CN103946212B - The removing method of impurity - Google Patents
The removing method of impurity Download PDFInfo
- Publication number
- CN103946212B CN103946212B CN201280057251.2A CN201280057251A CN103946212B CN 103946212 B CN103946212 B CN 103946212B CN 201280057251 A CN201280057251 A CN 201280057251A CN 103946212 B CN103946212 B CN 103946212B
- Authority
- CN
- China
- Prior art keywords
- distillation column
- packed layer
- impurity
- mentioned
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/16—Fractionating columns in which vapour bubbles through liquid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/02—Preparation of lactams
- C07D201/04—Preparation of lactams from or via oximes by Beckmann rearrangement
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/16—Separation or purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D223/08—Oxygen atoms
- C07D223/10—Oxygen atoms attached in position 2
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Other In-Based Heterocyclic Compounds (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of method removing impurity, including: there is the first packed layer with packing material filling and the second packed layer, supply from the gas supply part at the position of the lower section being positioned at the first packed layer and maybe can pass through the composition the being polymerized formation solid constituent mixing gas as impurity containing solid constituent；Above-mentioned distillation column distills, goes out, from first row, the gas that line drawing contains goal object；From second row outlet by the outside to above-mentioned distillation column of the liquid extraction containing above-mentioned impurity；At least some of using the liquid of said extracted is supplied from above the first packed layer as circulation fluid；Utilize above-mentioned circulation fluid and the backflow from the top of above-mentioned distillation column to rinse the impurity caught by the first packed layer, obtain the liquid containing impurity；Go out line drawing from first row and contain the liquid of above-mentioned impurity.Maybe can pass through solid constituent when separating goal object by the distillation in distillation column to be polymerized the method removing impurity that the composition forming solid constituent removes from the inside of distillation column as impurity in accordance with the invention it is possible to provide.
Description
Technical field
The present invention relates to the removing method by distilling impurity when separating goal object.
The application is based on the November 25th, 2011 of the Japanese Patent Application 2011-257557 CLAIM OF PRIORITY in Japanese publication, and its content is incorporated herein.
Background technology
When carrying out gas-phase reaction etc., when separating goal object in the mixing gas discharged from reactor, use the distillation column that mixing gas is supplied to distilling apparatus trip temperature of going forward side by side to regulate, utilize the method that the difference of boiling point is easily separated.Such as, the composition that boiling point is higher than goal object makes it condense by utilizing to cool down and extracts from the bottom of distillation column in fluid form and be removed, according to circumstances, sometimes also make the liquid of extraction return in distillation column and contact with mixing gas, be reused in the promotion of condensation.
On the other hand, such as, when using the reactor of fluid bed form, if containing the catalyst of middle use that responds, byproduct of reaction, the solid constituent such as composition from byproduct of reaction from the mixing gas that reactor is discharged, then this solid constituent cannot pass through to condense to remove sometimes, the inside of the distilling apparatus such as each several part in distillation column or the inside of pipe arrangement that is connected with distillation column is adhered to and piles up, and makes distilling apparatus block.Therefore, have studied the method suppressing solid constituent to be mixed in distillation column.Such as, have studied the reaction condition of pair reaction of formation by-product during for suppressing to react.
But, it is impossible to suppress solid constituent to being mixed in distillation column completely.Additionally, the composition that Tong Guo polymerization in the high boiling point composition that particularly boiling point is high forms solid constituent is (following, it is sometimes referred to as " polymerizable component ") even if being gaseous state just importing after in distillation column, also can generate polymer in the attachment of the inside of distilling apparatus, solidifying.Therefore, sometimes the same with above-mentioned solid constituent, distilling apparatus can be made to block.As above-mentioned byproduct of reaction, there is the byproduct of reaction generating such polymerizable component.
As it has been described above, solid constituent and polymerizable component in mixing gas can block distilling apparatus, hinder stable the continuously running of distilling apparatus.Therefore, have studied the solid constituent being mixed in distillation column and polymerizable component from the method removed in distillation column.
