CN108940354B - C10+Heavy aromatics selective hydrogenation ring-opening catalyst and preparation method thereof - Google Patents
C10+Heavy aromatics selective hydrogenation ring-opening catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 17
- 238000007142 ring opening reaction Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 46
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 40
- 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 38
- 239000002808 molecular sieve Substances 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 22
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 13
- 238000005470 impregnation Methods 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011148 porous material Substances 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 230000032683 aging Effects 0.000 claims description 12
- 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 12
- 238000005406 washing Methods 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 238000004898 kneading Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000003502 gasoline Substances 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- -1 aryl olefin Chemical class 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 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
- 239000006227 byproduct Substances 0.000 description 4
- 238000007323 disproportionation reaction Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000004687 hexahydrates Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- UZKBSZSTDQSMDR-UHFFFAOYSA-N 1-[(4-chlorophenyl)-phenylmethyl]piperazine Chemical compound C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)N1CCNCC1 UZKBSZSTDQSMDR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 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
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- 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
-
- B01J35/617—
-
- B01J35/633—
-
- B01J35/635—
-
- 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
Abstract
The invention discloses a C10 +A catalyst for selective hydrogenation ring opening of heavy aromatics and a preparation method thereof. The catalyst comprises the following components in percentage by mass based on the mass of the catalyst: 50-80% of HY molecular sieve, 0.05-0.35% of platinum metal and the balance of aluminum oxide; SiO of the catalyst2/A12O3The molar ratio is 8-13, and the specific surface area is 450-600 m2A pore volume of 0.35 to 0.7 cm/g3(ii)/g; the catalyst is prepared by performing composite modification on an HY molecular sieve by ammonium fluosilicate and a platinum-containing solution, extruding and molding the HY molecular sieve and aluminum oxide into strips, drying and roasting, and performing equal-volume impregnation modification, drying and roasting on the HY molecular sieve by the platinum-containing solution. The catalyst has higher activity and stability for lightening heavy aromatics, and is particularly suitable for selective hydrogenation ring opening and ring opening of inferior macromolecular heavy aromatics to produce light BTX aromatics or high-octane gasoline in a large amount.
Description
Technical Field
The invention relates to the field of heavy aromatic light catalysts, and in particular relates to C10 +A catalyst for selectively hydrogenating heavy aromatics to open rings and produce light BTX aromatics or high-octane gasoline in a large amount and a preparation method thereof.
Background
The heavy aromatic hydrocarbon mainly refers to C byproduct in the processing process of petroleum and coal10And the aromatic hydrocarbons are mainly from C byproduct of catalytic reforming unit in oil refinery10 +By-product C of heavy aromatics and ethylene cracking device10 +The heavy aromatics and the aromatics are disproportionated and isomerized to generate oil and heavy aromatics as by-products of high-temperature coking of coal. The composition of the heavy aromatics is very complex and cannot be fully utilized for a long time, and the heavy aromatics are sold or blended with fuel oil at low price basically in China, so that the resource waste is caused and the environment is polluted.
The Tatoray process is a typical toluene disproportionation and transalkylation process with toluene and C9 +Aromatic hydrocarbons (mainly C)9Aromatic hydrocarbon) as raw material, and adopts disproportionation and transalkylation catalyst to increase yield of light aromatic hydrocarbon under the condition of hydrogen, but monocyclic heavy aromatic hydrocarbon is easy to be hydrogenated and saturated, the liquid yield is low, and the C in the feed material needs to be strictly controlled10 +Aromatic content and indane content to prevent catalyst deactivation.
Patent CN98805980 discloses a catalyst C9 +A process for preparing light arylhydrocarbon from heavy arylhydrocarbon and toluene features that the beta-zeolite modified by Ni and Bi is used as catalyst, the total conversion rate of heavy arylhydrocarbon reaches 47%, the selectivity of benzene and xylene reaches 88%, and the C content in the raw material of mixed arylhydrocarbon is strictly limited10 +Content of aromatic hydrocarbons, and the patent does not disclose the catalyst pair C10 +The conversion capacity of aromatic hydrocarbons. In order to improve the stability of the catalyst, the patent proposes to introduce a hydrogenation metal component on the catalyst, but the excessively enhanced hydrogenation performance causes severe side reactions such as aromatic saturation and cracking, and the like, so that the yield of the aromatic hydrocarbon is reduced.
