CN108940354A - A kind of C10+Heavy aromatics selective hydrogenation ring opening catalyst and preparation method thereof - Google Patents
A kind of C10+Heavy aromatics selective hydrogenation ring opening catalyst and preparation method thereof Download PDFInfo
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- CN108940354A CN108940354A CN201810672063.XA CN201810672063A CN108940354A CN 108940354 A CN108940354 A CN 108940354A CN 201810672063 A CN201810672063 A CN 201810672063A CN 108940354 A CN108940354 A CN 108940354A
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- catalyst
- solution
- heavy aromatics
- platinum
- ammonium fluosilicate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000007142 ring opening reaction Methods 0.000 title description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 53
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 36
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 19
- 239000002808 molecular sieve Substances 0.000 claims abstract description 18
- 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 18
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000000465 moulding Methods 0.000 claims abstract description 9
- 238000005470 impregnation Methods 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 7
- 230000004048 modification Effects 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 17
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000007493 shaping process Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000007796 conventional method Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- -1 BTX aromatic hydrocarbons Chemical class 0.000 abstract description 9
- 239000003502 gasoline Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 14
- 239000002994 raw material Substances 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 238000007323 disproportionation reaction Methods 0.000 description 5
- 238000010555 transalkylation reaction Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BIIBYWQGRFWQKM-JVVROLKMSA-N (2S)-N-[4-(cyclopropylamino)-3,4-dioxo-1-[(3S)-2-oxopyrrolidin-3-yl]butan-2-yl]-2-[[(E)-3-(2,4-dichlorophenyl)prop-2-enoyl]amino]-4,4-dimethylpentanamide Chemical compound CC(C)(C)C[C@@H](C(NC(C[C@H](CCN1)C1=O)C(C(NC1CC1)=O)=O)=O)NC(/C=C/C(C=CC(Cl)=C1)=C1Cl)=O BIIBYWQGRFWQKM-JVVROLKMSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1096—Aromatics or polyaromatics
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of C10 +The catalyst and preparation method thereof of heavy aromatics selective hydrogenation open loop.Catalyst of the present invention, in terms of catalyst quality, each component mass percentage composition are as follows: HY molecular sieve 50~80%, platinum 0.05~0.35%, surplus are aluminium oxide；The SiO of the catalyst2/A12O3Molar ratio is 8~13, and specific surface area is 450~600m20.35~0.7cm of/g, Kong Rongwei3/g；The catalyst is HY molecular sieve first through ammonium fluosilicate and the solution combined modification of platiniferous, then with after aluminium oxide extruded moulding, drying, roasting, is most made after the modification of platiniferous solution incipient impregnation, dry, roasting afterwards.Catalyst of the present invention has higher heavy aromatics lighting activity and stability, is particularly suitable for the selective hydrogenation open loop fecund lightweight BTX aromatic hydrocarbons or high-knock rating gasoline of macromolecular heavy aromatics inferior.
Description
Technical field
The present invention relates to heavy aromatics lightening catalyst fields, and in particular to a kind of C10 +Heavy aromatics selective hydrogenation open loop
Voluminous lightweight BTX aromatic hydrocarbons or the catalyst of high-knock rating gasoline and preparation method thereof.
Background technique
Heavy aromatics refers mainly to the C of the by-product in petroleum and coal process10Or more aromatic hydrocarbons, be mainly derived from oil plant
The C of catalytic reforming unit by-product10 +The C of heavy aromatics, ethylene cracker by-product10 +Heavy aromatics, aromatic disproportion and isomerization generate
Oil, heavy aromatics of coal high-temperature coking by-product etc..The composition of heavy aromatics is extremely complex, is not fully used for a long time,
It is domestic substantially by heavy aromatics to undersell or fuel blend oil, not only resulted in waste of resources but also polluted environment.
Tatoray technique is typical toluene disproportionation and transalkylation technique, with toluene and C9 +Aromatic hydrocarbons (mainly C9Virtue
Hydrocarbon) it is raw material, light aromatics is increased production using disproportionation and transalkylation catalyst under hydro condition, but monocycle heavy aromatics is easy to
Hydrogen is added to be saturated, liquid receipts are lower, and need the C in strict control charging10 +Arene content and indane content, to prevent catalyst inactivation.
Patent CN98805980 discloses one kind with C9 +Heavy aromatics and toluene are the method that raw material produces light aromatics, with nickel
It is catalyst with the modified β zeolite of bismuth, the total conversion of heavy aromatics reaches 47%, and the selectivity of benzene and dimethylbenzene reaches 88%,
But C is also strictly limited in BTX aromatics raw material10 +The content of aromatic hydrocarbons, and the catalyst is not disclosed in patent to C10 +Aromatic hydrocarbons
Conversion capability.For the stability for improving catalyst, patent proposition introduces hydrogenation metal component on a catalyst, but excessively strong
The Hydrogenation of change causes the side reactions such as aromatic hydrocarbons saturation and cracking serious again, reduces aromatics yield.
