CN1057476A - The aromatization of hydrocarbons of Zincleaching-resistant contains the zinc zeolite catalyst - Google Patents

The aromatization of hydrocarbons of Zincleaching-resistant contains the zinc zeolite catalyst Download PDF

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CN1057476A
CN1057476A CN 91105256 CN91105256A CN1057476A CN 1057476 A CN1057476 A CN 1057476A CN 91105256 CN91105256 CN 91105256 CN 91105256 A CN91105256 A CN 91105256A CN 1057476 A CN1057476 A CN 1057476A
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zeolite
zinc
zsm
carbon
catalyst
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CN1040993C (en
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佘励勤
刘兴云
李宣文
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Peking University
China Petrochemical Corp
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China Petrochemical Corp
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Abstract

A kind of method that contains the zinc zeolite catalyst for preparing the low-carbon (LC) aromatization of hydrocarbons of Zincleaching-resistant, it is to adopt difficult reductive zinc compound on the thermodynamics, as ZnS, Zn 2SiO 4, Zn 2TiO 4, ZnAl 2O 4Deng, be stated from the ZSM-5 zeolite, can adopt the method for zinc compound direct impregnation ZSM-5 zeolite to prepare, also zinc compound and ZSM-5 zeolite mechanically mixing method can be prepared.This modification contain the zinc zeolite catalyst, be suitable for the aromizing of carbon 2 to carbon 12 aliphatic hydrocarbons.

Description

The aromatization of hydrocarbons of Zincleaching-resistant contains the zinc zeolite catalyst
Since the ZSM-5 zeolite came out, the ZSM-5 zeolite by some metallic element modification can make low molecular hydrocarbon be catalytically conveted to aromatic hydroxy compounds such as benzene, toluene and dimethylbenzene.In these modifying elements, be best with zinc and gallium.Compare with gallium, zinc is common element, and is cheap and easy to get; Gallium then is a rare metal.Therefore be many to contain the zinc supersiliceous zeolite as the patent application of the catalyzer of low molecular hydrocarbon aromizing.Because zinc has a fatal weakness, it exists in required high temperature and the reaction system in the aromatization process under the such reducing atmosphere of hydrogen and hydrocarbon, be easy to be reduced to metallic zinc, and the zinc in the zeolite catalyst is run off easily, thereby lose the catalytic activity of aromizing gradually.
Now existing the whole bag of tricks prevents the loss of zinc.
1. add certain second metal group and assign to stablize zinc, United States Patent (USP) 4,097,367,4,128,504 and 4,157,293 mention and add IB family or VIII family metal (as Pt, Pd, Cu, Ni) or metals such as Ge, Rh as second component beyond the zinc, can reduce the loss degree of zinc to some extent, United States Patent (USP) 4,490,569 mention the adding gallium can reduce the zinc loss that contains the zinc zeolite.
2. carry out prevulcanized with sulfurous gas to containing the zinc zeolite, the clear 62-115 of Japanese Patent, 087, adopt thiophene, dithiocarbonic anhydride, hydrogen sulfide to carry out pre-treatment to containing the zinc zeolite, contain in the aromatization of zinc zeolite catalyst at lower carbon number hydrocarbons through pretreated, can reduce the loss of zinc, can suppress C simultaneously 1And C 2The generation of light hydrocarbon.
3. add a kind of nonmetal oxide or sulfide in raw material, European patent EP 0325,859 adopts and adds the 0.05～20%(weight that accounts for the raw material total amount) nonmetal oxide or sulfide, as CO 2, water vapor, SO 2, CS 2Deng, can suppress the loss of zinc in the catalyzer.
4. Japanese universe intelligence row is incorporated on the zeolite structured skeleton when having reported zinc element that modification is used at zeolite synthesis in " Successful Design of Catalysts " book, makes the zinc that contains in the Pt/H-Zn-silicon zeolite more stable than crossover zinc.