CN1018423360A disclosesFirstly, C is added9 +The aromatic hydrocarbon raw material, hydrogen, benzene and/or toluene contact with a first catalyst (preferably Pt metal modified ZSM-5) to remove olefin components in the raw material, the obtained product contacts with a second catalyst (preferably Pt metal modified ZSM-12) under another condition to carry out transalkylation reaction, and xylene is obtained. C9 +The conversion rate of aromatic hydrocarbon is close to 60%.
CN1711341A reaction of C9 +The mixture of aromatic hydrocarbon and toluene is at 400-454 ℃, 1.48-3.55 MPa, hydrogen-hydrocarbon molar ratio of 1-3 and weight hourly space velocity of 1-5 h-1Under the condition of (A), contacting with a bed layer filled with two molecular sieve catalysts to produce benzene, dimethylbenzene and C9 +The conversion of aromatics can reach about 59%. The two processes adopt two catalysts for sectional treatment aiming at the characteristics of raw materials to realize C9 +The conversion rate of aromatic hydrocarbon is maximized, and the raw material composition is C9Aromatic hydrocarbon is the main component, the loss of alkyl is large, and a large amount of low-carbon non-aromatic hydrocarbon is generated.
The hydrogenation and lightening technology of heavy aromatics of RIPP has the advantages that the reaction temperature is 360-460 ℃, the reaction pressure is 1-3 MPa, and the weight hourly space velocity is 1-3 h-1The volume ratio of hydrogen to oil is 500-1500: 1, converting heavy aromatics into light aromatics such as BTX and the like. However, the alkyl loss in the hydrogenation process is large, and the liquid yield is only about 85%. Lower reaction pressures can be used to ensure that the liquid does not saturate the aromatic rings too much, but under these conditions, the ring opening of the polycyclic aromatic hydrocarbons is more difficult and therefore the reaction conversion is lower, and there is no competitive advantage over toluene and heavy aromatics disproportionation and transalkylation techniques.
In general, the raw material composition treated by the technology is mainly C9And a small amount of C10Aromatic hydrocarbons, the aromatic type being predominantly monocyclic, but C10 +The heavy aromatic hydrocarbon has larger difference with the composition and property, contains a large amount of components such as polycyclic aromatic hydrocarbon, aryl olefin and the like, can not be converted into light monocyclic aromatic hydrocarbon through disproportionation and transalkylation reactions, and is easy to coke and deposit carbon to cause catalyst deactivation. Therefore, there is a need for the targeted development of C rich in condensed ring aromatic hydrocarbons10 +Related art of heavy aromatic hydrocarbons such thatC10 +The heavy aromatics are effectively utilized.
Disclosure of Invention
The invention aims to solve the problem that C cannot be effectively utilized in the prior art10 +The disadvantage of heavy aromatics makes it highly useful, and provides a new catalyst for conversion of heavy aromatics to light aromatics, namely C10 +A catalyst for selective hydrogenation ring opening of heavy aromatics and a preparation method thereof. The catalyst prepared by the method has the characteristics of high conversion rate of C10+ heavy aromatic hydrocarbon raw materials, high-value product yield, good aromatic hydrocarbon selectivity and the like, and can realize high yield of light BTX aromatic hydrocarbon or high-octane gasoline.
The invention provides a compound C10 +The catalyst for selective hydrogenation and ring opening of heavy aromatics comprises a catalyst carrier, a catalyst carrier and a catalyst carrier, wherein the catalyst carrier consists of an HY molecular sieve and alumina, and the active component is a noble metal Pt; the catalyst comprises the following components in percentage by mass:
the HY molecular sieve content is 50-80%;
the platinum metal content is 0.05-0.35%;
the balance of alumina;
SiO of the catalyst2/A12O3The molar ratio is 8-13, and the specific surface area is 450-600 m2Per g, pore volume of 0.35-0.7 cm3/g；
Said C is10 +The heavy aromatic hydrocarbon is C10And above aromatic hydrocarbons, the final distillation point is less than or equal to 350 ℃;
the catalyst is prepared by performing composite modification on an HY molecular sieve by ammonium fluosilicate and a platinum-containing solution, extruding and molding the HY molecular sieve and aluminum oxide into strips, drying and roasting, and finally performing equal-volume impregnation modification, drying and roasting on the HY molecular sieve by the platinum-containing solution.
