CN107661775B - Catalyst containing UZM-8 molecular sieve and application thereof - Google Patents

Catalyst containing UZM-8 molecular sieve and application thereof Download PDF

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CN107661775B
CN107661775B CN201610603013.7A CN201610603013A CN107661775B CN 107661775 B CN107661775 B CN 107661775B CN 201610603013 A CN201610603013 A CN 201610603013A CN 107661775 B CN107661775 B CN 107661775B
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CN107661775A (en
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张凤美
石艳春
邢恩会
谢文华
慕旭宏
王卫东
秦凤明
刘强
舒兴田
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65

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Abstract

A catalyst comprising a UZM-8 molecular sieve, characterized in that said UZM-8 molecular sieve is27The ratio of the area of a tetra-coordinated aluminum peak of 55ppm to the area of a tetra-coordinated aluminum peak of 49ppm in an Al MAS NMR spectrogram is 3.5-6.0, and the catalyst taking the tetra-coordinated aluminum peak as an active component gives consideration to the advantages of beta and an MCM-22 molecular sieve in the reaction of synthesizing ethylbenzene by liquid-phase alkylation of ethylene and benzene, so that the catalyst has high activity and high ethylbenzene selectivity.

Description

Catalyst containing UZM-8 molecular sieve and application thereof
Technical Field
The invention relates to a catalyst containing a molecular sieve and application thereof, in particular to a catalyst containing UZM-8 molecular sieve and application thereof in a liquid-phase alkylation reaction of vinyl benzene.
Background
Ethylbenzene is used as an important chemical raw material, and is mainly used for dehydrogenation production of styrene, and further production of styrene series resins such as Polystyrene (PS), acrylonitrile-butadiene-styrene (ABS), styrene-acrylonitrile (SAN), Styrene Butadiene Rubber (SBR), and the like. In addition, small amounts of ethylbenzene are also used as solventDiluent and formation of diethylbenzene. In recent years, styrene is developed more rapidly, and the vigorous market demand for styrene drives the continuous increase of the yield of ethylbenzene; from 1998 to 2015, the global demand for ethylbenzene will increase at a rate of 3.7%. Commercially, ethylbenzene is synthesized primarily by the alkylation of ethylene with benzene, with only about 2% of the ethylbenzene being passed through the C8The separation method of the fractions.
At present, the production process of ethylbenzene mainly comprises the following steps: AlCl3A method, an Alkar gas phase method, a catalytic distillation process molecular sieve gas phase method, a molecular sieve liquid phase method and the like; the former two methods have been phased out due to the disadvantages of environmental pollution, corrosion of equipment, large energy consumption, etc. Since the 80's of the 20 th century, the production of ethylbenzene began to start with conventional AlCl3The Friedel-Crafts benzene alkylation process of the catalyst is converted into a molecular sieve catalysis process. The synthesis process of ethylbenzene by molecular sieve catalysis is divided into a gas phase method and a liquid phase method. The main defects of the molecular sieve gas phase catalytic synthesis of ethylbenzene are that the content of xylene is high, and the quality of the product is influenced; to a certain extent, the molecular sieve liquid phase method is a process developed aiming at the defects of the gas phase method, and the reaction temperature is low, so that the generation amount of side reaction products is reduced, particularly the generation amount of dimethylbenzene is greatly reduced, and the quality of an ethylbenzene product is improved. At present, Y, Beta and MCM-22 molecular sieve catalysts are used as catalysts for realizing industrialization of a liquid-phase ethylbenzene synthesis process.
Mobli Cheng et al (Studies in Surface Science and Catalysis,1999,121:53-60.) found by experimental comparison (Table 1): in the liquid phase alkylation reaction, the Beta molecular sieve has the highest activity, and the selectivity of ethylation (the total of ethylbenzene, diethylbenzene and triethylbenzene) is 99.7%; MCM-22 molecular sieve selectivity is best, ethylation selectivity reaches 99.9%, ethylbenzene selectivity is highest, polyethylbenzene such as diethylbenzene is rarely generated, the ratio of diethylbenzene to ethylbenzene generation is close to a balance value, and the ratio of diethylbenzene to ethylbenzene generation of Beta and Y greatly exceeds the balance value; the Y-type molecular sieve (USY) has poor activity and selectivity due to the supercage, and the ethylation selectivity is only 93%. Generally, the Beta molecular sieve has the highest activity, the MCM-22 molecular sieve ethylbenzene and the ethylation selectivity are the best, and the Y-type molecular sieve has the worst selectivity and quick inactivation due to the existence of super cages in the channel structure.