CN1018423360A discloses a kind of first by C9 +Aroamtic hydrocarbon raw material, hydrogen, benzene and (or) toluene and the first catalyst
Olefin component in (the metal-modified ZSM-5 of preferably Pt) contact removing raw material, products therefrom are urged with second in an other condition
Agent (the metal-modified ZSM-12 of preferably Pt) contact, carries out transalkylation reaction, obtains dimethylbenzene.C9 +The conversion ratio of aromatic hydrocarbons connects
Nearly 60%.
CN1711341A is by C9 +The mixture of aromatic hydrocarbons and toluene is in 400~454 DEG C, 1.48~3.55MPa, hydrogen hydrocarbon molar ratio
1~3,1~5h of weight (hourly) space velocity (WHSV)-1Under conditions of, there are two types of the beds of molecular sieve catalyst to contact with filling, produces benzene and diformazan
Benzene, C9 +The conversion ratio of aromatic hydrocarbons can reach about 59%.Both the above technique is directed to the characteristic of raw material, at two kinds of catalyst segments
Reason, to realize C9 +The conversion ratio of aromatic hydrocarbons maximizes, and raw material forms with C9Based on aromatic hydrocarbons, and alkyl loss is larger, has a large amount of low
The non-aromatic generation of carbon.
The heavy aromatics of RIPP adds hydrogen lighting technology, in 360~460 DEG C of reaction temperature, 1~3MPa of reaction pressure, weight
1~3h of air speed-1, under conditions of 500~1500:1 of hydrogen to oil volume ratio, the light aromatics such as BTX are converted by heavy aromatics.But it should
Alkyl loss is larger in technology hydrogenation process, and liquid receives only 85% or so.To guarantee that liquid receives not excessively saturation aromatic ring, can be used
Lower reaction pressure, but with this condition, condensed-nuclei aromatics open loop is more difficult, thus reaction conversion ratio is lower and toluene with again
Aromatic disproportion and transalkylation technology are compared, without competitive advantage.
The raw material composition for making a general survey of above-mentioned technical treatment is mainly C9With a small amount of C10Aromatic hydrocarbons, aromatic hydrocarbon type are with mononuclear aromatics
It is main, but C10 +Heavy aromatics composition and property and its difference are larger, contain the components such as a large amount of condensed-nuclei aromatics and aryl olefin, these groups
Lightweight mononuclear aromatics can not be converted by disproportionation and transalkylation reaction by dividing, while also easily coking carbon distribution causes catalyst to lose
It is living.Therefore, it is necessary to the C that targeted development process is rich in condensed-nuclei aromatics10 +The relevant technologies of heavy aromatics, make C10 +Heavy aromatics obtains
To effective use.
Summary of the invention
It is an object of the invention to solve the prior art not efficiently using C10 +The drawbacks of heavy aromatics, makes it obtain high level
Change and utilize, a kind of new heavy aromatics lightening catalyst, i.e., a kind of C are provided10 +The catalyst of heavy aromatics selective hydrogenation open loop and
Preparation method.The catalyst of this method preparation has, high level product yield height, aromatic hydrocarbons high to C10+ heavy aromatics feed stock conversion
The features such as selectivity is good is, it can be achieved that voluminous lightweight BTX aromatic hydrocarbons or high-knock rating gasoline.
A kind of C provided by the invention10 +The catalyst of heavy aromatics selective hydrogenation open loop, wherein the catalyst carrier
It is made of HY molecular sieve and aluminium oxide, active component is precious metals pt；In terms of catalyst quality, each component mass percentage composition
Are as follows:
HY molecular sieve content is 50~80%；
Platinum content is 0.05~0.35%；
Surplus is aluminium oxide；
The SiO of the catalyst2/A12O3Molar ratio is 8~13, and specific surface area is 450~600m2/ g, Kong Rongwei
0.35~0.7cm3/g；
The C10 +Heavy aromatics is C10And the above aromatic hydrocarbons, the end point of distillation≤350 DEG C；
The catalyst is by HY molecular sieve first through ammonium fluosilicate and the solution combined modification of platiniferous, then with aluminium oxide extrusion
After molding, dry, roasting, most it is made after the modification of platiniferous solution incipient impregnation, dry, roasting afterwards.
