WO2017206260A1 - Polystyrene sulfonic acid resin catalyst, preparation method therefor and use thereof - Google Patents

Abstract

A polystyrene sulfonic acid resin catalyst and a preparation method therefor. The catalyst is separately used for performing dehydration of tertiary butyl alcohol (TBA) and isobutene oligomerization to cogenerate isobutene and diisobutylene (DIB). The catalyst comprises a polystyrene sulfonic acid resin, a metal, and a metal sulfate. The metal contains two parts: metal coated with the polystyrene sulfonic acid resin, and metal not coated with the polystyrene sulfonic acid resin. The metal sulfate is formed by converting the exposed surface of the metal not coated with the polystyrene sulfonic acid resin in the catalyst. When the catalyst is separately used in the dehydration of TBA and the isobutene oligomerization, due to the high thermal conductivity of the catalyst, the two reactions are coupled, thus supplementing energy required by the dehydration of TBA and greatly reducing the hot-spot temperature of the bed layer of the isobutene oligomerization. In the reaction, the conversion rate per pass of the dehydration of TBA may be 40% or more, and the selectivity of isbutene is 99% or more. Moreover, there is no need to add a sustained-release agent when the isobutene oligomerization is catalyzed, because even if isbutene with a concentration greater than 80 wt% is used as a raw material, the selectivity of DIB is still 80% or more, and the conversion rate per pass is 90% or more.

Description

Polystyrene sulfonic acid resin catalyst and preparation method and application thereof Technical field

The invention relates to a polystyrene sulfonic acid resin catalyst and a preparation method thereof, and the use of the catalyst to catalyze the dehydration of t-butanol and the homopolymerization of isobutylene to produce isobutylene and diisobutylene, respectively.

Background technique

Isobutylene (IB), especially high-purity IB, is widely used in many fields, including organic chemicals, synthetic resins, synthetic rubber and many other fields.

Dehydration of tert-butanol (TBA) is one of the current mainstream methods for producing high purity isobutylene. The TBA is dehydrated to an endothermic reaction with an endotherm of 26 kJ/mol. The existing TBA dehydration generally adopts two processes of reactive distillation and fixed bed. The reactive distillation process requires the TBA of the column to be continuously vaporized to rise to the catalyst bed, and the IB vaporization caused by the dehydration of the TBA rises to the top of the column under the reaction pressure, in addition to the need to provide the required heat to the reaction. There is also a need to provide a large amount of additional heat to compensate for the heat of vaporization. The fixed bed process has two types of series reactors and tubular reactors. The former needs to provide heat between the sections, and the latter needs to provide heat to the tube process through the shell side of the reactor, and the single pass conversion rate is only 31-37% ( CN1609082A). In summary, the TBA dehydration process requires a large amount of heat from outside to react.

IB oligomerization can be used to prepare diisobutylene (2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene) (DIB), and the catalyst used in the reaction is generally Acidic ion exchange resin, molecular sieve, and the like. DIB is a kind of versatile chemical intermediate that can be hydrogenated to produce isooctane. Isooctane is an additive to increase the octane number of gasoline. DIB can also react with phenol to synthesize octylphenol, which is further used to produce antioxidants. Products such as tackifying resins and surfactants; DIB can also be used to prepare isodecyl aldehyde by hydroformylation, isodecyl alcohol by isophthalic acid hydrogenation, isophthalic acid by oxidation, and further used in the production of plasticizers, lubricating oils, etc. product.

IB oligomerization is a strong exothermic reaction, the exotherm is as high as 107kJ/mol, and the reaction is a secondary reaction, that is, the reaction rate and the exothermic power are directly proportional to the square of the reactant concentration, so the reaction is easily localized. Especially in the case where the IB concentration is high, the temperature is too high. Excessive local temperature can easily lead to high polymerization, carbon skeleton isomerization and cracking, which not only reduces the selectivity of the dimer C8 olefin, but also causes the DIB content of the effective component in the C8 olefin to decrease. Therefore, the reaction temperature must be strictly controlled. Single pass conversion of isobutylene. Patent CN103619785A reports that when the content of butene in the raw material is about 85%, even if the reaction temperature is only 37 ° C, the selectivity of the dimer is only 58%, and the content of DIB in the dimer is less than 93%. Further purification is required to achieve a purity of more than 95% of the market demand.

IB oligomerization to prepare DIB also includes both reactive distillation and fixed bed processes.

The catalyst in the reactive distillation column for the preparation of DIB by reactive distillation is a bed, which easily leads to local temperature. Too high, on the one hand, the selectivity of DIB is greatly reduced. On the other hand, the resin catalyst is deactivated due to sulfonic acid shedding, while the molecular sieve catalyst is prone to carbon deactivation. Other hydrocarbons are used to substantially dilute IB using other hydrocarbons in US Pat. No. 4,424,530, US Pat. No. 8,852, 834 B2 and US Pat. No. 6,100,137, 668, wherein although reactive distillation can utilize the heat of reaction to provide energy for the vaporization of IB, a large amount of diluent also requires an evaporation cycle with IB, energy consumption and Can not be significantly reduced.

The segmented fixed bed process requires strict control of the temperature rise of each section, and heat exchangers are added between the sections for heat transfer, resulting in more equipment and investment in the entire system.

The hot spots of the tube-type fixed bed oligomerization process are significantly higher than the inlet and outlet temperatures. In order to strictly control the hot spot, it is necessary to use a diluent to dilute the IB in the tube process. The C4 feedstock of US Pat. No. 6,875,900 B2 contains olefins of C3-C5 or higher and C12 or higher as a diluent for the purpose of controlling temperature rise. Moreover, the shell-side temperature of the tubular reactor must be significantly lower than the hot spot temperature for rapid heat transfer. This results in lower temperatures in other locations of the bed except for the vicinity of the hot spot, and the reaction efficiency is also reduced. In short, in the conventional tubular fixed-bed process, although IB oligomerization can release a large amount of heat, due to the limitation of the reaction temperature, it can only be converted into low-quality heat, can not be effectively utilized, and a large amount of added diluent Not only does it reduce the efficiency of the reactor, but it also greatly increases the energy consumption for separation.

In the prior art, the raw materials used in the simple IB oligomerization reaction are all derived from petroleum cracking. In addition to isobutylene, the raw materials contain components such as propylene, n-butene, propane and butane which have lower reactivity than isobutylene. The component, together with the oxygen-containing slow release agent, controls the IB single pass conversion and increases the DIB selectivity by reducing the isobutene concentration and the reaction rate. The oligomerization reaction in the absence of other hydrocarbon dilution bands in the presence of heat and a slow release agent, how to simultaneously obtain high isobutene conversion per pass and high DIB selectivity, has not been reported in the prior art. The isobutylene obtained by dehydration of t-butanol contains almost no other olefins or alkanes, and is suitable as a starting material for the IB oligomerization reaction to solve the above problems.

