CN103648606B - Droplet separator and reaction system - Google Patents
Droplet separator and reaction system Download PDFInfo
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- CN103648606B CN103648606B CN201280034918.7A CN201280034918A CN103648606B CN 103648606 B CN103648606 B CN 103648606B CN 201280034918 A CN201280034918 A CN 201280034918A CN 103648606 B CN103648606 B CN 103648606B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/30—Accessories for evaporators ; Constructional details thereof
- B01D1/305—Demister (vapour-liquid separation)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D45/00—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces
- B01D45/04—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by utilising inertia
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- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
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Abstract
The present invention relates to a kind of droplet separator, it comprises: Duo Geguan; Hold the shell of described multiple pipe; Inflow part, be arranged at described outer casing inner wall and towards described multiple pipe periphery and flow into unstrpped gas; And outflow portion, be arranged at described outer casing inner wall and the unstrpped gas flowed into from described inflow part is flowed out in the position away from described inflow part on the bearing of trend of described multiple pipe.According to the present invention, can fully catch the droplet contained in boil-off gas.
Description
Technical field
The present invention relates to droplet separator and reaction system.The application advocates that its content is incorporated herein based on the priority of on September 16th, 2011 in No. 2011-203108, the Japanese Patent Application of Japanese publication.
Background technology
Known a kind of reaction system, it has: the vaporising device making raw materials evaporate; To the heater evaporating the raw materials evaporate gas that obtains and heat; With the reaction unit making the boil-off gas after heating that chemical reaction occur in the presence of a catalyst.In this reaction system, when utilizing vaporising device to evaporate raw material, the droplet containing high-boiling-point impurity etc. can be generated.Tar (tar) can be formed when this droplet is heated to more than uniform temperature.Therefore, when the boil-off gas that will vaporising device utilized to generate imports heater, there is the problem that tar makes the tubule, pipe arrangement etc. of heater block.
Such as in patent document 1, between vaporising device and heater, be provided with droplet separator.This droplet separator is hung multiple chain at certain intervals by square from container and formed.By the flow direction of so multiple chain and boil-off gas being configured across, thus the droplet contained in boil-off gas can be captured.
Prior art file
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2007-29785 publication
Summary of the invention
The problem that invention will solve
In the droplet separator of patent document 1, boil-off gas containing droplet know from experience from the gap of multiple chain through.Boil-off gas through the gap of multiple chain is directed in heater with the state containing droplet.
The present invention is the invention completed in view of the foregoing, its object is to provide the droplet separator and reaction system that fully can catch the droplet contained in boil-off gas.
For the means of dealing with problems
In order to achieve the above object, droplet separator of the present invention, it is characterized in that, it comprises: Duo Geguan; Hold the shell of described multiple pipe; Be arranged at described outer casing inner wall and outer peripheral face towards described multiple pipe flows into the inflow part of unstrpped gas.
The invention is characterized in, based on the heating of described heat medium, the mode of the part vaporization of the droplet contained in the described unstrpped gas captured by described outer peripheral face is formed to make heat medium at described multiple Bottomhole pressure and to utilize.
The invention is characterized in, the position away from described inflow part on the bearing of trend of described multiple pipe of the inwall of described shell arranges the outflow portion of the unstrpped gas outflow making to flow into from described inflow part.
The invention is characterized in, be configured in described multiple pipe and be greater than in described multiple pipe apart from the distance between the outer peripheral face of the pipe of described inflow part proximal most position and described inflow part the distance be configured in apart between the outer peripheral face of the pipe of described outflow portion proximal most position and described outflow portion.
The invention is characterized in, the described spaced interval of multiple pipe is also configured abreast.
The invention is characterized in, section shape when plane orthogonal for the bearing of trend of the plurality of pipe of described multiple Guan Yiyu being cut off is circular.
The invention is characterized in, described multiple pipe be bending at least partially.
The invention is characterized in, described multiple pipe can slide along the bearing of trend of the plurality of pipe.
The invention is characterized in, described unstrpped gas contains the boil-off gas of cyclohexanone oxime.
Reaction system of the present invention, is characterized in that, it contains: the vaporising device making raw materials evaporate; The described droplet separator that the droplet that contains in the raw materials evaporate gas obtained is separated is evaporated to utilizing described vaporising device; With the reaction unit making to utilize described droplet separator to be separated chemical reaction occurs the raw materials evaporate gas after droplet in the presence of a catalyst.
That is, the present invention relates to following content.
(1) a droplet separator, it comprises:
Multiple pipe;
Shell, holds described multiple pipe;
Inflow part, is arranged at the inwall of described shell and the outer peripheral face towards described multiple pipe flows into unstrpped gas; With
Outflow portion, is arranged at the inwall of described shell and the unstrpped gas flowed into from described inflow part is flowed out in the position away from described inflow part on the bearing of trend of described multiple pipe.
(2) the droplet separator as described in (1), wherein, described multiple pipe is to enable heat medium flow therein and the mode of a part for the droplet contained in the described unstrpped gas captured by the outer peripheral face of described multiple pipe vaporization can be made to be formed.