US6756030B 1(2004), US 7268267B2(2007), US 7713513B2(2010) and US20110077442a1(2011) report for the first time that UZM-8 molecular sieve with MWW topology is synthesized by using dimethyl diethyl ammonium hydroxide (dedaoh) as a template, a silicon source used is a completely depolymerized silicon source such as tetraethoxysilane, and an aluminum source used is aluminum isopropoxide. Meanwhile, UOP company inspects the performance of the UZM-8 molecular sieve and other MWW structure molecular sieves (MCM-22, MCM-49 and MCM-56) for liquid-phase alkylation of ethylene and benzene, and finds that the UZM-8 molecular sieve has excellent catalytic activity and ethylbenzene selectivity. The silicon-grease-silicon source and the aluminum alkyl source used by the method greatly improve the preparation cost, so that the UZM-8 is not applied in a large scale.
The research results of UOP corporation, qian bin and the like in china petrochemical shanghai chemical research institute, examined the influence of the dosage of the dedaoh template agent, the guiding effect of the template agent and the ratio of the fed silicon to the synthesis of UZM-8 [ chemical bulletin, 2009(2): 2579-2584; petrochemical 2011(1):29-33.]. The silicon source is ethyl orthosilicate and the aluminum source is aluminum sec-butoxide. The research results show that: DEDMAOH/SiO2>0.3, the UZM-8 molecular sieve can be synthesized; when NaOH and seed crystals are added, the dosage of the template agent is correspondingly reduced, but the crystallinity of the synthesized UZM-8 is not high; feeding SiO2/Al2O320-100, and as the silicon-aluminum ratio increases, two diffraction peaks of UZM-8 at 2 theta angles of 6.6 degrees and 7.1 degrees become one peak, and the interlayer shrinks along the c-axis direction.
Disclosure of Invention
Based on a large number of experiments, the inventor of the invention unexpectedly finds that the product has a unique property different from the prior art27The UZM-8 molecular sieve with the characteristics of Al MAS NMR spectrogram and the catalyst taking the molecular sieve as an active component have better ethylene conversion rate and ethylbenzene selectivity in the reaction of synthesizing ethylbenzene by liquid-phase alkylation of ethylene and benzene. Based on this, the present invention was made.
Accordingly, it is an object of the present invention to provide a catalyst comprising UZM-8 molecular sieve which is different from the prior art; the second purpose is to provide a liquid phase alkylation reaction method of ethylene and benzene with better ethylene conversion rate and ethylbenzene selectivity.
In order to achieve one of the objects of the present invention, the present invention provides a catalyst comprising UZM-8 molecular sieve, characterized in that the UZM-8 molecular sieve, which is characterized in that27In the Al MAS NMR spectrum, the ratio of the area of the tetra-coordinated aluminum peak at 55ppm to the area of the tetra-coordinated aluminum peak at 49ppm is 3.5 to 6.0.
The catalyst of the present invention wherein the UZM-8 molecular sieve has unique characteristics27Characterization of Al MAS NMR spectrum. For characterizing molecular sieves in the invention27Fitting the peaks of the Al MAS NMR spectrogram into a Gaussian curve by using a generally adopted Gaussian fitting mode, wherein the abscissa position represents the chemical shift of the four-coordinate aluminum, namely the four-coordinate aluminum in different chemical environments; and the corresponding peak areas represent the amount of the corresponding tetracoordinated aluminum. The catalyst of the invention, wherein the UZM-8 molecular sieve is described in27In an Al MASNMR spectrogram, the ratio of peak areas of 55ppm of four-coordinate aluminum (marked as Al-IV-55) to 49ppm of four-coordinate aluminum (marked as Al-IV-49) is 3.5-6.0, and preferably 4.0-5.5; whereas the prior art, for example, of UZM-8 molecular sieves prepared according to the process described in US6756030B1(UOP)27In the Al MAS NMR spectrum, the ratio of the peak area of 55ppm of tetra-coordinated aluminum to the peak area of 49ppm of tetra-coordinated aluminum is 3.0 or less, for example, 2.6.
