CN111482195B - Solid acid catalyst - Google Patents
Solid acid catalyst Download PDFInfo
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- CN111482195B CN111482195B CN201910072245.8A CN201910072245A CN111482195B CN 111482195 B CN111482195 B CN 111482195B CN 201910072245 A CN201910072245 A CN 201910072245A CN 111482195 B CN111482195 B CN 111482195B
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
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- B01J29/00—Catalysts comprising molecular sieves
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7415—Zeolite Beta
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7476—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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Abstract
A solid acid catalyst is characterized in that the specific volume of macropores of the solid acid catalyst is 0.30-0.40ml/g, the ratio of the specific volume of the macropores to the specific length of catalyst particles is 1.0-2.5 ml/(g.mm), and the ratio of the specific surface area to the length of the particles is 3.40-4.50m2And/mm, the macropores refer to pores with the diameter of more than 50 nm.
Description
Technical Field
The invention relates to a solid acid catalyst, a preparation method and application thereof, in particular to a solid acid catalyst for an alkylation process, a preparation method and application thereof in an alkylation reaction process of isoparaffin and olefin.
Background
C4-C6Isoalkanes and C3-C6The process of alkylation of olefins to produce alkylated gasoline is an important process in the petroleum refining industry. The alkylated gasoline produced by the process has low steam pressure, low sensitivity, good anti-knock performance, no aromatic hydrocarbon and olefin, and low sulfur content, and is an ideal blending component for clean and high-octane gasoline.
The alkylation reaction is an acid-catalyzed reaction. The alkylation production processes currently used in industry include liquid acid processes of sulfuric acid process and hydrofluoric acid process, which use liquid acid (sulfuric acid or hydrofluoric acid) as a catalyst to synthesize alkylated gasoline. Due to the corrosivity and toxicity of sulfuric acid and hydrofluoric acid and the environmental hazard caused by the discharge of waste acid during the process, manufacturers face increasing pressure on safety and environmental protection.
To address these problems, many major oil companies and scientific research institutes around the world have been working on the research and development of solid acid alkylation process technologies to replace the liquid acid process with an environmentally friendly solid acid process.
The core of the development of the solid acid alkylation process is the development of a solid acid catalyst with excellent performance. The solid acid catalyst has the advantages of good stability, no corrosion to equipment, convenience for separation from products, less environmental pollution, relatively high safety in the transportation process and the like, and is an ideal form of the catalyst in the future. Solid acid alkylation catalysts are mainly classified into four types: metal halide, solid super acid, supported heteropoly acid and molecular sieve. Although the development of solid acid catalysts for the alkylation of isobutane with butenes has been over decades, the progress of the process technology industrialization has been affected by the problem of the rapid deactivation of the solid acid catalysts.
US5986158 discloses an alkylation process using a catalyst comprising a hydrogenation function and a solid acid component, regenerated by washing with saturated hydrocarbons and in the presence of hydrogen, the reaction being carried out in a fixed bed reactor, the active phase of the catalyst being only 4-10 hours, the catalyst having to be regenerated repeatedly, as can be seen from the examples, the alkylate gasoline has a Research Octane Number (RON) of 91.2, trimethylpentane/dimethylhexane of 2.9, C5-C7、C8、C9+30.4%, 58.2% and 11.4%, respectively.
EP1527035B1 discloses a continuous alkylation process carried out in an apparatus comprising at least two series-connected catalyst-containing reactors located in zone a and at least two series-connected catalyst-containing reactors located in zone B; each zone is cycled back and forth between an alkylation mode and a mild regeneration mode, each zone having at least two reactors in series, and the alkylate product stream may or may not be subjected to a prior batch separation in which a portion of the alkylate is removed; the catalyst employs a mild regeneration mode that includes contacting the catalyst with hydrogen and a portion of the alkylate effluent comprising the alkylation mode in each of at least two reactors of the zone.
EP1392627B1 discloses a process for the catalytic alkylation of hydrocarbons which comprises (i) reacting an alkylatable compound with an alkylating agent over a solid acid alkylation catalyst to form an alkylate and (ii) regenerating said catalyst under mild regeneration conditions in the presence of hydrogen and a hydrocarbon, wherein the hydrocarbon comprises at least a portion of the alkylate that has been formed.
CN103964994A discloses an alkylation reaction method, which is characterized in that the alkylation reaction of isobutane and butene is carried out under the condition of the existence of a catalyst and the alkylation reaction, wherein the catalyst is prepared by the steps of modifying a molecular sieve and introducing a matrix, the step of modifying the molecular sieve comprises the steps of uniformly mixing the molecular sieve, one or more substances selected from water, alcohol and ester and organic alkali, treating in a sealed reaction kettle at 100-250 ℃ under the autogenous pressure, recovering the treated product, and then carrying out rare earth ion salt exchange.