The invention also discloses above-mentioned C10 +A kind of preparation method of heavy aromatics selective hydrogenation ring opening catalyst, including such as
Lower step:
(1) ammonium fluosilicate is dissolved in deionized water, the ammonium fluosilicate solution of 0.02~0.06g/mL is made；
(2) chloroplatinic acid or platinum nitrate are dissolved in deionized water and platinum acid chloride solution or platinum nitrate solution or chloroplatinic acid is made
Solution is made according to a conventional method of spongy platinum；
(3) HY molecular sieve is add to deionized water at 70~95 DEG C and stirs into suspension, deionized water and molecule
The volume ratio of sieve is 5:1~20:1, and ammonium fluosilicate solution, fluorine silicon is added dropwise with the speed of 0.1~0.5mL/min into suspension
The volume ratio of acid ammonium solution and suspension be 0.5:1~2:1, respectively when ammonium fluosilicate solution drips 1/5~3/5 total amount and
Chloroplatinic acid is added when ammonium fluosilicate solution all drips or total amount is added dropwise twice and accounts for by Pt element for platinum nitrate solution, platiniferous solution
0.025~0.3% meter of final catalyst weight；After ammonium fluosilicate solution and platiniferous solution all drip, lasting stirring is old
Change 1~5h；
(4) it after aging, is filtered, deionized water washing, until fluorine element can not be detected in cleaning solution, 90
6~12h is dried under the conditions of~150 DEG C, 420~580 DEG C of 4~8h of roasting under air atmosphere obtain modified molecular screen；
(5) gained modified molecular screen in step (4) is uniformly mixed with alumina powder, being added containing mass concentration is 2
~10% dust technology kneading extruded moulding, dry 6~12h at 90~150 DEG C, 420~580 DEG C of roastings 4 under air atmosphere~
8h obtains shaping carrier；
(6) chloroplatinic acid obtained by a certain amount of step (2) or platinum nitrate solution is taken to be added drop-wise to step (5) resulting shaping carrier
In, it carries out incipient impregnation 2~8 hours, impregnated carrier is 6~12 hours dry at 90~150 DEG C in air atmosphere, air
420~580 DEG C of 4~8h of roasting, obtain catalyst under atmosphere, and final Pt constituent content on catalyst is made to reach the catalyst weight
The 0.05~0.35% of amount.
C of the present invention10 +Heavy aromatics selective hydrogenation ring opening catalyst has the advantage that compared with prior art
Catalyst of the present invention handles HY molecular sieve by ammonium fluosilicate solution, adjusts molecular sieve silica alumina ratio to preferred values, mentions
For the acid amount and acid strength for being suitable for；HY molecular sieve is handled simultaneously with ammonium fluosilicate solution and platiniferous solution, in the same of dealumination complement silicon
When supporting Pt element, promote Pt dispersion while make part Pt be distributed in dealuminzation generation fault location, guarantee molecular sieve on plus hydrogen
The high activity at center inhibits carbon distribution；After modified molecular screen and aluminium oxide molding, modification is impregnated again with platiniferous solution, guarantees oxygen
Changing also has enough plus hydrogen center on aluminium, provide hydrogenation activity position, inhibits coking；To by acidity and the tune for adding hydrogen center
Control improves the synergistic effect at support acidity center and noble metal so that the distribution of acid and noble metal is more reasonable；Finally it is prepared into
To catalyst can handle C under hydro condition10 +Heavy aromatics raw material, by C10 +Heavy aromatics is converted into the higher octane rich in BTX
It is worth gasoline component, C with higher10 +Heavy aromatics conversion ratio, higher high octane gasoline component yield and BTX light aromatics
Yield.
Specific embodiment
Illustrate C of the present invention below by example10 +The technical solution of the catalyst of heavy aromatics selective hydrogenation open loop, but simultaneously
It is non-to be only limitted to following embodiments.
