Alkylation solid acid catalyst, preparation method and application thereof, and alkylation method

Abstract

The invention relates to the technical field of alkylation, and discloses an alkylation solid acid catalyst, a preparation method and application thereof, and an alkylation method. The alkylation solid acid catalyst comprises a molecular sieve, a binder and an active metal, and the active metal is Cu; on the basis of the dry basis weight of the catalyst, the content of the molecular sieve is 50-95 wt%, the content of the binder is 4.9-50 wt%, and the content of the active metal in terms of elements is not higher than 20 wt%; compared with the pyridine infrared total acid content of the molecular sieve, the pyridine infrared total acid content of the catalyst is increased by not less than 20%. The alkylation solid acid catalyst has a high pyridine infrared total acid content, can improve the conversion rate of ethylene and prolong the service life of the catalyst when being used in an ethylene isobutane alkylation reaction, and has the advantages of simple preparation method operation, low cost and good industrial value.

Description

Technical Field

[0001] The invention relates to the technical field of alkylation, and in particular to an alkylation solid acid catalyst and a preparation method and application thereof, and an alkylation method. Background Art

[0002] With the increasing requirements for environmental protection and energy conservation and emission reduction, the number of hybrid vehicles is growing in order to reduce automobile fuel consumption. Since hybrid vehicle engines need to be started and stopped constantly, a certain amount of lighter high-octane components will help the engine start. Dimethylbutane and isopentane produced by the alkylation of isobutane and ethylene are ideal light gasoline blending components due to their high octane number, good combustion performance, and the absence of sulfides, aromatics, and olefins.

[0003] Solid acid catalysts are widely used in petrochemical and other fields due to their suitable acidity and low price, especially in catalytic cracking, hydrogenation, reforming, isobutane butene alkylation, benzene and olefin alkylation. Therefore, the research on solid acid catalysts not only has important academic value, but also has broad application prospects.

[0004] At present, there are few studies on the alkylation of ethylene and isobutane to produce isopentane and dimethylbutane at home and abroad. Patent application CN103168088A provides a method for producing high-octane alkylate from ethylene and isobutane. However, this method first allows ethylene to dimerize to produce butene under the catalytic action of a first catalytic material, and then butene and isobutane are catalyzed by a second catalytic material to produce C8 alkylated oil.

[0005] Studies have shown that solid acid catalysts are prone to deactivation in the ethylene isobutane alkylation reaction, and ethylene is difficult to completely convert. This is because ethylene has a large polarity and is easily adsorbed on acid sites, so that ethylene undergoes self-polymerization to generate macromolecular products that are difficult to diffuse out of the pores. The resulting carbon deposits cover the acid sites or block the pores, causing the catalyst to quickly deactivate. In order to improve the catalyst life and ethylene conversion rate, it is necessary to inhibit the adsorption of ethylene on acid sites, thereby inhibiting the self-polymerization of ethylene and enhancing the alkylation reaction of ethylene and isobutane. Summary of the invention

[0006] The purpose of the present invention is to overcome the technical problems of easy deactivation of the catalyst and low ethylene conversion rate in the ethylene isobutane alkylation reaction catalyzed by the solid acid catalyst in the prior art, and to provide an alkylation solid acid catalyst and its preparation method and application, and an alkylation method. The catalyst has a specific pyridine infrared total acid content, is not easy to deactivate, and can be used in the ethylene isobutane alkylation reaction to improve the ethylene conversion rate and increase the service life of the catalyst.

[0007] In order to achieve the above-mentioned object, the first aspect of the present invention provides an alkylation solid acid catalyst, wherein the catalyst comprises a molecular sieve, a binder and an active metal Cu; based on the dry weight of the catalyst, the content of the molecular sieve is 50-95wt%, the content of the binder is 4.9-50wt%, and the content of the active metal calculated as an element is not higher than 20wt%; the 200°C pyridine infrared total acidity of the catalyst is increased by 25-50% compared with the 200°C pyridine infrared total acidity of the molecular sieve.

[0008] Preferably, based on the dry weight of the catalyst, the content of the molecular sieve is 50-87wt%, the content of the binder is 8-45wt%, and the content of the active metal in terms of element is 0.5-5wt%.

[0009] Preferably, the total pyridine infrared acidity at 200°C of the catalyst is increased by 40-50wt% compared with the total pyridine infrared acidity at 200°C of the molecular sieve.

[0010] A second aspect of the present invention provides a method for preparing an alkylation solid acid catalyst, wherein the method comprises:

[0011] (1) mixing a sodium molecular sieve with a binder or its precursor, an auxiliary agent, an acid solution, and water to form a mixture, and then drying and calcining the mixture to obtain a calcined product;

[0012] (2) subjecting the obtained calcined product to ammonium exchange and acid treatment in sequence to obtain a catalyst precursor;

[0013] (3) ion-exchanging the catalyst precursor with the active metal precursor to obtain an alkylation solid acid catalyst;

[0014] Wherein, the active metal is Cu.

[0015] The third aspect of the present invention provides an alkylation solid acid catalyst prepared by the preparation method described in the second aspect.

[0016] The fourth aspect of the present invention provides a use of the alkylation solid acid catalyst described in the first aspect or the third aspect in the alkylation reaction of isoparaffin and olefin.

[0017] The fifth aspect of the present invention provides an alkylation method, wherein the method comprises alkylating isobutane with ethylene in the presence of an alkylation solid acid catalyst; wherein the alkylation solid acid catalyst is the alkylation solid acid catalyst described in the first aspect or the third aspect.

[0018] The alkylation solid acid catalyst provided by the present invention introduces active metal Cu into the alkylation solid acid catalyst, thereby increasing the synergistic effect between the active metal and the molecular sieve. The alkylation solid acid catalyst has a higher 200°C pyridine infrared total acid content and high acid strength, and can increase the service life of the alkylation solid acid catalyst.

[0019] The preparation method provided by the present invention introduces active metals by ion exchange during the catalyst preparation process. The method is simple, easy to operate and control. + Ions are directly exchanged to the acidic sites of the catalyst in ionic form, and metal ions are directly complexed with the acidic sites. However, the impregnation method often uses salt solutions to load metal salts onto the catalyst, and most of them are deposited on the carrier in the form of metal salts, which makes it difficult to complex with the acidic center in the form of ions.

[0020] The alkylation method provided by the present invention uses the alkylation solid acid catalyst of the present invention. The alkylation solid acid catalyst has high activity and is not easy to be deactivated. The active metal Cu in the catalyst can provide adsorption sites, reduce the adsorption of ethylene at the acid sites, significantly improve the conversion rate of ethylene, and improve the service life of the catalyst. In addition, the reaction temperature of the alkylation method is low, which is lower than the reaction temperature of 300° C. in the prior art. The target product and the alkylation solid acid catalyst are easy to separate. The alkylation solid acid catalyst can be recycled for multiple times, which greatly reduces the loss of the alkylation solid acid catalyst and the emission of solid waste, reduces energy consumption and carbon emissions, has a high ethylene conversion rate, good target product selectivity, and a high product octane number. The method has high industrial feasibility and economic value. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is the infrared spectra of pyridine of catalyst Y-1 of Example 1 of the present invention and catalyst DY-1 of comparative example 1 at 200°C;

[0022] Figure 2 It is the pyridine infrared spectra of catalyst Y-1 of Example 1 of the present invention and catalyst DY-1 of Comparative Example 1 at 350°C. DETAILED DESCRIPTION

[0023] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0024] The first aspect of the present invention provides an alkylation solid acid catalyst, wherein the catalyst comprises a molecular sieve, a binder and an active metal Cu; based on the dry weight of the catalyst, the content of the molecular sieve is 50-95wt%, the content of the binder is 4.9-50wt%, and the content of the active metal calculated as an element is not higher than 20wt%; the 200°C pyridine infrared total acidity of the catalyst is increased by 25-50% compared with the 200°C pyridine infrared total acidity of the molecular sieve.