(3) the droplet separator as described in (1) or (2), wherein, be configured in the outer peripheral face apart from the pipe of described inflow part proximal most position and described inflow part in described multiple pipe, be greater than in described multiple pipe apart from the distance between the outer peripheral face of the pipe of described inflow part proximal most position and described inflow part the mode be configured in apart from the outer peripheral face of the pipe of described outflow portion proximal most position and the distance of described outflow portion set to make to be configured in described multiple pipe.
(4) the droplet separator according to any one of (1) ~ (3), wherein, the described spaced interval of multiple pipe is also configured abreast.
(5) the droplet separator according to any one of (1) ~ (4), wherein, the section shape of each pipe when plane orthogonal for the bearing of trend of the plurality of pipe of described multiple Guan Yiyu being cut off is circular.
(6) the droplet separator according to any one of (1) ~ (5), wherein, described multiple pipe be bending at least partially.
(7) the droplet separator according to any one of (1) ~ (6), wherein, an end of described multiple pipe is kept by tube sheet.
(8) the droplet separator according to any one of (1) ~ (7), wherein, described multiple pipe can slide along the bearing of trend of the plurality of pipe.
(9) the droplet separator according to any one of (1) ~ (8), wherein, described unstrpped gas contains the boil-off gas of cyclohexanone oxime.
(10) reaction system, it contains:
Vaporising device, makes raw materials evaporate;
(1) the droplet separator according to any one of ~ (9), evaporates to utilizing described vaporising device the droplet contained in the raw materials evaporate gas obtained and is separated;
Heater, is heated to set point of temperature by boil-off gas; With
Reaction unit, makes the raw materials evaporate gas after utilizing described droplet separator to be separated droplet in the presence of a catalyst chemical reaction occur.
(11) manufacture method for epsilon-caprolactams, it comprises:
Evaporization process, makes cyclohexanone oxime evaporate;
Separation circuit, utilizes droplet separator to be separated to the droplet in obtained boil-off gas;
Heating process, is heated to set point of temperature by the boil-off gas of the cyclohexanone oxime after the described droplet of separation;
Obtain the operation of epsilon-caprolactams, make the boil-off gas of the cyclohexanone oxime after described heating in the presence of a catalyst vapor phase beckmann rearrangement reaction occur, obtain epsilon-caprolactams thus,
Wherein, the droplet separator of described droplet separator according to any one of (1) ~ (9).
Invention effect
According to the present invention, the droplet separator and reaction system that fully can catch the droplet contained in boil-off gas can be provided.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the reaction system representing an embodiment of the invention.
Fig. 2 A is the vertical view cutaway drawing of the droplet separator of an embodiment of the invention.
Fig. 2 B is the side view cutaway drawing of the droplet separator of an embodiment of the invention.
Fig. 3 A is the side view cutaway drawing of the droplet capture unit of an embodiment of the invention.
Fig. 3 B is the side view cutaway drawing of the droplet capture unit of an embodiment of the invention.
Fig. 4 A is the key diagram of the flowing of the boil-off gas represented in the droplet separator of an embodiment of the invention.
Fig. 4 B is the key diagram of the flowing of the boil-off gas represented in the droplet separator of an embodiment of the invention.
Fig. 4 C is the key diagram of the flowing of the boil-off gas represented in the droplet separator of an embodiment of the invention.
Fig. 5 A is the key diagram of the flowing of the boil-off gas represented in the droplet separator of an embodiment of the invention.
Fig. 5 B is the key diagram of the flowing of the boil-off gas represented in the droplet separator of an embodiment of the invention.
Fig. 5 C is the key diagram of the flowing of the boil-off gas represented in the droplet separator of an embodiment of the invention.
Fig. 6 is the key diagram of the flowing of the boil-off gas represented in the droplet separator of an embodiment of the invention.
Fig. 7 A is the schematic diagram of the variation representing pipe.
Fig. 7 B is the schematic diagram representing multiple pipe.
Detailed description of the invention
Hereinafter, with reference to the accompanying drawings of embodiments of the present invention, but the present invention is not by the restriction of following embodiment.
It should be noted that, in following whole accompanying drawings, in order to more easily observe accompanying drawing, and suitably changing the size and ratio etc. of each inscape.In addition, in the following description and accompanying drawing, identical symbol is marked to same or equivalent key element, omit the repeat specification to it.
Fig. 1 is the schematic diagram of the reaction system representing an embodiment of the invention.
As shown in Figure 1, reaction system 1 comprises vaporising device 2, pump 3, the 1st droplet separator 4, the 2nd droplet separator 5, heater 6, reaction unit 7 and various pipe arrangement 10,11,12,13,14,15,16,17,18 and forms.
