CN106540735B - Catalyst for benzene and methanol alkylation reaction - Google Patents
Catalyst for benzene and methanol alkylation reaction Download PDFInfo
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Abstract
The invention relates to a catalyst for benzene and methanol alkylation reaction, which mainly solves the problems of low benzene conversion rate, low toluene and xylene selectivity and poor catalyst stability in the practical application of a benzene and methanol alkylation catalyst. The invention better solves the problem by carrying out appropriate alkali treatment and acid treatment modification on the HZSM-5 molecular sieve and further loading a certain amount of oxide, and can be used for industrial production of benzene and methanol alkylation reaction.
Description
Technical Field
The invention belongs to the field of catalysts and catalytic reactions, and particularly relates to a catalyst for alkylation reaction of benzene and methanol.
Background
The xylene mainly comprises paraxylene, o-xylene and m-xylene, is an important chemical raw material, and has wide application. Among them, para-xylene (PX) is most widely used, mainly for Producing Terephthalic Acid (PTA) and dimethyl terephthalate (DMT). PTA and DMT can further react with dihydric alcohol and then are polycondensed to produce polyester products which are widely used in the fields of chemical fibers, synthetic resins, plastics and the like. The traditional production method of PX mainly uses toluene or mixed xylene as raw material, and adopts the processes of toluene disproportionation, xylene isomerization or toluene and C9Aromatic hydrocarbon transalkylation, etc. The traditional process has the defects of low raw material conversion rate, poor catalyst stability, large equipment, high operation cost and the like. Moreover, at present, xylene is mainly derived from petroleum (refinery catalytic reforming and aromatics complex), and the petroleum reserves are decreasing worldwide, so that it is economically and industrially very beneficial to find a new way to increase the yield of xylene.
The alkylation reaction of benzene and methanol is an effective way to increase the yield of xylene. Benzene can be obtained from petroleum and deep processing of coal, the petrochemical industry of China is still in a rapid development stage in the coming years, and the production capacity of pure benzene of China is continuously increased by combining the development of ethylene and aromatic hydrocarbon combination, refinery reforming and coking benzene processing projects. Therefore, the situation of excess capacity in the pure benzene market in China is expected to appear in the future. On the other hand, China vigorously develops coal chemical industry, the methanol production capacity is huge, and low-price methanol which takes natural gas as a raw material is imported abroad, so that the methanol market price is lower. Therefore, downstream products such as toluene, xylene and the like with high additional values are directly synthesized by utilizing benzene and methanol, and the method has good industrial development value.
The literature and patents on the research of benzene and methanol alkylation reaction catalysts are relatively rare at home and abroad. The patent CN102600887A adopts the technical scheme that HMCM-22 molecular sieve is used for loading alkaline earth and rare earth metal elements, and the HMCM-22 molecular sieve is used for the alkylation reaction of benzene and methanol, wherein the conversion rate of benzene is about 45%, the conversion rate of methanol is about 90%, and the selectivity of dimethylbenzene is about 60%. The patent CN102101818A takes HMCM-56 molecular sieve as a carrier and loads 3-15% of MoO3Or NiO is used for benzene and methanol alkylation reaction, the conversion per pass of benzene is more than 45 percent, and the selectivity of toluene and xylene is more than 89 percent. Patent CN102688771A uses HMCM-56 molecular sieve and gamma-Al2O3Is a composite carrier, loads oxides of molybdenum, nickel, magnesium, lanthanum, boron and the like, is used for the alkylation reaction of benzene and methanol, the conversion rate of benzene reaches 50 percent, and the selectivity of toluene and xylene reaches more than 90 percent, but the patent does not have the stability of a catalystReports on the aspects. The three patents use HMCM-22 and HMCM-56 molecular sieves, although the benzene conversion rate is improved, the selectivity of toluene and xylene is still low, and the stability of the catalyst is poor. Patents CN104109065A, CN102746080A, CN101624327A, etc. of shanxi hengyang scientific and chemical company, and ningxia pagoda petrochemical company, mainly describe the separation process and process optimization of benzene and methanol alkylation products, toluene, xylene, trimethylbenzene and benzene, and do not relate to catalyst research.