EP1286769B1, CN1431932A disclose a catalyst comprising catalyst particles containing a hydrogenation functional component and a solid acid, wherein the ratio of (i) the volume in the catalyst pores with a diameter of 40-8000nm to (ii) the specific length of the catalyst particles is 0.01-0.90 ml/(g-mm), and wherein the total pore volume of the catalyst is at least 0.20ml/g and the volume in the catalyst pores with a diameter of 40-8000nm is below 0.30ml/g, and its use in alkylation.
Disclosure of Invention
The object of the present invention is to provide a solid acid catalyst, a process for its preparation, a corresponding alkylation catalyst and its use, which differ from the prior art.
The solid acid catalyst provided by the invention is characterized in that the specific volume of macropores of the solid acid catalyst is 0.30-0.40ml/g, the ratio of the specific volume of the macropores to the specific length of catalyst particles is 1.0-2.5 ml/(g.mm), and the specific surface area to the particlesThe ratio of the grain lengths is 3.40-4.50m2And/mm, the macropores refer to pores with the diameter of more than 50 nm.
The preparation method of the solid acid catalyst is characterized by comprising the steps of mixing and stirring slurry containing solid acid components and aluminum sol uniformly, drying, mixing with extrusion aid and peptizing agent, and forming, wherein the particle size of the aluminum sol is 20-400 nm.
The invention also provides a solid acid alkylation catalyst, which is characterized by comprising 0.01-10 wt% of metal component with hydrogenation function in the solid acid alkylation catalyst, wherein the specific volume of macropores of the solid acid alkylation catalyst is 0.30-0.40ml/g, the ratio of the specific volume of the macropores to the specific length of catalyst particles is 1.0-2.5 ml/g.mm, and the macropores refer to pores with the diameter of more than 50 nm.
The present invention further provides an alkylation reaction process employing the solid acid alkylation catalyst described above.
The invention provides alkylation reaction processes, especially with C4-C6Isoalkanes and C3-C6The alkylation reaction method for synthesizing the alkylated gasoline by using the olefin as the raw material has the characteristics of long service life of the catalyst and high selectivity of trimethylpentane.
Drawings
FIG. 1 is an SEM and energy spectrum surface scanning of a solid acid catalyst sample to characterize the morphology and element distribution of a solid acid catalyst.
Detailed Description
The solid acid catalyst of the invention is characterized in that the specific volume of macropores of the solid acid catalyst is 0.30-0.40ml/g, the ratio of the specific volume of macropores to the specific length of catalyst particles is 1.0-2.5 ml/(g.mm), and the ratio of the specific surface area to the length of particles is 3.40-4.50m2And/mm, the macropores refer to pores with the diameter of more than 50 nm.
The International Union of Pure and Applied Chemistry (IUPAC) specifies that pores with a diameter greater than 50nm are denoted by "macropore", and the volume in the pores of such pores is denoted by "macropore volume".
The macropore specific volume refers to the volume of macropores per unit mass of catalyst particles. The solid acid catalyst of the invention has a macropore specific volume of 0.30-0.40ml/g, preferably at least 0.35 ml/g.
Catalyst particle specific length refers to the ratio of the geometric volume to the geometric surface of the solid portion of the catalyst particle. Methods for determining geometric volumes and geometric surfaces are well known to the person skilled in the art and can be determined, for example, as described in DE 2354558. It is to be noted that the specific length of the catalyst particles is different from the diameter of the catalyst particles. For example, for cylindrical catalyst particles, the diameter ratio of the particles is four to six times greater than the length (depending on the diameter and length of the particles), and for spherical catalyst particles, the diameter ratio of the particles is six times greater than the length. The solid acid catalyst provided by the invention has the particle specific length of preferably 0.15-0.4mm, more preferably 0.18-0.36mm, and most preferably 0.20-0.32 mm.
The solid acid catalyst of the present invention has a ratio of the specific volume of macropores to the specific length of catalyst particles of 1.0 to 2.5 ml/g.mm, preferably 1.1 to 1.8 ml/g.mm.
The total pore volume refers to the total pore volume per unit mass of the catalyst particles. The solid acid catalyst of the present invention has a total pore volume of at least 0.40ml/g, preferably at least 0.45 ml/g.
The particles of the solid acid catalyst of the present invention can have many different shapes including spherical, cylindrical, circular, and symmetrical or asymmetrical multi-lobed shapes (e.g., butterfly, trilobal, quadralobal). The average diameter of the catalyst particles is preferably at least 1.0mm, and its upper limit value is preferably 5.0 mm. The average diameter of the catalyst particles refers to the longest line segment among line segments connecting any two points on the cross section of one catalyst particle, and can be measured by a conventional measuring means such as a vernier caliper.
