CN114425286B - Olefin hydration reaction system and olefin hydration method - Google Patents
Olefin hydration reaction system and olefin hydration method Download PDFInfo
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- CN114425286B CN114425286B CN202011179636.9A CN202011179636A CN114425286B CN 114425286 B CN114425286 B CN 114425286B CN 202011179636 A CN202011179636 A CN 202011179636A CN 114425286 B CN114425286 B CN 114425286B
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 102
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000006703 hydration reaction Methods 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 39
- 230000036571 hydration Effects 0.000 title claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 106
- 239000000463 material Substances 0.000 claims abstract description 102
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000006185 dispersion Substances 0.000 claims abstract description 16
- 239000000835 fiber Substances 0.000 claims description 85
- 239000012071 phase Substances 0.000 claims description 24
- 239000010410 layer Substances 0.000 claims description 21
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- -1 polypropylene Polymers 0.000 claims description 12
- 239000004743 Polypropylene Substances 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 10
- 229920001155 polypropylene Polymers 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 7
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 2
- 229920002972 Acrylic fiber Polymers 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000000265 homogenisation Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920006306 polyurethane fiber Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 230000000887 hydrating effect Effects 0.000 claims 1
- 239000003054 catalyst Substances 0.000 description 10
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000005191 phase separation Methods 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000006276 transfer reaction Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000001949 Taraxacum officinale Species 0.000 description 1
- 235000005187 Taraxacum officinale ssp. officinale Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
Abstract
The invention discloses an olefin hydration reaction system and an olefin hydration method. The olefin hydration process is as follows: (1) The olefin and water with the mass ratio more than or equal to 1 are taken as first feeding materials to enter first mixing equipment to form first mixed materials; (2) Olefin and water with the mass ratio less than or equal to 1 are taken as second feeding materials to enter second mixing equipment to form second mixed materials; (3) The first mixed material and the second mixed material respectively enter a guide cylinder coaxially arranged in the material homogenizing equipment, collide after being sprayed by a nozzle after being guided, and form a material with uniform dispersion and stable state of olefin micro-droplets and water micro-droplets, and enter an olefin hydration reactor for reaction. The invention strengthens the mixing and dispersing state of olefin and water through improved mixing equipment and a reaction system, and improves the single-pass conversion rate of olefin hydration reaction.
Description
Technical Field
The invention belongs to the field of petrochemical industry, and particularly relates to an olefin hydration reaction system and an olefin hydration method.
Background
The olefin hydration reaction process is a typical liquid (olefin) -liquid (water) mass transfer reaction system, and the reaction rate and conversion rate are greatly affected by liquid-liquid mass transfer, which is mainly because of the small mutual solubility of olefin and water liquid phases, so that the reaction efficiency and the productivity of the olefin hydration process are restricted. In the prior art, a static mixing mode is generally adopted for mixing, and in the reaction process, the conventional mixing mode has the problems of low single-pass conversion rate of raw materials, long residence time, easy phase separation, high energy consumption of a device, low efficiency and the like because of large droplet size (in millimeter level in general) and unstable state, so that the contact surface area between two phases is large, phase separation is easy to occur, and the mass transfer reaction rate is very slow.
Typical olefin hydration reactions are cyclohexene hydration to cyclohexanol and n-butene hydration to sec-butanol. In the process of preparing cyclohexanol by cyclohexene hydration, the reactor of the cyclohexene direct hydration production device currently used in industry is a two-stage series-connection full-mixing reactor, the single-pass conversion rate is only 9%, the selectivity is 99%, the single-pass conversion rate of cyclohexene hydration reaction is low, and a large amount of unreacted cyclohexene and cyclohexanol are separated by repeated circulating rectification, so that the energy consumption is high.
CN109651081a proposes a reactive distillation method and apparatus for preparing cyclohexanol by hydration of cyclohexene, wherein a phase transfer catalyst is added to a reaction solution to form a slurry solution of cyclohexene, water, catalyst and phase transfer catalyst.
US3257469 uses polar organic solvents to increase the miscibility of olefins with water, thereby increasing the conversion of carbon penta-olefins by increasing the rate of diffusion of reactant molecules to the catalyst surface and the rate of diffusion of the product into the solvent.
