CN114602550A - C4Alkylation solid acid catalyst, preparation method and application - Google Patents

C4Alkylation solid acid catalyst, preparation method and application Download PDF

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Publication number
CN114602550A
CN114602550A CN202011461858.XA CN202011461858A CN114602550A CN 114602550 A CN114602550 A CN 114602550A CN 202011461858 A CN202011461858 A CN 202011461858A CN 114602550 A CN114602550 A CN 114602550A
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catalyst
solid acid
acid catalyst
acid
inorganic oxide
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崔佳
张永明
雷建龙
裴素鹏
李虹
胡长禄
韩晓琳
李知春
吕雉
张鹏
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Petrochina Co Ltd
Shanghai Jiaotong University
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Petrochina Co Ltd
Shanghai Jiaotong University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
    • B01J31/0227—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
    • B01J35/615—
    • B01J35/617—
    • B01J35/647—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/56—Addition to acyclic hydrocarbons
    • C07C2/58—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds

Abstract

The invention relates to a compound C4The alkylation solid acid catalyst comprises a carrier and perfluorosulfonic acid loaded on the carrier, wherein the carrier is a fluorinated modified hydroxyl-containing porous inorganic oxide, and the fluorinated modified hydroxyl-containing porous inorganic oxide is obtained by performing fluorinated modification on a hydroxyl porous inorganic oxide by using a fluorinated modifier; the catalyst is calculated by taking the mass of the catalyst as 100%, wherein the fluorosulfonic acid carrier content is 5% -60%, and the BET specific surface area of the catalyst is as follows: 10m2/g～1000m2Per g, the aperture is 2 nm-10 μm, and the acid density is 0.15-1.5 mol/g. The invention also relates to a method for preparing the compound C4A preparation method and application of an alkylation solid acid catalyst. The C is4The alkylation solid acid catalyst has high selectivity and good stability, and the preparation is simple and easy for industrial production.

Description

C4Alkylation solid acid catalyst, preparation method and application
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a C4An alkylation solid acid catalyst, a preparation method and application.
Background
The alkylate is an isoparaffin mixture generated by the reaction of isobutane and low-molecular olefin under the action of a strong acid catalyst. At present, the conventional sulfuric acid method and hydrofluoric acid method alkylation processes are mainly adopted for producing the alkylate. Although hydrofluoric acid and sulfuric acid alkylation technologies are well established, their safety and environmental impact motivate the development of safer and more environmentally friendly process technologies. CN107261997A discloses a microreactor, a system and a liquid acid alkylation method for liquid-liquid multiphase reaction, the liquid acid alkylation method comprises the following steps: (a) olefin and isoparaffin are used as raw materials, and liquid acid is used as a catalyst; introducing a continuous phase of liquid acid catalyst into the annular microchannel from the heavy phase inlet and introducing a dispersed phase of olefin and isoparaffin into the inner membrane tube from the light phase inlet; (b) the microemulsion liquid drops passing through the inner membrane tube enter the annular micro-channel to be mixed with the continuous phase, and after alkylation reaction, an alkylation product is output from the product outlet. The anion of the liquid acid comprises any one of or the combination of at least two of triflate, bisulfate or perfluorosulfonate.
In order to overcome the serious defects of high corrosivity and harm to human bodies of liquid strong acid, the existing traditional technology is continuously improved at home and abroad in recent years, and a new generation of solid strong acid is actively developed. The perfluorosulfonic acid resin (PFSA) is a cation exchange resin and is also a solid super acidic resin, and has a wide catalytic action in organic reactions. Compared with a liquid acid catalyst, the perfluorinated sulfonic acid resin has the advantages of no corrosivity, no generation of waste acid liquor, easy product separation, high selectivity, repeated use and the like, and compared with common solid acid, the perfluorinated sulfonic acid resin has the advantages of high yield, mild reaction conditions, high reaction speed and the like; compared with other acidic cation exchange resins, the perfluorinated sulfonic acid resin has the characteristics of stronger acidity, high use temperature and the like. Because the perfluorosulfonic acid is resistant to strong acid and strong base, has good stability and acid strength equivalent to 100 percent concentrated sulfuric acid, and is an ideal solid acid catalyst harmless to the environment. However, the specific surface of pure perfluorosulfonic acid is small, the acid center buried in the fluorocarbon matrix is not easily accessed by the reactant, and meanwhile, if the pure perfluorosulfonic acid is used as the catalyst, the production cost is greatly increased, and the production cost can be reduced by increasing the exposure of the acid site by loading the perfluorosulfonic acid on the porous carrier. The specific surface area of the pure perfluorosulfonic acid resin is very low, and even if the resin is made into porous perfluorosulfonic acid resin, the specific surface area is mostly 10m2On the order of/g, porous perfluorosulfonic acid resin is often low in mechanical strength and prone to collapse.
CN201210347099.3 discloses a strong acid type solid catalyst, its preparation method and application, mesoporous polymer material is mixed with Nafion micro emulsion solution (1-5% Nafion water-alcohol solution, Dupont), reflux reaction is carried out at 50-80 deg.CAnd drying the obtained solid for 2-8 h to obtain the catalyst. The mesoporous polymer material is prepared by introducing an organic polymer precursor into a surfactant self-assembly reaction system through a sol-gel technology, and the specific surface of the mesoporous polymer material is 800-1000 m2The pore diameter is 4-6 nm, and the pore wall is made of phenolic resin.