[0025] According to a preferred embodiment of the present invention, based on the dry weight of the catalyst, the content of the molecular sieve is 50-87wt%, the content of the binder is 8-45wt%, and the content of the active metal in terms of element is 0.5-5wt%, for example, it can be 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt% and values ​​between any two groups.

[0026] In the present invention, the content of each substance in the catalyst is measured by X-ray fluorescence spectrometry (XRF) full analysis method, and the specific test conditions include: the test conditions are: tungsten target, excitation voltage 40kV, excitation current 50mA. The sample powder is pressed into tablets, and the applied pressure is generally 500-1000kPa. The measuring instrument comes with a standard sample and establishes a working curve, and the content is found on the working curve by interpolation.

[0027] According to a preferred embodiment of the present invention, the total pyridine infrared acid content of the catalyst at 200°C is increased by 40-50% compared with the total pyridine infrared acid content of the molecular sieve at 200°C, for example, it can be 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50% and values ​​between any two groups.

[0028] The alkylation solid acid catalyst provided by the invention has a high pyridine infrared total acid content, and Cu is introduced as an active metal to provide adsorption sites. The catalyst is not easy to deactivate and has a long service life in the alkylation reaction.

[0029] In the present invention, "dry basis weight" refers to the mass of a unit mass of catalyst after calcination at 600°C for 4 hours.

[0030] In the present invention, the pyridine adsorption infrared acid amount of the alkylation solid acid catalyst is determined as follows, the instrument is a BrukerTensor II Fourier transform infrared spectrometer, the test process is: take about 25 mg of the catalyst sample 20MPa tablet for 5 minutes, place it in the infrared spectrometer in-situ cell and seal it, heat it to 450°C at a rate of 10°C / min, and evacuate it to 10 -6Pa for 2h, cooled to room temperature, statically saturated adsorbed pyridine, then vacuumed, heated to 200℃ and 350℃ in steps to desorb the adsorbed pyridine, measured the infrared spectra at the two temperatures and integrated them to calculate the infrared spectrum using the formula. -1 The absorption peak at 1450cm -1 The absorption peak is attributed to the L acidic site.

[0031] C is the concentration of B acid or L acid (mmol / g), C B With C L The calculation formula is:

[0032] C B =1.88A B R 2 / W (Formula 1)

[0033] C L =1.42A L R 2 / W (Formula 2)

[0034] A is the integrated area of ​​the B acid or L acid absorption peak; R is the radius of the sample piece (cm); W is the mass of the sample piece (mg).

[0035] In the present invention, it can be understood that the total pyridine infrared acid content of different hydrogen-type molecular sieves may be different. For example, the total pyridine infrared acid content of HX type molecular sieve at 200°C is about 360 μmol / g, the total pyridine infrared acid content of HY type molecular sieve at 200°C is about 310 μmol / g, the total pyridine infrared acid content of Hβ type molecular sieve at 200°C is about 560 μmol / g, the total pyridine infrared acid content of HMOR type molecular sieve at 200°C is about 285 μmol / g, and the total pyridine infrared acid content of HZSM type molecular sieve at 200°C is about 500 μmol / g.

[0036] In the present invention, it is understood that the acid amount measured at 200° C. is the total acid amount of the catalyst and the molecular sieve, and the acid amount measured at 350° C. is the strong acid amount of the catalyst and the molecular sieve.

[0037] In the present invention, there is no particular limitation on the type of molecular sieve. Preferably, the molecular sieve is selected from at least one of X-type, Y-type, β, ZSM-5 and MOR molecular sieves; more preferably, the molecular sieve is selected from Y-type molecular sieve and / or β molecular sieve, and more preferably Y-type molecular sieve. The advantages of adopting this preferred embodiment are the unique pore structure of Y-type molecular sieve, higher acid density and acid strength, and Cu + After complexation, the adsorption of olefins at acidic sites is reduced, thereby better improving the selectivity of the target product.

[0038] In the present invention, there is no particular limitation on the type of binder, as long as it meets the performance requirements of the present invention. Preferably, the binder is selected from at least one of aluminum chloride, aluminum oxide, silicon dioxide, titanium dioxide, kaolin and montmorillonite, preferably at least one of aluminum oxide, silicon dioxide and titanium dioxide. By selecting the above binder with good adhesion, it can interact with the molecular sieve, thereby improving the acidity and stability of the catalyst to a certain extent.

[0039] According to a preferred embodiment of the present invention, the aluminum oxide is aluminum oxide containing pseudo-boehmite phase and / or γ phase.

[0040] According to a preferred embodiment of the present invention, the molecular sieve is an X-type molecular sieve, the unit cell constant of the catalyst is 2.46-2.485 nm, the total acid content of pyridine infrared at 200°C is greater than 450 μmol / g, preferably the total acid content of pyridine infrared at 200°C is 460-550 μmol / g.

[0041] According to a preferred embodiment of the present invention, the molecular sieve is a Y-type molecular sieve, the unit cell constant of the catalyst is 2.441-2.466 nm, the total acid content of pyridine infrared at 200°C is greater than 400 μmol / g, preferably the total acid content of pyridine infrared at 200°C is 420-480 μmol / g.

[0042] According to a preferred embodiment of the present invention, the molecular sieve is a β molecular sieve, the unit cell constant of the catalyst is 1.249-1.262 nm, the total acid content of pyridine infrared at 200°C is greater than 700 μmol / g, preferably the total acid content of pyridine infrared at 200°C is 710-800 μmol / g.

[0043] According to a preferred embodiment of the present invention, the molecular sieve is ZSM-5 molecular sieve, the unit cell constant of the catalyst is 2.004-2.024nm, the total acid content of pyridine infrared at 200°C is greater than 500μmol / g, preferably the total acid content of pyridine infrared at 200°C is 600-750μmol / g.

[0044] According to a preferred embodiment of the present invention, the molecular sieve is a MOR type molecular sieve, the unit cell constant of the catalyst is 1.8-1.818 nm, the total acid content of pyridine infrared at 200°C is greater than 350 μmol / g, preferably the total acid content of pyridine infrared at 200°C is 360-450 μmol / g.

[0045] The catalyst unit cell constant referred to in the present invention is the unit cell constant of the molecular sieve in the catalyst, and the molecular sieve unit cell constant is well known to those in the industry, and is measured by fitting the spectrum unit cell with the standard XRD spectrum library using an X-ray diffraction method (hereinafter referred to as XRD). Different sodium-type molecular sieve unit cell constants may be different, for example, the unit cell constant of sodium X-type molecular sieve is generally about 2.485nm, the unit cell constant of sodium Y-type molecular sieve is generally about 2.466nm, the unit cell constant of sodium β-type molecular sieve is generally about 1.262nm, the unit cell constant of sodium MOR-type molecular sieve is generally about 1.818nm, and the unit cell constant of sodium ZSM-5-type molecular sieve is generally about 2.024nm.

[0046] According to a preferred embodiment of the present invention, the molecular sieve is an X-type molecular sieve, and the L acid content of the catalyst in pyridine infrared at 200°C is 250-300 μmol / g, and the B acid content is 200-250 μmol / g.

[0047] According to a preferred embodiment of the present invention, the molecular sieve is an X-type molecular sieve, and the L acid content of the catalyst at 350°C pyridine infrared is 50-150 μmol / g, and the B acid content is 100-200 μmol / g.

