APPARATUS AND METHOD FOR PREPARING POLY-ALPHA-OLEFIN

Abstract

An apparatus for preparing polyalpha-olefins has an input unit (1), a microchannel reactor (2), and a post-treatment unit (3) that are successively connected. The input unit has a mixer and/or pipeline(s) for delivering an olefin raw material, an auxiliary feed and a BF.sub.3 catalyst to the microchannel reactor (2). The apparatus and process that utilizes the apparatus allow flexible and rapid mixing of the catalyst, the auxiliary feed and the olefin raw material, and have the advantages of high polymerization reaction speed, good mass and heat transfer effects, high reaction conversion, good product selectivity and excellent performance, thereby being suitable for large-scale industrial production.

Claims

1. An apparatus for preparing polyalpha-olefins, comprising an input unit (1), a microchannel reactor (2), and a post-treatment unit (3) that are successively connected, the input unit comprises a mixer and/or pipeline(s) for delivering an olefin raw material, an auxiliary feed and a BF.sub.3 catalyst to the microchannel reactor (2), The input unit (1) at least comprises a mixer for mixing at least a part of the auxiliary feed and at least a part of the BF.sub.3 catalyst and a pipeline for individually feeding at least a part of the BF.sub.3 catalyst to the microchannel reactor (2).

2. The apparatus according to claim 1, which is characterized in that the input unit (1) comprises a mixer for mixing a part of the BF.sub.3 catalyst, a part of the auxiliary feed and a part of the olefin raw material, and pipelines for individually passing each of the residue of the BF.sub.3 catalyst, the residue of the auxiliary feed and the residue of the olefin raw material, based on the feedstock type, into the microchannel reactor (2); or, the input unit (1) comprises a mixer for mixing a part of the BF.sub.3 catalyst and the whole auxiliary feed, a pipeline for individually passing the residue of the BF.sub.3 catalyst into the microchannel reactor (2), and a pipeline for individually passing the whole olefin raw material into the microchannel reactor (2); or, the input unit (1) comprises a mixer for mixing a part of the BF.sub.3 catalyst and a part of the auxiliary feed, and pipelines for individually passing each of the residue of the BF.sub.3 catalyst, the residue of the auxiliary feed and the whole olefin raw material into the microchannel reactor (2); or the input unit (1) comprises a mixer for mixing a part of the BF.sub.3 catalyst, a part of the auxiliary feed and the whole olefin raw material, and pipelines for individually passing each of the residue of the BF.sub.3 catalyst, and the residue of auxiliary feed into the microchannel reactor (2); or the input unit (1) comprises a mixer for mixing a part of the BF.sub.3 catalyst, the whole auxiliary feed and a part of the olefin raw material, and pipelines for individually passing each of the residue of the BF.sub.3 catalyst, and the residue of the olefin raw material into the microchannel reactor (2); or the input unit (1) comprises a mixer for mixing a part of the BF.sub.3 catalyst, the whole auxiliary feed and the whole olefin raw material, and a pipeline for individually passing the residue of the BF.sub.3 catalyst into the microchannel reactor (2), preferably, in the case that the BF.sub.3 catalyst, the auxiliary feed and the olefin raw material are mixed in the input unit, the input unit comprises a first mixer for mixing any two of the above three feedstocks, and a second mixer for mixing the mixture from the first mixer and the residual one feedstock, wherein the first mixer is communicated with the second mixer, and the second mixer is communicated with the microchannel reactor (2).

3. The apparatus according to claim 1, , which is characterized in that the microchannel reactor (2) includes: a shell (003); a feeding zone (023), a mixing zone (008), a reaction zone (009), and a collection zone (024) are successively arranged and communicated along a first direction in the shell (003), wherein the shell (003) is provided with a feed pipe (002) communicated with the feeding zone (023) and a discharge pipe (001) communicated with the collection zone (024), and the mixing zone (008) is provided with a mixing channel (014) extending along the first direction; a fluid distribution pipe (017), the fluid distribution pipe (017) is extended from the exterior of the shell (003) into the mixing channel (014), the fluid distribution pipe (017) is connected with a fluid distributor (016) at an end of the mixing channel (014); the feed pipe (002) is used to input the feedstock from the input unit, the fluid distribution pipe (017) is connected to the pipeline for the individually fed BF.sub.3 catalyst of the input unit (1) and can be used to input the BF.sub.3 catalyst, the discharge pipe (001) is connected to the post-treatment unit (3).

4. The apparatus according to claim 3, which is characterized in that the fluid distributor is at least one selected from powder sintered body with micropores, mesoporous foam material, wire mesh, and tube with microslits or micropores, preferably, the fluid distributor is a cylindrical powder sintered body with micropores, preferably, the fluid distributor has a cross-sectional area of 0.01 cm.sup.2-200 cm.sup.2, and a length of 1 mm-2000 mm; and/or, the mixing zone is provided with 2-100 (preferably 2-50, more preferably 2-10) mixing channels, the fluid distribution pipe includes a main pipe extending from the exterior of the shell into the feeding zone and branch pipes extending from the feeding zone into each mixing channel with fluid distributors connected to branch pipe ends (preferably the mixing channel has a circular cross-section; preferably, the mixing channel has a cross-sectional area of 0.05 cm.sup.2-400 cm.sup.2, and a length of 50 mm-5000 mm); and/or in the mixing channel, a first mixing member is disposed downstream of the fluid distributor; and/or, the first mixing member is provided with a main flow portion and a branch flow portion that are alternately arranged and communicated along the first direction, the main flow portion is provided with a single main flow passage, and the branch flow portion is provided with a plurality of branch flow passages; and/or, a collection cavity communicated with a plurality of branch flow passages is disposed downstream of the branch flow portion; and/or, the mixing zone comprises a first heat exchange cavity disposed in the shell, the mixing channel is disposed in the first heat exchange cavity, the shell is provided with a first heat exchange medium inlet and a first heat exchange medium outlet that are communicated with the first heat exchange cavity; and/or, the volumetric ratio of the first heat exchange cavity to the mixing channel is 2-50 (preferably, the volumetric ratio of the first heat exchange cavity to the mixing channel is 5-30); and/or, a transition zone is provided between the mixing zone and the reaction zone, the transition zone is provided with a stabilization channel with constant cross-section and a diffusion channel with gradually enlarged cross-section arranged and communicated along the first direction, the stabilization channel is communicated with the mixing channel, the diffusion channel is communicated with the reaction zone; and/or, a discharge pipe extending to the exterior of the shell is connected to the stabilization channel; and/or, the diffusion channel is provided with a diffusion plate with meshes or slits; and/or, the reaction zone is provided with a plurality of parallel reaction channels (for example 2-10000 channels, preferably 2-5000 channels, more preferably 2-500 channels) extending along the first direction and communicated with the mixing channel via the transition zone; and/or, the reaction channel is provided with a second mixing member, and the second mixing member includes a base strip extending along the first direction and a tooth element connected to the base strip and extended transversely to the base strip; and/or, the tooth element is of at least one of triangular, arcual, wavy, and spiral shapes (preferably the tooth element is of triangular shape, and on one side of the triangle adjacent to the base strip, one corner is connected to the base strip, and the other corner is 0.01 mm-20 mm away from the base strip); and/or, each of reaction channels is each independently provided with a plurality of the second mixing members that are stacked at intervals, and the tooth elements of the second mixing member are staggered with each other; and/or, the reaction channel has a cross section in at least one of circular, rectangular and triangular shapes (preferably, the cross-section of the reaction channel is rectangular, and the tooth elements extend between a set of opposite sides of the rectangle); and/or, the reaction channel has a cross-sectional area of 1 mm.sup.2-150 mm.sup.2, and a length of 50 mm-5000 mm (preferably 100 mm-3000 mm), the minimum distance between the reaction channels is 1 mm-50 mm (preferably 3 mm-30 mm), and the second mixing member has a thickness of 0.1 mm-3 mm (preferably 0.2 mm-2 mm), and the spacing between adjacent tooth elements is 1 mm-50 mm (preferably 1.5 mm-20 mm); and/or, the reaction zone is provided with a second heat exchange cavity disposed in the shell, the reaction channel is disposed in the second heat exchange cavity, the shell is provided with a second heat exchange medium inlet and a second heat exchange medium outlet that are communicated with the second heat exchange cavity; and/or, the volumetric ratio of the second heat exchange cavity to the reaction channel is 2-50 (preferably, the volumetric ratio of the second heat exchange cavity to the reaction channel is 5-30).

5. The apparatus according to claim 1, which is characterized in that the post-treatment unit (3) allows the stream entering therein to be subjected to the post-treatment to produce a polyolefin product (the post-treatment unit (3) is preferably one or more of adsorption device, extraction device, distilling device, centrifugation device, sedimentation device, alkaline washing device and water washing device).

6. The apparatus according to claim 1, which is characterized in that, based on the total mass of BF.sub.3 in the microchannel reactor (2), the mass ratio of the BF.sub.3 catalyst that is directly fed to the microchannel reactor (2) to the BF.sub.3 catalyst that is mixed in the input unit is 90-10:10-90, preferably 80-40:20-60, more preferably 70-50:30-50.