Further, as disclosed in the patents CN104447167A, CN1609082A, CN102690159A, CN102485305A, and US4423271, the catalysts used in the currently disclosed t-butanol dehydration technology are mainly polystyrene sulfonic acid resins. Since the dehydration of t-butanol is an endothermic reaction, only the heat outside the bed containing the catalyst is transferred to the inside of the catalyst bed to ensure that the dehydration reaction of t-butanol proceeds rapidly, but the thermal conductivity of the polystyrene sulfonic acid resin is very high. Poor, often causes the internal temperature of the bed to be much lower than the outside of the bed, so that the reaction rate inside the bed is much lower than the outside of the bed. Therefore, in order to increase the overall catalyst efficiency of the bed, it is often necessary to increase the temperature of external heating. The reaction temperature disclosed in the patent US Pat. No. 4,423,271 is 80-150 ° C, wherein a large amount of free water formed by dehydration of t-butanol further increases the sulfonic acid shedding rate of the catalyst, resulting in a catalyst life of not more than 6 months. Therefore, if the thermal conductivity of the polystyrene sulfonic acid resin catalyst can be improved, it is not necessary to greatly increase the temperature outside the bed, and the catalyst as a whole can be subjected to a catalytic reaction at a relatively low temperature, and the life can be greatly prolonged.

The catalyst used in the IB oligomerization reaction includes solid heteropoly acid/activated alumina and macroporous polystyrene sulfonate. There are two types of acid resins, in which the macroporous polystyrene sulfonic acid resin has no carbon deposition problem, and the polymer formed by the oligomerization can pass through the macropores, but the problem of poor thermal conductivity of the polystyrenesulfonic acid catalyst also causes the heat released by the reaction. It is difficult to transfer from the inside of the bed to the outside of the bed. For the strong exothermic reaction of isobutene oligomerization, the bed temperature is often higher due to the inability to remove the heat quickly, resulting in more C8 isomers in the dimer. The selectivity and product purity of the DIB is greatly reduced, and the catalyst is also rapidly deactivated from the center of the bed. In order to avoid the above problems, in addition to the large dilution of isobutylene, the existing methods need to add a certain amount of slow release agent such as alcohol, ether, water to control the lower conversion rate of isobutylene, which is undoubtedly Increased separation of investment and energy consumption. The thermal conductivity and heat resistance of activated alumina and solid heteropolyacids are superior to those of polystyrene sulfonic acid resins, but as described in the patent CN103619785A, such catalysts have carbon deposition problems, especially when the raw materials contain small amounts of diolefins ( Such as butadiene), frequent catalyst regeneration is required.

Therefore, it is necessary to find a new type of catalyst to efficiently catalyze the dehydration of t-butanol and the oligomerization of isobutylene to solve the thermal deactivation of the catalyst due to insufficient thermal conductivity of the catalyst in the existing t-butanol dehydration and isobutylene oligomerization processes. The disadvantages of low concentration and low product selectivity increase the service life of the catalyst and the selectivity of the product, thereby reducing the production cost.

Summary of the invention

It is an object of the present invention to provide a polystyrene sulfonic acid resin catalyst which contains a metal in which a part of a metal is coated with a polystyrene sulfonic acid resin and a metal surface not coated with a polystyrene sulfonic acid resin is converted by vulcanization. Sulfate formation effectively improves the thermal conductivity of the resin catalyst and increases the activity of the catalyst.

Another object of the present invention is to provide a process for the preparation of the polystyrene sulfonic acid resin catalyst.

Still another object of the present invention is to provide a method for producing isobutylene and diisobutylene by dehydrating t-butanol and isobutylene, respectively, using the polystyrene sulfonic acid resin catalyst.

In order to achieve the above object, the technical solution adopted by the present invention is as follows:

A polystyrene sulfonic acid resin catalyst comprising: a polystyrene sulfonic acid resin, a metal and a metal sulfate; wherein the metal comprises two parts: a metal coated with a polystyrene sulfonic acid resin, and a polyphenylene a metal coated with a vinyl sulfonic acid resin; the metal sulfate is converted from an outer leakage surface of the metal not coated with the polystyrene sulfonic acid resin.

In the catalyst according to the present invention, the volume of metal coated with the polystyrene sulfonic acid resin is based on the total volume of the metal coated with the polystyrene sulfonic acid resin and the uncoated metal. 1 to 90%, preferably 10 to 70%, more preferably 30 to 50%; the volume of the metal not coated with the polystyrenesulfonic acid resin is 99 to 10%, preferably 90 to 30%, More preferably, it is 70-50%.

In the catalyst of the present invention, the metal includes, but is not limited to, one or more of Fe, Co, Ni, Ge, Sn, Pb, Zn, Cu, Cd and Sb, preferably Fe, Co and Ni. One or more.

In the catalyst of the present invention, the metal is in the form of one or more of metal microfibers, foams and powders; the metal has a minimum dimension of 0.1 to 100 μm and a maximum dimension of 2 mm or less.

The catalyst of the present invention has a particle diameter of 0.1 to 3 mm, preferably 0.5 to 2 mm; a specific surface area of 10 to 100 m ² /g; a pore diameter of 10 to 500 nm; and a pore volume of 0.1 to 0.5 ml/g.

In the catalyst of the present invention, the volume of the metal coated with the polystyrene sulfonic acid resin is from 5 to 50%, preferably from 10 to 30%, based on the total volume of the catalyst.

In the catalyst of the present invention, the number average molecular weight of the polystyrene is from 50,000 to 200,000, preferably from 8 to 150,000.

The preparation method of the polystyrene sulfonic acid resin catalyst of the invention comprises the following steps:

(1) placing the metal in a reaction vessel after the replacement of the inert gas, adding a long carbon chain organic compound having a polar group, stirring under an inert gas, and then leaching the liquid in the reaction vessel in an inert gas atmosphere. Dry the metal under;

(2) adding dibenzoyl peroxide, divinylbenzene, styrene, isopropanol and polyvinyl alcohol to the reaction vessel, stirring and heating, and when the apparent phase interface appears, it has been treated by step (1). The metal is added to the reaction vessel, stirred until the particles begin to become brittle, the heating is stopped, water is added to the reaction vessel to cool to room temperature, the liquid is drained, and the particles are washed and dried;

(3) oxidizing the exposed surface of the non-polystyrene-coated metal of the particles after the drying in the step (2) to obtain a metal oxide until the particle mass is constant;

(4) The pellet obtained in the step (3) is heated, the polystyrene on the outer surface of the pellet is sulfonated and the metal oxide is converted into a metal sulfate to obtain a catalyst.

The preparation of the catalyst of the present invention is carried out in a stirred reactor with a condensing reflux line.

In the catalyst preparation method of the present invention, the metal in the step (1) is one or more of the rust-removed metal fiber, the rust-removed metal foam and the rust-removed metal powder, preferably removed. Rust foam metal. The metal includes, but is not limited to, one or more of Fe, Co, Ni, Ge, Sn, Pb, Zn, Cu, Cd, and Sb, and the like, preferably one or more of Fe, Co, and Ni.

In the catalyst preparation method of the present invention, the inert gas in the step (1) is one or more of nitrogen, argon and helium, preferably nitrogen.