CN105665018A discloses a preparation method of a composite solid super acidic catalyst, which is characterized in that: preparing SiO by sol-gel method2Loading solid particles of perfluorosulfonic acid resin, and then calcining the solid particles to obtain perfluorosulfonic acid resin/SiO2The composite solid super acidic catalyst is used for preparing ethyl acetate by catalytic reaction.
The alkylation reaction of isobutane with olefins is a complex reaction, and besides the alkylation reaction to produce the desired product 2,2, 4-trimethylpentane, isomerization and polymerization among various olefins can also occur. The polarity of the butene is stronger than that of isobutane, a silicon dioxide/perfluorosulfonic acid composite material is used as an alkylation catalyst, and with the increase of the loading capacity of perfluorosulfonic acid, the specific surface of porous silicon dioxide is rapidly reduced, and the acid active sites are reduced; in addition, the surface polarity of the material is enhanced due to a large number of silicon hydroxyl groups on the surface of the silicon dioxide, and the olefin with stronger polarity is more likely to be in contact with an acid site in the alkylation reaction process, so that the alkane-olefin ratio of the actual reaction on the catalytic active site is smaller than the fed alkane-olefin ratio, the byproducts are increased, the octane number of the product is low, and the utilization efficiency of the catalyst is low, so that the development of the high-selectivity solid acid has important significance.
Disclosure of Invention
Based on the above, the present invention aims to develop a C4The alkylation solid acid catalyst has higher specific surface, higher acid density, weakened adsorption of olefin on the surface of the catalyst, reduced side reaction and higher selectivity.
Therefore, the invention provides a compound C4The alkylation solid acid catalyst comprises a carrier and perfluorosulfonic acid loaded on the carrier, wherein the carrier is a fluorinated modified hydroxyl-containing catalystThe fluorinated modified hydroxyl-containing porous inorganic oxide is obtained by performing fluorinated modification on a hydroxyl porous inorganic oxide by using a fluorinated modifier;
the mass of the catalyst is 100%, wherein the fluorosulfonic acid carrier content is 5% -60%, and preferably 20% -40%;
the BET specific surface area of the catalyst is as follows: 10m2/g～1000m2A/g, preferably of 10m2/g～600m2A/g, more preferably 50m2/g～500m2(ii)/g; the aperture is 2 nm-10 μm, preferably 2 nm-5 μm; the acid density is 0.15 to 1.5 mol/g.
Specifically, the kind of the hydroxyl group-containing porous inorganic oxide is not particularly limited in the present invention, as long as the modification by fluorination, that is, the modification by hydroxyl group-containing porous inorganic oxide satisfies the conditions of specific surface area and pore volume possessed by the catalyst.
Specifically, the invention improves the stability of the catalyst by fluorinating the modified carrier, weakens the adsorption of olefin on the surface of the catalyst and reduces the occurrence of side reactions. The invention can greatly improve the exposure of acid sites and the use temperature by loading the perfluorinated sulfonic acid on the fluorinated modified porous carrier, and is an ideal solid acid catalyst harmless to the environment.
C according to the invention4The alkylation solid acid catalyst, wherein the exchange capacity IEC of the perfluorinated sulfonic acid is preferably 1.0-2.0 mmol/g.
Specifically, the specific surface of the porous material is reduced along with the increase of the loading content of the perfluorosulfonic acid, and meanwhile, the polar hydroxyl on the surface of the porous carrier is easy to cause the selectivity of the catalyst to be poor. In order to overcome the defects, the invention enables the catalyst to have higher specific surface and higher acid density by loading the perfluorosulfonic acid with high exchange capacity.
C according to the invention4Alkylating a solid acid catalyst, wherein preferably the fluorinated modification comprises the steps of: reacting hydroxyl-containing porous inorganic oxide with a fluorinated modifier at the temperature of 30-150 ℃ for 0.1-100h, filtering, washing and drying to obtain the hydroxyl-containing porous inorganic oxide; the addition amount of the fluorinated modifier is the hydroxyl-containing porous inorganic oxygen0.1 to 100% by mass of the compound, and more preferably 5 to 50% by mass of the compound.
C according to the invention4An alkylated solid acid catalyst, wherein preferably the conditions of said fluorination modification are: the temperature is 50-110 ℃, and the time is 1-12 h.
C according to the invention4The catalyst is characterized by comprising an alkylation solid acid catalyst, wherein the modifying agent is preferably one or more of fluorine-containing siloxane, and the fluorination modifying agent is further preferably one or more of perfluorooctyl triethoxysilane, 1H,2H, 2H-perfluoroheptadecatrimethyl oxysilane, perfluorooctyl triethoxysilane, perfluorodecyl triethoxysilane and perfluorodecyl trimethoxysilane.
C according to the invention4The alkylation solid acid catalyst, wherein, preferably, the hydroxyl-containing porous inorganic oxide is hydroxyl-containing porous inorganic oxide with mesopores, further preferably porous silica with mesopores, further preferably the porous silica is selected from one or more of SBA-15, MCM-14, MCM-48 and MCM-50, and most preferably SBA-15.
Therefore, the invention also provides the C4The preparation method of the alkylation solid acid catalyst comprises the following steps:
soaking a carrier of the solid acid catalyst in a perfluorinated sulfonic acid solution, reacting for 0.5-12 h, preferably 3-8 h, at the temperature of 20-100 ℃, and drying to obtain the solid acid catalyst.