The catalyst of the invention, wherein the UZM-8 molecular sieve has high crystallinity and large specific surface area, and the crystallinity is more than 130%; BET specific surface area of more than 380m2·g-1Wherein the specific surface area of the micropores is more than 250m2·g-1(ii) a The pore volume is 0.6-0.7 cm3·g-1Wherein the micropore volume is greater than 0.1cm3·g-1. The UZM-8 molecular sieve prepared according to the method described in the prior art, for example, in comparative example 3, US6756030B1(UOP), has a crystallinity defined as 100% and a BET specific surface area of 253m2·g-1Wherein the specific surface area of the micropores is 166m2·g-1(much lower than the present invention); pore volume 0.53cm3·g-1Wherein the volume of the micro pores is 0.08cm3·g-1. Hair brushThe catalysts described therein, UZM-8 molecular sieves, are relatively highly crystalline, i.e., more crystalline, resulting in a significant increase in micropore area, which may be27The reason why the peak area of the tetradentate skeleton aluminum at 55ppm in the Al MAS NMR spectrum was relatively large.
The catalyst of the present invention, the UZM-8 molecular sieve, SiO2With Al2O3The molar ratio is preferably 10 to 200, and more preferably 15 to 100. In addition, the first and second substrates are,29the Si MAS NMR spectrum shows that the characteristic peak of the silicon spectrum is more obvious, which indicates that the UZM-8 molecular sieve has more complete structure and clearer silicon spectrum structure.
The catalyst of the invention, the UZM-8 molecular sieve, can be obtained by the following synthesis method: crystallizing a mixture comprising silica-alumina gel, dimethyl diethyl ammonium hydroxide and deionized water in a closed reaction kettle and recovering a product, wherein the specific surface area of the silica-alumina gel is more than 330m2G, pore volume is more than 1.0cm3·g-1Which is27In the Al MAS NMR spectrum, characteristic peaks are all at 48-62ppm, which indicates that aluminum exists in a four-coordinate form, and no six-coordinate aluminum characteristic peak is at 0 ppm.
In the catalyst, the UZM-8 molecular sieve is synthesized by uniformly stirring silica-alumina gel, dimethyl diethyl ammonium hydroxide and deionized water to obtain the catalyst with the preferred molar ratio of SiO2/Al2O3＝10-100、DEDMAOH/SiO2＝0.05-1.0、H2O/SiO210 to 100, more preferably SiO2/Al2O3＝10～50、DEDMAOH/SiO2＝0.3～1.0、H2O/SiO210 to 50, most preferably SiO2/Al2O3＝15～30、DEDMAOH/SiO2＝0.3～0.5、H2O/SiO210-20, wherein DEDMAOH represents dimethyl diethyl ammonium hydroxide; the crystallization is preferably performed for 5 to 21 days under the autogenous pressure of 130 to 180 ℃, and more preferably for 10 to 17 days under the autogenous pressure of 150 to 160 ℃. The recovery of the product, well known to those skilled in the art, generally involves cooling the closed reactor, depressurizing, and crystallizingAnd filtering, washing the product until the pH value is close to 7, drying and roasting to obtain the molecular sieve raw powder.
In the method for synthesizing the UZM-8 molecular sieve, the silica-alumina gel used as the silica-alumina source can be selected from silica-alumina gels (SiO) with different silica-alumina ratios2/Al2O310 ∞ to +∞); the silica-alumina gel can contain sodium, and can also adopt silica-alumina gel without sodium, wherein the silica-alumina gel without sodium is preferred, and sodium-free synthesis can be realized. The silica-alumina gel can be obtained by commercial or synthetic method as long as the specific surface area is more than 330m2G, pore volume is more than 1.0cm3·g-1Which is27In the Al MAS NMR spectrum, characteristic peaks are all located at 48-62ppm, and the condition that the characteristic peak of the hexacoordinated aluminum is not present at 0ppm can be used for synthesizing the UZM-8 molecular sieve in the catalyst disclosed by the invention.
