CN114471378A

CN114471378A - Olefin hydration reactor and olefin hydration method

Info

Publication number: CN114471378A
Application number: CN202011172321.1A
Authority: CN
Inventors: 周峰; 马会霞; 杨秀娜; 乔凯; 张淑梅; 姜睿
Original assignee: China Petroleum and Chemical Corp; Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Priority date: 2020-10-28
Filing date: 2020-10-28
Publication date: 2022-05-13

Abstract

The invention discloses an olefin hydration reactor and an olefin hydration method. The olefin hydration reactor comprises a micromixing zone and an olefin hydration reaction zone. The method comprises the steps of enabling a mixture of olefin raw materials and water to enter a micro mixing reaction zone of an olefin hydration reactor, enabling the mixture to flow through micro channels among fiber filaments in a micro channel assembly, continuously cutting the mixture for many times by the fiber filaments to form a mixed fluid containing a large number of micron-sized particles, enabling the mixed fluid to enter a catalyst bed layer of the olefin hydration reaction zone to perform olefin hydration reaction, and enabling a reaction effluent to leave the reactor. The method can uniformly disperse the water phase in the olefin phase by micro-scale particles, realize the micro-mixing and the high-efficiency contact mass transfer of the olefin and the water, greatly improve the hydration reaction rate of the olefin and the one-way conversion rate of the raw material, reduce the number and the volume of reactors, reduce the water-olefin ratio and improve the production efficiency of the device.

Description

Olefin hydration reactor and olefin hydration method

Technical Field

The invention belongs to the technical field of organic chemical industry, and particularly relates to an olefin hydration reactor and an olefin hydration method.

Background

The low carbon olefin hydration process is an important method for industrially producing low carbon alcohol. The reaction process is a three-phase reaction of liquid (olefin), liquid (water) and solid (catalyst), so the reaction rate and the conversion rate are greatly influenced by mass transfer. The relatively low mutual solubility of olefin and water restricts the reaction efficiency and the productivity of the whole process. In the olefin hydration reaction, the preparation of tert-butyl alcohol by isobutylene hydration, the preparation of cyclohexanol by cyclohexene hydration and the preparation of tert-amyl alcohol by direct hydration of isoamylene are typical and important organic reaction processes.

In the process of preparing tert-butyl alcohol by isobutene hydration, the mutual solubility of hydrocarbons such as isobutene and the like and water is small, and two liquid phases are easily formed when the hydrocarbons and the water are mixed in a liquid state. The key technology for isobutylene hydration is to form a homogeneous dispersion or solution of carbon-tetramixed hydrocarbons with water to increase the conversion of the reaction. CN1304917A adopts an operation mode that isobutene and water are fed into a tower in a countercurrent mode, and the product tert-butyl alcohol is continuously discharged from the tower, so as to improve the concentration difference of two phases and improve the reaction rate and the isobutene conversion rate, but the method has the problems of large water ratio, small space velocity, difficult catalyst forming and the like. CN02151547.6 provides a method for preparing tert-butyl alcohol by hydration reaction by using mixed C4 containing isobutene as raw material, which is characterized in that isobutene in mixed C four fraction reacts with water in a catalytic distillation tower in the presence of non-ionic surfactant and catalyst to generate tert-butyl alcohol. The tertiary butanol preparation method provided by the invention greatly improves the conversion rate of isobutene and the tertiary butanol selectivity, and reduces the cost for producing tertiary butanol. CN98812676.1 provides a method for producing tertiary butanol, in order to increase the intersolubility of mixed C4 and water, tertiary butanol is added into the reaction raw material, the conversion rate of the reaction can reach 80-90%, the method relies on the centrifugal pump to force the tertiary butanol, water and liquid phase C four hydrocarbon to mix, promote dissolving, but actually uses the centrifugal pump method to force the mixing, also only the macroscopic mixing between phases, is difficult to mix on the microcosmic.

In the process of preparing cyclohexanol by cyclohexene hydration, the reactor form of the cyclohexene direct hydration production device used in the industry at present is a two-stage series full-mixing kettle reactor, the single-pass conversion rate is only 9 percent, the selectivity is 99 percent, the single-pass conversion rate of the cyclohexene hydration reaction is low, a large amount of unreacted cyclohexene and cyclohexanol are subjected to multiple cyclic rectification separation, and the energy consumption is high. Therefore, in order to improve the cyclohexene hydration reaction rate and the reaction conversion rate, CN 109651081 a proposes a reactive distillation method and a device thereof for preparing cyclohexanol by cyclohexene hydration, wherein a phase transfer catalyst is added into a reaction solution, so that cyclohexene, water, the catalyst and the phase transfer catalyst form a slurry solution, and cyclohexene hydration reaction occurs in a reactive distillation column to generate cyclohexanol. US3257469 uses polar organic solvents to increase the miscibility of olefins with water, and increases the conversion of carbon pentaolefins by increasing the diffusion rate of reactant molecules to the catalyst surface and the diffusion rate of product into the solvent. US4182920 patent uses a three-stage olefin hydration reactor, the reaction temperature is 30-80 deg.C, the reaction pressure is 0.46-1.4 MPa (absolute pressure), the weight ratio of water/pentene is 0.59-1.18, the weight ratio of acetone/pentene is 4.18-7.85, and the reaction rate is still very slow.