Above-mentioned four kinds of methods all have in various degree effect to the Zincleaching-resistant of zeolite catalyst, but they all also have certain weak point.For example United States Patent (USP) 4,097, and 367,4,128,504 add second kind of metal such as IB family, VIII family metal or germanium, rhenium, rare earth, gallium, and these second metal majorities are rare metals, cost is than higher, and adds second metal and tend to reduce the selectivity that generates aromatic hydrocarbons.For clear 62-115 of day, 087 pre-vulcanization process that proposes has then increased the operation to catalyst treatment, makes technology more complicated.For EP 0325,859 patents add nonmetal oxide or the sulfide method in the reaction raw materials, its shortcoming is that raw material is diluted, the result reduces production efficiency, the adding water vapor also can cause the slowly hydrolysis of zeolite framework aluminium, reduce the activity of such catalysts position, and then influence the performance of catalyzer.For the method for introducing zinc when the synthetic zeolite, its shortcoming is will use organic amine in building-up process, like this preparation contain zinc zeolite cost height, and environmental pollution problems is arranged, the hydrothermal stability of this catalyzer is also not very good, therefore influences life of catalyst.
Purpose of the present invention is exactly in order to overcome some shortcomings of aforesaid method, adopting the zinc compound or the mixture of common easy row is the aromatized catalyst of feedstock production Zincleaching-resistant, be suitable for the aromizing of carbon 2, produce benzene, toluene and dimethylbenzene to the aliphatic hydrocarbon of carbon 12.
For achieving the above object, the present invention selects reductive zinc compound on thermodynamics for use, as ZnS, Zn 2SiO 4, Zn 2TiO 4, ZnAl 2O 4Or be the ZSM-5 zeolite catalyst of feedstock production zinc modification with the mixing salt of common zinc salt and water miscible sulfide, vitriol.
Catalyzer is made up of with zinc compound greater than 24 ZSM-5 zeolite and modification a kind of silica alumina ratio.Zinc compound can be ZnS, ZnSO 4, Zn 2SiO 4, Zn 2SiO 4, ZnAl 2O 4Be stated from the zeolite etc. form.Zinc content is 0.1～30%(weight of amount of zeolite).
The ZSM-5 zeolite can adopt direct method synthetic ZSM-5, can reduce cost and avoid the pollution of organic amine to environment like this.
Sodium type ZSM-5 zeolite is earlier with dilute mineral acid [HCL or HNO 3And ammonium salt is (as NH 4NO 3)] exchange, make to contain the sodium amount and drop to≤0.02%, obtain ammonium type ZSM-5 zeolite.
Ammonium type ZSM-5 zeolite can add an amount of difficulty reduction zinc salt with mechanical mixing.These zinc salts comprise ZnS, ZnSiO 4, ZnTiO 4, ZnAl 2O 4Deng.
The adding of zinc can by contain the zinc mixing salt wet pickling process be downloaded on the ammonium type ZSM-5 zeolite.Contain the zinc mixing salt and comprise that a kind of water-soluble zinc salt (can be zinc sulfate, zinc acetate, zinc nitrate etc.) and a kind of water miscible sulfocompound (can be ammonium sulfides, and the water soluble sulfate of elements such as Mg or Al, Ti) form, dipping is after drying and roasting is made the zinc modification zeolite.
In order to improve the reactivity worth of zeolite, zeolite can give earlier with some chemical dealuminization agent (NH for example 4SiF 6, oxalic acid-ammonium oxalate, EDTA etc.) the control dealuminzation is arranged, also can carry out the hydrothermal treatment consists of appropriateness.
The zinc modification zeolite can add 0～50%(weight) binding agent, binding agent comprises porous amorphous silica gel, amorphous alumina etc.
Producing aromatic hydrocarbons raw materials used can be by the aliphatic hydrocarbon of carbon 2 to carbon 12, can be single hydrocarbon of planting, and also can be the mixture of hydro carbons, can be alkane, also can be alkene, or the mixture of alkene and alkane.For example, refinery's liquefied gas, 4 mixtures, pyrolysis gasoline etc. from the isolated carbon 2 of Sweet natural gas to carbon.Reaction conditions is different because of raw material, and temperature of reaction is 400～600 ℃, and pressure is 1～10 normal atmosphere, and the charging air speed is 0.1～100 hour -1
With the zinc catalyst that contains of the inventive method preparation, it is stable that its zinc component can keep under reaction system atmosphere.Compare with the common zinc ZSM-5 zeolite catalyst that contains, estimate under the same conditions, the present invention contains zinc zeolite catalyst zinc turnover rate and only is common 1/10th to 1/4th (the seeing attached list 1) that contain the zinc zeolite catalyst.Its aromizing performance also be improved significantly, its selectivity be significantly improved (seeing attached list 2).Test from reaction stability, catalyst runs 1000 hours (regenerating therebetween six times), the yield that is changed into benzene,toluene,xylene by refinery's liquefaction vapour remains between 35～45%.
