CN1050777C - Containing rare-earth Cx-Cx aromatic dealkyl catalyst and preparing method thereof - Google Patents

Containing rare-earth Cx-Cx aromatic dealkyl catalyst and preparing method thereof Download PDF

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Publication number
CN1050777C
CN1050777C CN94118235A CN94118235A CN1050777C CN 1050777 C CN1050777 C CN 1050777C CN 94118235 A CN94118235 A CN 94118235A CN 94118235 A CN94118235 A CN 94118235A CN 1050777 C CN1050777 C CN 1050777C
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China
Prior art keywords
catalyst
benzene
carrier
al2o3
drying
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CN94118235A
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CN1107077A (en
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王士文
秦永宁
廖巧丽
梁珍成
关毅
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Tianjin University
China Petrochemical Corp
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Tianjin University
China Petrochemical Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention provides a novel Cr2O3-RE/Al2O3 catalyst for preparing xylene, toluene and benzene from C9-10 alkyl arene by catalytic dealkylation, which is prepared after a carrier Al2O3 is processed by rare earth. The catalyst has a stable structure, and the selectivity of the catalyst to the three kinds of benzene is larger than 95% (the conversion rate is 58%). The catalyst of the present invention is characterized in that rare earth La2O3 is loaded on a gama-Al2O3 surface to be processed at high temperature, and the acidity of gamma Al2O3 is regulated; meanwhile, Cr2O3 crystal particles are prompted to be uniformly distributed on the gama-Al2O3 surface. The catalyst is prepared from the following chemical components: 10 to 20 wt% of Cr2O3, 1 to 6 wt% of La2O3 and gamma Al2O3 as the rest. The catalyst can also be used in the technical process of preparing benzene from toluene by catalytic dealkylation.