US4182920 uses a three-stage olefin hydration reactor at a reaction temperature of 30-80 ℃, a reaction pressure of 0.46-1.4 MPa (absolute pressure), a weight ratio of water/pentene of 0.59-1.18, and a weight ratio of acetone/pentene of 4.18-7.85.
In the above patent, the problems of poor mixing and dispersing effect and low mass transfer efficiency existing between olefin hydration reactants are not fundamentally solved by adding an auxiliary agent for improving two-phase mixing or increasing the reaction progression.
Disclosure of Invention
Aiming at the defects of the prior art, the invention discloses an olefin hydration reaction system and an olefin hydration method, which strengthen the mixed dispersion state of olefin and water which are not easy to dissolve mutually through improved mixing equipment and a reaction system, strengthen mass transfer and improve the single-pass conversion rate of the olefin hydration reaction.
The olefin hydration reaction system comprises a reaction raw material mixing zone and an olefin hydration reaction zone, wherein the reaction raw material mixing zone comprises first mixing equipment, second mixing equipment and material homogenizing equipment;
the first mixing device and the second mixing device comprise a micro-channel assembly and a shell, wherein the micro-channel assembly is fixed in the shell, one end of the shell is provided with an olefin and water raw material inlet, and the other end of the shell is provided with a mixed material outlet; the microchannel assembly comprises a plurality of stacked thin sheets, lipophilic fiber filaments and hydrophilic fiber filaments filled between the cracks of the adjacent thin sheets, a plurality of microchannels are formed between the fiber filaments, and the fiber filaments are clamped and fixed through the thin sheets; wherein the ratio of lipophilic fiber filaments to hydrophilic fiber filaments in the first mixing device is 1: 1-50: 1, preferably 1: 1-20: 1, a step of; the ratio of the lipophilic fiber filaments to the hydrophilic fiber filaments in the second mixing equipment is 1:1-1:50, preferably 1:1-1:20; the first mixing equipment is used for mixing the olefin and water in the reaction raw materials in a mass ratio of more than or equal to 1, and is generally 300:1 to 1:1, preferably 30:1 to 1:1, a step of; the second mixing equipment is used for mixing raw materials with the mass ratio of olefin to water in the reaction raw materials being less than or equal to 1, generally 1:300-1:1, and preferably 1:30-1:1;
the material homogenizing equipment comprises a shell and at least one group of homogenizing components, and 1-3 groups are preferably arranged; each group of homogenizing components is a pair of coaxially arranged guide cylinders, one end of each guide cylinder is a nozzle, and the other end of each guide cylinder is respectively communicated with a mixed material outlet of the first mixing equipment and a mixed material outlet of the second mixing equipment; the top or bottom of the shell is provided with a homogeneous material outlet; the material homogenizing device is used for impinging and mixing the effluent materials of the first mixing device and the second mixing device; the two materials enter the nozzle under the flow guiding effect of the guide cylinder, collide after being sprayed by the nozzle, and the homogenization of the materials is realized;
the homogenizing components are fixed in the shell and are connected in parallel; the nozzle is fixed at one end of the guide cylinder, and the nozzle can be one or a combination of a plurality of centrifugal type, slit type, kong Guanshi and the like structurally, so that the material sprayed from the nozzle is uniformly distributed on the radial section of the material homogenizing equipment, the contact efficiency is ensured, and the ineffective contact is reduced.
In the first mixing device and the second mixing device, the fiber filaments can be arranged in a single layer or multiple layers, preferably 1-50 layers, more preferably 1-5 layers; when the fiber yarns are arranged in multiple layers, the projection of two adjacent layers of fiber yarns along the vertical direction of the sheet is preferably a net structure; the mesh shape in the mesh structure can be any shape, such as one or more of a polygon, a circle, an ellipse, etc.; in each layer of fiber filaments, the spacing between adjacent fiber filaments is generally 0.5-50 μm, preferably the fiber filaments are distributed at equal intervals, and the fiber filaments are arranged along any one of the transverse direction, the longitudinal direction or the oblique direction of the surface of the sheet; the filaments may be of any curvilinear shape, preferably a periodically varying curvilinear shape, such as wavy, zigzag, etc., preferably the filaments of the same layer are of the same shape, more preferably the filaments of all layers are of the same shape.