The inventor researches and discovers that the specific surface, the pore diameter and the pore volume of the silica-alumina gel are closely related to the contact mode of silica and alumina, the aging temperature and the like. The industrial preparation process of the silica-alumina gel comprises the steps of mixing an aluminum source solution with sodium silicate to form silica-alumina gel, aging, pickling, drying and the like, and granulating. During the preparation process of the silica-alumina gel adopted by the invention, the preparation system needs to be ensured to be alkaline, such as pH is more than or equal to 8 (such as 8-10) so as to avoid the generation of Al-O-Al bonds, and the proportion of a silicon source and an aluminum source is determined by the silica-alumina ratio of a final product. For example, a typical laboratory procedure would be to add aluminum sulfate (or other aluminum salts such as aluminum nitrate) slowly to a vigorously stirred solution of water glass (sodium silicate) and then dry the mixture by washing with water, wherein the aging process is strictly controlled at a temperature above 60 ℃, e.g., 70-90 ℃. The silica-alumina gel adopted by the invention has the following index requirements: the specific surface area is more than 330m2A pore volume of more than 1.0cc/g, which27In the Al MAS NMR spectrum, characteristic peaks are all at 48-62ppm, and no hexacoordinate aluminum characteristic peak is at 0ppm, which indicates that the coordination of Al exists in a four-coordination form, Al is connected with four surrounding Si through O, and the connection of Al with Al through O (hexacoordinate aluminum) does not occur, and the connection of Al with a terminal hydroxyl group (defect) does not occur; while the silica-alumina gel contains four-coordinate aluminum and six-coordinate aluminum.
In the catalyst of the invention, in the synthesis method of the UZM-8 molecular sieve, an alkali source can be added to shorten the crystallization time. The alkali source may be at least one selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide, and sodium hydroxide is preferred. For example, NaOH is introduced as an alkali source, and the crystallization time is reduced by about half after the introduction of NaOH, for example, from 14 days to 7 days, which also indicates that UZM-8 molecular sieve can be synthesized by the presence of sodium in the synthesis system.
The catalyst of the invention takes UZM-8 molecular sieve as a catalytic active component and inorganic oxide as a carrier, and the catalyst comprises the following components: 30 to 70% by weight of SiO2/Al2O320-40 parts of UZM-8 molecular sieve, 1-40% of inorganic oxide and a proper amount of deionized water.
In the catalyst of the present invention, the UZM-8 molecular sieve described therein is generally required to first reduce the alkali metal content, for example, to 0.05% by weight or less of alkali metal oxide in an ammonium exchange manner. Wherein the inorganic oxide carrier accounts for 1-40% of the weight of the catalyst, preferably 20-30% of the weight of the catalyst, calculated as oxide. The inorganic oxide carrier is, for example, dry glue powder.
In order to achieve the second object of the present invention, the present invention also provides a liquid phase alkylation method of ethylene and benzene, which comprises carrying out alkylation reaction under alkylation reaction conditions in the presence of a catalyst, wherein the catalyst is a catalyst containing UZM-8 molecular sieve, and the UZM-8 molecular sieve27The ratio of the area of a tetra-coordinated aluminum peak at 55ppm to the area of a tetra-coordinated aluminum peak at 49ppm in an Al MAS NMR spectrum is 3.5 to 6.0.
The alkylation reaction method provided by the invention is generally carried out under the conditions that the temperature is 180-260 ℃, the preferable temperature is 200-260 ℃, the pressure is 2.0-4.0 MPa, the preferable pressure is 3.0-3.5MPa, and the weight space velocity of benzene is 1-5 h-1The molar ratio of benzene to ethylene is 2-12.