7. A process for preparing polyalpha-olefins, comprising: a BF.sub.3 catalyst, an auxiliary feed and an olefin raw material are passed into a microchannel reactor through an input unit, and subjected to the polymerization reaction in the microchannel reactor and then the post-treatment to produce a polyolefin product, wherein in the input unit, at least a part of the auxiliary feed and at least a part of the BF.sub.3 catalyst are mixed, and at the same time, at least a part of the BF.sub.3 catalyst is individually fed to the microchannel reactor, preferably, in the microchannel reactor, the mass ratio of the auxiliary feed, the olefin raw material and the BF.sub.3 catalyst in total is 1:1-1000:1-500 (preferably 1:1-500:1-200, most preferably 1:10-250:1-100).

8. The process according to claim 7, which is characterized in that in the input unit, a part of the BF.sub.3 catalyst, a part of the auxiliary feed and a part of the olefin raw material are mixed and then passed into the microchannel reactor, and the residual BF.sub.3 catalyst, the residual auxiliary feed and the residual olefin raw material, based on the feedstock type, are individually passed into the microchannel reactor; or, in the input unit, a stream obtained by mixing a part of the BF.sub.3 catalyst and the whole auxiliary feed is passed into the microchannel reactor, and, each of the residue of the BF.sub.3 catalyst and the whole olefin raw material is individually passed into the microchannel reactor (preferably, in the case of mixing a part of the BF.sub.3 catalyst and the whole auxiliary feed in the mixer, the speed for passing a part of the BF.sub.3 catalyst into the mixer is 1-100000 L/h, preferably 1-80000 L/h, most preferably 1-30000 L/h, the speed for passing the whole auxiliary feed into the mixer is 0.01-1000 L/h, preferably 0.1-800 L/h, most preferably 0.2-500 L/h, the speed for passing the mixture obtained after mixing a part of the BF.sub.3 catalyst and the whole auxiliary feed in the mixer into the microchannel reactor is 0.01-2000 L/h, preferably 0.1-1600 L/h, most preferably 0.2-1000 L/h, the speed for individually passing the residue of the BF.sub.3 catalyst into the microchannel reactor is 1-150000 L/h, preferably 5-100000 L/h, most preferably 10-50000 L/h, the speed for individually passing the whole olefin raw material into the microchannel reactor is 10-5000 L/h, preferably 20-4000 L/h, most preferably 40-2500 L/h); or, in the input unit, the stream obtained by mixing a part of the BF.sub.3 catalyst and a part of the auxiliary feed is passed into the microchannel reactor, and each of the residue of the BF.sub.3 catalyst, the residue of the auxiliary feed, and the whole olefin raw material is individually passed into the microchannel reactor (preferably, in the case of mixing a part of the BF.sub.3 catalyst and a part of the auxiliary feed in the mixer, the speed for passing a part of the BF.sub.3 catalyst into the mixer is 1-100000 L/h, preferably 1-80000 L/h, most preferably 1-30000 L/h, the speed for passing a part of the auxiliary feed into the mixer is 0.01-800 L/h, preferably 0.1-500 L/h, most preferably 0.2-400 L/h, the speed for passing the mixture obtained by mixing a part of the BF.sub.3 catalyst and a part of the auxiliary feed in the mixer into the microchannel reactor is 0.01-1600 L/h, preferably 0.1-1400 L/h, most preferably 0.2-800 L/h, the speed for individually passing the residue of the BF.sub.3 catalyst into the microchannel reactor is 1-120000 L/h, preferably 5-80000 L/h, most preferably 10-40000 L/h, the speed for passing the residue of the auxiliary feed into the mixer is 0.01-200 L/h, preferably 0.1-150 L/h, most preferably 0.2-100 L/h, the speed for individually passing the whole olefin raw material into the microchannel reactor is 10-5000 L/h, preferably 20-4000 L/h, most preferably 40-2500 L/h); or, In the input unit, the stream obtained by mixing a part of the BF.sub.3 catalyst, a part of the auxiliary feed and the whole olefin raw material is passed into the microchannel reactor, and each of the residue of the BF.sub.3 catalyst, and the residue of the auxiliary feed is individually passed into the microchannel reactor (preferably, in the case of mixing a part of the BF.sub.3 catalyst, a part of the auxiliary feed, and the whole olefin raw material in the mixer, the speed for passing a part of the BF.sub.3 catalyst into the mixer is 1-100000 L/h, preferably 1-80000 L/h, most preferably 1-30000 L/h, the speed for passing a part of the auxiliary feed into the mixer is 0.01-800 L/h, preferably 0.1-500 L/h, most preferably 0.2-400 L/h, the speed for passing the whole olefin raw material into the mixer is 10-5000 L/h, preferably 20-4000 L/h, most preferably 40-2500 L/h, the speed for passing the mixture obtained by mixing a part of the BF.sub.3 catalyst, a part of the auxiliary feed, and the whole olefin raw material in the mixer into the microchannel reactor is 0.01-6000 L/h, preferably 0.1-4600 L/h, most preferably 0.2-3000 L/h, the speed for individually passing the residue of the BF.sub.3 catalyst into the microchannel reactor is 1-150000 L/h, preferably 5-100000 L/h, most preferably 10-50000 L/h, the speed for individually passing the residue of the auxiliary feed into the microchannel reactor is 0.01-200 L/h, preferably 0.1-150 L/h, most preferably 0.2-100 L/h); or, in the input unit, the stream obtained by mixing a part of the BF.sub.3 catalyst, the whole auxiliary feed and a part of the olefin raw material is passed into the microchannel reactor, and each of the residue of the BF.sub.3 catalyst, and the residue of the olefin raw material is individually passed into the microchannel reactor (preferably, in the case of mixing a part of the BF.sub.3 catalyst, the whole auxiliary feed and a part of the olefin raw material in the mixer, the speed for passing a part of the BF.sub.3 catalyst into the mixer is 1-100000 L/h, preferably 1-80000 L/h, most preferably 1-30000 L/h, the speed for passing the whole auxiliary feed into the mixer is 0.01-1000 L/h, preferably 0.1-800 L/h, most preferably 0.2-500 L/h, the speed for passing a part of the olefin raw material into the mixer is 1-2000 L/h, preferably 5-1000 L/h, most preferably 10-500 L/h, the speed for passing the mixture obtained by mixing a part of the BF.sub.3 catalyst, the whole auxiliary feed and a part of the olefin raw material in the mixer into the microchannel reactor is 0.01-3000 L/h, preferably 0.1-1800 L/h, most preferably 0.2-1000 L/h, the speed for individually passing the residue of the BF.sub.3 catalyst into the microchannel reactor is 1-150000 L/h, preferably 5-100000 L/h, most preferably 10-50000 L/h, the speed for individually passing the residue of the olefin raw material into the microchannel reactor is 9-3000 L/h, preferably 15-3000 L/h, most preferably 30-2000 L/h); or, in the input unit, the stream obtained by mixing a part of the BF.sub.3 catalyst, the whole auxiliary feed, and the whole olefin raw material is passed into the microchannel reactor, and, the residue of the BF.sub.3 catalyst is individually passed into the microchannel reactor (preferably, in the case of mixing a part of the BF.sub.3 catalyst, the whole auxiliary feed, and the whole olefin raw material in the mixer, the speed for passing a part of the BF.sub.3 catalyst into the mixer is 1-100000 L/h, preferably 1-80000 L/h, most preferably 1-30000 L/h, the speed for passing the whole auxiliary feed into the mixer is 0.01-1000 L/h, preferably 0.1-800 L/h, most preferably 0.2-500 L/h, the speed for passing the whole olefin raw material into the mixer is 10-5000 L/h, preferably 20-4000 L/h, most preferably 40-2500 L/h, the speed for passing the mixture obtainted by mixing a part of the BF.sub.3 catalyst, the whole auxiliary feed, and the whole olefin raw material in the mixer into the microchannel reactor is 10-6000 L/h, preferably 0.1-4600 L/h, most preferably 0.2-3000 L/h, the speed for individually passing the residue of the BF.sub.3 catalyst into the microchannel reactor is 1-150000 L/h, preferably 5-100000 L/h, most preferably 10-50000 L/h), preferably, In the input unit, a part of the BF.sub.3 catalyst and the whole auxiliary feed are subjected to a first mixing in the first mixer, then subjected to a second mixing with the whole olefin raw material in a second mixer, and then the mixed stream is passed into the microchannel reactor, and, the residue of the BF.sub.3 catalyst is individually passed into the microchannel reactor (preferably, when a part of the BF.sub.3 catalyst and the whole auxiliary feed are subjected to the first mixing in the first mixer, the speed for passing a part of the BF.sub.3 catalyst into the first mixer is 1-100000 L/h, preferably 1-80000 L/h, most preferably 1-30000 L/h, the speed for passing the whole auxiliary feed into the first mixer is 0.01-1000 L/h, preferably 0.1-800 L/h, most preferably 0.2-500 L/h, the stream obtained after the first mixing is then subjected to a second mixing with the whole olefin raw material in the second mixer, the speed for passing the stream obtained after the first mixing into the second mixer is 0.01-2000 L/h, preferably 0.1-1600 L/h, most preferably 0.2-1000 L/h, the speed for passing the whole olefin raw material into the second mixer is 10-5000 L/h, preferably 20-4000 L/h, most preferably 40-2500 L/h, the speed for passing the stream obtained after the second mixing into the microchannel reactor is 10-7000 L/h, preferably 20-5600 L/h, most preferably 40-3500 L/h, the speed for individually passing the residue of the BF.sub.3 catalyst into the microchannel reactor is 1-150000 L/h, preferably 5-100000 L/h, most preferably 10-50000 L/h).