In the preparation method of the catalyst of the present invention, the purpose of adding a long-chain carbon organic compound having a polar group in the step (1) is to form a lipophilic layer on the surface of the metal to increase the binding ability of the metal in the polymerization step to polystyrene. The long carbon chain organic compound having a polar group is a sulfonate of the formula R-SO ₃ , a carboxylic acid of the formula R-COOH and (R-COO) _n M and a soap thereof, One or more of a lipid of the formula RCOOR', an amine of the formula R-NH ₂ and a sulfur-nitrogen heterocyclic compound, preferably a lipid, wherein R and R' are each a carbon number greater than 4, preferably greater than a long carbon chain alkyl group; n is an integer of from 1 to 7; the long carbon chain organic compound having a polar group is more preferably sorbitan monooleate, beeswax, pentaerythritol monooleate and lanolin One or more of the above; the long carbon chain organic compound having a polar group is preferably used in an amount less than the metal, preferably from 1 to 10 times the volume of the metal, more preferably It is 2-5 times.

In the catalyst preparation method of the present invention, the step (1) is carried out by stirring at normal temperature for 0.1 to 20 hours, preferably 1 to 10 hours.

In the catalyst preparation method of the present invention, the metal drying temperature in the step (1) is 50 to 500 ° C, preferably 100 to 200 ° C.

In the catalyst preparation method of the present invention, in the step (2), the dibenzoyl peroxide is used as an initiator, divinylbenzene is a crosslinking agent, styrene is a polymerization monomer, isopropanol and polyvinyl alcohol are used as a solvent. .

In the catalyst preparation method of the present invention, the volume ratio of the total volume of dibenzoyl peroxide, divinylbenzene and styrene to metal in the step (2) is from 0.4:1 to 10:1.

In the catalyst preparation method of the present invention, the mass ratio of divinylbenzene to styrene in the step (2) is 1:1-20, preferably 1:5～1:10; the total mass and peroxidation of divinylbenzene and styrene The mass ratio of dibenzoyl is from 20:1 to 200:1, preferably from 50:1 to 100:1.

In the catalyst preparation method of the present invention, the polyvinyl alcohol in the step (2) is added in the form of an aqueous solution, and the polyvinyl alcohol in the aqueous solution of polyvinyl alcohol has a mass content of 0.5 to 5%, preferably 1 to 3%; The mass ratio of the alcohol to the polyvinyl alcohol in the aqueous polyvinyl alcohol solution is from 5:1 to 30:1, preferably from 10:1 to 15:1.

In the step (2) of the present invention, dibenzoyl peroxide, divinylbenzene, styrene, isopropanol and polyvinyl alcohol are reacted to form a suspended polymer, and the polymer oil droplets suspended between the solution and the solution are carried out as the reaction proceeds. A distinct phase interface will begin to appear, followed by the metal treated in step (1).

In the catalyst preparation method of the present invention, the mass ratio of the total mass of divinylbenzene to styrene and the aqueous solution of polyvinyl alcohol in the step (2) is from 1:3 to 1:30, preferably from 1:5 to 1:10.

By controlling the ratio of the polymerized monomer styrene and divinylbenzene in the step (2) to obtain a polystyrene resin having a different degree of crosslinking, controlling the number average molecular weight molecular weight of the polystyrene to be from 50,000 to 200,000, preferably from 8 to 150,000; Further, the volume content of the metal in the particles is controlled by controlling the mass ratio of the polystyrene resin to the metal, referring to the density of the resin of different crosslinking degrees, and the metal density.

In the catalyst preparation method of the present invention, the temperature rising process in the step (2) is to raise the temperature to 85 ° C in half an hour. By monitoring the viscosity and hardness of the particles during the reaction, the particles begin to phase out. Mutual adhesion, when starting to become brittle (when crushed by external force, no plastic deformation occurs), stop heating and add water to the reaction kettle while stirring to cool to room temperature, drain the liquid and then wash the surface of the particles and the pores. The polyvinyl alcohol and isopropyl alcohol are then heated to dry the moisture of the granules, and the drying temperature is 60 to 110 ° C, preferably 90 to 100 ° C.

In the catalyst preparation method of the present invention, in the step (3), an oxygen diluted with an inert gas or an air diluted with an inert gas is introduced into the reaction vessel to oxidize a metal surface not covered with polystyrene, the inert gas. The volume concentration of oxygen in the diluted air of diluted oxygen or inert gas is 0.1 to 25%, preferably 1 to 5%. The internal temperature of the particle stack is not more than 150 ° C during the oxidation process, and the oxidation rate is controlled to prevent the metal oxidation rate from being too fast. The temperature is too high and the catalyst polystyrene portion is burned out.

In the preparation method of the catalyst of the present invention, the polystyrene gas diluted on the outer surface of the particle is sulfonated using an inert gas diluted sulfur trioxide gas, specifically, the pellet obtained in the step (3) is heated to 60 to 100 in a fixed bed. Sulfation at °C, preferably 70-80 ° C; pre-heating the sulfur trioxide gas diluted with inert gas to 60-100 ° C, preferably 70-80 ° C, and then passing into a fixed bed to sulfonate the particles; wherein, the inert gas is diluted The volume concentration of sulfur trioxide in the sulfur trioxide gas is 0.5 to 10%, preferably 1 to 5%; the surface of the particle is not converted into a corresponding metal sulfate by the polystyrene-coated metal oxide, and the polystyrene is sulfonated. Is a polystyrene sulfonic acid resin; the particles contain pores, the outer surface of the particles and the polystyrene on the surface of the pores are sulfonated to a polystyrene sulfonic acid resin; after the sulfonation is completed, the sulfur trioxide is replaced with nitrogen, and the catalyst is prepared. Finished, sealed and stored to avoid water absorption.

The invention also provides a method for catalyzing the dehydration of t-butanol with isobutylene to produce isobutylene and diisobutylene, the steps comprising:

(1) charging the polystyrene sulfonic acid resin catalyst in the shell side and the tube length of the tubular reactor; preheating the tert-butanol and then introducing it into the reactor tube, under the action of the catalyst, Performing a dehydration reaction to form isobutylene;

(2) separating isobutene and tert-butanol in the reaction liquid obtained in the step (1), recycling the tert-butanol to the tube of the reactor to continue the dehydration reaction; and all or part of the isobutylene Entering the shell side of the reactor, performing an oligomerization reaction under the action of the catalyst to form diisobutylene, wherein isobutene which is not subjected to oligomerization in the shell side of the reactor is produced as a product;

(3) separating isobutylene and diisobutylene in the reaction liquid obtained in the step (2), and producing the diisobutylene as a product; recycling all or part of the isobutylene back to the shell side of the reactor for oligomerization, wherein Isobutene which is not circulated into the shell side of the reactor is produced as a product;

Alternatively, a method of using the above catalyst for catalyzing the dehydration of t-butanol with isobutylene to produce isobutylene and diisobutylene comprises the steps of:

(1) charging the polystyrene sulfonic acid resin catalyst in the shell side and the tube length of the tubular reactor; preheating the tert-butanol and then passing it into the shell side of the reactor, under the action of the catalyst, Performing a dehydration reaction to form isobutylene;

(2) separating isobutene and tert-butanol in the reaction liquid obtained in the step (1), recycling the tert-butanol back to the shell side of the reactor to continue the dehydration reaction; and all or part of the isobutylene Into the tube of the reactor, performing an oligomerization reaction under the action of the catalyst to form diisobutylene, wherein isobutene which is not subjected to the oligomerization reaction of the tube of the reactor is produced as a product;

(3) separating isobutylene and diisobutylene in the reaction liquid obtained in the step (2), and producing the diisobutylene as a product; and recycling the isobutylene in whole or in part to the tube of the reactor for oligomerization, wherein Isobutylene, which is not circulated through the tube of the reactor, is produced as a product; the remainder is a by-product of trimerization or more.

