CN104549456A - Heavy aromatic lightening catalyst and preparation method thereof - Google Patents
Heavy aromatic lightening catalyst and preparation method thereof Download PDFInfo
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- CN104549456A CN104549456A CN201310512276.3A CN201310512276A CN104549456A CN 104549456 A CN104549456 A CN 104549456A CN 201310512276 A CN201310512276 A CN 201310512276A CN 104549456 A CN104549456 A CN 104549456A
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- heavy aromatics
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 title abstract 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 22
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010457 zeolite Substances 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002808 molecular sieve Substances 0.000 claims abstract description 16
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims description 11
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 244000275012 Sesbania cannabina Species 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229940095064 tartrate Drugs 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 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 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000002383 tung oil Substances 0.000 claims description 2
- 230000009849 deactivation Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- BFIMMTCNYPIMRN-UHFFFAOYSA-N 1,2,3,5-tetramethylbenzene Chemical compound CC1=CC(C)=C(C)C(C)=C1 BFIMMTCNYPIMRN-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- 241001120493 Arene Species 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- CNSKBOOEAKAYDJ-UHFFFAOYSA-N C1=CC=CC=C1.CC1=CC=CC=C1.CCC1=CC=CC=C1.CC1=CC=CC=C1C Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1.CCC1=CC=CC=C1.CC1=CC=CC=C1C CNSKBOOEAKAYDJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000010165 autogamy Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- -1 polyoxyethylene Polymers 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a heavy aromatic lightening catalyst and a preparation method thereof and mainly aims at solving the problems that the conversion level of heavy aromatic is low, the yield of mononuclear aromatic is low, the selectivity is low and the catalyst deactivation rate is high in the prior art. The heavy aromatic lightening catalyst comprises the following components in percentage by weight: 30-70% of an MCM-41 molecular sieve containing a BEA-type zeolite structural unit, 29.5-69.9% of at least one of gamma-alumina, eta-alumina and pseudo boehmite, which serves as a binding agent, and 0.1-0.5% of at least one metal selected from Pt, Pd and Ir. By adopting the technical scheme, the problems are well solved, and the heavy aromatic lightening catalyst can be applied to industrial production of lightening heavy aromatic into the mononuclear aromatic.
Description
Technical field
The present invention relates to a kind of heavy aromatics lightening catalyst and preparation method thereof.
Background technology
Heavy aromatics refers to the C of by-product in oil and the coal course of processing
9above aromatic hydrocarbons.Current heavy aromatics is through simple distillation operation, isolate the higher durol of value, isodurene, naphthalene, methylnaphthalene etc., all the other small parts are for the production of solvent oil or the blending component as gasoline, major part is used as fuel at a low price, raw material availability is low, both wastes resource, also serious environment pollution, infringement HUMAN HEALTH, is difficult to play the due economic benefit of Heavy Aromatic Hydrocarbons.Therefore for meeting the growth of the petroleum demand that Economic development brings, by development heavy oil deep conversion technology, the light-end products of volume increase high added value will be the significant development strategies of 21 century oil refining industry.The various techniques of heavy aromatics lighting are all to maximize processing heavy aromatics, and improving xylol yield is target, improves air speed simultaneously, increases device processing power.Domestic and international industrialized technique at present, actual treatment heavy aromatics, particularly C
10and the ability of above heavy aromatics still is apparent not enough, following technique research and development should as emphasis.Rapid to sought-after, the increment of triphen in recent years, and will produce the situation that supply falls short of demand, how by development heavy oil deep conversion, the light-end products such as the triphen of volume increase high added value are various countries petrochemical industry worker problems in the urgent need to address.
USP4,341,622 disclose a kind of method utilizing heavy reformate to produce BTX.The method employing restricted index is 1 ~ 12, silica/alumina molar ratio (silica alumina ratio) is more than 12, the zeolite of low acid activity is catalyzer, reformate is reacted under the condition of 427 ~ 540 DEG C, then resultant fractionation by distillation is obtained benzene, toluene and dimethylbenzene.Described catalyzer contains the VIII precious metal of hydro-dealkylation function, preferred platinum, and the silica alumina ratio of zeolite used is preferably greater than 200, and more preferably greater than 500, preferred zeolite is ZSM-5.Selecting the zeolite of high silica alumina ratio for reducing zeolite acidity, retaining dimethylbenzene as far as possible and not being converted in the reaction.