9. The process according to claim 7, which is characterized in that the olefin in the olefin raw material is one or more of C.sub.3-C.sub.20 alpha-olefins; optionally the olefin raw material further contains a mixture of C.sub.5-C.sub.20 alkanes and/or C.sub.1-C.sub.20 oxygen-containing compound (preferably the olefin raw material is Fischer-Tropsch olefin raw material); and/or, the auxiliary feed is one or more of an alcohol having a carbon atom number of 1-20, an ether having a carbon atom number of 1-20, an aldehyde having a carbon atom number of 1-20, a ketone having a carbon atom number of 1-20, an ester having a carbon atom number of 1-30, a carboxylic acid having a carbon atom number of 1-20 and a phenol having a carbon atom number of 1-20.

10. The process according to claim 7, which is characterized in that the reaction temperature in the microchannel reactor is 0-120° C. (preferably 10-80° C., more preferably 20-60° C.); the reaction pressure in the microchannel reactor is 0.01-10 MPa (preferably 0.01-8 MPa, more preferably 0.1-6 MPa); the residence time of the olefin raw material in the microchannel reactor is 1-3600 seconds (preferably 10-1800 seconds, more preferably 15-1000 seconds).

11. The process according to claim 7, which is characterized in that based on the total mass of the BF.sub.3 in the microchannel reactor, the mass ratio of the BF.sub.3 catalyst individually fed to the microchannel reactor to the BF.sub.3 catalyst that is mixed in the input unit is 90-10:10-90, preferably 80-40:20-60, more preferably 70-50:30-50.

12. The process according to claim 7, which is characterized in that the post-treatment method is one or more of adsorption, centrifugation, sedimentation, alkaline washing, water washing and gas-liquid separation method (preferably the adsorption method), in the case that the post-treatment method is sedimentation or centrifugation, optionally the obtained heavy liquid phase is returned to the input unit or the microchannel reactor to continue the participation in the continuous reaction.

13. The process according to claim 7, which is characterized in that the polyalpha-olefin is prepared by utilizing the apparatus for preparing polyalpha-olefins comprising an input unit (1), a microchannel reactor (2), and a post-treatment unit (3) that are successively connected, the input unit comprises a mixer and/or pipeline(s) for delivering an olefin raw material, an auxiliary feed and a BF.sub.3 catalyst to the microchannel reactor (2), The input unit (1) at least comprises a mixer for mixing at least a part of the auxiliary feed and at least a part of the BF.sub.3 catalyst and a pipeline for individually feeding at least a part of the BF.sub.3 catalyst to the microchannel reactor (2).

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0091] FIG. 1 is a schematic diagram of the apparatus of the present invention.

[0092] FIG. 2 is a schematic diagram of the apparatus of the present invention.

[0093] FIG. 3 is a schematic diagram of the preferred microchannel reactor of the present invention.

[0094] FIG. 4 is a sectional view of the first mixing member according to the present invention.

[0095] FIG. 5 is a structural representation of the second mixing member according to the present invention.

[0096] FIG. 6 is a structural representation for superimposing a plurality of the second mixing members according to the present invention.

[0097] FIG. 7 is a schematic diagram of the comparative apparatus of the present invention.

TABLE-US-00001 Description of the reference numerals 1: Input unit 2: Microchannel reactor 3: Post-treatment unit 01: BF.sub.3 catalyst inlet 02: Auxiliary feed inlet 03: Olefin raw material inlet 001: Discharge pipe 002: Feed pipe 003: Shell 004: First heat exchange medium inlet 005: First heat exchange medium outlet 006: Second heat exchange medium inlet 007: Second heat exchange medium outlet 008: Mixing zone 009: Reaction zone 010: Reaction channel 011: Second mixing member 012: Second heat exchange cavity 013: First heat exchange cavity 014: Mixing channel 015: First mixing member 016: Fluid distributor 017: Fluid distribution pipe 018: Discharge pipe 019: First partition plate 020: Transition zone 021: Stabilization channel 022: Diffusion channel 023: Feeding zone 024: Collection zone 025: Second partition plate 0001: Main flow passage 0002: Branch flow passage 0003: Collection cavity 0004: Base strip 0005: Tooth element

DETAILED DESCRIPTION

[0098] The present invention will be further described below through examples and in conjunction with the accompanying drawings.

[0099] FIG. 1 is a schematic diagram of the apparatus for preparing polyalpha-olefins of the present invention, the apparatus comprises an input unit 1, a microchannel reactor 2, and a post-treatment unit 3 that are successively connected, the input unit 1 comprises a mixer 11 for mixing the BF.sub.3 catalyst and the auxiliary feed, a mixer 12 for mixing a mixture of the BF.sub.3 catalyst and the auxiliary feed and the olefin raw material, pipelines for individually inputting the BF.sub.3 catalyst and the olefin raw material, one branch of the mixer 11 can be communicated with the mixer 12, and the other branch of the mixer 11 can be communicated with the microchannel reactor 2, and the mixer 12 is communicated with the mixer 12.

[0100] FIG. 2 is a schematic diagram of the apparatus for preparing polyalpha-olefins of the present invention, the apparatus comprises an input unit 1, a microchannel reactor 2, and a post-treatment unit 3 that are successively connected, the input unit 1 comprises a mixer 11 for mixing the BF.sub.3 catalyst and the auxiliary feed, a mixer 12 for mixing a mixture of the BF.sub.3 catalyst and the auxiliary feed and the olefin raw material, a pipeline for individually inputting the BF.sub.3 catalyst, the mixer 11 is communicated with the mixer 12, and the mixer 12 is communicated with the microchannel reactor 2.

[0101] FIG. 3 is a schematic diagram of the preferred microchannel reactor of the present invention, comprising: [0102] a shell 003; a feeding zone 023, a mixing zone 008, a reaction zone 009, and a collection zone 024 are successively arranged and communicated along a first direction in the shell 003, wherein the shell 003 is provided with a feed pipe 002 communicated with the feeding zone 023 and a discharge pipe 001 communicated with the collection zone 024, and the mixing zone 008 is provided with a mixing channel 014 extending along the first direction; [0103] a fluid distribution pipe 017, the fluid distribution pipe 017 is extended from the exterior of the shell 003 into the mixing channel 014, the fluid distribution pipe 017 is connected with a fluid distributor 016 at an end of the mixing channel 014.

[0104] The shell 003 is the main container for accommodating the reactant and the product, and the feeding zone 023, the mixing zone 008, the reaction zone 009 and the collection zone 024 are different zones of the inner space of the shell 003 (all of which can store the stream), these zones are arranged in a straight line so that the reactant (and the product) advances in a straight line. In the present invention, the flow direction of the stream is referred to as the first direction. Preferably, as shown in FIG. 3, the shell 003 is positioned such that the first direction is the elevation direction, and the feeding zone 023, the mixing zone 008, the reaction zone 009 and the collection zone 024 are arranged in a bottom-to-top direction.

[0105] A first group of the reaction stream (the mixed stream from the input unit 1, there can be two or more feed pipes 002, the number of which corresponds to the number of the pipelines from the input unit 1, except for the pipeline for individually feeding the BF.sub.3 catalyst) can be supplied into the feeding zone 023 through the feed pipe 002 on the shell 003, and the feeding zone 023 has a relatively large cavity and can act as storing the first group of the reaction stream, the first group of the reaction stream in the feeding zone 023 can enter the adjacent mixing zone 008, that is, the mixing channel 014. The fluid distribution pipe 017 is connected to the pipeline for individually feeding the BF.sub.3 catalyst in the input unit 1, hence the input of a second group of the reaction stream (the individually fed BF.sub.3 catalyst) can be provided to the mixing channel 014 through the fluid distribution pipe 017, so as to allow mixing the first group of the reaction stream and the second group of the reaction stream each other in the mixing channel 014 of the mixing zone 008. Among others, the outlet end of the fluid distribution pipe 017 is provided with a fluid distributor 016. The fluid distributor 016 can form the second group of the reaction stream into smaller droplets or bubbles, so that the second group of the reaction stream can be more uniformly distributed to the first group of the reaction stream in the mixing channel 014. Among others, the mixing structure in the mixing channel 014 is more suitable for mixing the liquid-phase stream and the gas-phase stream. The first group of the reaction stream is a liquid-phase stream, and the second group of the reaction stream is a gas-phase stream. The gas-phase stream can be formed into dispersed micro-bubbles through the fluid distributor 016 to increase the contact area with the liquid-phase stream, and at the same time, also can impact the liquid-phase stream to a greater extent, thereby improving the uniformity of mixing the two.

[0106] In addition, as shown in FIG. 3, the mixing channel 014 is a cavity extending along the first direction, that is, the mixing channel 014 has a substantially tubular structure, thereby allowing the stream therein to flow along the first direction to form a stable plug flow.

[0107] The preferred microchannel reactor provided by the present invention, by designing the structure of the mixing channel and the mixing mode therein, can realize continuous and efficient mixing of the reaction stream and at the same time can maintain the reaction fluid to flow in a plug flow-like manner, ensure the consistency of the residence time of the reaction fluid as much as possible, and avoid the undesirable product selectivity due to residence time distribution.

[0108] More specifically, the fluid distributor 016 is at least one selected from powder sintered body with micropores, mesoporous foam material, wire mesh, tube with microslits or micropores. The powder sintered body with micropores can be obtained by sintering the powder into a structure with micropores through a powder metallurgy process, the hollow/mesoporous foam material is a hollow microchannel with network skeletons, and the wire mesh is a network structure with micropores, and the tube is provided with microslits or microholes, all of which can disperse the fluid from the fluid distributor tube 017 into smaller bubbles or droplets.

