CN111217661B - Method for preparing isooctane by isobutene superposition-hydrogenation - Google Patents
Method for preparing isooctane by isobutene superposition-hydrogenation Download PDFInfo
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- CN111217661B CN111217661B CN201811425246.8A CN201811425246A CN111217661B CN 111217661 B CN111217661 B CN 111217661B CN 201811425246 A CN201811425246 A CN 201811425246A CN 111217661 B CN111217661 B CN 111217661B
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- 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
- C07C2/74—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition with simultaneous hydrogenation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
Abstract
The invention relates to a method for preparing isooctane by isobutene polymerization-hydrogenation, which comprises the steps of contacting hydrogen and a raw material containing isobutene with a polymerization-hydrogenation bifunctional solid acid catalyst in a reactor to generate polymerization-hydrogenation reaction; wherein the folding-hydrogenating bifunctional solid acid catalyst comprises an inert or acidic carrier, a hydrogenation active component and an acidic component. The method can effectively simplify the existing process for preparing isooctane from isobutene, has the advantages of simple process, long service life of the catalyst, high isobutene conversion rate and high isooctane selectivity, and can obviously reduce the production cost in the process of preparing isooctane from isobutene.
Description
Technical Field
The invention belongs to the technical field of isooctane preparation, and particularly relates to a method for preparing isooctane by isobutene superposition-hydrogenation.
Background
Under the great trend of global forbidden methyl tert-butyl ether (MTBE) as a high-octane additive of gasoline, a plurality of devices for producing MTBE face the problem of modification, as the raw materials are isobutene, the processes are similar, and the most common and low-cost method is to perform indirect alkylation process modification on the MTBE device, and the isobutene is subjected to two procedures of dimerization and hydrogenation to produce isooctane. IsobuteneThe dimerization reaction of (2) belongs to oligomerization reaction of low-carbon olefin, also called as polymerization reaction. The mature indirect alkylation technology mainly comprises Inalk process of UOP, CDIsoether process developed by combining Snamprogetti with CDTECH, NExOCTANE process developed by combining Fortum and KBR, and Alkylate100 developed by combining Lyondell and Kvaerner SM The process, the Polynaphtha Selecttopol process of IFP and the OilHyd process of China Shanghai petrochemical institute of petrochemical engineering. The processes all use a two-step method to produce isooctane, wherein the first step is a reaction for preparing isooctene by isobutene superposition, a catalyst is sulfonic acid resin, solid phosphoric acid, a large-pore molecular sieve or a silicon-aluminum composite oxide, the second step is a reaction for preparing isooctane by hydrogenation saturation of isooctene, and the catalyst is Al 2 O 3 Or SiO 2 A hydrogenation catalyst of supported noble metal Pd, pt or non-noble metal Ni.
The following is a detailed description of the state of the art with respect to the related art reported in the patent, and is not limited to the respective mature technologies described above.
US8188327B reports the preparation of isooctenes and isooctanes from a carbon-four feed from FCC, ethylene cracking or dehydrogenation process via three reactors, a rectification column and a multi-stage catalyst bed. The material is washed to remove alkaline compounds, and then is put into a first reactor, wherein the first reactor is divided into an upper section and a lower section of catalyst bed layers, the upper section is a section for catalyzing butadiene by a Pd-doped resin catalyst to be selectively hydrogenated and removed, the lower section is a section for catalyzing a part of isobutene to be superposed to prepare isooctene by a sulfonic acid resin catalyst and catalyzing a part of propylene to react with water to generate isopropanol, after the isooctene is separated from the material at the outlet of the first reactor through the bottom of a rectifying tower, the material at the top of the rectifying tower is put into a second reactor, the second reactor is a section for catalyzing unreacted isobutene in the first reactor to be superposed to prepare isooctene by the sulfonic acid resin catalyst, the material at the outlet of the second reactor is also led into the rectifying tower, the isooctene is separated from the tower bottom, then, a part or all of the isooctene is led into a third reactor, and the third reactor is a section for preparing isooctene by hydrogenation and saturation under the catalysis of noble metal Pd or Pt. Wherein, isopropanol is used for improving the selectivity of the catalyst to dimer isooctene, and other carbon-four materials which do not participate in the reaction are used for diluting isobutene, thereby increasing the heat removal effect and improving the selectivity of isooctene. The butadiene selective hydrogenation catalyst bed is used for protecting the lower sulfonic acid resin polymerization catalyst, and the service life of the polymerization catalyst is prolonged by reducing coking.
U.S. Pat. No. 7556728B reports a technology for preparing isooctane by hydrogenation saturation of a carbon octaolefin mixture generated by polymerization of low carbon olefins catalyzed by acidic ion exchange resin under catalysis of an alumina-supported Pt catalyst.