For example, Patent Document 1 discloses when utilizing the ammoxidation reaction of organic compound to manufacture unsaturated nitrile, make the mixing gas obtained in reaction contact with the circulation fluid containing product, the seizure of the impurity circulation fluid such as polymer and catalyst removed.
Prior art literature
Patent documentation
Patent documentation 1: No. 3270479 publication of Japanese Patent
Summary of the invention
But, unexposed in order to remove composition concrete necessary to impurity with circulation fluid in patent documentation 1, the effective method removing the impurity such as polymer and catalyst from the inside of distillation column is not substantially disclosed.
The present invention completes in view of the foregoing, problem is in that to provide a kind of removing method of impurity, described method when separating goal object by the distillation in distillation column from the mixing gas of the composition that maybe can pass through polymerization formation solid constituent containing solid constituent, it is possible to the composition that solid constituent maybe can pass through to be polymerized formation solid constituent removes as impurity from the inside of distillation column.
In order to solve above-mentioned problem,
The present invention provides a kind of removing method of impurity, it is characterized in that, be pass through distill from containing solid constituent maybe can pass through be polymerized formed solid constituent composition as the mixing gas of impurity separate goal object time, from the method that the inside of distillation column carrying out distilling removes above-mentioned impurity, in described method: in the inside of above-mentioned distillation column, the short transverse of above-mentioned distillation column arranges the packed layer filled with packing material of more than a layer, by the above-mentioned mixing gas position from the lower section of the above-mentioned packed layer being externally supplied foot of above-mentioned distillation column, distill, from above-mentioned distillation column, the gas containing goal object is extracted in the top of the above-mentioned packed layer of topmost, and at least some of above-mentioned packed layer being supplied from above foot as circulation fluid of the liquid that the extract part of the lower section of the supply unit from above-mentioned mixing gas is extracted, backflow with above-mentioned circulation fluid with from the top of above-mentioned distillation column rinses the above-mentioned impurity caught by the above-mentioned packed layer of foot, the liquid containing above-mentioned impurity is extracted from the extract part of above-mentioned lower section.
In the removing method of the impurity of the present invention, it is preferable that the specific surface area of the packing material in the above-mentioned packed layer of foot is 70～300m2/m3。
In the removing method of the impurity of the present invention, it is preferable that the above-mentioned circulation fluid in face that the short transverse with above-mentioned distillation column of the above-mentioned packed layer of foot is vertical is 1.5 × 10 with the total flow of backflow4～1.2 × 105kg/m2/h。
In the removing method of the impurity of the present invention, it is preferable that be supplied to the above-mentioned packed layer of foot after above-mentioned circulation fluid and backflow being filtered device and filters and removing solid constituent.
In the removing method of the impurity of the present invention, it is preferable that above-mentioned mixing gas is under the coexisting of lower alcohol, use solid acid catalyst, cyclohexanone-oxime generate the gas after the gas-phase reaction of epsilon-caprolactams.
That is, the present invention relates to herein below.
