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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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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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catalyst
carrier
toluene
benzene
drying
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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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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
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

本发明提供一种载体Al2O3用稀土处理后，制得的C9-10烷基芳烃催化脱烷基制二甲苯、甲苯及苯的Cr2O3-RE/Al2O3新型催化剂，其结构稳定，对三苯的选择性大于95%(转化率58%)。The present invention provides a new Cr 2 O 3 -RE/Al 2 O 3 catalyst for producing xylene, toluene and benzene by catalytic dealkylation of C 9-10 alkyl aromatics prepared after the carrier Al 2 O 3 is treated with rare earth , its structure is stable, and the selectivity to triphenyl is greater than 95% (58% conversion rate).

本发明的催化剂是将稀土La2O3负载在γ-Al2O3表面上，经高温处理，调节γ-Al2O3的酸性，同时促使Cγ2O3晶粒均匀分布在γ-Al2O3表面上。其化学组成(wt%)：Cr2O310-20；La2O31-6；其余为γ-Al2O3。In the catalyst of the present invention, the rare earth La 2 O 3 is supported on the surface of γ-Al 2 O 3 , and after high temperature treatment, the acidity of γ-Al 2 O 3 is adjusted, and at the same time, C γ2 O 3 grains are evenly distributed on the γ-Al 2 O 3 on the surface. Its chemical composition (wt%): Cr 2 O 3 10-20; La 2 O 3 1-6; the rest is γ-Al 2 O 3 .

该催化剂也可用于甲苯催化脱烷基制苯的工艺过程。The catalyst can also be used in the process of producing benzene by catalytic dealkylation of toluene.

Description

C9-10芳烃脱烷基的含稀土催化剂及其制备方法 Rare earth-containing catalyst for dealkylation of C9-10 aromatics and preparation method thereof

本发明属于石油化工加工过程中所用的催化剂领域，直接涉及烷基C9-C10芳烃脱烷基催化剂的改进。The invention belongs to the field of catalysts used in petrochemical processing, and directly relates to the improvement of alkyl C 9 -C 10 aromatic hydrocarbon dealkylation catalysts.

众所周知石油芳烃包括苯、甲苯、二甲苯和萘。国外烷基芳烃催化脱烷基技术是提高C9-C10芳烃利用率和调节甲苯和苯供需平衡的重要手段。为了满足对苯和二甲苯的需求，1961年美国UOP公司首先建成甲苯临氢脱烷基制苯工业化装置，1969年C9芳烃催化脱烷基制二甲苯的工业化装置由日本石油化学株式社建成，其后，日本和欧洲先后建成一批烷基芳烃催化脱烷基工业化装置，大多采用热稳定性好、耐毒的Cr2O3/Al2O3系催化剂，负载型过渡金属或氧化物，Ni/Al2O3、MoO3/Al2O3和Cr2O3/Al2O3催化剂均可催化烷基芳烃脱烷基，而Cr2O3/Al2O3催化剂的活性，选择性及抗积碳能力与Cr2O3的含量及其在Al2O3表面的分布状态Al2O3的酸性及孔结构，引入助剂的种类及方式密切相关，即Cr2O3系催化剂的催化性能取决于它的制备方法和相应的微观结构，胡德利工艺化学公司开发的迪托法烷基芳烃即甲苯，C9芳烃脱烷基工艺采用含有碱金属助剂的Cr2O3/Al2O3催化剂，有关文献和专利涉及的内容多为酸性或MoO3系催化剂，1976年日本专利报导了以C9-C10芳烃为原料制取二甲苯的催化剂是MoO3-NiO/Al2O3其含Mo13％(wt)，Ni5％(wt)，1980年和1986年Khattab和Salaeve等人分别研究了MoO3-WO3-丝光沸石催化剂在烷基芳烃催化脱烷基中的应用；Bezukhanova等人在阳离子X型和Y型分子筛上研究C9芳烃的转化反应。Well known petroleum aromatics include benzene, toluene, xylene and naphthalene. Catalytic dealkylation technology of alkylaromatics in foreign countries is an important means to improve the utilization rate of C 9 -C 10 aromatics and adjust the supply and demand balance of toluene and benzene. In order to meet the demand for benzene and xylene, in 1961, UOP Corporation of the United States first built an industrialized device for producing benzene by hydrodealkylation of toluene, and in 1969, an industrialized device for producing xylene by catalytic dealkylation of C9 aromatics was built by Nippon Petrochemical Co., Ltd. Afterwards, Japan and Europe successively built a number of industrialized units for catalytic dealkylation of alkylaromatics, most of which used Cr 2 O 3 /Al 2 O 3 catalysts with good thermal stability and poison resistance, supported transition metals or oxides, Ni/Al 2 O 3 , MoO 3 /Al 2 O 3 and Cr 2 O 3 /Al 2 O 3 catalysts can all catalyze the dealkylation of alkylaromatics, and the activity of Cr 2 O 3 /Al 2 O 3 catalysts, select The properties and anti-coking ability are closely related to the content of Cr 2 O 3 and its distribution on the surface of Al 2 O 3. The acidity and pore structure of Al 2 O 3 , the type and method of introducing additives are closely related, that is, the Cr 2 O 3 system The catalytic performance of the catalyst depends on its preparation method and the corresponding microstructure. The dealkylation process of Ditofa alkyl aromatics developed by Hoodley Process Chemicals, namely toluene, and C 9 aromatics uses Cr 2 O 3 / Al 2 O 3 catalysts, the relevant literature and patents are mostly acidic or MoO 3- based catalysts. In 1976, the Japanese patent reported that the catalyst for producing xylene from C 9 -C 10 aromatics was MoO 3 -NiO/Al 2 O 3 contains Mo13% (wt), Ni5% (wt). In 1980 and 1986, Khattab and Salaeve et al. respectively studied the application of MoO 3 -WO 3 -mordenite catalyst in the catalytic dealkylation of alkylaromatics ; Bezukhanova et al. studied the conversion reaction of C 9 aromatics on cationic X-type and Y-type molecular sieves.