Embodiment 1 preparation ammonium type ZSM-5 zeolite
A. to by organic amine synthetic ZSM-5 zeolite,, use 2MNH then earlier 540 ℃ of roastings 3 hours 4NO 3Solution (sieve liquor ratio=1: 10) exchange six times refluxed 2 hours down at 90～98 ℃ at every turn, washed, filtered 110 ℃ of following dried overnight with deionized water again.
B. by direct method (is raw material without organic amine) synthetic ZSM-5 zeolite, with 0.5N HCL(sieve liquor ratio=1: 10) exchange four times, use 2M NH again 4NO 3Solution exchange twice, washing, filtration, 110 ℃ of following dried overnight.
The ZSM-5 zeolite that obtains by a and b step process contain sodium amount≤0.02%.
C. prepare dealuminzation ammonium type ZSM-5 zeolite,
In the zeolite that 62 gram a or b steps make, add 25 gram (NH 4) 2SO 4, add 500ml water, add H again 2C 2O 4Solution (8.3 gram H 2C 2O 42H 2O+9.4 restrains (NH 4) 2C 2O 4The solution that+350ml water obtains), about 90 ℃, refluxed 3 hours, filter, washing, 110 ℃ dry 3 hours down.
D. the hydrothermal treatment consists of dealuminzation ammonium type ZSM-5 zeolite
The ammonium type ZSM-5 zeolite that the c step is obtained places crystal reaction tube, and bubbling air (50ml/ minute) is warming up to 500 ℃, constant temperature is after half an hour, feed water vapor (making steam partial pressure=200mm mercury column or 414mm mercury column) and handled 2 hours, the steam of cutting off the water, bubbling air drops to room temperature.
Embodiment 2 preparation Zn-Ti(SO 4) 2/ zeolite catalyst
With 0.45 gram Ti(SO 4) 2Join to give and use H earlier 2SO 424.14 milliliters of 0.1023MZn(NO of acidifying 3) 2In the solution, add the ammonium type ZSM-5 zeolites of 5 grams with the preparation of embodiment 1 method, stir slowly be heated to down dried, 110 ℃ of following dried overnight, 550 ℃ of following roastings 3 hours.
Adopt the ammonium type zeolite dipping of Different Silicon calorize, correspondingly obtain four catalyzer and be respectively I (52.7), II (27), II *(27, steam is handled), III (30), III *(30, steam is handled), the silica alumina ratio in the number of scraping in the numeral zeolite.
Embodiment 3 preparation ZnS/ zeolite catalysts
Ammonium type ZSM-5 zeolite and the blunt ZnS of fluorescent with the preparation of embodiment 1 method grind in agate mortar evenly.Make ZnS/ zeolite catalyst VI (77), V(30), VI (27), VII (25, water treatment).
Embodiment 4 preparation ZnSO 4/ zeolite catalyst
Use ZnSO 4The ammonium type ZSM-5 zeolite of solution impregnation embodiment 1 method preparation, 110 ℃ of following dried overnight, 550 ℃ of following roastings 3 hours obtain ZnSO 4/ zeolite catalyst VIII (27).
Embodiment 5 preparation Zn-(NH 4) 2The S/ zeolite catalyst
Join with 4 gram dealuminzation ammonium type zeolites of embodiment 1 method preparation that to regulate PH with ammoniacal liquor be 6.5 the 0.42 gram Zn(NO that contains 3) 26H 2In the aqueous solution of O, under 90 ℃ of left and right sides temperature, refluxed 4 hours, obtain Zn-(NH 4) 2S/ zeolite catalyst IX (27).
Embodiment 6 preparation Zn 2SiO 4/ zeolite catalyst
With 3.2 gram (NH 4) 2SiF 6Be dissolved in 50 ml waters 16.5 gram Zn(NO 3) 26H 2O is dissolved in 50 ml waters, and with these two kinds of aqueous solution, regulating PH with ammoniacal liquor is 7, generate precipitation, under 90～100 ℃ of temperature, refluxed 12 hours, filter, washing, dried overnight under 110 ℃ of temperature, roasting is 3 hours in 800 ℃ of retort furnaces, and the sample that obtains is through compressing tablet, pulverizing, gets 40～60 order particles and packs in the silica tube, with hydrogen handle 6 hours (593 ℃, H 2Flow velocity is 240 ml/min), obtain pure α-ZnSiO 4Sample.With α-ZnSiO 4Sample and the ammonium type ZSM-5(30 that makes with embodiment 1 method) grinding of zeolite mixed together, obtain ZnSiO 4/ zeolite catalyst X.