(1) a kind of method removing impurity, be pass through distill from containing solid constituent maybe can pass through be polymerized formed solid constituent composition as the mixing gas of impurity separate goal object time, the method removed from the inside of distillation column carrying out distilling by above-mentioned impurity, above-mentioned distillation column has: the packed layer that the least one layer of packing material arranged in the short transverse of above-mentioned distillation column is filled；It is arranged at the gas supply part at the position of the lower section of the above-mentioned packed layer of foot；It is arranged at the first extract part of the top of the above-mentioned packed layer of topmost；With the second extract part of the lower section being arranged at above-mentioned gas supply unit, the method for above-mentioned removing impurity includes: at the position of lower section of the above-mentioned packed layer of foot, and from above-mentioned distillation column, above-mentioned mixing gas is externally supplied to inside；Above-mentioned distillation column distills, the gas containing goal object is extracted from above-mentioned first extract part of the top of the above-mentioned packed layer being arranged at topmost the outside of above-mentioned distillation column；Liquid containing above-mentioned impurity is extracted from the second extract part of the lower section being arranged at above-mentioned gas supply unit the outside of above-mentioned distillation column；Using at least some of packed layer being supplied from above above-mentioned foot as circulation fluid of the liquid of said extracted；Utilize above-mentioned circulation fluid and the backflow from the top of above-mentioned distillation column to rinse the above-mentioned impurity caught by the packed layer of above-mentioned foot, obtain the liquid containing above-mentioned impurity；Liquid containing above-mentioned impurity is extracted from above-mentioned second extract part the outside of above-mentioned distillation column,
(2) method removing impurity according to (1), wherein, the specific surface area of the packing material in the packed layer of above-mentioned foot is 70～300m2/m3,
(3) method removing impurity according to (1) or (2), wherein, it is 1.5 × 10 at the vertical above-mentioned circulation fluid in arbitrary face of the short transverse with above-mentioned distillation column of the packed layer of above-mentioned foot with the total flow of above-mentioned backflow4～1.2 × 105kg/m2/ h,
(4) method removing impurity according to any one of (1)～(3), farther include the part cooling of the gas containing goal object extracted from above-mentioned first extract part, it is made to be condensed into liquid, and make aforesaid liquid from the upper return of above-mentioned distillation column
(5) method removing impurity recorded any one of (1)～(4), further include at the top from above-mentioned distillation column make aforesaid liquid backflow before, the liquid of above-mentioned condensation is filtered device filtration and removes solid constituent
(6) method removing impurity recorded any one of (1)～(5), further include at before at least some of packed layer being supplied from above above-mentioned foot as circulation fluid of the liquid extracted from above-mentioned second extract part, the liquid extracted from above-mentioned second extract part is filtered device filter and remove solid constituent, and
(7) method removing impurity according to any one of (1)～(6), wherein, above-mentioned mixing gas is under the coexisting of lower alcohol, uses solid acid catalyst, cyclohexanone-oxime generate the gas obtained in the gas-phase reaction of epsilon-caprolactams.
In accordance with the invention it is possible to provide when separating goal object by the distillation in distillation column, solid constituent maybe can pass through to be polymerized the removing method of the impurity that the composition forming solid constituent removes as impurity from the inside of distillation column.
Accompanying drawing explanation
Fig. 1 is an illustration for the schematic diagram of the removing method of the impurity that first embodiment of the present invention relates to.
Fig. 2 is an illustration for the schematic diagram of the removing method of the impurity that second embodiment of the present invention relates to.
Fig. 3 is an illustration for the schematic diagram of the removing method of existing impurity.
Fig. 4 is an illustration for the schematic diagram of the removing method of other impurity existing.
Fig. 5 indicates that the figure of the data of the valve opening of the LCV in embodiment 2～4.
Detailed description of the invention
The removing method of the impurity that the present invention relates to be pass through distill from containing solid constituent maybe can pass through be polymerized formed solid constituent composition (polymerizable component) as the mixing gas of impurity separate goal object time, from the method that the inside of distillation column carrying out distilling removes above-mentioned impurity, above-mentioned distillation column has: the packed layer that the least one layer of packing material arranged in the short transverse of above-mentioned distillation column is filled, it is arranged at the gas supply part of the lower portion of the above-mentioned packed layer of foot, it is arranged at the first extract part of the top of the above-mentioned packed layer of topmost, the second extract part with the lower section being arranged at above-mentioned gas supply unit, above-mentioned impurity removes method and includes: in the lower portion of the above-mentioned packed layer of foot, above-mentioned mixing gas is externally supplied to inside from above-mentioned distillation column, above-mentioned distillation column distills, gas containing goal object is extracted from above-mentioned first extract part of the top of the above-mentioned packed layer being arranged at topmost the outside of above-mentioned distillation column；Liquid containing above-mentioned impurity is extracted from the extract part (above-mentioned second extract part) of the lower section of above-mentioned gas supply unit the outside of above-mentioned distillation column；Using at least some of packed layer being supplied from above above-mentioned foot as circulation fluid of the liquid of said extracted；Utilize above-mentioned circulation fluid and the backflow from the top of above-mentioned distillation column to rinse the above-mentioned impurity caught by the packed layer of above-mentioned foot, obtain the liquid containing above-mentioned impurity；Liquid containing above-mentioned impurity is extracted from the extract part (above-mentioned second extract part) of above-mentioned lower section the outside of above-mentioned distillation column.