In conclusion, for the olefin hydration (preparation of tert-butyl alcohol by hydration of isobutene, preparation of cyclohexanol by hydration of cyclohexene, preparation of tert-amyl alcohol by direct hydration of isoamylene and the like), the reaction rate is greatly influenced by the intersolubility of olefin and water, so that microscopically enhancing the mixing state of olefin and water is a process route capable of effectively solving the problems of low reaction rate, long retention time and the like caused by low mass transfer rate of olefin hydration.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides an olefin hydration reactor and an olefin hydration method, which can uniformly disperse an organic phase in a water phase by micron-sized particles, realize micromixing and efficient contact mass transfer of olefin and water, greatly improve the olefin hydration reaction rate and the single-pass conversion rate of raw materials, reduce the number and the volume of the reactors, reduce the water-olefin ratio and improve the production efficiency of an olefin hydration device.

The olefin hydration reactor comprises a micro mixing area and an olefin hydration reaction area, wherein the micro mixing area comprises at least one micro channel component, preferably 1-3 micro channel components; the microchannel component comprises a plurality of stacked sheets, and lipophilic fiber yarns and hydrophilic fiber yarns which are filled between gaps of the adjacent sheets, wherein a plurality of microchannels are formed between the fiber yarns, and the fiber yarns are clamped and fixed through the sheets; at least one catalyst bed layer is arranged in the olefin hydration reaction zone, and the number of the catalyst bed layers is preferably 1-3.

In the olefin hydration reactor, the number ratio of the lipophilic fiber yarns and the hydrophilic fiber yarns filled between the gaps of the adjacent sheets is 1: 50-1: 1; the fiber yarns can be arranged in a single layer or multiple layers, 1-50 layers are preferred, 1-5 layers are more preferred, and the lipophilic fiber yarns in any layer are preferably uniformly distributed among the hydrophilic fiber yarns; preferably, the number ratio of the lipophilic fiber yarns to the hydrophilic fiber yarns in any layer is 1: 50-1: 1. When the fiber yarns are arranged in a multilayer mode, the projections of two adjacent layers of fiber yarns along the vertical direction of the sheet are preferably of a net structure; the shape of the mesh in the mesh structure can be any shape, such as one or more combinations of polygons, circles, ellipses and the like; in each layer of fiber yarns, the distance between adjacent fiber yarns is generally 0.5-50 μm, preferably the adjacent fiber yarns are arranged at equal intervals, and the fiber yarns are arranged along the surface of the sheet transversely, longitudinally or obliquely; the fiber filaments may be in any curved shape, preferably in a periodically changing curved shape, such as a wave shape, a zigzag shape, etc., preferably the fiber filaments in the same layer have the same shape, and more preferably the fiber filaments in all layers have the same shape.

In the micro-channel component, the diameter of the fiber filament is generally 0.5 to 50 μm, preferably 0.5 to 5 μm, and more preferably 0.5 to 1 μm. The oleophilic fiber is generally selected from polyester fibersAt least one of the fiber yarn, nylon fiber yarn, polyurethane fiber yarn, polypropylene fiber yarn, polyacrylonitrile fiber yarn and polyvinyl chloride fiber yarn, or the fiber yarn with oleophylic surface treated by physical or chemical method; the hydrophilic fiber is generally selected from carboxyl (-COOH), amido (-CONH-), amino (-NH) with main chain or side chain₂-.

In the microchannel assembly, the thickness of the thin sheet is generally 0.05 mm-5 mm, preferably 0.1-1.5 mm. The material of the sheet is generally determined according to the properties of the overflowing material and the operating conditions, and can be any one of materials such as metal, ceramic, organic glass, polyester and the like, and stainless steel (SS 30403, SS30408, SS32168 and SS 31603) materials in the metal are preferred. The shape of the sheet may be any of a rectangle, a square, a polygon, a circle, an ellipse, a fan, and the like, and a rectangle or a square is preferable. The size and the number of the sheets can be designed and adjusted according to the actual needs of the reaction.