In the present invention, the t-butanol dehydration reaction and the isobutylene oligomerization can be carried out in the shell side/tube length and the tube side/shell side. The dehydration of tert-butanol is an endothermic reaction, the isobutene is oligomerized in an exothermic reaction, the isobutene oligomerization and the tert-butanol dehydration are carried out in the tube and shell side or shell side and tube side of the reactor, respectively, due to the exothermic heat of isobutene oligomerization. The heat absorption of the reaction which is greater than the dehydration of t-butanol is therefore preferably carried out by dehydration of t-butanol as a cold side in the shell side and oligomerization of isobutene as a hot side in the tube side. Since isobutene is oligomerized into a secondary reaction, the exothermic power is large, and the oligomerization reaction is placed in the tube process to shorten the heat transfer distance from the center of the catalyst to the wall surface. If the oligomerization reaction is to be carried out in the shell side, control is required. The distance between the outer walls of the tubes is such that heat within the catalyst bed is difficult to remove, the distance not exceeding 50 mm. The present invention uses a polystyrene sulfonic acid resin to catalyze the dehydration of t-butanol and the isobutene oligomerization to produce isobutylene and diisobutylene. The separation in step (2) and step (3) can be carried out by methods well known in the art, including but It is not limited to flash distillation, rectification, extraction, and the like.

The present invention uses a polystyrene sulfonic acid resin catalyst to catalyze the dehydration of t-butanol and the homopolymerization of isobutylene to produce isobutylene and diisobutylene, respectively. The raw material t-butanol is an aqueous solution of t-butanol or tert-butanol, of which tert-butyl The content of the alcohol is from 1 to 100% by weight, preferably from 30 to 100% by weight, more preferably from 70 to 100% by weight. Since the freezing point of t-butanol is higher (24.5 ° C), the temperature of lower than 24.5 ° C will cause the t-butanol to solidify. Therefore, the raw material of dehydration of t-butanol must be kept above 24.5 ° C to make it liquid; When the alcohol is an aqueous solution, the presence of water lowers the freezing point, and the temperature of the raw material can be appropriately lowered.

In the present invention, the tert-butanol is dehydrated to an upper feed or a lower feed. The isobutylene produced by the dehydration of t-butanol is a non-polar substance, and the solubility in the polar substance t-butanol and water is small, and isobutylene is added. The density is lower than that of tert-butanol and water, the water in the reaction liquid tends to sink, and the isobutylene tends to float. Therefore, the tert-butanol is preferably an upper feed, which facilitates the discharge of water and shifts the reaction equilibrium in the direction of dehydration.

In the present invention, the tert-butanol dehydration reaction temperature is 40 to 200 ° C, preferably 60 to 120 ° C, wherein the reaction temperature is the range between the lowest temperature and the hot spot temperature in the reactor; the reaction pressure (absolute pressure) is The liquid hour volume space velocity of the tert-butanol is 0.1 to 50 h ^-1 , preferably 0.5 to 20 h ^-1 , more preferably 2 to 10 h ^-1 .

In the present invention, the tert-butanol enters the reactor in the form of a liquid phase, and the preheating temperature does not exceed its boiling point at the operating pressure. For example, the boiling point of t-butanol is 82.5 ° C at an absolute pressure of 0.1 MPa. The thermal temperature must not exceed 82.5 °C. The isobutylene oligomerization reaction temperature is from 30 to 150 ° C, preferably from 60 to 110 ° C, wherein the reaction temperature is in the range between the lowest temperature in the reactor and the hot spot temperature. The isobutylene needs to be fed and reacted in a liquid form. Therefore, the preheating temperature and the reaction temperature cannot exceed the boiling point at the corresponding reaction pressure, for example, the preheating temperature and the reaction temperature are controlled below 100 ° C under an absolute pressure of 2 MPa. Similarly, when the reaction temperature is determined, the reaction pressure must also be maintained above the saturated vapor pressure of isobutylene at the corresponding temperature. For example, at a reaction temperature of 100 ° C, the reaction pressure must be maintained at an absolute pressure of 2 MPa or more.

In the present invention, since the isobutylene oligomerized raw material isobutylene and the products diisobutylene, triisobutylene and the like are non-polar substances, the layer does not stratify in the bed layer, so the feed direction or the lower feed of the isobutylene is in the feed direction. can.

In the present invention, the isobutylene oligomerization reaction temperature is 30 to 150 ° C, preferably 60 to 110 ° C; the reaction pressure (absolute pressure) is 0.3 to 20 MPa, preferably 1 to 10 MPa, more preferably 1 to 5 MPa; The space velocity is from 1 to 50 h ^-1 , preferably from 1 to 20 h ^-1 , more preferably from 2 to 10 h ^-1 .

The dehydration reaction of tert-butanol is an endothermic reaction, and the temperature at the inlet of the reactor is the highest, and the reaction rate is the fastest. As the reaction progresses, the temperature of the bed gradually decreases, and the reaction rate is also greatly reduced. The isobutene is oligomerized to an exothermic reaction. As the reaction progresses, the bed temperature gradually increases. If the heat is not removed, the reaction is out of control, the polymer is increased, and the selectivity of the diisobutylene is lowered. Therefore, the two reactions of dehydration of tert-butanol and oligomerization of isobutylene are respectively placed in the shell side and the tube process of the tubular reactor, and a downstream feed mode is adopted, that is, t-butanol and isobutylene are both upper feeds. The low temperature portion of the lower portion of the shell-side t-butanol dehydration bed can receive the heat released from the tube-range isobutene, so that the dehydration of the t-butanol continues rapidly, while the temperature rise of the isobutene oligomerization is controlled to ensure high diisobutylene selectivity. .

Since the tert-butyl alcohol dehydration and the isobutylene oligomerization adopt the metal-coated polystyrene sulfonic acid resin catalyst, the thermal conductivity is greatly improved, so that the heat of the isobutylene oligomer can be quickly transferred from the inside of the tube to the wall of the tube, and further transmitted. To the inside of the bed dehydrated to tert-butanol.

The isobutylene concentration in the initial stage of isobutylene oligomerization is the highest, the reaction rate is the fastest, and the exothermic power is the largest. It is necessary to remove the heat as soon as possible. Otherwise, local temperature will be too high, resulting in high polymerization, isomerization and cracking, and sulfonation. The acid group shedding rate is accelerated and the catalyst deactivation is accelerated. The catalyst of the invention is coated with metal in the polystyrene, so that the thermal conductivity of the catalyst is greatly improved. When the isobutylene is used for oligomerization, the heat generated inside the reactor bed can be quickly transferred to the outside of the bed, thereby reducing The effect of low bed temperature; when desorbing the endothermic t-butanol, the heat outside the bed can also be quickly transferred to the inside of the bed.

The concentration of t-butanol in the initial stage of the dehydration reaction of t-butanol is high, the reaction rate is fast, the endothermic power is large, and high-power heat is required for replenishment. Especially when the resin catalyst is used, the thermal conductivity of the catalyst is low, and the heat transfer is slow. The heat cannot be transferred to the inside of the catalyst bed in time, and the reaction rate is greatly reduced. The catalyst of the present invention allows the heat outside the bed to be transferred to the interior of the bed more quickly, allowing the reaction to proceed faster.

