CN101352690B - Preparation method and use of molecular sieve catalyst for producing phenylethane from alkylation of benzene with dilute ethylene - Google Patents
Preparation method and use of molecular sieve catalyst for producing phenylethane from alkylation of benzene with dilute ethylene Download PDFInfo
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 36
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 21
- 230000029936 alkylation Effects 0.000 title claims abstract description 16
- 239000005977 Ethylene Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000004927 clay Substances 0.000 claims abstract description 14
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 150000007524 organic acids Chemical class 0.000 claims abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 52
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 230000001404 mediated effect Effects 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 239000007791 liquid phase Substances 0.000 description 9
- 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 8
- 239000007864 aqueous solution Substances 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 241000282346 Meles meles Species 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 229910052934 alunite Inorganic materials 0.000 description 4
- 239000010424 alunite Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- KPZTWMNLAFDTGF-UHFFFAOYSA-D trialuminum;potassium;hexahydroxide;disulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KPZTWMNLAFDTGF-UHFFFAOYSA-D 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
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- 238000010555 transalkylation reaction Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method for generating a phenylethane molecular sieve catalyst by the alkylation of dilute ethylene and benzene as well as the application thereof. The preparation method and the application are characterized in that (I) components of the catalyst: the catalyst comprises one of MCM-22 molecular sieve and MCM-49 molecular sieve or a mixed molecular sieve thereof, aluminum oxide and clay component; (II) preparation steps: (1) an MCM-22 or MCM-49 molecular sieve with silica-aluminum ratio being 25 to 35 is exchanged in ammonium salt with density being 0.5N to 0.8N at 90 DEG C to 100 DEG C, then the mixture is filtered and washed, and drying is carried out at 100 DEG C to 120 DEG C, and the ammonium salt exchange is carried out for a plurality of times; (2) the product obtained from step (1) is kneaded, squeezed and shaped with a binding agent, drying is carried out at 100 DEG C to 120 DEG C and calcination is carried out for 4 hours to 6 hours in flowing atmosphere; (3) the product obtained from step (2) is treated by the ammonium salt with the concentration being 0.6N to 1.0N and organic acid with the weight concentration being 5 percent to 10 percent at 90 DEG C to 100 DEG C for 2 hours to 4 hours, the product obtained is filtered and washed, drying is carried out at 100 DEG C to 120 DEG C, and the treatment of the ammonium salt and the organic acid is carried out for a plurality of times.
Description
Technical field:
The present invention relates to produce the molecular sieve catalyst of ethylbenzene, be specifically related to MWW structure molecular screen Preparation of catalysts method and purposes that a kind of rare ethene and benzene alkylation prepare ethylbenzene.
Background technology:
Ethylbenzene mainly is used to produce styrene, and styrene can be produced impact-resistant polystyrene rubber, ABS dimer, SAN dimer, butadiene-styrene rubber and the unsaturated-resin etc. of the high polystyrene of transparency, modification.Independent ethylbenzene market is actually rare, and about ethylbenzene more than 99% is used to produce styrene.
The core of ethylbenzene production Technology is benzene and ethylene alkylation catalyst, and the catalyst composition has caused the different of reaction condition and product distribution with the difference of performance, different production technologies therefore occurred.Nineteen thirty-five Dow Chemical is with AlCl
3Adopt liquid phase alkylation process to produce ethylbenzene as catalyst by benzene and ethene.At present, the various improved methods of this method are also adopted in 40% of global ethylbenzene production, as Asahi, and Dow, Amoco, BASF.But liquid phase AlCl
3Method has been in the status that is eliminated.Newly-built alkylation to prepare ethylbenzene process units then all adopts sieve method.Cover commercialization Mobil/Badger molecular sieve gas phase hydrocarbonylation device was pushed out to existing in the world 37 cover process units of the present in 1980 first, had occupied about half of the total ethylbenzene production capacity in the world.The liquid phase molecular sieve hydrocarbylation process of Lummus/UOP exploitation in 1989 is in the formal commercialized running of Japan.From ethylbenzene production development trend, the molecular sieve liquid phase alkylation process will be occupied an leading position in one period from now on.At present, Mobil/Badger has released and has adopted the unique liquid-phase alkylation and the EBMaxSM technology of gas phase transalkylation process, has vast potential for future development.