In the olefin hydration reactor of the present invention, it is preferable to provide a plurality of micro mixing zones and olefin hydration reaction zones, the micro mixing zones and the olefin hydration reaction zones being alternately arranged, and it is more preferable that the number of the micro mixing zones and the number of the olefin hydration reaction zones are the same. According to the material flow direction, the material flow firstly passes through the micro-mixing reaction zone and then passes through the olefin hydration reaction zone.

In the olefin hydration reactor of the present invention, a make-up water line is provided outside the micromixing zone for maintaining the water concentration during the hydration reaction, and preferably, a make-up water line may be provided at the inlet of each microchannel module.

The invention also provides an olefin hydration method, which comprises the following steps: the method comprises the following steps of enabling a mixture of olefin raw materials and water to enter a micro mixing reaction zone of an olefin hydration reactor, enabling the mixture to flow through micro channels among fiber filaments in a micro channel assembly, continuously cutting the mixture for many times by the fiber filaments to form a mixed fluid containing a large number of micron-sized particles, enabling the mixed fluid to enter a catalyst bed layer of the olefin hydration reaction zone to carry out olefin hydration reaction, enabling reaction effluent to leave the reactor, and enabling the reaction effluent to enter a next separation unit.

In the method of the invention, the olefin raw material is any one of ethylene, propylene, n-butene, isobutene, isoamylene or cyclohexene.

In the method of the present invention, preferably, the olefin raw material and water are premixed and then enter the olefin hydration reactor, and the premixing can be performed by any equipment with mixing function, such as any one or more combinations of a static mixer, a colloid mill, a shearing machine, a stirring kettle, a ceramic membrane tube, etc., and is used for the primary mixing of the two phases of the olefin and the water.

In the method, the olefin hydration reactor can adopt a lower-in and upper-out mode and also can adopt an upper-in and lower-out mode; one or more olefin hydration reactors can be arranged, and the reactors can be connected in series or in parallel.

In the process of the present invention, the olefin hydration conditions are generally: the temperature is 80-250 ℃, the pressure is 1.0-10.0 MPaG, and the airspeed is 0.1-3.0 h^-1The reaction conditions required are different according to the different olefin raw materials; the conditions for premixing the olefin feedstock with water may be the same as or different from the conditions for hydrating the olefin, and are preferably the same.

In the method, the total water-olefin ratio in the olefin hydration reaction is determined according to the type of the olefin subjected to the olefin hydration reaction and the difficulty degree of the reaction, and the water-olefin mass ratio is generally 1: 1-20: 1.

In the method, the reaction raw material at the inlet of the olefin hydration reactor can be partially or completely added with water, preferably partially added, when the water is partially added, the addition amount is 30-90 wt% of the total water amount, the rest water can be added in the form of make-up water, the make-up water is supplemented at the inlet of each group of micro-channel assemblies through a make-up water pipeline and is used for maintaining the concentration of the water in the hydration reaction process, so that a high two-phase mass transfer driving force is kept, the addition amount of the make-up water at the inlet of each group of micro-channel assemblies is 1-30 wt% of the total water amount, preferably, the make-up water amount along the flowing direction of materials in the reactor is gradually increased, because the reaction products are gradually increased along with the progress of the reaction, the mass transfer driving force in the reaction process is gradually reduced, and the high reaction rate is kept through the gradually increased make-up water amount. The olefin may also be added in part or in whole, preferably in whole.

In the process of the present invention, a catalyst having an acid catalytic function, such as mineral acid, benzenesulfonic acid, ion exchange resin, molecular sieve, etc., can be generally used in the catalyst bed of the olefin hydration reaction zone.

In the method, under the general condition, the particle size of the dispersed phase in water formed by mixing the olefin raw material and water through the microchannel component is generally 0.5-900 microns, the dispersed phase enters the catalyst bed layer for reaction, and the preferable dispersion uniformity is more than or equal to 80 percent.

When conventional mixing equipment or components with mixing functions are adopted to mix olefin and water in the prior art, the problems of uneven mixing, unstable state and easy phase separation exist, in the olefin hydration reactor of the invention, the micro-channel component is arranged in the micro-mixing area, because the oleophylic \ hydrophilic fiber yarns with a certain proportion are filled between the gaps of the adjacent sheets in the micro-channel component, the water in the olefin and water mixed feed is adhered and spread along the surface of the hydrophilic fiber yarns, and is repeatedly and forcibly cut into particles with micron-sized size by the hydrophilic fiber yarns, the olefin is adhered and spread on the surface of the oleophylic fiber yarns, and the two micron-sized particles are mixed through micro-channels between the fiber yarns to form two phases of materials which are uniformly mixed on the micron-sized particles, and the two phases of materials enter a catalyst bed layer to carry out olefin hydration reaction. The olefin hydration reactor of the invention mixes the olefin and the water into a stable uniform phase, which is beneficial to improving the contact mass transfer of the two phases, and enables the organic phase to exist in the water phase as micron-sized particles, thereby greatly improving the contact area of the two phases and reducing the water-olefin ratio, which has good improvement effect on the problem of low reaction rate caused by the immiscible two phases like the olefin hydration reaction.

