example 2 and make zeolite 100 grams, with concentration is 100 milliliters of dip treating of ammonium sulfide solution of 0.5%Wt, filter and remove redundant solution, drying is 3 hours under 110～120 ℃ of conditions, handled 1.5 hours under hydrogen stream and 450～480 ℃ of conditions, getting product contains lanthanum and sulphur Pentasil type Si-Al zeolite catalyzer again.This product contains lanthanum 1.25%Wt, sulphur 0.1%Wt, and the medium tenacity acid site that the TPD method is measured in its 325～450 ℃ of scopes accounts for (to total acid site amount of sample) about 65%.
Embodiment 4:
Replace 29.9 gram Lanthanum trichlorides in the above-mentioned example 1 with chlorination mishmetal 37.0 gram, all the other conditions and method and example 1 identical makes and contains the Pentasil type Si-Al zeolite that mixes rare earth.The SiO of this product
2/ Al
2O
3(molecular ratio) is 47, contains to mix rare earth content 2.51%Wt, surface-area 362m
2/ g, and normal hexane loading capacity 9.5%Wt.
Embodiment 5:
With the zeolite product of above-mentioned example 4,, promptly make the finished product zeolite catalyst that contains mixing rare earth and sulphur through further handling with above-mentioned example 2 and example 3 identical conditions and method.This finished product contains and mixes rare earth 1.56%Wt, sulphur 0.1%Wt, and the acid site that the TPD method is measured medium tenacity in its 325～450 ℃ of scopes accounts for (to total acid site amount of sample) about 60%.
Embodiment 6:
Be on 5 milliliters the continuous flow fixed bed reactor in the zeolite catalyst loading amount, and at reaction pressure 7kg/cm
2(gauge pressure), 375 ℃ of temperature of reaction, ethylene content 20%(body in the work material ethylene gas body) (all the other are 20%H
2, 60%N
2), ethene (pure) weight space velocity 1.0hr
-1, the reaction result of the zeolite catalyst of use-case 3 is mainly: conversion of ethylene 98.4%Wt, benzene transformation efficiency 20.5%Wt, ethylbenzene selectivity 91.1%, and ethylbenzene ten diethylbenzene selectivity 99.0%.
Embodiment 7:
In reaction unit described in the example 6 and under the identical reaction conditions, the zeolite catalyst reaction result of example 5 is mainly: conversion of ethylene 98.0%Wt, benzene transformation efficiency 19.8%Wt, ethylbenzene selectivity 88.7%, and ethylbenzene ten diethylbenzene selectivity 98.0%.
Embodiment 8:
On reaction unit described in the example 6, adopting the pure ethylene of concentration＞99% is unstripped gas, at pressure 10kg/cm
2, 400 ℃ of temperature of reaction, weight ethylene air speed 2.0hr
-1And benzene/ethene (molecular ratio) is that the reaction result of the zeolite catalyst of use-case 3 is mainly: conversion of ethylene＞99.5%Wt, ethylbenzene selectivity 91.0%, ethylbenzene ten diethylbenzene selectivity＞99.0%Wt under 5 the reaction conditions.
Embodiment 9:
Adopt the zeolite catalyst of example 3 and the reaction unit of example 6, but unstripped gas is used catalytic cracked dry gas instead, the consisting of of this dry gas (%V): ethene 19.6, propylene 3.5, butylene 4-5, hydrogen 10, oxygen 1, carbonic acid gas 5-6, carbon monoxide 2, hydrogen sulfide 5000-6000PPm, surplus is N
2And C
1～C
4Saturated hydrocarbons.At reaction pressure 10kg/cm
2(gauge pressure), 375 ℃ of temperature of reaction, weight ethylene air speed 2.4hr
-1And benzene/ethene (molecular ratio) is under 3 the condition, conversion of ethylene 90%, and propylene conversion 85% and butene conversion 84%, ethylbenzene selectivity are more than 82%, and the selectivity of ethylbenzene ten diethylbenzene is more than 98%; In addition, also have propyl benzene and butylbenzene and 1% left and right sides C
+ 5Alkane alkene generates.
Embodiment 10:
Under the condition of example 9, the reaction process parameter of having carried out system changes test.Think at reaction pressure 7～11kg/cm
2(gauge pressure), 375～450 ℃ of temperature of reaction, ethylene feed weight space velocity 1.0～3.0hr
-1, the processing condition of benzene/ethene (molecular ratio) 3～6 are relatively more suitable.In these scopes, more than the conversion of ethylene 83%Wt, ethylbenzene selectivity is more than 82%, and the selectivity of ethylbenzene ten diethylbenzene is more than 98%.The main technique condition test result such as the following table of the catalyzer of example 3 are listed.
Embodiment 11:
Adopt 100 milliliters of the zeolite catalysts of example 3 and be on 150 milliliters the heat-insulating continuous flow fixed bed reactor in scale, and the catalytic cracked dry gas of use-case 9 is reactor feed gas, at pressure 7kg/cm
2(gauge pressure), weight ethylene air speed 1.0, benzene/ethene (molecular ratio) be 5 and the reaction conditions of 350 ℃ of beds temperature ins and 430 ℃ of bed temperature outs under, on-line continuous operation 31 days, conversion of ethylene is kept 95～90%Wt, the transformation efficiency of propylene and butylene also more than 90%Wt, the selectivity about 90% of ethylbenzene ten diethylbenzene.Adopt the way that improves temperature in gradually from being operated to 32 yuan, keep more than the per pass conversion 90%Wt of ethene, the running of the on-line continuous of this zeolite catalyst can reach 60 days.