U.S. Pat. No. 4,4324646A reports a technology for preparing isooctane by catalytic hydrogenation of mixed carbon tetraolefin with a Pd catalyst supported on alumina after catalytic polymerization with a silica-alumina composite oxide.
US2005080305A reports the technological process of preparing isooctane with isobutene successively through superposing reaction, adsorption desulfurizing reaction and hydrogenating reaction, the catalyst for the superposing reaction is acid sulfonic acid resin, the adsorbing desulfurizing agent is macroporous molecular sieve, and the hydrogenating catalyst is Ni/SiO 2 A catalyst.
U.S. Pat. No. 5,252,252,252 reports a technique for preparing isooctane from isobutane by three reactors, namely dehydrogenation, superposition and hydrogenation, wherein a solid phosphoric acid catalyst is filled in a superposition reactor, and an alumina-loaded Co-Mo or Ni-Mo catalyst is filled in a hydrogenation reactor.
US6274783B reports a technology for preparing isooctane from isobutylene in a catalytic distillation column through a single reactor of a polymerization reaction and a hydrogenation reaction, in the catalytic distillation column, a polymerization catalyst and a hydrogenation catalyst can be alternately filled in two or more layers or can be mixed, the polymerization catalyst is an acidic cation exchange resin or a molecular sieve, and the hydrogenation catalyst is alumina or a group VIII metal loaded on a carbon material.
U.S. patent No. 2007123743A reports a technology for preparing isooctane by carrying out a polymerization reaction and a hydrogenation reaction on isobutene in a single reactor in a catalytic rectification tower, wherein the catalytic rectification tower is divided into an upper bed layer and a lower bed layer, and the upper layer is filled with NiSO which is uniformly mixed and has a volume ratio of 1 4 /γ-Al 2 O 3 Catalyst and Intalox saddle-shaped filler are superposed, and Pd/gamma-Al is filled in the lower layer 2 O 3 Hydrogenation catalyst by a catalystThe chemical rectifying tower realizes the polymerization reaction of isobutene and the hydrogenation reaction of diisobutylene to prepare isooctane.
Chinese patent CN1211458C reports a method for producing isooctane and liquefied petroleum gas for vehicles by oligomerization-hydrogenation of mixed carbon four, in which a mixed carbon four raw material is first passed through two fixed bed reactors connected in series for oligomerization reaction, and the reactors are filled with a solid acid catalyst (solid phosphoric acid catalyst, hydrogen type ZSM-5 zeolite catalyst or silicon-aluminum pellet catalyst); and then putting the generated oligomerization product isooctene into a reactor filled with nickel loaded by alumina or zeolite and a hydrogenation catalyst of at least one element selected from molybdenum, cobalt, tungsten or palladium for hydrogenation saturation reaction to prepare isooctane.
U.S. Pat. No. 4,2137,1806 reports a process for preparing isooctane by isobutene oligomerization-hydrogenation, wherein solid phosphoric acid (pyrophosphoric acid/diatomaceous earth) is added as oligomerization catalyst in a tank reactor, reduced Fe and NiO are added as hydrogenation catalyst, raw isobutene and catalyst are stirred at 250 ℃ and 8MPa in hydrogen atmosphere to generate isobutene oligomerization reaction and isooctene hydrogenation reaction, and isooctane is generated in one pot (belonging to a single reactor).
In the existing technology for preparing isooctane from isobutene, isobutene is mainly in contact reaction with beds of a superposed catalyst and a hydrogenation catalyst in a single reactor or a plurality of reactors in sequence, or isobutene is in contact reaction with a catalyst bed formed by mixing two catalysts, or isobutene is in contact reaction with two catalysts in a stirred tank reactor. The technical contents disclosed by the technologies can not enable the polymerization reaction of isobutene and the hydrogenation reaction of isooctene to be completed on a single catalyst, and the essence of the technical contents is the mechanical combination of the polymerization reaction function and the hydrogenation reaction function which are respectively possessed by the two catalysts, so that the synergistic effect of two active function centers of polymerization and hydrogenation in the single catalyst can not be exerted. The constraint of heat transfer and mass transfer to the reaction can be effectively overcome by making the superposition reaction and the hydrogenation reaction occur in a single catalyst, so that the organic combination of the two functions of the superposition reaction and the hydrogenation reaction is realized.