In the present invention, the catalyst is loaded into the tube and shell sides of the reactor according to different amounts of metal addition, and the purpose of the step filling of the bed is: the highest rate of isobutylene oligomerization and the position of maximum exothermic power. The corresponding t-butanol dehydration reaction rate is also the highest, and the endothermic power is also the largest. At this position, the catalyst with the highest metal content is loaded, so that the heat released by the isobutene is rapidly transferred to the inside of the dehydrated bed of t-butanol, two reactions The absorption and release heat are complementary to achieve the purpose of optimizing the bed temperature and reaction effect. For the isobutene oligomerization reaction, the bed has the highest concentration of isobutylene, the fastest reaction rate and the highest exothermic power. Therefore, the catalyst with the highest metal content is charged at the inlet of the reactor, so that the heat of the isobutene oligomerization reaction is transferred to the bed in time. The outer wall; the concentration of isobutene in the back section of the bed is gradually reduced. At this time, the bed temperature needs to be maintained to ensure that the reaction can continue. Therefore, the metal content of the catalyst in the middle and the back stage is gradually lowered. The lowering of the temperature of the inlet section reduces the conversion of isobutylene in the inlet section, and more isobutene reacts in the middle and rear stages, so the bed temperature in the middle and the back section will increase. Therefore, the temperature in the front and back sections of the bed tends to be higher. gentle. Similarly, for the dehydration reaction of t-butanol, the concentration of t-butanol at the inlet of the reactor is the highest, the reaction rate is also the fastest, the endothermic power is also the fastest, the bed temperature is rapidly decreased, and the catalyst with a high metal content in the inlet bed can be used. The heat generated by the oligomerization of isobutylene is more quickly transferred to the bed of the t-butanol dehydration catalyst, which promotes the reaction to proceed faster. As the concentration of the t-butanol decreases, the reaction gradually becomes slower and needs to continue to provide heat, while isobutene is required. The increase in bed temperature in the latter stage of the polymerization can continuously transfer heat to the dehydration reaction of t-butanol.

In the present invention, the optimization of the bed temperature and the heat transfer efficiency causes the temperature of the hot spot to be greatly reduced, and the DIB can be directly prepared by using an oligomer having an isobutylene content of 80% or more, preferably a raw material having an isobutylene content of 90% or more, more preferably isobutylene. A raw material having a content of 99% or more.

In addition, the catalyst of the present invention is not converted to a sulfate after the surface of the metal coated with polystyrene, and has the ability of coordination catalysis during the oligomerization of isobutylene, and the coordination catalysis is not compared with pure acid catalysis. The carbon skeleton is heterogeneous, so there is almost no useless C8 isomer in the isobutylene oligomerization product, and the selectivity of DIB is high. When the catalyst is used for the dehydration of t-butanol, the sulfate solution is combined to lose the catalytic activity due to the presence of a large amount of water in the system. Therefore, when the catalyst of the present invention is used for the dehydration reaction of t-butanol, the metal sulfate does not participate in the catalytic reaction. Therefore, it does not affect the selectivity of isobutylene due to its high oligomerization catalytic activity; when it is used for the oligomerization of isobutylene, a small amount of water will be mixed with isobutylene due to a large excess of isobutylene. The olefin is hydrated to form tert-butanol and is carried out of the reactor with the product. Therefore, the present invention separates isobutene and tert-butanol in the reaction liquid obtained in the step (1) in the step (2), and ensures the isobutene. The water content (mass content) should not exceed 2000 ppm, preferably less than 1000 ppm, more preferably less than 500 ppm.

The specific reaction mechanism of the catalyst for catalyzing the oligomerization of isobutylene according to the present invention is exemplified by the coating of metal Ni, as follows: the sulfonic acid group on the polystyrene resin has weak interaction with nickel sulfate, and forms between Ni and H. Ni-H bond, isobutene and nickel are coordinated, hydrogen ion addition reaction occurs, sulfonic acid group and tert-butyl group directly form σ covalent bond with nickel, and then another molecule of isobutylene is coordinated with nickel to generate carbon-carbon bond The reaction is inserted to form an octyl group attached to nickel, and finally β-hydrogen elimination occurs to form diisobutylene, and the catalyst completes the catalytic cycle.

The metal sulfate of the catalyst of the present invention is partially deactivated after being hydrated with water during use, and is dehydrated and regenerated by vacuum drying until the weight is no longer reduced, and the regeneration temperature is below 150 ° C, preferably 110 ° C. the following.

In the present invention, the shell-side material of the tubular reactor is up-and-down or down-in and out. Feeding in the liquid phase ensures that the entire bed is filled with liquid, closer to the plug flow, thereby reducing the effects of back mixing. When the liquid is fed, the liquid will be preferentially passed through the flow channel with the least resistance, and the channel flow and the short circuit are easily formed. The residence time distribution in the reactor is widened and the temperature distribution is more irregular, resulting in different tubes. The external temperature distribution is different, and the heat absorption and release heat of the tube and shell sides are difficult to couple. In order to make up for Insufficient flow unevenness, the general bed reactor requires a liquid distributor at the top of the reactor and a redistributor in the middle of the reactor, which increases the difficulty in reactor design and processing.

In the present invention, the reactor of the tubular reactor has an aspect ratio of from 1 to 100, preferably from 2 to 50, more preferably from 3 to 10. The low aspect ratio is not favorable for uniform distribution of the shell-side stream flow field. The inner diameter of the tube of the tubular reactor is 3 to 100 mm, preferably 10 to 60 mm, more preferably 20 to 50 mm; and the tube is one or more of a light tube, an inner fin tube and an outer fin tube. Combination, using an inner finned tube or an outer finned tube can increase the heat transfer comparison area. The maximum spacing between the outer walls of the tubes is controlled to be from 3 to 100 mm, preferably from 10 to 60 mm, more preferably from 20 to 50 mm.

In the present invention, the number of shell-side inlets of the tubular reactor is from 1 to 100, preferably from 2 to 40, more preferably from 4 to 20. The inlets are evenly distributed along the same horizontal line around the shell side of the reactor, or evenly distributed in groups of several, such as a total of 20 inlets, which can be evenly distributed according to the angle of 9°, or divided into 4 groups of 4 groups, the center line of 4 groups. The angle is 90 ° C, and the angle in the group is less than 9 °.

In the present invention, the number of shell-side outlets of the tubular reactor is from 1 to 100, preferably from 2 to 40, more preferably from 4 to 20; the inlets are uniformly distributed along the same horizontal line around the shell side of the reactor, or each The group is evenly distributed, such as a total of 20 inlets, which can be evenly distributed according to the angle of 9°, or divided into 4 groups every 5 groups. The center line of the 4 groups has an angle of 90 ° C, and the angle within the group is less than 9 °.

In the present invention, the number of shell-side outlets and inlets of the tubular reactor may be the same or different, and the inlet and outlet ports are aligned or staggered in the vertical direction, preferably staggered. The staggered arrangement of the multiple inlets and outlets in the vertical direction can make the distribution of the shell-side fluid more reasonable and minimize the dead zone.