Hereinafter, with reference to accompanying drawing, the present invention is described in detail.
Fig. 1 is an illustration for the schematic diagram of the removing method of the impurity that first embodiment of the present invention relates to.
Distilling apparatus 1 shown here possesses the first packed layer 12 and the second packed layer 13 filled with packing material in the inside of distillation column 11 carrying out distilling.First packed layer 12 and the second packed layer 13 play separate configuration successively from below in the short transverse of distillation column 11.
First packed layer 12 contributes to goal object separation from the mixing gas of distillation object, and catches the solid constituent in above-mentioned mixing gas or polymerizable component.It addition, the second packed layer 13 mainly promotes goal object separation from above-mentioned mixing gas, but can be constituted in the way of catching solid constituent or polymerizable component in the same manner as the first packed layer 12.
In this manual, " be filled material fill " refers to and is paved with packing material the direction vertical with the short transverse of distillation column (direction of the arrow Z in Fig. 1) (such as, distillation column for time cylindric for it radially).
In the bottom of distillation column 11, the packed layer as orlop (foot) the first packed layer 12 be connected with for by gas from distillation column 11 be externally supplied inside gas supply part 111.So, in the inside of distillation column 11, it is not provided with other packed layer filled with packing material in the lower section (tower bottom side) of gas supply part 111.That is, above-mentioned packed layer 12 is arranged at the top of gas supply part 111.
Top of tower at distillation column 11 is connected to first row outlet 14, and it is the first extract part of the gas for extracting the goal object containing separate object, is connected to second row outlet 15 at tower bottom, and it is the second extract part for extracting liq.
For first row outlet 14, it is provided with cooler 140 in midway, the return wire 141 different from above-mentioned first row outlet is branched out, being connected above of the second packed layer 13 of the packed layer as the superiors' (topmost) in one end not being connected of above-mentioned return wire 141 and distillation column 11 with above-mentioned cooler 140 from cooler 140.As cooler 140, the known coolers such as exchange type cooler can be illustrated.
Circular route 151 is gone out, the top of the first packed layer 12 in one end not being connected of above-mentioned circular route 151 and distillation column 11 and being connected below of the second packed layer 13 with above-mentioned second row outlet 15 from the element branches of the midway of second row outlet 15.That is, the first packed layer 12 within distillation column 11 and the space between the second packed layer 13 are connected by circular route 151 with second row outlet 15.
The specific surface area of the packing material in the first packed layer 12 is preferably 70～300m2/m3, more preferably 70～260m2/m3, more preferably 70～160m2/m3.By being set to more than above-mentioned lower limit, thus the separating effect that goal object is from mixing gas improves further, by being set to below above-mentioned higher limit, thus the developing result of the solid constituent caught or polymerizable component improves further.
The specific surface area of the packing material in the second packed layer 13 suitably regulates according to purpose, it is preferred to 70～270m2/m3, more preferably 90～260m2/m3.By being set to more than above-mentioned lower limit, thus the separating effect that goal object is from mixing gas improves further, by being set to below above-mentioned higher limit, even if thus containing solid constituent or polymerizable component in the mixing gas by the first packed layer 12, it is also possible to they are caught and is more effectively carried out rinsing.
The height H of the first packed layer 121Height H preferably with respect to distillation column 110It is 20～30%.By being set to more than above-mentioned lower limit, thus the seizure effect of the solid constituent mixed in gas or polymerizable component improves further, by being set to below above-mentioned higher limit such that it is able to efficiency separates goal object more well from mixing gas.