Lanthanum or the alloy containing mixed rare earth Pentasil type Si-Al zeolite catalyst of containing of the present invention is applicable to that benzene and ethene carry out alkylated reaction, particularly is suitable for and contains H2S and H2The refinery exhaust of the impurity such as O (such as catalytic cracked dry gas) is the benzene alkylation reaction process of raw material. Compare catalyst of the present invention with the method that present industry is adopted, not only demonstrate good reactivity worth and operation stability, and production technology is simple and easy has a significant economic benefit.
Claims (5)
1, a kind ofly be used for the Pentasil type Si-Al zeolite catalyzer that benzene and ethene carry out alkylation reaction, feature of the present invention is to contain rare earth and element sulphur in the catalyzer, and it is formed weight percent and is: mishmetal 0.3～6% or lanthanum: 0.2～3%; Sulphur 0.05～0.2%; Zeolite: 30～70%; Al
2O
3: 70～30%; The SiO of zeolite
2/ Al
2O
3Be 40～100.
2, according to the described Preparation of catalysts method of claim 1, it is characterized in that:
(1) zeolite synthetic is with water glass (or water glass) and ammonium hydroxide (or diamine), and Tai-Ace S 150 (or sodium metaaluminate) is hybridly prepared into solution respectively with rare earth halide, under violent stirring, two solution are mixed into glue after crystallization get zeolite;
(2) with (1) synthetic zeolite and aluminum oxide and rare nitric acid mixing moulding, oven dry, roasting heats up in inert gas;
(3) (2) zeolite is exchanged into the ammonium type with ammonium salt aqueous solution, 80～90 ℃ of ion-exchange temperatures, after the ion-exchange under air 450～540 ℃, roasting is more than 6 hours;
(4) zeolite that (3) were handled 500～650 ℃ of temperature, carries out hydrothermal treatment consists under the condition of flooding quantity 2～20ml/g sample hour;
(5) zeolite that (4) were handled carries out obtaining finished catalyst after the sulfidizing.
3,, it is characterized in that the zeolite synthesis process does crystallization promotor with ammonium hydroxide or diamine according to the described preparation method of claim 2.
4, according to the described preparation method of claim 2, it is characterized in that the sulfidizing of zeolite can adopt dry method or wet method, vulcanizing agent can be used hydrogen sulfide, sulfurous gas and ammonium sulfide, and best sulfidizing is to adopt wet method, vulcanizing agent ammonium sulfide.
5, the alkylated reaction that is used for ethene and benzene according to the described catalyzer of claim 1 is characterized in that ethene can directly adopt rare ethene (10～20%) of impurity such as containing hydrogen sulfide and water to make raw material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87105054A CN1022404C (en) | 1987-08-04 | 1987-08-04 | Process for preparing ethylbenzene by alkylating dilute ethylene and zeolite catalyst used in process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87105054A CN1022404C (en) | 1987-08-04 | 1987-08-04 | Process for preparing ethylbenzene by alkylating dilute ethylene and zeolite catalyst used in process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1031072A true CN1031072A (en) | 1989-02-15 |
| CN1022404C CN1022404C (en) | 1993-10-13 |
Family
ID=4815143
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87105054A Expired - Fee Related CN1022404C (en) | 1987-08-04 | 1987-08-04 | Process for preparing ethylbenzene by alkylating dilute ethylene and zeolite catalyst used in process |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055075C (en) * | 1996-01-16 | 2000-08-02 | 中国石油化工总公司 | Technology for prepn. of ethyl benzene by reaction of thin ethylene and benzene |
| CN1074401C (en) * | 1997-09-22 | 2001-11-07 | 中国石油化工总公司 | Process for preparing ethyl benzene and propyl benzene by reaction of dilute ethylene, propene and benzene |
| CN1074398C (en) * | 1999-08-27 | 2001-11-07 | 中国石油天然气集团公司 | Combined catalytic rectification and absorption process of preparing alkyl arene through the reaction of low-density olefine and arene |
| 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 |
| US6504071B2 (en) | 1999-12-10 | 2003-01-07 | Beijing Institute Of Clothing Technology | Process and apparatus for preparation of ethylbenzene by alkylation of benzene with dilute ethylene contained in dry gas by catalytic distillation |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048655C (en) * | 1996-06-24 | 2000-01-26 | 中国石油化工总公司 | Alkyl catalyst and application thereof |
-
1987
- 1987-08-04 CN CN87105054A patent/CN1022404C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055075C (en) * | 1996-01-16 | 2000-08-02 | 中国石油化工总公司 | Technology for prepn. of ethyl benzene by reaction of thin ethylene and benzene |
| 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 |
| CN1074401C (en) * | 1997-09-22 | 2001-11-07 | 中国石油化工总公司 | Process for preparing ethyl benzene and propyl benzene by reaction of dilute ethylene, propene and benzene |
| CN1074398C (en) * | 1999-08-27 | 2001-11-07 | 中国石油天然气集团公司 | Combined catalytic rectification and absorption process of preparing alkyl arene through the reaction of low-density olefine and arene |
| US6504071B2 (en) | 1999-12-10 | 2003-01-07 | Beijing Institute Of Clothing Technology | Process and apparatus for preparation of ethylbenzene by alkylation of benzene with dilute ethylene contained in dry gas by catalytic distillation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1022404C (en) | 1993-10-13 |
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