C according to the invention4A process for the preparation of an alkylated solid acid catalyst, wherein preferably the drying conditions are: drying for 4-24 h at 50-150 ℃. The acid amount of the porous fluorinated solid acid catalyst can be increased by adopting high-temperature drying.
C according to the invention4The preparation method of the alkylation solid acid catalyst is preferably that the perfluorinated sulfonic acid solution is a perfluorinated sulfonic acid hydroalcoholic solution, wherein the mass content of the perfluorinated sulfonic acid is 1-20%, and more preferably 3-10%.
Therefore, the invention also provides the C4Of alkylated solid acid catalystsThe application comprises the steps of taking the carbon-tetrahydrocarbon and the carbon-tetraolefin as raw materials, adding the raw materials into a fixed bed reactor, wherein the molar charge ratio of the carbon-tetrahydrocarbon to the carbon-tetraolefin is 10: 1-100: 1, preferably 20: 1-80: 1, the reaction temperature is 40-100 ℃, preferably 60-95 ℃, and C is used4The catalytic reaction of the alkylated solid acid catalyst is carried out at an airspeed of 0.1-5 h-1Preferably 0.5 to 1.5 hours-1And obtaining an alkylation reaction product.
C according to the invention4The application of the alkylation solid acid catalyst is characterized in that the preferable carbon tetraene is one or more of 1-butene and isomers thereof, 2-butene and isomers thereof.
C according to the invention4Use of an alkylated solid acid catalyst, wherein preferably the fixed bed reactor is a tubular fixed bed reactor.
C provided by the invention4The preparation method of the alkylation solid acid catalyst specifically comprises the following steps:
(1) reacting the hydroxyl-containing porous inorganic oxide with a fluorination modifier at the temperature of 30-150 ℃ for 0.1-100h, preferably at the temperature of 50-90 ℃ for 1-12 h, filtering, washing and drying to obtain a fluorination modified hydroxyl-containing porous inorganic oxide carrier; wherein the addition amount of the fluorinated modifier is 0.1-100% of the addition amount of the hydroxyl-containing porous inorganic oxide, and more preferably 5-50%;
2) and (2) soaking the carrier obtained in the step (1) in a perfluorinated sulfonic acid solution for 0.5-12 h, preferably 3-8 h, and drying to obtain the porous fluorinated solid acid catalyst.
In summary, the invention has the following advantages:
(1) the invention enables the catalyst to have higher specific surface and higher acid density by loading the perfluorosulfonic acid with high exchange capacity.
(2) The fluorinated modified porous catalyst has good stability, and the problem that the acid strength of the catalyst is weakened because the surface of the catalyst contains a large number of hydroxyl groups is avoided.
(3) The invention reduces the adsorption of olefin on the surface of the catalyst by modifying the surface of the catalyst through fluorination, thereby reducing the occurrence of side reactions and improving the octane number of the product.
(4) The invention has simple process and is easy for industrialized production.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
C provided by the invention4The alkylation solid acid catalyst comprises a carrier and perfluorosulfonic acid loaded on the carrier, wherein the carrier is a fluorinated modified hydroxyl-containing porous inorganic oxide, and the fluorinated modified hydroxyl-containing porous inorganic oxide is obtained by performing fluorinated modification on a hydroxyl porous inorganic oxide by using a fluorinated modifier;
the mass of the catalyst is 100%, wherein the fluorosulfonic acid carrier content is 5% -60%, and preferably 20% -40%;
the BET specific surface area of the catalyst is as follows: 10m2/g～1000m2A/g, preferably of 10m2/g～600m2A/g, more preferably 50m2/g～500m2(ii)/g; the aperture is 2 nm-10 μm, preferably 2 nm-5 μm; the acid density is 0.15 to 1.5 mol/g.
Specifically, the kind of the hydroxyl group-containing porous inorganic oxide is not particularly limited in the present invention, as long as the modification by fluorination, that is, the modification by hydroxyl group-containing porous inorganic oxide satisfies the conditions of specific surface area and pore volume possessed by the catalyst.
Specifically, the invention improves the stability of the catalyst by fluorinating the modified carrier, weakens the adsorption of olefin on the surface of the catalyst and reduces the occurrence of side reactions. The invention can greatly improve the exposure of acid sites and the use temperature by loading the perfluorinated sulfonic acid on the fluorinated modified porous carrier, and is an ideal solid acid catalyst harmless to the environment.
In some embodiments, it is preferred that the exchange capacity IEC of the perfluorosulfonic acid is 1.0 to 2.0 mmol/g.
Specifically, the specific surface of the porous material is reduced along with the increase of the loading content of the perfluorosulfonic acid, and meanwhile, the polar hydroxyl on the surface of the porous carrier is easy to cause the selectivity of the catalyst to be poor. In order to overcome the defects, the invention enables the catalyst to have higher specific surface and higher acid density by loading the perfluorosulfonic acid with high exchange capacity.
In some embodiments, it is preferred that the fluorinated modification comprises the steps of: reacting hydroxyl-containing porous inorganic oxide with a fluorinated modifier at the temperature of 30-150 ℃ for 0.1-100h, filtering, washing and drying to obtain the hydroxyl-containing porous inorganic oxide; the addition amount of the fluorinated modifier is 0.1-100% of the mass of the hydroxyl-containing porous inorganic oxide, and the preferable amount is 5-50%.