[0048] According to a preferred embodiment of the present invention, the molecular sieve is a Y-type molecular sieve, and the L acid content of the catalyst at 200°C pyridine infrared is 70-230 μmol / g, and the B acid content is 240-395 μmol / g.

[0049] According to a preferred embodiment of the present invention, the molecular sieve is a Y-type molecular sieve, and the L acid content of the catalyst at 350°C pyridine infrared is 30-140 μmol / g, and the B acid content is 160-310 μmol / g.

[0050] According to a preferred embodiment of the present invention, the molecular sieve is a β molecular sieve, and the L acid content of the catalyst at 200°C pyridine infrared is 90-370 μmol / g, and the B acid content is 382-505 μmol / g.

[0051] According to a preferred embodiment of the present invention, the molecular sieve is a β molecular sieve, and the L acid content of the catalyst at 350°C pyridine infrared is 50-170 μmol / g, and the B acid content is 230-370 μmol / g.

[0052] According to a preferred embodiment of the present invention, the molecular sieve is a ZSM-5 molecular sieve, and the L acid content of the catalyst at 200°C pyridine infrared is 120-325 μmol / g, and the B acid content is 350-630 μmol / g.

[0053] According to a preferred embodiment of the present invention, the molecular sieve is a ZSM-5 molecular sieve, and the L acid content of the catalyst at 350°C pyridine infrared is 60-180 μmol / g, and the B acid content is 200-330 μmol / g.

[0054] According to a preferred embodiment of the present invention, the molecular sieve is a MOR type molecular sieve, and the catalyst has a pyridine infrared L acid content of 120-220 μmol / g and a B acid content of 140-300 μmol / g at 200°C.

[0055] According to a preferred embodiment of the present invention, the molecular sieve is a MOR type molecular sieve, and the L acid content of the catalyst at 350°C pyridine infrared is 60-190 μmol / g, and the B acid content is 90-130 μmol / g.

[0056] According to a preferred embodiment of the present invention, the molecular sieve is an X-type molecular sieve, and the ratio of pyridine infrared B acid / L acid of the catalyst at 200°C is 0.5-1, and the ratio of pyridine infrared B acid / L acid at 350°C is 1-5.

[0057] According to a preferred embodiment of the present invention, the molecular sieve is a Y-type molecular sieve, and the ratio of pyridine infrared B acid / L acid of the catalyst at 200°C is 1.5-4, and the ratio of pyridine infrared B acid / L acid at 350°C is 1.3-5.

[0058] According to a preferred embodiment of the present invention, the molecular sieve is a β-type molecular sieve, and the ratio of pyridine infrared B acid / L acid of the catalyst at 200°C is 0.5-1.5, and the ratio of pyridine infrared B acid / L acid at 350°C is 1-2.

[0059] According to a preferred embodiment of the present invention, the molecular sieve is a ZSM-5 molecular sieve, and the ratio of pyridine infrared B acid / L acid of the catalyst at 200°C is 0.5-1.5, and the ratio of pyridine infrared B acid / L acid at 350°C is 0.5-1.5.

[0060] According to a preferred embodiment of the present invention, the molecular sieve is a MOR type molecular sieve, and the ratio of pyridine infrared B acid / L acid of the catalyst at 200°C is 0.2-0.7, and the ratio of pyridine infrared B acid / L acid at 350°C is 0.5-1.

[0061] A second aspect of the present invention provides a method for preparing an alkylation solid acid catalyst, wherein the method comprises:

[0062] (1) mixing a sodium molecular sieve with a binder or its precursor, an auxiliary agent, an acid solution, and water to form a mixture, and then drying and calcining the mixture to obtain a calcined product;

[0063] (2) subjecting the obtained calcined product to ammonium exchange and acid treatment in sequence to obtain a catalyst precursor;

[0064] (3) ion-exchanging the catalyst precursor with the active metal precursor to obtain an alkylation solid acid catalyst;

[0065] Wherein, the active metal is Cu.

[0066] The method provided by the present invention first mixes the molecular sieve and the binder into a mixture, and then performs a high-temperature pressure calcination, that is, only a high-temperature pressure calcination process is performed after the molding, and then the active metal Cu is introduced for ion exchange to provide adsorption sites. The method provided by the present invention omits a high-temperature calcination step and introduces ion exchange, so the method is simple and easy to operate.

[0067] The method provided by the present invention uses an ion exchange method to better exchange metal ions such as cuprous ions directly into the acidic sites in the molecular sieve cage in the form of ions, and complex with the acidic sites. Subsequent acid treatment can increase the acid strength of the acidic sites and enhance the Cu + The complexation with the acidic sites reduces the adsorption of olefin molecules (preferably ethylene) at the acidic sites, thereby increasing the adsorption of alkane molecules (preferably ethylene) at the acidic sites, reducing the self-polymerization of olefin molecules (preferably ethylene), increasing the alkylation reaction of ethylene and isobutane, increasing the ethylene conversion rate and target product selectivity, and thus increasing the octane number of the product.

[0068] According to a preferred embodiment of the present invention, in step (1), the sodium-type molecular sieve is at least one of X-type, Y-type, β, ZSM-5 and MOR-type molecular sieves, preferably Y-type molecular sieve and / or β molecular sieve, and further preferably Y-type molecular sieve.

[0069] According to a preferred embodiment of the present invention, in step (1), the silicon-aluminum molar ratio of the sodium molecular sieve is 1-1000, preferably 1.5-500.

[0070] In the present invention, the type of the binder in step (1) has been described in the first aspect and will not be repeated here.

[0071] In the present invention, there is no particular limitation on the type of binder precursor in step (1). Preferably, the binder precursor is mainly aluminum salt, silicate, titanium salt and zirconium salt. For example, the aluminum salt may include pseudo-boehmite, aluminum chloride (AlCl3), aluminum sulfate (Al2(SO4)3), etc.; the silicate may include sodium silicate, potassium silicate, calcium silicate, etc.; the titanium salt may include titanium sulfate, titanium tetrachloride, etc.; the zirconium salt may include zirconium chloride, zirconium sulfate, etc.

[0072] According to a preferred embodiment of the present invention, in step (1), the amount of sodium molecular sieve and binder or its precursor is such that the weight ratio of sodium molecular sieve to binder in the catalyst is 99:1-20:80, preferably 90:10-50:50, calculated on a dry basis.

[0073] In the present invention, the acid solution and the auxiliary agent in step (1) can be selected from a wide range of types, and can be the acid solution and auxiliary agent conventionally defined in the art. For example, the acid solution is selected from at least one of hydrochloric acid solution, nitric acid solution, oxalic acid solution and citric acid solution, and the auxiliary agent is selected from at least one of sesbania powder, methylcellulose, polyether, polyvinyl alcohol, cyclodextrin and chitosan.

[0074] In the present invention, whether to add acid solution is considered according to the type of the binder or its precursor. If the binder is aluminum oxide or the binder precursor is aluminum salt, acid solution is added; if the binder is silicon dioxide, titanium oxide, zirconium oxide or the binder precursor is silicate, titanium salt or zirconium salt, acid solution may or may not be added; in the present invention, the auxiliary agent plays a role of lubrication and pore formation, and the auxiliary agent may or may not be added. When no auxiliary agent is added, the dried mixed molded product is directly calcined to obtain a calcined product; when a certain amount of auxiliary agent is added, the dried mixed molded product is first calcined, and then air-calcined to remove the auxiliary agent therein to obtain a calcined product.

[0075] In the present invention, there is no particular limitation on the amount of the acid solution and the auxiliary agent. In step (1), the amount of the acid solution and the auxiliary agent is independently 0-5 wt% of the total weight of the sodium molecular sieve and the binder on a dry basis.