Description

C 9-10What aromatic hydrocarbons took off alkyl contains rare earth catalyst and preparation method thereof
The invention belongs to catalyst field used in the petrochemical complex course of processing, directly relate to alkyl C 9-C 10The improvement of aromatic hydrocarbons dealkylation catalyst.
Well-known petroleum aromatic comprises benzene,toluene,xylene and naphthalene.External alkylaromatic hydrocarbon catalytic dealkylation technology is to improve C 9-C 10The important means of aromatic hydrocarbons utilization ratio and the adjusting toluene and the benzene equilibrium of supply and demand.In order to satisfy the demand to benzene and dimethylbenzene, American UOP company at first built up toluene hydrodealkylation benzene industrialized unit processed, C in 1969 in 1961 9The industrialized unit of arenes catalytic dealkylation dimethylbenzene processed is built up by Japan petroleum chemistry strain formula society, and thereafter, a collection of alkylaromatic hydrocarbon catalytic dealkylation industrialized unit is successively built up in Japan and Europe, mostly adopts the Cr of Heat stability is good, anti-poison 2O 3/ Al 2O 3Series catalysts, carrier-borne transition metal or oxide, Ni/Al 2O 3, MoO 3/ Al 2O 3And Cr 2O 3/ Al 2O 3But catalyst all catalysis alkylaromatic hydrocarbon takes off alkyl, and Cr 2O 3/ Al 2O 3The activity of catalyst selectively reaches carbon accumulation resisting ability and Cr 2O 3Content and at Al 2O 3The distribution Al on surface 2O 3Acidity and pore structure, kind and the mode of introducing auxiliary agent are closely related, i.e. Cr 2O 3The catalytic performance of series catalysts depends on its preparation method and corresponding microstructure, and the Di Tuofa alkylaromatic hydrocarbon of Hu Deli process chemistry company exploitation is toluene, C 9Aromatic hydrocarbons takes off the Cr that the alkyl process using contains alkali metal promoter 2O 3/ Al 2O 3Catalyst, the content that related documents and patent relate to mostly is acidity or MoO 3Series catalysts, Japan Patent had been reported with C in 1976 9-C 10Aromatic hydrocarbons is that the catalyst of waste dimethylbenzene is MoO 3-NiO/Al 2O 3It contains Mo13% (wt), Ni5% (wt), and 1980 and the people such as Khattab in 1986 and Salaeve have studied respectively MoO 3-WO 3The application of-mordenite catalyst in the alkylaromatic hydrocarbon catalytic dealkylation; The people such as Bezukhanova study C at cation X-type and Y zeolite 9The conversion reaction of aromatic hydrocarbons.
It is C that purpose of the present invention provides a kind of conversion that is used for heavy alkylaromatic hydrocarbon 9-C 10The catalyzer of alkylaromatic hydrocarbon catalytic dealkylation system dimethylbenzene, toluene and benzene, wherein dimethylbenzene is main products and C in the raw material 9Above aromatic hydrocarbons accounts for more than 95%.
The invention provides a kind of Stability Analysis of Structures that has, with Cr 2O 3/ Al 2O 3With the Cr that contains alkaline-earth metal 2O 3/ Al 2O 3Compare have selective height, new catalyst that carbon accumulation resisting ability is strong, its preparation method is carrier A l 2O 3Earlier with RE-treated, with the oven dry (drying) and high-temperature calcination, formation rare earth oxide-Al 2O 3Prefabricated carrier, again with infusion process with its surface of chromium load, drying (drying) and calcining and activating, make Cr 2O 3-RE/Al 2O 3Catalyst.Rare earth oxide with alkalescence is except regulating Al 2O 3Acidity outside, also can impel Cr 2O 3Be evenly distributed on Al 2O 3The surface.
Cr provided by the invention 2O 3-RE/Al 2O 3Catalyst is to adopt activated alumina, i.e. γ-Al 2O 3Be carrier, with the branch mode of soaking prepare and, i.e. γ-Al 2O 3Soak earlier rare earth La, after high-temperature process, obtain prefabricated carrier and then soak active component chromium and the catalyst prod that makes, this catalyst is mainly used in the conversion of heavy alkylaromatic hydrocarbon, namely by C 9-C 10Alkylaromatic hydrocarbon dimethylbenzene processed, toluene and benzene, wherein dimethylbenzene is major product.
Cr 2O 3-RE/Al 2O 3The preparation method of catalyst:
1. the present invention adopts industrial Al 2O 3, X light diffracting analysis is determined as the γ type, and this carrier has been processed into strip 2-4 millimeter when producing; Long 40-60 millimeter; Specific surface 100-250 rice 2/ gram; Al 2O 3Under 100-150 ℃ through at least 2 hours dry preliminary treatment.
2. be dissolved in respectively through in the distilled water or deionized water that measure through the chromic anhybride of metering or nitrate and the lanthanum nitrate of chromium, and it is dissolved fully.
3. through the Al of super-dry 2O 3Place and dissolve good lanthanum nitrate hexahydrate and carry out dip operation, make Al 2O 3Upper load capacity reaches 1-16% (wt).
4. flood the Al of lanthanum nitrate 2O 3Under 100-130 ℃, carry out heating, drying (drying), at least 2 hours, be warming up to again 400-600 ℃ of lower calcining 4-6 hour.
5. through the pretreated Al of rare earth 2O 3Place chromic anhydride (CrO 3) soak the chromium operation in the nitrate of the aqueous solution or chromium, make Cr 2O 3Content reaches 10-20% on catalyst.
6. the material that soaks chromium carries out heat drying under 100-130 ℃, and at least 2 hours, be warming up to 550-700 ℃, at least 2 hours, make the chromium of its load be decomposed into Cr fully 2O 3
Through above-mentioned technical process, can obtain Cr provided by the invention 2O 3-RE/Al 2O 3Catalyst, its chemical composition is:
Cr 2O 3 10-20％(wt)
La 2O 3 1-6％(wt)
All the other are Al 2O 3Effect Cr of the present invention 2O 3-RE/Al 2O 3Catalyst is through X diffraction and scanning electron microprobe analysis, La 2O 3And Cr 2O 3Be evenly distributed on Al 2O 3The surface; Catalyst is through carbon distribution repeatedly, Stability Analysis of Structures behind the charcoal regeneration.
With C 9-C 10Aromatic hydrocarbons is raw material (C 6H 60.421, Meph1.286, Xylene1.421, C 9Aroms21.257, C 10Aroms71.071,＞C 10Aroms4.545wt%) pressure 5MPa, temperature 550-570 ℃, C 9-C 10During aromatics conversion rate 58.32%, to the selectivity of benzene, toluene and dimethylbenzene greater than 95%.See Table 1
Table 1TDC γ-RE-1 catalyzer transformation efficiency selectivity
Temperature C 9-C 10Transformation efficiency % three benzene selective #% dimethylbenzene selective %
550℃ 58.32 95.55 56.97
560℃ 66.17 93.01 50.47
570℃ 70.00 92.88 45.45
Embodiment 1
Take by weighing 1.5 gram La (NO 3) 36H 2O and 5 gram CrO 3Place respectively beaker, add respectively about 30 milliliters and 35 ml distilled waters or deionized water, make La (NO 3) 3And CrO 3Fully dissolving earlier will be through 42 gram strip Al of super-dry 2O 3Be immersed in La (NO 3) 3In the solution, pull then leaching out, 100 ℃ of oven dry, at least 2 hours, be warming up to 500 ℃ and reduce nitrate, finally by 750 ℃ of calcinings 4 hours, namely make La 2O 3-AL 2O 3Prefabricated carrier, this carrier places CrO 3In the aqueous solution beaker, pull then leaching out, 100-130 ℃ of oven dry at least 1.5 hours, is warming up to 650 ℃ of calcinings and makes the catalyst finished product.
CrO 3-La 2O 3/ Al 2O 3Its chemical composition is:
Cr 2O 3 11％(wt)
La 2O 3 2％(wt)
Al 2O 3 87％(wt)
Embodiment 2
Take by weighing 4 gram La (NO 3) 36H 2O and 7 gram CrO 3Place respectively beaker to add respectively 40 milliliters and 45 ml distilled waters or deionized water, they are dissolved fully, claim 58 gram strip Al 2O 3, dipping La (N) 3) 3Method is with 1,130 ℃ of oven dry of embodiment, and at least 2 hours, rise to 550 ℃ of temperature, divide and terminated an agreement 1 hour, finally by 800 ℃ of calcinings 4 hours, thereafter, dipping chromium and drying materials method be with embodiment 2,700 ℃ of calcining and activatings 3 hours, namely makes finished catalyst Cr at last 2O 3-La 2O 3/ Al 2O 3, its chemical composition is:
Cr 2O 3 19％(wt)
La 2O 3 5.5％(wt)
Al 2O 3 75.5％(wt)
Catalyzer provided by the invention can also be used among the technological process that toluene catalytically takes off alkyl system benzene, and its temperature of reaction is in 590-620 ℃ of scope.