[0109] Preferably, the fluid distributor 016 is a cylindrical powder sintered body with micropores, and the mixing channel 014 has a circular cross-section. The fluid distributor 016 may be a structure having the substantially same outer diameter as the fluid distribution pipe 017, the cross-sectional shape of the fluid distributor 016 substantially corresponds to the cross-sectional shape of the mixing channel 014, and the fluid distributor 016 can be arranged coaxially with the mixing channel 014 so as to allow the fluid stream dispersed by the fluid distributor 016 to be more uniformly mixed with the stream in the mixing channel 014, and form a stable and uniform plug flow to avoid the inconsistency in the residence time of the stream.

[0110] Among others, the fluid distributor 016 has a cross-sectional area of 0.01 cm.sup.2-200 cm.sup.2, and a length of 1 mm-2000 mm. The mixing channel 014 has a cross-sectional area of 0.05 cm.sup.2-400 cm.sup.2, and a length of 50 mm-5000 mm. The length and the cross-sectional area of the mixing channel 014 are both greater than the length and the cross-sectional area of the fluid distributor 016.

[0111] In addition, the mixing zone 008 is provided with 2-100 (preferably 2-50, more preferably 2-10) mixing channels 014, the fluid distribution pipe 017 includes a main pipe extending from the exterior of the shell 003 into the feeding zone 023 and branch pipes extending from the feeding zone 023 into each mixing channel 014 with fluid distributors 016 connected to branch pipe ends. A plurality of mixing channels 014 are respectively communicated with the feeding zone 023, and the first group of the reaction stream is divided into a plurality of parts in the mixing channels, which play the role of dispersing the first group of the reaction stream, and allow the first group of the reaction stream to form the stable, uniform plug flow. The fluid distribution pipe 017 includes a main pipe and branch pipes, wherein the main pipe is connected to the pipeline for independently feeding the BF.sub.3 catalyst in the input unit 1, and extends from the position of the shell 003 corresponding to the feeding zone 023 into the feeding zone 023, and the branch pipes extend from the feeding zone 023 into the mixing channels 014. That is, the fluid distribution pipe 017 extends from the feeding zone 023 into the mixing channels 014. The mixing zone 008 and the feeding zone 023 can be partitioned by a first partition plate 019. The first partition plate 019 is provided with a plurality of through holes, and each mixing channel 014 is aligned with each through hole, so that the mixing zone 008 is communicated with the feeding zone 023.

[0112] In addition, in the mixing channel 014, a first mixing member 015 is disposed downstream of the fluid distributor 016. In the mixing channel 014, the downstream of the fluid distributor 016 refers to the downstream of the fluid flow direction (i.e., the downstream of the fluid distributor 016 in the first direction), that is, the position closer to the reaction zone 009 than the fluid distributor 016. Through the first mixing member 015, the fluid can be further mixed to improve the mixing uniformity of the two groups of streams.

[0113] Specifically, the first mixing member 015 is provided with a main flow portion and a branch flow portion that are alternately arranged and communicated along the first direction. The main flow portion is provided with a single main flow passage 0001, and the branch flow portion is provided with a plurality of branch flow passages 0002. As shown in FIG. 4, one or more main flow portions/branch flow portions may be provided respectively and arranged alternately, wherein only a single main flow passage 0001 is arranged in the main flow portion, and a plurality of branch flow passages 0002 are arranged in the branch flow portion. The fluid converges in the main flow passage 0001 and disperses in the branch flow passages 0002 of each branch flow portion. Through such a converging-dispersing process, the degree of turbulence can be fully increased and the mixing uniformity of the fluid can be improved.

[0114] Further, in the first mixing member 015, the collection cavity 0003 that is communicated with a plurality of branch flow passages 0002 is disposed downstream of the branch flow portion 0002. As shown in FIG. 4, the volume (especially the cross-sectional area) of the collection cavity 0003 is larger than the volume (especially the cross-sectional area) of the main flow passage 0001, and the collection cavity 0003 can converge a plurality of upstream branch flow passages 0002 together, and it is communicated with the next main flow passage 0001 or the next stage of the reaction zone 009 or the transition zone 020.

[0115] As shown in FIG. 4, the first mixing member 015 according to an embodiment of the present invention is shown, which is formed by splicing a plurality of plate members (the number can be 2-100, preferably 2-50, more preferably 10-30) (the thickness is about 0.2 mm-10 mm) arranged along the first direction, and the structures such as holes and cavities that correspond to the main flow passage 0001, the branch flow passage 0002 and the collection cavity 0003 are formed on each plate member, which is convenient for processing and manufacturing.

[0116] In addition, the mixing zone 008 comprises a first heat exchange cavity disposed in the shell 003, the mixing channel 014 is disposed in the first heat exchange cavity 013, the shell 003 is provided with a first heat exchange medium inlet 004 and a first heat exchange medium outlet 005 that are communicated with the first heat exchange cavity 013. In the mixing zone 008, the mixing channel 014 and the first heat exchange cavity 013 are isolated from each other and not communicated with each other, but the heat conduction can be achieved between each other, and pipe fittings with good thermal conductivity can be used in the mixing channel 014. By supplying the heat exchange medium to the first heat exchange medium inlet 004 and discharging the heat exchange medium through the first heat exchange medium outlet 005, a circulating flow of the heat exchange medium can be formed in the first heat exchange cavity 013 to realize the heat exchange with the mixing channel 014 and the fluid therein, that is, to realize the heat dissipation of the mixing channel 014 and the fluid therein, ensure that the heat generated by the mixing and dissolving of the fluid in the mixing channel 014 is dissipated in time, so that the fluid therein is in a suitable temperature range.

[0117] Among others, the volumetric ratio of the first heat exchange cavity 013 to the mixing channel 014 is 2-50, preferably, the volumetric ratio of the first heat exchange cavity 013 to the mixing channel 014 is 5-30. The volume of the first heat exchange cavity 013 is larger than the volume of the mixing channel 014 so that the heat generated by the mixing and dissolving of the first group of the reaction stream and the second group of the reaction stream is conducted out in time.

[0118] In addition, a transition zone 020 is provided between the mixing zone 008 and the reaction zone 009, the transition zone 020 is provided with a stabilization channel 021 with constant cross-section and a diffusion channel 022 with gradually enlarged cross-section arranged and communicated along the first direction, the stabilization channel 021 is communicated with the mixing channel 014, the diffusion channel 022 is communicated with the reaction zone 009. The transition zone 020 can converge the mixed fluids from a plurality of the mixing channels 014 together in the stabilization channel 021 to achieve another uniform mixing, and then deliver the mixed fluids into the reaction zone 009 via the diffusion channel 022. Among others, the transition area 020 is provided with a stabilization channel 021 and a diffusion channel 022, the stabilization channel 021 mainly realizes the converging and mixing of the fluids, and the diffusion channel 022 is in a bell mouth shape, which can diffuse, for example, can disperse the mixed fluid into a plurality of the reaction channel 010 as described hereinafter. The two ends of the transition zone 020 are respectively provided with partition plates with through holes, so as to be respectively isolated from the mixing zone 008 (mainly the first heat exchange cavity 013) and the reaction zone 009 (mainly the second heat exchange cavity 012), and communicated with each mixing channel 014 and each of reaction channels 010 in parallel through each through hole on each partition plate, and the diffusion channel 022 and the stabilization channel 021 can be pipe fittings provided between two partition plates.

[0119] In addition, the stabilization channel 021 can be connected to a discharge pipe 018 extending to the exterior of the shell 003. As mentioned above, the stabilization channel 021 has the function of converging and mixing, and the discharge pipe 018 can discharge the bubbles and streams accumulated in the stabilization channel 021 to avoid the influence of the bubble accumulation on the mixing uniformity, and the blockage of streams. A valve can be set on the discharge pipe 018, and the valve can be opened when it is necessary to discharge bubbles or streams.

[0120] In addition, the diffusion channel 022 is provided with a diffusion plate with meshes or slits. The diffusion plate may be substantially perpendicular to the first direction. The fluid in the diffusion channel 022 can flow through meshes or slits on the diffusion plate, so that the fluid is dispersed and the uniformity of the mixed fluid is enhanced.

[0121] Specifically, the reaction zone 009 is provided with a plurality of parallel reaction channels 010 extending along the first direction and communicated with the mixing channel 014 via the stabilization channel 021 and the diffusion channel 022. The reaction channel 010 provides a reaction space for the mixed fluid, and bears the mixed fluid to flow to the next stage of the collection area 024 along the first direction, so that the mixed fluid reacts while forming a stable plug flow in the reaction channel 010 to avoid undesired products due to inconsistent residence time distributions. As stated above, a transition zone 020 may be provided between the reaction zone 009 and the mixing zone 008, and a plurality of reaction channels 010 may be communicated with the diffusion channel 022, so that the mixed fluid in the diffusion channel 022 is uniformly dispersed into a plurality of the reaction channels 010. The number of reaction channels is, for example, 2-10000 channels, preferably 2-5000 channels, and more preferably 2-500 channels. The reaction channel 010 can have a cross-section in at least one of circular, rectangular and triangular shapes.

[0122] In addition, the reaction channel 010 is provided with a second mixing member 011, and the second mixing member 011 includes a base strip 0004 extending along the first direction and a tooth element 0005 connected to the base strip 0004 and extended transversely to the base strip 0004. In the second mixing member 011, the base strip 0004 provides a support for a plurality of tooth elements 0005, so that the tooth elements 0005 can be stably held in the reaction channel 010, and the tooth elements 0005 extend approximately transversely to the reaction channel 010, which can improve the turbulence degree of the fluid in the reaction channel 010, thereby improving the mixing uniformity between the reaction streams.