The catalyst for benzene and methanol alkylation reaction uses HZSM-5 molecular sieve as active main body, and after alkali treatment and acid treatment, it has high activity, high selectivity and good stability, and has good industrial development value.
Disclosure of Invention
The invention aims to solve the problems of low activity, low selectivity and poor stability of a benzene and methanol alkylation catalyst. The catalyst for benzene and methanol alkylation reaction has the features of high benzene converting rate, high toluene and xylene selectivity and high stability.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a catalyst for benzene and methanol alkylation reaction comprises the following components in percentage by mass: including the silicon to aluminum ratio (SiO)2/Al2O3) 200-1000 of HZSM-5 molecular sieve and proper alkali treatment and acid treatment, and adhesive gamma-Al2O310-40% and oxide loading of 1-15%.
In the technical scheme, the HZSM-5 molecular sieve has the silicon-aluminum ratio (SiO)2/Al2O3) The preferable range is 200-500, and the mass percentage is as follows: the preferred range of the dosage of the HZSM-5 molecular sieve is 65 to 80 percent; the supported oxide is preferably MgO, NiO, P2O5、CeO2The preferable range of the load amount of one or more of the above is 0.3% -10%; binder gamma-Al2O3Is preferably in the range of 20 to 35%. The alkali used for alkali treatment is preferably NaOH or KOH and NaAlO2、KAlO2Of NaOH or KOH, preferably in a concentration of 0.1-0.5mol/L，NaAlO2Or KAlO2The concentration is preferably 0.005-0.1 mol/L, the liquid-solid ratio is preferably 20-30, the treatment frequency is preferably 1-3, the treatment time is preferably 20-60min, and the treatment temperature is preferably 50-90 ℃. The acid used for acid treatment is preferably citric acid, oxalic acid, phosphoric acid or their mixture, preferably the concentration is 0.1-5mol/L, the treatment frequency is preferably 1-2 times, the treatment time is preferably 45-180min, and the treatment temperature is preferably 60-90 ℃.
The preparation method of the catalyst of the invention is as follows.
Alkali treatment and acid treatment of the HZSM-5 molecular sieve: firstly, treating the molecular sieve with an alkali solution for one or more times, drying the molecular sieve at 120 ℃ for 5 to 12 hours, then treating the molecular sieve with an acid for one or more times, drying the molecular sieve at 120 ℃ for 5 to 12 hours, and roasting the molecular sieve at the temperature of 450-600 ℃ for 3 to 6 hours to obtain the HZSM-5 molecular sieve to be treated.
Preparing a catalyst: taking HZSM-5 molecular sieve treated by alkali and acid as an active main body, adding a binder, mixing uniformly, extruding and forming. The binder is gamma-Al2O3The catalyst accounts for 10-40% of the total mass of the catalyst, and 4-30% of nitric acid, aluminum sol or silica sol is added as an extrusion aid in the forming process. After the catalyst is formed, the supported oxide is modified, the precursor of the oxide is nitrate or organic acid salt of corresponding metal, and the introduction method can adopt an ion exchange method, an impregnation method or a mechanical mixing method. Drying and roasting to obtain the required catalyst.
The invention carries out proper alkali treatment and acid treatment on the HZSM-5 molecular sieve, and introduces oxide for modification. At a mass space velocity of 2-60h-1The reaction temperature is 400-2The evaluation of the catalyst for benzene and methanol alkylation reaction was carried out under the condition of a flow rate of 50 ml/min. The data show that the HZSM-5 molecular sieve is modified by proper alkali treatment and acid treatment and is loaded with oxides, so that the activity and selectivity of the catalyst can be obviously improved, the catalyst can keep good stability, and a better technical effect is achieved.
The invention is further illustrated by the following examples.
Drawings
FIG. 1 is a graph for examining the stability of catalyst N.