In the first and second mixing devices, the diameters of the lipophilic fiber filaments and the hydrophilic fiber filaments filled between the seams of adjacent sheets in the microchannel assembly are generally 0.5-50 μm, preferably 0.5-5 μm, and more preferably 0.5-1 μm. Wherein the lipophilic fiber yarn is generally selected from at least one of polyester fiber yarn, nylon fiber yarn, polyurethane fiber yarn, polypropylene fiber yarn, polyacrylonitrile fiber yarn and polyvinyl chloride fiber yarn, or fiber yarn with surface subjected to lipophilic treatment by a physical or chemical method; the hydrophilic fiber yarn is generally selected from carboxyl (-COOH), amido (-CONH-) and amino (-NH) in main chain or side chain 2 Polymer with hydrophilic groups such as (-), or hydroxyl (-OH), and the more hydrophilic groups, the better the hydrophilicity, such as polypropylene fiber, polyamide fiber, acrylic fiber, or fiber yarn from materials hydrophilic treated by physical or chemical methods.
In the first and second mixing devices, the thickness of the sheet in the microchannel assembly is generally 0.05mm to 5mm, preferably 0.1 to 1.5mm. The material of the sheet is generally determined by the nature of the overcurrent material and the operating conditions, and may be any of metal, ceramic, organic glass, polyester, etc., preferably stainless steel (SS 30403, SS 30508, SS32168, SS 31603) among metals. The shape of the sheet may be any of rectangle, square, polygon, circle, ellipse, fan, etc., preferably rectangle or square. The size and number of the flakes can be designed and adjusted according to the actual needs of the reaction.
In the first mixing equipment and the second mixing equipment, the micro-channel component in the shell is divided into a feeding end and a discharging end along the crack direction, a feeding distribution space is arranged between the material inlet and the feeding end, a discharging distribution space is arranged between the material outlet and the discharging end, and other ends of the micro-channel component except the feeding end and the discharging end are in sealing connection with the shell.
The olefin hydration reaction zone is used for carrying out olefin hydration reaction on the mixed materials from the reaction raw material mixing zone. The olefin hydration reaction zone is internally provided with 1 or more olefin hydration reactors, and the olefin hydration reactors can be one or more combinations of a fixed bed reactor, a fluidized bed reactor, a suspension bed reactor, a bubbling bed reactor, a moving bed reactor, a tower reactor, a tubular reactor or a jet reactor and the like. Preferably, tubular reactors are used, and the tubular reactors may be connected in parallel or in series.
For the hydration reaction of olefin, the olefin and water phases are not easy to dissolve, a certain retention time is needed to achieve higher single pass conversion, and the two phases are subjected to intensified mixing in a reaction raw material mixing zone to form a uniform phase, but the two phases still have phase separation after a quite long retention time to reduce the reaction rate.
The invention also provides an olefin hydration method, which comprises the following steps: (1) Olefin and water with the mass ratio of more than or equal to 1 are taken as first feeding materials to enter first mixing equipment, two phases flow through micro-channels formed among fiber filaments in the micro-channel assembly, and the fiber filaments are continuously cut for a plurality of times, so that a first mixed material containing a large number of micron-sized particles is formed; (2) Olefin and water with the mass ratio less than or equal to 1 are taken as second feeding materials to enter second mixing equipment, two phases flow through micro-channels formed among fiber filaments in the micro-channel assembly, and the fiber filaments are continuously cut for a plurality of times, so that a second mixed material containing a large number of micron-sized particles is formed; (3) The first mixed material and the second mixed material respectively enter a guide cylinder coaxially arranged in the material homogenizing equipment, collide after being sprayed by a nozzle after diversion, so as to form a material with uniform dispersion and stable state of olefin micro-droplets and water micro-droplets, and the material is discharged from a discharge port and enters an olefin hydration reactor in an olefin hydration reaction zone for reaction, so that a reaction product is obtained.