[0123] Among others, the tooth elements 0005 are in one of triangular, arcual, wavy, and spiral shapes. Tooth elements 0005 can be in various shapes, as long as they extend transversely to the reaction channel 010 and can achieve the effect of increasing the turbulence degree of the fluid.

[0124] Preferably, the tooth element 0005 is of triangular shape, and on one side of the triangle adjacent to the base strip 0004, one corner is connected to the base strip 0004, and the other corner is 0.01 mm-20 mm away from the base strip 0004. The tooth elements 0005 may be triangular plate members and are connected to the base strip 0004 only with one corner.

[0125] Preferably, each reaction channel 010 is provided with a plurality of the second mixing members 011 (the number can be 2-100, preferably 2-50, more preferably 10-30), which are stacked at intervals, and a plurality of the second mixing members 011 are stacked at intervals, and correspondingly the tooth elements 0005 are also stacked at intervals, and the tooth elements 0005 of different second mixing members 011 are arranged staggeredly, so that different second mixing members 011 are arranged more irregularly and the turbulence degree of the fluid in the reaction channel 010 can be better improved.

[0126] Preferably, the cross-section of the reaction channel 010 is rectangular, and the tooth elements 0005 extend between a set of opposite sides of the rectangle. Specifically, the reaction channel 010 includes four side walls, namely two sets of opposite parallel side walls, the base strip 0004 is disposed at one side wall of the reaction channel 010, and the tooth elements 0005 extend toward the other opposite side wall, a plurality of second mixing elements 011 can better accommodate the inner cavity structure having a square pillar shape of the reaction channel 010.

[0127] Specifically, the reaction channel 010 has a cross-sectional area of 1 mm.sup.2-150 mm.sup.2, and a length of 50 mm-5000 mm, the minimum distance between the reaction channels 010 is 1 mm-50 mm, and the second mixing member 011 has a thickness of 0.1 mm-3 mm, and the spacing between adjacent tooth elements 0005 is 1 mm-50 mm.

[0128] Preferably, the reaction channel 010 has a length of 100 mm-3000 mm, the minimum spacing between the reaction channels 010 is 3 mm-30 mm, the second mixing member 011 has a thickness of 0.2 mm-2 mm, the spacing between adjacent tooth elements 0005 is 1.5 mm-20 mm. The minimum spacing of the reaction channels 010 reflects the density of the reaction channels 010 in the reaction zone 009. Preferably, in the second mixing member 011, the tooth element 0005 is a plate member that can be coplanar with the base strip 0004, and the thickness of the second mixing member 011 is approximately the thickness of the tooth element 0005.

[0129] In addition, the reaction zone 009 can be provided with a second heat exchange cavity 012 disposed in the shell 003, the reaction channel 010 is disposed in the second heat exchange cavity 012, the shell 003 is provided with a second heat transfer medium inlet 006 and a second heat transfer medium outlet 007 that are communicated with the second heat exchange cavity 012. The second heat exchange cavity 012 may be mainly formed by the shell 003, and at two ends are respectively the second partition plate 025 between the reaction zone 009 and the collection zone 024 and the partition plate between the reaction zone 009 and the transition zone 020. Through the second heat exchange medium inlet 006 and the second heat exchange medium outlet 007, the heat exchange medium can be introduced into the second heat exchange cavity 012 to realize the heat exchange treatment of the reaction channel 010, so as to ensure that the fluid in the reaction channel 010 is reacted in an appropriate temperature range, and avoid the production of undesired products.

[0130] In addition, the first heat exchange cavity 013 and the second heat exchange cavity 012 may be connected in series with each other and arranged in a single heat exchange circulation flow path, or may also be arranged in parallel in a single heat exchange circulation flow path, or may be arranged in two different heat exchange circulation flow paths respectively.

[0131] Among others, the volumetric ratio of the second heat exchange cavity 012 to the reaction channel 010 is 2-50, preferably, the volumetric ratio of the second heat exchange cavity 012 to the reaction channel 010 is 5-30. The volume of the second heat exchange cavity 012 is larger than the volume of the reaction channel 010, so that the heat in the reaction channel 010 can be discharged in time to ensure that the reaction channel 010 is at a suitable temperature.

[0132] The preferred microchannel reactor of the present invention can be used to synthesize the polyalpha-olefin synthetic oil, the feed pipe 002 can be used to input the liquid-phase stream (continuous phase) (the mixed stream from the input unit 1), and the fluid distribution pipe 017 can be used to input the gas phase stream (dispersion phase) (the individually fed BF.sub.3 catalyst from the input unit 1). The liquid-phase stream is used as the continuous phase to enter the feeding zone 023 of the microchannel reactor from the feed pipe 002, and the gas phase stream is used as the dispersed phase to enter the mixing channel 014 of the reactor from the fluid distribution pipe 017, and dissolved in the continuous phase through the fluid distributor 016. The mixed fluid that has completed the reaction in the reaction channel 010 enters the collection area 024, and finally is discharged from the discharge pipe 001.

[0133] In the embodiments of the present invention, the preferred structural components or parameters are employed without repeated recitation when using the preferred microchannel reactor, unless otherwise specified.

[0134] FIG. 7 is a schematic diagram for a comparative apparatus of the present invention, wherein the apparatus comprises an input unit 1, a tubular reactor 2, and a post-treatment unit 3 that are successively connected, the input unit 1 comprises a mixer 12 for the auxiliary feed and the olefin raw material, and a pipeline for individually feeding the BF.sub.3 catalyst.

Example 1

[0135] In this example, the mass ratio of the BF.sub.3 directly fed to the microchannel reactor to the BF.sub.3 fed to the mixer to participate in the mixing was 60:40, the stream obtained by mixing a part of the BF.sub.3 catalyst and the whole auxiliary feed was passed into the microchannel reactor, and each of the residue of the BF.sub.3 catalyst and the whole olefin raw material was individually passed into the microchannel reactor (the above-mentioned configuration mode 2 and feeding mode 2 according to the present invention).

[0136] In the apparatus, the structure and parameter of the mixer was as follows: The mixer had a cylindrical structure with an outer diameter of 10 cm and an inner diameter of 6 cm. The mixer had two feed inlets at the lower end and one discharge outlet at the uppermost end. The mixer was equipped with a filler layer, and the filler was ceramic balls. The mixer had a heat exchange layer having a temperature of 0-100° C.

[0137] In the apparatus, the used microchannel reactor was the preferred microchannel reactor of the present invention as described above containing 5 reaction channels 010 in parallel, each reaction channel 010 had a rectangular cross-section with a cross-sectional area of 20 mm.sup.2, and the reaction channel 010 had a length of 2000 mm. The second mixing member 011 in the reaction channel 010 had triangular tooth elements 0005, and the spacing between adjacent tooth elements 0005 was 5 mm. In the reaction channel 010, a total of four layers of superimposed second mixing members 011 as shown in FIG. 5 were arranged. The reactor contained two mixing channels 014, which had a cross-sectional area of 10 cm.sup.2 and a length of 800 mm. The fluid distributor 016 was a metal powder sintered body having an average pore size of 5 microns, a cross-sectional area of 8.5 cm.sup.2 and a length of 150 mm. Three first mixing members 015 were provided in each mixing channel 014.

[0138] In the apparatus, the post-treatment unit 3 was a solid adsorption device, and its structure and parameter was as follows: open type, an effective volume of 10L, operating at normal temperature, feeding at the lower end, discharging at the upper end, and filling the tank with potassium oxide.

[0139] The BF.sub.3 gas at a flow rate of 126 L/h and n-butanol at 0.6 L/h were mixed in a mixer. Into the microchannel reactor 2, the stream in the mixer at a flow rate of 1.2 L/h, the BF.sub.3 gas at a flow rate of 189 L/h that was additionally independently fed, and decene at a flow rate of 60 L/h were each individually fed. The polymerization reaction occurred, the reaction temperature was 20° C., and the pressure was 5 MPa. The stream obtained after the polymerization reaction entered the alkaline washing and water washing devices for the post-treatment. The polyolefin product was obtained after the catalyst was removed. After the system run stably, a sample was taken and measured by the gas chromatography for the content of each component in the product. The test results were as shown in Table 1.

TABLE-US-00002 Olefin composition distribution Content Monomer, % 1.2 Dimer, % 3.1 Trimer, % 43.1 Tetramer, % 32.1 Pentamer, % 17.0 ≥Hexamer, % 3.5 Conversion, % 98.8

Example 2

[0140] In this example, the mass ratio of the BF.sub.3 directly fed to the microchannel reactor to the BF.sub.3 fed to the mixer to participate in the mixing was 60:40, the stream obtained by mixing a part of the BF.sub.3 catalyst and a part of the auxiliary feed was passed into the microchannel reactor, and each of the residue of the BF.sub.3 catalyst, the residue of the auxiliary feed and the whole olefin raw material was individually passed into the microchannel reactor (the above-mentioned configuration mode 3 and feeding mode 3 according to the present invention).

[0141] The mixer and the microchannel reactor had the same structures as those of Example 1.

[0142] In the apparatus, the post-treatment unit 3 was a solid adsorption device, and its structure and parameter was as follows: open type, an effective volume of 10 L, operating at normal temperature, feeding at the lower end, discharging at the upper end, and filling the tank with potassium oxide.

