Regeneration method of solid acid catalyst and method for preparing alkylate oil
By in situ hydrogenation of the inactivated solid acid catalyst in a hydrogen environment, the problem of easy deactivation of the catalyst is solved, effective regeneration of the catalyst and long-term continuous operation are achieved, production costs are reduced, and industrial continuous production is supported. .
Patent Information
- Application Number
- CN202310789327.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-06-30
- Publication Date
- 2024-12-31
AI Technical Summary
Solid acid catalysts are prone to deactivate during alkylation reactions, and the existing regeneration methods are complex in operation or high in cost, making it difficult to achieve long-term continuous operation.
In situ hydrogen regeneration is carried out in the presence of hydrogen, and the hydrogen overflow effect of the hydrogenated functional components is used to restore catalyst activity and reduce production costs through simple operations.
It realizes effective regeneration of catalysts, extends the service life of the catalyst, reduces production costs, and supports industrial continuous production.
Smart Images
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of solid acid catalyst regeneration, and in particular to a solid acid catalyst regeneration method and a method for preparing alkylate oil. Background Art
[0002] The reaction of isoparaffins and olefins to form alkylate oil under the action of acidic catalysts is an important process for producing high-octane gasoline components in the petroleum industry. This reaction is an organic addition reaction between alkane molecules and olefin molecules following the positive carbon ion chain reaction process under the action of acidic catalysts.
[0003] With the continuous improvement of environmental protection requirements and energy conservation and emission reduction requirements, the number of hybrid vehicles is growing in order to reduce automobile fuel consumption. Since the engine of hybrid vehicles needs 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.
[0004] Molecular sieves have a regular three-dimensional pore structure. Their suitable acidity and low price facilitate the diffusion of reactant molecules in the molecular sieve pores and their reaction at the acidic center. Molecular sieve catalysts are widely used in petrochemical and other fields, especially in catalytic cracking, hydrogenation, reforming, isobutane ethylene alkylation, benzene and olefin alkylation. Therefore, the research on molecular sieve catalysts not only has important academic value, but also has broad application prospects.
[0005] Solid acid catalysts are prone to coking and deactivation, and need to be regenerated frequently. The regeneration methods of deactivated catalysts generally include hydrogenation regeneration (Chinese patent application CN1238747A), reaction solvent dissolution cleaning (Chinese patent application CN1281839A), high-temperature oxidation roasting (US patent application US5365010), oxidant cleaning, etc. Among them, hydrogenation regeneration and reaction solvent dissolution cleaning regeneration are easier to achieve in industry, while high-temperature roasting is only suitable for catalysts with good thermal stability.
[0006] The coking reaction on the catalyst starts with low-order olefins, followed by polymerization and hydrogen transfer reactions to generate polyene species and low-ring aromatics, and then hydrogen transfer, alkylation and cyclization reactions continue to occur to form non-volatile coke deposits with a multi-ring structure. The alkylation reaction is carried out at a relatively low temperature, and the carbon deposits on the catalyst are generally considered to be long-chain alkanes, olefins, and monocyclic aromatic compounds. These carbon deposits are called soft coke, which can be easily removed from the acidic position of the catalyst by hydrogenation reactions. Therefore, when the deactivated catalyst is regenerated, the platinum loaded on the catalyst is used to produce hydrogenolysis function in a hydrogen atmosphere to achieve the regeneration of the catalyst, and the acidity and stability of the catalyst itself are not negatively affected. The catalyst can be operated continuously for a long period of time, which is conducive to industrial continuous production and greatly saves production costs. Summary of the invention
[0007] The purpose of the present invention is to overcome the problem of easy deactivation of solid acid catalysts in the practical process in the prior art, and to provide a solid acid catalyst and a method for preparing alkylate oil. The regeneration method is simple to operate, has a low content of loaded hydrogenation components and a good regeneration effect, so that the method device and the catalyst of the present invention can be fully utilized.
[0008] In order to achieve the above object, the first aspect of the present invention provides a method for regenerating a solid acid catalyst, wherein the catalyst to be regenerated is regenerated in the presence of hydrogen;
[0009] The catalyst to be regenerated is a solid acid catalyst deactivated in the alkylation reaction;
[0010] The solid acid catalyst comprises a molecular sieve, a binder and a hydrogenation active component. Based on the dry weight of the catalyst, the content of the molecular sieve is 20-90wt%, the content of the binder is 5-79.99wt%, and the content of the hydrogenation active component in terms of element is 0.01-5wt%; the 200°C pyridine infrared total acidity of the catalyst is increased by 30-110% compared with the 200°C pyridine infrared total acidity of the molecular sieve; the mesopore volume of the catalyst is increased by 70-215% compared with the mesopore volume of the molecular sieve.