In view of the above, none of the prior art relates to a process for simultaneously carrying out a polymerization reaction of isobutylene and a hydrogenation reaction of isooctene in a single catalyst to produce isooctane. Therefore, there is a problem in that research and development of a method for preparing isooctane by isobutene metathesis-hydrogenation, in which a metathesis reaction of isobutene and a hydrogenation reaction of isobutene are simultaneously performed synergistically in a single catalyst, is urgently required.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing isooctane by isobutene polymerization-hydrogenation aiming at the defects of the prior art. The method adopts a polymerization-hydrogenation difunctional curing acid catalyst to catalyze isobutylene polymerization-hydrogenation, so that the preparation of isooctane is completed in one step by carrying out a synergistic polymerization-hydrogenation reaction on a single catalyst. The method effectively simplifies the existing process for preparing isooctane from isobutene, has the advantages of simple process, long service life of the catalyst, high isobutene conversion rate and high isooctane selectivity, and can obviously reduce the generation cost in the process of preparing isooctane from isobutene.
To this end, the present invention provides a process for the polymerization-hydrogenation of isobutylene to produce isooctane, comprising contacting hydrogen and a feedstock comprising isobutylene in a reactor with a polymerization-hydrogenation bifunctional solid acid catalyst to effect polymerization-hydrogenation reaction; wherein the polymerization-hydrogenation difunctional solid acid catalyst comprises an inert or acidic carrier, a hydrogenation active component and an acidic component.
In the polymerization-hydrogenation difunctional solid acid catalyst, a hydrogenation active component and an acid component are independently loaded on an inert or acid carrier and in a pore channel. That is, the hydrogenation active component and the acidic component are two independent active components, and the relationship of the two active components is parallel, and the two active components are not affiliated to each other and are not interfered with each other and are loaded on an inert or acidic carrier and in a pore channel.
The polymerization-hydrogenation bifunctional solid acid catalyst used in the method comprises three functional parts or structural support parts, wherein an inert or acidic carrier is used as a carrier for providing a surface and a pore channel structure, an acidic component provides a polymerization reaction active site of isobutene, and a hydrogenation active component provides a hydrogenation active site of isooctene.
In some embodiments, the hydrogenation active component is selected from one or more of group VIII, group ib, and group vib metals, preferably selected from one or more of Pd, pt, ni, and Cu; more preferably Pd.
In some embodiments, the inert or acidic support is selected from Al 2 O 3 、SiO 2 One or more of silicon-aluminum composite oxide, amorphous aluminum silicate, molecular sieve, activated carbon and mineral material. Preferably the mineral material is selected from diatomaceous earth and/or kaolin. Preferably, the inert or acidic support is selected from Al 2 O 3 、SiO 2 And diatomaceous earth, more preferably Al 2 O 3 . The Al is 2 O 3 The carrier is selected from gamma-Al 2 O 3 And/or alpha-Al 2 O 3 。
In some embodiments, the acidic component is a solid acid, preferably the acidic component is a macroporous strong acid cation exchange resin.
In some specific embodiments, the macroporous strong acid cation exchange resin is a macroporous sulfonic acid resin; preferably, the strong acid cation exchange resin is selected from one or more of styrene series macroporous sulfonic acid resin, acrylic series macroporous sulfonic acid resin, epoxy series macroporous sulfonic acid resin, phenolic series macroporous sulfonic acid resin and urea-formaldehyde series macroporous sulfonic acid resin; more preferably, the macroporous strong-acid cation exchange resin is a styrene macroporous sulfonic acid resin.
In some preferred embodiments, the styrenic resin is selected from one or more of styrene-divinylbenzene macroporous sulfonic acid resin, styrene-dipropenylcyanoethyl acetate macroporous sulfonic acid resin, and styrene-diallyl phthalate macroporous sulfonic acid resin. The acrylate macroporous sulfonic resin is selected from one or more of methacrylic anhydride-methacrylic acid methanol macroporous sulfonic resin, methacrylic anhydride-vinyl acetate macroporous sulfonic resin and acrylic anhydride-vinyl acetate macroporous sulfonic resin. The epoxy macroporous sulfonic acid resin is selected from one or more of bisphenol-methacrylic acid epoxy macroporous sulfonic acid resin, brominated bisphenol-methacrylic acid epoxy macroporous sulfonic acid resin and phenolic aldehyde-methacrylic acid epoxy macroporous sulfonic acid resin. The phenolic aldehyde series macroporous sulfonic acid resin is selected from one or more of phenol-formaldehyde-hydroquinone macroporous sulfonic acid resin, phenol-formaldehyde-resorcinol macroporous sulfonic acid resin and cresol-formaldehyde-hydroquinone macroporous sulfonic acid resin.