In the solid acid catalyst of the present invention, the solid acid component is preferably a molecular sieve. The molecular sieve may be selected from a variety of molecular sieves, for example, may be one or more selected from Y-type molecular sieves, beta, MOR, MCM-22 and MCM-36. The unit cell size of the Y-type molecular sieve is 2.430-2.470nm, the preferable unit cell size is 2.440-2.460nm, and the molar ratio of silicon dioxide to aluminum oxide is 5-15. If desired, the solid acid component may also include non-zeolitic solid acids such as heteropolyacids, silica-aluminas, sulfated oxides such as sulfated oxides of zirconium, titanium or tin, mixed oxides of zirconium, molybdenum, tungsten, phosphorus, or the like, chlorinated aluminas or clays, and the like.
The solid acid catalyst of the present invention further comprises a matrix material. The content of the base material is 2-98 wt%, and the preferable content is 10-70 wt%.
The solid acid catalyst of the present invention preferably comprises from 2 to 98 wt% of the solid acid component and from 2 to 98 wt% of the base material, further preferably from 5 to 95 wt% of the solid acid component and from 5 to 95 wt% of the base material, more preferably from 15 to 85 wt% of the solid acid component and from 15 to 85 wt% of the base material, may comprise from 20 to 80 wt% of the solid acid component and from 20 to 80 wt% of the base material, or may comprise from 60 to 80 wt% of the solid acid component and from 20 to 40 wt% of the base material, based on the total weight of the solid acid component and the base material present in the catalyst. Wherein the matrix material comprises alumina, and the precursor of the alumina is at least partially derived from an alumina sol with the granularity of 20-400 nm.
The specific surface area of the solid acid catalyst of the present invention is not less than 500m2(ii) in terms of/g. In the solid acid catalyst, the solid acid component is highly dispersed in the base material in micron level, and the specific surface area of the solid acid component is not less than 650m2The specific surface area of the base material is not more than 400m2(ii) in terms of/g. After the solid acid component is dispersed in the substrate material in a micron-level height, the specific surface area of the catalyst particles per unit length is required to fluctuate within a narrow range, and the large change caused by the large difference between the specific surface area of the solid acid component and the specific surface area of the substrate material is avoided. The solid acid catalyst of the invention has a ratio of the specific surface area to the particle length of 3.40 to 4.50m2And/mm. The particle length is obtained by randomly selecting 1g of catalyst particles, measuring the length of each of the 1g of catalyst particles, and adding the lengths of each of the particles. For spherical particles, the particle length is the diameter of the sphere; for a particle in the form of a rod (including butterfly, trilobe, and quadralobe cross-sections, among others), the length of the particle is the average rod length of the particle; for annular particles, the particle length is the outer diameter of the annulus.
The invention also provides a preparation method for obtaining the solid acid catalyst, which comprises the steps of mixing and stirring the slurry containing the solid acid component and an aluminum sol uniformly, drying, mixing with an extrusion aid and a peptizing agent, and forming, wherein the particle size of the aluminum sol is 20-400 nm.
In the preparation method, the particle size of the aluminum sol is 20-400nm, preferably 20-300 nm. The extrusion aid is well known to those skilled in the art, and the commonly used extrusion aid is selected from sesbania powder, oxalic acid, tartaric acid, citric acid and the like, preferably sesbania powder; the peptizing agent is also well known to those skilled in the art, and commonly used peptizing agents are selected from the group consisting of nitric acid, hydrochloric acid, acetic acid, formic acid, citric acid, trichloroacetic acid, and the like, preferably nitric acid.
After the solid acid catalyst is loaded with the regeneration auxiliary agent with the hydrogenation function, the solid acid catalyst can be regenerated under the condition of inactivation and the hydrogen and proper conditions, so that the repeated regeneration and the recycling of the catalyst are realized. Therefore, the invention provides an alkylation catalyst, which is characterized by comprising 0.01-10 wt% of metal component with hydrogenation function based on the alkylation catalyst, wherein the alkylation catalyst has a macropore specific volume of 0.30-0.40ml/g, a ratio of the macropore specific volume to the specific length of catalyst particles of 1.0-2.5 ml/g.mm, and a ratio of the specific surface area to the length of the particles of 3.40-4.50m2And/mm, the macropores refer to pores with the diameter of more than 50 nm.
In the alkylation catalyst of the invention, the regeneration auxiliary component is composed of metal with hydrogenation function. Suitable hydrogenation-functional metals are mainly group VIII metals, preferably group VIII noble metals. More preferably, the group VIII noble metal is one or more of rhodium, palladium and platinum. The metal having a hydrogenation function is contained in an amount of 0.01 to 10 wt%, preferably 0.1 to 1 wt%, calculated as metal, based on the weight of the alkylation catalyst.