Reaction system 1 is as described below, namely, cyclohexanone oxime as raw material is evaporated in vaporising device 2, the 1st droplet separator 4 is utilized to be separated with the 2nd droplet separator 5 droplet containing impurity in the boil-off gas of gained, after utilizing heater 6 to be heated to set point of temperature to the boil-off gas of the cyclohexanone oxime after removing droplet, the boil-off gas of the cyclohexanone oxime after heating is sent into reaction unit 7, under the existence of solid catalyst, make cyclohexanone oxime generation Beckmann rearrangement, thus generate epsilon-caprolactams.
Vaporising device 2 is connected with the 1st raw material supplying pipe arrangement 10 and the 2nd raw material supplying pipe arrangement 11.
Initiation material when manufacturing epsilon-caprolactams is cyclohexanone oxime.Be used as the mixed liquor of this cyclohexanone oxime of raw material and the solvent of this cyclohexanone oxime of dilution in the present embodiment.This mixed liquor is supplied in vaporising device 2 via the 1st raw material supplying pipe arrangement 10 and these two pipe arrangements of the 2nd raw material supplying pipe arrangement 11.It should be noted that, when above-mentioned mixed liquor being transferred to vaporising device 2 via the 1st raw material supplying pipe arrangement 10 and the 2nd raw material supplying pipe arrangement 11, preferably the lower alcohols such as methyl alcohol being imported together with the inactive gas such as nitrogen.
Pressure when evaporating described mixed liquor is preferably the scope of below 133kPa.In addition, temperature when evaporating described mixed liquor is preferably more than 130 DEG C and the scope of less than 170 DEG C.The boil-off gas obtained by vaporising device 2 is supplied to the 1st droplet separator 4 via boil-off gas supplying tubing 14.
On the other hand, also exist and do not evaporate in vaporising device 2 and remain in the non-evaporated liquor bottom vaporising device 2.This non-evaporated liquor is supplied to pump 3 from vaporising device 2 via discharge pipe arrangement 12.Pump 3 is utilized to make this non-evaporated liquor by circulation pipe 13 and be again supplied in vaporising device 2 via the 1st raw material supplying pipe arrangement 10.
To the boil-off gas being supplied to the 1st droplet separator 4 via boil-off gas supplying tubing 14, the 1st droplet separator 4 is utilized to be separated droplet.The crude separation (pre-separation) of the droplet for catching amount is to a certain degree carried out in the 1st droplet separator 4.
As the 1st droplet separator 4, the droplet separator such as shown in patent document 1 (portion hangs multiple chain and the droplet trapping mesh screen formed at predetermined intervals from container) can be used.
The 2nd droplet separator 5 of the present invention is supplied to via pre-separation gas supplying tubing 15 by the boil-off gas after the 1st droplet separator 4 pre-separation.
To the boil-off gas supplied via pre-separation gas supplying tubing 15, the 2nd droplet separator 5 is utilized to be separated droplet.2nd droplet separator 5 is for catching the remaining droplet contained in the boil-off gas catch the droplet of amount to a certain degree in the 1st droplet separator 4 after.The degree carrying out blocking so that droplet can not be made in heater 6 to form tar tubule, pipe arrangement etc. in the 2nd droplet separator 5 fully catches the separation (main separation) of droplet.
Fig. 2 A and Fig. 2 B is the schematic diagram representing the 2nd droplet separator 5.Fig. 2 A is the vertical view cutaway drawing of the 2nd droplet separator 5, and Fig. 2 B is the side view cutaway drawing of the 2nd droplet separator.
As shown in Figure 2 A, the 2nd droplet separator 5 is formed from the outflow portion 52 of the boil-off gas of inflow part 51 inflow containing droplet capture unit 53, the shell 50 holding droplet capture unit 53, the inflow part 51 flowing into boil-off gas towards droplet capture unit 53 and outflow.Inflow part 51 and outflow portion 52 are arranged at the inwall of shell 50 respectively.
It should be noted that, shell 50 can flow into heat medium with barrel forms.
Droplet capture unit 53 has multiple pipe 530 and tube sheet 532.Droplet capture unit 53 is by being bundled into roughly cylindric by multiple pipe 530 and being formed.In the present embodiment, droplet capture unit 53 is so-called tube bank (tubebundle).
As shown in Figure 2 A, multiple pipe 530 is bending with the part of tube sheet 532 opposite side.Multiple pipes 530 in present embodiment are U casts.
Can be flowed heat medium in multiple pipe 530.As heat medium, the medium (such as temperature is higher than the steam of droplet boiling point) that the outer peripheral face temperature of multiple pipe 530 can be made higher than the boiling point of the droplet contained in boil-off gas can be used.By making flowing heat medium in multiple pipe 530, the heating based on this heat medium can be utilized thus and a part for the droplet captured by the outer peripheral face of multiple pipe 530 is vaporized.
Inflow part 51 and outflow portion 52 to be configured on the bearing of trend of multiple pipe 530 position away from each other.Inflow part 51 is configured at the side of tube sheet 532, and outflow portion 52 is configured at the side contrary with tube sheet 532 of multiple pipe 530.It should be noted that, the allocation position of inflow part 51 and outflow portion 52 is not limited thereto.Such as, also can be contrary with above-mentioned allocation position, inflow part 51 is configured at the side contrary with tube sheet 532 of multiple pipe 530, and outflow portion 52 is configured at the side of tube sheet 532.