[0143] The BF.sub.3 gas at a flow rate of 126 L/h and n-butanol at 0.3 L/h were mixed in a mixer. Into the microchannel reactor 2, the stream in the mixer at a flow rate of 1.2 L/h, the BF.sub.3 gas at a flow rate of 189 L/h that was additionally independently fed, n-butanol at 0.3 L/h, and decene at a flow rate of 60 L/h were each individually fed. The polymerization reaction occurred, the reaction temperature was 20° C., and the pressure was 5 MPa. The stream obtained after the polymerization reaction entered the alkaline washing and water washing devices for the post-treatment. The polyolefin product was obtained after the catalyst was removed. After the system run stably, a sample was taken and measured by the gas chromatography for the content of each component in the product. The test results were as shown in Table 2.

TABLE-US-00003 Olefin composition distribution Content Monomer, % 1.1 Dimer, % 3.5 Trimer, % 43.2 Tetramer, % 31.7 Pentamer, % 17.1 ≥Hexamer, % 3.4 Conversion, % 98.9

Example 3

[0144] In this example, the mass ratio of the BF.sub.3 directly fed to the microchannel reactor to the BF.sub.3 fed to the mixer to participate in the mixing was 60:40, the stream obtained by mixing a part of the BF.sub.3 catalyst, a part of the auxiliary feed and the whole olefin raw material was passed into the microchannel reactor, and each of the residue of the BF.sub.3 catalyst, and the residue of the auxiliary feed was individually passed into the microchannel reactor (the above-mentioned configuration mode 4 and feeding mode 4 according to the present invention).

[0145] The polymerization of the olefin raw material was carried out by using the apparatus for preparing polyalpha-olefins shown in FIG. 1.

[0146] In the apparatus, the structure and parameter of the mixer 11 was as follows: the mixer had a cylindrical structure with an outer diameter of 10 cm and an inner diameter of 6 cm. The mixer had two feed inlets at the lower end and one discharge outlet at the uppermost end. The mixer was equipped with a filler layer, and the filler was ceramic balls. The mixer had a heat exchange layer having a temperature of 0-100° C.

[0147] In the apparatus, the structure and parameter of the mixer 12 was as follows: the mixer had a cylindrical structure with an outer diameter of 10 cm and an inner diameter of 6 cm. The mixer had two feed inlets at the lower end and one discharge outlet at the uppermost end. The mixer was equipped with a filler layer, and the filler was a regular filler. The mixer had a heat exchange layer having a temperature of 0-50° C.

[0148] The microchannel reactor had the same structure as that of Example 1.

[0149] In the apparatus, the post-treatment unit 3 was a solid adsorption device, and its structure and parameter was as follows: open type, an effective volume of 10 L, operating at normal temperature, feeding at the lower end, discharging at the upper end, and filling the tank with potassium oxide.

[0150] The BF.sub.3 gas at a flow rate of 126 L/h and n-butanol at 0.3 L/h were mixed in a mixer 11, and then the mixture and decene at a flow rate of 60 L/h were mixed in a mixer 12. Into the microchannel reactor 2, the stream in the mixer 12 at a flow rate of 60.6 L/h, the BF.sub.3 gas at a flow rate of 189 L/h that was additionally independently fed, and n-butanol at 0.3 L/h were each individually fed. The polymerization reaction occurred, the reaction temperature was 20° C., and the pressure was 5 MPa. The stream obtained after the polymerization reaction entered the alkaline washing and water washing devices for the post-treatment. The polyolefin product was obtained after the catalyst was removed. After the system run stably, a sample was taken and measured by the gas chromatography for the content of each component in the product. The test results were as shown in Table 3.

TABLE-US-00004 Olefin composition distribution Content Monomer, % 0.9 Dimer, % 2.9 Trimer, % 43.2 Tetramer, % 32.3 Pentamer, % 17.0 ≥Hexamer, % 3.7 Conversion, % 99.1

Example 4

[0151] In this example, the mass ratio of the BF.sub.3 directly fed to the microchannel reactor to the BF.sub.3 fed to the mixer to participate in the mixing was 60:40, the stream obtained by mixing a part of the BF.sub.3 catalyst, the whole auxiliary feed and a part of the olefin raw material was passed into the microchannel reactor, and each of the residue of the BF.sub.3 catalyst, and the residue of the olefin raw material was individually passed into the microchannel reactor (the above-mentioned configuration mode 5 and feeding mode 5 according to the present invention).

[0152] The polymerization of the olefin raw material was carried out by using the apparatus for preparing polyalpha-olefins shown in FIG. 1.

[0153] The mixer and the microchannel reactor had the same structures as those of Example 3.

[0154] In the apparatus, the post-treatment unit 3 was a solid adsorption device, and its structure and parameter was as follows: open type, an effective volume of 10 L, operating at normal temperature, feeding at the lower end, discharging at the upper end, and filling the tank with potassium oxide.

[0155] The BF.sub.3 gas at a flow rate of 126 L/h and n-butanol at 0.6 L/h were mixed in a mixer 11, and then the mixture and decene at a flow rate of 30 L/h were mixed in a mixer 12. Into the microchannel reactor 2, the stream in the mixer 12 at a flow rate of 30.6 L/h, the BF.sub.3 gas at a flow rate of 189 L/h that was additionally independently fed, and decene at 0.3 L/h were each individually fed. The polymerization reaction occurred, the reaction temperature was 20° C., and the pressure was 5 MPa. The stream obtained after the polymerization reaction entered the alkaline washing and water washing devices for the post-treatment. The polyolefin product was obtained after the catalyst was removed. After the system run stably, a sample was taken and measured by the gas chromatography for the content of each component in the product. The test results were as shown in Table 4.

TABLE-US-00005 Olefin composition distribution Content Monomer, % 1.7 Dimer, % 3.7 Trimer, % 42.6 Tetramer, % 32.1 Pentamer, % 16.6 ≥Hexamer, % 3.3 Conversion, % 98.3

Example 5

[0156] In this example, the mass ratio of the BF.sub.3 directly fed to the microchannel reactor to the BF.sub.3 fed to the mixer to participate in the mixing was 60:40, the stream obtained by mixing a part of the BF.sub.3 catalyst, the whole auxiliary feed, and the whole olefin raw material was passed into the microchannel reactor, and the residue of the BF.sub.3 catalyst was individually passed into the microchannel reactor (the above-mentioned configuration mode 6 and feeding mode 6 according to the present invention).

[0157] The mixer and the microchannel reactor had the same structures as those of Example 1, except that the used mixer had three feed inlets.

[0158] In the apparatus, the post-treatment unit 3 was a solid adsorption device, and its structure and parameter was as follows: open type, an effective volume of 10 L, operating at normal temperature, feeding at the lower end, discharging at the upper end, and filling the tank with potassium oxide.

[0159] The BF.sub.3 gas at a flow rate of 126 L/h, n-butanol at 0.6 L/h and decene at a flow rate of 60 L/h were passed into the mixer to perform the mixing. Into the microchannel reactor 2, the stream in the mixer at a flow rate of 61.2 L/h and the BF.sub.3 gas at a flow rate of 189 L/h that was additionally independently fed were each individually fed. The polymerization reaction occurred, the reaction temperature was 20° C., and the pressure was 5 MPa. The stream obtained after the polymerization reaction entered the alkaline washing and water washing devices for the post-treatment. The polyolefin product was obtained after the catalyst was removed. After the system run stably, a sample was taken and measured by the gas chromatography for the content of each component in the product. The test results were as shown in Table 5.

TABLE-US-00006 Olefin composition distribution Content Monomer, % 0.7 Dimer, % 2.5 Trimer, % 43.3 Tetramer, % 32.4 Pentamer, % 17.2 ≥Hexamer, % 3.9 Conversion, % 99.3

Example 6

[0160] In this example, the mass ratio of the BF.sub.3 directly fed to the microchannel reactor to the BF.sub.3 fed to the mixer to participate in the mixing was 60:40. In the input unit, a part of the BF.sub.3 catalyst and the whole auxiliary feed were subjected to a first mixing, then subjected to a second mixing with the whole olefin raw material, then the mixed stream was passed into the microchannel reactor, and the residue of the BF.sub.3 catalyst was individually passed into the microchannel reactor (the above-mentioned configuration mode 6 and feeding mode 6 according to the present invention).

[0161] The polymerization of the olefin raw material was carried out by using the apparatus for preparing polyalpha-olefins shown in FIG. 2.

[0162] The mixer and the microchannel reactor had the same structures as those of Example 3.

[0163] In the apparatus, the post-treatment unit 3 was a solid adsorption device, and its structure and parameter was as follows: open type, an effective volume of 10 L, operating at normal temperature, feeding at the lower end, discharging at the upper end, and filling the tank with potassium oxide.

[0164] The BF.sub.3 gas at a flow rate of 126 L/h and n-butanol at 0.6 L/h were mixed in the mixer 11, and the mixed stream and decene at a flow rate of 60 L/h were passed into the mixer 12. Into the microchannel reactor 2, the stream in the mixer 12 at a flow rate of 61.2 L/h and the BF.sub.3 gas at a flow rate of 189 L/h that was additionally independently fed were each individually fed. The polymerization reaction occurred, the reaction temperature was 20° C., and the pressure was 5 MPa. The stream obtained after the polymerization reaction entered the alkaline washing and water washing devices for the post-treatment. The polyolefin product was obtained after the catalyst was removed. After the system run stably, a sample was taken and measured by the gas chromatography for the content of each component in the product. The test results were as shown in Table 6.