In the present invention, the shell-and-tube reactor may be provided with a baffle or a baffle without a baffle, and the baffle is one of an arcuate shape, a rectangular shape, and a spiral shape, preferably a spiral shape. The arcuate and rectangular baffles allow the shell-side fluid to fold back and forth on the same plane, while the spiral baffles allow the shell-side fluid to spiral, with no dead zones and a more uniform flow field distribution.

The positive effects of the present invention are:

The polystyrene sulfonic acid resin catalyst of the present invention can greatly improve the heat conduction problem of the catalyst in the fixed bed reaction process, and can optimize the temperature distribution of the reaction bed. In the isobutylene oligomerization reaction, the single pass conversion rate and product selectivity are greatly improved under the condition that the isobutylene does not need to be greatly diluted;

In addition, the preparation steps of the polystyrene sulfonic acid resin catalyst of the invention are relatively simple, and the form and content of each component are easy to be characterized;

On the other hand, the invention solves the problem that the dehydration of t-butanol and the homopolymerization of isobutylene to produce butene and diisobutylene requires dehydration of t-butanol to provide external heat, and the oligomerization of isobutylene requires external removal of heat, which reduces the whole process. Energy consumption.

And using the catalyst of the invention, the single pass conversion of the tert-butanol dehydration reaction reaches 40% Above, the isobutylene selectivity is more than 99%; isobutylene oligomerization can directly use high concentration of isobutylene as a raw material, without requiring a large amount of dilution, the single pass conversion of isobutylene is more than 90%, the selectivity of the dimer is more than 80%, and the dimer The content of DIB in the medium is more than 99%, no secondary purification is required; the energy consumption of the reaction of dehydration of tert-butanol and oligomerization of isobutylene is reduced, and the energy consumption for separation is also reduced.

DRAWINGS

Figure 1 is a schematic diagram of the inlet and outlet arrangement and shell side flow of the shell-and-tube reactor;

2 is a scanning electron microscope image of the catalyst 1;

Figure 3 is a scanning electron microscope image of the uncoated metal of the catalyst 1 after it has been completely dissolved;

Figure 4 is a schematic view of the structure of the catalyst.

detailed description

The following examples are intended to further illustrate the methods of the present invention, but the invention is not limited to the examples shown, but also includes any other well-known variations within the scope of the claims.

instrument:

Gas Chromatography: Agilent 7890, equipped with a 30m × 0.3mm DB-5 capillary column and FID detector; inlet temperature 280 ° C, temperature program: 50 ° C for 3 min, 15 ° C / min to 300 ° C for 3 min The detector temperature is 280 ° C, the argon carrier gas flow rate is 20 ml/min, the hydrogen flow rate is 30 ml/min, and the air flow rate is 300 ml/min. The split ratio is 10:1.

Scanning electron microscope: JSM-6360LV, JEOL Ltd.

Gel chromatography: (Waters 2410 Refractive Index Detector).

Tert-butanol, 99.9wt%, Hisun Chemical Co., Ltd.

Styrene, ≥99%, Sinopharm Chemical Reagent Co., Ltd.

Divinylbenzene, ≥99%, Aladdin reagent.

Dibenzoyl peroxide, ≥98%, Sinopharm Chemical Reagent Co., Ltd.

Pentaerythritol monooleate, ≥99%, Hubei Chushengwei Chemical Co., Ltd.

Isopropyl alcohol, ≥99%, Sinopharm Chemical Reagent Co., Ltd.

Test method for ratio of coated and uncoated metal in catalyst:

The total volume V1 of the prepared catalyst was measured by a liquid discharge method; then the uncoated metal on the surface of the catalyst was slowly dissolved using 0.1 mol% of dilute hydrochloric acid, and the uncoated gold was determined by sampling electron microscopic analysis. To the extent that the uncoated metal is completely dissolved (converted to metal chloride and hydrogen), the catalyst is removed for cleaning and the volume V2 is retested;

Dissolving polystyrene in the catalyst using tetrahydrofuran, filtering to obtain filter residue (remaining metal), the volume of the metal coated with polystyrene is V3;

The volume of uncoated metal is (V1-V2), the total volume of metal (V1-V2+V3), and the ratio of uncoated metal to total metal volume is (V1-V2)/(V1-V2+V3 ).

Polystyrene sulfonic acid resin molecular weight test method:

The prepared polystyrene sulfonic acid resin was dissolved in tetrahydrofuran, and its number average molecular weight was measured using gel chromatography.

Example 1

Preparation of Catalyst 1:

(1) 323 L of rust-removed foamed nickel having a minimum dimensional dimension of 0.1 mm and a maximum dimension of 0.3 mm was added to a 1 m3 stirred tank after nitrogen replacement. Then, 350 L of pentaerythritol monooleate was added to the stirred tank, and the mixture was stirred at room temperature for 2 h under a nitrogen atmosphere. The liquid in the autoclave was then leached through a lower outlet with a screen under a nitrogen atmosphere, and the pentaerythritol monooleate on the surface of the foamed nickel powder was dried under nitrogen atmosphere for use.

(2) In a 5 m3 stirred tank with condensing reflux, 1920 kg of an aqueous solution of polyvinyl alcohol (1.5 wt%), 288 kg of isopropanol, 23 kg of divinylbenzene (density 0.93 kg/L), 68 kg were added. Styrene (density 0.90 kg / L), 1.8 kg of dibenzoyl peroxide (density 1.33 kg / L) and 50 L of foamed nickel treated in step (1). Under reflux condensation, the reaction temperature was raised to 85 ° C in half an hour while stirring, the temperature was controlled not to exceed 100 ° C, the state of the particles was monitored, and the heating was stopped when the particles began to become brittle and passed through the reaction kettle while stirring. The cooling coil is cooled to the reaction vessel, and deionized water is added to the reaction vessel to cool it to below 30 ° C; the liquid is drained through the lower outlet of the filter screen, and then deionized water is added to wash the polyethylene on the surface of the particle and the channel. Alcohol and isopropanol until the content of isopropanol in the outlet deionized water was determined to be less than 1% by gas chromatography.

(3) drying the granules obtained in the step (2), and then slowly introducing the air diluted with the polystyrene-coated foam nickel to form nickel oxide on the surface of the granules, which is diluted with an equal volume of nitrogen, and keep the granules in the process. The internal temperature does not exceed 150 °C.

(4) The particles prepared in the step (3) are placed in a fixed bed and heated to 75 ° C, and the sulfur trioxide gas diluted to 2% with nitrogen is preheated to 75 ° C and then passed through the above fixed bed to the particle surface. The nickel oxide not coated with polystyrene is converted into nickel sulfate, and the polystyrene is sulfonated into a polystyrene sulfonic acid resin; after the sulfonation is completed, the sulfur trioxide is replaced with nitrogen, and the catalyst 1 is prepared and sealed and stored.

The catalyst 1 prepared in the above procedure (Fig. 2 is a scanning electron micrograph of the catalyst 1, and Fig. 3 is a scanning electron micrograph after the uncoated metal in the catalyst 1 is completely digested). It has been tested that the proportion of foamed nickel in which the polystyrene sulfonic acid resin is coated is 70% based on the total volume of the foamed nickel, and the foamed nickel which is not coated with the polystyrene sulfonic acid resin is 30%, and the number of the polystyrene resin The average molecular weight was 150,000, and the catalyst 1 had an average particle diameter of 1 mm, a specific surface area of 50 m ² /g, an average pore diameter of 300 nm, a pore volume of 0.3 ml/g, and an exchange capacity of 3.5 mol/L. The volume ratio of the total volume of dibenzoyl peroxide, divinylbenzene and styrene to the metal is 2:1.