In Fig. 2 A, symbol L1 is the distance between the outer peripheral face of the pipe 530 being configured in distance inflow part 51 proximal most position in multiple pipe 530 and inflow part 51.Symbol L2 is the distance between the outer peripheral face of the pipe 530 being configured in distance outflow portion 52 proximal most position in multiple pipe 530 and outflow portion 52.As shown in Figure 2 A, in the 2nd droplet separator 5, the distance L1 be configured in multiple pipe 530 between the outer peripheral face of the pipe 530 of distance inflow part 51 proximal most position and inflow part 51 is greater than in multiple pipe 530 the distance L2 between the outer peripheral face of the pipe 530 being configured in distance outflow portion 52 proximal most position and outflow portion 52.
Be configured in outer peripheral face and the inflow part 51 of the pipe 530 of distance inflow part 51 proximal most position in multiple pipe 530, the mode being at least 200mm with the distance L1 guaranteeing between the outer peripheral face of the pipe 530 being configured in distance inflow part 51 proximal most position in multiple pipe 530 and inflow part 51 configures.In addition, the outer peripheral face of pipe 530 and inflow part 51, formed in the mode making the flow velocity of the boil-off gas flowed at the outer peripheral face of pipe 530 and the gap portion of inflow part 51 be less than the flow velocity of the boil-off gas of the internal flow in inflow part 51.
As shown in Figure 2 B, droplet capture unit 53 is more partial to outflow portion 52 in shell 50.In fig. 2b, symbol L3 is the distance between the central shaft of the central shaft of columned droplet capture unit 53 and the shell 50 of cylindrical shape.The eccentricity of droplet capture unit 53 is 10% ~ 30%.
Fig. 3 A and Fig. 3 B is the schematic diagram representing droplet capture unit 53.Fig. 3 A is the sectional view of droplet capture unit 53, and Fig. 3 B is the top view of droplet capture unit 53.
As shown in Figure 3A, droplet capture unit 53 possess multiple pipe 530, the length direction of multiple pipe 530 spaced apart and configuration multiple baffle plates 531 and keep the tube sheet 532 of the end of multiple pipe 530 and form.
Multiple spaced interval of pipe 530 is also configured abreast.Multiple baffle plate 531 is roughly semicircle.Herein, roughly semicircle refers to excision 50%, and this section shape is not limited to semicircle, also comprises half elliptic.In addition, the section shape of baffle plate also can be ring-like (centre is cavity and only periphery has the structure of shape).As shown in Figure 3A, multiple baffle plate 531 is by separating predetermined distance alternately up and down to configure in the mode of the flow velocity not hindering the boil-off gas of flowing in shell 50.
As shown in Figure 3 B, the multiple effective hole 532a that can insert multiple pipe 530 is formed at tube sheet 532.The multiple effective hole 532a that the end of multiple pipe 530 is formed on tube sheet 532 supports.
The interval of multiple effective hole 532a becomes 1.5 times ~ 2.0 times sizes of the diameter of pipe 530.The mode that multiple effective hole 532a is generally 60 ° ~ 120 °, preferably 70 ° ~ 110 °, more preferably 80 ° ~ 100 ° with the effective hole 532a angulation θ of an effective hole 532a and adjacent two in the plurality of effective hole 532a configures.
Section shape when being cut off with the plane orthogonal with the bearing of trend of the plurality of pipe 530 by multiple pipe 530 is for circular.Herein, circular refers to: this section shape is not limited to circle, also comprises ellipse.
Fig. 4 A, Fig. 4 B, Fig. 4 C, Fig. 5 A, Fig. 5 B, Fig. 5 C and Fig. 6 are the key diagrams of the flowing of the boil-off gas represented in the 2nd droplet separator 5.Fig. 4 A, Fig. 4 B and Fig. 4 C are the vertical view cutaway drawings corresponding with Fig. 2 A, and Fig. 5 A, Fig. 5 B and Fig. 5 C are the side view cutaway drawings corresponding with Fig. 2 B, and Fig. 6 is the side view cutaway drawing of the multiple pipes 530 in the 2nd droplet separator 5.
2nd droplet separator 5 of present embodiment collides with the outer peripheral face passing through boil-off gas and the multiple pipe 530 flowed into from inflow part 51 and the droplet contained boil-off gas is formed by the mode that this outer peripheral face catches.
Below, Fig. 4 A, Fig. 4 B, Fig. 4 C, Fig. 5 A, Fig. 5 B, Fig. 5 C and Fig. 6 is used to be illustrated in the state of shell 50 internal flow boil-off gas in the 2nd droplet separator 5.
Utilize the boil-off gas after the 1st droplet separator 4 pre-separation can be supplied to the 2nd droplet separator 5 via pre-separation gas supplying tubing 15 (with reference to Fig. 1).This boil-off gas can import to the inside of shell 50 via inflow part 51.The boil-off gas flowed into from inflow part 51 can flow towards the outer peripheral face of multiple pipe 530 (with reference to Fig. 4 A, Fig. 5 A).