The invention also discloses the compound C10 +A preparation method of a heavy aromatics selective hydrogenation ring-opening catalyst comprises the following steps:
(1) dissolving ammonium fluosilicate in deionized water to prepare 0.02-0.06 g/mL of ammonium fluosilicate solution;
(2) dissolving chloroplatinic acid or platinum nitrate in deionized water to prepare a chloroplatinic acid solution or a platinum nitrate solution, or preparing the chloroplatinic acid solution from spongy platinum by a conventional method;
(3) adding an HY molecular sieve into deionized water, and stirring at 70-95 ℃ to form a suspension, wherein the volume ratio of the deionized water to the molecular sieve is 5: 1-20: 1, dropwise adding an ammonium fluosilicate solution into the suspension at a speed of 0.1-0.5 mL/min, wherein the volume ratio of the ammonium fluosilicate solution to the suspension is 0.5: 1-2: 1, respectively adding a chloroplatinic acid or platinum nitrate solution when the ammonium fluosilicate solution is completely added in an amount of 1/5-3/5 and when the ammonium fluosilicate solution is completely added in an amount, wherein the total amount of the platinum-containing solution added in two times is calculated by that Pt element accounts for 0.025-0.3% of the weight of the final catalyst; after the ammonium fluosilicate solution and the platinum-containing solution are completely added dropwise, continuously stirring and aging for 1-5 h;
(4) after the aging is finished, filtering and washing with deionized water until fluorine element cannot be detected in the washing liquid, drying for 6-12 h at the temperature of 90-150 ℃, and roasting for 4-8 h at the temperature of 420-580 ℃ in an air atmosphere to obtain the modified molecular sieve;
(5) uniformly mixing the modified molecular sieve obtained in the step (4) with alumina powder, adding dilute nitric acid with the mass concentration of 2-10%, kneading, extruding, molding, drying at 90-150 ℃ for 6-12 h, and roasting at 420-580 ℃ for 4-8 h under an air atmosphere to obtain a molded carrier;
(6) and (3) dropwise adding a certain amount of chloroplatinic acid or platinum nitrate solution obtained in the step (2) into the formed carrier obtained in the step (5), carrying out isovolumetric impregnation for 2-8 hours, drying the impregnated carrier at 90-150 ℃ for 6-12 hours in an air atmosphere, and roasting at 420-580 ℃ for 4-8 hours in an air atmosphere to obtain the catalyst, wherein the final Pt element content on the catalyst is 0.05-0.35% of the weight of the catalyst.
Invention C10 +Compared with the prior art, the heavy aromatics selective hydrogenation ring-opening catalyst has the following advantages:
the catalyst provided by the invention is used for treating the HY molecular sieve by using an ammonium fluosilicate solution, and the silicon-aluminum ratio of the molecular sieve is adjusted to a better value, so that proper acid amount and acid strength are provided; an HY molecular sieve is treated by an ammonium fluosilicate solution and a platinum-containing solution simultaneously, Pt element is loaded while dealuminizing and supplementing silicon, Pt is promoted to be dispersed, and part of P is simultaneously addedt is distributed at the defect position generated by dealumination, so that the high activity of the hydrogenation center on the molecular sieve is ensured, and carbon deposition is inhibited; after the modified molecular sieve and alumina are formed, dipping and modifying the modified molecular sieve and alumina again by using a platinum-containing solution, ensuring that the alumina also has enough hydrogenation centers, providing hydrogenation active sites and inhibiting coking; therefore, the acidity and the noble metal are distributed more reasonably by regulating and controlling the acidity and the hydrogenation center, and the synergistic effect of the carrier acidity center and the noble metal is improved; the finally prepared catalyst can be treated under the hydrogen condition10 +Heavy aromatics feed from10 +Heavy aromatics are converted into BTX-rich high-octane gasoline component with higher C10 +Heavy aromatics conversion, higher high octane gasoline component yield and BTX light aromatics yield.
Detailed Description
The invention C is illustrated by the following examples10 +The technical scheme of the catalyst for selective hydrogenation ring opening of heavy aromatics is not limited to the following examples.