[0076] In the present invention, there is no particular limitation on the amount of water, as long as the mixture including the sodium molecular sieve, the binder or its precursor, the acid solution and the auxiliary agent can be mixed uniformly. Preferably, the weight of water is in a ratio of (0.5-10) to the total weight of the dry basis of the other mixtures: 1, wherein the other mixtures refer to the mixture of the sodium molecular sieve, the binder or its precursor and the auxiliary agent.

[0077] In the present invention, the drying conditions can be selected in a wide range. Preferably, in step (1), the drying conditions are such that the dry weight of the mixed molding after drying is above 60 wt%.

[0078] According to a preferred embodiment of the present invention, in step (1), the calcination includes a first stage calcination and a second stage calcination; preferably, the first stage calcination is performed first and then the second stage calcination. The advantage of adopting this preferred embodiment is that the organic additive added in the preparation process can be flexibly removed as needed without causing secondary damage to the catalyst.

[0079] According to a preferred embodiment of the present invention, in step (1), the conditions of the first stage roasting include: roasting temperature of 450-650°C, roasting time of 0.5-12h, and roasting pressure of 0-0.5MPa; preferably, in step (1), the conditions of the second stage roasting include: roasting temperature of 500-600°C, roasting time of 1-6h, and roasting pressure of 0-0.3MPa. The advantage of adopting this preferred embodiment is that the catalyst is formed by one roasting (two-stage roasting) and the Na of the sodalite cage is simultaneously + , diffuse out, and reduce the Na2O content through subsequent ammonium exchange, reducing the number of calcination times of the catalyst and inhibiting the framework dealumination of the molecular sieve under high temperature conditions.

[0080] In the present invention, there is no particular limitation on the calcination atmosphere used in the first and second calcinations. The calcination atmosphere available in the art can be used, for example, air atmosphere, ammonia water vapor atmosphere, water vapor atmosphere, N2 atmosphere, He atmosphere or Ar atmosphere. Preferably, the first calcination is carried out in water vapor or ammonia water vapor atmosphere, and the second calcination is carried out in air atmosphere. The advantage of adopting this preferred embodiment is that water vapor or ammonia water vapor can enhance the interaction between the molecular sieve and the binder, promote the Na + Migration to the supercage facilitates subsequent ion exchange.

[0081] In the present invention, in step (2), the conditions for the ammonium exchange are operations familiar to those skilled in the art, and the present invention has no special requirements for this. After the ammonium exchange, the Na2O content of the catalyst is reduced to less than 1% by weight, preferably less than 0.9% by weight. In the present invention, there is no special limitation on the type of ammonium solution used for the ammonium exchange, for example, it can be at least one of ammonium nitrate solution, ammonium chloride solution and ammonium sulfate solution. In the present invention, preferably, the ammonium solution contains NH4 + The concentration is 0.05-8 mol / L. In the present invention, preferably, in step (2), the conditions of the ammonium exchange include: temperature of 50-150°C, liquid-to-solid mass ratio of 1-100, and time of 0.5-24h. The above ammonium exchange makes the Na + NH4 + Substitution makes the molecular sieve have B acid and L acid sites.

[0082] In the present invention, the method further comprises washing, filtering and drying the product after the ammonium exchange in sequence. The present invention has no particular limitation on the above operations, and existing methods in the art can be used.

[0083] According to a preferred embodiment of the present invention, the acid treatment conditions include: temperature of 30-110° C. and time of 0.5-24 h. The advantage of adopting the above preferred embodiment is that the L acid of the catalyst can be reduced.

[0084] In the present invention, there is no particular limitation on the type of acid used in the acid treatment process, and it can be, for example, oxalic acid, hydrofluoric acid, citric acid, lactic acid or hydrochloric acid. In the present invention, there is no particular limitation on the concentration of the acid, and it can be, for example, 0.1-20 wt %, and those skilled in the art can select it according to actual needs.

[0085] The present invention further includes washing, filtering and drying the product after the acid treatment in sequence. The present invention has no particular limitation on the above operations and the existing methods in the art can be used.

[0086] In the present invention, the range of selection of the type of active metal precursor is relatively wide. Preferably, the active metal precursor is selected from soluble salts of copper, preferably selected from at least one of copper nitrate, copper chloride, copper sulfate, copper carbonate, cuprous chloride, cuprous sulfate and cuprous nitrate. The advantage of adopting the above preferred embodiment is that the selected metal is cheap and easy to obtain, and can be easily added to the catalyst by ion exchange.

[0087] According to a preferred embodiment of the present invention, in step (3), the amount of the active metal precursor used is such that the content of the active metal in the catalyst, calculated as the element, is not higher than 20 wt%, preferably 0.5-5 wt%.

[0088] According to a preferred embodiment of the present invention, in step (3), the conditions of the ion exchange include: a temperature of 50-150°C and a time of 0.5-24h, and more preferably, a temperature of 60-120°C and a time of 1-12h. The advantages of adopting the above preferred embodiment are convenient operation, and the metal ions can be simply and effectively loaded into the catalyst to provide adsorption sites.

[0089] In the present invention, preferably, the method further comprises pre-treating the molecular sieve before mixing the sodium molecular sieve with other reaction raw materials, wherein the pre-treating method comprises: exchanging the molecular sieve with ammonium solution for 0.1-10h at 30-180°C, and then filtering and drying. Preferably, the ammonium solution contains NH4 + The concentration of ammonium is 0.05-8 mol / L. Preferably, the ammonium solution is selected from at least one of ammonium nitrate solution, ammonium chloride solution and ammonium sulfate solution.

[0090] The third aspect of the present invention provides an alkylation solid acid catalyst prepared by the preparation method described in the second aspect.

[0091] The fourth aspect of the present invention provides a use of the alkylation solid acid catalyst described in the first aspect or the third aspect in the alkylation reaction of isoparaffin and olefin.

[0092] The fifth aspect of the present invention provides an alkylation method, wherein the method comprises alkylating isobutane with ethylene in the presence of an alkylation solid acid catalyst; wherein the alkylation solid acid catalyst is the alkylation solid acid catalyst described in the first aspect or the third aspect.

[0093] In the alkylation solid acid catalyst used in the present invention, in order to reduce the adsorption of ethylene at the acidic site in the catalytic reaction of ethylene and isobutane, Cu is introduced as an active metal in the alkylation solid acid catalyst, which significantly improves the conversion rate of ethylene and improves the service life of the catalyst; further, dimethylbutane and isopentane with high octane number are generated under the reaction, the reaction temperature is low, the target product and the catalyst are easy to separate, the catalyst can be recycled for multiple times, the loss of the catalyst and the emission of solid waste are greatly reduced, the energy consumption and carbon emission are reduced, the ethylene conversion rate is high, the target product selectivity is good, and the product octane number is high. It has high industrial feasibility and economic value.

[0094] The method provided by the present invention partially reduces the metal ions by hydrogen reduction before the reaction, thereby avoiding the conventional method in which the cuprous metal is easily oxidized and then loses the effect of the synergistic effect of the metal ions and the acidic sites to reduce the adsorption of olefins.

[0095] According to a preferred embodiment of the present invention, a reduction reaction is performed under a reducing atmosphere before the alkylation reaction, and the reducing atmosphere is hydrogen. 2+ Reduction to Cu + , can form complexes with acidic sites, reduce the adsorption of olefins at acidic sites, thereby reducing the occurrence of olefin self-polymerization, reducing the generation of macromolecules that cannot diffuse out of the pores, thereby reducing carbon deposition and improving the activity and stability of the catalyst. It can also improve the alkylation reaction of olefins and alkanes, improve the selectivity of the target product, and thus improve the octane number of the product.