In the method, the mass ratio of the first feed to the first feed is 0.5-2: 1, preferably 1:1.
in the method of the invention, the olefin is ethylene, propylene, n-butene, isobutene, isoamylene, cyclohexene or hexene, etc.
In the process of the present invention, the mass ratio of olefin to water in the first feed is generally from 300:1 to 1:1, preferably from 20:1 to 1:1; the mass ratio of olefin to water in the second feed is generally from 1:300 to 1:1, preferably from 1:1 to 1:20.
In the method of the invention, the dispersion size d1 of the aqueous phase liquid drops in the first mixed material is 0.5-900 mu m, and the dispersion uniformity is preferably more than or equal to 80%; the dispersion size d2 of olefin liquid drops in the second mixed material is 0.5-900 mu m, and the dispersion uniformity is preferably more than or equal to 80%. The good dispersion uniformity can keep the two phases from phase separation within the reaction residence time, improve the mass transfer reaction rate, and achieve better reaction effect and raw material conversion rate.
In the prior art, when olefin hydration reaction is carried out, two raw materials are generally mixed conventionally and then introduced into a reactor, and the problems of unsatisfactory mixing effect, uneven mixing and easy phase separation exist in a conventional mixing method and mixing equipment, so that the mass transfer rate and the single pass conversion rate of the olefin hydration reaction are very low. According to the olefin hydration reaction system and method, specific mixing equipment is adopted, and the mixing effect of olefin and water phases is improved by adjusting the feeding mode, the feeding proportion and the intensified mixing among feeds, so that the two mixed materials are mutually penetrated, diffused and wrapped and adhered, and the contact degree between lipophilic olefin micro-droplets and water micro-droplets is intensified; meanwhile, a proper tubular reactor is matched, so that on one hand, the two phases in the initial mixing process can be kept in a uniform and non-split phase state in the long residence time of the reaction feed in the liquid-liquid reaction process, thereby keeping continuous and efficient mass transfer between the two phases, overcoming the problem that the mass transfer of the reaction is influenced due to easy split phase separation of the two phases in the existing olefin hydration reaction process, on the other hand, on the basis of the fact that the concentration of the two phases gradually decreases along with the progress of the olefin hydration reaction in the traditional process, the two-phase main body needs to pass through a phase interface to carry out the interphase mass transfer so as to continue the reaction, and the reaction rate is influenced due to the fact that the diffusion mass transfer between the two phases is lower and lower. The invention not only ensures more uniform reaction, but also greatly improves the reaction rate because a large number of small-sized liquid drops of two liquid phases are uniformly dispersed in the reaction feed, all the reaction materials have the same residence time in the reactor and have no reaction in the axial direction by introducing the reaction feed into the tubular reactor, which is beneficial to preventing the olefin phase and the water phase from generating phase separation caused by disturbance, thereby ensuring the reaction materials to keep an initial mixing state for a long time, ensuring higher olefin hydration reaction rate and having good improvement effect on solving the problem of low reaction rate caused by easy phase separation in the olefin hydration reaction process.
Drawings
FIG. 1 is a schematic diagram of an olefin hydration system of the present invention
Fig. 2 is a schematic view of a microchannel assembly within a first mixing device.
Fig. 3 is a schematic view of a microchannel assembly within a second mixing device.
Wherein 1 is alkene I,2 is water I,3 is first feeding, 4 is microchannel subassembly I,5 is microchannel subassembly's casing I,6 is microchannel flake I,7 is the crack I between the microchannel flake, 8 is lipophilic cellosilk I,9 is hydrophilic cellosilk I,10 is first mixed material, 11 is alkene II,12 is water II,13 second feeding, 14 is microchannel subassembly II,15 is microchannel subassembly's casing II,16 is microchannel flake II,17 is the crack II between the microchannel flake, 18 is lipophilic cellosilk II,19 is hydrophilic cellosilk II,20 is the second mixed material, 21 is material homogeneity equipment, 22 is the guide cone, 23 is the nozzle, 24 is material homogeneity equipment discharge gate, 25 is tubular reactor, 26 is alkene hydration reaction product.