Example 1
(1) Dissolving 40g of ammonium fluosilicate in 1000mL of deionized water to prepare an ammonium fluosilicate solution;
(2) dissolving 5g of chloroplatinic acid hexahydrate in 500mL of deionized water to prepare a chloroplatinic acid solution;
(3) adding 100g of HY molecular sieve into 600mL of deionized water, stirring at 90 ℃, dropwise adding 1000mL of ammonium fluorosilicate solution at the speed of 5mL/min, and adding the same amount of chloroplatinic acid solution when the ammonium fluorosilicate solution is completely added in 1/2 percent and when the ammonium fluorosilicate solution is completely added in, wherein the total adding amount of Pt element is 0.1 percent of the weight of the final catalyst; after the ammonium fluosilicate solution and the chloroplatinic acid solution are completely added, continuously stirring and aging for 3 hours;
(4) after the aging is finished, filtering, washing with deionized water until fluorine element cannot be detected in the washing liquid, drying for 8h at 120 ℃, and roasting for 4h at 500 ℃ in an air atmosphere to obtain the modified molecular sieve;
(5) uniformly mixing the modified molecular sieve obtained in the step (4) with 43g of alumina powder, adding dilute nitric acid with the mass concentration of 4%, kneading, extruding, molding, drying at 120 ℃ for 8 hours, and roasting at 500 ℃ for 4 hours in an air atmosphere to obtain a molded carrier;
(6) dropwise adding the chloroplatinic acid solution obtained in the step (2) into the carrier obtained in the step (5), carrying out equal-volume impregnation for 4 hours, drying the impregnated carrier at 120 ℃ for 8 hours in an air atmosphere, and roasting the impregnated carrier at 500 ℃ for 4 hours in the air atmosphere to obtain a catalyst 1, wherein the final Pt element content on the catalyst 1 is 0.15% of the weight of the catalyst; evaluation of Performance
The performance evaluation method for applying the obtained heavy aromatic hydrocarbon light catalyst to the selective ring opening of heavy aromatic hydrocarbons to produce light BTX aromatic hydrocarbons in a high yield comprises the following steps:
loading 10g of heavy aromatic hydrocarbon conversion catalyst into a fixed bed reactor, and carrying out pretreatment on the heavy aromatic hydrocarbon conversion catalyst, wherein the pretreatment conditions are as follows: raising the temperature to 250 ℃ at a speed of 5-10 ℃/min in a hydrogen atmosphere, keeping the temperature at 250 ℃ for 2 hours, raising the temperature to 320-360 ℃ at a speed of 1-2 ℃/min, and keeping the temperature for 2 hours. The reaction conditions of the catalyst are 360-430 ℃, the reaction pressure is 3-6 MPa, and the weight hourly space velocity is 0.5-2.0 h-1The volume ratio of hydrogen to hydrocarbon is 800 to 1200. The specific reaction conditions of the example are that the temperature is 380 ℃, the reaction pressure is 4MPa, and the weight hourly space velocity is 1.5h-1The hydrogen-hydrocarbon volume ratio was 900.
The properties of the raw materials used for the evaluation are shown in Table 1, and the evaluation results are shown in Table 2.
Example 2
(1) Dissolving 40g of ammonium fluosilicate in 1000mL of deionized water to prepare an ammonium fluosilicate solution;
(2) dissolving 5g of chloroplatinic acid hexahydrate in 500mL of deionized water to prepare a chloroplatinic acid solution;
(3) 100g of HY molecular sieve is added into 600mL of deionized water and stirred at 90 ℃, 1000mL of ammonium fluosilicate solution is dropwise added at the speed of 10mL/min, the same amount of chloroplatinic acid solution is respectively added when the dropwise addition of the ammonium fluosilicate solution is finished by 1/2 and when the dropwise addition of the ammonium fluosilicate solution is finished, and the total addition amount of Pt element is 0.1 percent of the weight of the final catalyst. After the ammonium fluosilicate solution and the chloroplatinic acid solution are completely added, continuously stirring and aging for 3 hours;
(4) after the aging is finished, filtering, washing with deionized water until fluorine element cannot be detected in the washing liquid, drying for 8h at 120 ℃, and roasting for 4h at 500 ℃ in an air atmosphere to obtain the modified molecular sieve;
(5) uniformly mixing the modified molecular sieve obtained in the step (4) with 43g of alumina powder, adding dilute nitric acid with the mass concentration of 4%, kneading, extruding, molding, drying at 120 ℃ for 8 hours, and roasting at 500 ℃ for 4 hours in an air atmosphere to obtain a molded carrier;
(6) dropwise adding the chloroplatinic acid solution obtained in the step (2) into the carrier obtained in the step (5), carrying out equal-volume impregnation for 4 hours, drying the impregnated carrier at 120 ℃ for 8 hours in an air atmosphere, and roasting the impregnated carrier at 500 ℃ for 4 hours in the air atmosphere to obtain a catalyst 2, wherein the final Pt element content on the catalyst 2 is 0.15% of the weight of the catalyst;
the evaluation method of catalyst 2 is shown in example 1, the properties of the raw materials used for the evaluation are shown in Table 1, and the evaluation results are shown in Table 2.