MCM-22 and Beta molecular sieves are the two most commonly used liquid phase ethylene and benzene alkylation catalysts, but have distinctly different characteristics. Beta molecular sieve has high activity, but low ethylbenzene selectivity; while MCM-22 molecular sieve has low activity, but high ethylbenzene selectivity. Ethylene and benzene are subjected to a series reaction, ethylbenzene is an intermediate product of the reaction, and the ethylbenzene can be continuously subjected to alkylation reaction with the ethylene to generate diethylbenzene, triethylbenzene and the like, so that the selectivity of the ethylbenzene is reduced. Although diethylbenzene and triethylbenzene can be further converted to ethylbenzene by transalkylation with benzene, separation of benzene, ethylbenzene and heavier components is critical to the overall energy consumption of the ethylbenzene plant. Thus, maintaining a high ethylbenzene selectivity while increasing conversion is a very challenging problem. Especially for the series of reactions in which the intermediate product is the target product. There is often a concomitant increase in ethylene conversion and a decrease in ethylbenzene selectivity. As shown in fig. 1 and 2, beta, although having a higher conversion, has a low ethylbenzene selectivity; whereas MCM-22 has low ethylene conversion but high ethylbenzene selectivity. In general, these two catalysts are distinguished. The UZM-8 molecular sieve has both high activity and high selectivity, and the UZM-8 has activity close to beta but the selectivity is obviously higher than that of the beta molecular sieve; similarly, UZM-8 has higher activity than MCM-22 molecular sieve, and simultaneously has selectivity equivalent to that of MCM-22. Therefore, UZM-8 has the advantages of both beta and MCM-22 molecular sieve, not only has higher activity, but also has high ethylbenzene selectivity, can meet the operating conditions of low benzene-olefin ratio, and has good application prospect.
The catalyst of the present invention may be also used in benzene and propylene alkylation reaction, aromatization, cracking, isomerization and other reactions.
Drawings
FIG. 1 is a graph showing a comparison of ethylene conversion (%) in liquid phase alkylation of ethylene and benzene over different catalysts.
FIG. 2 is a graph showing a comparison of the ethylbenzene selectivities (%) for liquid phase alkylation of ethylene and benzene over different catalysts.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
In the examples and comparative examples, the X-ray diffraction (XRD) phase diagrams of the samples were measured on a Siemens D5005 type X-ray diffractometer.
In the examples and comparative examples, the pore structure data of the molecular sieves were determined using a Micromeritics ASAP 2010 static nitrogen adsorption apparatus. And (3) testing conditions are as follows: the sample was placed in a sample handling system and evacuated to 1.33X 10 at 350 deg.C-2Pa, keeping the temperature and the pressure for 15h, and purifying the sample. Measuring the specific pressure p/p of the purified sample at-196 deg.C under liquid nitrogen0And (3) obtaining a nitrogen adsorption-desorption isothermal curve according to the adsorption quantity and the desorption quantity of the nitrogen under the condition. Then, the BET specific surface area is calculated by using a BET formula, the specific surface area and the micropore volume of the sample are calculated by using a t-plot method, and the total pore volume is calculated as P/P0Calculated as adsorption amount at 0.98 (S)exter＝SBET–Smicro；Vexter＝Vtotal-Vmicro)。
Example 1
This example illustrates the catalyst and the liquid phase alkylation of ethylene with benzene and the results provided by the present invention.
Synthesis of UZM-8 molecular sieve: mixing silica alumina gel (SiO)2/Al2O325, Qingdao maritime works, it27The characteristic peaks of the Al MAS NMR are all 48-62ppm, no characteristic peak is at 0ppm, and the specific surface area is 350m2The molar ratio of the obtained mixture colloid is as follows: SiO 22：0.04Al2O3：0.50DEDMAOH：13H2And O. And then transferring the obtained mixture to a closed crystallization kettle, dynamically crystallizing for 14 days at 150 ℃, cooling, taking out a product, and filtering, washing, drying and roasting to obtain a molecular sieve sample.
XRD test diffraction pattern shows that the molecular sieve sample is UZM-8 molecular sieve, the crystallinity is obviously higher than that of the sample in the comparative example, the SEM appearance presents a single-layer sheet structure, and the specific surface area is 421m2Per g, wherein the specific surface area of the micropores is 316m2(ii)/g; pore volume of 0.67cm3In terms of a volume of micropores of 0.15cm3/g。27Al MAS NMR measurement of the area of the tetra-coordinated aluminum (Al-IV-55) peak at the 55ppm position and the peak of the tetra-coordinated aluminum (Al-IV-49) at the 49ppm positionThe area ratio of (a) to (b) was 4.6.
Preparation of the catalyst: the sample and carrier dry rubber powder (dry basis is 70%) are uniformly mixed without ammonium exchange, and then nitric acid and a proper amount of deionized water are mixed into uniform liquid and slowly added while uniformly mixed. The mass ratio of the obtained mixture is as follows: 70% molecular sieve dry basis: 30% of dry rubber powder dry basis: 100% deionized water (catalyst dry basis ═ molecular sieve dry basis + support dry basis, defined as 100%). And further mixing the mixture uniformly on a strip extruding machine, extruding into strips, drying and roasting to obtain the catalyst with the catalyst number of A1.