In some embodiments, it is preferred that the conditions of the fluorination modification are: the temperature is 50-110 ℃, and the time is 1-12 h.
In some embodiments, it is preferable that the modifying agent is one or more of fluorine-containing siloxane, and the fluorinated modifying agent is further preferably one or more of perfluorooctyltriethoxysilane, 1H,2H, 2H-perfluoroheptadecyltrimethyloxysilane, perfluorooctyltriethoxysilane, perfluorodecyltriethoxysilane, and perfluorodecyltrimethoxysilane.
In some embodiments, it is preferable that the hydroxyl group-containing porous inorganic oxide is a hydroxyl group-containing porous inorganic oxide having mesopores, further preferably a porous silica having mesopores, further preferably the porous silica is selected from one or more of SBA-15, MCM-14, MCM-48, and MCM-50, and most preferably SBA-15.
The present invention provides the above-mentioned C4The preparation method of the alkylation solid acid catalyst comprises the following steps:
soaking a carrier of the solid acid catalyst in a perfluorinated sulfonic acid solution, reacting for 0.5-12 h, preferably 3-8 h, at the temperature of 20-100 ℃, and drying to obtain the solid acid catalyst.
In some embodiments, it is preferred that the drying conditions are: drying for 4-24 h at 50-150 ℃. The acid amount of the porous fluorinated solid acid catalyst can be increased by adopting high-temperature drying.
In some embodiments, it is preferable that the perfluorosulfonic acid solution is a perfluorosulfonic acid hydroalcoholic solution, wherein the mass content of the perfluorosulfonic acid is 1 to 20%, and more preferably 3 to 10%.
The present invention provides the above-mentioned C4The application of the alkylation solid acid catalyst is characterized in that a carbon-tetra-hydrocarbon and a carbon-tetra-olefin are used as raw materials and are added into a fixed bed reactor, the molar charge ratio of the carbon-tetra-hydrocarbon to the carbon-tetra-olefin is 10: 1-100: 1, preferably 20: 1-80: 1, the reaction temperature is 40-100 ℃, preferably 60-95 ℃, and C is used4The catalytic reaction of the alkylated solid acid catalyst is carried out at an airspeed of 0.1-5 h-1Preferably 0.5 to 1.5 hours-1And obtaining an alkylation reaction product.
In some embodiments, it is preferred that the tetracarbon is one or more of 1-butene and its isomers, 2-butene and its isomers.
In some embodiments, it is preferred that the fixed bed reactor is a tubular fixed bed reactor.
Example 1:
(1) 20g of a material having a pore diameter of 5nm and a BET specific surface area of 628m2Each g of SBA-15 silica was mixed with 30g of perfluorooctyltriethoxysilane at 80 ℃ and 500rpm for 10 hours, filtered, and dried at 90 ℃ for 2 hours to give 22.6g of a fluorinated modified SBA-15 porous support. (since part of the sulfonic acid group may be buried if the sulfonic acid is carried before the modification, the present invention requires the modification before the carrying)
(2) Pouring the porous carrier obtained in the step (1) into 60ml of perfluorinated sulfonic acid (exchange capacity is 2.0mmol/g) solution with the mass fraction of 5% at normal temperature, soaking for 1h, filtering, drying at 110 ℃ for 1h to obtain a catalyst with a certain load, and repeating the steps for three times to obtain the high-selectivity C with the load of 5.6%423.9g of an alkylated solid acid catalyst having a BET specific surface area of 560m2Per g, pore diameter 4.5nm, acid density: 0.112 mmol/g.
(3) Filling the catalyst obtained in the step (2) into a tubular fixed bed reactor, wherein isobutane and 1-butene are mixed according to a molar ratio of 20:1,2Mpa, at 65 ℃ and a flow rate of 20ml/h, through a fixed bed reactor, with a space velocity of 0.6h-1. The conversion rate of butene is 100 percent, and the selectivity of trimethylpentane is 80 percent.
Comparative example 1:
(1) 20g of a material with a pore diameter of 5nm and a BET specific surface area of 628m at normal temperature2Soaking SBA-15 silicon oxide of/g and perfluorosulfonic acid (exchange capacity is 2.0mmol/g) solution of 60ml with the mass fraction of 5% for 1h, filtering, drying at 110 ℃ for 1h to obtain catalyst with certain loading capacity, and repeating the steps for three times to obtain C with the loading capacity of 5.7%421.2g of an alkylated solid acid catalyst having a BET specific surface area of 540m2Per g, pore diameter 4.2nm, acid density: 0.114 mmol/g.
(2) Filling the catalyst obtained in the step (1) in a tubular fixed bed reactor, and enabling isobutane and 1-butene to pass through the fixed bed reactor at a molar ratio of 20:1 and 2Mpa at 65 ℃ and a flow rate of 20ml/h, wherein the space velocity is 0.6h-1. The conversion rate of butene is 85 percent, and the selectivity of trimethylpentane is 72 percent.
Comparative example 2:
(1) 20g of a material having a pore diameter of 5nm and a BET specific surface area of 628m2Stirring SBA-15 silica and 30g perfluorooctyltriethoxysilane at 80 deg.C and 500rpm for 10h, filtering, and drying at 90 deg.C for 2h to obtain 22.5g of fluorinated modified SBA-15 porous carrier.