[0011] A second aspect of the present invention provides a method for preparing alkylate oil, wherein the method comprises:
[0012] (1) subjecting an alkylation reaction raw material to an alkylation reaction in the presence of a solid acid catalyst to obtain a spent catalyst;
[0013] (2) subjecting the catalyst to be regenerated to a regeneration reaction according to the regeneration method described in the first aspect;
[0014] The method further comprises recycling the regenerated solid acid catalyst obtained in step (2) back to step (1).
[0015] The regeneration method provided by the present invention performs in-situ hydrogenation regeneration on a deactivated solid acid catalyst containing a component with a hydrogenation function, and utilizes the hydrogen overflow effect of the hydrogenation functional component to achieve regeneration of the catalyst to be regenerated. The regeneration method is simple to operate, and the catalyst can be regenerated by decomposing the hydrogenation functional component in a hydrogen atmosphere, which greatly saves production costs.
[0016] The method for preparing alkylate oil provided by the present invention combines alkylation reaction with regeneration reaction, and the two are cyclically performed in sequence to realize continuous reaction and ensure industrial continuous production. DETAILED DESCRIPTION
[0017] 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.
[0018] The first aspect of the present invention provides a method for regenerating a solid acid catalyst, wherein the catalyst to be regenerated is subjected to a regeneration treatment in the presence of hydrogen;
[0019] The catalyst to be regenerated is a solid acid catalyst deactivated in the alkylation reaction;
[0020] The solid acid catalyst comprises a molecular sieve, a binder and a hydrogenation active component. Based on the dry weight of the catalyst, the content of the molecular sieve is 20-90wt%, the content of the binder is 5-79.99wt%, and the content of the hydrogenation active component in terms of elements is 0.01-5wt%. The 200°C pyridine infrared total acidity of the catalyst is increased by 30-110% compared with the 200°C pyridine infrared total acidity of the molecular sieve; and the mesopore volume of the catalyst is increased by 70-215% compared with the mesopore volume of the molecular sieve.
[0021] In the present invention, it can be understood that the spent catalyst refers to a solid acid catalyst that is deactivated after an alkylation reaction.
[0022] The regeneration method provided by the present invention is to regenerate the solid acid catalyst containing a component having a hydrogenation function by in-situ hydrogenation, wherein the component having a hydrogenation function can decompose H2 into H + , H + The solid acid catalyst to be regenerated can be regenerated by reacting with the carbon precursor to generate saturated olefins, which are desorbed from the acidic sites and restore the activity of the catalyst. The hydrogen overflow effect of the hydrogenation functional component can be used to regenerate the solid acid catalyst to be regenerated, and the regeneration method is simple to operate.
[0023] In the present invention, there is no particular limitation on the conditions of the alkylation reaction, and the conditions may be the alkylation reaction conditions conventionally defined in the art, and the present invention does not make any specific limitation on this.
[0024] In the present invention, preferably, when the conversion rate of the alkylation reaction raw material in the alkylation reaction reaches less than 80%, the spent catalyst is obtained. It is understood that when the conversion rate of the alkylation reaction raw material in the alkylation reaction reaches less than 80%, the catalyst is considered to be deactivated and the spent catalyst is obtained.
[0025] According to a preferred embodiment of the present invention, the regeneration treatment conditions include: regeneration temperature of 150-300°C, hydrogen pressure of 0.1-5MPa, regeneration time of 0.1-5 hours, relative to 1g of solid acid catalyst,, hydrogen flow rate of 1-5000mL / min; preferably, the regeneration treatment conditions include: temperature of 170-250°C, pressure of 0.5-3MPa, regeneration time of 0.5-4 hours, relative to 1g of solid acid catalyst,, hydrogen flow rate of 50-5000mL / min. By regenerating the catalyst to be regenerated under the above preferred embodiment, it is conducive to the complete degradation of carbon deposits and complete regeneration of the catalyst.
[0026] In the present invention, by selecting a solid acid catalyst with a hydrogenation component as the original catalyst to be regenerated, after the catalyst is deactivated, it is regenerated in situ with the help of its hydrogenation functional component, so that the effective regeneration of the catalyst to be regenerated can be achieved. Preferably, based on the dry weight of the catalyst, the content of the molecular sieve is 25-84wt%, the content of the binder is 15-75wt%, and the content of the hydrogenation active component in terms of element is 0.1-1wt%.
[0027] In the present invention, the content of each substance in the catalyst is measured by X-ray fluorescence spectrometry (XRF), 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 standard sample is measured and a working curve is established, and the content is found on the working curve by interpolation.