Drawings

FIG. 1 is a schematic diagram of an olefin hydration reactor of the present invention.

FIG. 2 is a schematic view of a microchannel assembly disposed within a reactor.

Wherein, 1 is olefin raw material, 2 is water, 3 is olefin \ water mixed material, 4 is reaction process make-up water, 5 is olefin hydration reactor, 6 is olefin hydration reaction product, 7 is first micro mixed zone, 8 is microchannel component in the first micro mixed zone, 9 is first olefin hydration reaction zone, 10 is first catalyst bed layer, 11 is second (or Nth) micro mixed zone, 12 is microchannel component in the second (or Nth) micro mixed zone, 13 is second (or Nth) olefin hydration reaction zone, 14 is second (or Nth) catalyst bed layer, 15 is microchannel shell, 16 is microchannel sheet, 17 is crack between microchannel sheets, 18 is hydrophilic fiber yarn, 19 is lipophilic fiber yarn.

Detailed Description

The invention is described in detail below with reference to the figures and examples, but the invention is not limited thereby.

The olefin hydration reactor and olefin hydration process of the present invention is illustrated by way of example in FIG. 1 of the accompanying drawings:

firstly, mixing an olefin raw material 1 and water 2 to obtain an olefin/water mixed material 3, wherein the mixed material enters a bottom inlet of an olefin hydration reactor 5, and the reactor comprises a first micro mixing zone 7, a first olefin hydration reaction zone 9, a first catalyst bed layer 10, a second (or Nth) micro mixing zone 11, a second (or Nth) olefin hydration reaction zone 13 and a second (or Nth) catalyst bed layer 14. The olefin/water mixed material 3 firstly enters a first micro mixing zone 7, passes through a crack 17 between microchannel sheets 16 in a microchannel assembly 8 arranged in a microchannel shell 15, is continuously cut for a plurality of times by hydrophilic fiber filaments 18 and lipophilic fiber filaments 19 filled between the cracks 17 to form two-phase uniformly mixed materials containing a large number of micron-sized particles, and enters a first catalyst bed layer 10 in a first olefin hydration reaction zone 9 to generate olefin hydration reaction. Along with the reaction, the reaction raw materials are continuously converted into products, so that the concentration of the raw materials including water is gradually reduced, and the reaction mass transfer driving force is reduced, therefore, in the reaction process, the raw materials continuously enter the second (or N) catalyst bed layer 14 to perform further olefin hydration reaction after being intensively mixed with the mixed materials through the micro-channel component 12 in the second (or N) micro-mixing zone again by adding the make-up water 4, and the mixture leaves as a reaction product 6 after the mass transfer reaction is completed.

The olefin hydration reactor is respectively applied to propylene, n-butene hydration, isobutene hydration and cyclohexene hydration reactions. The specific reaction conditions are shown in comparative example 1, comparative example 2, comparative example 3, comparative example 4, example 1, example 2, example 3, example 4, example 5 and example 6. The olefin raw materials are commercially available, and the specific properties are respectively shown in tables 1, 2 and 3. The catalyst for propylene hydration is a DIAP type catalyst produced by Dangerzhu special resin Co., Ltd, the catalyst for n-butene hydration is a DNW-II type catalyst produced by Dangerzhu special resin Co., Ltd, the catalyst for isobutene hydration is a DT-017 type catalyst produced by Dangerzhu special resin Co., Ltd, and the catalyst for cyclohexene hydration is an amberlyst 36 type resin catalyst.

TABLE 1 propylene feed composition

TABLE 2 composition of n-butene feedstock

TABLE 3 isobutene feed composition

Comparative example 1

Propylene in the table 1 is used as a raw material, and the propylene and water are subjected to n-butene hydration reaction under the action of a catalyst to prepare isopropanol. The propylene raw material and water pass through a conventional static mixer, the model number of SK-1.6/25-10-150, and the mixed material of the propylene raw material and the water enters a propylene hydration reactor to carry out hydration reaction. The reactor adopts a common upflow reactor, four sections of catalyst beds are arranged in the reactor, and a water replenishing pipeline and a nozzle component for mixing olefin/water are arranged between the catalyst beds. Introducing an olefin/water mixed material into an olefin hydration reactor from the bottom of the reactor, mixing the olefin/water mixed material by an olefin/water mixing nozzle component, then entering a catalyst bed layer to perform olefin hydration reaction, mixing the olefin/water mixed material with make-up water again by the olefin/water mixing nozzle component after the reaction is performed for a period of time, entering the catalyst bed layer again to continue the olefin hydration reaction, and finally leaving the olefin hydration reactor from a discharge hole at the top of the reactor. The mixing conditions of the propylene raw material and water are as follows: the temperature was 155 ℃ and the pressure was 8.1 MPaG.