The height H of the second packed layer 132Height H preferably with respect to distillation column 110It is 20～30%.By being set to more than above-mentioned lower limit, thus the separating effect that goal object is from mixing gas improves further, by being set to below above-mentioned higher limit such that it is able to efficiency separates goal object more well from mixing gas.
In the present invention, use and contain solid constituent or polymerizable component as the mixing gas of impurity, distill in distillation column 11, when separating the goal object in mixing gas, remove above-mentioned impurity from the inside of distillation column 11.Specific as follows.
First, above-mentioned mixing gas is supplied to from gas supply part 111 inside of distillation column 11.
As long as above-mentioned mixing gas is just not particularly limited as impurity containing solid constituent or polymerizable component, as preferably mixing gas, the gas after gas-phase reaction can be illustrated, also can illustrate the mixing gas carried by the reactor of fluid bed form.At this, as solid constituent, catalyst can be illustrated；The byproducts of reaction such as the compound beyond the polymer of polymerizable component or above-mentioned polymer；Or the composition from above-mentioned byproduct of reaction.As above-mentioned polymerizable component, the byproduct of reaction produced in reaction can be illustrated.
As preferred above-mentioned gas-phase reaction, can be illustrated under the coexisting of lower alcohol use solid acid catalyst and generated by cyclohexanone-oxime the reaction of epsilon-caprolactams, but be not limited to this.At this, as above-mentioned lower alcohol, methanol, ethanol, 1-propanol (normal propyl alcohol), 2-propanol (isopropanol), n-butyl alcohol (n-butyl alcohol), 2-butanol (sec-butyl alcohol), 2-methyl isophthalic acid-propanol (isobutanol), 1-amylalcohol (n-amyl alcohol), 1-hexanol (hexanol) or 2 can be illustrated, the carbon numbers such as 2,2-trifluoroethanols are the alcohol of 1～6.As above-mentioned lower alcohol, it is preferable that methanol, ethanol, 1-propanol, 2-propanol and n-butyl alcohol, more preferably methanol and ethanol.
As above-mentioned solid acid catalyst, pentasil type zeolite catalysts etc. can be enumerated.
Further, by carrying out distilling, the gas containing goal object is extracted from first row outlet 14 outside of distillation column 11.Now, solid constituent or polymerizable component (impurity) in the mixing gas being supplied to are caught by the first packed layer 12, and in the inside of distillation column 11, be mixed into (movement) to the top of the first packed layer 12 is inhibited.
On the other hand, due to the inside at distillation column 11, a part for mixing gas is condensed, so the liquid being condensed extracts the outside of distillation column 11 from second row outlet 15.Then, by least some of inside separated and return to distillation column 11 via circular route 151 of the liquid of extraction, the first packed layer 12 it is supplied from above.Thus, the aforesaid liquid (circulation fluid) passing through the first packed layer 12 from the top to the bottom is utilized to rinse the above-mentioned impurity caught by the first packed layer 12.Now, the cooled device 140 of a part of the gas by extracting from first row outlet 14 cools down, or the inside at distillation column 11, gas is cooled above the first packed layer 12, thus in the inside of distillation column 11, a part of gas becomes liquid in the first packed layer 12 condensing above and flows down.That is, as the another side of the present invention, it is preferable that also include the part cooling of the gas containing goal object extracted from the first extract part (first row outlet 14) so that it is be condensed into liquid, and make aforesaid liquid from the upper return of above-mentioned distillation column.
For the cooling utilizing above-mentioned cooler 140 to carry out, it is preferable that in the way of making the gas condensation from the gas containing goal object that above-mentioned first row outlet 14 is extracted, boiling point is higher than goal object become liquid, design temperature cools down.