(2) Pouring the porous carrier obtained in the step (1) into 60ml of sulfonated graphene (exchange capacity is 4.3mmol/g) solution with the mass fraction of 10% at normal temperature, soaking for 1h, filtering, drying at 110 ℃ for 1h to obtain a catalyst with a certain load, and repeating the steps for three times to obtain the high-selectivity C with the load of 1.6%422.83g of an alkylated solid acid catalyst having a BET specific surface area of 523m2Per g, pore diameter 4.2nm, acid density: 0.688 mmol/g.
(3) Filling the catalyst obtained in the step (2) into a tubular fixed bed reactor, and enabling isobutane and 1-butene to pass through the fixed bed reactor at a molar ratio of 20:1 and 2Mpa at 65 ℃ and a flow rate of 20ml/h, wherein the space velocity is 0.6h-1. Butene conversion 33% and trimethylpentane selectivity 27%.
The use of a one-fold lower perfluorosulfonic acid exchange capacity in this comparative example means that more perfluorosulfonic acid is required to be loaded to achieve the same acid density, with the result that the pores of the support become embedded and the acid site exposure itself is reduced.
Comparative example 3:
(1) 20g of a material with a pore diameter of 5nm and a BET specific surface area of 628m at normal temperature2Adding SBA-15 silicon oxide per gram into 60ml of perfluorinated sulfonic acid (exchange capacity is 2.0mmol/g) solution with the mass fraction of 5%, soaking for 1h, filtering, drying at 110 ℃ for 1h to obtain a certain load of catalyst, and repeating the steps for three times to obtain the high-selectivity C with the load of 5.7%421.14g of an alkylated solid acid catalyst having a BET specific surface area of 580m2G, pore diameter of 4.9nm, acid density: 0.114 mmol/g.
(2) And (2) stirring the catalyst obtained in the step (1) and 30g of perfluorooctyltriethoxysilane at 80 ℃ and 500rpm for 10h, filtering, and drying at 90 ℃ for 2h to obtain 21.9g of the fluorinated modified SBA-15 porous carrier.
(3) Filling the catalyst obtained in the step (2) into a tubular fixed bed reactor, wherein isobutane and 1-butene pass through the fixed bed reactor at the molar ratio of 20:1 and 2Mpa at 65 ℃ and the flow rate of 20ml/h, and the space velocity is 0.6h-1. The conversion of butene was 65% and the selectivity of trimethylpentane was 56%.
Comparative example 4:
the conditions of example 1 were used, with different concentrations of perfluorosulfonic acid solution
(1) 20g of a material having a pore diameter of 5nm and a BET specific surface area of 628m2Each g of SBA-15 silica was mixed with 30g of perfluorooctyltriethoxysilane at 80 ℃ and 500rpm for 10 hours, filtered, and dried at 90 ℃ for 2 hours to give 22.6g of a fluorinated modified SBA-15 porous support.
(2) Pouring the porous carrier obtained in the step (1) into 60ml of perfluorinated sulfonic acid (exchange capacity is 2.0mmol/g) solution with the mass fraction of 20% to soak for 1h at normal temperature, filtering, drying for 1h at 110 ℃ to obtain a catalyst with a certain load, and repeating the steps for three times to obtain C with the load of 22%423.9g of an alkylated solid acid catalyst having a BET specific surface area of 120m2G, pore diameter of 3.5nm, acid density: 0.440 mmol/g.
(3) Filling the catalyst obtained in the step (2) in a tubular shape for fixingA bed reactor, wherein isobutane and 1-butene pass through the fixed bed reactor at a molar ratio of 20:1 and 2Mpa at 65 ℃ and a flow rate of 20ml/h, and the space velocity is 0.6h-1. The conversion rate of butene is 92 percent, and the selectivity of trimethylpentane is 70 percent.
Example 2:
(1) 20g of a material having a pore diameter of 48nm and a BET specific surface area of 100m2Per g of the porous silica material and 30g of perfluorooctyltriethoxysilane were stirred at 500rpm for 10 hours at 80 ℃ and filtered, and dried at 90 ℃ for 2 hours to obtain 20.6g of a fluorinated modified porous silica support.
(2) Pouring the porous carrier obtained in the step (1) into 60ml of perfluorinated sulfonic acid (exchange capacity is 2.0mmol/g) solution with the mass fraction of 10% at 25 ℃, soaking for 1h, filtering, performing heat treatment at 110 ℃ and drying for 1h to obtain a catalyst with a certain load, and repeating the steps for four times to obtain the high-selectivity C with the load of about 57.1%448.02g of an alkylated solid acid catalyst having a BET specific surface area of 70m2Per g, pore diameter 23nm, acid density: 1.14 mmol/g.
(3) Filling the catalyst obtained in the step (2) into a tubular fixed bed reactor, and enabling isobutane and 1-butene to pass through the solid fixed bed reactor at a molar ratio of 90:1 and 2Mpa at 70 ℃ and at a flow rate of 40ml/h, wherein the space velocity is 1.1h-1. The conversion rate of butene is 99.8 percent, and the selectivity of trimethylpentane is 87.3 percent.
Comparative example 5:
the conditions of example 2 were used, but with different perfluorosulfonic acid loadings
(1) 20g of a material having a pore diameter of 48nm and a BET specific surface area of 100m2The preparation method comprises the steps of mixing the silicon oxide porous material SBA-15 per gram with 30g of perfluorooctyl triethoxysilane at 80 ℃ and 500rpm for 10 hours, filtering, and carrying out heat treatment at 90 ℃ for 2 hours to obtain 20.7g of the fluorinated modified porous silicon oxide carrier.