[0028] According to a preferred embodiment of the present invention, the total pyridine infrared acidity of the catalyst at 200°C is increased by 52-80% compared with the total pyridine infrared acidity of the molecular sieve at 200°C. The advantage of adopting this preferred embodiment is that the mesoporous volume and the accessibility of the acidic center of the catalyst are effectively increased without destroying the acidity of the catalyst.
[0029] According to a preferred embodiment of the present invention, the unit cell parameters of the catalyst are smaller than those of the molecular sieve. The advantage of adopting this preferred embodiment is that the bonding agent and the molecular sieve can effectively protect the skeleton of the molecular sieve from being damaged.
[0030] According to a preferred embodiment of the present invention, the mesopore volume of the catalyst is increased by 110-215% compared with the mesopore volume of the molecular sieve. The advantage of adopting this preferred embodiment is that the SOD cage of the catalyst is directionally expanded without damaging the acidic sites.
[0031] 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.
[0032] 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 -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, 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.
[0033] C is the concentration of B acid or L acid (mmol / g), C B With C L The calculation formula is:
[0034] C B =1.88A B R 2 / W (Formula 1)
[0035] C L =1.42A L R 2 / W (Formula 2)
[0036] 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).
[0037] 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, and the total pyridine infrared acid content of Hβ type molecular sieve at 200°C is about 560 μmol / g.
[0038] 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.
[0039] According to a preferred embodiment of the present invention, the molecular sieve is at least one of X-type, Y-type and β-type molecular sieves, preferably Y-type molecular sieve. The advantage of adopting this preferred embodiment is that the Na cage of the catalyst is effectively expanded in a directional manner without destroying the acidity of the catalyst, thereby increasing the mesopore volume of the catalyst and the accessibility of the acidic center.
[0040] According to a preferred embodiment of the present invention, the binder is selected from at least one of alumina, silica, titania, kaolin and montmorillonite, preferably at least one of alumina, silica and titania.
[0041] According to a preferred embodiment of the present invention, the alumina contains pseudo-boehmite phase and γ phase.
[0042] According to a preferred embodiment of the present invention, the hydrogenation active component is selected from at least one of Pt, Pd, Ru and Ir, preferably Pt and / or Pd, and more preferably Pt. The selection of the above hydrogenation components is conducive to regenerating the catalyst in a hydrogen environment at a certain temperature and pressure.
[0043] According to a preferred embodiment of the present invention, the Pt content in terms of element is 0.1-0.5 wt % based on the dry weight of the catalyst. The advantage of adopting this preferred embodiment is that the Pt content is effectively reduced and the catalyst cost is reduced while ensuring that the catalyst can be regenerated.
[0044] 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 acidity of pyridine infrared at 200 ° C is greater than 360 μmol / g, preferably the total acidity of pyridine infrared at 200 ° C is 430-540 μmol / g, and the mesopore volume is 0.048-0.106 cm 3 / g.
[0045] 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 acidity of pyridine infrared at 200 ° C is greater than 310 μmol / g, preferably the total acidity of pyridine infrared at 200 ° C is 372-465 μmol / g, and the mesopore volume is 0.07-0.128 cm 3 / g.
[0046] According to a preferred embodiment of the present invention, the molecular sieve is a β-type molecular sieve, the unit cell constant of the catalyst is 1.249-1.262nm, the total acidity of pyridine infrared at 200℃ is greater than 560μmol / g, preferably the total acidity of pyridine infrared at 200℃ is 670-840μmol / g, and the mesopore volume is 0.024-0.051cm 3 / g.
[0047] The catalyst unit cell constant referred to in the present invention is the unit cell constant of the molecular sieve in the catalyst, which is well known to those in the industry and is measured by fitting the unit cell of the spectrum in the standard XRD spectrum library using an X-ray diffraction method (hereinafter referred to as XRD). Different sodium-type molecular sieves may have different unit cell constants, 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, and the unit cell constant of sodium β-type molecular sieve is generally about 1.262nm.
[0048] The mesopore volume of the catalyst referred to in the present invention is determined by the BET method. Different sodium molecular sieves may have different mesopore volumes. For example, the mesopore volume of sodium X molecular sieve is generally 0.032 cm 3 / g, and the mesopore volume of sodium Y-type molecular sieve is generally 0.04cm 3 / g, and the mesopore volume of sodium β-type molecular sieve is generally 0.016cm 3 / g or so.
[0049] 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 1.2-3, and the ratio of pyridine infrared B acid / L acid at 350°C is 1-3.5.
[0050] 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 0.95-3.5, and the ratio of pyridine infrared B acid / L acid at 350°C is 0.95-3.5.