The liquid (backflow) supplied from the top of above-mentioned distillation column by this backflow is utilized to rinse the above-mentioned impurity caught by the first packed layer 12.Now, from the mixing gas of gas supply part 111 supply and above-mentioned circulation fluid and backflow generation gas-to-liquid contact.By so rinsing above-mentioned impurity, thus the solid constituent mixed in gas and the solid constituent caught by the first packed layer 12 move to the tower bottom of distillation column 11.Equally, the polymerizable component caught by the first packed layer 12 moves becoming polymer forward direction tower bottom.Therefore, not only impurity moves to tower bottom, and polymerizable component polymerization is also inhibited, therefore, it is possible to significantly reduce the total amount of solid constituent within distillation column 11.
The liquid containing above-mentioned impurity rinsed is extracted from second row outlet 15 outside of distillation column 11.The flushing of the above-mentioned impurity caught by the first packed layer 12 it is used to equally after a part for the liquid being extracted.By process above, above-mentioned impurity is extracted to the outside of distillation column 11 from second row outlet 15, except a part, does not all return to the inside of distillation column 11, is therefore removed by the inside from distillation column 11.
By removing above-mentioned impurity, thus the attachment in each portion that solid constituent is in distillation column 11, first row outlet 14 and second row outlet 15 for primary distilling apparatus 1 and accumulation are inhibited, therefore the blocking of the inside of distilling apparatus 1 is suppressed.
In the present invention, it is preferred to make the flow of liquid by the first packed layer 12, namely above-mentioned circulation fluid is 1.5 × 10 with the flow that adds up to of backflow in the face vertical with the short transverse Z of distillation column 114～1.2 × 105kg/m2/ h.By being set to more than above-mentioned lower limit, thus the developing result of the above-mentioned impurity in the first packed layer 12 improves further.It addition, by being set to below above-mentioned higher limit, thus the separation efficiency of goal object improves further, and avoid the excessive pump being arranged to obtain the above-mentioned total flow of regulation.The flow of above-mentioned circulation fluid such as can be adjusted by the amount of the liquid that adjustment is separated to circular route 151 from second row outlet 15.It addition, the flow of above-mentioned backflow such as can be adjusted by the temperature etc. of the temperature of adjustment distillation column 11 or cooler 140.
Above-mentioned total flow measures by utilizing the methods such as the metering of the effusion meter being arranged at the pipe arrangement that each liquid flows through.
As long as the packing material of the distillation column that the present invention relates to can catch impurity and just be not particularly limited, irregular implant as cascade ring or rule implant etc. can be enumerated.Under the coexisting of lower alcohol, solid acid catalyst will be used, the gas after the gas-phase reaction of cyclohexanone-oxime generation epsilon-caprolactams when distilling, as above-mentioned packing material, irregular implant as cascade ring or rule implant etc. can be enumerated.When above-mentioned distillation column possesses the packed layer of more than 2, above-mentioned packing material can be the same or different.
Fig. 2 is an illustration for the schematic diagram of the removing method of the impurity that second embodiment of the present invention relates to.Constitute identical with the composition shown in Fig. 1 in composition shown in Fig. 2 is marked the symbol identical with Fig. 1, omits detail explanation.In this figure thereafter too.
Distilling apparatus 2 shown in Fig. 2 possesses the first filter house 16 in the midway of return wire 141, possesses the second filter house 17 in the midway of second row outlet 15, in addition, identical with the distilling apparatus 1 shown in Fig. 1.
The method removing impurity that second embodiment of the present invention relates to farther includes: make backflow from before the upper return of distillation column 11, the liquid of condensation is filtered device and filters and remove solid constituent.
Namely, first filter house 16 be configured in cooler 140 and return wire 141 and between the connecting portion of distillation column 11, even if solid constituent is mixed in the liquid of cooled device 140 condensation, it is also possible to be filtered off and make not contain the liquid (backflow) of solid constituent and be back to distillation column 11.Like this, by being supplied back to flow liquid at removing the rear of solid constituent to the second packed layer 13 and the first packed layer 12 such that it is able to improve the developing result of the impurity caught by the first packed layer 12 further.