Typical preparation steps for the alkylation catalyst of the present invention include impregnation of the particles by a solution containing a hydrogenation function metal and/or addition of a hydrogenation function metal to the solid acid catalyst of the present invention by ion exchange; a typical preparation procedure may also be to add a precursor of the metal having the hydrogenation function to a liquid phase mixture comprising the solid acid component and an aluminum sol having a particle size of 20 to 400nm, dry the resulting mixture and shape it.
The alkylation catalyst of the invention is preferably applied to a method for alkylation reaction of isoparaffin and olefin. Preferred isoparaffins are C4-C6Isoparaffins, preferably olefins C3-C6A single-bond olefin; more preferably, said C4～C6The isoparaffin is isobutane, the C3～C6The single-bond olefin is one or more of butene-1, butene-2 and isobutene.
In the alkylation reaction method, the reaction conditions are that the temperature is 30-100 ℃, the pressure is 1.5-5.0MPa, and the feeding flow is 10-3000mL/gcatH, the molar ratio of isobutane to butene is from 6 to 1000; under the optimized alkylation reaction condition, the temperature is 40-100 ℃, the pressure is 2.0-5.0MPa, and the feeding flow is 10-3000 mL/(g)catH) the molar ratio of isobutane to butene is from 15 to 1000.
The alkylation process of the present invention may be carried out using a variety of reactor configurations. The reactors include fluidized bed reactors, slurry bed reactors and fixed bed reactor forms. The process can be carried out in single and multiple reactors.
The alkylation process according to the invention using the alkylation catalyst according to the invention with specific physicochemical parameters, in particular C4-C6Isoalkanes and C3-C6The alkylation reaction method for synthesizing alkylated gasoline by using olefin as raw material has the characteristics of long service life of catalyst and high selectivity of trimethylpentane, and can limit C9+ byproduct amount; the alkylation catalyst can be regenerated in the presence of hydrogen, and the activity of the regenerated alkylation catalyst can be restored to the level of a fresh agent.
In the isoparaffin-olefin alkylation reaction provided by the invention, if the ratio of the large pore volume ratio to the particle length ratio and/or the ratio of the specific surface area to the particle length ratio of the alkylation catalyst is outside the range defined by the invention, the isoparaffin-olefin alkylation reaction is poor.
In the examples, the physicochemical parameter characterization method of the solid acid catalyst particles was as follows:
the macropore volume and total pore volume were determined by mercury intrusion based on the Washbum equation. D (-4 γ cos θ)/p where D is the pore diameter, p is the pressure applied during the measurement, γ is the surface tension, taking 485 dynes/cm, θ is the contact angle, taking 130 °.
Measurement of the average diameter of the catalyst particles: and measuring the longest side distance of the cross section of the particle by using a vernier caliper to obtain the average diameter of the particle.
Measurement of specific surface area: the specific surface area of the catalyst is measured by adopting a nitrogen low-temperature adsorption method, and the specific surface area is calculated by using a BET formula.
Measurement of particle length: randomly selecting 1g of catalyst particles, measuring the length of each particle in the 1g of catalyst particles, and adding the lengths of the particles; the length of each particle was measured using a vernier caliper.
In the examples, the evaluation and analysis method of the technical effect of the alkylation reaction method is as follows:
weighing quartz sand (20-40 meshes) and filling the quartz sand into a non-constant temperature section at the lower end of a tubular reactor, compacting, then filling a three-layer nickel screen, filling 100g of alkylation catalyst, compacting, filling the three-layer nickel screen, filling the quartz sand with 20-40 meshes into the non-constant temperature section at the upper layer of the reactor, and compacting. Finally, proper quartz cotton and nickel net are filled in sequence.
The reactor is connected into a pipeline, after the airtightness and the smoothness of the pipeline are detected, air in the nitrogen replacing device is replaced for more than three times, and then hydrogen is used for replacing for three times. Setting the hydrogen flow rate to be 300mL/min, the back pressure to be 3.0MPa, opening a heating source, setting the heating speed to be 1 ℃/min, heating to 200 ℃ and keeping for 1 h; then the temperature is raised to 450 ℃ at 1 ℃/min and kept for 3 h. After the pretreatment, the alkylation catalyst was cooled to the reaction temperature in the examples, the hydrogen in the nitrogen displacement device was displaced three times or more, and after the displacement, the catalyst was fed at a certain feed rate and reacted under the reaction conditions described in the examples.
Distribution of the alkylation reaction product through the Al-containing layer2O3And Agilent 7890A gas chromatography using PONA column and high pressure sampler. Sampling after back pressure valve and before exhaust gas emptying, sampling every two hours, and separating the sample into two parts at the sample inlet, 0.01-0.1 min of low boiling point mixture (C)4The following hydrocarbons) into Al2O3Column, high boiling point material (C) for 0.2-9.5 min5The above hydrocarbons) is blown into the PONA column by a carrier gas. The obtained spectrogram is identified by gasoline analysis software (developed by institute of petrochemical science) and the percentage content of each component is calculated.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Starting materials used in examples or comparative examples:
1. y-type molecular sieve (China petrochemical catalyst Co., Ltd.) with specific surface area of 680m2Pore volume 0.36mL/g, unit cell constant 2.457nm, m (SiO)2/Al2O3) No. 9, No. Ya.