Detailed Description
[ examples 1 to 3 ]
Taking the ratio of silicon to aluminum (SiO)2/Al2O3) 30g of 300 HZSM-5 molecular sieve, 900ml of 0.24mol/L NaAlO and 0.012mol/L NaAlO2The mixed solution is treated for 45min under the water bath condition of 65 ℃, dried for 12h after chilling and suction filtration, then treated for 120min under the condition of 90 ℃ by 900ml of 1.0mol/L phosphoric acid, citric acid and oxalic acid solution respectively, dried for 12h after chilling and suction filtration, and roasted for 6h at 540 ℃. Mixing the treated HZSM-5 molecular sieve with gamma-Al2O3Uniformly mixing according to the mass ratio of 7:3, adding 10% dilute nitric acid, kneading, extruding into strips, drying at 120 ℃ for 10h, sieving out particles of 20 ~ 40 meshes from the strip catalyst, roasting at 540 ℃ for 6h, and respectively obtaining the catalyst A, B, C treated by phosphoric acid, citric acid and oxalic acid according to different acids used for acid treatment.
[ example 4 ]
Taking the ratio of silicon to aluminum (SiO)2/Al2O3) 30g of 300 HZSM-5 molecular sieve, 600ml of 0.20mol/L NaOH and 0.01mol/L NaAlO2The mixed solution is treated for 45min under the condition of water bath at the temperature of 80 ℃, dried for 12h after chilling and suction filtration, treated for 130min under the condition of 65 ℃ by 600ml of 0.2mol/LHCl, chilled, dried for 10h at the temperature of 120 ℃ and roasted for 5h at the temperature of 540 ℃. Mixing the roasted HZSM-5 molecular sieve with gamma-Al2O3Uniformly mixing according to the mass ratio of 7:3, adding 4% nitric acid, kneading, extruding into strips, drying, screening out particles of 20 ~ 40 meshes, and roasting at 540 ℃ for 6 hours to obtain the catalyst D.
[ example 5 ]
Taking the ratio of silicon to aluminum (SiO)2/Al2O3) 30g of 300 HZSM-5 molecular sieve, 600ml of 0.24mol/L NaOH and 0.012mol/L NaAlO2The mixed solution is treated for 45min under the water bath condition of 65 ℃, dried for 12h after chilling and suction filtration, and then treated for 1 time by the same method. After the 2 nd alkali treatment, the mixture is treated for 120min by 600ml of 1.0mol/L citric acid solution at the temperature of 90 ℃, and then is chilled, dried and roasted. Mixing the roasted HZSM-5 molecular sieve with gamma-Al2O3Uniformly mixing according to the mass ratio of 7:3, adding 4% dilute nitric acid, kneading, extruding into strips, drying, screening out particles of 20 ~ 40 meshes, and roasting at 540 ℃ for 6 hours to obtain the catalyst E.
[ example 6 ]
Taking the ratio of silicon to aluminum (SiO)2/Al2O3) 30g of 300 HZSM-5 molecular sieve, 600ml of 0.24mol/L NaOH and 0.012mol/L NaAlO2The mixed solution is treated for 20min under the water bath condition of 65 ℃, dried for 12h after chilling and suction filtration, and then treated for 2 times by the same method. After 3 rd alkali treatment, treating for 120min at 90 ℃ by using 600ml of 1.0mol/L citric acid solution, chilling, drying and roasting. Mixing the roasted HZSM-5 molecular sieve with gamma-Al2O3Uniformly mixing according to the mass ratio of 7:3, adding 4% dilute nitric acid, kneading, extruding into strips, drying, screening out particles of 20 ~ 40 meshes, and roasting at 540 ℃ for 6 hours to obtain the catalyst F.
[ example 7 ]
Taking the ratio of silicon to aluminum (SiO)2/Al2O3) 30g of 300 HZSM-5 molecular sieve, 600ml of 0.20mol/L NaOH and 0.01mol/L NaAlO2The mixed solution is treated for 20min under the condition of water bath at the temperature of 80 ℃, is dried for 10h after chilling and suction filtration, and is treated for 2 times by the same method. Treating with 600ml 1.0mol/L citric acid at 90 deg.C for 120min after 3 rd alkali treatment, chilling, drying, and roasting. Mixing the roasted HZSM-5 molecular sieve with gamma-Al2O3Uniformly mixing according to the mass ratio of 7:3, adding 4% dilute nitric acid, kneading, extruding into strips, drying, screening out particles of 20 ~ 40 meshes, and roasting at 540 ℃ for 6 hours to obtain the catalyst G.