The technology of ethylene production ethylbenzene mainly contains the Alkar method alkylation process of UOP, the technology of Monsanto company and the technology of Mobil/Badger company in the overseas utilization catalytic cracked dry gas.The common feature of these 3 kinds of technology is to H in the unstripped gas
2S, CO
2, H
2Impurity content such as O and propylene is strict, and unstripped gas all need pass through comparatively complicated refining such as desulfurization, dehydration, deoxidation and cryogenic separation propylene, H
2S, CO
2, H
2O all need purify to 10
-6The order of magnitude, propylene content requires less than 0.15 (volume fraction).Wherein the technology of Mobil/Badger company has at present the 160kt/a catalytic cracked dry gas system ethylbenzene device of maximum-norm in the world than the tool advantage at Britain's shell Stanlow oil plant, and ethylbenzene per ton consumes benzene 0.749t, and energy consumption is 20.38GJ.Adopt Mobil/Badger technology; reaction temperature is higher; accessory substance is more; dimethylbenzene volume fraction in the product reaches 1%-2%; this gas phase synthesis method does not have corrosion substantially, and equipment can adopt carbon steel, so investment cost is low; compare three waste discharge with the liquid-phase alkylation method and reduce significantly, help environmental protection.
The eighties in 20th century, domestic Dalian Chemistry and Physics Institute has also developed the technology that the shape-selective molecular sieve zeolite catalyst is used for vapor phase method benzene-alkylation synthesizing ethyl benzene, and in early 1990s, build up industrial amplifying device in Fushun No.3 Petroleum Factory, the catalysis drying gas of this technology can not need be made with extra care, directly with rare ethene and benzene preparing ethylbenzene by reaction [CN1840236A, CN1103607A] in the dry gas.The initial activity and the selectivity height of zeolite catalyst of exploitation, but prolong in time, activity then descends gradually, inactivation almost at last, reason is a catalyst carbon deposit, has stopped up the duct of zeolite, makes the generation condensation reaction, forms the high polymer that desorption does not go out the duct.
CN1128249 has reported that a kind of pure ethylene is a raw material, is catalyst with the Beta molecular sieve, is 3.5Mpa in reaction pressure, and reaction temperature is that the liquid phase method fixed bed reaction prepares ethylbenzene under 230-300 ℃ the condition.
USP3929672,4169111,4459426,5600048 and 4891458 etc. have reported that pure ethylene is a raw material, are 3.0Mpa in reaction pressure, reaction temperature is under 230-300 ℃ the condition, liquid phase method Solid Bed prepared in reaction ethylbenzene.The catalyst that is applied to this process can be MCM-22, MCM-56, and Hbeta and Y zeolite, but the selectivity of the above catalyst product is also not high, and life of catalyst is short.
With the MCM-22 molecular sieve is that the MWW structure molecular screen of representative is the very distinctive practical new catalytic material of a class, with be the benzene of catalyst and propylene, the industrialization of benzene alkylation with ethylene technology, and in reactions such as catalytic cracking, isomerization, aromatisation and etherificate, potential application prospect is arranged.
The present invention has reported that a kind of is the rare ethene and the benzene alkylation Preparation of catalysts method of active component with MWW structure molecular screen (MCM-22 or MCM-49 wherein one or both), catalyst has activity, stability and selectivity preferably, up to now, do not see the method for preparing catalyst report of similar composition.
Summary of the invention:
The object of the present invention is to provide a kind of MWW structure molecular screen Preparation of catalysts method and purposes that is used for rare ethene and producing phenylethane from alkylation of benzene.
The method for making of a kind of rare ethene and molecular sieve catalyst for producing phenylethane from alkylation of benzene is characterized in that:
(1) catalyst is formed
Catalyst is made up of MCM-22 or MCM-49 one of them or the two mixed molecular sieve, aluminium oxide and clay composition, wherein molecular sieve shared weight content in catalyst is 40-80%, the weight content of aluminium oxide is 15-50%, the weight content of clay is 5-20%, the silica alumina ratio of MCM-22 or MCM-49 molecular sieve is 25-35, Na
2The mass content of O is less than 0.5%, and crystal grain is the 3-5 micron;
Described clay component: the silica weight content is 40-60%, and alumina weight content is 15-30%, and all the other are impurity and moisture content; Aluminium oxide is a boehmite;
(2) preparation process:
(1) with silica alumina ratio be MCM-22 or the MCM-49 molecular sieve of 25-35, concentration be in the ammonium salt of 0.5-0.8N in 90-100 ℃ of exchange, filtration washing, 100-120 ℃ of oven dry; The ammonium salt exchange repeats for several times.