US2007062848A1 discloses and a kind ofly first will carry out selective opening and de-alkyl after polycyclic aromatic hydrocarbons fractional saturation again to obtain the method for light aromatics.The method can to meet in feed stream polycyclic aromatic hydrocarbon content at more than 20wt%, saturation stage temperature at 300 ~ 500 DEG C, pressure 2 ~ 10MPa; Open loop phase temperature at 200 ~ 600 DEG C, pressure 1 ~ 12MPa.Because two-stage catalytic agent is contained in same reactor, so require that logistics needs to ensure that certain residence time could obtain good transformation efficiency, therefore air speed is lower.
CN1472181A discloses a kind of heavy aromatics lightening catalyst, and comprise group VIII metal and the complex carrier of 0.01 ~ 2.0 heavy %, described complex carrier comprises the aluminum oxide of the ZSM-5 zeolite of 30 ~ 70 heavy %, mordenite and 10 ~ 65 % by weight of 5 ~ 20 heavy %.This catalyzer is used for heavy aromatic hydrocarbon light, can improve C
9 +the productive rate of aromatics conversion rate and benzene and dimethylbenzene, and reduce carbon distribution.
CN1082539C discloses the separation method of a kind of heavy arenes lightening catalyst and lighting product.Described catalyzer is made up of the platinum of 0.05 ~ 0.3 heavy % or the aluminum oxide of palladium, the zeolite with MOR structure of 20 ~ 59 heavy %, the ZSM-5 zeolite of 20 ~ 50 heavy % and 20 ~ 40 heavy %.By the raw material of the heavy arene containing C9+ 350 ~ 450 DEG C, carry out with above-mentioned catalyzer under 0.3 ~ 3.5MPa condition contacting, gained lighting product can obtain the organic raw material such as BTX and sym-trimethylbenzene, unsym-trimethyl benzene, durol through fractionation.
CN1048425C discloses a kind of heavy arenes lightening catalyst and lightening method.This catalyzer weighs γ-or the η-Al of % with the ZSM-5 zeolite of 30 ~ 70 heavy % and 30 ~ 70
2o
3for carrier, the palladium composition of the tin of the heavy % of load 0.1 ~ 0.5 and the platinum of 0.05 ~ 0.3 heavy % or 0.2 ~ 0.8 heavy %.350 ~ 450 DEG C, 0.5 ~ 3.5MPa, weight space velocity 1 ~ 5 time
-1, hydrogen/hydrocarbon volume ratio is under the condition of 500 ~ 1200, this catalyzer has higher activity and stability and lower hydrogen consumption.
Summary of the invention
One of technical problem to be solved by this invention is low in order to overcome heavy aromatics depth of conversion when the catalyzer existed in prior art reacts for heavy aromatics lighting, mononuclear aromatics yield is low and selectivity is low, the problem that catalyst deactivation rate is fast, provides a kind of catalyzer for heavy aromatics lighting newly.It is high that this catalyzer has heavy aromatics depth of conversion, and yield and the selectivity of mononuclear aromatics are high, the advantage that catalyst deactivation rate is slow.
Two of technical problem to be solved by this invention is to provide a kind of preparation method of the heavy aromatics lightening catalyst corresponding with one of technical solution problem.
Three of technical problem to be solved by this invention is to provide a kind of purposes of the heavy aromatics lightening catalyst corresponding with one of technical solution problem.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of heavy aromatics lightening catalyst, in catalyst weight percent, comprises following component:
A) 30 ~ 70% containing the MCM-41 molecular sieve of BEA type zeolite building units;
B) 29.5 ~ 69.9% at least one be selected from gama-alumina, η-aluminum oxide or pseudo-boehmite are binding agent;
C) 0.1 ~ 0.5% at least one metal in Pt, Pd or Ir or its oxide compound is selected from.