本发明的目的提供一种用于重烷基芳烃的转化即C9-C10烷基芳烃催化脱烷基制二甲苯、甲苯和苯的催化剂，其中二甲苯是主要产品而原料中C9以上芳烃占95％以上。The object of the present invention is to provide a catalyst for the conversion of heavy alkyl aromatics, that is, catalytic dealkylation of C 9 -C 10 alkyl aromatics to produce xylene, toluene and benzene, wherein xylene is the main product and C 9 or more in the raw material Aromatics account for more than 95%.

本发明提供一种具有结构稳定，与Cr2O3/Al2O3和含有碱土金属的Cr2O3/Al2O3相比具有选择性高、抗积碳能力强的新型催化剂，其制备方法是载体Al2O3先用稀土处理、以烘干(干燥)和高温煅烧、形成稀土氧化物-Al2O3预制载体，再用浸渍法将铬负载其表面，经烘干(干燥)和煅烧活化、制得Cr2O3-RE/Al2O3催化剂。具有碱性的稀土氧化物除可调节Al2O3的酸性外，还可促使Cr2O3较均匀分布在Al2O3的表面。The present invention provides a novel catalyst with stable structure, high selectivity and strong carbon deposition resistance compared with Cr 2 O 3 /Al 2 O 3 and Cr 2 O 3 /Al 2 O 3 containing alkaline earth metals. The preparation method is that the carrier Al 2 O 3 is first treated with rare earth, dried (dried) and calcined at high temperature to form a rare earth oxide-Al 2 O 3 prefabricated carrier, and then chromium is loaded on the surface by impregnation method, and dried (dried) ) and calcination activation to obtain Cr 2 O 3 -RE/Al 2 O 3 catalyst. In addition to adjusting the acidity of Al 2 O 3 , rare earth oxides with basicity can also promote the uniform distribution of Cr 2 O 3 on the surface of Al 2 O 3 .

本发明提供的Cr2O3-RE/Al2O3催化剂是采用活性氧化铝，即γ-Al2O3为载体，以分浸方式制备而得的，即γ-Al2O3先浸稀土La，经高温处理后，得到预制载体然后再浸活性组分铬而制得的催化剂产品，本催化剂主要用于重烷基芳烃的转化，即由C9-C10烷基芳烃制二甲苯、甲苯和苯，其中二甲苯是主要产品。The Cr 2 O 3 -RE/Al 2 O 3 catalyst provided by the present invention is prepared by using activated alumina, that is, γ-Al 2 O 3 as a carrier, and prepared by separate leaching, that is, γ-Al 2 O 3 is first impregnated Rare earth La is a catalyst product obtained by prefabricating the carrier after high temperature treatment and then impregnating the active component chromium. This catalyst is mainly used for the conversion of heavy alkyl aromatics, that is, the production of xylene from C 9 -C 10 alkyl aromatics , toluene and benzene, of which xylene is the main product.