The reaction conditions for hydrating the propylene are as follows: the temperature is 152-160 ℃, the pressure is 8.0MPaG, and the space velocity is 0.25h^-1The total water/olefin mass ratio was 15.

Propylene in table 1 was used as a raw material, and a reaction product was obtained by a propylene hydration reactor, and the reaction residence time and the raw material conversion rate are shown in table 4.

Comparative example 2

The n-butene in the table 2 is taken as a raw material, and the n-butene is subjected to hydration reaction with water under the action of a catalyst to prepare the sec-butyl alcohol. The n-butene raw material and water are continuously mixed for three times through a conventional static mixer with the model number of SK-1.6/25-10.0-200, and the mixed material enters an n-butene hydration reactor to generate hydration reaction. The reactor adopts a common upflow reactor, four sections of catalyst beds are arranged in the reactor, and a water replenishing pipeline and a nozzle component for mixing olefin/water are arranged between the catalyst beds. Introducing the n-butene/water mixed material into an olefin hydration reactor from the bottom of the reactor, mixing the n-butene/water mixed material by using the n-butene/water mixed nozzle component, then introducing the n-butene/water mixed material into a catalyst bed layer to perform olefin hydration reaction, mixing the n-butene/water mixed nozzle component with make-up water after the reaction is performed for a period of time, introducing the n-butene/water mixed nozzle component into the catalyst bed layer again to continue to perform olefin hydration reaction, and finally leaving the olefin hydration reactor from a discharge port at the top of the reactor. The mixing conditions of the n-butene raw material and water are as follows: the temperature was 180 ℃ and the pressure was 8.1 MPaG.

The n-butene hydration reaction conditions are as follows: the temperature is 175-180 ℃, the pressure is 8.0MPaG, and the space velocity is 1.0h^-1The total water/olefin mass ratio was 2.5. The reaction product was obtained from the n-butene hydration reactor using the n-butene shown in Table 2, and the residence time and the conversion of the n-butene raw material are shown in Table 4.

Comparative example 3

Isobutene in the table 3 is used as a raw material and undergoes isobutene hydration reaction with water under the action of a catalyst to prepare the tert-butyl alcohol. The isobutene raw material and water pass through a conventional static mixer with the model number of SK-1.6/25-5-200, and the mixed material of the isobutene raw material and the water enters an isobutene hydration reactor to carry out hydration reaction. The reactor adopts a common upflow reactor, two catalyst bed layers are arranged in the reactor, and a water replenishing pipeline and a nozzle component for mixing olefin/water are arranged between the catalyst bed layers. Introducing an isobutene/water mixed material into an olefin hydration reactor from the bottom of the reactor, mixing the isobutene/water mixed material by an isobutene/water mixing nozzle component, then introducing the isobutene/water mixed material into a catalyst bed layer to perform olefin hydration reaction, mixing the isobutene/water mixed material with make-up water again by the isobutene/water mixing nozzle component after the reaction is carried out for a period of time, introducing the isobutene/water mixed material into the catalyst bed layer again to continue the olefin hydration reaction, and finally leaving the olefin hydration reactor from a discharge port at the top of the reactor. The mixing conditions of the isobutene raw material and water are as follows: the temperature was 80 ℃ and the pressure was 2.6 MPaG.

The reaction conditions for isobutylene hydration are as follows: the temperature is 105-110 ℃, the pressure is 2.5MPaG, and the space velocity is 1.0h^-1The total water/olefin mass ratio was 3.

Isobutene of table 3 was used as a raw material, and a reaction product was obtained through an isobutene hydration reactor, and the residence time and the raw material conversion rate are shown in table 4.