Embodiment 7 preparation Zn 2SiO 4-SiO 2/ zeolite catalyst
11.16 gram (9.70 milliliters) silicon sol are joined the NH of 100 milliliters of 2N 4NO 3In the solution, stir α-Zn that the back adds the preparation of 0.5110 gram embodiment, 6 methods 2SiO 4, stir half an hour after, the heating evaporate to dryness, roasting is 3 hours in 550 ℃ retort furnace, obtains Zn 2SiO 4/ SiO 2Sample.With 40～60 order particulate Zn 2SiO 4-SiO 2Ammonium type ZSM-5(52.7 with the preparation of embodiment 1 method) the zeolite mixed grinding obtains Zn 2SiO 4-SiO 2/ zeolite catalyst XI.
Embodiment 8 preparation ZnAl 2O 4/ zeolite catalyst
With 7.8656 gram Zn(NO 3) 26H 2O and 20.4540 gram Al(NO 3) 39H 2O is dissolved in 200 ml waters, stirs down and drips 18.6 milliliters of ammoniacal liquor to pH value to 7.5, generates precipitation.Slurries continue to stir two hours, leave standstill three days after-filtration.Filter cake 120 ℃ dry 4 hours down, move on in the retort furnace 330 ℃ of following roastings 7.5 hours again, 538 ℃ of following roastings 12 hours.The gained sample through compressing tablet, be ground into 20～40 orders, put in the silica tube and handled 2 hours at 552 ℃ of following steam, 800 ℃ of following roastings 3 hours in retort furnace again obtain pure ZnAl 2O 4ZnAl with appropriate amount 2O 4With ammonium type ZSM-5(52.7) the zeolite mechanically mixing, obtain ZnAl 2O 4/ zeolite catalyst (containing Zn3%) (XII) and ZnAl 2O 4/ zeolite catalyst (containing Zn20%) (XII).
The preparation of embodiment 9 contrast samples
The employing silica alumina ratio is respectively 77,52.7,30,27 ammonium type ZSM-5 zeolite, uses Zn(NO 3) 2Solution impregnation, dried overnight under 110 ℃ of temperature, 550 ℃ of roasting temperatures 3 hours obtain contrasting sample catalyst A (77), B(52.7), C(30), D(27) four catalyzer.With ZnO and ammonium type ZSM-5(52.7) mechanically mixing makes contrast sample catalyzer E.
Embodiment 10 zinc loss simultaneous tests
Get the catalyst sample of 0.75 gram embodiment 1 to 8, together place crystal reaction tube with comparative sample, feed hydrogen with 10 ml/min, heat up simultaneously as for 593 ℃, promptly improve air speed to 240 ml/min after stable, handled 12 hours continuously, the zinc content before and after the analyzing and processing, it the results are shown in subordinate list 1.
The test of embodiment 11 propane aromatizations
Adopt the ZnTi(SO of embodiment 2 4) 2The comparative catalyst of zeolite catalyst and embodiment 8 carries out the propane aromatization test, and adopting air speed is 2.5, and temperature of reaction is 550 ℃, and by the fixed-bed reactor of catalyzer are housed, aromizing the results are shown in subordinate list 2 to propane continuously.The aromizing performance of the zeolite catalyst of embodiment 2～8 sees attached list 3.
Embodiment 12 stability tests
Adopt the Zn-Ti(SO of embodiment 2 4) 2The zeolite catalyst IV is carried out aromatization, reaction velocity 1～2 hour to liquefied petroleum gas (LPG) (consist of: methane-0.3%, ethane-1.3%, ethene-0.4%, propane-21.5%, propylene-34.9%, butane-22.9%, butene-1 7.6%, carbon more than 5 0.6%) -1, 500～550 ℃ of temperature of reaction, in 168 hours reaction times, benzene,toluene,xylene, yield drop to 33% at last from 42.0% of beginning.