Additionally, the method removing impurity that second embodiment of the present invention relates to farther includes: before at least some of packed layer being supplied from above foot as circulation fluid of the liquid that will extract from the second extract part, the liquid extracted from above-mentioned second extract part is filtered device and filters and remove solid constituent.
Namely, second filter house 17 be configured in second row outlet 15 and distillation column 11 connecting portion and and the branch of circular route 151 between, it is possible to the solid constituent contained in the liquid extracted from distillation column 11 is leached and makes not contain the liquid (circulation fluid) of solid constituent and circulate in distillation column 11.Like this, by supplying circulation fluid at removing the rear of solid constituent to the first packed layer 12 such that it is able to improve the developing result of the impurity caught by the first packed layer 12 further.
As long as the first filter house 16 and the second filter house 17 can filter solid constituent and just be not particularly limited, the known filter defecators such as filter screen can be illustrated.
The filter capacity of the first filter house 16 and the second filter house 17 suitably regulates according to the kind of the mixing gas of each distillation object.First filter house 16 and the second filter house 17 can be the same or different each other.
In fig. 2, illustrate the example that the second filter house 17 is configured between connecting portion and the branch of circular route 151 of distillation column 11 in second row outlet 15, but the distilling apparatus that the present invention relates to is not limited thereto, such as, can also be configured in circular route 151 and distillation column 11 connecting portion and between the branch of second row outlet 15 (omit diagram), now also can obtain effect similar to the above.
In fig 1 and 2, it is shown that possess the first packed layer 12 and second this two-layer of packed layer 13 distilling apparatus as packed layer, but the distilling apparatus used in the present invention is not limited to these, possesses least one layer of packed layer.The number of packed layer is one layer～three layers preferably, more preferably one layer～bis-layers.
During for only possessing the distilling apparatus of one layer of packed layer, for instance preferably make the height height H relative to above-mentioned first packed layer 12 of packed layer1Height H with the second packed layer 132Aggregate value be equal more than.And, as long as the other end of the circular route branched out from second row outlet and the other end of return wire 141 that branches out from cooler 140 are both connected to the top of packed layer.Such distilling apparatus can be used, adopt the method identical with the situation using the distilling apparatus shown in Fig. 1 and 2 to separate impurity.
On the other hand, during for possessing the distilling apparatus of the packed layer of more than three layers, such as, in the distilling apparatus shown in Fig. 1 and 2, above the inside of distillation column 11, the second packed layer 13, with the packed layer that the second packed layer 13 is configured with more than a layer dividually, these packed layers of more than one layer configure separated from each other.These packed layers of the top of the second packed layer 13 are such as identical with the second packed layer 13.Such distilling apparatus can be used, adopt the method identical with the situation using the distilling apparatus shown in Fig. 1 and 2 to separate impurity.
But, if considering the removing effect of the separating effect of goal object, solid constituent and polymerizable component, operability or cost etc., the distilling apparatus that the present invention relates to the particularly preferably distilling apparatus possessing two layers of packed layer as illustrated in fig. 1 and 2.
Additionally, illustrate the example that first row outlet 14 is connected with the top of tower of distillation column 11, second row outlet 15 is connected with the tower bottom of distillation column 11 in fig 1 and 2, but the distilling apparatus that the present invention relates to is not limited thereto, as long as being connected above of first row outlet 14 and the second packed layer 13, second row outlet 15 is connected below with gas supply part 111.That is, in distillation column 11, as long as extracting the gas containing goal object from the first extract part of the top of the packed layer being positioned at topmost, the liquid containing impurity is extracted from the second extract part of the lower section being positioned at gas supply part 111.
According to the present invention, when separating goal object by the distillation in distillation column, even if the mixing gas being fed into the inside of distillation column contains solid constituent or polymerizable component as impurity, it is also possible to effectively remove these impurity from the inside of distillation column.Therefore, the inside of the distilling apparatus such as the inside of the pipe arrangement that each portion in distillation column is connected with distillation column, the attachment of solid constituent and piling up is suppressed, and the blocking of distilling apparatus is suppressed.And, it is possible to make distilling apparatus stably continuously run for a long time.