[0096] In the present invention, the reduction conditions have a wide range of selection. Preferably, the reduction reaction conditions include: a reduction temperature of 100-400°C and a time of 0.5-10h.

[0097] In the present invention, there is no particular limitation on the rate of hydrogen introduction. Preferably, the rate of hydrogen introduction is 0.5-50 min / L.

[0098] According to a preferred embodiment of the present invention, the conditions of the alkylation reaction include: temperature 60-295°C, pressure 0.5-10 MPa, mass space velocity 0.01-1000 h -1, the alkane-olefin molar ratio is 1-1000; further preferably, the temperature is 150-290°C, the pressure is 1-6MPa, and the mass space velocity is 0.5-100h -1 , alkane-ene molar ratio is 5-300. The advantages of adopting the above preferred embodiment are that the reaction conditions are relatively mild and the operation is simple.

[0099] According to a preferred embodiment of the present invention, the alkylation reaction is carried out in at least one of a fixed bed reactor, a fluidized bed reactor, a slurry bed reactor, a moving bed reactor and a reactor. It is further preferred that the alkylation reaction is carried out in a fixed bed reactor.

[0100] According to a preferred embodiment of the present invention, the isoparaffin is a liquid phase feed and the ethylene is a gas phase feed. In the present invention, the liquid phase feed refers to the isobutane fed in the liquid phase and the reaction conditions satisfy that the isobutane will not vaporize during the reaction; the gas phase feed refers to the ethylene fed in the gas phase and the reaction conditions satisfy that the ethylene will not liquefy during the reaction.

[0101] Unless otherwise specified, the pressures described in the present invention refer to gauge pressures.

[0102] The present invention will be described in detail below by way of examples. In the following examples, unless otherwise specified, all the raw materials used can be obtained from commercial channels.

[0103] Y-type molecular sieve: unit cell constant is 2.466nm, silicon-aluminum molar ratio is 3, average particle size is 1μm, total acid content of pyridine infrared at 200℃ is 310μmol / g, China Petrochemical Catalyst Co., Ltd.

[0104] ZSM-5 molecular sieve: unit cell constant is 2.024nm, silicon-aluminum molar ratio is 10, average particle size is 40μm, total acid content of pyridine infrared at 200℃ is 500μmol / g, China Petrochemical Catalyst Co., Ltd.

[0105] X-type molecular sieve: unit cell constant is 2.485nm, silicon-aluminum molar ratio is 1.8, average particle size is 0.5μm, total acid content of pyridine infrared at 200℃ is 360μmol / g, China Petrochemical Catalyst Co., Ltd.

[0106] β-type molecular sieve: unit cell constant is 1.262nm, silicon-aluminum molar ratio is 50, average particle size is 10μm, total acid content of pyridine infrared at 200℃ is 560μmol / g, China Petrochemical Catalyst Co., Ltd.

[0107] MOR type molecular sieve: unit cell constant is 1.82nm, silicon-aluminum molar ratio is 10, average particle size is 5μm, total acid content of pyridine infrared at 200℃ is 285μmol / g, China Petrochemical Catalyst Co., Ltd.

[0108] Pseudo-boehmite: average particle size is 100 μm, Sinopec Catalyst Co., Ltd.

[0109] In the following examples, X-ray diffraction (XRD) was used to determine the unit cell constant and crystallinity of the catalyst molecular sieve.

[0110] The pyridine adsorption infrared acid content of the alkylation solid acid catalyst is determined as follows: the instrument is a Bruker TensorII Fourier transform infrared spectrometer. The test process is as follows: about 25 mg of the catalyst sample is pressed into a tablet at 20 MPa for 5 minutes, placed in an in-situ cell of the infrared spectrometer and sealed, and the temperature is raised to 450°C at a rate of 10°C / min, and the vacuum is evacuated to 10 -6 Pa for 2h, cooled to room temperature, statically saturated adsorbed pyridine, then vacuumed, heated to 200℃ and 350℃ in steps to desorb the adsorbed pyridine, and measured the infrared spectra at the two temperatures and integrated. -1 The absorption peak at 1450cm -1 The absorption peak is attributed to the L acidic site.

[0111] C is the concentration of B acid or L acid (mmol / g), C B With C L The calculation formula is:

[0112] C B =1.88A B R 2 / W (Formula 1)

[0113] C L =1.42A L R 2 / W (Formula 2)

[0114] A is the integrated area of ​​the absorption peak of B acid or L acid;

[0115] R is the radius of the sample piece (cm);

[0116] W is the mass of the sample piece (mg).

[0117] The selectivity distribution of C5 and C6 of the obtained alkylate oil was determined by anglient-7890 gas chromatography analysis equipped with a high pressure injector (the chromatographic column was an HP-PONA 50 m×0.2 mm capillary column).

[0118] In the present invention, the octane number is determined by the research method in the national standard GB / T 5487-1995.

[0119] Example 1

[0120] (1) At 80°C, use ammonium chloride solution (NH4 + The concentration of 3 mol / L) was used to ammonium exchange the Y-type molecular sieve for 2 h, and then filtered and dried;

[0121] (2) The ammonium-exchanged NH4NaY molecular sieve and pseudo-boehmite are mixed in a dry weight percentage of 9:1, and 3wt% of sesbania powder and 1wt% of nitric acid are added respectively (both based on the dry weight of the ammonium-exchanged Y molecular sieve and the binder), and deionized water is added in a ratio of 1:1 to the weight of the water and the dry weight of the other mixture (a mixture of the sodium molecular sieve, the binder or its precursor and the auxiliary agent), and the mixture is extruded after being mixed evenly, and dried at 120°C so that the dry weight of the mixed molded product after drying is 70wt%, and then steam-roasted at 600°C for 2h and a pressure of 0.1MPa; and air-roasted at 600°C for 4h and a pressure of 0.1MPa;

[0122] (3) The obtained calcined product is mixed with ammonium chloride solution (NH4 + The concentration of the calcined product is 2 mol / L) with a liquid-solid mass ratio of 50:1, and ammonium exchange is performed at 80°C for 24 hours to reduce the content of Na2O in the calcined product to 0.5wt%, and then the calcined product is washed, filtered and dried;

[0123] (4) mixing the product obtained in step (3) with a hydrochloric acid solution (concentration of 5 wt%), subjecting the mixture to an acid treatment at 60° C. for 1 h, and then washing, filtering and drying;

[0124] (5) The product obtained in step (4) was subjected to ion exchange in a copper nitrate solution (concentration of 5 wt%) at 80° C. for 2 h to obtain catalyst Y-1. The total pyridine infrared acid content of the catalyst at 200° C. is as follows: Figure 1 As shown, Figure 1 Explanation: Y-1 at 1540cm -1 The B acid absorption peak at 1450cm -1 The L acid absorption peak area at is much smaller than the B acid peak, that is, the total B acid content of the catalyst is much higher than that of the L acid; the total pyridine infrared acid content of the catalyst at 350 ° C is as follows Figure 2 As shown, Figure 2 This indicates that the strong B acid absorption peak of Y-1 is also much larger than the strong L acid absorption peak, that is, the amount of strong B acid is greater than the amount of strong L acid. Figure 1 and Figure 2 It can be seen that the catalyst prepared by the method provided by the present invention does not significantly damage the B acid of the catalyst, and can even enhance the B acid of the catalyst to a certain extent to improve the performance of the catalyst.

[0125] Example 2

[0126] The method of Example 1 is followed, except that 0.5 wt % cuprous chloride solution is used instead of cupric nitrate solution.