In some embodiments, the catalyst has a dry acid content of 1.0 to 12.0mol H + Per kg, preferably 2.0 to 10.0mol of H + Per kg, more preferably from 2.0 to 8.0mol of H + In terms of/kg. The catalyst has a dry-based hydrogenation active component content of 0.01-6.0wt%, preferably 0.1-5.0wt%, more preferably 0.1-3.0wt%. The specific surface area of the catalyst is 20-50m 2 Per g, pore volume of 0.1-0.4mL/g, average pore diameter of 10-40nm.
The invention adopts a polymerization-hydrogenation bifunctional solid acid catalyst (namely, the polymerization of isobutene and the hydrogenation of isooctene (diisobutylene) are realized on a single catalyst) to prepare isooctane by a one-step method, so that the technical process of preparing isooctane from isobutene is greatly simplified, and the mechanism that the conversion rate of isobutene and the selectivity of isooctane are high is as follows.
Firstly, due to the existence of a plurality of active functional sites in the single catalyst, the reactant molecule isobutene and the intermediate diisobutylene in the pore channel of the catalyst can be contacted with the corresponding active sites in the pore channel more quickly, conveniently and frequently, the surface and pore channel structure of the catalyst are more effectively utilized, the isobutene is converted into isooctane in one step, and a reaction similar to in-situ reaction is macroscopically completed.
Secondly, the coexistence of two active sites of superposition and hydrogenation in the catalyst pore channel can effectively promote each other and generate a positive synergistic effect, namely on one hand, after diisobutylene generated by the isobutene superposition reaction is desorbed from the superposition site, diisobutylene can be quickly adsorbed by the hydrogenation site and converted into isooctane in the same pore channel, the concentration of diisobutylene in the pore channel is objectively reduced, and the chemical balance of the reaction is favorably moved to the reaction direction of diisobutylene generated by isobutene superposition; on the other hand, the positive shift of the chemical balance of the isobutylene polymerization reaction can objectively make the concentration of diisobutylene in the pore channel develop towards the improvement direction, and further improve the concentration of the raw material of the hydrogenation reaction, so that the hydrogenation reaction is accelerated, reactions occurring on two active functional sites of polymerization and hydrogenation in the same pore channel are mutually promoted macroscopically, and the reaction process of converting isobutylene into isooctane is accelerated.
Thirdly, the polymerization functional site in the catalyst pore channel is an acid site, carbon deposition is easy to occur when the acid site is in contact reaction with olefin, and the hydrogen atmosphere can inhibit coking and carbon deposition of the olefin to a certain extent and quench chain development of carbonium ions to a certain extent, so that the polymerization reaction of isobutene can better stay at the stage of generating dimer diisobutylene, trimer and polymer with higher carbon number are generated as little as possible, and the selectivity of the product isooctane is finally improved.
According to some specific embodiments, the feedstock comprising isobutylene is diluted with a diluent prior to use; preferably the diluent is selected from C 4 -C 20 More preferably selected from isobutane and/or isooctane, most preferably isooctane. The dilution ratio of the diluent to isobutylene in the isobutylene-containing feedstock is (1-30): 1, preferably (2-15): 1, by weight.
In some embodiments, the reaction temperature of the folding-hydrogenation reaction is in the range of 30 to 150 ℃, preferably 50 to 140 ℃, more preferably 50 to 120 ℃. The reaction pressure of the superposition-hydrogenation reaction is 0.3-2.0MPa, and preferably 0.5-1.2MPa. The molar ratio of the hydrogen to the isobutene in the isobutene-containing feedstock is from 0.5 to 6.0, preferably from 0.5 to 5.0. The volume space velocity of the raw material containing isobutene is 0.5-6.0h -1 。
According to some specific embodiments, the method further comprises subjecting the stacking-hydrogenating bifunctional solid acid catalyst to a reductive activation treatment prior to the contacting. It can also be subjected to reductive activation treatment in the preparation stage of the catalyst. The reduction activation treatment is preferably performed using hydrogen gas. More preferably, the reduction activation treatment comprises activating the polymerization-hydrogenation bifunctional solid acid catalyst for 4-18h under the conditions of the temperature of 50-140 ℃, the pressure of 0-2.0MPa and the hydrogen flow rate of 1-15 mL/(min. ML catalyst).
According to some specific embodiments, the process is carried out in the presence of an isooctene selectivity modulator. Preferably the isooctene selectivity modulator is selected from the group consisting of fatty ethers and/or cyclic ethers; more preferably one or more selected from tetrahydrofuran, methyltetrahydrofuran, dioxane, diethyl ether, isopropyl ether, methyl tert-butyl ether (MTBE) and ethyl tert-butyl ether (ETBE); most preferably selected from tetrahydrofuran and/or isopropyl ether.