(2) step 1 product and binding agent are mediated extruded moulding, 100-120 ℃ of drying, in the atmosphere that flows 400-550 ℃ roasting 4-6 hour;
(3) be that the ammonium salt of 0.6-1.0N and organic acid that weight concentration is 5-10% were handled 2-4 hour filtration washing, 100-120 ℃ of oven dry down at 90-100 ℃ with step 2 product concentration; Ammonium salt and organic acid are handled and are repeated for several times.
According to the method for making of described catalyst, its preferred version is characterised in that: the mole silica alumina ratio of molecular sieve was 28-32 during catalyst was formed, Na
2The O mass content is less than 0.4%, and crystallite dimension is the 3-4 micron; The weight content of molecules of active components sieve is 60-80% in the catalyst; The weight content of aluminium oxide is 20-30% in the catalyst; The weight content of catalyst medium clay soil is 10-20%.
Method for making according to described catalyst is characterized in that: the purposes of described catalyst in rare ethene of catalysis and producing phenylethane from alkylation of benzene:
Activation heats up catalyst earlier under inert gas atmosphere, the activation condition of catalyst is: temperature 300-400 ℃, pressure is 0.5-1.0Mpa, and the flow of inert gas is a per hour 0.5-5 liter of every milliliter of catalyst, and inert gas is one or more mixtures in nitrogen, the helium;
The reaction pressure of ethene and benzene system ethylbenzene is in the catalysis drying gas: 1.5-3.0, and reaction temperature is 180-300 ℃, and the mol ratio of benzene and ethene is 4.5, and benzene liquid volume air speed is 4-6h
-1It is 10-20% that the rare ethene of catalysis contains volume of ethylene, and nitrogenous gas amasss 80-90%; The conversion ratio of ethene is more than 98%, and the selectivity of ethylbenzene is greater than 95%; The ethylization selectivity is greater than 99%, and life of catalyst was greater than 1000 hours.
The benzene feedstock that the present invention uses is industrial purified petroleum benzin, and unstripped gas is that pure ethylene and pure nitrogen gas configuration form, and ethylene contents is 10-20%.
Description of drawings
Fig. 1 is the described MWW structure molecular screen XRD figure of embodiment 1.
Below by example this invention process is described, but is not limited only to these examples.
The specific embodiment:
Embodiment 1
Take by weighing 100gMCM-22 molecular sieve (self-control), the mole silica alumina ratio is 32, relative crystallinity is 98%, 3 microns of crystal sizes, 1000 milliliters of the aqueous ammonium nitrate solutions of adding 0.5N concentration, 95 ℃ of exchanges 2 hours, repeated exchanged 3 times, filtration washing was dried 20 hours down at 110 ℃ then, make HMCM-22, Na
20 weight content 0.5%.XRD as shown in Figure 1.
With above-mentioned HMCM-22 molecular sieve (butt), add 20g aluminium oxide and 5g clay, be that 3% the mixed alunite of aqueous solution of nitric acid is agglomerating with weight concentration, column type orifice plate extruded moulding with Φ 2.0,110oC oven dry 24 hours through 520 ℃ of roastings 4 hours, is cooled to room temperature under moving air.Bar shaped catalyst after the above-mentioned moulding was handled 3 hours under 100 ℃ of conditions in 0.8N ammonium nitrate and 8% citric acid mixed aqueous solution, dried 24 hours for 110 ℃, obtaining code name is the MEBZ-1 catalyst.
Take by weighing 100gMCM-49 molecular sieve (self-control), the mole silica alumina ratio is 25, relative crystallinity is 97%, 4 microns of crystal sizes, 1200 milliliters of the aqueous ammonium nitrate solutions of adding 0.8N concentration, 95 ℃ of exchanges 4 hours, repeated exchanged 4 times, filtration washing was dried 24 hours down at 110 ℃ then, make HMCM-49, Na
2O weight content 0.4%.