[0051] 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 1-2, and the ratio of pyridine infrared B acid / L acid at 350°C is 1-2.
[0052] According to a preferred embodiment of the present invention, the preparation method of the solid acid catalyst comprises the following steps:
[0053] (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;
[0054] (2) The calcined product obtained in step (1) is sequentially subjected to crystallization treatment, ammonium exchange, acid treatment and introduction of hydrogenation active components to obtain a solid acid catalyst.
[0055] By using the preparation method provided by the present invention, the catalyst is expanded without destroying the catalyst skeleton, thereby avoiding the acid damage caused by the conventional acid-base treatment of the molecular sieve. The method provided by the present invention can achieve a balance between the molecular sieve pore structure and the acidity.
[0056] 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.
[0057] In the present invention, the types of adhesives have been described in the above content and will not be repeated here.
[0058] 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.
[0059] 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 90:10-20:80, preferably 90:10-50:50, calculated on a dry basis.
[0060] 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.
[0061] 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.
[0062] In the present invention, there is no particular limitation on the amount of the acid solution and the auxiliary agent. Preferably, 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.
[0063] According to a preferred embodiment of the present invention, in step (1), the drying conditions are such that the dry basis weight of the mixed molded product after drying is above 60 wt%.
[0064] According to a preferred embodiment of the present invention, in step (1), the calcination includes a first stage calcination and a second stage calcination. The advantages of adopting this preferred embodiment are that the interaction between the molecular sieve and the binder can be enhanced, the organic matter in the catalyst can be removed at one time, and the damage to the catalyst skeleton structure can be reduced.
[0065] According to a preferred embodiment of the present invention, the conditions of the first stage roasting include: a roasting temperature of 450-650° C., a roasting time of 0.5-12 h, and a roasting pressure of 0-0.5 MPa.
[0066] According to a preferred embodiment of the present invention, 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 normal pressure-0.3 MPa.
[0067] In the present invention, there is no particular limitation on the calcination atmosphere used for the first-stage calcination and the second-stage calcination. The existing calcination atmosphere in the art can be used, for example, it can be an air atmosphere, an ammonia water vapor atmosphere, a water vapor atmosphere, an N2 atmosphere, a He atmosphere or an Ar atmosphere. Preferably, the first-stage calcination is carried out in a water vapor or an ammonia water vapor atmosphere, and the second-stage calcination is carried out in an air atmosphere.
[0068] According to a preferred embodiment of the present invention, the crystallization treatment comprises: subjecting the calcined product to a hydrothermal crystallization treatment in the presence of a template.
[0069] In the present invention, the template agent has a wide selection range. Preferably, the template agent is selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, hexadecyltrimethylammonium bromide and dodecyltrimethylammonium bromide.
[0070] According to a preferred embodiment of the present invention, the concentration of the template is 0.05-1.5 mol / L.
[0071] According to a preferred embodiment of the present invention, the conditions of the crystallization treatment include: temperature of 80-300° C., time of 1-24 h, and liquid-to-solid mass ratio of 0.05-10:1.
[0072] In the present invention, in step (2), the conditions for 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 in 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. Preferably, in step (2), the conditions for the ammonium exchange include: a temperature of 50-150°C, a liquid-to-solid mass ratio of 5-50, and a time of 2-24 hours.
[0073] 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.
[0074] In the present invention, the mesoporous volume of the catalyst can be effectively increased by acid treatment. Preferably, in step (2), the acid treatment conditions include: a temperature of 10-350° C. and a time of 0.5-36 h.
[0075] According to a preferred embodiment of the present invention, the acid used for the acid treatment is selected from at least one of hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, lactic acid, oxalic acid, fluorosilicic acid, hydrofluoric acid and ammonium fluorosilicate.
[0076] According to a preferred embodiment of the present invention, the concentration of the acids is independently 0.01-20 wt %.
[0077] According to a preferred embodiment of the present invention, in step (3), the hydrogenation component is provided by a hydrogenation component precursor. Preferably, the hydrogenation component precursor is selected from at least one of chloroplatinic acid, tetraamine platinum dichloride, tetraamine platinum nitrate, dinitrosodiammine platinum, tetraamine platinum acetate, palladium chloride, palladium nitrate, sodium chloropalladate and potassium chloropalladate, preferably at least one of tetraamine platinum dichloride, tetraamine platinum nitrate, sodium chloropalladate and potassium chloropalladate.
[0078] According to a preferred embodiment of the present invention, in step (2), the amount of the hydrogenation component is such that the content of the hydrogenation component in the catalyst is 0.01-5wt%, preferably 0.1-0.5wt%, calculated as an element. The advantage of adopting this preferred embodiment is that the loading of the precious metal is effectively reduced, which greatly saves the catalyst cost.