Embodiment 13 longevity tests
Adopt the ZnTi(SO of embodiment 2 4) 2Zeolite catalyst (III *), (consist of: methane-0.05%, ethane-1.0%, ethene-0.3%, propane-17.8%, propylene-29.6%, normal butane-4.5%, Trimethylmethane-24.9%, butylene with liquefied petroleum gas (LPG) -1-12.5%, maleic -2-3.80%, anti-butylene -2-6.04%) is raw material, reaction velocity 1～2 hour -1, 500～550 ℃ of temperature of reaction, 1000 hours reaction times, (middle) through 6 regeneration, activation recovering, aromatics yield is between 35～45%.
Subordinate list 1 Zincleaching-resistant effect comparison
Catalyzer title numbering turnover rate %
Zn-Ti(SO 4) 2/ zeolite I 23.7
The contrast sample contains Zn zeolite B 80.8
ZnS/ zeolite VI 15.6
The contrast sample contains Zn zeolite A 77.9
ZnS/ zeolite II *13.6
The contrast sample contains Zn zeolite C 58.7
Zn 2SiO 4/ zeolite V 13.2
ZnSO 4Zeolite VIII 21.5
Zn-Ti(SO 4) 2/ zeolite II 16.5
ZnS/ zeolite VI 9.1
Zn-(NH 4) 2S/ zeolite IX 10.7
The contrast sample contains Zn zeolite D 44.5
ZnAl 2O 4/ zeolite XI 9.3
The contrast sample contains Zn zeolite E 85.4
The test of subordinate list 2 propane aromatizations
Reaction conditions: air speed 2.5 hours -1, 550 ℃ of temperature of reaction are analyzed the 8th hour result
Catalyzer Zn-Ti(SO 4) 2/ zeolite catalyst contrast sample catalyzer C
Transformation efficiency 52.2 54.4
Selectivity 46.1 34.7
Product is formed weight % weight %
Methane 25.6 18.6
Ethane 18.1 30.5
Ethene 6.6 3.1
Propylene 3.6 6.8
Butylene 00
Butane 00
Benzene 17.2 14.2
Toluene 20.1 13.7
Ethylbenzene 0.63 0
Dimethylbenzene 8.1 6.8
Subordinate list 3 Zincleaching-resistant catalyzer aromizing performances of the present invention
Catalyzer air speed temperature ℃ conversion of propane % selectivity %
Zn-Ti（SO 4） 22.5 550 49.1 48.6
/ zeolite (III)
ZnS/ zeolite 2.5 550 49.4 49.7
（Ⅱ ＊）
Zn-（NH 4） 2S 2.5 550 59.3 46.8
/ zeolite (IX)
ZnS/ zeolite 2.5 560 47.7 52.7
（Ⅶ）
ZnSO 4/ zeolite 2.5 550 52.4 46.7
（Ⅷ）
Zn 2SiO 4- 1.0 550 54.7 47.4
SiO 2/ zeolite (XI)
ZnAl 2O 42.5 550 49.7 47.7
/ zeolite (XII)

Claims (5)

1, a kind of method that contains the zinc zeolite catalyst for preparing the low-carbon (LC) aromatization of hydrocarbons of Zincleaching-resistant.It is characterized in that adopting that difficult reductive zinc compound is stated from the ZSM-5 zeolite on the thermodynamics, the preparation modification contain the zinc zeolite catalyst, be suitable for the aromizing of carbon 2 to the aliphatic hydrocarbon of carbon 12.
2, difficult reductive zinc compound such as ZnS, Zn on the thermodynamics according to claim 1 2SiO 4, Zn 2TiO 4, ZnAl 2O 4Deng.The zinc zeolite that contains of ZnS modification can be prepared by the mixture direct impregnation ZSM-5 zeolite of common zinc salt and water miscible sulfide, vitriol, also available ZnS directly and ZSM-5 zeolite mechanically mixing form Zn 2SiO 4, Zn 2TiO 4, ZnAl 2O 4Available corresponding salts solution makes through co-precipitation, filtration, washing, suitable roasting or hydrothermal treatment consists, is added in the ZSM-5 zeolite with appropriate means again, makes the ZSM-5 zeolite of zinc modification, 0.1～30%(weight that its zinc content is amount of zeolite).
3, ZSM-5 zeolite according to claim 1 can be to adopt direct method synthetic, and also available organic formwork agent is synthetic to be obtained.Sodium type ZSM-5 zeolite is earlier with dilute mineral acid (HCL or HNO 3) and ammonium salt (NH 4NO 3) handle, the sodium amount that contains of zeolite is dropped to≤0.02%, ammonium type ZSM-5 zeolite become.