Embodiment 1
(1) ammonium fluosilicate of 40g is dissolved in 1000mL deionized water, ammonium fluosilicate solution is made；
(2) the hydration chloroplatinic acid of 5g six is dissolved in 500mL deionized water, platinum acid chloride solution is made；
(3) 100g HY molecular sieve is added in 600mL deionized water and is stirred at 90 DEG C, and thereto with 5mL/min
Speed ammonium fluosilicate solution 1000mL is added dropwise, respectively when ammonium fluosilicate solution drips 1/2 total amount and ammonium fluosilicate solution
Same amount of platinum acid chloride solution is added when all dripping, 0.1% that total amount is final catalyst weight is added in Pt element；Fluorine silicon
After acid ammonium solution and platinum acid chloride solution all drip, aging 3h is persistently stirred；
(4) it after aging, is filtered and is washed with deionized, until fluorine element can not be detected in cleaning solution,
8h is dried under the conditions of 120 DEG C, the lower 500 DEG C of roastings 4h of air atmosphere obtains modified molecular screen；
(5) gained modified molecular screen in step (4) is uniformly mixed with 43g alumina powder, addition contains mass concentration
For 4% dust technology kneading extruded moulding, dry 8h, the lower 500 DEG C of roastings 4h of air atmosphere obtain shaping carrier at 120 DEG C；
(6) it takes platinum acid chloride solution obtained by step (2) to be added drop-wise in step (5) resulting carrier, it is small to carry out incipient impregnation 4
When, 4h is roasted at impregnated carrier is 8 hours, lower 500 DEG C of air atmosphere dry at 120 DEG C in air atmosphere, obtains catalyst
1, final Pt constituent content is the 0.15% of catalyst weight on catalyst 1；Performance evaluation
It will obtain heavy aromatics lightening catalyst and apply to comment in the performance of heavy aromatics selective opening fecund lightweight BTX aromatic hydrocarbons
Valence method is as follows:
10g heavy aromatics lightening catalyst is packed into fixed bed reactors, carries out the pretreatment of heavy aromatics lightening catalyst,
Pretreatment condition are as follows: rise to 250 DEG C of temperature in nitrogen atmosphere with 5~10 DEG C/min, kept for 2 hours at 250 DEG C, then with 1~2
DEG C/min is warming up to 320~360 DEG C, it is kept for 2 hours.The reaction condition of the catalyst is 360~430 DEG C, reaction pressure 3~
6MPa, weight (hourly) space velocity (WHSV) are 0.5~2.0h-1, hydrogen hydrocarbon volume ratio is 800~1200.The specific reaction condition of the present embodiment is temperature 380
DEG C, reaction pressure 4MPa, weight (hourly) space velocity (WHSV) 1.5h-1, hydrogen hydrocarbon volume ratio is 900.
Evaluation raw material property is shown in Table 1, and evaluation result is shown in Table 2.
Embodiment 2
(1) ammonium fluosilicate of 40g is dissolved in 1000mL deionized water, ammonium fluosilicate solution is made；
(2) the hydration chloroplatinic acid of 5g six is dissolved in 500mL deionized water, platinum acid chloride solution is made；
(3) 100g HY molecular sieve is added in 600mL deionized water and is stirred at 90 DEG C, and thereto with 10mL/
Ammonium fluosilicate solution 1000mL is added dropwise in the speed of min, respectively when ammonium fluosilicate solution drips 1/2 total amount and ammonium fluosilicate is molten
Same amount of platinum acid chloride solution is added when liquid all drips, 0.1% that total amount is final catalyst weight is added in Pt element.Fluorine
After ammonium silicate solution and platinum acid chloride solution all drip, aging 3h is persistently stirred；
(4) it after aging, is filtered and is washed with deionized, until fluorine element can not be detected in cleaning solution,
8h is dried under the conditions of 120 DEG C, the lower 500 DEG C of roastings 4h of air atmosphere obtains modified molecular screen；
(5) gained modified molecular screen in step (4) is uniformly mixed with 43g alumina powder, addition contains mass concentration
For 4% dust technology kneading extruded moulding, dry 8h, the lower 500 DEG C of roastings 4h of air atmosphere obtain shaping carrier at 120 DEG C；
(6) it takes platinum acid chloride solution obtained by step (2) to be added drop-wise in step (5) resulting carrier, it is small to carry out incipient impregnation 4
When, 4h is roasted at impregnated carrier is 8 hours, lower 500 DEG C of air atmosphere dry at 120 DEG C in air atmosphere, obtains catalyst
2, final Pt constituent content is the 0.15% of catalyst weight on catalyst 2；
2 evaluation method of catalyst is shown in that embodiment 1, evaluation raw material property are shown in Table 1, and evaluation result is shown in Table 2.