[0079] In the present invention, the method for introducing the hydrogenation active component in step (2) can be a method conventionally defined in the art, such as an impregnation method, an atomic deposition method or a rotary evaporation method, preferably a rotary evaporation method, so that the hydrogenation active component is dispersed more evenly.
[0080] 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.
[0081] A second aspect of the present invention provides a method for preparing alkylate oil, wherein the method comprises:
[0082] (1) subjecting an alkylation reaction raw material to an alkylation reaction in the presence of a solid acid catalyst to obtain a spent catalyst;
[0083] (2) subjecting the catalyst to be regenerated to a regeneration reaction according to the regeneration method described in the first aspect;
[0084] The method further comprises recycling the regenerated solid acid catalyst obtained in step (2) back to step (1).
[0085] In the present invention, the solid acid catalyst is the solid acid catalyst described in the first aspect, the spent catalyst is the spent catalyst described in the first aspect, and the specific parameters and properties of the catalyst are not further described.
[0086] According to a preferred embodiment of the present invention, in step (1), the conditions of the alkylation reaction include: a temperature of 100-280°C, a liquid hourly space velocity of 5-150h -1 Preferably, the temperature is 150-280°C and the liquid hourly space velocity is 30-70h -1 .
[0087] According to a preferred embodiment of the present invention, in step (1), the alkylation reaction raw materials are isoparaffins and olefins; preferably, the isoparaffins are C3-C5 isoparaffins, more preferably isobutane.
[0088] According to a preferred embodiment of the present invention, the olefin is a C2-C3 olefin, more preferably ethylene.
[0089] According to a preferred embodiment of the present invention, the molar ratio of the isoparaffin to the olefin is 1-100:1, more preferably 5-50:1.
[0090] According to a preferred embodiment of the present invention, in step (1), the alkylation reaction is carried out in a fixed bed reactor and / or a moving bed reactor.
[0091] In the present invention, preferably, the alkylation reaction is carried out in an alkylation reactor, and the regeneration reaction is carried out in a regeneration reactor. Specifically, the method comprises setting one or more of the multiple reactors as an alkylation reactor, and setting the remaining one or more as a regeneration reactor, the isoparaffin-containing material and the olefin-containing material contacting with the solid acid catalyst in the alkylation reactor to undergo an alkylation reaction, the deactivated solid acid catalyst to be regenerated in situ in the regeneration reactor, and the regenerated solid acid catalyst undergoes an alkylation reaction again.
[0092] According to a preferred embodiment of the present invention, the method is a continuous reaction, which ensures the possibility of industrial continuous production.
[0093] In the following examples and comparative examples, the weight distribution of the obtained alkylate oil is determined by anglient-7890 gas chromatography analysis (the chromatographic column is a HP-PONA 50m×0.2mm capillary column) equipped with a high-pressure injector. The detection idea and method for determining the one-way life of the solid acid catalyst are as follows: in normal reaction, the ethylene conversion rate is 100%. If ethylene is detected by gas chromatography, it indicates that the solid acid catalyst has begun to deactivate; when the ethylene conversion rate is lower than 80%, the reaction time experienced by the solid acid catalyst is the one-way life of the solid acid catalyst.
[0094] The pyridine infrared acid content of the catalyst was determined by pyridine adsorption infrared (Py-IR) method.
[0095] Instrument: Bruker TensorⅡ Fourier transform infrared spectrometer
[0096] Test process: Take about 25 mg of catalyst sample and press it into a tablet at 20 MPa for 5 minutes, place it in the in-situ cell of the infrared spectrometer and seal it, heat it to 450℃ at a rate of 10℃ / 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, and measured the infrared spectra at the two temperatures and integrated. -1 The absorption peak at Acidic site (B acid), 1450 cm -1 The absorption peak is attributed to the Lewis acid site (L acid).
[0097] C B =1.88A B R 2 / W (Formula 1)
[0098] C L =1.42A L R 2 / W (Formula 2)
[0099] C is the concentration of B acid or L acid (mmol / g), C B With C L All are selected from literature values; 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).
[0100] Example 1
[0101] (1) At 80°C, use ammonium chloride solution (NH4 + The concentration of 3 mol / L) was used to carry out ammonium exchange on the NaY type molecular sieve for 2 hours, and then filtered and dried;
[0102] (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 and a pressure of 0.15MPa for 2h, and air-roasting at 600°C for 4h, at a pressure of normal pressure;
[0103] (3) placing the obtained calcined product and 0.5 mol / L tetramethylammonium hydroxide solution in a mass ratio of 10:1 into a hydrothermal kettle, hydrothermally heating at 200° C. for 12 h, and washing, filtering and drying the obtained product;
[0104] (4) 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;
[0105] (5) mixing the product obtained in step (4) 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;
[0106] (6) The product obtained in step (5) is subjected to rotary evaporation in a tetraammineplatinum dichloride solution to obtain catalyst Y-1.