2. Several nano-alumina sols (china petrochemical catalyst division):
code Al 1: the alumina concentration was 5% and the average particle size was 20 nm.
Code Al 2: the alumina concentration was 15% and the average particle size was 150 nm.
Code Al 3: the alumina concentration was 20% and the average particle size was 300 nm.
3、Al2O3Binder powder: specific surface area 280m2G, pore volume 0.98 mL/g.
Examples 1 to 3
This example illustrates the solid acid catalyst and the molding process of the present invention.
Adding water into the Y-shaped molecular sieve numbered Ya and pulping to obtain the product with the solid content of 200kg/m3Adding aluminum sol numbered Al1 into the molecular sieve slurry according to the weight percentage of 60:40, 80:20 and 95:5 of Ya and Al1 in a dry basis ratio, stirring for 4 hours, uniformly mixing, adding 3 weight percent (based on the weight of the molecular sieve and the aluminum sol calcined at 600 ℃) of nitric acid and sesbania powder into the dried mixed powder, adding water to ensure that the water-powder ratio is 0.8, kneading and kneadingAnd extruding the mixture evenly, and drying and roasting the obtained wet strips to obtain a molded solid acid catalyst sample.
The solid acid catalyst samples were designated 60a1, 80a1, and 95a1, respectively, with properties shown in table 1.
Examples 4 to 6
This example illustrates the solid acid catalyst and the molding process of the present invention.
Adding water into the Y-shaped molecular sieve numbered Ya and pulping to obtain the product with the solid content of 200kg/m3Adding aluminum sol numbered Al2 into the molecular sieve slurry according to the weight percentage of dry basis of Ya and Al2 of 60:40, 80:20 and 95:5 respectively, stirring for 4 hours to uniformly mix the aluminum sol, adding 3 weight percent (based on the weight of dry basis of the molecular sieve and the aluminum sol calcined at 600 ℃) of nitric acid and sesbania powder into the dried mixed powder, adding water to ensure that the water-powder ratio is 0.8, extruding the mixture after uniformly mixing and kneading, and drying and calcining the obtained wet strip to obtain a molded solid acid catalyst sample.
The solid acid catalyst samples were designated 60a2, 80a2, and 95a2, respectively, with properties shown in table 1.
Examples 7 to 9
This example illustrates the solid acid catalyst and the molding process of the present invention.
Adding water into the Y-shaped molecular sieve numbered Ya and pulping to obtain the product with the solid content of 200kg/m3Adding aluminum sol numbered Al3 into the molecular sieve slurry according to the weight percentage of dry basis of Ya and Al3 of 60:40, 80:20 and 95:5 respectively, stirring for 4 hours to uniformly mix the aluminum sol, adding 3 weight percent (based on the weight of dry basis of the molecular sieve and the aluminum sol calcined at 600 ℃) of nitric acid and sesbania powder into the dried mixed powder, adding water to ensure that the water-powder ratio is 0.8, extruding the mixture after uniformly mixing and kneading, and drying and calcining the obtained wet strip to obtain a molded solid acid catalyst sample.
The solid acid catalyst samples were designated 60A3, 80A3, and 95A3, respectively, with properties shown in table 1.
Comparative example 1
This comparative example illustrates the use of a Y-type molecular sieve and Al2O3Binder powder solid phase mixing formation process and resulting comparative solid acid catalyst samplesAnd (5) preparing the product.
Mixing the Y-type molecular sieve with Al2O3Mixing the binder powder at a weight ratio of 60:40, adding 3 wt% (based on molecular sieve and Al)2O3The dry basis weight of the binder powder after being roasted at 600 ℃) is determined), water and powder ratio of the final mixed powder is ensured to be 0.8 by adding water, the mixture is extruded after being uniformly kneaded, and the obtained wet strip is dried and roasted to obtain a formed comparative solid acid catalyst sample.
The comparative solid acid catalyst sample was designated 60A and the properties are shown in table 1.
Comparative example 2
This comparative example illustrates the use of a Y-type molecular sieve and Al2O3Binder powder solid phase mixing molding procedure and comparative solid acid catalyst samples obtained.
Mixing the Y-type molecular sieve with Al2O3Mixing the binder powder at a weight ratio of 80:20, adding 3 wt% (based on molecular sieve and Al)2O3The dry basis weight of the binder powder after being roasted at 600 ℃) is determined), water and powder ratio of the final mixed powder is ensured to be 0.8 by adding water, the mixture is extruded after being uniformly kneaded, and the obtained wet strip is dried and roasted to obtain a formed comparative solid acid catalyst sample.