The boil-off gas flowed into from inflow part 51 sets in the mode can collided with the outer peripheral face of multiple pipe 530.Thus, a part for the droplet contained in boil-off gas is caught by the outer peripheral face of multiple pipe 530.In addition, can flow in multiple pipe 530 inside heat medium (high-temperature steam).Therefore, can utilize the heating based on heat medium that a part for the droplet captured by this outer peripheral face is vaporized.
First, from inflow part 51 flow into and and flow the gap of multiple pipes 530 that configures at spaced interval of the outer peripheral face of multiple pipe 530 part of boil-off gas of colliding, and flow to the outer peripheral face (with reference to Fig. 6) of multiple pipe 530.Thus, a part for the droplet contained in boil-off gas is caught by the outer peripheral face of multiple pipe 530.In addition, utilize the heating based on heat medium that a part for the droplet captured by this outer peripheral face is vaporized.
Multiple pipe 530 sets as follows, namely, when there is charing and block the gap of multiple pipe 530 in the droplet captured by the outer peripheral face of multiple pipe 530, flow into from inflow part 51 and can flow along the bearing of trend of multiple pipe 530 with a part for the boil-off gas of the outer peripheral face collision rift of multiple pipe 530, and flowing to the outer peripheral face (with reference to Fig. 4 B) of multiple pipe 530.Thus, a part for the droplet contained in boil-off gas is caught by the outer peripheral face of multiple pipe 530.
In addition, multiple pipe 530 also sets as follows, namely, make flow into from inflow part 51 and flow with the part of the boil-off gas of the outer peripheral face collision rift of multiple pipe 530 circumferencial direction along the droplet capture unit 53 of substantial cylindrical, and flow to the outer peripheral face (with reference to Fig. 5 B) of multiple pipe 530.Thus, a part for the droplet contained in boil-off gas is caught by the outer peripheral face of multiple pipe 530.
In addition, the mode fully being caught the outflow of the boil-off gas after droplet by the outer peripheral face of multiple pipe 530 can also be made to set multiple pipe 530 (with reference to Fig. 4 C, Fig. 5 C) to utilize outflow portion 52.
Get back to Fig. 1, heater 6 can be supplied to via divided gas flow supplying tubing 16 by the boil-off gas after described 2nd droplet separator 5 is fully separated droplet.Heater 6 is the heat exchangers possessing multiple tubule (diameter is about 2 ~ 3cm).Heater 6 sets as follows, that is, in multiple tubule, pass into boil-off gas, carries out heat exchange, and boil-off gas is heated to set point of temperature by the outside of the thermal medium such as steam, hot blast and tubule.This temperature is more than 250 DEG C and temperature in the scope of less than 500 DEG C.In addition, this heater 6 multiple can be arranged.
The boil-off gas utilizing heater 6 to be heated to the cyclohexanone oxime of set point of temperature is supplied to reaction unit 7 by heated air supplying tubing 17.
In reaction unit 7, carry out making rearrangement of cyclohexanone-oxime become the Beckmann rearrangement of epsilon-caprolactams under the coexisting of solid catalyst with lower alcohol.This Beckmann rearrangement is undertaken by the gas phase haptoreaction of such as fluidized bed type.
As solid catalyst, include, for example: boric acid catalyst, silica alumina catalyst, phosphoric acid catalyst, O composite metallic oxide catalyst, zeolite catalyst etc.Wherein, preferred zeolite catalyst, more preferably five silicon ring (pentasil) type zeolites, particularly preferably MFI zeolite.
Zeolite catalyst can be the crystallinity silica that its skeleton is in fact only made up of silicon and oxygen, also can be to comprise the crystallinity metal silicate etc. of other elements as the element of formation skeleton further.When zeolite catalyst is crystallinity metal silicate, as the element that can exist beyond silica removal and oxygen, include, for example Be, B, Al, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Sb, La, Hf, Bi etc., also can two or more containing in these elements.Silicon is generally more than 5 relative to the atomic ratio of these elements, and preferably more than 50, more preferably more than 500.In addition, this atomic ratio can utilize atom light absorption method, fluorescent X-ray method etc. to measure.
Zeolite catalyst can preferably be prepared for example, in the following way, namely, using silicon compound, quaternary ammonium compound, water and metallic compound as required etc. as raw material for Hydrothermal Synthesis, to obtained crystallizing and drying, burn till after, contact pairs is carried out with ammoniacal liquor, ammonium salt, next, carry out drying, prepare this zeolite catalyst thus.
The particle diameter preferably 0.001 ~ 5mm of solid catalyst, more preferably 0.01 ~ 3mm.In addition, solid catalyst can be the formed body be such as in fact only made up of catalyst component, also can be the material supported by catalyst component in carrier.