In technique scheme, the MCM-41 molecular sieve containing BEA type zeolite building units in used catalyst composition is for being Hydrogen or ammonium type molecular sieve, and in molecular sieve, sodium weight content is lower than 2%, and its mole consists of n SiO
2: Al
2o
3, n=30 ~ 60 in formula.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method of heavy aromatics lightening catalyst, comprises the following steps:
1., after the binding agent containing the MCM-41 molecular sieve of BEA type zeolite building units and at least one be selected from gama-alumina, η-aluminum oxide or pseudo-boehmite of aequum of aequum being carried out kneading, shaping, drying, support of the catalyst is obtained at 450 ~ 650 DEG C of roasting 0.5 ~ 24h;
2. the precursor solution being selected from least one metal in Pt, Pd or Ir or its oxide compound of aequum is impregnated into 0.5 ~ 24h in support of the catalyst in 30 ~ 50 DEG C, obtains finished catalyst at 300 ~ 450 DEG C of roasting 0.5 ~ 24h after drying.
In technique scheme, in catalyst support preparation process, preferred version is, adds and presses the extrusion aid of carrier dry basis 2 ~ 5%, and extrusion aid is at least one in sesbania powder or tung oil; Add and press the gelatinizing agent of carrier dry basis 3 ~ 6%, gelatinizing agent is selected from least one in hydrochloric acid, nitric acid, acetic acid, tartrate, citric acid or oxalic acid and water volume ratio 1:1 ~ 1:5.
In technique scheme, the precursor solution preferred version of Pt metal used is Platinic chloride; The precursor solution preferred version of metal Pd is at least one in Palladous nitrate or Palladous chloride; The precursor solution preferred version of metal Ir is chloro-iridic acid.
For solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: a kind of method of heavy aromatics lighting, raw material heavy aromatics mixture mixes with hydrogen, pass through beds, at temperature of reaction 350 ~ 440 DEG C, reaction pressure 4 ~ 7 MPa, weight hourly space velocity degree 0.5 ~ 6 hr
-1, under hydrogen/hydrocarbon mol ratio 4.0 ~ 8.0 condition with above-mentioned catalyst exposure described in any one, heavy aromatics is converted into the mononuclear aromatics comprising benzene,toluene,xylene.
In technique scheme, preferred technical scheme is, temperature of reaction is 350 ~ 390 DEG C, reaction pressure is 5 ~ 6 MPa, weight hourly space velocity degree is 1 ~ 2 hr
-1, hydrogen/hydrocarbon mol ratio is 6.0 ~ 7.0.
Catalyzer provided by the invention can be used for heavy aromatics lightweight and turns in the industrial production of the mononuclear aromatics such as benzene, toluene and dimethylbenzene.
Owing to employ in skeleton structure containing the MCM-41 mesoporous molecular sieve of BEA type zeolite building units as catalyst acid center in the present invention, the existence of the BEA type zeolite building units of crystalline state, the unformed hole wall overcoming conventional MCM-41 molecular sieve causes the shortcoming of hydrothermal stability difference, improve the stability of catalyzer, the having of macropore is beneficial to the acid site that heavy arene macromole enters in duct and carries out ring-opening reaction, product molecule after conversion can passing hole channel rapid diffusion, thus has delayed the deactivation rate of catalyzer; Be there is by load the precious metal element of hydrogenating function, control its charge capacity at a zone of reasonableness, effectively can improve the degree of unsaturation of Polycyclic Aromatic Hydrocarbon Mixture raw material, help deep conversion heavy aromatics molecule; The rational proportion of catalyst acid center and metallic element makes to retain original mononuclear aromatics component in feedstream as far as possible in lighting reaction process, and the mononuclear aromatics of heavy aromatics to lightweight is transformed, maximize with the yield and selectivity that make mononuclear aromatics, achieve good technique effect.