[0127] Example 3

[0128] (1) At 130°C, use ammonium chloride solution (NH4 + The concentration of Y-type molecular sieve is 2 mol / L) and the ammonium exchange is carried out for 6 hours, followed by suction filtration and drying;

[0129] (2) mixing the ammonium-exchanged NH4NaY molecular sieve and pseudo-boehmite at a dry weight percentage of 9:1, adding 3wt% of sesbania powder and 1wt% of nitric acid (based on the total dry weight of the ammonium-exchanged Y molecular sieve and the binder), adding deionized water at a ratio of 1:1 of the weight of water to the total dry weight of other mixtures (a mixture of sodium molecular sieve, binder or its precursor and auxiliary agent), mixing well and extruding, drying at 120°C so that the dry weight of the mixed molded product after drying is 70wt%, and then steam roasting at 600°C for 2h and a pressure of 0.3MPa; and air roasting at 600°C for 4h and a pressure of 0.3MPa;

[0130] (3) The obtained calcined product is mixed with ammonium chloride solution (NH4 + The concentration of the calcined product is 2 mol / L) with a liquid-to-solid mass ratio of 50:1, and ammonium exchange is performed at 80°C for 24 hours to reduce the content of Na2O in the calcined product to 0.5 wt%, and then the calcined product is washed, filtered and dried;

[0131] (4) mixing the product obtained in step (3) with a hydrochloric acid solution (concentration of 5 wt%), subjecting the mixture to an acid treatment at 100° C. for 1 h, and then washing, filtering and drying;

[0132] (5) The product obtained in step (4) was subjected to ion exchange in a copper nitrate solution (concentration of 20 wt%) at 120° C. for 2 h to obtain catalyst Y-3.

[0133] Example 4

[0134] (1) At 80°C, use ammonium chloride solution (NH4 + The concentration of 1 mol / L) was used to ammonium exchange the X-type molecular sieve for 2 hours, and then filtered and dried;

[0135] (2) mixing the ammonium-exchanged NH4NaX molecular sieve and pseudo-boehmite at a dry weight percentage of 5:1, adding 2wt% of sesbania powder and 0.5wt% of nitric acid (based on the total dry weight of the ammonium-exchanged X molecular sieve and the binder), adding deionized water at a ratio of 0.8:1 of the weight of water to the total dry weight of the other mixtures, mixing evenly and extruding, drying at 100°C so that the dry weight of the mixed molded product after drying is 70wt%, and then steam roasting at 550°C for 1h and a pressure of 0MPa; and air roasting at 580°C for 3h and a pressure of 0MPa;

[0136] (3) The obtained calcined product is mixed with ammonium chloride solution (NH4 + The concentration of the calcined product is 1.5 mol / L) with a liquid-to-solid mass ratio of 5:1, and ammonium exchange is performed at 80°C for 1 hour to reduce the content of Na2O in the calcined product to 0.8 wt%, and then washing, filtering and drying are performed;

[0137] (4) mixing the product obtained in step (3) with a hydrochloric acid solution (concentration: 1 wt%), subjecting the mixture to an acid treatment at 70° C. for 3 h, and then washing, filtering and drying the mixture;

[0138] (5) The product obtained in step (4) was subjected to ion exchange in a cuprous chloride solution (concentration of 10 wt%) at 80° C. for 1 h to obtain catalyst X-1.

[0139] Example 5

[0140] (1) At 60°C, use ammonium chloride solution (NH4 + The concentration of β-type molecular sieve is 3 mol / L) and ammonium exchange is performed for 0.5 h, followed by filtration and drying;

[0141] (2) mixing the ammonium-exchanged NH4Naβ molecular sieve and pseudo-boehmite in a dry weight percentage of 1:1, adding 1wt% of sesbania powder and 3wt% of nitric acid (based on the total dry weight of the ammonium-exchanged β molecular sieve and the binder), adding deionized water in a ratio of 5:1 of the weight of water to the total dry weight of the other mixtures, mixing well and extruding, drying at 150°C so that the dry weight of the mixed molded product after drying is 60wt%, and then steam roasting at 500°C for 0.5h and a pressure of 0.2MPa; and air roasting at 520°C for 0.5h and a pressure of 0.1MPa;

[0142] (3) The obtained calcined product is mixed with ammonium chloride solution (NH4 +The concentration of the calcined product is 3 mol / L) with a liquid-to-solid mass ratio of 20:1, and ammonium exchange is performed at 80°C for 5 hours to reduce the content of Na2O in the calcined product to 0.1 wt%, and then washing, filtering and drying are performed;

[0143] (4) mixing the product obtained in step (3) with a hydrochloric acid solution (concentration: 0.2 wt%), subjecting the mixture to an acid treatment at 50° C. for 0.5 h, and then washing, filtering and drying the mixture;

[0144] (5) The product obtained in step (4) was subjected to ion exchange in a cuprous nitrate solution (concentration of 0.1 wt%) at 60° C. for 0.5 h to obtain catalyst β-1.

[0145] Example 6

[0146] The method of Example 1 is followed, except that in step (3), the ammonium chloride solution NH4 + The concentration is 0.5 mol / L, the liquid-to-solid mass ratio is 100:1, the exchange temperature is 10°C, and the exchange time is 24 h, so that the content of Na2O in the calcined product is reduced to 1.5 wt%, and catalyst Y-4 is obtained.

[0147] Example 7

[0148] (1) At 130°C, use ammonium chloride solution (NH4 + The concentration of 8 mol / L) was used to carry out ammonium exchange on the MOR molecular sieve for 10 hours, and then filtered and dried;

[0149] (2) mixing the ammonium-exchanged NH4NaMOR molecular sieve and pseudo-boehmite in a dry weight percentage of 1:2, adding 0.1wt% of sesbania powder and 5wt% of nitric acid (based on the total dry weight of the ammonium-exchanged MOR molecular sieve and the binder), adding deionized water in a ratio of 0.5:1 of the weight of water to the total dry weight of the other mixtures, mixing well and extruding, drying at 180°C so that the dry weight of the mixed molded product after drying is 50wt%, and then steam roasting at 480°C for 0.5h and a pressure of 0.4MPa; and air roasting at 620°C for 6h and a pressure of 0MPa;

[0150] (3) The obtained calcined product is mixed with ammonium chloride solution (NH4 + The concentration of the calcined product is 8 mol / L) with a liquid-solid mass ratio of 2:1, and ammonium exchange is performed at 80°C for 20 hours to reduce the content of Na2O in the calcined product to 0.2 wt%, and then the calcined product is washed, filtered and dried;

[0151] (4) mixing the product obtained in step (3) with a hydrochloric acid solution (concentration of 15 wt%), subjecting the mixture to an acid treatment at 110° C. for 12 h, and then washing, filtering and drying;

[0152] (5) The product obtained in step (4) was subjected to ion exchange in a cuprous chloride solution (concentration of 20 wt%) at 100° C. for 0.5 h to obtain catalyst MOR-1.

[0153] Comparative Example 1

[0154] The catalyst DY-1 was obtained by following the method of Example 1, except that the copper nitrate solution in step (5) was replaced with a silver nitrate solution of the same concentration. The total pyridine infrared acidity of the catalyst at 200°C was as follows: Figure 1 As shown, Figure 1 DY-1 at 1540cm -1 The B acid absorption peak at 1450cm -1 The L acid absorption peak area at 350°C is much larger than the B acid peak, the total B acid content of the catalyst is much lower than the L acid, the total B acid content of catalyst DY-1 is much lower than that of catalyst Y-1, while the L acid content is higher than that of Y-1; the total pyridine infrared acid content of the catalyst at 350°C is as follows Figure 2 As shown, Figure 2 This indicates that the absorption peak of strong B acid in DY-1 is also much lower than that of strong L acid, that is, the amount of strong B acid is less than that of strong L acid. The amount of strong B acid in DY-1 is much lower than that in Y-1, while the amount of strong L acid is higher than that in DY-1. Figure 1 and Figure 2 It can be seen that using silver nitrate solution to carry out ion exchange on the catalyst will inhibit the acid sites of the catalyst, causing a significant decrease in the total acid and acid sites of the catalyst, thereby reducing the performance of the catalyst.