The action mechanism of the selectivity regulator adopted in the invention is that ethers are used as compounds with stronger polarity, can be combined with the acid sites of the catalyst, weaken the acidity of the acid sites, and inhibit the generation of polymers, and meanwhile, the addition of the compounds with stronger polarity also plays roles in diluting isobutene and carrying away reaction heat, thereby integrally improving the selectivity of the polymerization functional sites of the catalyst to diisobutylene.
In some preferred embodiments, the isooctene selectivity modifier is added in an amount of from 0.5 to 30wt%, preferably from 3 to 20wt%, based on the weight of the isobutylene-containing feedstock.
According to some embodiments, the method further comprises the step of recycling the reactor outlet material back to the reactor inlet. In some preferred embodiments, the weight ratio of the recycle to the isobutylene-containing feedstock recycled to the reactor inlet is (5-30): 1.
The method of the invention adopts the operation of circulating the material at the outlet of the reactor, namely, the retention time of isobutene molecules on acid sites (polymerization functional sites) is shortened through high space velocity and low one-way conversion rate, and polymers are prevented from being generated, thereby realizing the high selectivity of the polymerization functional sites of the catalyst to diisobutylene.
In some embodiments, the step of recycling the reactor outlet stream back to the reactor inlet comprises: directly circulating a part of materials in the outlet of the reactor back to the inlet of the reactor, and feeding the rest of materials in the outlet of the reactor into a rectifying tower to separate an isooctane product; or
After the materials at the outlet of the reactor are completely separated into the isooctane product and the heavy components through the rectifying tower, all or part of the remaining light components are recycled to the inlet of the reactor. The purity of isooctane extracted from the rectifying tower is more than 97 wt%.
The term "heavy component" as used herein is an organic substance having a carbon number greater than 8. For example, dodecene, dodecane, and hexadecene may be included. Heavy components are formed by the side reaction of isobutene with multiple molecules (three molecules and more) of polymerization.
The term "light component" as used herein includes isobutylene, hydrogen, isobutane and organic ethers (e.g., tetrahydrofuran, isopropyl ether, etc.) for adjusting selectivity.
The terms "diisobutylene" and "isooctene" as used herein are of the same kind.
The reactor used in the process of the present invention is not particularly limited, and the reactor may be a fixed bed, moving bed, fluidized bed or tank reactor, preferably a fixed bed reactor.
The method for preparing isooctane by isobutene polymerization-hydrogenation provided by the invention has the advantages that hydrogen and raw materials containing isobutene are contacted with a polymerization-hydrogenation bifunctional solid acid catalyst in a reactor to catalyze isobutene polymerization-hydrogenation, and the preparation of isooctane is completed in one step on a single catalyst. The reaction in the method preferably uses isooctane as a diluting solvent, preferably uses tetrahydrofuran and/or isopropyl ether as a selective regulator of isooctene (diisobutylene), and preferably uses Al 2 O 3 Macroporous strong-acid styrene cation exchange resin and Pd loaded by a carrier are used as catalysts. The method can effectively simplify the existing process for preparing isooctane from isobutene, has the advantages of simple process, long service life of the catalyst, high isobutene conversion rate and high isooctane selectivity, and can obviously reduce the production cost in the process of preparing isooctane from isobutene.
Detailed Description
In order that the invention may be more readily understood, the invention will now be described in detail with reference to the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention.
The calculation formula of the total conversion rate of isobutene and the total selectivity of isooctane in the invention is as follows:
examples
Example 1
50mL of gamma-Al was charged into the fixed bed reactor 2 O 3 Catalyst loaded with Pd and styrene-divinylbenzene macroporous sulfonic acid resin, the dry acid content of the catalyst is 3.1mol H + Per kg, the Pd content on a dry basis was 0.5 wt.%. The specific surface area of the catalyst was 40m 2 Pore volume 0.25mL/g, average pore diameter 31nm. Activating the catalyst for 8 hours under the conditions of 110 ℃, 0.5MPa of pressure and 4 mL/(min. ML of catalyst) of hydrogen flow rate to complete reduction activation treatment, taking mixed hydrocarbon with 5 weight ratio of isooctane to isobutene as a raw material, doping 10wt% of isopropyl ether as a dimer selectivity regulator into the raw material according to the weight of the raw material, uniformly mixing the mixture with the hydrogen flow, and performing reaction at 80 ℃, 0.8MPa of pressure, 2.0 of hydrogen/isobutene molar ratio and 3.0 hour of volume space velocity of fresh raw material -1 Under the reaction conditions of (1), the catalyst continuously passes through a catalyst bed layer, isooctane and heavy components are firstly separated from materials at the outlet of the reactor through a rectifying tower, then the rest light components are partially circulated to the inlet of the reactor, and the weight ratio of the circulating materials to fresh raw materials (namely raw materials containing isobutene) is 10. The specific reaction results are shown in Table 1.