The comparative solid acid catalyst sample was designated 80A and the properties are shown in table 1.
Comparative example 3
This comparative example illustrates the use of a Y-type molecular sieve and Al2O3Binder powder solid phase mixing molding procedure and comparative solid acid catalyst samples obtained.
Mixing the Y-type molecular sieve with Al2O3Mixing the binder powder at a weight ratio of 95:5, adding 3 wt% (based on molecular sieve and Al)2O3Dry basis weight of the binder powder after roasting at 600 ℃) is taken as the standard), water and powder ratio of the final mixed powder is ensured to be 0.8 by adding water, the mixture is extruded after being uniformly kneaded, and the obtained wet strip is dried and roasted to obtain a formed comparative solid acid catalyst sample。
The comparative solid acid catalyst sample was designated 95A and the properties are shown in table 1.
TABLE 1
The solid acid catalyst sample numbered 80A2 and the comparative solid acid catalyst sample numbered 80A were characterized using SEM and energy spectral surface scanning. The morphology and the element distribution results are shown in FIG. 1.
As can be seen from FIG. 1, the Si-Al element distribution of the sample of solid acid catalyst No. 80A2 is more uniform, which shows that the Y-type molecular sieve and Al are mixed in the liquid phase2O3The particle size distribution is uniform, and the acid site dispersibility is good.
Examples 10 to 18
Examples 10-18 illustrate alkylation catalysts of the present invention.
The alkylation catalysts of examples 10-18 were obtained by supporting the hydrogenation metal on the solid acid catalysts of examples 1-9, respectively.
Samples of the solid acid catalysts of examples 1-9, 60A1, 80A1, 95A1, 60A2, 80A2, 95A2, 60A3, 80A3, 95A3, were each charged with hydrogenation-containing metal Pt (H) under vacuum (H-S-H-S-H2PtCl6·6H2O is a precursor) and impregnation liquid with a liquid-solid ratio of 2:1, after the addition is finished, the impregnation is finished under normal pressure for no more than 10 hours, the vacuum pumping is carried out at the temperature of no more than 80 ℃, the moisture in the catalyst is evaporated until the weight of the catalyst is 1.2-1.5 times of that of a solid acid catalyst precursor, and the catalyst is taken out after the evaporation, dried and roasted.
The obtained alkylation catalysts are respectively numbered as C1, C2, C3, C4, C5, C6, C7, C8 and C9, and the Pt content is 0.25 wt%.
Examples 19 to 22
Examples 19-22 illustrate alkylation catalysts of the present invention.
Obtained by supporting a hydrogenation metal on the basis of the solid acid catalyst 80a2 of example 5. The same procedure as in example 14 gave alkylation catalyst samples having the numbers C10-C13.
In sample alkylation catalysts C10-C13, the Pt content was 0.1 wt%, 0.5 wt%, 0.7 wt%, 0.9 wt%, respectively.
Example 23
This example illustrates an alkylation catalyst of the present invention.
The alkylation catalyst, code C14, was obtained by supporting the hydrogenation metal on the solid acid catalyst 80a2 of example 5, except that the hydrogenation metal was Pd (palladium nitrate was the precursor) and the Pd content was 0.5 wt%.
Example 24
This example illustrates an alkylation catalyst of the present invention.
The hydrogenation metal was supported on the solid acid catalyst 80a2 of example 5 to provide an alkylation catalyst, No. C15, except that the hydrogenation metal was Ru (ruthenium chloride as precursor)) and the Ru content was 0.5 wt%.
Example 25
This example illustrates an alkylation catalyst of the present invention.
The alkylation catalyst, code C16, was obtained by loading the hydrogenation metal on the solid acid catalyst 80a2 of example 5, except that the hydrogenation metal was Mn (manganese nitrate was the precursor) with a Mn content of 3.5 wt%.
Example 26
This example illustrates an alkylation catalyst of the present invention.
Loading the hydrogenation metal on the solid acid catalyst 80a2 of example 5 gave alkylation catalyst C17 with the difference that the hydrogenation metal was Ni (nickel nitrate was the precursor) and the Ni content was 3.5 wt%.
Examples 27 to 35
Examples 27-35 illustrate the alkylation reaction process provided by the present invention.
The alkylation processes of examples 27-35 utilize alkylation catalysts having the respective numbers C1, C2, C3, C4, C5, C6, C7, C8, C9.
Reaction conditions are as follows: the weight ratio of isobutane to mixed butene is 200, the reaction temperature is 75 ℃, the reaction pressure is 3MPa, and the total feed flow is 100 ml/(g)cat·h)。
The results of the alkylation reaction are shown in Table 2.
Example 36
This example illustrates the alkylation process provided by the present invention.