Cr2O3-RE/Al2O3催化剂的制备方法：The preparation method of Cr 2 O 3 -RE/Al 2 O 3 catalyst:

1.本发明采用工业生产的Al2O3，X光衍射分析测定为γ型，该载体在生产时已加工成条状2-4毫米；长40-60毫米；比表面100-250米2/克；Al2O3在100-150℃下经过至少2小时的干燥预处理。1. The present invention adopts industrially produced Al 2 O 3 , which is determined to be gamma type by X-ray diffraction analysis. The carrier has been processed into strips of 2-4 millimeters during production; length 40-60 millimeters; specific surface 100-250 meters 2 /g; Al 2 O 3 has been pre-dried at 100-150°C for at least 2 hours.

2.经过计量的铬酸酐或铬的硝酸盐和硝酸镧分别溶解在经过计量的蒸馏水或无离子水中，并使其完全溶解。2. Dissolve the metered chromic anhydride or chromium nitrate and lanthanum nitrate in metered distilled water or deionized water respectively, and make them dissolve completely.

3.经过干燥的Al2O3置于已溶解好的硝酸镧溶液中进行浸渍操作，使Al2O3上负载量达1-16％(wt)。3. The dried Al 2 O 3 is placed in the dissolved lanthanum nitrate solution for impregnation, so that the loading on the Al 2 O 3 reaches 1-16% (wt).

4.浸渍硝酸镧的Al2O3在100-130℃下进行加热烘干(干燥)，至少2小时，再升温至400-600℃下煅烧4-6小时。4. The Al 2 O 3 impregnated with lanthanum nitrate is heated and dried (dried) at 100-130°C for at least 2 hours, and then heated to 400-600°C for calcination for 4-6 hours.

5.经稀土预处理的Al2O3置于铬酐(CrO3)水溶液或铬的硝酸盐中进行浸铬操作，使Cr2O3在催化剂上含量达10-20％。5. Al 2 O 3 pretreated by rare earth is placed in chromic anhydride (CrO 3 ) aqueous solution or chromium nitrate for chromium immersion operation, so that the content of Cr 2 O 3 on the catalyst reaches 10-20%.

6.浸铬的物料在100-130℃下进行加热干燥，至少2小时，升温至550-700℃，至少2小时，使其负载的铬完全分解为Cr2O3。6. The chromium-impregnated material is heated and dried at 100-130°C for at least 2 hours, and then heated to 550-700°C for at least 2 hours to completely decompose the loaded chromium into Cr 2 O 3 .

经过上述工艺过程，即可得到本发明提供的Cr2O3-RE/Al2O3催化剂，其化学组成为：Through the above process, the Cr2O3 - RE/ Al2O3 catalyst provided by the present invention can be obtained, and its chemical composition is:

Cr2O3     10-20％(wt)Cr 2 O 3 10-20%(wt)

La2O3     1-6％(wt)La 2 O 3 1-6%(wt)

其余为Al2O3本发明的效果Cr2O3-RE/Al2O3催化剂经X衍射和扫描电子探针分析，La2O3和Cr2O3均匀分布在Al2O3表面；催化剂经反复积碳，烧碳再生后结构稳定。The rest is Al 2 O 3 The effect of the present invention Cr 2 O 3 -RE/Al 2 O 3 catalyst is analyzed by X-ray diffraction and scanning electron probe, La 2 O 3 and Cr 2 O 3 are evenly distributed on the surface of Al 2 O 3 ; After repeated carbon deposition, the catalyst has a stable structure after carbon burning and regeneration.