Alkylation of benzene with ethylene: the weight space velocity of benzene is 3.0h-1The mol ratio of benzene to ethylene is 12, the temperature is 200 to 260 ℃, the pressure is 3.0 to 3.5MPa, and A1 is used as a catalyst.
The results for ethylene conversion and ethylbenzene selectivity are shown in the corresponding curves of fig. 1 and 2. Among them, it was found that the ethylene conversion at 220 ℃ was 99.9% and the ethylbenzene selectivity was 95.5%.
Comparative example 1
This comparative example illustrates the catalyst with Beta molecular sieve as the active component and the process and results for the liquid phase alkylation of ethylene with benzene.
Beta molecular sieves (catalyst, Chang Ling Brand, SiO)2/Al2O325) ammonium exchange: ammonium exchange for 2h under the condition of water bath at 90 ℃, and then the mixture is taken out, filtered and dried for standby. Wherein the ammonium ion precursor is ammonium nitrate, and the ratio of the exchange liquid is as follows: 1g of molecular sieve: 1g of ammonium nitrate: 20g of deionized water.
Uniformly mixing the ammonium-crosslinked Beta molecular sieve (dry basis 80%) with carrier dry rubber powder (dry basis 70%), mixing nitric acid and a proper amount of deionized water into uniform liquid, slowly adding the uniform liquid while adding the uniform liquid. The mass ratio of the obtained mixture is as follows: 70% Beta molecular sieve dry basis: 30% of dry rubber powder dry basis: 100% deionized water (catalyst dry basis ═ molecular sieve dry basis + support dry basis, defined as 100%). And further mixing the mixture uniformly on a strip extruding machine, extruding the mixture into strips, drying and roasting to obtain a comparative catalyst with the number D1.
The alkylation reaction conditions of example 1 were the same.
The results for ethylene conversion and ethylbenzene selectivity are shown in the corresponding curves of fig. 1 and 2. Among them, it was found that the ethylene conversion at 220 ℃ was 100% and the ethylbenzene selectivity was 92.8%.
Comparative example 2
This comparative example illustrates the catalyst with MCM-22 molecular sieve as the active component and the liquid phase alkylation reaction of ethylene with benzene and the results.
The MCM-22 molecular sieve was prepared according to the method of CN 103771435A: dissolving solid Haliotis silica gel (dry basis 97%) in deionized water, adding hexamethyleneimine and aniline, stirring to dissolve completely, adding the above solution, adding sodium metaaluminate (analytically pure) and sodium hydroxide (analytically pure), stirring uniformly to obtain a mixture with a colloid molar ratio of: 0.18 NaOH: SiO 22：0.04Al2O3：0.10HMI：0.20AN：15H2And O. Then transferring the obtained mixture colloid into a closed crystallization kettle, dynamically crystallizing for 72 hours at 145 ℃, cooling, taking out the product, filtering, washing, drying and roasting to obtain the MCM-22 molecular Sieve (SiO)2/Al2O325) for standby.
Ammonium exchange, catalyst preparation as in comparative example 1, a comparative catalyst, No. D2, was obtained.
The alkylation reaction conditions of example 1 were the same.
The results for ethylene conversion and ethylbenzene selectivity are shown in the corresponding curves of fig. 1 and 2. Among them, it was found that the ethylene conversion at 220 ℃ was 87.4% and the ethylbenzene selectivity was 96.2%.
As shown in figures 1 and 2, beta and MCM-22 are respectively characterized, the method of the catalyst taking beta as an active component in comparative example 1 has high conversion rate but low ethylbenzene selectivity; in contrast, in the method of the catalyst using MCM-22 as an active component of comparative example 2, ethylbenzene selectivity was high although ethylene conversion was low. The catalyst taking the UZM-8 molecular sieve as an active component in the embodiment 1 of the invention has both activity and selectivity, wherein the UZM-8 has activity close to beta, but the selectivity is obviously higher than that of the beta molecular sieve; similarly, UZM-8 has higher activity than MCM-22 molecular sieve, and simultaneously has selectivity equivalent to that of MCM-22. Therefore, UZM-8 has the advantages of both beta and MCM-22 molecular sieve, i.e. higher activity and high ethylbenzene selectivity.