In the alkylation process of this example, the alkylation catalyst designated C5 was used.
Reaction conditions are as follows: the weight ratio of isobutane to mixed butene is 20, the reaction temperature is 40 ℃, the reaction pressure is 2MPa, and the total feed flow is 10 ml/(g)cat·h)。
The results of the alkylation reaction are shown in Table 2.
Example 37
This example illustrates the alkylation process provided by the present invention.
In the alkylation process of this example, the alkylation catalyst designated C5 was used.
Reaction conditions are as follows: the weight ratio of isobutane to mixed butene is 500, the reaction temperature is 75 ℃, the reaction pressure is 3MPa, and the total feed flow is 1000 ml/(g)cat·h)。
The results of the alkylation reaction are shown in Table 2.
Example 38
This example illustrates the alkylation process provided by the present invention.
In the alkylation process of this example, the alkylation catalyst designated C5 was used.
Reaction conditions are as follows: the weight ratio of isobutane to mixed butene is 1000, the reaction temperature is 100 ℃, the reaction pressure is 5MPa, and the total feed flow is 3000 ml/(g)cat·h)。
The results of the alkylation reaction are shown in Table 2.
Examples 39 to 46
This example illustrates the alkylation process provided by the present invention.
The alkylation reaction process of examples 39-46 uses alkylation catalysts having the respective numbers C10, C11, C12, C13, C14, C15, C16 and C17 under the same alkylation reaction conditions as in example 27.
The results of the alkylation reaction are shown in Table 2.
Comparative examples 4 to 6
Comparative examples 4-6 illustrate comparative alkylation catalysts and comparative alkylation processes.
The alkylation catalysts of comparative examples 4 to 6 were obtained by supporting the hydrogenation metal Pt on the comparative solid acid catalysts 60A, 80A, 95A obtained in comparative examples 1, 2, 3, respectively (Pt content of 0.25 wt%). The numbers are DB1, DB2 and DB3 respectively.
The alkylation conditions were the same as in example 31.
The results of the alkylation reaction are shown in Table 2.
Comparative example 7
This comparative example illustrates a comparative alkylation catalyst and comparative alkylation process.
The comparative alkylation catalyst composition and preparation in this comparative example was the same as the alkylation catalyst of example 13 (Pt content 0.25 wt%), except that: the shaped solid acid catalyst is cylindrical in shape: the ratio of the specific volume of macropores to the specific length of catalyst particles was 0.82 ml/(g.mm) (specific volume of macropores: 0.4ml/g, specific length: 0.49mm (average diameter: 2.2mm, average length: 5.0mm)), and the total specific volume of pores was 0.5 ml/g. The specific surface area is 545m2G, the length of the particles was 140mm, and the ratio of the specific surface area to the length of the particles was 3.89. Numbered DB 4.
The alkylation reaction conditions in this comparative example were the same as in example 31.
The results of the alkylation reaction are shown in Table 2.
Comparative example 8
This comparative example illustrates a comparative alkylation catalyst and comparative alkylation process.
The alkylation catalyst composition and preparation procedure in this comparative example were the same as the alkylation catalyst of example 13 (Pt content 0.25 wt%), except that: (ii) a The shaped solid acid catalyst is spherical in shape: the ratio of the specific volume of macropores to the specific length of the catalyst particles was 0.51 ml/(g.mm) (specific volume of macropores: 0.42ml/g, specific length: 0.83mm (average diameter: 5.0mm), total specific volume of pores was 0.55ml/g, specific surface area was 555m2(ii)/g, the length of the particles was 145mm, and the ratio of the specific surface area to the length of the particles was 3.83.Numbered DB 5.
The alkylation reaction conditions in this comparative example were the same as in example 31.
The results of the alkylation reaction are shown in Table 2.
Comparative example 9
This comparative example illustrates a comparative alkylation catalyst and comparative alkylation process.
The solid acid catalyst in this comparative example was compared to the Y-type molecular sieve and Al described in comparative example 22O3The binder powder solid phase mixing formation procedure was the same as the composition of the comparative solid acid catalyst sample 80A obtained, the alkylation catalyst preparation procedure was the same as the alkylation catalyst of example 14, and the Pt content was 0.25 wt%; except that the shape was cylindrical, and the ratio of the specific volume of macropores to the specific length of catalyst particles was 1.90 ml/(g.mm) (specific volume of macropores: 0.40ml/g, specific length: 0.21mm (average diameter: 1.8mm, average length: 5.5 mm)). The total pore volume was 0.48 ml/g. The weight of the catalyst particles was 0.16g, and the specific surface area of the catalyst was 570m2G, catalyst particle length 175mm, the ratio of the specific surface area to the particle length being 3.26m2/mm。
Numbered DB 6.
The alkylation reaction conditions in this comparative example were the same as in example 31.