Example 2-4

Preparation of Catalyst 2-4

Except that the ratio of foamed nickel to polymer monomer (styrene and divinylbenzene) was changed, the same method as that in the first embodiment was employed, and the amount of foamed nickel was 50 L, respectively, to obtain a catalyst 2-4, see Table 1.

Table 1 Catalyst 2-4

Example 5-7

Preparation of Catalyst 5:

The other methods in the preparation of Catalyst 5 were the same as in Example 1 except that the following conditions were changed: the metal was changed to 50 L of fibrous cobalt having a minimum dimension of 10 μm and a maximum dimension of 30 μm, dibenzoyl peroxide, divinylbenzene and The ratio of the total volume of styrene to the volume of metal is 10:1, the mass ratio of divinylbenzene to styrene is 1:10, the ratio of benzoyl peroxide to the total mass of polymerized monomers is 1:100, isopropanol The mass ratio of the polyvinyl alcohol in the aqueous solution of polyvinyl alcohol (1.5 wt%) was 10:1, and the mass ratio of the total mass of the polymerized monomer to the aqueous solution of polyvinyl alcohol was 1:30. The obtained catalyst 5 is composed of a metal coated with polystyrene sulfonic acid resin, which accounts for 50% of the total volume of the metal, and the uncoated metal accounts for 50% of the total volume of the metal. The average particle diameter of the catalyst is 1 mm, and the specific surface area is 10 m. ² / g, an average pore diameter of 500 nm, a pore volume of 0.1 ml / g, and an exchange capacity of 1.5 mol / L.

Example 6

Preparation of Catalyst 6:

The other conditions in the preparation of Catalyst 6 were the same as in Example 1 except that the following conditions were met: the metal was changed to powder iron having a minimum dimension of 0.1 μm and a maximum dimension of 0.2 μm, dibenzoyl peroxide, divinylbenzene. The ratio of the total volume of styrene to the volume of metal is 1:2, the mass ratio of divinylbenzene to styrene is 1:7, and the ratio of dibenzoyl peroxide to the total mass of polymerized monomers is 1:70. The mass ratio of the polyvinyl alcohol in the aqueous solution of propanol to polyvinyl alcohol is 12:1, and the mass ratio of the total mass of the polymerized monomer to the aqueous solution of polyvinyl alcohol is 1:10. The obtained catalyst 6 has a metal coated with polystyrene sulfonic acid resin accounting for 50% of the total volume of the metal, the uncoated metal accounts for 50% of the total volume of the metal, and the average particle diameter of the catalyst is 0.5 mm, and the specific surface area is 30 m ² /g, an average pore diameter of 100 nm, a pore volume of 0.2 ml/g, and an exchange capacity of 1.5 mol/L.

Example 7

Preparation of Catalyst 7:

The other conditions in the preparation of Catalyst 7 were the same as in Example 1 except that the following conditions were changed: the metal was changed to a foamed nickel and foamed iron mixture (volume ratio 1:1) having a minimum dimension of 10 μm and a maximum dimension of 2 mm. The volume ratio of the total volume of dibenzoyl peroxide, divinylbenzene and styrene to metal is 1.2:1, the mass ratio of divinylbenzene to polystyrene is 1:4, dibenzoyl peroxide and polymerized monomer The total mass ratio is 1:20, the mass ratio of isopropanol to polyvinyl alcohol in the aqueous solution of polyvinyl alcohol is 15:1, and the mass ratio of the total mass of the polymerized monomer to the aqueous solution of polyvinyl alcohol is 1:5. The obtained catalyst 7 is composed of a metal coated with polystyrene sulfonic acid resin, which accounts for 50% of the total volume of the metal, and the uncoated metal accounts for 50% of the total volume of the metal. The average particle diameter of the catalyst is 2 mm, and the specific surface area is 100 m. ² / g, an average pore diameter of 10 nm, a pore volume of 0.5 ml / g, and an exchange capacity of 1.5 mol / L.

Example 8-13

Catalysts 1-7 were uniformly packed in the shell side and tube length of the tubular reactor in the order shown in Table 2 below, wherein the polymerization was carried out in the tube section, and the reaction conditions and results are shown in Table 2 below. The reactor parameters are as follows: tube reactor, column equilateral triangle arrangement, column center spacing 80mm, tube length 5m, tube tube 37; shell diameter 0.56m, line angle 90°; no fold in the shell Flow board.

Table 2 Examples 8-13 reaction conditions and results

It can be seen that the TBA single-pass conversion rate of TBA dehydration is above 40%, the selectivity of isobutylene is above 98%; above 90%, the selectivity of DIB is above 80%.

Comparative example 1

The TBA dehydration reaction produces isobutylene.

Tube reactor, tube inner diameter 40mm, wall thickness 4mm, tube equilateral triangle arrangement, tube center spacing 80mm, tube length 5m, tube tube 37; shell diameter 0.56m, axis of the two inlets and The axes of the two outlets are at an angle of 90°; there is no baffle in the shell. TBA reacted in the tube, filled with Rohm and Haas Amberlyst-70 polystyrene resin (Dow Chemical) with a height of 4.8m, tert-butanol (99.9%) as raw material, liquid hourly space velocity of 2.0h ^-1 , tert-butyl The alcohol inlet temperature was 80 ° C, the pressure was 0.3 MPa, and water of 80 ° C was introduced from the shell inlet, and the flow rate was 10 m ³ /h. The single pass conversion of tert-butanol was 21% and the selectivity of IB was 99.9%.

Comparative example 2

IB is oligomerized to prepare DIB.

The reactor was the same as that used in Comparative Example 1. Isobutylene is polymerized in the tube process, and the tube is filled with Rohm and Haas Amberlyst-70 polystyrene resin (Dow Chemical) with a filling height of 4.8 m, isobutylene purity of 99.9%, and tert-butyl alcohol as a sustained release agent. The alcohol content is 5 wt% of isobutylene, the liquid hourly space velocity is 2.0 h ^-1 , the inlet temperature is 80 ° C, the pressure is 5 MPa, and water of 80 ° C is introduced from the shell inlet, and the flow rate is 10 m ³ /h.

The composition of the outlet material (wt): IB = 2.9%, TBA = 4.8%, C8 = 30.1%, C12 + = 62.3%, the content of DIB in C8 was 73%, and the balance was C8 olefin isomer; the conversion per pass was 97%. The temperature in the front part of the catalyst is too high, and the hot spot reaches 185 °C. The reaction temperature is too high, resulting in a strong reaction in the front stage. A large amount of high polymerization occurs and the isomer is produced, and the selectivity of DIB decreases. Since the isobutylene in the previous stage has been consumed in a large amount, the concentration of isobutylene in the latter stage is greatly reduced. As a result, the reaction rate in the latter stage is very low, the bed temperature is also low, and the catalyst cannot be fully utilized.