[0155] Comparative Example 2

[0156] The method of Example 1 is followed, except that the copper nitrate solution in step (5) is replaced with a nickel nitrate solution of the same concentration to obtain catalyst DY-2.

[0157] Comparative Example 3

[0158] The method of Example 1 is followed, except that in step (5), copper is loaded by impregnation to obtain catalyst DY-3.

[0159] Comparative Example 4

[0160] Catalyst DY-4 was prepared according to the method of Example 1 in the CN114054070A patent application, and the acid content of the catalyst was determined according to the test method of Example 1 of the present invention.

[0161] Comparative Example 5

[0162] The method of Example 1 is followed, except that (5) the product obtained in step (4) is subjected to ion exchange in a ferrous chloride solution (concentration of 10 wt%) at 80° C. for 1 h to obtain catalyst DY-5.

[0163] The element contents in the catalysts of the above-mentioned embodiments and comparative examples are shown in Table 1, the catalyst structural parameters are shown in Table 2, and the catalyst acid content is shown in Table 3.

[0164] Table 1

[0165]

[0166] Table 2

[0167]

[0168] Table 3

[0169]

[0170]

[0171] Performance Testing

[0172] Test Example 1-7

[0173] The alkylation solid acid catalyst prepared in the above Examples 1-7 was used in a fixed bed reactor for alkylation of isobutane and ethylene. The reaction conditions were: alkane-olefin molar ratio of 100, reaction temperature of 280°C, reaction pressure of 5 MPa, mass space velocity of 0.5 h -1 The reaction results are shown in Table 4.

[0174] The alkylation solid acid catalyst needs to be subjected to hydrogen reduction treatment before use, and the reduction conditions are: temperature 250° C., time 1 h, and hydrogen introduction rate 5 min / L.

[0175] Comparative test examples 1-5

[0176] The alkylation solid acid catalysts prepared in Comparative Examples 1-5 were tested according to the test methods and conditions of Test Examples 1-7. The reaction results are shown in Table 4.

[0177] Test Case 8

[0178] The alkylation solid acid catalyst prepared in Example 1 was used in a high-pressure reactor to carry out an isobutane-ethylene alkylation reaction. The reaction conditions were: an alkane-ene molar ratio of 50, a reaction temperature of 250°C, a reaction pressure of 2 MPa, and a mass space velocity of 1 h -1 The reaction results are shown in Table 4.

[0179] Test Example 9

[0180] The alkylation solid acid catalyst prepared in Example 1 was used in a slurry bed reactor to carry out isobutane ethylene alkylation reaction. The reaction conditions were: alkane / olefin molar ratio of 50, reaction temperature of 250°C, reaction pressure of 2 MPa, mass space velocity of 1 h -1 The reaction results are shown in Table 4.

[0181] Test Example 10

[0182] The alkylation solid acid catalyst prepared in Example 1 was used in a moving bed reactor to carry out an isobutane-ethylene alkylation reaction. The reaction conditions were: an alkane-olefin molar ratio of 50, a reaction temperature of 250°C, a reaction pressure of 2 MPa, and a mass space velocity of 1 h -1 The reaction results are shown in Table 4.

[0183] Test Example 11

[0184] The alkylation solid acid catalyst prepared in Example 1 was used in a fixed bed reactor for isobutane-butene alkylation reaction. The reaction conditions were: alkane-ene molar ratio of 100, reaction temperature of 250°C, reaction pressure of 2MPa, mass space velocity of 0.1h -1 The reaction results are shown in Table 4.

[0185] Among them, the conversion rate of ethylene is:

[0186] In the formula, A C2 t is the integrated area percentage of ethylene in the reaction product at a certain moment; A C2 0 The percentage of the total mass of ethylene entering the reactor at that moment is defined as the integrated area ratio of ethylene in the feed composition, wherein it is assumed that the ethylene content in the feed does not change.

[0187] Selectivity refers to the proportion of a certain component in alkylation gasoline. Selectivity is defined as

[0188] s n选择性 =A Cn ×100% (Formula 4)

[0189] In the formula, s n A is the integrated area ratio of butene in the gas chromatogram of hydrocarbons with carbon number n at a certain time; Sn It is the integrated area ratio of hydrocarbons with carbon number n in alkylate gasoline in the gas chromatogram.

[0190] Table 4

[0191]

[0192]

[0193] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. An alkylation solid acid catalyst, characterized in that: The catalyst comprises a molecular sieve, a binder and active metal Cu; based on the dry weight of the catalyst, the content of the molecular sieve is 50-95wt%, the content of the binder is 4.9-50wt%, and the content of the active metal calculated as an element is not higher than 20wt%; the total pyridine infrared acid content of the catalyst at 200°C is increased by 25-50% compared with the total pyridine infrared acid content of the molecular sieve at 200°C.

2. The catalyst according to claim 1, wherein Based on the dry weight of the catalyst, the content of the molecular sieve is 50-87wt%, the content of the binder is 8-45wt%, and the content of the active metal in terms of element is 0.5-5wt%; And / or, the total pyridine infrared acidity at 200°C of the catalyst is increased by 40-50% compared with the total pyridine infrared acidity at 200°C of the molecular sieve.

3. The catalyst according to claim 1 or 2, wherein The molecular sieve is at least one of X-type, Y-type, β, ZSM-5 and MOR-type molecular sieves, preferably Y-type molecular sieve and / or β molecular sieve, and more preferably Y-type molecular sieve; and / or, the binder is selected from at least one of alumina, silica, titania, kaolin and montmorillonite, preferably at least one of alumina, silica and titania; Preferably, the alumina is alumina containing pseudo-boehmite phase and / or γ phase.

4. The catalyst according to claim 1 or 2, wherein The molecular sieve is an X-type molecular sieve, the unit cell constant of the catalyst is 2.46-2.485 nm, and the total acidity of pyridine infrared at 200°C is greater than 450 μmol / g, preferably the total acidity of pyridine infrared at 200°C is 460-550 μmol / g; And / or, the molecular sieve is a Y-type molecular sieve, the unit cell constant of the catalyst is 2.441-2.466 nm, the total acidity of pyridine infrared is greater than 400 μmol / g, preferably the total acidity of pyridine infrared at 200°C is 420-480 μmol / g; And / or, the molecular sieve is a β molecular sieve, the unit cell constant of the catalyst is 1.249-1.262 nm, and the total acidity of pyridine infrared at 200°C is greater than 700 μmol / g, preferably the total acidity of pyridine infrared at 200°C is 710-800 μmol / g; And / or, the molecular sieve is a ZSM-5 molecular sieve, the unit cell constant of the catalyst is 2.004-2.024 nm, and the total acidity of pyridine infrared at 200°C is greater than 500 μmol / g, preferably the total acidity of pyridine infrared at 200°C is 600-750 μmol / g; And / or, the molecular sieve is a MOR type molecular sieve, the unit cell constant of the catalyst is 1.8-1.818 nm, the total acidity of pyridine infrared at 200°C is greater than 350 μmol / g, preferably the total acidity of pyridine infrared at 200°C is 360-450 μmol / g.