Claims (6)

1. one kind is used for C 9-10Aromatic hydrocarbons takes off the catalyst of alkyl dimethylbenzene processed, toluene and benzene, it is characterized in that La 2O 3And Cr 2O 3Be evenly distributed in γ-Al 2O 3The surface, the chemical composition of catalyst is: Cr 2O 3Be 10-20% (wt), La 2O 3Be 1-16% (wt) that all the other are γ-Al 2O 3
2. catalyst according to claim 1 is characterized in that catalyst chemical consists of Cr 2O 315-18% (wt), La 2O 33-4% (wt).
3. one kind is used for C 9-10Aromatic hydrocarbons takes off the method for preparing catalyst of alkyl dimethylbenzene processed, toluene and benzene, it is characterized in that through RE-treated Al 2O 3Carrier, behind the dipping chromium, drying or drying, calcining and activating makes Cr 2O 3-La 2O 3/ Al 2O 3Catalyst.
4. method for preparing catalyst according to claim 3 is characterized in that carrier A l 2O 3, its crystal formation is the γ type, is shaped as strip, diameter phi 2-4 millimeter, and length is the 40-60 millimeter, specific surface is 100-250 rice 2/ gram.
5. method for preparing catalyst according to claim 3 is characterized in that the Al of RE-treated 2O 3Carrier be by infusion process with rare earth loaded in γ-Al 2O 3, earlier at 100-130 ℃ of lower heating, drying, be warming up to 400-600 ℃ nitrate decomposed fully; Calcining heat 700-850 ℃, calcination time 4-8 hour.
6. Preparation of catalysts method according to claim 3, it is characterized in that earlier at 100-130 ℃ of following heating, drying, being warming up to 450-500 ℃ with the carrier of the aqueous solution dipping of chromic anhydride or chromium nitrate, nitrate or chromic anhydride are decomposed fully, at 650-700 ℃ of calcining and activating 4-6 hour.
CN94118235A 1994-11-15 1994-11-15 Containing rare-earth Cx-Cx aromatic dealkyl catalyst and preparing method thereof Expired - Fee Related CN1050777C (en)

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CN103721711B (en) * 2012-10-10 2016-06-29 中国石油化工股份有限公司 A kind of palladium series catalyst for heavy aromatics hydro-dealkylation

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD94172A (en) *
BE844030A (en) * 1975-07-15 1977-01-12 NEW CATALYSTS FOR THE DEALKYLATION OF ALKYLAROMATIC HYDROCARBONS IN THE PRESENCE OF WATER VAPOR
FR2483254A1 (en) * 1980-06-02 1981-12-04 Catalyse Soc Prod Francais Hydrocarbon conversion catalysts, esp. for reforming - contg. platinum-group metal, hafnium and group=VIIa metal
US4599470A (en) * 1982-11-18 1986-07-08 The British Petroleum Company P.L.C. Process for the transalkylation or dealkylation of alkyl aromatic hydrocarbons
EP0284397A1 (en) * 1987-03-26 1988-09-28 The British Petroleum Company p.l.c. Lithiated clays and uses thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD94172A (en) *
BE844030A (en) * 1975-07-15 1977-01-12 NEW CATALYSTS FOR THE DEALKYLATION OF ALKYLAROMATIC HYDROCARBONS IN THE PRESENCE OF WATER VAPOR
FR2483254A1 (en) * 1980-06-02 1981-12-04 Catalyse Soc Prod Francais Hydrocarbon conversion catalysts, esp. for reforming - contg. platinum-group metal, hafnium and group=VIIa metal
US4599470A (en) * 1982-11-18 1986-07-08 The British Petroleum Company P.L.C. Process for the transalkylation or dealkylation of alkyl aromatic hydrocarbons
EP0284397A1 (en) * 1987-03-26 1988-09-28 The British Petroleum Company p.l.c. Lithiated clays and uses thereof

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