[ example 8 ]
Taking the ratio of silicon to aluminum (SiO)2/Al2O3) 30g of 400 HZSM-5 molecular sieve using 900ml of 0.24mol/L NaAlO and 0.012mol/L NaAlO2The mixed solution is treated for 45min under the condition of water bath at 65 ℃, is dried for 12h after chilling and suction filtration, and is then treated for 1 time again by the previous method. After the 2 nd alkali treatment, the mixture is treated for 120min by 900ml of 1.0mol/L oxalic acid solution at the temperature of 90 ℃, and then is chilled, dried and roasted. Mixing the roasted HZSM-5 molecular sieve with gamma-Al2O3Uniformly mixing according to the mass ratio of 7:3, adding 4% dilute nitric acid, kneading, extruding into strips, drying, screening out particles of 20 ~ 40 meshes, and roasting at 540 ℃ for 6 hours to obtain the catalyst H.
[ example 9 ]
Taking the ratio of silicon to aluminum (SiO)2/Al2O3) 30g of 300 HZSM-5 molecular sieve, 900ml of 0.24mol/L NaOH and 0.012mol/L NaAlO2The mixed solution of (3) was treated 2 times. After the 2 nd alkali treatment, the mixture is treated for 120min by 900ml of 1.0mol/L phosphoric acid solution at the temperature of 90 ℃, and then is chilled, dried and roasted. Mixing the roasted HZSM-5 molecular sieve with gamma-Al2O3Uniformly mixing according to the mass ratio of 7:3, adding 4% dilute nitric acid, kneading, extruding into strips, drying, screening out particles of 20 ~ 40 meshes, and roasting at 540 ℃ for 6 hours to obtain the catalyst I.
[ examples 10 to 18 ]
Respectively taking 10g of the catalyst A-I, soaking 3.2g of magnesium acetate in the same volume for 24h, drying at 120 ℃ for 12h, and roasting at 540 ℃ for 6 h. Namely, the catalyst J-R is obtained by loading 6 percent of MgO on the catalyst A-I in sequence.
[ example 19 ]
And (3) carrying out benzene and methanol alkylation activity and selectivity evaluation on the catalysts A-I on a fixed bed reaction evaluation device. The loading of the catalyst is 2.5g, and the mass space velocity is 8h-1The reaction temperature is 450 ℃, the reaction pressure is 0.2MPa, the nitrogen flow is 50ml/min, and the molar ratio of benzene to methanol is 1.0.
The reaction results are shown in Table 1. Wherein the ratio of silicon to aluminum (SiO)2/Al2O3) The HZSM-5 molecular sieve raw powder of 300 was designated as YF.
The conversion X (B) of benzene, the total selectivity S (TX) and the total yield Y (TX) of toluene and xylene, and the selectivity S (T) of toluene and the selectivity S (X) of xylene. Their calculation methods are as follows:
(1)
(2)
(3)
(4)
(5)
in the formula, M: moles of benzene in the feedstock;
n: the mole number of benzene series in the product;
p: the moles of toluene in the product;
q: moles of xylene in the product.
TABLE 1 results of the reactions of catalysts A-I
[ example 20 ]
And (3) carrying out benzene and methanol alkylation activity and selectivity evaluation on the catalysts J-R on a fixed bed reaction evaluation device. The loading of the catalyst is 2.5g, and the mass space velocity is 8h-1The reaction temperature is 450 ℃, the reaction pressure is 0.2MPa, the nitrogen flow is 50ml/min, and the molar ratio of benzene to methanol is 1.0.
The reaction results are shown in Table 2.
TABLE 2 catalyst J-R reaction results
[ example 21 ]
In a fixed bed reactionThe service life of the catalyst N is inspected on an evaluation device, the loading amount of the catalyst is 2.5g, and the mass space velocity is 8h-1The reaction temperature is 450 ℃, the reaction pressure is 0.2MPa, the nitrogen flow is 50ml/min, and the molar ratio of benzene to methanol is 1.0.