Example 2
The "methacrylic anhydride-methacrylic acid methanol macroporous sulfonic acid resin catalyst" was used instead of the "styrene-divinylbenzene macroporous sulfonic acid resin catalyst" in example 1, and the reaction was started under the same reaction conditions as in example 1. The specific reaction results are shown in Table 1.
Example 3
The reaction was started under the same reaction conditions as in example 1 except that "bisphenol-methacrylic acid epoxy macroporous sulfonic acid resin catalyst" was used instead of "styrene-divinylbenzene macroporous sulfonic acid resin catalyst" in example 1. The specific reaction results are shown in Table 1.
Example 4
The reaction was started under the same reaction conditions as in example 1 except that "phenol-formaldehyde-hydroquinone macroporous sulfonic acid resin catalyst" was used instead of "styrene-divinylbenzene macroporous sulfonic acid resin catalyst" in example 1. The specific reaction results are shown in Table 1.
Example 5
The "catalyst had a Pd content on a dry basis of 2.5% by weight" was used in place of the "catalyst had a Pd content on a dry basis of 0.5% by weight" in example 1, and the reaction was started under the same reaction conditions as in example 1. The specific reaction results are shown in Table 1.
Example 6
"the amount of dry acid of the catalyst used was 7.2mol of H + Perkg "catalyst in alternative example 1" amount of dry acid 3.1mol H + Kg ", the remaining reaction conditions were the same as in example 1, the reaction was started. The specific reaction results are shown in Table 1.
Example 7
The reaction was started under the same reaction conditions as in example 1 except that "the catalyst was activated at 60 ℃ under a pressure of 1.5MPa and a hydrogen flow rate of 12 mL/(min. ML catalyst)" was used instead of "the catalyst was activated at 110 ℃ under a pressure of 0.5MPa and a hydrogen flow rate of 4 mL/(min. ML catalyst)" in example 1. The specific reaction results are shown in Table 1.
Example 8
The reaction was started under the same conditions as in example 1 except that "the hydrogen/isobutylene molar ratio was 2.0 at a temperature of 110 ℃ and a pressure of 0.8 MPa" in example 1 was replaced with "the hydrogen/isobutylene molar ratio was 2.0 at a temperature of 80 ℃ and a pressure of 0.8 MPa". The specific reaction results are shown in Table 1.
Example 9
The reaction was started under the same conditions as in example 1 except that "at a temperature of 80 ℃ and a pressure of 1.1MPa and a hydrogen/isobutylene molar ratio of 2.0" was used instead of "at a temperature of 80 ℃ and a pressure of 0.8MPa and a hydrogen/isobutylene molar ratio of 2.0" in example 1. The specific reaction results are shown in Table 1.
Example 10
The reaction was started under the same conditions as in example 1 except that "the molar ratio of hydrogen/isobutylene at a temperature of 80 ℃ and a pressure of 0.8MPa and a molar ratio of hydrogen/isobutylene of 4.0" in example 1 was used instead of "the molar ratio of hydrogen/isobutylene at a temperature of 80 ℃ and a pressure of 0.8 MPa" in example 1. The specific reaction results are shown in Table 1.
Example 11
The procedure of "activating the catalyst at 110 ℃ under 0.5MPa and under a hydrogen flow of 4 mL/(min. ML catalyst) for 8 hours to complete the reductive activation treatment" was omitted, and the reaction was started under the same reaction conditions as in example 1. The specific reaction results are shown in Table 1.
Example 12
The procedure of "blending 10wt% of isopropyl ether as a dimer selectivity modifier to the starting material based on the weight of the starting material" was omitted, and the remaining reaction conditions were the same as in example 1, and the reaction was started. The specific reaction results are shown in Table 1.
Example 13
The process comprises the steps of separating isooctane and heavy components from reactor outlet materials through a rectifying tower, recycling the residual light components to the inlet of the reactor, wherein the weight ratio of the recycled materials to fresh raw materials (namely raw materials containing isobutene) is 10 ", omitting the steps, and starting the reaction under the same reaction conditions as in example 1. The specific reaction results are shown in Table 1.
Example 14
The reaction was started under the same conditions as in example 1 except that "the hydrogen/isobutylene molar ratio was 2.0 at a temperature of 150 ℃ and a pressure of 0.8 MPa" in example 1 was replaced with "the hydrogen/isobutylene molar ratio was 2.0 at a temperature of 80 ℃ and a pressure of 0.8 MPa". The specific reaction results are shown in Table 1.