Detailed Description
The invention will now be described in more detail with reference to the accompanying drawings and examples, which are not intended to limit the invention thereto.
Taking the attached figure 1 as an example, the liquid-liquid reaction device and the reaction method of the invention are as follows:
firstly, introducing olefin I1 and water I2 into first mixing equipment according to the mass ratio of not less than 1, wherein the first mixing equipment comprises at least one group of micro-channel components I4, a crack I7 between micro-channel sheets 6I is formed, and lipophilic fiber filaments I8 and hydrophilic fiber filaments I9 filled between the crack I7 are continuously cut for a plurality of times to form a first mixed material 10; introducing the olefin II 11 and the water II 12 into a second mixing device according to the mass ratio of < 1, wherein the second mixing device comprises at least one group of micro-channel components II 14, and after a plurality of continuous cutting of the lipophilic fiber filaments II 18 and the hydrophilic fiber filaments II 19 filled between the micro-channel sheets II 16 and the gaps II 17, a second mixed material 20 is formed; the first mixed material 10 and the second mixed material 20 are respectively introduced into a material homogenizing device 21, guided by a guide cylinder 22, ejected from a nozzle 23 to collide with each other, and the two phases are separated from a discharge hole 24 of the material homogenizing device after penetrating and diffusing, then enter a tubular reactor 25, and are separated as an olefin hydration reaction product 26 after undergoing an enhanced mass transfer reaction in the tubular reactor.
The olefin hydration system and the olefin hydration method of the present invention are applied to the n-butene hydration process under specific reaction conditions as described in comparative example 1, example 2 and example 3. The properties of the n-butene feedstock are shown in Table 1, and the catalyst used for the hydration of n-butene is DNW-II catalyst manufactured by Dandelion specialty resins Co.
TABLE 1 n-butene feedstock composition
Comparative example 1
The normal butene raw material and water pass through a conventional static mixer with the model SL-1.6/25-10.0-250, are continuously mixed for three times, and the mixed material enters a normal butene hydration reactor to carry out hydration reaction. The reactor adopts a common up-flow reactor, three sections of catalyst beds are arranged in the reactor, a distribution sieve plate is arranged at the inlet of the catalyst beds, and the aperture of the sieve plate is 2mm. The n-butene/water mixture is introduced into an olefin hydration reactor from the bottom of the reactor, uniformly distributed along the section of the reactor by a distribution sieve plate, enters a catalyst bed layer for olefin hydration reaction, and finally leaves the olefin hydration reactor from a discharge hole at the top of the reactor.
The reaction conditions, residence times and conversion of the starting materials are shown in Table 2.
Example 1
Introducing the mass ratio of olefin to water into a first mixing device in a ratio of 4:1 to form a first mixed material, and introducing the mass ratio of olefin to water into a second mixing device in a ratio of 1:9 to form a second mixed material; the mass ratio of the first mixed material to the second mixed material is 1:1. The first mixed material and the second mixed material are mixed by a pipeline and then introduced into a tubular reactor for olefin hydration reaction, the bottom of the reactor is fed, the reactor is divided into four sections of reactors, each section of reactor has a straight pipe section of 2 meters, the four sections of reactors are connected in a tail-to-tail mode in sequence, the straight pipe sections of the reactors are 8 meters in total, and olefin hydration catalysts are filled in the straight pipe sections of the reactors.
In the first mixing equipment, the thin sheet in the micro-channel mixing assembly is made of stainless steel, the thickness of the thin sheet is 1.5mm, 5 layers of glass fiber filaments with the diameter of 1 mu m and 1 layer of polypropylene fiber filaments with the diameter of 1 mu m are filled between the thin sheet cracks, and the fiber filaments are distributed at equal intervals with the interval of 1 mu m. The fiber yarn is in a curve shape with a wavy line periodically changing; in the second mixing equipment, the thin sheet in the micro-channel mixing assembly is made of stainless steel, the thickness of the thin sheet is 1.5mm, 2 layers of polyester fiber filaments with the diameter of 1 mu m and 5 layers of polypropylene fiber filaments with the diameter of 1 mu m are filled between the thin sheet cracks, and the fiber filaments are distributed at equal intervals with the interval of 1 mu m. The fiber yarn is in a curve shape with a wavy line periodically changing.