(2) Pouring the porous carrier obtained in the step (1) into 60ml of perfluorinated sulfonic acid (exchange capacity is 1.0mmol/g) solution with the mass fraction of 10% at the temperature of 25 ℃, soaking for 1h, filtering, carrying out heat treatment at the temperature of 110 ℃ for 1h to obtain a catalyst with a certain load, and repeating the process for four times to obtain C with the load of 63.2%456.25g of an alkylated solid acid catalyst having a BET specific surface area of 67m2G, pore diameter of 25nm, acid density: 0.632 mmol/g.
(3) The obtained catalyst is filled in a tubular fixed bed reactor, isobutane and 1-butene pass through the solid fixed bed reactor at the molar ratio of 90:1 and 2Mpa at the temperature of 70 ℃ and the flow rate of 40ml/h, and the reaction space velocity is 1.1h-1. Butene conversion 71% and trimethylpentane selectivity 46.7%.
Example 3:
(1) 20g of a material having a pore diameter of 21nm and a BET specific surface area of 345m2SBA-12/g and perfluorooctyltriethoxysilane 30g, stirring at 500rpm for 10h at 80 deg.C, filtering, and heat treating at 90 deg.C for 2h to obtain 21.6g of fluorinated modified porous silica support.
(2) Pouring the porous carrier obtained in the step (1) into 60ml of perfluorinated sulfonic acid (exchange capacity is 2.0mmol/g) solution with the mass fraction of 10% at the temperature of 25 ℃, soaking for 1h, filtering, carrying out heat treatment at the temperature of 110 ℃ for 1h to obtain a catalyst with a certain load, and repeating the steps for 2 times to obtain the high-selectivity C with the load of about 21.1%427.37g of an alkylated solid acid catalyst having a BET specific surface area of 280m2G, pore diameter of 18nm, acid density of 0.42 mmol/g.
(3) Filling the catalyst obtained in the step (2) into a tubular fixed bed reactor, and enabling isobutane and 1-butene to pass through a solid fixed bed reactor at a molar ratio of 85:1 and 2Mpa at 75 ℃ and at a flow rate of 30ml/h, wherein the space velocity is 0.6-1. The conversion rate of butene is 99.2 percent, and the selectivity of trimethylpentane is 77.2 percent.
Example 4:
(1) 20g of a material having a pore diameter of 21nm and a BET specific surface area of 345m2SBA-12/g and perfluorooctyltriethoxysilane 30g, stirring at 500rpm for 10h at 80 deg.C, filtering, and heat treating at 90 deg.C for 2h to obtain 21.7g of fluorinated modified porous silica support.
(2) Pouring the porous carrier obtained in the step (1) into 60ml of perfluorinated sulfonic acid (exchange capacity is 2.0mmol/g) solution with the mass fraction of 10% at the temperature of 25 ℃, soaking for 1h, filtering, carrying out heat treatment at the temperature of 110 ℃ for 1h to obtain a catalyst with a certain load, and repeating the steps for 2 times to obtain high-selectivity C with the load of about 42.7%437.87g of alkylated solid acid catalyst, BET specific surface area 220m2G, pore diameter of 12nm, acid density of 0.85 mmol/g.
(3) Filling the catalyst obtained in the step (2) into a tubular fixed bed reactor, and enabling isobutane and 2-butene to pass through a solid fixed bed reactor at a molar ratio of 90:1 and 2Mpa at 80 ℃ and at a flow rate of 80ml/h, wherein the reverse space velocity is 1.0h-1. And 3 h. The conversion rate of butene is 100 percent, and the selectivity of trimethylpentane is 81.3 percent.
Example 5:
(1) 20g of a material having a pore diameter of 9nm and a BET specific surface area of 525m2The fluorine modified porous silica carrier 22.1g is obtained by stirring 30g of perfluorooctyl triethoxysilane and MCM-48 porous material per g at 80 ℃ and 500rpm for 10h, filtering and carrying out heat treatment at 90 ℃ for 2 h.
(2) Then pouring the porous carrier obtained in the step (1) into 60ml of perfluorinated sulfonic acid (exchange capacity is 1.5mmol/g) solution with the mass fraction of 10%, soaking for 1h, filtering, carrying out heat treatment at 110 ℃ for 1h to obtain a catalyst with a certain load, and repeating the steps for 3 times to obtain high-selectivity C with the load of about 36.4%434.75g of alkylated solid acid catalyst with BET specific surface area of 369m2(iv)/g, pore size 6nm, acid density; 0.546 mmol/g.
(3) Filling the catalyst obtained in the step (2) into a tubular fixed bed reactor, and enabling a mixture of isobutane and butene (wherein the molar ratio of 1-butene to 2-butene is 1:3) to pass through a solid fixed bed reactor at a molar ratio of 85:1 and 2Mpa at 70 ℃ according to a flow rate of 4ml/h, wherein the space velocity is 0.7h-1. The conversion rate of butene is 100 percent, and the selectivity of trimethylpentane is 80.4 percent.
Example 6:
(1) 20g of a mixture having a pore diameter of 6nm and a BET specific surface area of 420m2The fluorinated modified porous silica carrier 22.9g was obtained by stirring 30g of perfluorodecyltrimethoxysilane per g of MCM-14 porous material at 80 ℃ and 500rpm for 10 hours, filtering, and heat treating at 90 ℃ for 2 hours.