4, carbon 2 according to claim 1 is to carbon 12 aliphatic hydrocarbons, it can be single hydrocarbon of planting, it also can be hydrocarbon mixture, can be alkane, also can be alkene, or the mixture of alkane and alkene, for example refinery's liquefied gas, from Sweet natural gas, separate and obtain the mixture of carbon 2 to carbon 4, pyrolysis gasoline etc.
5, the aromatization condition of aliphatic hydrocarbon according to claim 1 is, temperature of reaction is 400～600 ℃, and reaction pressure is 1～10 normal atmosphere, and reaction velocity is 0.1～100 hour -1
CN 91105256 1991-08-05 1991-08-05 Zincleaching-resistant hydrocarbon type aromatized zinc-bearing zeolite catalyst Expired - Lifetime CN1040993C (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1039917C (en) * 1995-11-14 1998-09-23 中国石油化工总公司 Pt-Sn-Ti multi-metal reforming catalyst
CN1058284C (en) * 1998-04-10 2000-11-08 中国石油化工总公司 Light hydrocarbon aromatization catalyst and its preparing process
CN1100124C (en) * 2000-08-30 2003-01-29 中国石油化工股份有限公司 Aromatizing catalyst for light hydrocarbon and its preparing process
CN1100849C (en) * 2000-09-21 2003-02-05 中国石油化工集团公司 Catalyst for catalytic cracking and its preparing process
CN107469857A (en) * 2016-06-07 2017-12-15 中国科学院大连化学物理研究所 A kind of method of the direct conversion for preparing arene of catalyst and synthesis gas
CN107970988A (en) * 2016-10-24 2018-05-01 中国科学院大连化学物理研究所 A kind of catalyst and its preparation method for being used to synthesize aromatic hydrocarbons
WO2019218489A1 (en) * 2018-05-17 2019-11-21 中国科学院大连化学物理研究所 Catalyst for synthesising p-xylene, preparation method therefor, and application thereof
CN112774724A (en) * 2019-11-04 2021-05-11 中国科学院大连化学物理研究所 Catalyst and preparation method and application thereof
US11097263B2 (en) 2019-08-30 2021-08-24 China University of Petroleum—Beijing Aromatization catalyst, preparation method, regeneration method thereof, and aromatization method

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1039917C (en) * 1995-11-14 1998-09-23 中国石油化工总公司 Pt-Sn-Ti multi-metal reforming catalyst
CN1058284C (en) * 1998-04-10 2000-11-08 中国石油化工总公司 Light hydrocarbon aromatization catalyst and its preparing process
CN1100124C (en) * 2000-08-30 2003-01-29 中国石油化工股份有限公司 Aromatizing catalyst for light hydrocarbon and its preparing process
CN1100849C (en) * 2000-09-21 2003-02-05 中国石油化工集团公司 Catalyst for catalytic cracking and its preparing process
CN107469857A (en) * 2016-06-07 2017-12-15 中国科学院大连化学物理研究所 A kind of method of the direct conversion for preparing arene of catalyst and synthesis gas
CN107469857B (en) * 2016-06-07 2020-12-01 中国科学院大连化学物理研究所 Catalyst and method for preparing aromatic hydrocarbon by directly converting synthesis gas
US11014076B2 (en) 2016-10-24 2021-05-25 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Catalyst for synthesizing aromatic hydrocarbons and preparation method therefor
CN107970988A (en) * 2016-10-24 2018-05-01 中国科学院大连化学物理研究所 A kind of catalyst and its preparation method for being used to synthesize aromatic hydrocarbons
CN107970988B (en) * 2016-10-24 2020-05-12 中国科学院大连化学物理研究所 Catalyst for synthesizing aromatic hydrocarbon and preparation method thereof
WO2019218489A1 (en) * 2018-05-17 2019-11-21 中国科学院大连化学物理研究所 Catalyst for synthesising p-xylene, preparation method therefor, and application thereof
US11097263B2 (en) 2019-08-30 2021-08-24 China University of Petroleum—Beijing Aromatization catalyst, preparation method, regeneration method thereof, and aromatization method
CN112774724A (en) * 2019-11-04 2021-05-11 中国科学院大连化学物理研究所 Catalyst and preparation method and application thereof
CN112774724B (en) * 2019-11-04 2022-04-19 中国科学院大连化学物理研究所 Catalyst and preparation method and application thereof

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