Example 3
(1) Dissolving 40g of ammonium fluosilicate in 1000mL of deionized water to prepare an ammonium fluosilicate solution;
(2) dissolving 5g of chloroplatinic acid hexahydrate in 500mL of deionized water to prepare a chloroplatinic acid solution;
(3) 100g of HY molecular sieve is added into 600mL of deionized water and stirred at 90 ℃, 1000mL of ammonium fluosilicate solution is dropwise added at the speed of 5mL/min, the same amount of chloroplatinic acid solution is respectively added when the dropwise addition of the ammonium fluosilicate solution is finished by 1/2 and when the dropwise addition of the ammonium fluosilicate solution is finished, and the total addition amount of Pt element is 0.05 percent of the weight of the final catalyst. After the ammonium fluosilicate solution and the chloroplatinic acid solution are completely added, continuously stirring and aging for 3 hours;
(4) after the aging is finished, filtering, washing with deionized water until fluorine element cannot be detected in the washing liquid, drying for 8h at 120 ℃, and roasting for 4h at 500 ℃ in an air atmosphere to obtain the modified molecular sieve;
(5) uniformly mixing the modified molecular sieve obtained in the step (4) with 43g of alumina powder, adding dilute nitric acid with the mass concentration of 4%, kneading, extruding, molding, drying at 120 ℃ for 8 hours, and roasting at 500 ℃ for 4 hours in an air atmosphere to obtain a molded carrier;
(6) dropwise adding the chloroplatinic acid solution obtained in the step (2) into the carrier obtained in the step (5), carrying out equal-volume impregnation for 4 hours, drying the impregnated carrier at 120 ℃ for 8 hours in an air atmosphere, and roasting the impregnated carrier at 500 ℃ for 4 hours in the air atmosphere to obtain a catalyst 3, wherein the final Pt element content on the catalyst 3 is 0.1% of the weight of the catalyst;
the evaluation method of catalyst 3 is shown in example 1, the properties of the raw materials used for the evaluation are shown in Table 1, and the evaluation results are shown in Table 2.
TABLE 1C10 +Heavy aromatics feedstock composition
TABLE 2 evaluation results of different catalysts
Note: the reaction conditions are that the temperature is 380 ℃, the reaction pressure is 4MPa, and the weight hourly space velocity is 1.5h-1The hydrogen-hydrocarbon volume ratio was 900.