(2) Then pouring the porous carrier obtained in the step (1) into 60ml of perfluorinated sulfonic acid (exchange capacity is 1.5mmol/g) solution with the mass fraction of 10%, soaking for 1h, filtering, carrying out heat treatment at 110 ℃ for 1h to obtain a catalyst with a certain load, and repeating the steps for 3 times to obtain high-selectivity C with the load of about 30.4%432.65g of alkylated solid acid catalyst with a BET specific surface area of 340m2Per g, pore size 4nm, acid density;0.450mmol/g。
(3) filling the catalyst obtained in the step (2) into a tubular fixed bed reactor, and enabling a mixture of isobutane and butene (wherein the molar ratio of 1-butene to 2-butene is 1:3) to pass through a solid fixed bed reactor at a molar ratio of 85:1 and 2Mpa at 70 ℃ according to a flow rate of 4ml/h, wherein the space velocity is 0.7h-1. The conversion rate of butene is 100 percent, and the selectivity of trimethylpentane is 82.3 percent.
Example 7:
(1) 10g of a material having a pore diameter of 5nm and a BET specific surface area of 628m2SBA-15/g, 10g pore size 6nm, BET specific surface 420m2Per g of MCM-14 porous material, with 15g of perfluorooctyltriethoxysilane, 15g of perfluorodecyltrimethoxysilane and 15g of perfluorodecyltriethylsilane, stirred at 150 ℃ for 0.1 hour at 500rpm, filtered, and heat-treated at 90 ℃ for 2 hours to give 23.8g of a fluorinated modified porous silica support.
(2) Then pouring the porous carrier obtained in the step (1) into 60ml of perfluorinated sulfonic acid (exchange capacity is 1.2mmol/g) solution with the mass fraction of 10%, soaking for 1h, filtering, carrying out heat treatment at 120 ℃ for 4h to obtain a catalyst with a certain load, and repeating the steps for 3 times to obtain high-selectivity C with the load of about 50.1%447.70g of alkylated solid acid catalyst, the BET specific surface area of the mixture was 480m2G, pore diameter of 4.1nm, acid density of 0.6 mmol/g.
(3) Filling the catalyst obtained in the step (2) into a tubular fixed bed reactor, and enabling a mixture of isobutane and butene (wherein the molar ratio of 1-butene to 2-butene is 1:3) to pass through a solid fixed bed reactor at a molar ratio of 70:1 and 2Mpa at 85 ℃ and at a flow rate of 4ml/h, wherein the space velocity is 1.3h-1. The conversion rate of butene is 100 percent, and the selectivity of trimethylpentane is 81.8 percent.
Example 8:
(1) 10g of a material having a pore diameter of 5nm and a BET specific surface area of 628m2SBA-15/g, 10g pore size 6nm, BET specific surface 420m210g MCM-14/g with a pore diameter of 9nm and a BET specific surface of 525m2The fluorine modified porous silica carrier 32.6g is obtained by stirring 10g of perfluorooctyltriethoxysilane, 30g of 1H,1H,2H, 2H-perfluoroheptadecatrimethylsiloxysilane at 50 ℃ and 500rpm for 20H, filtering, and performing heat treatment at 90 ℃ for 2H.
(2) Then pouring the porous carrier obtained in the step (1) into 60ml of perfluorinated sulfonic acid (exchange capacity is 1.2mmol/g) solution with the mass fraction of 20%, soaking for 1h, filtering, carrying out heat treatment at 150 ℃ for 4h to obtain a catalyst with a certain load, and repeating the steps for 3 times to obtain high-selectivity C with the load of about 21%437.6g of an alkylated solid acid catalyst having a BET specific surface area of 513m2Per g, pore diameter of 6.3nm, acid density; 0.252 mmol/g.
(3) Filling the catalyst obtained in the step (2) into a tubular fixed bed reactor, and enabling a mixture of isobutane and butene (wherein the molar ratio of 1-butene to 2-butene is 1:3) to pass through a solid fixed bed reactor at 70 ℃ and 4ml/h of flow rate according to a molar ratio of 70:1 and 2Mpa, wherein the space velocity is 0.7h-1. The conversion of butene was 100% and the selectivity of trimethylpentane was 79.3%.
Example 9:
(1) 10g of a material having a pore diameter of 5nm and a BET specific surface area of 628m2SBA-15/g, 10g pore size 6nm, BET specific surface 420m210g MCM-14/g with a pore diameter of 9nm and a BET specific surface of 525m2The fluorinated modified porous silica carrier 33.1g was prepared by mixing 10g of perfluorooctyltriethoxysilane, 30g of 1H,1H,2H, 2H-perfluoroheptadecatrimethylsiloxysilane at 90 ℃ and 500rpm for 2 hours, filtering, and heat treating at 90 ℃ for 2 hours.
(2) Then pouring the porous carrier obtained in the step (1) into 60ml of perfluorinated sulfonic acid (exchange capacity is 1.2mmol/g) solution with the mass fraction of 10%, soaking for 1h, filtering, carrying out heat treatment at 150 ℃ for 4h to obtain a catalyst with a certain load, and repeating the steps for 3 times to obtain high-selectivity C with the load of about 16%439.4g of an alkylated solid acid catalyst having a BET specific surface area of 563m2G, pore diameter of 6.4nm, acid density of 0.192 mmol/g.