The present invention uses overcritical fixed-bed reactor to carry out the Performance of heavy aromatics lighting reaction, reactor inside diameter Ф 12 millimeters, length 800 millimeters, stainless steel.Adopt electrically heated, temperature automatic control.It is upholder that reactor bottom fills Ф 2 ~ 3 millimeters of granulated glass spherees, catalyst filling 5 grams in reactor, and Ф 2 ~ 3 millimeters of granulated glass spherees are filled on top, is made for the use of raw material preheating and vaporization.Raw material heavy aromatics mixture mixes with hydrogen, passes through beds, at temperature of reaction 350 ~ 440 DEG C, reaction pressure 4 ~ 7 MPa, weight hourly space velocity degree 0.5 ~ 6 hr
-1, hydrogen/hydrocarbon mol ratio 4.0 ~ 8.0 condition under contact with catalyzer, make heavy aromatics be converted into the mononuclear aromatics such as benzene,toluene,xylene.
Heavy aromatics mixture is autogamy raw material, and experimental data is calculated as follows.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
Preparation method containing the MCM-41 molecular sieve of BEA type zeolite building units: by 60g Beta zeolite in the hydrochloric acid soln (0.2mol/L) of 100ml after 50 DEG C of process 1h, then add silica-gel powder, hydrochloric acid, cetyl trimethylammonium bromide (CTAB), alkylphenol polyoxyethylene (OP-10) and deionized water and make the mol ratio of thing phase in solution be 1SiO
2: 0.25CTAB:0.04OP-10:1.98HCl:160H
2o, in addition, W
beta/ W
siO2(g/g)=0.50, after stirring 2h, solution is dry through filtration washing after 100 DEG C of hydrothermal treatment consists 48h, and in 500 DEG C of nitrogen atmosphere roasting 1h, 500 DEG C of air atmosphere roasting 5h are for subsequent use.
Be MCM-41 molecular sieve (self-control) and the 50 g γ-Al that 50 g contain BEA type zeolite building units by butt weight
2o
3(industrial goods) add mixing tank to evenly, in mixture, then add 3 g sesbania powder, 5 g volume ratio 1:1 HNO
3solution and 40 g deionized waters, the dough being suitable for extruding evenly is made in grinding.It extruded by mould, shape is elongated cylindrical (diameter 1.7 mm), in 550 DEG C of roasting 4 h after 120 DEG C of oven dry, is then cut into the carrier granule (1.7 × 4.0 mm) of consistent size, is designated as Z1.
Flooded carrier granule at 40 DEG C by Platinic chloride wiring solution-forming, the amount containing Pt in steeping fluid is 0.2% of carrier butt weight, and dipping 8h also after drying, at 450 DEG C of roasting 3 h, obtains finished catalyst A.
[embodiment 2 ~ 10]
The preparation method provided according to embodiment 1 and process, by changing the contamination of metal precursor in carrier composition and steeping fluid, prepared a series of finished catalyst, in table 1.
Table 1
[embodiment 11-19]
(wherein B is benzene with catalyst A ~ J (highest response pressure 10MPa, use temperature are room temperature ~ 600 DEG C) investigation on overcritical fixed-bed reactor that embodiment 1 ~ 10 is obtained, heavy aromatics mixture to be converted into BTX, T is toluene, and X is dimethylbenzene) etc. the ability of mononuclear aromatics.Table 2 is for evaluating raw material composition.Catalyst loading 5 g, at temperature of reaction 370 DEG C, reaction pressure 5.5MPa, weight hourly space velocity degree 1.0hr
-1, contact with catalyzer under hydrogen/hydrocarbon mol ratio 6.0 condition, product to be reclaimed and component detects, conversion results is shown in Table 3.