The hydration reaction conditions, residence time and conversion of the starting materials are shown in Table 2.
Example 2
Introducing the mass ratio of the water to the alkene into first mixing equipment in a ratio of 5:1 to form a first mixed material, introducing the mass ratio of the water to the alkene into second mixing equipment in a ratio of 1:11 to form a second mixed material, and enabling the mass ratio of the first mixed material to the second mixed material to be 1:1. Two materials are introduced into two ends of a homogenizer, are guided by guide cylinders at the two ends and are ejected by nozzles to generate relative collision, liquid drops in the two materials are mutually penetrated and diffused to form a uniform mixture, the uniform mixture is introduced into a tubular reactor to generate olefin hydration reaction, the bottom of the mixture is fed, the mixture is divided into three sections of reactors, each section of straight pipe is 3 meters long, the three sections of reactors are connected in a tail-end mode in sequence, the total length of the three sections of reactors is 9 meters, and catalyst is filled in the straight pipe sections in the reactors.
In the first mixing equipment, the thin sheet in the micro-channel mixing assembly is made of stainless steel, the thickness of the thin sheet is 1.5mm, 3 layers of glass fiber filaments with the diameter of 1 mu m and 2 layers of polypropylene fiber filaments with the diameter of 1 mu m are filled between the thin sheet cracks, and the fiber filaments are distributed at equal intervals with the interval of 1 mu m. The fiber yarn is in a curve shape with a wavy line periodically changing; in the second mixing equipment, the thin sheet in the micro-channel mixing assembly is made of stainless steel, the thickness of the thin sheet is 1.5mm, 1 layer of polyester fiber yarn with the diameter of 1 mu m and 4 layers of polypropylene fiber yarn with the diameter of 1 mu m are filled between the thin sheet cracks, and the fiber yarn is distributed at equal intervals with the interval of 1 mu m. The fiber yarn is in a curve shape with a wavy line periodically changing.
The hydration reaction conditions, residence time and conversion of the starting materials are shown in Table 2.
Example 3
Introducing the mass ratio of the water to the olefin into first mixing equipment in a ratio of 6:1 to form a first mixed material, and introducing the mass ratio of the water to the olefin into second mixing equipment in a ratio of 1:13 to form a second mixed material; the mass ratio of the first mixed material to the second mixed material is 1:1. Two materials are introduced into two ends of a homogenizer, are guided by guide cylinders at the two ends and are ejected by nozzles to generate relative collision, liquid drops in the two materials are mutually penetrated and diffused to form a uniform mixture, the uniform mixture is introduced into a tubular reactor to generate olefin hydration reaction, the bottom is fed, the two materials are divided into five sections of reactors, each section of straight pipe is 2m long, the five sections of reactors are connected in a tail-end mode in sequence, the total length of each section of straight pipe is 10 m, and catalyst is filled in each section of straight pipe in the reactor.
In the first mixing equipment, the thin sheet in the micro-channel mixing assembly is made of stainless steel, the thickness of the thin sheet is 1.5mm, 3 layers of glass fiber filaments with the diameter of 1 mu m and 2 layers of polypropylene fiber filaments with the diameter of 1 mu m are filled between the thin sheet cracks, and the fiber filaments are distributed at equal intervals with the interval of 1 mu m. The fiber yarn is in a curve shape with a wavy line periodically changing; in the second mixing equipment, the thin sheet in the micro-channel mixing assembly is made of stainless steel, the thickness of the thin sheet is 1.5mm, 1 layer of polyester fiber yarn with the diameter of 1 mu m and 4 layers of polypropylene fiber yarn with the diameter of 1 mu m are filled between the thin sheet cracks, and the fiber yarn is distributed at equal intervals with the interval of 1 mu m. The fiber yarn is in a curve shape with a wavy line periodically changing.
The hydration reaction conditions, residence time and conversion of the starting materials are shown in Table 2.