以C9-C10芳烃为原料(C6H60.421，Meph1.286，Xylene1.421，C9aroms21.257，C10aroms71.071，＞C10aroms4.545wt％)压力5MPa，温度550-570℃，C9-C10芳烃转化率58.32％时，对苯、甲苯及二甲苯的选择性大于95％。见表1Using C 9 -C 10 aromatics as raw material (C 6 H 6 0.421, Meph1.286, Xylene1.421, C 9 aromas21.257, C 10 aromas71.071, >C 10 aromas4.545wt%) pressure 5MPa, temperature 550- The selectivity to benzene, toluene and xylene is greater than 95% when the conversion rate of C 9 -C 10 aromatics is 58.32% at 570°C. see table 1

           表1TDCγ-RE-1催化剂转化率选择性        Table 1 TDCγ-RE-1 Catalyst Conversion Selectivity

温度      C9-C10转化率％  三苯选择性#％    二甲苯选择性％Temperature C 9 -C 10 Conversion % Triphenyl Selectivity #% Xylene Selectivity %

550℃     58.32             95.55            56.97550℃ 58.32 95.55 56.97

560℃     66.17             93.01            50.47560℃ 66.17 93.01 50.47

570℃     70.00             92.88            45.45570℃ 70.00 92.88 45.45

                     实施例1Example 1

称取1.5克La(NO3)3·6H2O和5克CrO3分别置于烧杯中，分别加约30毫升和35毫升蒸馏水或无离子水，使La(NO3)3和CrO3完全溶解，先将经过干燥的42克条状Al2O3浸泡在La(NO3)3溶液中，然后捞出沥滤，100℃烘干，至少2小时，升温至500℃分解硝酸盐，最后经750℃煅烧4小时，即制得La2O3-AL2O3预制载体，该载体置于CrO3水溶液烧杯中，然后捞出沥滤，100-130℃烘干，至少1.5小时，升温至650℃煅烧制得催化剂成品。Weigh 1.5 grams of La(NO 3 ) 3 6H 2 O and 5 grams of CrO 3 and place them in a beaker respectively, add about 30 ml and 35 ml of distilled water or deionized water to make La(NO 3 ) 3 and CrO 3 completely To dissolve, first soak 42 grams of dried strips of Al 2 O 3 in La(NO 3 ) 3 solution, then remove and leach, dry at 100°C for at least 2 hours, heat up to 500°C to decompose nitrate, and finally After calcination at 750°C for 4 hours, the La 2 O 3 -AL 2 O 3 prefabricated support is obtained. The support is placed in a CrO 3 aqueous solution beaker, then taken out and leached, dried at 100-130°C for at least 1.5 hours, and then heated up Calcined at 650°C to obtain the finished catalyst.

CrO3-La2O3/Al2O3其化学组成为：The chemical composition of CrO 3 -La 2 O 3 /Al 2 O 3 is:

             Cr2O3           11％(wt)Cr 2 O 3 11%(wt)

             La2O3           2％(wt)La 2 O 3 2%(wt)

             Al2O3           87％(wt)Al 2 O 3 87%(wt)

                    实施例2Example 2

称取4克La(NO3)3·6H2O和7克CrO3分别置于烧杯中分别加入40毫升和45毫升蒸馏水或无离子水，使它们完全溶解，称58克条状Al2O3，浸渍La(N)3)3方法同实施例1，130℃烘干，至少2小时，升至温度550℃，分解约1小时，最后经800℃煅烧4小时，其后，浸渍铬和物料烘干方法同实施例2，最后在700℃煅烧活化3小时，即制得成品催化剂Cr2O3-La2O3/Al2O3，其化学组成为：Weigh 4 grams of La(NO 3 ) 3 6H 2 O and 7 grams of CrO 3 into a beaker and add 40 milliliters and 45 milliliters of distilled water or deionized water to dissolve them completely, and weigh 58 grams of strip-shaped Al 2 O 3. Impregnate La(N) 3 ) 3. The method is the same as in Example 1. Dry at 130°C for at least 2 hours, rise to a temperature of 550°C, decompose for about 1 hour, and finally calcinate at 800°C for 4 hours. After that, impregnate chromium and The drying method of the material is the same as that in Example 2, and finally it is calcined and activated at 700°C for 3 hours to obtain the finished catalyst Cr 2 O 3 -La 2 O 3 /Al 2 O 3 , whose chemical composition is:

            Cr2O3          19％(wt)Cr 2 O 3 19%(wt)

            La2O3          5.5％(wt)La 2 O 3 5.5%(wt)

            Al2O3          75.5％(wt)Al 2 O 3 75.5%(wt)

本发明提供的催化剂还能用于甲苯催化脱烷基制苯的工艺过程之中，其反应温度在590-620℃范围内。The catalyst provided by the invention can also be used in the process of producing benzene by catalytic dealkylation of toluene, and the reaction temperature is in the range of 590-620°C.

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

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Publication number Priority date Publication date Assignee Title
DD94172A (en) *
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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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