Use the Beckmann rearrangement of the cyclohexanone oxime of solid catalyst can carry out under gas phase condition.Reaction temperature is generally 250 ~ 500 DEG C, preferably 300 ~ 450 DEG C.Reaction pressure is generally 0.005 ~ 0.5MPa, preferably 0.005 ~ 0.2MPa.In addition, feed speed (kg/h), i.e. the space velocity WHSV (h of the raw material cyclohexanone oxime of every 1kg catalyst
-1) be generally 0.1 ~ 20h
-1, preferred 0.2 ~ 10h
-1.
It is also favourable that cyclohexanone oxime is coexisted with water simultaneously, and the amount of water is preferably the amount of less than 2.5 moles times of cyclohexanone oxime.
As under the coexisting of solid catalyst and lower alcohol, under gas phase condition, make cyclohexanone oxime generation Beckmann rearrangement and generate epsilon-caprolactams time the lower alcohol that uses, the lower alcohol of preferred carbon number less than 6.Such as can use in methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, sec-butyl alcohol, isobutanol, n-amyl alcohol, n-hexyl alcohol, 2,2,2-trifluoroethanols etc. one or more.Especially, when using methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, one or more in n-butanol, remarkable result is had for the selection rate of improvement epsilon-caprolactams and catalyst life, therefore more preferred.Wherein, when using methyl alcohol or ethanol, show remarkable result, the most preferred from the viewpoint of industry.
In addition, the amount of lower alcohol is usually to use relative to the amount that cyclohexanone oxime is 0.1 ~ 20 times according to mass ratio range.The amount of lower alcohol is preferably less than 10 times according to mass ratio range relative to cyclohexanone oxime, more preferably 0.3 ~ 8 times.
Thus, generating with gaseous state in reaction unit 7 take epsilon-caprolactams as the reaction product of principal component.This generation gas is discharged pipe arrangement 18 via generation gas and is discharged outside system.
2nd droplet separator 5 of present embodiment sets towards the mode of the outer peripheral face inflow unstrpped gas of multiple pipe to utilize inflow part.Therefore, the unstrpped gas flowed into from inflow part and outer peripheral face collide, thus the droplet contained in unstrpped gas is caught by outer peripheral face.
As Patent Document 1, when portion hangs the formation of multiple chain at predetermined intervals from container, from the gap of multiple chain through the boil-off gas containing droplet.
On the other hand, adopt the formation that unstrpped gas is collided towards outer peripheral face and multiple pipe of multiple pipe in the present embodiment, therefore boil-off gas can not through this outer peripheral face.Thus, the droplet contained in unstrpped gas is attached on this outer peripheral face.Therefore, the droplet contained in boil-off gas can fully be caught.
In addition, can flow heat medium in multiple pipe, by multiple Bottomhole pressure heat medium, thus utilizes the heating based on heat medium that a part for the droplet contained in the unstrpped gas captured by outer peripheral face is vaporized.In addition, the droplet do not captured by outer peripheral face also can be vaporized by heating because of unstrpped gas and disappear.Therefore, it is possible to the droplet contained in minimizing boil-off gas.
In addition, outflow portion is configured at the position away from inflow part on the bearing of trend of multiple pipe.Therefore, to make the unstrpped gas that flows into from inflow part flow and the mode flowing to outer peripheral face sets outflow portion along the bearing of trend of multiple pipe.Thus, the droplet contained in unstrpped gas is caught by outer peripheral face.
In addition, be configured at outer peripheral face and the inflow part 51 of the pipe 530 of distance inflow part 51 proximal most position in multiple pipe 530, set in the mode of the outer peripheral face of pipe 530 and the distance L2 of outflow portion 52 that make the distance L1 between the outer peripheral face of the pipe 530 being configured at distance inflow part 51 proximal most position in multiple pipe 530 and inflow part 51 be greater than to be configured at distance outflow portion 52 proximal most position.Therefore, the outer peripheral face that can be configured at the pipe 530 of the nearest position of distance inflow part 51 in multiple pipe 530 captures the droplet of q.s.In addition, even if when the outer peripheral face of the pipe 530 being configured at distance inflow part 51 proximal most position exists a large amount of droplet, this droplet is also difficult to block gap portion.
In addition, multiple pipe 530 sets as follows, that is, make and the part of boil-off gas that the outer peripheral face of multiple pipe 530 collides to be flowed by the gap of multiple pipes 530 that configures abreast at spaced interval, and flow to the outer peripheral face of multiple pipe 530.Therefore, a part for the droplet contained in boil-off gas is caught by the outer peripheral face of multiple pipe 530.
In addition, the side elevational cross-section shape of each pipe of multiple pipe 530 is circular.Therefore, the circumferencial direction along droplet capture unit 53 flows, and flow to the outer peripheral face of multiple pipe 530.Thus, a part for the droplet contained in boil-off gas is caught by the outer peripheral face of multiple pipe 530.
In addition, multiple pipe 530 is U cast.Therefore, an end of multiple pipe 530 is kept by tube sheet 532.Therefore, it is possible to realize the simple droplet separator 5 formed.