TABLE 2 reaction conditions and results
| Sequence number | Temperature, DEG C | Pressure, MPaG | Volume space velocity, h -1 | Mass ratio of total olefins to water | Single pass conversion of raw material, wt% | Selectivity,% | |
| 1 | Comparative example 1 | 175～180 | 8.0 | 1.0 | 0.4 | 6.8 | 96.2 |
| 2 | Example 1 | 155～160 | 7.0 | 1.6 | 0.5 | 62.6 | 99.1 |
| 3 | Example 2 | 138～145 | 6.5 | 1.5 | 0.5 | 63.4 | 99.1 |
| 4 | Example 3 | 138～145 | 7.0 | 1.5 | 0.5 | 67.2 | 99.1 |
The dispersion size and the dispersion effect of the lipophilic liquid drops in the hydrophilicity in the method are obtained by a high-speed camera, and the uniformity of disperse phase particles is obtained by selecting a plurality of characteristic particles, so that the smaller the particle size is, the higher the uniformity is, and the better the mixing and dispersion effect is. For this reason, the method for measuring the mixing and dispersing effect of the present example and comparative example is as follows: under the same condition, at least 10 groups of mixed material samples are obtained by different mixing and dispersing methods (such as a mixed material I formed by a conventional static mixer and the oil-water micro-channel mixing equipment and a mixed material II formed by the oil-water micro-channel mixing equipment), the particle size of a disperse phase in the mixed material samples is shot by using a British IX I-SPEED 5 high-SPEED camera, particles in a photo are added, the percentage content of 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.
Claims (18)
1. The olefin hydration reaction system is characterized by comprising a reaction raw material mixing zone and an olefin hydration reaction zone, wherein the reaction raw material mixing zone comprises first mixing equipment, second mixing equipment and material homogenizing equipment; the first mixing device and the second mixing device comprise a micro-channel component and a shell of the micro-channel component, the micro-channel component is fixed in the shell of the micro-channel component, one end of the shell of the micro-channel component is provided with an olefin and water raw material inlet, and the other end of the shell of the micro-channel component is provided with a mixed material outlet; the microchannel assembly comprises a plurality of stacked thin sheets, lipophilic fiber filaments and hydrophilic fiber filaments filled between the cracks of the adjacent thin sheets, a plurality of microchannels are formed between the fiber filaments, and the fiber filaments are clamped and fixed through the thin sheets; wherein the ratio of lipophilic fiber filaments to hydrophilic fiber filaments in the first mixing device is 1: 1-50: 1, a step of; the ratio of the lipophilic fiber yarn to the hydrophilic fiber yarn in the second mixing equipment is 1:50-1:1; the material homogenizing equipment comprises a shell and at least one group of homogenizing components; each group of homogenizing components is a pair of coaxially arranged guide cylinders, one end of each guide cylinder is a nozzle, and the other end of each guide cylinder is respectively communicated with a mixed material outlet of the first mixing equipment and a mixed material outlet of the second mixing equipment; the top or bottom of the shell is provided with a homogeneous material outlet;
the first mixing equipment is used for reacting olefin and water in a mass ratio of 300:1 to 4: 1;
the second mixing equipment is used for mixing the olefin and water in the reaction raw materials in a mass ratio of 1:300-1:9;
the material homogenizing device is used for impinging and mixing the effluent materials of the first mixing device and the second mixing device; the two materials enter the nozzle under the flow guiding effect of the guide cylinder, collide after being sprayed by the nozzle, and the homogenization of the materials is realized;
the olefin hydration reaction zone is used for carrying out olefin hydration reaction on the mixed material from the reaction raw material mixing zone; the olefin hydration reaction zone is internally provided with 1 or more olefin hydration reactors, wherein the olefin hydration reactors are tubular reactors, and the tubular reactors are connected in parallel or in series.
2. The system according to claim 1, wherein: the homogenizing components are fixed in the shell and are connected in parallel; the nozzle is fixed at one end of the guide cylinder, and the nozzle adopts one or more of centrifugal type, slit type or hole pipe type, so that the material sprayed from the nozzle is uniformly distributed on the radial section of the material homogenizing equipment.
3. The system according to claim 1, wherein: in the first mixing equipment and the second mixing equipment, the fiber filaments are arranged in a single layer or multiple layers; when the fiber yarns are arranged in multiple layers, the projection of two adjacent layers of fiber yarns along the vertical direction of the sheet is a net structure.