Table 2
| Raw material forms | Non-aromatic | Benzene | Toluene | Ethylbenzene | Dimethylbenzene | Perhydronaphthalene | Naphthane | Naphthalene |
| Content (wt%) | 0.02 | 24.54 | 24.61 | 5.00 | 0.02 | 14.81 | 15.25 | 15.75 |
Table 3
| Catalyzer is numbered | Total conversion rate (wt%) | Mononuclear aromatics selectivity (wt%) | BTX selectivity (wt%) |
| A | 59.9 | 76.2 | 51.3 |
| B | 61.6 | 75.1 | 50.6 |
| C | 58.7 | 77.0 | 53.4 |
| D | 63.2 | 74.3 | 49.7 |
| E | 64.0 | 74.0 | 49.1 |
| F | 66.7 | 73.2 | 49.0 |
| G | 55.3 | 80.1 | 55.8 |
| H | 59.0 | 77.5 | 53.2 |
| I | 65.1 | 73.7 | 48.9 |
| J | 62.6 | 74.7 | 49.2 |
[embodiment 20 ~ 24]
Catalyst A ~ the E obtained by embodiment 1 ~ 5 investigates ability heavy aromatics mixture being converted into the mononuclear aromatics such as BTX on overcritical fixed-bed reactor.Catalyst loading 5g, at temperature of reaction 380 DEG C, reaction pressure 6MPa, weight hourly space velocity degree 1.0 hr
-1, contact with catalyzer under hydrogen/hydrocarbon mol ratio 6.5 condition, product to be reclaimed and component detects, conversion results is shown in Table 4.
Table 4
| Catalyzer is numbered | Total conversion rate (wt%) | Mononuclear aromatics selectivity (wt%) | BTX selectivity (wt%) |
| A | 62.4 | 78.0 | 52.6 |
| B | 63.6 | 77.1 | 51.1 |
| C | 62.5 | 78.6 | 53.9 |
| D | 63.0 | 76.8 | 50.5 |
| E | 62.1 | 78.3 | 52.7 |
[embodiment 25 ~ 29]
Catalyst A ~ the E obtained by embodiment 1 ~ 5 investigates ability heavy aromatics mixture being converted into the mononuclear aromatics such as BTX on overcritical fixed-bed reactor.Catalyst loading 5 g, at temperature of reaction 370 DEG C, reaction pressure 5.5MPa, weight hourly space velocity degree 2.0 hr
-1, contact with catalyzer under hydrogen/hydrocarbon mol ratio 6.0 condition, product to be reclaimed and component detects, conversion results is shown in Table 5.
Table 5
| Catalyzer is numbered | Total conversion rate (wt%) | Mononuclear aromatics selectivity (wt%) | BTX selectivity (wt%) |
| A | 58.0 | 78.1 | 52.5 |
| B | 58.6 | 77.5 | 51.8 |
| C | 57.5 | 78.9 | 54.4 |
| D | 58.3 | 77.8 | 50.8 |
| E | 57.1 | 78.3 | 50.3 |
[embodiment 30 ~ 34]
Catalyst A ~ the E obtained by embodiment 1 ~ 5 investigates ability heavy aromatics mixture being converted into the mononuclear aromatics such as BTX on overcritical fixed-bed reactor.Catalyst loading 5 g, at temperature of reaction 370 DEG C, reaction pressure 6MPa, weight hourly space velocity degree 1.0 hr
-1, contact with catalyzer under hydrogen/hydrocarbon mol ratio 6.5 condition, product to be reclaimed and component detects, conversion results is shown in Table 6.
Table 6
| Catalyzer is numbered | Total conversion rate (wt%) | Mononuclear aromatics selectivity (wt%) | BTX selectivity (wt%) |
| A | 59.8 | 75.7 | 51.9 |
| B | 61.8 | 75.9 | 50.2 |
| C | 58.3 | 76.3 | 52.8 |
| D | 62.9 | 72.8 | 49.9 |
| E | 63.5 | 74.5 | 49.5 |
[embodiment 35 ~ 39]
Catalyst A ~ the E obtained by embodiment 1 ~ 5 investigates ability heavy aromatics mixture being converted into the mononuclear aromatics such as BTX on overcritical fixed-bed reactor.Catalyst loading 5 g, at temperature of reaction 380 DEG C, reaction pressure 6MPa, weight hourly space velocity degree 2.0 hr
-1, contact with catalyzer under hydrogen/hydrocarbon mol ratio 6.5 condition, product to be reclaimed and component detects, conversion results is shown in Table 7.