Example 1

Propylene in the table 1 is used as a raw material, and the propylene is subjected to hydration reaction with water under the action of a catalyst to prepare isopropanol. The mixed material of propylene material and water is fed into a propylene hydration reactor to produce hydration reaction, the reactor adopts the reactor of the invention, and the reactor is provided with two sections of micro-channel components and two sections of catalyst bed layersThe microchannel components and the catalyst beds are alternately arranged. The thin slices in the micro-channel mixing assembly are made of stainless steel materials, the thickness of the thin slices is 1.5mm, 1 layer of 5-micrometer-diameter fiber yarns are filled between gaps of the thin slices, the fiber yarns comprise lipophilic polypropylene fiber yarns and hydrophilic polypropylene fiber yarns, the number ratio of the lipophilic polypropylene fiber yarns to the hydrophilic polypropylene fiber yarns is 1:10, the fiber yarns are arranged at equal intervals, and the intervals are 1 micrometer. The fiber filaments are in the shape of a curve with periodically changing wavy lines. The propylene raw material and hydrogen are mixed by pipelines and then are introduced into the olefin hydration reactor, firstly enter the microchannel component at the bottom of the reactor to obtain mixed fluid containing a large amount of micron-sized particles, then enter the catalyst bed layer to carry out propylene hydration reaction, the material after reaction for a certain residence time enters the microchannel component again to be dispersed, then enter the catalyst bed layer to continuously carry out propylene hydration reaction, and finally leave the olefin hydration reactor from a discharge port at the top of the reactor. The mixing conditions of the propylene raw material and water are as follows: the temperature is 155 ℃, and the pressure is 8.1 MPaG; the reaction conditions for hydrating the propylene are as follows: the temperature is 150-158 ℃, the pressure is 8.0MPaG, and the space velocity is 0.25h^-1The total water/olefin mass ratio was 15, and the uniformity of dispersion of the microchannel module to propylene in the mixed material was 75%.

The propylene of Table 1 was used as a raw material, and the conditions of the hydration reaction of propylene, the reaction residence time, the conversion of the raw material, etc. are shown in Table 4.

Example 2

In this example, the reaction raw materials, the reactor structure, the mixing conditions of the propylene raw material and water, and the reaction process were the same as in example 1. Unlike example 1, this example employs more mild reaction conditions. The uniformity of dispersion of the microchannel module to propylene in the mixture was 80%, and the reaction conditions and results are shown in Table 4.

Example 3

The n-butene in the table 2 is taken as a raw material, and the n-butene is subjected to hydration reaction with water under the action of a catalyst to prepare the sec-butyl alcohol. The mixed material of the n-butene raw material and water enters an n-butene hydration reactor to generate hydration reaction, the reactor adopts the reactor of the invention, the reactor enters from the bottom and goes out from the top, two sections of micro-channel assemblies and two sections of catalyst bed layers are arranged in the reactor, and the micro-channel assemblies and the catalyst bed layers are alternately arranged. The thin slices in the micro-channel mixing assembly are made of stainless steel materials, the thickness of the thin slices is 1.0mm, 5 layers of fiber yarns with the diameter of 1 mu m are filled between gaps of the thin slices, the fiber yarns comprise oleophilic nylon fiber yarns and hydrophilic polyamide fiber yarns, the number ratio of the oleophilic nylon fiber yarns to the hydrophilic polyamide fiber yarns is 1:15, the fiber yarns are arranged at equal intervals, and the intervals are 1 mu m. The fiber filaments are in the shape of a curve with periodically changing wavy lines. The n-butene raw material and water are mixed by a pipeline and then are introduced into the n-butene hydration reactor, the mixture firstly enters a micro-channel component at the bottom of the reactor to obtain a mixed fluid containing a large amount of micron-sized particles, then enters a catalyst bed layer to carry out n-butene hydration reaction, the material after reaction for a certain retention time enters the micro-channel component again to be dispersed, then enters the catalyst bed layer to continue carrying out the n-butene hydration reaction, and finally leaves the olefin hydration reactor from a discharge port at the top of the reactor. The mixing conditions of the n-butene raw material and water are as follows: the temperature is 180 ℃ and the pressure is 8.1 MPaG;

the n-butene hydration reaction conditions are as follows: the temperature is 175-180 ℃, the pressure is 8.0MPaG, and the space velocity is 1.0h^-1The total water/olefin mass ratio was 2.5, and the dispersion uniformity of the microchannel module to n-butene in the mixed material was 80%.

The n-butene of Table 2 was used as the raw material, and the hydration reaction conditions, reaction residence time, conversion of the raw material, etc. are shown in Table 4.

Example 4

In this example, the reaction raw materials, the reactor structure, the reaction process, and the mixing conditions of the n-butene raw material and water were the same as in example 3. Unlike example 3, this example employs more mild reaction conditions. The uniformity of dispersion of n-butene in the mixed material by the microchannel module was 85%, and the reaction conditions and results are shown in Table 4.