4. A system according to claim 3, characterized in that: in the first mixing equipment and the second mixing equipment, the number of the fiber filaments is 1-50.
5. A system according to claim 3, characterized in that: in each layer of fiber filaments, the distance between adjacent fiber filaments is 0.5-50 μm.
6. The system according to claim 1, wherein: in the first mixing equipment and the second mixing equipment, the diameters of lipophilic fiber filaments and hydrophilic fiber filaments filled between adjacent sheet cracks in the microchannel assembly are 0.5-50 mu m; the lipophilic fiber yarn is one or more selected from polyester fiber yarn, polyurethane fiber yarn, polypropylene fiber yarn, polyacrylonitrile fiber yarn, polyvinyl chloride fiber yarn or fiber yarn with surface subjected to lipophilic treatment by a physical or chemical method.
7. The system according to claim 6, wherein: the hydrophilic fiber yarn is selected from high molecular polymers with carboxyl, amido, amino or hydroxyl groups in the main chain or side chains.
8. The system according to claim 6, wherein: the hydrophilic fiber yarn is selected from one or more of polypropylene fiber, polyamide fiber and acrylic fiber or fiber yarn which is formed by hydrophilic treatment of materials by a physical or chemical method.
9. The system according to claim 1, wherein: in the first mixing equipment and the second mixing equipment, the thickness of the thin sheet in the micro-channel component is 0.05 mm-5 mm; the sheet is made of any one or more of metal, ceramic, organic glass or polyester materials; the shape of the sheet is one or more of polygonal, circular, elliptical or fan-shaped.
10. The system according to claim 1, wherein: in the first mixing equipment and the second mixing equipment, the micro-channel component in the shell of the micro-channel component is divided into a feeding end and a discharging end along the crack direction, a feeding distribution space is arranged between a material inlet and the feeding end, a discharging distribution space is arranged between a material outlet and the discharging end, and other ends of the micro-channel component except the feeding end and the discharging end are in sealing connection with the shell of the micro-channel component.
11. A process for hydrating an olefin comprising: (1) mass ratio 300:1 to 4:1 as a first feed into a first mixing device, the two phases flowing through microchannels formed between filaments in a microchannel module and being successively cut multiple times by the filaments to form a first mixed material containing a plurality of micron-sized particles; (2) Olefin and water with the mass ratio of 1:300-1:9 are taken as second feeding materials to enter second mixing equipment, two phases flow through micro-channels formed among fiber filaments in the micro-channel assembly, and the fiber filaments are continuously cut for a plurality of times, so that a second mixed material containing a large amount of micron-sized particles is formed; (3) The first mixed material and the second mixed material respectively enter a guide cylinder coaxially arranged in the material homogenizing equipment, collide after being sprayed by a nozzle after diversion to form a material with uniform dispersion and stable state of olefin micro-droplets and water micro-droplets, and are discharged from a discharge hole to enter an olefin hydration reactor in an olefin hydration reaction zone for reaction to obtain a reaction product; the olefin hydration reactor is a tubular reactor.
12. The method according to claim 11, wherein: the mass ratio of the first feeding to the second feeding is 0.5-2: 1.
13. The method according to claim 11, wherein: the mass ratio of the first feeding material to the second feeding material is 1:1.
14. the method according to claim 11, wherein: the olefin is ethylene, propylene, n-butene, isobutene, isoamylene, or cyclohexene.
15. The method according to claim 11, wherein: the mass ratio of the olefin to the water in the first feed is 20:1-4:1.
16. The method according to claim 11, wherein: the mass ratio of the olefin to the water in the second feeding is 1:9-1:20.
17. The method according to claim 11, wherein: the dispersion size d1 of the aqueous phase liquid drops in the first mixed material is 0.5-900 mu m, and the dispersion uniformity is more than or equal to 80%.
18. The method according to claim 11, wherein: the dispersion size d2 of olefin liquid drops in the second mixed material is 0.5-900 mu m, and the dispersion uniformity is more than or equal to 80%.
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