Table 7
| Catalyzer is numbered | Total conversion rate (wt%) | Mononuclear aromatics selectivity (wt%) | BTX selectivity (wt%) |
| A | 60.9 | 78.5 | 52.9 |
| B | 61.6 | 77.9 | 52.0 |
| C | 60.8 | 79.0 | 54.3 |
| D | 60.6 | 77.1 | 51.6 |
| E | 59.9 | 78.7 | 53.7 |
Claims (10)
1. a heavy aromatics lightening catalyst, in catalyst weight percent, comprises following component:
A) 30 ~ 70% containing the MCM-41 molecular sieve of BEA type zeolite building units;
B) 29.5 ~ 69.9% at least one be selected from gama-alumina, η-aluminum oxide or pseudo-boehmite are binding agent;
C) 0.1 ~ 0.5% at least one metal in Pt, Pd or Ir or its oxide compound is selected from.
2. heavy aromatics lightening catalyst according to claim 1, it is characterized in that the MCM-41 molecular sieve containing BEA type zeolite building units is Hydrogen or ammonium type molecular sieve, in molecular sieve, sodium weight content is lower than 2%.
3. heavy aromatics lightening catalyst according to claim 1, is characterized in that the MCM-41 molecular sieve mole containing BEA type zeolite building units consists of n SiO
2: Al
2o
3, n=30 ~ 60 in formula.
4. the preparation method of heavy aromatics lightening catalyst according to claim 1, comprises the following steps:
1., after the binding agent containing the MCM-41 molecular sieve of BEA type zeolite building units and at least one be selected from gama-alumina, η-aluminum oxide or pseudo-boehmite of aequum of aequum being carried out kneading, shaping, drying, support of the catalyst is obtained at 450 ~ 650 DEG C of roasting 0.5 ~ 24h;
2. the precursor solution being selected from least one metal in Pt, Pd or Ir or its oxide compound of aequum is impregnated into 0.5 ~ 24h in support of the catalyst in 30 ~ 50 DEG C, obtains finished catalyst at 300 ~ 450 DEG C of roasting 0.5 ~ 24h after drying.
5. the preparation method of heavy aromatics lightening catalyst according to claim 4, is characterized in that the extrusion aid added in catalyst support preparation process by carrier dry basis 2 ~ 5%; Adding at least one acid solution be selected from hydrochloric acid, nitric acid, acetic acid, tartrate, citric acid or oxalic acid in catalyst support preparation process is gelatinizing agent.
6. the preparation method of heavy aromatics lightening catalyst according to claim 5, is characterized in that extrusion aid is at least one in sesbania powder or tung oil.
7. the preparation method of heavy aromatics lightening catalyst according to claim 5, it is characterized in that, with carrier dry basis, the gelatinizing agent of add in catalyst support preparation process 3 ~ 6 % by weight, in gelatinizing agent, the volume ratio being selected from least one in hydrochloric acid, nitric acid, acetic acid, tartrate, citric acid or oxalic acid and water is 1:1 ~ 1:5.
8. the preparation method of heavy aromatics lightening catalyst according to claim 4, is characterized in that the precursor solution of described Pt metal is Platinic chloride; The precursor solution of metal Pd is at least one in Palladous nitrate or Palladous chloride; The precursor solution of metal Ir is chloro-iridic acid.
9. a method for heavy aromatics lighting, raw material heavy aromatics mixture mixes with hydrogen, passes through beds, at temperature of reaction 350 ~ 440 DEG C, reaction pressure 4 ~ 7 MPa, weight hourly space velocity degree 0.5 ~ 6 hr
-1, under hydrogen/hydrocarbon mol ratio 4.0 ~ 8.0 condition with catalyst exposure described in any one in claim 1 ~ 3, heavy aromatics is converted into the mononuclear aromatics comprising benzene,toluene,xylene.
10. the method for heavy aromatics lighting according to claim 9, is characterized in that temperature of reaction 350 ~ 390 DEG C, reaction pressure 5 ~ 6MPa, weight hourly space velocity degree 1 ~ 2 hr
-1, hydrogen/hydrocarbon mol ratio 6.0 ~ 7.0 condition under with catalyst exposure.
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| CN110639545A (en) * | 2018-06-27 | 2020-01-03 | 中国石油化工股份有限公司 | Heavy distillate oil selective hydrogenation catalyst and application thereof |
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