Example 2
This example illustrates the catalyst and alkylation process and results provided by the present invention.
Synthesis of UZM-8 molecular sieve: mixing silica alumina gel (SiO)2/Al2O320, Qingdao maritime works, it27The characteristic peaks of the Al MAS NMR are all 48-62ppm, no characteristic peak is at 0ppm, and the specific surface area is 360m2The molar ratio of the obtained mixture colloid is as follows: SiO 22：0.05Al2O3：0.50DEDMAOH：13H2And O. And then transferring the obtained mixture to a closed crystallization kettle, dynamically crystallizing for 14 days at 150 ℃, cooling, taking out a product, and filtering, washing, drying and roasting to obtain a molecular sieve sample.
XRD test diffraction pattern shows that the molecular sieve sample is UZM-8 molecular sieve, the crystallinity is obviously higher than that of the sample in the comparative example, the SEM appearance presents a single-layer sheet structure, and the specific surface area is 410m2Per g, wherein the specific surface area of the micropores is 310m2(ii)/g; pore volume of 0.63cm3In terms of a volume of micropores of 0.15cm3/g。27The ratio of the area of the peak of tetra-coordinated aluminum (Al-IV-55) at the 55ppm position to the area of the peak of tetra-coordinated aluminum (Al-IV-49) at the 49ppm position was 4.3 as measured by Al MAS NMR.
Catalyst preparation the procedure of example 1 was followed to give a catalyst numbered A2.
The benzene and ethylene alkylation conditions were the same as in example 1.
The conversion rate of ethylene is 99.1% and the selectivity of ethylbenzene is 94.9% at the reaction temperature of 220 ℃.
Example 3
This example illustrates the catalyst and alkylation process and results provided by the present invention.
Synthesis of UZM-8 molecular sieve: mixing silica alumina gel (SiO)2/Al2O325, Qingdao seaAn ocean chemical plant of27The characteristic peaks of the Al MAS NMR are all 48-62ppm, no characteristic peak is at 0ppm, and the specific surface area is 350m2The molar ratio of the obtained mixture colloid is as follows: SiO 22：0.05Al2O3：0.50DEDMAOH：13H2And O. And then transferring the obtained mixture to a closed crystallization kettle, dynamically crystallizing for 10 days at 150 ℃, cooling, taking out a product, and filtering, washing, drying and roasting to obtain a molecular sieve sample.
XRD test diffraction pattern shows that the molecular sieve sample is UZM-8 molecular sieve, SEM appearance presents a single-layer sheet structure, and specific surface area is 403m2Per g, wherein the specific surface area of the micropores is 298m2(ii)/g; pore volume of 0.65cm3In terms of a volume of micropores of 0.15cm3/g。27The ratio of the area of the peak of tetra-coordinated aluminum (Al-IV-55) at the 55ppm position to the area of the peak of tetra-coordinated aluminum (Al-IV-49) at the 49ppm position was 4.0 as measured by Al MAS NMR.
Preparing a catalyst: the molecular sieve was ammonium exchanged to reduce the sodium oxide content to below 0.05 wt.% and the catalyst prepared in the same manner as in example 1, was identified as A3.
The benzene and ethylene alkylation conditions were the same as in example 1.
The reaction temperature was 220 ℃, the ethylene conversion of the catalyst was 99.4%, and the ethylbenzene selectivity was 95.0%.
Example 4
This example illustrates the catalyst and alkylation process and results provided by the present invention.
Synthesis of UZM-8 molecular sieve: mixing silica alumina gel (SiO)2/Al2O316 Qingdao oceanic chemical plant, specific surface area 360m2The molar ratio of the obtained mixture colloid is as follows: SiO 22：0.0625Al2O3：0.50DEDMAOH：13H2And O. Then the mixture is transferred to a closed crystallization kettle at 15 DEGAnd (3) dynamically crystallizing for 8 days at 0 ℃, cooling, taking out a product, and filtering, washing, drying and roasting to obtain a sample.