The experimental results are shown in fig. 1:
the 200-hour catalyst life experiment shows that the catalyst has good stability, the average conversion rate of benzene reaches 53%, and the average total selectivity of toluene and xylene reaches 92.50%. The catalyst successfully solves the defects of low benzene conversion rate, low toluene and xylene selectivity and poor stability of benzene and methanol alkylation catalysts, thereby having good industrial application value.
Claims (1)
1. A catalyst for the alkylation reaction of benzene and methanol is prepared from HZSM-5 molecular sieve with Si/Al ratio of 300-1000, alkali treating, acid treating and gamma-Al modifying2O3The catalyst is formed by loading one or more oxides as a binder, and comprises 60-90% of alkali-treated and acid-treated HZSM-5 molecular sieve by mass percent, 10-40% of the binder, and the loaded oxides account for 1-15% of the total mass of the catalyst;
the alkali used for the alkali treatment is NaOH, KOH or NaAlO2、KAlO2At a concentration of 0.1-5 mol/L; the alkali treatment time is 10-200min, and the treatment temperature is 20-100 ℃; the acid used for acid treatment is HCl and HNO3One or more of oxalic acid, citric acid, tartaric acid, acetic acid and phosphoric acid, the concentration is 0.1-5 mol/L; the acid treatment time is 30-600min, and the treatment temperature is 20-100 ℃; the number of the alkali treatment and the acid treatment is two;
the supported oxides are MgO and MoO3、P2O5、NiO、SiO2、CeO2The precursor used for loading is corresponding nitrate or organic acid salt, and the loading amount is 1-15 wt%;
the amount of alkali or acid used per gram of molecular sieve treated is 5-60 mL.
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| CN112295589B (en) * | 2019-08-02 | 2024-01-09 | 中国石油化工股份有限公司 | Catalyst for synthesizing durene and preparation method thereof |
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| CN102688771A (en) * | 2011-03-23 | 2012-09-26 | 中国石油天然气股份有限公司 | Catalyst for alkylation of benzene and methanol, and preparation and application thereof |
| CN104549452A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Toluene and methanol alkylation catalyst and preparation method and application thereof |
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| CN104492476A (en) * | 2014-12-01 | 2015-04-08 | 上海应用技术学院 | Modified ZSM-5 molecular sieve and preparation method thereof |
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| CN104549452A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Toluene and methanol alkylation catalyst and preparation method and application thereof |
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| 苯、甲醇烷基化催化剂改性及反应特性的研究;张超;《中国优秀硕士学位论文全文数据库（电子期刊）》;20130630;第24页第5.1节第一段及第28页第5.3节第一段，第53页第7.2.2节和表7.4，第26页第5.2节，第51页7.2.1节 * |
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Effective date of registration: 20201204 Address after: No.16 ande Road, Dongcheng District, Beijing 100120 Patentee after: PetroChina Co.,Ltd. Patentee after: EAST CHINA University OF SCIENCE AND TECHNOLOGY Address before: 200237 East China University of Science and Technology, 130 Meilong Road, Shanghai, Xuhui District Patentee before: EAST CHINA University OF SCIENCE AND TECHNOLOGY |
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Inventor after: Xu Yarong Inventor after: Zhao Yanmao Inventor after: Liu Minghui Inventor after: Yang Fan Inventor after: Cao Qingsheng Inventor after: Zhou Zhuo Inventor after: Wang Meng Inventor after: Zhu Xuedong Inventor after: Feng Limei Inventor after: Wen Zhenhao Inventor after: He Xuan Inventor after: Yang Daqiang Inventor after: Wei Zhenhao Inventor after: Xia Tengfei Inventor after: Zhong Jie Inventor before: Zhu Xuedong Inventor before: Yang Fan Inventor before: Cao Qingsheng Inventor before: Zhou Zhuo Inventor before: Wang Meng Inventor before: Wen Zhenhao Inventor before: He Xuan Inventor before: Yang Daqiang Inventor before: Wei Zhenhao Inventor before: Xia Tengfei Inventor before: Zhong Jie Inventor before: Zhao Yanmao Inventor before: Liu Minghui |