[0107] Example 2
[0108] (1) At 100°C, use ammonium chloride solution (NH4 + The concentration of 2 mol / L) was used to ammonium exchange the NaY molecular sieve for 2 h, and then filtered and dried;
[0109] (2) mixing the ammonium-exchanged NH4NaY molecular sieve and pseudo-boehmite at a dry weight percentage of 50:50, adding 5% nitric acid, adding deionized water at a ratio of 1:1 of the weight of water to the total weight of the other mixture (a mixture of sodium molecular sieve, binder or its precursor and auxiliary agent), mixing evenly 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 450° C. for 2 h, the pressure is 0.3MPa, and air roasting at 500° C. for 3 h, the pressure is normal pressure;
[0110] (3) placing the obtained calcined product and 0.05 mol / L tetraethylammonium hydroxide solution in a mass ratio of 5:1 into a hydrothermal kettle, hydrothermally heating at 200° C. for 1 h, and washing, filtering and drying the obtained product;
[0111] (4) 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 120°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;
[0112] (5) mixing the product obtained in step (4) 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;
[0113] (6) The product obtained in step (5) is subjected to rotary evaporation in a chloroplatinic acid solution to obtain catalyst Y-2.
[0114] Example 3
[0115] (1) At 60°C, use ammonium chloride solution (NH4 + The concentration of 2 mol / L) was used to carry out ammonium exchange on the Naβ molecular sieve for 10 hours, and then filtered and dried;
[0116] (2) mixing the ammonium-exchanged NH4Naβ molecular sieve and pseudo-boehmite at a dry weight percentage of 75:25, adding 5% sesbania powder and 2% nitric acid, adding deionized water at a ratio of 0.8:1 of the weight of water to the total weight of the other mixture (a mixture of sodium molecular sieve, binder or its precursor and auxiliary agent), mixing evenly and extruding, drying at 150°C so that the dry weight of the mixed molded product after drying is 70wt%, and then steam roasting at 550°C for 1h, the pressure is 0.1MPa, and air roasting at 550°C for 2h, the pressure is normal pressure;
[0117] (3) placing the obtained calcined product and 1 mol / L tetraethylammonium hydroxide solution in a mass ratio of 1:20 into a hydrothermal kettle, hydrothermalizing at 100° C. for 6 h, and washing, filtering and drying the obtained product;
[0118] (4) With ammonium chloride solution (NH4 + The concentration of the calcined product is 1 mol / L) with a liquid-solid mass ratio of 5:1, and ammonium exchange is performed at 60°C for 2 hours to reduce the content of Na2O in the calcined product to 0.1 wt%, and then the calcined product is washed, filtered and dried;
[0119] (5) mixing the product obtained in step (4) with an ammonium fluorosilicate solution (concentration: 5 wt%), subjecting the mixture to an acid treatment at 60° C. for 1 h, and then washing, filtering and drying the mixture;
[0120] (6) The product obtained in step (5) is subjected to rotary evaporation in a chloroplatinic acid solution to obtain catalyst β-1.
[0121] Example 4
[0122] The method of Example 1 is followed, except that the crystallization treatment is performed before calcination to obtain Y-3.
[0123] Example 5
[0124] Catalyst Y-4 was obtained by following the method of Example 1, except that deionized water was used to replace tetramethylammonium hydroxide during the hydrothermal treatment, and the hydrothermal temperature was 300° C.
[0125] Example 6
[0126] The method of Example 1 is followed, except that the concentration of hydrochloric acid in step (5) is 10 wt %, and the reaction is carried out at 150° C. for 24 h to obtain catalyst Y-5.
[0127] Example 7
[0128] The method of Example 1 is followed, except that type X molecular sieve is selected to obtain catalyst X-1.
[0129] Example 8
[0130] Catalyst Y-6 was obtained by following the method of Example 1, except that the hydrothermal crystallization treatment in step (3) was not performed.
[0131] Comparative Example 1
[0132] Catalyst DY-1 was prepared according to the method of Example 1 of patent application CN114054071A, and the acid content of the catalyst was determined according to the test method of Example 1 of the present invention.
[0133] Comparative Example 2
[0134] Catalyst DY-2 was obtained by following the method of Example 1 except that tetraammineplatinum dichloride solution was not introduced.