With above-mentioned HMCM-49 molecular sieve (butt), add 15g aluminium oxide and 10g clay, be that 2% the mixed alunite of aqueous solution of nitric acid is agglomerating with weight concentration, column type orifice plate extruded moulding with Φ 2.0, dried 24 hours, and under moving air,, be cooled to room temperature for 110 ℃ through 550 ℃ of roastings 4 hours.Bar shaped catalyst after the above-mentioned moulding was handled 4 hours under 95 ℃ of conditions in 0.5N ammonium nitrate and 10% citric acid mixed aqueous solution, dried 24 hours for 110 ℃, obtaining code name is the MEBZ-2 catalyst.
Embodiment 3
Take by weighing 50gMCM-22 molecular sieve (the mole silica alumina ratio is 35) and 50gMCM-49 molecular sieve (the mole silica alumina ratio is 25), average relative crystallinity is 98%, 3.5 microns of average crystalline sizes, 1000 milliliters of the aqueous ammonium nitrate solutions of adding 0.8N concentration are in 95 ℃ of exchanges 6 hours, repeated exchanged 3 times, filtration washing then, dried 24 hours down at 110 ℃, make HMCM-22/49, Na
2O weight content 0.5%.
With above-mentioned HMCM-49 molecular sieve (butt), add 20g aluminium oxide and 10g clay, be that 2% the mixed alunite of aqueous solution of nitric acid is agglomerating with weight concentration, column type orifice plate extruded moulding with Φ 2.0, dried 24 hours, and under moving air,, be cooled to room temperature for 110 ℃ through 550 ℃ of roastings 4 hours.Bar shaped catalyst after the above-mentioned moulding was handled 4 hours under 95 ℃ of conditions in 0.5N ammonium nitrate and 8% citric acid mixed aqueous solution, dried 24 hours for 110 ℃, obtaining code name is the MEBZ-3 catalyst.
Embodiment 4
Take by weighing 100gBeta molecular sieve (the mole silica alumina ratio is 32), average relative crystallinity is 99%, 2 microns of average crystalline sizes, 1000 milliliters of the aqueous ammonium nitrate solutions of adding 0.8N concentration are in 95 ℃ of exchanges 6 hours, repeated exchanged 3 times, filtration washing then, dried 24 hours down at 110 ℃, make HBeta, Na
2O weight content 0.5%.
With above-mentioned HBeta molecular sieve (butt), add 20g aluminium oxide and 10g clay, be that 2% the mixed alunite of aqueous solution of nitric acid is agglomerating with weight concentration, column type orifice plate extruded moulding with Φ 2.0, dried 24 hours, and under moving air,, be cooled to room temperature for 110 ℃ through 550 ℃ of roastings 4 hours.Bar shaped catalyst after the above-mentioned moulding was handled 4 hours under 95 ℃ of conditions in 0.5N ammonium nitrate and 8% citric acid mixed aqueous solution, dried 24 hours for 110 ℃, obtaining code name is the MEBZ-4 catalyst.
Press the catalytic reaction evaluating apparatus to estimate above-mentioned catalyst in the employing.The cylinder catalyst bar of the 15g granularity of packing in fixed bed bed bioreactor Φ 2 * 3 is used N
2Reactor is raised to reaction pressure, is heated to reaction temperature, then N
2Switch to catalytic cracked dry gas, and continuous pump people liquid benzene, make rare ethene and benzene generation alkylated reaction in the dry gas.Reaction effluent carries out the chromatogram on-line analysis to gas phase and liquid phase respectively after gas-liquid separation.Raw materials used gas consists of: ethene is 15%, and nitrogen is 85%.Used benzene raw materials is the analysis purified petroleum benzin of purity 99.9%.Alkylation reaction condition and the results are shown in Table 2.In the condition and range of investigating, the conversion ratio of ethene is more than 95% as can be seen from the table, and ethylbenzene selectivity is more than 90%, and the ethylization selectivity is more than 99%.The alkylation catalyst that the MWW structure molecular screen makes has preferable reactivity and selectivity of product.
The evaluation result of table 1 different catalysts
Annotate: reaction temperature: 230 ℃, reaction pressure: 2.5MPa, benzene liquid volume air speed: 5h
-1, the reaction time: 6h
The foregoing description is the part preferred embodiment, is not the present invention is limited.Can realize the present invention as long as in fact meet the condition that summary of the invention partly sets forth.