XRD test diffraction pattern shows that the molecular sieve sample is UZM-8 molecular sieve, SEM appearance presents single-layer sheet structure and specific surface area is 395m2Per g, wherein the specific surface area of the micropores is 286m2(ii)/g; pore volume of 0.60cm3In terms of a volume of micropores of 0.15cm3/g。27The ratio of the area of the peak of tetra-coordinated aluminum (Al-IV-55) at the 55ppm position to the area of the peak of tetra-coordinated aluminum (Al-IV-49) at the 49ppm position was 5.2 in an Al MAS NMR test.
Preparing a catalyst: the molecular sieve was ammonium exchanged to reduce the sodium oxide content to below 0.05 wt.% and the catalyst prepared in the same manner as in example 1, was identified as A4.
The benzene and ethylene alkylation conditions were the same as in example 1.
The reaction temperature was 220 ℃, the ethylene conversion of the catalyst was 99.8%, and the ethylbenzene selectivity was 95.1%.

Claims (9)

1. A catalyst comprising a UZM-8 molecular sieve, characterized in that said UZM-8 molecular sieve is27In an Al MAS NMR spectrum, the ratio of the area of a tetra-coordinated aluminum peak at 55ppm to the area of a tetra-coordinated aluminum peak at 49ppm is 3.5-6.0, and the aluminum alloy is obtained by the following synthesis method: crystallizing a mixture comprising silica-alumina gel, dimethyl diethyl ammonium hydroxide and deionized water in a closed reaction kettle and recovering a product; wherein, the specific surface area of the silica-alumina gel is more than 330m2G, pore volume is more than 1.0cm3·g-1And the silica alumina gel27In the Al MAS NMR spectrum, characteristic peaks are all at 48-62ppm, and no hexacoordinate aluminum characteristic peak is at 0 ppm.
2. The catalyst according to claim 1 wherein said UZM-8 molecular sieve is27In the Al MAS NMR spectrum, the ratio of the area of the tetra-coordinated aluminum peak at 55ppm to the area of the tetra-coordinated aluminum peak at 49ppm is 4.0 to 5.5.
3. The catalyst according to claim 1 wherein the UZM-8 molecular sieve has a BET specific surface area of greater than 380m2·g-1Wherein the specific surface area of the micropores is more than 250m2·g-1Pore volume of 0.6-0.7 cm3·g-1Wherein the micropore volume is greater than 0.1cm3·g-1。
4. The catalyst according to claim 1, which comprises 30 to 70% by weight of UZM-8 molecular sieve on an inorganic oxide carrier.
5. A liquid-phase alkylation process for preparing ethylene and benzene features that the alkylation reaction is carried out under the condition of alkylation reaction and in the presence of a catalyst containing UZM-8 molecular sieve27In an AlMAS NMR spectrum, the ratio of the area of a tetra-coordinated aluminum peak at 55ppm to the area of a tetra-coordinated aluminum peak at 49ppm is 3.5-6.0, and the AlMAS NMR spectrum is obtained by the following synthesis method: crystallizing a mixture comprising silica-alumina gel, dimethyl diethyl ammonium hydroxide and deionized water in a closed reaction kettle and recovering a product; wherein, the specific surface area of the silica-alumina gel is more than 330m2G, pore volume is more than 1.0cm3·g-1And the silica alumina gel27In the Al MAS NMR spectrum, characteristic peaks are all at 48-62ppm, and no hexacoordinate aluminum characteristic peak is at 0 ppm.
6. The method according to claim 5, wherein the alkylation reaction is carried out at 180-260 deg.C under 2.0-4.0 MPa and at a benzene weight space velocity of 1-5 h-1And the molar ratio of benzene to ethylene is 2-12.
7. The process of claim 5 wherein the UZM-8 molecular sieve is27In the Al MAS NMR spectrum, the ratio of the area of the tetra-coordinated aluminum peak at 55ppm to the area of the tetra-coordinated aluminum peak at 49ppm is 4.0-6.0.
8. A method according to claim 5, wherein saidUZM-8 molecular sieve with BET specific surface area greater than 380m2·g-1Wherein the specific surface area of the micropores is more than 250m2·g-1Pore volume of 0.6-0.7 cm3·g-1Wherein the micropore volume is greater than 0.1cm3·g-1。
9. The process of claim 5 wherein the catalyst is supported on an inorganic oxide and contains 30 to 70 wt.% UZM-8 molecular sieve.
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