[0135] The contents of hydrogenation active components in the catalysts of the above-mentioned examples 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.
[0136] Table 1
[0137] Content of hydrogenation component as element (wt%) Example 1 0.35 Example 2 0.29 Example 3 0.15 Example 4 0.38 Example 5 0.34 Example 6 0.35 Example 7 0.31 Example 8 0.39 Comparative Example 1 0.35 Comparative Example 2 0
[0138] Table 2
[0139]
[0140]
[0141] Table 3
[0142]
[0143] Reaction Example 1-10
[0144] The solid acid catalysts prepared in the above-mentioned embodiment and comparative example were respectively used to carry out an alkylation reaction of isoparaffin and ethylene in a fixed bed reactor, and the reaction conditions were: the molar ratio of isobutane to ethylene was 50, the reaction temperature was 300°C, the reaction atmosphere was pure nitrogen, the reaction pressure was 3MPa, and the feed flow rate was 300mL / (g·h). When the ethylene conversion rate detected in the product was less than 80%, it was considered that the catalyst was deactivated, and a catalyst to be spent was obtained. The reaction time before the catalyst was deactivated was defined as the catalyst cycle life.
[0145] After the catalyst was deactivated, the feed was stopped and pure hydrogen was introduced in situ for regeneration. The regeneration conditions were: temperature 250°C, hydrogen pressure 5MPa, hydrogen flow rate 500mL / min relative to 1g solid acid catalyst, hydrogen was stopped after two hours, and the raw material was introduced again for reaction. The results of the alkylation reaction are shown in Table 4.
[0146] Reaction Example 11
[0147] According to the method of Reaction Example 1, the solid acid catalyst in Example 1 was selected, except that the regeneration conditions were: temperature 150°C, hydrogen pressure 0.3MPa, hydrogen flow rate 20mL / min relative to 1g solid acid catalyst, hydrogen was stopped after 4 hours, and the raw material was introduced again for reaction. The results of the alkylation reaction are shown in Table 4.
[0148] Table 4
[0149]
[0150] It can be seen from the results in the above table that Examples 1-7 using the catalyst prepared by the present invention have significantly better lifespans than Comparative Examples 1-5, and the catalyst can be completely regenerated by hydrogen regeneration.
[0151] 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. A method for regenerating a solid acid catalyst, characterized in that: Regenerating the catalyst to be regenerated in the presence of hydrogen; The catalyst to be regenerated is a solid acid catalyst deactivated in the alkylation reaction; The solid acid catalyst comprises a molecular sieve, a binder and a hydrogenation active component. Based on the dry weight of the catalyst, the content of the molecular sieve is 20-90wt%, the content of the binder is 5-79.99wt%, and the content of the hydrogenation active component in terms of elements is 0.01-5wt%. The 200°C pyridine infrared total acidity of the catalyst is increased by 30-110% compared with the 200°C pyridine infrared total acidity of the molecular sieve; and the mesopore volume of the catalyst is increased by 70-215% compared with the mesopore volume of the molecular sieve.
2. The regeneration method according to claim 1, wherein: In the alkylation reaction, when the conversion rate of the alkylation reaction raw material is lower than 80%, a spent catalyst is obtained; Preferably, the regeneration treatment conditions include: regeneration temperature of 150-300°C, hydrogen pressure of 0.1-5MPa, regeneration time of 0.1-5 hours, and hydrogen flow rate of 1-5000mL / min relative to 1g of solid acid catalyst; Further preferably, the regeneration treatment conditions include: regeneration temperature of 170-250° C., hydrogen pressure of 0.5-3 MPa, regeneration time of 0.5-4 hours, and hydrogen flow rate of 50-1000 mL / min.
3. The regeneration method according to claim 1 or 2, wherein: Based on the dry weight of the catalyst, the content of the molecular sieve is 25-84wt%, the content of the binder is 15-75wt%, and the content of the hydrogenation active component in terms of element is 0.1-1wt%; And / or, the total pyridine infrared acidity of the catalyst at 200°C is increased by 52-80% compared with the total pyridine infrared acidity of the molecular sieve at 200°C; And / or, the mesopore volume of the catalyst is increased by 110-215% compared with the mesopore volume of the molecular sieve.
4. The regeneration method according to claim 1 or 2, wherein: The molecular sieve is at least one of X-type, Y-type and β-type molecular sieves, 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; And / or, the hydrogenation active component is selected from at least one of Pt, Pd, Ru and Ir, preferably Pt and / or Pd, and more preferably Pt.