Claims (3)
1. the method for making of rare ethene and molecular sieve catalyst for producing phenylethane from alkylation of benzene is characterized in that:
(1) catalyst is formed
Catalyst is made up of MCM-22 or MCM-49 one of them or the two mixed molecular sieve, aluminium oxide and clay composition, wherein molecular sieve shared weight content in catalyst is 40-80%, the weight content of aluminium oxide is 15-50%, the weight content of clay is 5-20%, the silica alumina ratio of MCM-22 or MCM-49 molecular sieve is 25-35, Na
2The mass content of O is less than 0.5%, and crystal grain is the 3-5 micron;
Described aluminium oxide is a boehmite; Described clay component: the silica weight content is 40-60%, and alumina weight content is 15-30%, and all the other are impurity and moisture content; It is 10-20% that described rare ethene contains volume of ethylene, and nitrogenous gas amasss 80-90%;
(2) preparation process:
(1) with silica alumina ratio is MCM-22 or MCM-49 molecular sieve or the two mixed molecular sieve of 25-35; Concentration be in the ammonium salt of 0.5-0.8N in 90-100 ℃ of exchange, filtration washing, 100-120 ℃ of oven dry; The ammonium salt exchange repeats for several times;
(2) step 1 product and aluminium oxide and clay are mediated extruded moulding, 100-120 ℃ of drying, in the atmosphere that flows 400-550 ℃ roasting 4-6 hour;
(3) be that the ammonium salt of 0.6-1.0N and organic acid that weight concentration is 5-10% were handled 2-4 hour filtration washing, 100-120 ℃ of oven dry down at 90-100 ℃ with step 2 product concentration; Ammonium salt and organic acid are handled and are repeated for several times.
2. according to the method for making of the described catalyst of claim 1, it is characterized in that: the silica alumina ratio of molecular sieve was 28-32 during catalyst was formed, Na
2The O mass content is less than 0.4%, and crystallite dimension is the 3-4 micron; The weight content of molecules of active components sieve is 60-80% in the catalyst; The weight content of aluminium oxide is 20-30% in the catalyst; The weight content of catalyst medium clay soil is 10-20%, and the above three kinds of composition sum is absolutely.
3. according to the method for making of the described catalyst of claim 1, it is characterized in that: the purposes of described catalyst in rare ethene of catalysis and producing phenylethane from alkylation of benzene:
Activation heats up catalyst earlier under inert gas atmosphere, the activation condition of catalyst is: temperature 300-400 ℃, pressure is 0.5-1.0MPa, and the flow of inert gas is a per hour 0.5-5 liter of every milliliter of catalyst, and inert gas is one or more mixtures in nitrogen, the helium;
The reaction pressure of rare ethene and benzene system ethylbenzene is: 1.5-3.0MPa, and reaction temperature is 180-300 ℃, and the mol ratio of benzene and ethene is 4.5, and benzene liquid volume air speed is 4-6h
-1It is 10-20% that rare ethene contains volume of ethylene, and nitrogenous gas amasss 80-90%; The conversion ratio of ethene is more than 98%, and the selectivity of ethylbenzene is greater than 95%; The ethylization selectivity is greater than 99%, and life of catalyst was greater than 1000 hours.
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| US8414851B2 (en) | 2010-06-11 | 2013-04-09 | Uop Llc | Apparatus for the reduction of gasoline benzene content by alkylation with dilute ethylene |
| US8895793B2 (en) | 2010-06-11 | 2014-11-25 | Uop Llc | Process for the reduction of gasoline benzene content by alkylation with dilute ethylene |
| CN102935379A (en) * | 2011-08-16 | 2013-02-20 | 中国科学院大连化学物理研究所 | Preparation method of MCM-22 molecular sieve catalyst |
| CN105289704A (en) * | 2015-11-09 | 2016-02-03 | 中国海洋石油总公司 | Preparation method of C8 aromatic isomerization catalyst |
| CN113880682B (en) * | 2020-07-01 | 2023-09-29 | 中国石油化工股份有限公司 | Alkylation reaction method and application thereof |
| CN115770610B (en) * | 2021-09-08 | 2024-02-13 | 中国石油化工股份有限公司 | Method for producing p-tert-butyl toluene by catalysis of solid acid catalyst |
| CN115770611B (en) * | 2022-12-12 | 2024-02-06 | 大连龙缘化学有限公司 | Preparation method and application of catalyst for preparing mesitylene by pseudocumene isomerization |
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