Example 15
The reaction was started under the same conditions as in example 1 except that "the molar ratio of hydrogen/isobutylene at a temperature of 80 ℃ and a pressure of 0.8MPa and a molar ratio of hydrogen/isobutylene of 6.0" in example 1 was replaced with "the molar ratio of hydrogen/isobutylene at a temperature of 80 ℃ and a pressure of 0.8 MPa" in example 1. The specific reaction results are shown in Table 1.
Example 16
The "catalyst had a dry Pd content of 6.0wt%" was used in place of the "catalyst had a dry Pd content of 0.7wt%" in example 1, and the reaction was started under the same reaction conditions as in example 1. The specific reaction results are shown in Table 1.
Example 17
"the amount of dry acid of the catalyst was 12mol of H + Perkg "catalyst in alternative example 1" amount of dry acid 3.1mol H + Kg ", the remaining reaction conditions were the same as in example 1, the reaction was started. The specific reaction results are shown in Table 1.
Example 18
The catalyst of example 1 was evaluated for its reaction performance (i.e., catalyst life) with the cumulative operating time under the conditions of example 1, and the results are shown in Table 2.
Comparative example 1
Using "Charge 50mL of γ -Al into the upper layer of the fixed bed reactor 2 O 3 The specific surface area of the upper layer catalyst is 40m 2 Per g, pore volume 0.25mL/g, mean pore diameter 31nm, dry basis weight of catalyst 3.1mol H + Per kg; the lower layer is filled with 50mL of gamma-Al 2 O 3 A supported Pd catalyst, the Pd content of which is 0.5wt%, and the specific surface area of the lower catalyst layer being 40m 2 Per g, pore volume 0.25mL/g, mean pore diameter 31nm "and" volume space velocity of fresh feed 1.5h -1 "separately replace example 1" by charging 50mL of γ -Al into a fixed bed reactor 2 O 3 Catalyst loaded with Pd and styrene-divinylbenzene macroporous sulfonic acid resin, the dry acid content of the catalyst being 3.1mol H + Kg, pd content 0.5 wt.% on a dry basis. The specific surface area of the catalyst was 40m 2 Pore volume of 0.25mL/g, mean pore diameter of 31nm "and" volumetric space velocity of fresh feed of 3.0h -1 ", the reaction conditions were otherwise the same as in example 1, and the reaction was started. The specific reaction results are shown in Table 2.
Comparative example 2
The upper and lower layers of the catalyst in comparative example 1 were mixed uniformly and then charged into a reactor, and the reaction was started under the same conditions as in comparative example 1. The specific reaction results are shown in Table 1.
TABLE 1 results of the superposition-hydrogenation reactions of the examples and comparative examples
TABLE 2 evaluation of catalyst service life
As can be seen from tables 1 and 2, the method for preparing isooctane by isobutene polymerization-hydrogenation provided by the invention has the advantages of long service life of the catalyst, high isobutene conversion rate and high selectivity of isooctane, and obtains better effect.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (21)
1. A method for preparing isooctane by isobutene polymerization-hydrogenation comprises the steps of contacting hydrogen and a raw material containing isobutene with a polymerization-hydrogenation bifunctional solid acid catalyst in a reactor to generate polymerization-hydrogenation reaction; wherein the polymerization-hydrogenation bifunctional solid acid catalyst comprises an inert or acidic carrier, a hydrogenation active component and an acidic component;
the hydrogenation active component is selected from one or more of Pd, pt, ni and Cu;
the inert or acidic support is selected from Al 2 O 3 、SiO 2 One or more of silicon-aluminum composite oxide, amorphous aluminum silicate, molecular sieve, activated carbon and mineral material; the mineral material is selected from diatomaceous earth and/or kaolin;
the acidic component is macroporous strong-acid cation exchange resin;
the dry acid content of the catalyst is 1.0-12.0mol H + /kg；
The content of the dry-based hydrogenation active component of the catalyst is 0.01-6.0wt%;
the specific surface area of the catalyst is 20-50m 2 Per g, pore volume of 0.1-0.4mL/g, average pore diameter of 10-40nm.
2. The process according to claim 1, characterized in that the inert or acidic support is selected from Al 2 O 3 、SiO 2 And diatomaceous earth.
3. The method of claim 1, wherein the macroporous strong acid cation exchange resin is a macroporous sulfonic acid resin.
4. The method according to claim 3, wherein the macroporous strong acid cation exchange resin is selected from one or more of a styrenic macroporous sulfonic acid resin, an acrylic macroporous sulfonic acid resin, an epoxy macroporous sulfonic acid resin, and a phenolic macroporous sulfonic acid resin.