5. The regeneration method 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, the total acidity of pyridine infrared at 200°C is greater than 360 μmol / g, preferably the total acidity of pyridine infrared at 200°C is 430-540 μmol / g, and the mesopore volume is 0.048-0.106 cm 3 / 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 at 200°C is greater than 310 μmol / g, preferably the total acidity of pyridine infrared at 200°C is 372-465 μmol / g, and the mesopore volume is 0.07-0.128 cm 3 / g; And / or, the molecular sieve is a β-type molecular sieve, the unit cell constant of the catalyst is 1.249-1.262nm, the total acidity of pyridine infrared at 200℃ is greater than 560μmol / g, preferably the total acidity of pyridine infrared at 200℃ is 670-840μmol / g, and the mesopore volume is 0.024-0.051cm 3 / g.
6. The regeneration method according to claim 1 or 2, wherein: 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 1.2-3, and the ratio of pyridine infrared B acid / L acid at 350°C is 1-3.5; 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 0.95-3.5, and the ratio of pyridine infrared B acid / L acid at 350°C is 0.95-3.5; And / or, 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 1-2, and the ratio of pyridine infrared B acid / L acid at 350°C is 1-2.
7. The regeneration method according to claim 1 or 2, wherein: The preparation method of the solid acid catalyst comprises the following steps: (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) The calcined product obtained in step (1) is sequentially subjected to crystallization treatment, ammonium exchange, acid treatment and introduction of hydrogenation active components to obtain a solid acid catalyst.
8. The regeneration method according to claim 7, wherein: In step (1), the amount of the sodium molecular sieve and the binder or its precursor is such that the weight ratio of the sodium molecular sieve to the binder in the catalyst is 90:10-20:80, preferably 90:10-50:50, based on dry weight; And / or, 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; And / or, 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 normal pressure-0.3 MPa.
9. The regeneration method according to claim 7, wherein: The crystallization treatment comprises: subjecting the calcined product to a hydrothermal crystallization treatment in the presence of a template; Preferably, the template is selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, hexadecyltrimethylammonium bromide and dodecyltrimethylammonium bromide; Preferably, the concentration of the template is 0.05-1.5 mol / L; Preferably, in step (2), the conditions of the crystallization treatment include: temperature of 80-300°C, time of 1-24h, liquid-to-solid mass ratio of 0.05-10:1; The conditions of the ammonium exchange include: temperature of 50-150°C, liquid-to-solid mass ratio of 5-50, and time of 2-24h; And / or, in step (2), the acid treatment conditions include: temperature of 10-350° C., time of 0.5-36 h; And / or, the acid used for the acid treatment is at least one selected from hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, lactic acid, oxalic acid, fluorosilicic acid, hydrofluoric acid and ammonium fluorosilicate; And / or, the concentration of the acid is 0.1-20 wt %.
10. The regeneration method according to claim 7, wherein: In step (3), the hydrogenation component is provided by a hydrogenation component precursor; Preferably, the hydrogenation component precursor is selected from at least one of chloroplatinic acid, tetraamine platinum dichloride, tetraamine platinum nitrate, dinitrosodiammine platinum, tetraamine platinum acetate, palladium chloride, palladium nitrate, sodium chloropalladate and potassium chloropalladate, preferably at least one of tetraamine platinum dichloride, tetraamine platinum nitrate, sodium chloropalladate and potassium chloropalladate; Preferably, in step (2), the amount of the hydrogenation component used is such that the content of the hydrogenation component in the catalyst, calculated as an element, is 0.01-5 wt%.
11. A method for preparing an alkylate, wherein: The method includes: (1) subjecting an alkylation reaction raw material to an alkylation reaction in the presence of a nitrogen atmosphere and a solid acid catalyst to obtain a spent catalyst; (2) subjecting the catalyst to be regenerated to a regeneration reaction according to the regeneration method according to any one of claims 1 to 10; The method further comprises recycling the regenerated solid acid catalyst obtained in step (2) back to step (1).
12. The method according to claim 11, wherein: In step (1), the conditions of the alkylation reaction include: a temperature of 100-300° C. and a feed flow rate of 50-1000 mL / (g·h); Preferably, in step (1), the conditions of the alkylation reaction include: a temperature of 150-300° C., a feed flow rate of 100-300 mL / (g·h); Preferably, in step (1), the alkylation reaction raw materials are isoparaffins and olefins; Preferably, the isoalkane is a C3-C5 isoalkane, more preferably isobutane; Preferably, the olefin is a C2-C3 olefin, more preferably ethylene; Preferably, the molar ratio of the isoparaffin to the olefin is 1-100:1, more preferably 5-50:1; Preferably, in step (1), the alkylation reaction is carried out in a fixed bed reactor and / or a moving bed reactor.
13. The method according to claim 11 or 12, wherein: The method is a continuous reaction.