Claims (11)

1. A polystyrene sulfonic acid resin catalyst comprising: a polystyrene sulfonic acid resin, a metal and a metal sulfate, wherein the metal comprises two parts: a metal coated with a polystyrene sulfonic acid resin, and a polyphenylene a metal coated with a vinyl sulfonic acid resin; the metal sulfate is converted from an outer leakage surface of the metal not coated with the polystyrene sulfonic acid resin.
2. The catalyst according to claim 1, characterized by being coated with said polystyrene sulfonic acid resin based on a total volume of a metal coated with said polystyrene sulfonic acid resin and an uncoated metal The volume fraction of the metal is from 1 to 90%, preferably from 10 to 70%, more preferably from 30 to 50%; the proportion of the metal not coated with the polystyrenesulfonic acid resin is from 99 to 10%, preferably 90 to 30%, more preferably 70 to 50%.
3. The catalyst according to claim 1 or 2, wherein the metal is one or more of Fe, Co, Ni, Ge, Sn, Pb, Zn, Cu, Cd and Sb, preferably Fe, Co and Ni One or more of the metals; the metal is one or more of metal fibers, metal foam, and metal powder; the metal has a minimum dimension of 0.1 to 100 μm and a maximum dimension of 2 mm or less.
4. The catalyst according to any one of claims 1 to 3, wherein the catalyst has a particle diameter of 0.1 to 3 mm, preferably 0.5 to 2 mm, a specific surface area of 10 to 100 m ² /g, and a pore diameter of 10 to 500 nm. The pore volume is 0.1 to 0.5 ml/g.
5. The catalyst according to any one of claims 1 to 4, wherein the polystyrene sulfonic acid resin has a number average molecular weight of from 50,000 to 200,000, preferably from 8 to 15,000,000.
6. A method of producing a polystyrene sulfonic acid resin catalyst according to any one of claims 1 to 5, the method comprising the steps of:

   (1) placing the metal in a reaction vessel after replacement with an inert gas, adding a long carbon chain organic compound having a polar group, stirring under an inert gas, and then leaching the liquid in the reaction vessel to be inert Drying and waiting for the metal under a gas atmosphere;

   (2) adding dibenzoyl peroxide, divinylbenzene, styrene, isopropanol and polyvinyl alcohol to the reaction vessel, stirring and heating, and when the reaction has a distinct phase interface, it will be treated by step (1). The metal is added to the reaction vessel, stirred until the particles begin to become brittle, the heating is stopped, water is added to the reaction vessel to cool to room temperature, the liquid is drained, and the obtained particles are washed and dried;

   (3) oxidizing the exposed surface of the non-polystyrene-coated metal of the particles after the drying in the step (2) to obtain a metal oxide until the particle mass is constant;

   (4) The pellet obtained in the step (3) is heated, the polystyrene is sulfonated and the metal oxide is converted into a metal sulfate to obtain the catalyst.
7. The preparation method according to claim 7, wherein the total volume of the dibenzoyl peroxide, divinylbenzene and styrene in the step (2) is the same as that added in the step (2) The volume ratio of the metal is from 0.4:1 to 10:1.
8. The preparation method according to claim 6 or 7, wherein the mass ratio of the divinylbenzene to styrene in the step (2) is 1:1 to 1:20, preferably 1:5 to 1: 10; the mass ratio of the total mass of divinylbenzene and styrene to dibenzoyl peroxide is from 20:1 to 200:1, preferably from 50:1 to 100:1, and the polyvinyl alcohol is added as an aqueous solution, isopropyl The mass ratio of the alcohol to the polyvinyl alcohol in the aqueous solution of polyvinyl alcohol is 5:1 to 30:1, preferably 10:1 to 15:1, and the mass ratio of the total mass of divinylbenzene to styrene to the aqueous solution of polyvinyl alcohol is 1 : 3 to 1:30, preferably 1:5 to 1:10.
9. The preparation method according to any one of claims 6 to 8, wherein the long carbon chain organic compound having a polar group in the step (1) is a sulfonic acid having the formula R-SO ₃ a salt, a carboxylic acid of the formula R-COOH and (R-COO) _n M and a soap thereof, a lipid of the formula RCOOR', an amine of the formula R-NH ₂ and a sulfur-nitrogen heterocycle One or more of the compounds, preferably a lipid, wherein R and R' are each a long carbon alkyl group having a carbon number of greater than 4, preferably greater than 8, and n is an integer from 1 to 7; said polar group having a polar group The long carbon chain organic compound is more preferably one or more of sorbitan monooleate, beeswax, pentaerythritol monooleate, and lanolin.
10. A catalyst according to any one of claims 1 to 5 or a catalyst prepared according to the method of any one of claims 6 to 9 for catalyzing the dehydration of t-butanol and the homopolymerization of isobutylene to produce isobutylene and diisobutylene, respectively. Method, the method comprising the steps of:

    (1) charging the polystyrene sulfonic acid resin catalyst in the shell side and the tube length of the tubular reactor; preheating the tert-butanol and then introducing it into the reactor tube, under the action of the catalyst, Performing a dehydration reaction to form isobutylene;

    (2) separating isobutene and tert-butanol in the reaction liquid obtained in the step (1), recycling the tert-butanol to the tube of the reactor to continue the dehydration reaction; and all or part of the isobutylene Entering the shell side of the reactor, performing an oligomerization reaction under the action of the catalyst to form diisobutylene, wherein isobutene which is not subjected to oligomerization in the shell side of the reactor is produced as a product;

    (3) separating isobutylene and diisobutylene in the reaction liquid obtained in the step (2), and producing the diisobutylene as a product; recycling all or part of the isobutylene back to the shell side of the reactor for oligomerization, wherein Isobutene which is not circulated into the shell side of the reactor is produced as a product;

    or,

    (1) charging the polystyrene sulfonic acid resin catalyst in the shell side and the tube length of the tubular reactor; preheating the tert-butanol and then passing it into the shell side of the reactor, under the action of the catalyst, Performing a dehydration reaction to form isobutylene;

    (2) separating isobutene and tert-butanol in the reaction liquid obtained in the step (1), recycling the tert-butanol back to the shell side of the reactor to continue the dehydration reaction; and all or part of the isobutylene Into the tube of the reactor, performing an oligomerization reaction under the action of the catalyst to form diisobutylene, wherein isobutene which is not subjected to the oligomerization reaction of the tube of the reactor is produced as a product;

    (3) separating isobutylene and diisobutylene in the reaction liquid obtained in the step (2), and producing the diisobutylene as a product; and recycling the isobutylene in whole or in part to the tube of the reactor for oligomerization, wherein Isobutylene, which is not circulated through the tube of the reactor, is produced as a product.
11. The method according to claim 10, wherein the temperature of the dehydration reaction of the tert-butanol is 40 to 200 ° C, preferably 60 to 120 ° C; and the absolute pressure of the reaction is 0.1 to 10 MPa, preferably 0.2 to 5 MPa, more preferably 1 ～4 MPa; the liquid hourly space velocity of tert-butanol is 0.1 to 50 h ^-1 , preferably 0.5 to 20 h ^-1 , more preferably 2 to 10 h ^-1 ; the temperature of the isobutylene oligomerization reaction is 30 to 150 ° C, preferably 60 to 110 The absolute pressure is 0.3 to 20 MPa, preferably 1 to 10 MPa, more preferably 1 to 5 MPa; and the isobutylene liquid has a volume space velocity of 1 to 50 h ^-1 , preferably 1 to 20 h ^-1 , more preferably 2 to 10 h ^-1 .

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