Example 5

Isobutene in the table 3 is used as a raw material and undergoes isobutene hydration reaction with water under the action of a catalyst to prepare the tert-butyl alcohol. The mixed material of isobutene raw material and water is fed into isobutene hydration reactor to make hydration reaction, said reactor adopts the invented reactor, and its lower portion is fed into upper portion, and its interior is equipped with two sections of microchannel component and two sections of catalyst bed layers, and the microchannel component and catalyst bed layers are alternatively set. The thin slice in the micro-channel mixing component is made of stainless steel, the thickness of the thin slice is 1.0mm, 3 layers of fiber yarns with the diameter of 5 mu m are filled between gaps of the thin slice, the fiber yarns comprise oleophylic polyurethane fiber yarns and hydrophilic polypropylene fiber yarns, the number ratio of the oleophylic polyurethane fiber yarns to the hydrophilic polypropylene fiber yarns is 1:25, and the fiber yarns are distributed at equal intervals, and the intervals are 1 mu m. The fiber filaments are in the shape of a curve with periodically changing wavy lines. Isobutene raw materials and water are mixed through a pipeline and then are introduced into the isobutene hydration reactor, the isobutene raw materials and the water firstly enter a micro-channel component at the bottom of the reactor to obtain mixed fluid containing a large number of micron-sized particles, then the mixed fluid enters a catalyst bed layer to carry out isobutene hydration reaction, the materials after reaction for a certain residence time enter the micro-channel component again to be dispersed, then the materials enter the catalyst bed layer to continuously carry out isobutene hydration reaction, and finally the materials leave the olefin hydration reactor through a discharge hole at the top of the reactor. The mixing conditions of the n-butene raw material and water are as follows: the temperature was 108 ℃ and the pressure was 2.6 MPaG;

the reaction conditions for isobutylene hydration are as follows: the temperature is 105-110 ℃, the pressure is 2.5MPaG, and the space velocity is 1.0h^-1The total water/olefin mass ratio was 3.0, and the uniformity of dispersion of the microchannel module to isobutylene in the mixed material was 70%.

Using the isobutene of Table 3 as a raw material, the hydration reaction conditions, the reaction residence time, the conversion of the raw material, etc., are shown in Table 4.

Example 6

In this example, the reaction raw materials, the reactor structure, the reaction process, and the mixing conditions of the isobutylene raw material and water were the same as in example 5. Unlike example 5, this example employs more mild reaction conditions. The uniformity of dispersion of the microchannel module with respect to isobutylene in the mixture was 70%, and the reaction conditions and results are shown in Table 4.

TABLE 4 reaction conditions and results

The dispersion and mixing effect of the olefin/water phase in the method is that the size of water phase particles is obtained through a high-speed camera, the uniformity of dispersed phase particles is obtained through selecting a plurality of characteristic particles, and the smaller the particle size is, the higher the uniformity is, the better the mixing and dispersing effect is. Therefore, the method for measuring the mixing and dispersing effect of the present example and the comparative example is as follows: mixing the dispersed phase and the continuous phase by different mixing and dispersing methods (such as a conventional static mixer and a mixing method of the micro-channel assembly in the reactor of the invention) under the same condition, wherein each method at least obtains 10 groups of mixed material samples, a British IX i-SPEED 5 high-SPEED camera is used for shooting the particle size of the dispersed phase in the mixed material samples, the particles in the pictures are added, the percentage content of the particles with various sizes is calculated, and a normal distribution diagram of the particles with various sizes is obtained, so that the particle uniformity is obtained.

It can be seen from the mixing effect of the present embodiment and the comparative example that, by using the olefin hydration reactor of the present invention, an immiscible system of olefin and water forms a uniform phase which is uniformly mixed and contains a large amount of particles with micron-sized dimensions, the two phases exist in a stable state, and the phases are not easily separated during the reaction process, so that the contact chance and the mass transfer area of the two phases can be greatly increased, the mass transfer reaction resistance is eliminated, and the high mass transfer reaction rate is maintained. When the method is used for preparing sec-butyl alcohol by hydrating n-butene, compared with the prior art, the conversion per pass of raw materials is greatly improved, and more moderate conditions can be adopted. When the catalyst is used for preparing isopropanol and isobutylene hydrated tertiary butyl alcohol by propylene hydration, compared with the prior art, the reaction rate is greatly improved, and the raw materials can reach higher per pass conversion rate by adopting milder conditions.

Claims

1. An olefin hydration reactor, characterized by: comprising a micromixing zone and an olefin hydration reaction zone, wherein the micromixing zone comprises at least one microchannel component; the microchannel component comprises a plurality of stacked sheets, and lipophilic fiber yarns and hydrophilic fiber yarns which are filled between gaps of the adjacent sheets, wherein a plurality of microchannels are formed between the fiber yarns, the fiber yarns are clamped and fixed by the sheets, and the fiber yarns are arranged in a single layer or multiple layers; at least one catalyst bed is disposed within the olefin hydration reaction zone.

2. The reactor of claim 1, wherein: the number ratio of the lipophilic fiber yarns to the hydrophilic fiber yarns filled between the adjacent thin sheet gaps is 1: 50-1: 1.

3. The reactor of claim 1, wherein: the oleophilic fiber yarns in any layer are uniformly distributed among the hydrophilic fiber yarns.

4. The reactor of claim 1, wherein: the number ratio of the oleophilic fiber yarns to the hydrophilic fiber yarns in any layer is 1: 50-1: 1.