5. The method of claim 4, wherein the styrenic macroporous sulfonic acid resin is selected from one or more of styrene-divinylbenzene macroporous sulfonic acid resin, styrene-dipropenylcyanoethyl acetate macroporous sulfonic acid resin, and styrene-diallyl phthalate macroporous sulfonic acid resin;
the acrylic acid series macroporous sulfonic acid resin is selected from one or more of methacrylic anhydride-methacrylic acid methanol macroporous sulfonic acid resin, methacrylic anhydride-vinyl acetate macroporous sulfonic acid resin and acrylic anhydride-vinyl acetate macroporous sulfonic acid resin;
the epoxy series macroporous sulfonic acid resin is selected from one or more of bisphenol-methacrylic acid epoxy macroporous sulfonic acid resin, brominated bisphenol-methacrylic acid epoxy macroporous sulfonic acid resin and phenolic aldehyde-methacrylic acid epoxy macroporous sulfonic acid resin;
the phenolic aldehyde series macroporous sulfonic acid resin is selected from one or more of phenol-formaldehyde-hydroquinone macroporous sulfonic acid resin, phenol-formaldehyde-resorcinol macroporous sulfonic acid resin and cresol-formaldehyde-hydroquinone macroporous sulfonic acid resin.
6. The method of claim 1, wherein the catalyst has a dry acid content of 2.0 to 10.0mol H + /kg；
The content of the dry hydrogenation active component of the catalyst is 0.1-5.0wt%.
7. The process according to claim 1, characterized in that the isobutene-containing feedstock is diluted with a diluent before use; and/or
The dilution ratio of the diluent to isobutylene in the isobutylene-containing feedstock is (1-30): 1 by weight.
8. The method of claim 7, wherein the diluent is selected from the group consisting of C 4 -C 20 One or more of (a); and/or
The dilution ratio of the diluent to isobutylene in the isobutylene-containing feedstock is (2-15): 1 by weight.
9. The process according to claim 8, characterized in that the diluent is selected from isobutane and/or isooctane.
10. The process of claim 1, wherein the reaction temperature of the superposition-hydrogenation reaction is between 30 ℃ and 150 ℃;
the reaction pressure of the superposition-hydrogenation reaction is 0.3-2.0MPa;
the molar ratio of the hydrogen to the isobutylene in the feed comprising isobutylene is from 0.5 to 6.0;
the volume space velocity of the raw material containing isobutene is 0.5-6.0h -1 。
11. The process of claim 10, wherein the reaction temperature of the folding-hydrogenation reaction is 50-140 ℃;
the reaction pressure of the superposition-hydrogenation reaction is 0.5-1.2MPa.
12. The process of claim 1, further comprising subjecting the stacked-hydrobifunctional solid acid catalyst to a reductive activation treatment prior to the contacting.
13. The method according to claim 12, wherein the reductive activation treatment is performed using hydrogen gas.
14. The method of claim 13, wherein the reductive activation treatment comprises activating the stacked-hydrogenated bifunctional solid acid catalyst for 4-18h at a temperature of 50-140 ℃, a pressure of 0-2.0MPa, and a hydrogen flow rate of 1-15 mL/(min-mL catalyst).
15. The process of claim 1, wherein the process is carried out in the presence of an isooctene selectivity modulator;
the isooctene selectivity modulator is selected from fatty ethers and/or cyclic ethers.
16. The process of claim 15, wherein the isooctene selectivity modulator is selected from the group consisting of one or more of tetrahydrofuran, methyltetrahydrofuran, dioxane, diethyl ether, isopropyl ether, methyl tert-butyl ether, and ethyl tert-butyl ether.
17. The process according to any one of claims 15 to 16, characterized in that the isooctene selectivity modifier is added in an amount of 0.5 to 30 wt. -%, based on the weight of the isobutene-containing feedstock.
18. The process of claim 17, wherein the isooctene selectivity modifier is added in an amount of from 3 to 20wt% based on the weight of the isobutylene-containing feedstock.
19. The method of claim 1, further comprising the step of recycling reactor outlet material back to the reactor inlet.
20. The process of claim 19, wherein the weight ratio of recycle to isobutylene-containing feedstock recycled to the reactor inlet is (5-30): 1.
21. The method of claim 19, wherein the step of recycling the reactor outlet material back to the reactor inlet comprises: directly circulating a part of materials in the outlet of the reactor back to the inlet of the reactor, and sending the rest of materials in the outlet of the reactor into a rectifying tower to separate an isooctane product; or
After the materials at the outlet of the reactor are completely separated into the isooctane product and the heavy components through the rectifying tower, all or part of the remaining light components are recycled to the inlet of the reactor.
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