Reaction system 1 according to the present embodiment, owing to possessing described droplet separator 5, the droplet therefore contained in boil-off gas can fully be caught, and can not block tubule, pipe arrangement etc. in heater 6 because described droplet forms tar.Therefore, reaction system can be made to operate continuously for a long time.
In addition, in the reaction unit of present embodiment, cyclohexanone oxime can be used as raw material, but be not limited thereto.In addition, the various raw materials that can generate the droplet containing high-boiling-point impurity etc. when it evaporates can also be used in.
In addition, in the reaction unit of present embodiment, as droplet separator, there is the 1st droplet separator 4 and the 2nd droplet separator 5 and form, but being not limited to this.Such as, as droplet separator, also only can have the 2nd droplet separator 5 and form.
In addition, in the reaction unit of present embodiment, under the coexisting of solid catalyst and lower alcohol, make cyclohexanone oxime generation Beckmann rearrangement and generate epsilon-caprolactams, but being not limited to this.Such as also can generate epsilon-caprolactams under not containing the environment of lower alcohol.That is, as long as generate epsilon-caprolactams under the existence of at least solid catalyst.
In addition, in the droplet separator of present embodiment, be illustrated for the situation that multiple pipe is U-tube, but be not limited to this.For multiple Guan Eryan, being not limited only to its part is bending (U-tube), and its many places also can be made to bend.
As shown in Figure 7 A, such as, as multiple pipe 530A, the so-called 3 stream forms that 2 places are bending can be adopted.That is, as long as make the bending at least partially of multiple pipe.
In addition, as shown in Figure 7 B, such as, as multiple pipe 530B, 1 stream form can be adopted.
In addition, in the droplet separator of present embodiment, tube sheet 532 is fixed in shell 50, but is not limited only to this.The what is called that tube sheet 532 such as also can be adopted can to slide along the bearing of trend of cylindrical housing 50 is moved about plate-tube type.That is, multiple pipe also can be enable to slide along the bearing of trend of the plurality of pipe.Thus, easily make the thermal stress that produces at multiple pipe discrete.
Above, illustrate with reference to accompanying drawing and the preferred embodiment of the present invention example is described, certain the present invention is not limited to above-mentioned example.All Multiple Shapes of each member of formation shown in above-mentioned example and combination etc. are only an example, can carry out various change without departing from the scope of the subject in the invention based on designing requirement etc.
Utilizability in industry
Because droplet separator of the present invention can fully catch the droplet contained in boil-off gas, therefore can be suitable in manufacture of the epsilon-caprolactams such as using cyclohexanone oxime to carry out as raw material etc.
Symbol description
1... reaction system, 2... vaporising device, 5... the 2nd droplet separator (droplet separator), 7... reaction unit, 50... shell, 51... inflow part, 52... outflow portion, 530... pipe, be configured in distance apart from being configured in the distance between the outer peripheral face of the pipe of described inflow part proximal most position and inflow part, L2... many pipes between the outer peripheral face of the pipe of distance outflow portion proximal most position and outflow portion in L1... many pipes.
Claims (19)
1. a droplet separator, it comprises:
Droplet capture unit, possesses the tube sheet of the end being bundled into roughly columned multiple pipe and keeping described multiple pipe;
Shell, holds described multiple pipe;
Inflow part, be arranged at the inwall of described shell, the described tube sheet side of described droplet capture unit and outer peripheral face towards described multiple pipe flows into unstrpped gas; With
Outflow portion, be arranged at the inwall of described shell, the position away from described inflow part with tube sheet opposite side and on the bearing of trend of described multiple pipe of described droplet capture unit flows out the unstrpped gas flowed into from described inflow part,
Be configured in the outer peripheral face apart from the pipe of described inflow part proximal most position and described inflow part in described multiple pipe, be greater than in described multiple pipe apart from the distance between the outer peripheral face of the pipe of described inflow part proximal most position and described inflow part the mode be configured in apart from the outer peripheral face of the pipe of described outflow portion proximal most position and the distance of described outflow portion set to make to be configured in described multiple pipe.
2. droplet separator as claimed in claim 1, wherein, described multiple pipe is to enable heat medium flow therein and the mode of a part for the droplet contained in the described unstrpped gas captured by the outer peripheral face of described multiple pipe vaporization can be made to be formed.
3. droplet separator as claimed in claim 1 or 2, wherein, the described spaced interval of multiple pipe is also configured abreast.
4. droplet separator as claimed in claim 1 or 2, wherein, the section shape of each pipe when plane orthogonal for the bearing of trend of the plurality of pipe of described multiple Guan Yiyu being cut off is circular.
5. droplet separator as claimed in claim 3, wherein, the section shape of each pipe when plane orthogonal for the bearing of trend of the plurality of pipe of described multiple Guan Yiyu being cut off is circular.
6. droplet separator as claimed in claim 1 or 2, wherein, described multiple pipe be bending at least partially.
7. droplet separator as claimed in claim 3, wherein, described multiple pipe be bending at least partially.