5. The reactor of claim 1, wherein: the projections of two adjacent layers of fiber filaments along the vertical direction of the sheet are of a net structure.

6. The reactor of claim 1, wherein: in any layer, the distance between adjacent fiber yarns is 0.5-50 μm, preferably, the adjacent fiber yarns are arranged at equal intervals, and the fiber yarns can be arranged along the surface of the sheet in any one of the transverse direction, the longitudinal direction or the oblique direction.

7. The reactor of claim 1, wherein: the fiber filaments are in any curve shape, and preferably in a curve shape with periodic variation.

8. The reactor of claim 1, wherein: the filaments of the same layer are of the same shape, more preferably the filaments of all layers are of the same shape.

9. The reactor of claim 1, wherein: the diameter of the fiber filament is 0.5-50 μm, preferably 0.5-5 μm, and more preferably 0.5-1 μm.

10. The reactor of claim 1, wherein: the oleophylic fiber yarn is at least one of polyester fiber yarn, nylon fiber yarn, polyurethane fiber yarn, polypropylene fiber yarn, polyacrylonitrile fiber yarn, polyvinyl chloride fiber yarn or other fiber yarn with oleophylic surface treatment.

11. The reactor of claim 1, wherein: the hydrophilic fiber is one or more selected from high molecular polymer with hydrophilic groups on the main chain or side chain or fiber silk made of hydrophilic materials through physical or chemical methods.

12. The reactor of claim 1, wherein: the hydrophilic fiber is selected from one or more of polypropylene fiber, polyamide fiber or acrylic fiber.

13. The reactor of claim 1, wherein: in the micro-channel component, the thickness of the thin sheet is 0.05 mm-5 mm, preferably 0.1-1.5 mm.

14. The reactor of claim 1, wherein: the thin sheet is made of any one of metal, ceramic, organic glass or polyester materials.

15. The reactor of claim 1, wherein: a plurality of micro mixing areas and olefin hydration reaction areas are arranged, the micro mixing areas and the olefin hydration reaction areas are alternately arranged, and more preferably, the number of the micro mixing areas is the same as that of the olefin hydration reaction areas; according to the material flow direction, the material flow firstly passes through the micro-mixing reaction zone and then passes through the olefin hydration reaction zone.

16. The reactor of claim 1, wherein: a makeup water line is provided outside the micromixing zone for maintaining the concentration of water during the hydration reaction.

17. The reactor of claim 1, wherein: and the inlet position of each group of micro-channel assembly is provided with a water replenishing pipeline.

18. Use of a reactor according to any one of claims 1 to 17 in an olefin hydration reaction.

19. A process for hydrating an olefin, comprising: the method comprises the following steps of enabling a mixture of olefin raw materials and water to enter a micro mixing reaction zone of an olefin hydration reactor, enabling the mixture to flow through micro channels among fiber filaments in a micro channel assembly, continuously cutting the mixture for many times by the fiber filaments to form a mixed fluid containing a large number of micron-sized particles, enabling the mixed fluid to enter a catalyst bed layer of the olefin hydration reaction zone to carry out olefin hydration reaction, enabling reaction effluent to leave the reactor, and enabling the reaction effluent to enter a next separation unit.

20. The method of claim 19, wherein: the olefin raw material is any one of ethylene, propylene, n-butene, isobutene, isoamylene or cyclohexene.

21. A method as claimed in claim 19, wherein: the olefin raw material and water are premixed and then enter an olefin hydration reactor, and the premixing adopts any one or combination of a static mixer, a colloid mill, a shearing machine, a stirring kettle or a ceramic membrane tube for primary mixing of olefin and water phases.

22. The method of claim 19, wherein: the olefin hydration reactor adopts a lower-in and upper-out mode or an upper-in and lower-out mode; one or more olefin hydration reactors are arranged, and the reactors are connected in series or in parallel.

23. The method of claim 19, wherein: the mass ratio of water to olefin in the olefin hydration reaction is 1: 1-20: 1.

24. The method of claim 19, wherein: the reaction raw material at the inlet of the olefin hydration reactor and water are partially or completely added; when the water is added partially, the adding amount is 30-90 wt% of the total water amount, and the rest water is added in the form of make-up water.

25. The method of claim 24, wherein: the addition amount of the make-up water at the inlet of each group of microchannel components is 1 to 30 weight percent of the total water amount, and the make-up water amount along the flowing direction of the materials in the reactor is preferably gradually increased.

26. The method of claim 19, wherein: the catalyst with acid catalysis function is adopted in the catalyst bed layer of the olefin hydration reaction zone.

27. The method of claim 19, wherein: the olefin raw material and water pass through the micro-channel assembly to form particles with the size of 0.5-900 mu m.