5. The catalyst according to claim 1 or 2, wherein The molecular sieve is an X-type molecular sieve, and the catalyst has a 200°C pyridine infrared L acid content of 250-300 μmol / g and a B acid content of 200-250 μmol / g; And / or, the molecular sieve is an X-type molecular sieve, the catalyst has a 350°C pyridine infrared L acid content of 50-150 μmol / g and a B acid content of 100-200 μmol / g; And / or, the molecular sieve is a Y-type molecular sieve, and the catalyst has a pyridine infrared L acid content of 70-230 μmol / g and a B acid content of 240-395 μmol / g at 200°C; And / or, the molecular sieve is a Y-type molecular sieve, the catalyst has a 350°C pyridine infrared L acid content of 30-140 μmol / g and a B acid content of 160-310 μmol / g; And / or, the molecular sieve is a β molecular sieve, and the catalyst has a pyridine infrared L acid content of 90-370 μmol / g and a B acid content of 382-505 μmol / g at 200°C; And / or, the molecular sieve is a β molecular sieve, the catalyst has a 350°C pyridine infrared L acid content of 50-170 μmol / g and a B acid content of 230-370 μmol / g; And / or, the molecular sieve is ZSM-5 molecular sieve, the catalyst has a pyridine infrared L acid content of 120-325 μmol / g and a B acid content of 350-630 μmol / g at 200°C; And / or, the molecular sieve is a ZSM-5 molecular sieve, the catalyst has a 350°C pyridine infrared L acid content of 60-180 μmol / g and a B acid content of 200-330 μmol / g; And / or, the molecular sieve is a MOR type molecular sieve, the catalyst has a pyridine infrared L acid content of 120-220 μmol / g and a B acid content of 140-300 μmol / g at 200°C; And / or, the molecular sieve is a MOR type molecular sieve, and the catalyst has a 350°C pyridine infrared L acid content of 60-190 μmol / g and a B acid content of 90-130 μmol / g.

6. The catalyst according to claim 1 or 2, wherein The molecular sieve is an X-type molecular sieve, the ratio of pyridine infrared B acid / L acid of the catalyst at 200°C is 0.5-1, and the ratio of pyridine infrared B acid / L acid at 350°C is 1-5; And / or, the molecular sieve is a Y-type molecular sieve, and the ratio of pyridine infrared B acid / L acid of the catalyst at 200°C is 1.5-4, and the ratio of pyridine infrared B acid / L acid at 350°C is 1.3-5; And / or, the molecular sieve is a β molecular sieve, the ratio of pyridine infrared B acid / L acid of the catalyst at 200°C is 0.5-1.5, and the ratio of pyridine infrared B acid / L acid at 350°C is 1-2; And / or, the molecular sieve is ZSM-5 molecular sieve, the ratio of pyridine infrared B acid / L acid of the catalyst at 200°C is 0.5-1.5, and the ratio of pyridine infrared B acid / L acid at 350°C is 0.5-1.5; And / or, the molecular sieve is a MOR type molecular sieve, and the ratio of pyridine infrared B acid / L acid of the catalyst at 200°C is 0.2-0.7, and the ratio of pyridine infrared B acid / L acid at 350°C is 0.5-1.

7. A method for preparing an alkylation solid acid catalyst, wherein: The method includes: (1) mixing a sodium molecular sieve with a binder or its precursor, an auxiliary agent, an acid solution, and water to form a mixture, and then drying and calcining the mixture to obtain a calcined product; (2) subjecting the obtained calcined product to ammonium exchange and acid treatment in sequence to obtain a catalyst precursor; (3) ion-exchanging the catalyst precursor with the active metal precursor to obtain an alkylation solid acid catalyst; Wherein, the active metal is Cu.

8. The method according to claim 7, wherein: In step (1), the sodium-type molecular sieve is at least one selected from X-type, Y-type, β, ZSM-5 and MOR-type molecular sieves, preferably Y-type molecular sieve and / or β molecular sieve, and more preferably Y-type molecular sieve; And / or, in step (1), the binder is selected from at least one of aluminum chloride, aluminum oxide, silicon dioxide, titanium dioxide, kaolin and montmorillonite, preferably at least one of aluminum oxide, silicon dioxide and titanium dioxide; Preferably, the alumina contains alumina in pseudo-boehmite phase and / or γ phase.

9. The method according to claim 7 or 8, wherein: In step (1), the amount of sodium molecular sieve and binder or its precursor is such that the weight ratio of sodium molecular sieve to binder in the catalyst is 99:1-20:80, preferably 90:10-50:50, calculated on a dry basis.

10. The method according to claim 7 or 8, wherein: In step (1), the amount of the acid solution and the auxiliary agent is independently 0-5wt% of the total weight of the sodium molecular sieve and the binder on a dry basis; Preferably, in step (1), the drying conditions are such that the dry basis weight of the mixed molding after drying is above 60wt%; Preferably, in step (1), the roasting includes a first stage roasting and a second stage roasting; Preferably, the conditions of the first stage roasting include: roasting temperature of 450-650°C, roasting time of 0.5-12h, roasting pressure of 0-0.5MPa; Preferably, the conditions of the second-stage roasting include: a roasting temperature of 500-600° C., a roasting time of 1-6 h, and a roasting pressure of 0-0.3 MPa.

11. The method according to claim 7 or 8, wherein: In step (2), the conditions for the ammonium exchange include: a temperature of 50-150° C., a liquid-to-solid mass ratio of 1-100, and a time of 0.5-24 h; Preferably, the acid treatment conditions include: temperature of 30-110° C. and time of 0.5-24 h.

12. The method according to claim 7 or 8, wherein: In step (3), the active metal precursor is selected from soluble salts of copper, preferably selected from at least one of copper nitrate, copper chloride, copper sulfate, copper carbonate, cuprous chloride, cuprous sulfate and cuprous nitrate; Preferably, in step (3), the amount of the active metal precursor used is such that the content of the active metal in the catalyst, calculated as the element, is not higher than 20 wt%, preferably 0.5-5 wt%; Preferably, in step (3), the conditions for the ion exchange include: a temperature of 50-150° C. and a time of 0.5-24 h. More preferably, the temperature is 60-120° C. and the time is 1-12 h.

13. The alkylation solid acid catalyst obtained by the preparation method according to any one of claims 7 to 12.

14. Use of the alkylation solid acid catalyst according to any one of claims 1 to 6 and 13 in the alkylation reaction of isoparaffin and olefin.

15. An alkylation process, wherein: The method comprises: in the presence of an alkylation solid acid catalyst, subjecting isobutane to an alkylation reaction with ethylene; wherein the alkylation solid acid catalyst is the alkylation solid acid catalyst according to any one of claims 1-6 and 13.

16. The method according to claim 15, wherein: Before the alkylation reaction, a reduction reaction needs to be carried out under a reducing atmosphere, and the reducing atmosphere is hydrogen; Preferably, the reduction reaction conditions include: reduction temperature of 100-400°C and time of 0.5-10h; Preferably, the conditions of the alkylation reaction include: temperature 60-295°C, pressure 0.5-10 MPa, mass space velocity 0.01-1000 h -1 , the alkane-olefin molar ratio is 1-1000; further preferably, the temperature is 150-290°C, the pressure is 1-6MPa, and the mass space velocity is 0.5-100h -1 , alkane-ene molar ratio 5-300; Preferably, the alkylation reaction is carried out in at least one of a fixed bed reactor, a fluidized bed reactor, a slurry bed reactor, a moving bed reactor and a reactor, and more preferably, the alkylation reaction is carried out in a fixed bed reactor; Preferably, the isoparaffin is a liquid feed and the ethylene is a gas feed.

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