8. droplet separator as claimed in claim 4, wherein, described multiple pipe be bending at least partially.
9. droplet separator as claimed in claim 1 or 2, wherein, described multiple pipe can slide along the bearing of trend of the plurality of pipe.
10. droplet separator as claimed in claim 3, wherein, described multiple pipe can slide along the bearing of trend of the plurality of pipe.
11. droplet separators as claimed in claim 4, wherein, described multiple pipe can slide along the bearing of trend of the plurality of pipe.
12. droplet separators as claimed in claim 5, wherein, described multiple pipe can slide along the bearing of trend of the plurality of pipe.
13. droplet separators as claimed in claim 1 or 2, wherein, described unstrpped gas is the boil-off gas containing cyclohexanone oxime.
14. droplet separators as claimed in claim 3, wherein, described unstrpped gas is the boil-off gas containing cyclohexanone oxime.
15. droplet separators as claimed in claim 4, wherein, described unstrpped gas is the boil-off gas containing cyclohexanone oxime.
16. droplet separators as claimed in claim 5, wherein, described unstrpped gas is the boil-off gas containing cyclohexanone oxime.
17. droplet separators as claimed in claim 6, wherein, described unstrpped gas is the boil-off gas containing cyclohexanone oxime.
18. 1 kinds of reaction systems, it contains:
Vaporising device, makes raw materials evaporate;
Droplet separator according to any one of claim 1 ~ 17, evaporates to utilizing described vaporising device the droplet contained in the raw materials evaporate gas obtained and is separated;
Heater, is heated to set point of temperature by boil-off gas; With
Reaction unit, makes the raw materials evaporate gas after utilizing described droplet separator to be separated droplet in the presence of a catalyst chemical reaction occur.
The manufacture method of 19. 1 kinds of epsilon-caprolactams, it comprises:
Evaporization process, makes cyclohexanone oxime evaporate;
Separation circuit, utilizes droplet separator to be separated to the droplet in obtained boil-off gas;
Heating process, is heated to set point of temperature by the boil-off gas of the cyclohexanone oxime after the described droplet of separation;
Obtain the operation of epsilon-caprolactams, make the boil-off gas of the cyclohexanone oxime after described heating in the presence of a catalyst vapor phase beckmann rearrangement reaction occur, obtain epsilon-caprolactams thus,
Wherein, the droplet separator of described droplet separator according to any one of claim 1 ~ 17.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-203108 | 2011-09-16 | ||
| JP2011203108 | 2011-09-16 | ||
| PCT/JP2012/070737 WO2013038864A1 (en) | 2011-09-16 | 2012-08-15 | Mist separation device and reaction system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103648606A CN103648606A (en) | 2014-03-19 |
| CN103648606B true CN103648606B (en) | 2016-03-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280034918.7A Active CN103648606B (en) | 2011-09-16 | 2012-08-15 | Droplet separator and reaction system |
Country Status (3)
| Country | Link |
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| JP (1) | JP2013075290A (en) |
| CN (1) | CN103648606B (en) |
| WO (1) | WO2013038864A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105188879A (en) * | 2013-03-15 | 2015-12-23 | 住友化学株式会社 | Mist separation apparatus, reactive system, epsilon-caprolactam production method, and use in production of epsilon-caprolactam |
| CN104557607A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method and device for preparing cyclohexanone oxime gas |
| CN104557608A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method and device for preparing cyclohexanone oxime gas |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1269360A (en) * | 1999-02-09 | 2000-10-11 | 住友化学工业株式会社 | Process for producing epsilon-hexanolactam |
| JP2007029785A (en) * | 2005-07-22 | 2007-02-08 | Sumitomo Chemical Co Ltd | MIST SEPARATION APPARATUS AND PRODUCTION METHOD FOR epsi-CAPROLACTAM USING THE SAME |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2529185Y (en) * | 2002-02-27 | 2003-01-01 | 傅光胜 | Heat exchanger having glass-lined U-bend tube |
| JP5198230B2 (en) * | 2008-11-21 | 2013-05-15 | 株式会社東芝 | Moisture separator heater |
| JP5248357B2 (en) * | 2009-02-03 | 2013-07-31 | 株式会社東芝 | Moisture separator heater |
-
2012
- 2012-08-15 CN CN201280034918.7A patent/CN103648606B/en active Active
- 2012-08-15 WO PCT/JP2012/070737 patent/WO2013038864A1/en active Application Filing
- 2012-08-27 JP JP2012186646A patent/JP2013075290A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1269360A (en) * | 1999-02-09 | 2000-10-11 | 住友化学工业株式会社 | Process for producing epsilon-hexanolactam |
| JP2007029785A (en) * | 2005-07-22 | 2007-02-08 | Sumitomo Chemical Co Ltd | MIST SEPARATION APPARATUS AND PRODUCTION METHOD FOR epsi-CAPROLACTAM USING THE SAME |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013075290A (en) | 2013-04-25 |
| CN103648606A (en) | 2014-03-19 |
| WO2013038864A1 (en) | 2013-03-21 |
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