TABLE-US-00007 Olefin composition distribution Content Monomer, % 0.2 Dimer, % 1.9 Trimer, % 43.9 Tetramer, % 32.2 Pentamer, % 18.0 ≥Hexamer, % 3.8 Conversion, % 99.8

Example 7

[0165] In this example, the mass ratio of the BF.sub.3 directly fed to the microchannel reactor to the BF.sub.3 fed to the mixer to participate in the mixing was 50:50. In the input unit, a part of the BF.sub.3 catalyst and the whole auxiliary feed were subjected to a first mixing, then subjected to a second mixing with the whole olefin raw material, then the mixed stream was passed into the microchannel reactor, and the residue of the BF.sub.3 catalyst was individually passed into the microchannel reactor.

[0166] The polymerization of the olefin raw material was carried out by using the apparatus for preparing polyalpha-olefins shown in FIG. 2.

[0167] The mixer and the microchannel reactor had the same structures as those of Example 3.

[0168] In the apparatus, the post-treatment unit 3 was a solid adsorption device, and its structure and parameter was as follows: open type, an effective volume of 10 L, operating at normal temperature, feeding at the lower end, discharging at the upper end, and filling the tank with potassium oxide.

[0169] The BF.sub.3 gas at a flow rate of 126 L/h and n-butanol at 0.6 L/h were mixed in the mixer 11, and the mixed stream and decene at a flow rate of 60 L/h were passed into the mixer 12. Into the microchannel reactor 2, the stream in the mixer 12 at a flow rate of 61.2 L/h and the BF.sub.3 gas at a flow rate of 126 L/h that was additionally independently fed were each individually fed. The polymerization reaction occurred, the reaction temperature was 20° C., and the pressure was 5 MPa. The stream obtained after the polymerization reaction entered the alkaline washing and water washing devices for the post-treatment. The polyolefin product was obtained after the catalyst was removed. After the system run stably, a sample was taken and measured by the gas chromatography for the content of each component in the product. The test results were as shown in Table 7.

TABLE-US-00008 Olefin composition distribution Content Monomer, % 0.9 Dimer, % 2.2 Trimer, % 43.3 Tetramer, % 32.5 Pentamer, % 17.3 ≥Hexamer, % 3.8 Conversion, % 99.1

Comparative Example 1

[0170] The olefin polymerization was carried out by using the apparatus for preparing polyalpha-olefins shown in FIG. 2. In this example, the mass ratio of the BF.sub.3 directly fed to the microchannel reactor to the BF.sub.3 fed to the mixer to participate in the mixing was 60:40, a part of the BF.sub.3 catalyst and the whole auxiliary feed were subjected to a first mixing, then subjected to a second mixing with the whole olefin raw material, then the mixed stream was passed into the microchannel reactor, and the residue of the BF.sub.3 catalyst was individually passed into the microchannel reactor.

[0171] The mixer had the same structure as that of Example 3.

[0172] In the apparatus, the microchannel reactor 2 contained 5 reaction channels 010 in parallel, each reaction channel 010 had a rectangular cross-section with a cross-sectional area of 20 mm.sup.2, and the reaction channel 010 had a length of 2000 mm. The second mixing member 011 in the reaction channel 010 had triangular tooth elements 0005, and the spacing between adjacent tooth elements 0005 was 5 mm. In the reaction channel 010, a total of four layers of superimposed second mixing members 011 as shown in FIG. 5 were arranged. Neither the mixing channel 014 nor the fluid distributor 016 was in the reactor.

[0173] In the apparatus, the post-treatment unit 3 was an adsorption device, and its structure and parameter was as follows: open type, an effective volume of 10 L, operating at normal temperature, feeding at the lower end, discharging at the upper end, and filling the adsorption device with calcium oxide.

[0174] The BF.sub.3 gas at a flow rate of 126 L/h and n-butanol at 0.6 L/h were mixed in the mixer 11, and the mixed stream and decene at a flow rate of 60 L/h were passed into the mixer 12. Into the microchannel reactor 2, the stream in the mixer 12 at a flow rate of 61.2 L/h and the BF.sub.3 gas at a flow rate of 189 L/h that was additionally independently fed were each individually fed. The polymerization reaction occurred in the microchannel reactor 2, the reaction temperature was 20° C., and the pressure was 5 MPa. The stream obtained after the polymerization reaction entered the adsorption device, and the catalyst was removed by adsorption to produce a polyolefin product. A small amount of the sample was taken, and measured by the gas chromatography for the content of each component in the product. The test results were as shown in Table 8.

TABLE-US-00009 Olefin composition distribution Content Monomer, % 19.4 Dimer, % 13.2 Trimer, % 23.9 Tetramer, % 23.4 Pentamer, % 14.5 ≥Hexamer, % 5.6 Conversion, % 80.6

Comparative Example 2

[0175] The polymerization reaction was carried out by using the apparatus for preparing polyalpha-olefins shown in FIG. 2. In this example, the mass ratio of the BF.sub.3 directly fed to the microchannel reactor to the BF.sub.3 fed to the mixer to participate in the mixing was 60:40, a part of the BF.sub.3 catalyst and the whole auxiliary feed were subjected to a first mixing, then subjected to a second mixing with the whole olefin raw material, then the mixed stream was passed into the microchannel reactor, and the residue of the BF.sub.3 catalyst was individually passed into the microchannel reactor.

[0176] The microchannel reactor had the same structure as that of Example 3.

[0177] In the apparatus, the microchannel reactor 2 contained 5 reaction channels 010 in parallel, each reaction channel 010 had a rectangular cross-section with a cross-sectional area of 20 mm.sup.2, and the reaction channel 010 had a length of 2000 mm. The second mixing member 011 in the reaction channel 010 had triangular tooth elements 0005, and the spacing between adjacent tooth elements 0005 was 5 mm. In the reaction channel 010, a total of four layers of superimposed second mixing members 011 as shown in FIG. 5 were arranged. The reactor contained one mixing channel 014, which had a cross-sectional area of 10 cm.sup.2 and a length of 800 mm. The fluid distributor 016 was a metal powder sintered body having an average pore size of 5 microns, a cross-sectional area of 8.5 cm.sup.2 and a length of 150 mm. Three first mixing members 015 were provided in the mixing channel 014.

[0178] In the apparatus, The post-treatment unit 3 was a centrifugation device, and its structure and parameter was as follows: tubular type centrifuge, operating at normal temperature, and separation factor of 8000G.

[0179] The BF.sub.3 gas at a flow rate of 126 L/h and n-butanol at 0.6 L/h were mixed in the mixer 11, and the mixed stream and decene at a flow rate of 60 L/h were passed into the mixer 12. Into the microchannel reactor 2, the stream in the mixer 12 at a flow rate of 61.2 L/h and the BF.sub.3 gas at a flow rate of 189 L/h that was additionally independently fed were each individually fed. The polymerization reaction occurred in the microchannel reactor 2, the reaction temperature was 20° C., and the pressure was 5 MPa. The stream obtained after the polymerization reaction entered a centrifugation device, centrifugally separated to remove the catalyst, water washed for three times to produce a polyolefin product. After the system run stably, a small amount of the sample was taken, and measured by the gas chromatography for the content of each component in the product. The test results were as shown in Table 9.

TABLE-US-00010 Olefin composition distribution Content Monomer, % 15.5 Dimer, % 7.8 Trimer, % 32.5 Tetramer, % 26.8 Pentamer, % 13.2 ≥Hexamer, % 4.2 Conversion, % 84.5

Example 8

[0180] The polymerization of the olefin raw material was carried out by using the apparatus for preparing polyalpha-olefins shown in FIG. 2. In this example, the mass ratio of the BF.sub.3 directly fed to the microchannel reactor to the BF.sub.3 fed to the mixer to participate in the mixing was 60:40. In the input unit, a part of the BF.sub.3 catalyst and the whole auxiliary feed were subjected to a first mixing, then subjected to a second mixing with the whole olefin raw material, then the mixed stream was passed into the microchannel reactor, and the residue of the BF.sub.3 catalyst was individually passed into the microchannel reactor.

[0181] The mixer and the microchannel reactor had the same structures as those of Example 3.

[0182] In the apparatus, the microchannel reactor 2 contained 5 reaction channels 010 in parallel, each reaction channel 010 had a rectangular cross-section with a cross-sectional area of 20 mm.sup.2, and the reaction channel 010 had a length of 2000 mm. The second mixing member 011 in the reaction channel 010 had triangular tooth elements 0005, and the spacing between adjacent tooth elements 0005 was 5 mm. In the reaction channel 010, a total of four layers of superimposed second mixing members 011 as shown in FIG. 5 were arranged. The reactor contained two mixing channels 014, which had a cross-sectional area of 10 cm.sup.2 and a length of 800 mm. Three first mixing members 015 were provided in each mixing channel 014. The fluid distributor 016 was made of micro/mesoporous tube material, and the hollow microchannels constituting the network framework of the micro/mesoporous tube material had a cross-sectional area of 8.5 cm.sup.2, an average pore diameter of 2 microns, and a length of 150 mm.

[0183] In the apparatus, the post-treatment unit 3 was a centrifugation device, and its structure and parameter was as follows: tubular type centrifuge, operating at normal temperature, and separation factor of 8000 G.