(3) Filling the catalyst obtained in the step (2) into a tubular fixed bed reactor, and enabling a mixture of isobutane and butene (wherein the molar ratio of 1-butene to 2-butene is 1:3) to pass through a solid fixed bed reactor at 70 ℃ and a molar ratio of 70:1 and 2Mpa at a flow rate of 5ml/h and a space velocity of 1.1h-1. The conversion rate of butene is 100 percent, and the selectivity of trimethylpentane is 82.4 percent.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.

Claims (12)

1. C4An alkylated solid acid catalyst characterized by: the carrier is a fluorinated modified hydroxyl-containing porous inorganic oxide, and the fluorinated modified hydroxyl-containing porous inorganic oxide is obtained by performing fluorination modification on a hydroxyl porous inorganic oxide by using a fluorination modifier;
the mass of the catalyst is 100%, wherein the fluorosulfonic acid carrier content is 5% -60%, and preferably 20% -40%;
the BET specific surface area of the catalyst is as follows: 10m2/g～1000m2A/g, preferably of 10m2/g～600m2A/g, more preferably 50m2/g～500m2(ii)/g; the aperture is 2 nm-10 μm, preferably 2 nm-5 μm; the acid density is 0.15 to 1.5 mol/g.
2. C according to claim 14The alkylation solid acid catalyst is characterized in that the exchange capacity IEC of the perfluorosulfonic acid is 1.0-2.0 mmol/g.
3. C according to claim 14An alkylated solid acid catalyst characterized in that said fluorinated modification comprises the steps of: reacting hydroxyl-containing porous inorganic oxide with a fluorinated modifier at the temperature of 30-150 ℃ for 0.1-100h, filtering, washing and drying to obtain the hydroxyl-containing porous inorganic oxide; the addition amount of the fluorinated modifier is 0.1-100% of the mass of the hydroxyl-containing porous inorganic oxide, and preferably 5-50%.
4. C according to claim 34An alkylated solid acid catalyst characterized in that said fluorination modification conditions are: the temperature is 50-110 ℃, and the time is 1-12 h.
5. C according to claim 14The alkylated solid acid catalyst is characterized in that the modifier is one or more of fluorine-containing siloxane, and the fluorinated modifier is preferably one or more of perfluorooctyl triethoxysilane, 1H,2H, 2H-perfluoroheptadecyltrimethyloxysilane, perfluorooctyl triethoxysilane, perfluorodecyl triethoxysilane and perfluorodecyl trimethoxysilane.
6. The C4 alkylated solid acid catalyst according to claim 1, wherein the hydroxyl-containing porous inorganic oxide is hydroxyl-containing porous inorganic oxide having mesopores, preferably porous silica having mesopores, more preferably the porous silica is selected from one or more of SBA-15, MCM-14, MCM-48, MCM-50.
7. C according to claim 14The preparation method of the alkylation solid acid catalyst is characterized by comprising the following steps:
soaking a carrier of the solid acid catalyst in a perfluorinated sulfonic acid solution, reacting for 0.5-12 h, preferably 3-8 h, at the temperature of 20-100 ℃, and drying to obtain the solid acid catalyst.
8. C according to claim 74A process for the preparation of an alkylated solid acid catalyst, characterized in that the drying conditions are: drying for 4-24 h at 50-150 ℃.
9. C according to claim 74The preparation method of the alkylation solid acid catalyst is characterized in that the perfluorinated sulfonic acid solution is a perfluorinated sulfonic acid hydroalcoholic solution, wherein the mass content of the perfluorinated sulfonic acid is 1-20%, and preferably 3-10%.
10. C according to claim 14Use of an alkylated solid acid catalyst, characterized in that a carbotetracarbon and a carbotetraolefin are used as starting materials and are added toIn a fixed bed reactor, C is used under the conditions that the molar charge ratio of the carbon tetracarbon to the carbon tetraolefin is 10: 1-100: 1, preferably 20: 1-80: 1, the reaction temperature is 40-100 ℃, preferably 60-95 DEG C4The catalytic reaction of the alkylated solid acid catalyst is carried out at an airspeed of 0.1-5 h-1Preferably 0.5 to 1.5 hours-1And obtaining an alkylation reaction product.
11. The C of claim 104The application of the alkylation solid acid catalyst is characterized in that the carbon tetraene is one or more of 1-butene and isomers thereof, 2-butene and isomers thereof.
12. The porous fluorinated solid acid catalyst of claim 10 at C4The application of alkylation reaction is characterized in that the fixed bed reactor is a tubular fixed bed reactor.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5824622A (en) * 1994-01-12 1998-10-20 E. I. Du Pont De Nemours And Company Porous microcomposite of perfluorinated ion-exchange polymer and metal oxide, a network of silica, or a network of metal oxide and silica derived via a sol-gel process

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5824622A (en) * 1994-01-12 1998-10-20 E. I. Du Pont De Nemours And Company Porous microcomposite of perfluorinated ion-exchange polymer and metal oxide, a network of silica, or a network of metal oxide and silica derived via a sol-gel process

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
WEI SHEN等: "Alkylation of isobutane/1-butene on methyl-modified Nafion/SBA-15 materials", APPLIED CATALYSIS A: GENERAL, pages 1 - 8 *
郭庆中等: "氟烷基改性的二氧化硅纳米球的制备与应用研究", 有机硅材料, pages 238 - 241 *

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