Claims (2)
1. C10 +The catalyst for selective hydrogenation and ring opening of heavy aromatics is characterized by comprising the following components in percentage by mass: 50-80% of HY molecular sieve, 0.05-0.35% of platinum metal and the balance of aluminum oxide; SiO of the catalyst2/A12O3The molar ratio is 8-13, and the specific surface area is 450-600 m2A pore volume of 0.35 to 0.7 cm/g3/g；
The catalyst is prepared by the following steps:
(1) dissolving ammonium fluosilicate in deionized water to prepare 0.02-0.06 g/mL ammonium fluosilicate solution;
(2) dissolving chloroplatinic acid or platinum nitrate in deionized water to prepare a chloroplatinic acid solution or a platinum nitrate solution;
(3) adding an HY molecular sieve into deionized water, and stirring at 70-95 ℃ to form a suspension, wherein the volume ratio of the deionized water to the HY molecular sieve is 5: 1-20: 1, dropwise adding an ammonium fluosilicate solution into the suspension at a speed of 0.1-0.5 mL/min, wherein the volume ratio of the ammonium fluosilicate solution to the suspension is 0.5: 1-2: 1, respectively adding a chloroplatinic acid or platinum nitrate solution when the ammonium fluosilicate solution is completely added in an amount of 1/5-3/5 and when the ammonium fluosilicate solution is completely added in an amount, wherein the total amount of the platinum-containing solution added in two times is calculated by that Pt element accounts for 0.025-0.3% of the weight of the final catalyst; after the ammonium fluosilicate solution and the platinum-containing solution are completely added dropwise, continuously stirring and aging for 1-5 h;
(4) after the aging is finished, filtering and washing with deionized water until fluorine element cannot be detected in the washing liquid, drying for 6-12 h at the temperature of 90-150 ℃, and roasting for 4-8 h at the temperature of 420-580 ℃ in an air atmosphere to obtain the modified molecular sieve;
(5) uniformly mixing the modified molecular sieve obtained in the step (4) with alumina powder, adding dilute nitric acid with the mass concentration of 2-10%, kneading, extruding, molding, drying at 90-150 ℃ for 6-12 h, and roasting at 420-580 ℃ for 4-8 h under an air atmosphere to obtain a molded carrier;
(6) and (3) dropwise adding a certain amount of chloroplatinic acid or platinum nitrate solution obtained in the step (2) into the carrier obtained in the step (5), carrying out isovolumetric impregnation for 2-8 hours, drying the impregnated carrier in an air atmosphere at 90-150 ℃ for 6-12 hours, and roasting in an air atmosphere at 420-580 ℃ for 4-8 hours to obtain the catalyst, wherein the final Pt element content on the catalyst is 0.05-0.35% of the weight of the catalyst.
2. A compound of claim 1 as C10 +A preparation method of a catalyst for selective hydrogenation ring opening of heavy aromatics is characterized in that,
the preparation method comprises the following steps:
(1) dissolving ammonium fluosilicate in deionized water to prepare 0.02-0.06 g/mL ammonium fluosilicate solution;
(2) dissolving chloroplatinic acid or platinum nitrate in deionized water to prepare a chloroplatinic acid solution or a platinum nitrate solution;
(3) adding an HY molecular sieve into deionized water, and stirring at 70-95 ℃ to form a suspension, wherein the volume ratio of the deionized water to the HY molecular sieve is 5: 1-20: 1, dropwise adding an ammonium fluosilicate solution into the suspension at a speed of 0.1-0.5 mL/min, wherein the volume ratio of the ammonium fluosilicate solution to the suspension is 0.5: 1-2: 1, respectively adding a chloroplatinic acid or platinum nitrate solution when the ammonium fluosilicate solution is completely added in an amount of 1/5-3/5 and when the ammonium fluosilicate solution is completely added in an amount, wherein the total amount of the platinum-containing solution added in two times is calculated by that Pt element accounts for 0.025-0.3% of the weight of the final catalyst; after the ammonium fluosilicate solution and the platinum-containing solution are completely added dropwise, continuously stirring and aging for 1-5 h;
(4) after the aging is finished, filtering and washing with deionized water until fluorine element cannot be detected in the washing liquid, drying for 6-12 h at the temperature of 90-150 ℃, and roasting for 4-8 h at the temperature of 420-580 ℃ in an air atmosphere to obtain the modified molecular sieve;
(5) uniformly mixing the modified molecular sieve obtained in the step (4) with alumina powder, adding dilute nitric acid with the mass concentration of 2-10%, kneading, extruding, molding, drying at 90-150 ℃ for 6-12 h, and roasting at 420-580 ℃ for 4-8 h under an air atmosphere to obtain a molded carrier;
(6) and (3) dropwise adding a certain amount of chloroplatinic acid or platinum nitrate solution obtained in the step (2) into the carrier obtained in the step (5), carrying out isovolumetric impregnation for 2-8 hours, drying the impregnated carrier in an air atmosphere at 90-150 ℃ for 6-12 hours, and roasting in an air atmosphere at 420-580 ℃ for 4-8 hours to obtain the catalyst, wherein the final Pt element content on the catalyst is 0.05-0.35% of the weight of the catalyst.
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