The results of the alkylation reaction are shown in Table 2.
TABLE 2
As can be seen from Table 2, the catalyst having the ratio of the specific volume of the macropores to the specific length and the ratio of the specific surface area to the particle length within the scope of the present invention has better specific surface distribution and pore distribution, and the product has better diffusion performance, so that the catalyst has higher TMP selectivity and lower C in the alkylation reaction of isobutane and butene9+ selectivity, catalyst life is also longer. While the ratio of the specific volume of the macropores to the specific length or the ratio of the specific surface area of the catalyst to the length of the catalyst particles is not in the scope of the present patentDifference, C9The selectivity is higher.
Example 47
This example illustrates an alkylation catalyst having β as the active component and the results of the alkylation reaction.
The process of example 14 was repeated, except that the Y-type molecular sieve was replaced with a beta molecular sieve (China petrochemical catalyst division, 89% relative crystallinity).
The alkylation catalyst prepared was numbered C18, wherein the hydrogenation metals were all platinum and were present at 0.25 wt%.
The alkylation conditions of example 27 were the same, and the results are shown in Table 3.
Example 48
This example illustrates the alkylation catalyst and the alkylation reaction results using MCM-22 as the active component.
The process of example 14 was repeated, except that the Y-type molecular sieve was replaced with MCM-22 (Nankai catalyst works, 86% crystallinity).
The alkylation catalyst prepared was numbered C19, wherein the hydrogenation metals were all platinum and were present at 0.25 wt%.
The alkylation conditions of example 27 were the same, and the results are shown in Table 3.
Example 49
This example illustrates the alkylation catalyst with MOR as the active component and the results of the alkylation reaction.
The process of example 14 was followed except that the Y-type molecular sieve was replaced with MOR zeolite (China petrochemical catalyst division, 117.6% relative crystallinity).
The alkylation catalyst prepared was numbered C20, wherein the hydrogenation metals were all platinum and were present at 0.25 wt%.
The alkylation conditions of example 27 were the same, and the results are shown in Table 3.
TABLE 3
Claims (16)
1. The solid acid catalyst features the specific macro pore volume of 0.30-0.40mL/g, the ratio of the specific macro pore volume to the specific catalyst grain length of 1.0-2.5 mL/(g-mm), and the ratio of the specific surface area to the grain length of 3.40-4.50m2And/mm, the macropores refer to pores with the diameter of more than 50 nm.
2. The catalyst of claim 1, wherein the macropore specific volume is at least 0.35 mL/g.
3. The catalyst of claim 1 wherein the ratio of the macropore specific volume to the catalyst particle specific length is from 1.1 to 1.8 mL/(g-mm).
4. The catalyst of claim 1, wherein said catalyst particles have a specific length of 0.15 to 0.4 mm.
5. The catalyst of claim 4 wherein said catalyst particles have a specific length of 0.18 to 0.36 mm.
6. The catalyst of claim 5 wherein said catalyst particles have a specific length of 0.20 to 0.32 mm.
7. The catalyst of claim 1, wherein the total pore specific volume is at least 0.40 mL/g.
8. The catalyst of claim 7, wherein the total pore specific volume is at least 0.45 mL/g.
9. The catalyst according to claim 1, wherein the specific surface area is not less than 500m2/g。
10. The catalyst of claim 1 wherein said solid acid is a molecular sieve.
11. The catalyst of claim 10 wherein said molecular sieve is selected from one or more of Y-type molecular sieve, beta, MCM-22 and MOR.
12. The catalyst of claim 11, wherein the Y-type molecular sieve has a unit cell size of 2.430 to 2.470 nm.
13. The catalyst of claim 12, wherein the Y-type molecular sieve has a unit cell size of 2.440 to 2.460 nm.
14. The catalyst of claim 1, further comprising a matrix material comprising alumina.
15. The catalyst of claim 14 wherein said matrix material is present in an amount of 2 to 98 wt%.
16. The catalyst of claim 15 wherein said matrix material is present in an amount of 10 to 70 wt%.
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| EP20745843.1A EP3915681A4 (en) | 2019-01-25 | 2020-01-20 | Solid acid catalyst, preparation therefor and use thereof |
| KR1020217027208A KR20210116649A (en) | 2019-01-25 | 2020-01-20 | Solid acid catalyst, preparation method thereof and use thereof |
| PCT/CN2020/073171 WO2020151646A1 (en) | 2019-01-25 | 2020-01-20 | Solid acid catalyst, preparation therefor and use thereof |
| JP2021542428A JP7444894B2 (en) | 2019-01-25 | 2020-01-20 | Solid acid catalyst, its production, and its use |
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| EP0216938A1 (en) * | 1985-03-29 | 1987-04-08 | Catalysts & Chemicals Industries Co., Ltd. | Hydrotreatment catalyst |
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