[0184] The BF.sub.3 gas at a flow rate of 126 L/h and n-butanol at 0.6 L/h were mixed in the mixer 11, and the mixed stream and decene at a flow rate of 60 L/h were passed into the mixer 12. Into the microchannel reactor 2, the stream in the mixer 12 at a flow rate of 61.2 L/h and the BF.sub.3 gas at a flow rate of 189 L/h that was additionally independently fed were each individually fed. The polymerization reaction occurred in the microchannel reactor 2, the reaction temperature was 20° C., and the pressure was 5 MPa. The stream obtained after the polymerization reaction entered a centrifugation device, centrifugally separated to remove the catalyst, water washed for three times to produce a polyolefin product. After the system run stably, a small amount of the sample was taken, and measured by the gas chromatography for the content of each component in the product. The test results were as shown in Table 10.

TABLE-US-00011 Olefin composition distribution Content Monomer, % 0.6 Dimer, % 2.7 Trimer, % 42.6 Tetramer, % 31.7 Pentamer, % 18.3 ≥Hexamer, % 4.1 Conversion, % 99.4

Comparative Example 3

[0185] In this example, the structure and the parameter of the microchannel reactor 2 were identical to those of Example 1.

[0186] In the apparatus, the post-treatment unit 3 was an adsorption device, and its structure and parameter process was as follows: open type, an effective volume of 10L, operating at normal temperature, feeding at the lower end, discharging at the upper end, and filling the adsorption device with calcium oxide.

[0187] Into the microchannel reactor 2 were each independently fed the BF.sub.3 gas at a flow rate of 315 L/h, n-butanol at 0.6 L/h and decene at a flow rate of 60 L/h. The polymerization reaction occurred in the microchannel reactor 2, the reaction temperature was 20° C., and the pressure was 5 MPa. The stream obtained after the reaction entered the adsorption device, and the catalyst was removed by adsorption to produce a polyolefin product. After the system run stably, a sample was taken and measured by the gas chromatography for the content of each component in the product. The test results were as shown in Table 11.

TABLE-US-00012 Olefin composition distribution Content Monomer, % 7.4 Dimer, % 6.9 Trimer, % 38.1 Tetramer, % 29.5 Pentamer, % 15.9 ≥Hexamer, % 2.2 Conversion, % 92.6

Comparative Example 4

[0188] In this example, the structure and the parameter of the mixer and the microchannel reactor 2 were identical to those of Example 1.

[0189] In the apparatus, the post-treatment unit 3 was an adsorption device, and its structure and parameter process was as follows: open type, an effective volume of 10L, operating at normal temperature, feeding at the lower end, discharging at the upper end, and filling the adsorption device with calcium oxide.

[0190] The BF.sub.3 gas at a flow rate of 315 L/h and n-butanol at 0.6 L/h were mixed in the mixer. The mixed stream and decene at a flow rate of 60 L/h were each independently fed to the microchannel reactor 2. The polymerization reaction occurred in the microchannel reactor 2, the reaction temperature was 20° C., and the pressure was 5 MPa. The stream obtained after the reaction entered the adsorption device, and the catalyst was removed by adsorption to produce a polyolefin product. After the system run stably, a sample was taken and measured by the gas chromatography for the content of each component in the product. The test results were as shown in Table 12.

TABLE-US-00013 Olefin composition distribution Content Monomer, % 5.5 Dimer, % 2.8 Trimer, % 40.5 Tetramer, % 28.8 Pentamer, % 18.2 ≥Hexamer, % 4.2 Conversion, % 94.5

Comparative Example 5

[0191] In this example, the structure and parameter of the mixer and the microchannel reactor 2 were identical to those of Example 1.

[0192] In the apparatus, the post-treatment unit 3 was an adsorption device, and its structure and parameter process was as follows: open type, an effective volume of 10 L, operating at normal temperature, feeding at the lower end, discharging at the upper end, and filling the adsorption device with calcium oxide.

[0193] n-butanol at 0.6 L/h and decene at a flow rate of 60 L/h were mixed in the mixer. The mixed stream at a flow rate of 61.2 L/h and the BF.sub.3 gas at a flow rate of 315 L/h were each independently fed to the microchannel reactor 2. The polymerization reaction occurred in the microchannel reactor 2, the reaction temperature was 20° C., and the pressure was 5 MPa. The stream obtained after the polymerization reaction entered the adsorption device, and the catalyst was removed by adsorption to produce a polyolefin product. After the system run stably, a sample was taken and measured by the gas chromatography for the content of each component in the product. The test results were as shown in Table 13.

TABLE-US-00014 Olefin composition distribution Content Monomer, % 1.9 Dimer, % 2.7 Trimer, % 43.2 Tetramer, % 32.1 Pentamer, % 15.6 ≥Hexamer, % 4.5 Conversion, % 98.1

Comparative Example 6

[0194] The polymerization of the olefin raw material was carried out by using the apparatus for preparing polyalpha-olefins shown in FIG. 7.

[0195] In the apparatus, the mixer had the same structure and parameter as that of Example 1.

[0196] In the apparatus, the tubular reactor included a reaction tube and a hollow cylindrical shell for accommodating a heat exchange medium, and the reaction tube was arranged in the hollow cylindrical shell in form of spiral coil. Baffle plates were arranged in the hollow cylindrical shell at intervals along the circumferential direction, the baffle plates extending along the cross section direction of the reaction tubes, and provided with through holes capable of accommodating the reaction tubes, so that the reaction tubes passed through the baffle plates. The cylindrical shell was provided with a heat exchange medium inlet and a heat exchange medium outlet respectively.

[0197] In the apparatus, the post-treatment unit was an adsorption device, which had the same structure and process parameter as that of Example 3.

[0198] N-butanol at 0.6 L/h and decene at a flow rate of 60 L/h were mixed in the mixer 12. The mixed stream at a flow rate of 61.2 L/h and the BF.sub.3 gas at a flow rate of 315 L/h were each independently fed to the microchannel reactor 2. The polymerization reaction occurred in the tubular reactor, the reaction temperature was 20° C., and the pressure was 5 MPa. The stream obtained after the reaction entered the adsorption device, and the catalyst was removed by adsorption to produce a polyolefin product. After the system run stably, a sample was taken and measured by the gas chromatography for the content of each component in the product. The test results were as shown in Table 14.

TABLE-US-00015 Olefin composition distribution Content Monomer, % 22.7 Dimer, % 6.3 Trimer, % 25.1 Tetramer, % 22.2 Pentamer, % 14.6 ≥Hexamer, % 9.1 Conversion, % 77.3

Comparative Example 7

[0199] In this example, the structure and parameter of the mixer and the microchannel reactor 2 were identical to those of Example 1.

[0200] The BF.sub.3 gas at a flow rate of 5 L/h and n-butanol at 0.6 L/h were mixed in the mixer, the mixed stream was passed into the microchannel reactor 2, and 1-decene at a flow rate of 30 L/h was passed into the microchannel reactor 2. The polymerization reaction occurred in the microchannel reactor, the reaction temperature was 20° C., and the pressure was 5 MPa. The stream obtained after the polymerization reaction entered the adsorption device, and the catalyst was removed by adsorption to produce a polyolefin product. After the system run stably, a sample was taken and measured by the gas chromatography for the content of each component in the product. The test results were as shown in Table 15.

TABLE-US-00016 Olefin composition distribution Content Monomer, % 33.5 Dimer, % 12.9 Trimer, % 25.6 Tetramer, % 14.7 Pentamer, % 9.2 ≥Hexamer, % 4.1 Conversion, % 66.5

[0201] The polyolefin products of Example 1-8 and Comparative Example 1-7 were distilled and cut respectively to obtain polyalpha-olefin synthetic oils above 280° C., and the kinematic viscosity at 100° C. and the viscosity index were tested. The test results were shown in Table 16.

TABLE-US-00017 Performance evaluation Kinematic viscosity at 100° C., mm.sup.2/s Viscosity index Example 1 5.154 141 Example 2 5.201 143 Example 3 5.223 144 Example 4 5.163 143 Example 5 5.364 144 Example 6 5.728 148 Example 7 5.248 146 Example 8 5.295 149 Comparative Example 1 4.167 134 Comparative Example 2 4.124 135 Comparative Example 3 4.277 134 Comparative Example 4 4.251 136 Comparative Example 5 4.769 139 Comparative Example 6 4.617 135 Comparative Example 7 4.316 129

[0202] It can be seen from the above examples and comparative examples that by using the specific process for preparing polyalpha-olefin synthetic oil of the present invention, the conversion of the target product could be improved. In addition, by using the preferred microchannel reactor, the process for synthesizing polyalpha-olefin synthetic oil had a high conversion. This is because the reaction channel 010 and the mixing channel 014 are both tubular structures arranged in the same direction, so that the mixed fluid can form a stable plug flow along the first direction, improving the consistency of the residence time of the mixed fluid, and avoiding or reducing the formation of the undesired products. In addition, the reaction channel 10 is provided with a second mixing member 011, and the mixing channel 014 is provided with a fluid distributor 016 and a first mixing member 015, which can further improve the turbulence degree of the mixed fluid, improve the uniformity of mixing, and further avoid or reduce the production of undesired products, and improve the conversion of the target product.

[0203] Moreover, it can be seen from the above examples and comparative examples that by using the process for preparing polyalpha-olefin synthetic oil of the present invention, polyalpha-olefin synthetic oil with excellent results of both kinematic viscosity and viscosity index could be obtained. The preferred embodiments of the present invention have been described above in detail with reference to the accompanying drawings, however, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including the combinations of various specific technical features in any suitable manner. In order to avoid unnecessary repetition, the various possible combinations will not be described in detail herein. However, these simple modifications and combinations should also be regarded as the disclosed content of the present invention, and all belong to the protection scope of the present invention.