Embodiment 3
(1) ammonium fluosilicate of 40g is dissolved in 1000mL deionized water, ammonium fluosilicate solution is made；
(2) the hydration chloroplatinic acid of 5g six is dissolved in 500mL deionized water, platinum acid chloride solution is made；
(3) 100g HY molecular sieve is added in 600mL deionized water and is stirred at 90 DEG C, and thereto with 5mL/min
Speed ammonium fluosilicate solution 1000mL is added dropwise, respectively when ammonium fluosilicate solution drips 1/2 total amount and ammonium fluosilicate solution
Same amount of platinum acid chloride solution is added when all dripping, 0.05% that total amount is final catalyst weight is added in Pt element.Fluorine
After ammonium silicate solution and platinum acid chloride solution all drip, aging 3h is persistently stirred；
(4) it after aging, is filtered and is washed with deionized, until fluorine element can not be detected in cleaning solution,
8h is dried under the conditions of 120 DEG C, the lower 500 DEG C of roastings 4h of air atmosphere obtains modified molecular screen；
(5) gained modified molecular screen in step (4) is uniformly mixed with 43g alumina powder, addition contains mass concentration
For 4% dust technology kneading extruded moulding, dry 8h, the lower 500 DEG C of roastings 4h of air atmosphere obtain shaping carrier at 120 DEG C；
(6) it takes platinum acid chloride solution obtained by step (2) to be added drop-wise in step (5) resulting carrier, it is small to carry out incipient impregnation 4
When, roasting 4h obtains catalyst 3 at impregnated carrier is 8 hours, lower 500 DEG C of air atmosphere dry at 120 DEG C in air atmosphere,
Final Pt constituent content is the 0.1% of catalyst weight on catalyst 3；
3 evaluation method of catalyst is shown in that embodiment 1, evaluation raw material property are shown in Table 1, and evaluation result is shown in Table 2.
1 C of table10 +Heavy aromatics raw material composition
The evaluation result of 2 different catalysts of table
Note: reaction condition is 380 DEG C of temperature, reaction pressure 4MPa, weight (hourly) space velocity (WHSV) 1.5h-1, hydrogen hydrocarbon volume ratio is 900.
Claims (2)
1. a kind of C10 +The catalyst of heavy aromatics selective hydrogenation open loop, which is characterized in that in terms of catalyst quality, the catalysis
Agent each component mass percentage composition are as follows: HY molecular sieve 50~80%, platinum 0.05~0.35%, surplus are aluminium oxide；Institute
State the SiO of catalyst2/A12O3Molar ratio is 8~13, and specific surface area is 450~600m20.35~0.7cm of/g, Kong Rongwei3/g；
The catalyst be HY molecular sieve first through ammonium fluosilicate and the solution combined modification of platiniferous, then with aluminium oxide extruded moulding,
After dry, roasting, most it is made after the modification of platiniferous solution incipient impregnation, dry, roasting afterwards.
2. C described in a kind of claim 110 +The preparation method of the catalyst of heavy aromatics selective hydrogenation open loop, which is characterized in that
Include the following steps:
(1) ammonium fluosilicate is dissolved in the ammonium fluosilicate solution that 0.02~0.06g/mL is made in deionized water；
(2) chloroplatinic acid or platinum nitrate are dissolved in deionized water and platinum acid chloride solution or platinum nitrate solution or the chlorine is made
Platinic acid solution is made according to a conventional method of spongy platinum；
(3) HY molecular sieve is add to deionized water at 70~95 DEG C and stirs into suspension, deionized water and HY molecular sieve
Volume ratio be 5:1~20:1, and ammonium fluosilicate solution, fluosilicic acid are added dropwise with the speed of 0.1~0.5mL/min into suspension
The volume ratio of ammonium salt solution and suspension is 0.5:1~2:1, respectively when ammonium fluosilicate solution drips 1/5~3/5 total amount and fluorine
Chloroplatinic acid is added when ammonium silicate solution all drips or total amount is added dropwise twice and accounts for most by Pt element for platinum nitrate solution, platiniferous solution
0.025~0.3% meter of whole catalyst weight；After ammonium fluosilicate solution and platiniferous solution all drip, aging 1 is persistently stirred
~5h；
(4) it after aging, is filtered, deionized water washing, until fluorine element can not be detected in cleaning solution, 90~
6~12h is dried under the conditions of 150 DEG C, 420~580 DEG C of 4~8h of roasting under air atmosphere obtain modified molecular screen；
(5) gained modified molecular screen in step (4) is uniformly mixed with alumina powder, be added contain mass concentration for 2~
10% dust technology kneading extruded moulding, dry 6~12h at 90~150 DEG C, 420~580 DEG C of 4~8h of roasting under air atmosphere,
Obtain shaping carrier；
(6) chloroplatinic acid obtained by a certain amount of step (2) or platinum nitrate solution is taken to be added drop-wise in step (5) resulting carrier, carry out etc.
Volume impregnation 2~8 hours, impregnated carrier was 6~12 hours dry at 90~150 DEG C in air atmosphere, 420 under air atmosphere
~580 DEG C of 4~8h of roasting, obtain catalyst, and final Pt constituent content on catalyst is made to reach the 0.05 of the catalyst weight
~0.35%.
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