Embodiment
Hereinafter, by specific embodiment, the present invention is further elaborated.But, the present invention is not by any restriction of embodiment described below.
[embodiment 1]
It is used under the coexisting of lower alcohol use solid acid catalyst and is generated, by cyclohexanone-oxime, the mixing gas obtained in the reaction of epsilon-caprolactams, when using the distilling apparatus shown in Fig. 2 to separate the epsilon-caprolactams as goal object, carry out the removing of impurity.Specific as follows.
The methanol as lower alcohol and the pentasil type zeolite catalysts as solid acid catalyst is used to react respectively.Then, the mixing gas obtained contains the epsilon-caprolactams containing byproduct of reaction containing the noble gas of water, about 34 mass % of the methanol of about 60 mass %, about 6 mass % respectively mean temperature 379 DEG C.
In distilling apparatus 2, using specific surface area respectively is 257m2/m3Packing material (cascade ring 1P) as the packing material of the first packed layer 12 and the second packed layer 13, make the height H of the first packed layer 12 respectively1Height H with the second packed layer 132Height H relative to distillation column 110It is 22%.
Above-mentioned mixing gas is supplied to the inside of the distillation column 11 being set as pressure 97.3kPa (730Torr), temperature 200～220 DEG C, extract the liquid of the amount corresponding approximately to 14 mass % relative to the epsilon-caprolactams containing byproduct of reaction the mixing gas of supply from the second row outlet 15 being connected with tower bottom with Liquid level adjusting valve (hereinafter referred to as LCV), for mixing the remainder of gas, while make the amount in mean temperature 178 DEG C condensation extract from the first row outlet 14 being connected with top of tower on the internal reflux limit of distillation column 11.The circulation fluid of the radial direction of the first packed layer 12 and the total flow of backflow are set to 2.4 × 104kg/m2/ h.As circulation fluid, the liquid extraction obtained solid constituent being filtered device filtration via the filter screen being arranged at second row outlet 15 as the second filter house 17 uses to circular route 151.
Carry out the removing of distillation and impurity by above-mentioned condition after, through about 30 days, stable from the valve opening of the amount of the liquid of second row outlet 15 extraction and LCV, almost no solids observed composition is in the attachment of the inside of distilling apparatus 2, it is possible to confirm to inhibit blocking.In such manner, it is possible to make distilling apparatus 2 stably continuously run.
[comparative example 1]
It is used under the coexisting of lower alcohol use solid acid catalyst and is generated, by cyclohexanone-oxime, the mixing gas obtained in the reaction of epsilon-caprolactams, when using the distilling apparatus shown in Fig. 3 to separate the epsilon-caprolactams as goal object, carry out the removing of impurity by existing method.Specific as follows.
Distilling apparatus 8 shown in Fig. 3 is constituted as follows, namely, in the distilling apparatus 2 shown in Fig. 2, the supply line of the other end of circular route 151 with the mixing gas supply of the upstream side being connected to gas supply part 111 is connected, thus replacing the space between the first packed layer 12 and the second packed layer 13 within distillation column 11.That is, in distilling apparatus 8, circular route 158 is to be supplied to the mixing gas before the inside of distillation column 11 and circulation fluid gas-to-liquid contact, and the cooled mode of mixing gas is connected with supply line 18.In addition, distilling apparatus 8 is identical with the distilling apparatus 2 shown in Fig. 2.
The methanol as lower alcohol and the pentasil type zeolite catalysts as solid acid catalyst is used to react respectively.Then, the mixing gas obtained contains the epsilon-caprolactams containing byproduct of reaction containing the noble gas of water, about 35 mass % of the methanol of about 61 mass %, about 4 mass % respectively mean temperature 390 DEG C.
Above-mentioned mixing gas is supplied to the inside of the distillation column 11 being set as pressure 97.3kPa (730Torr), temperature 200～220 DEG C, extract the liquid of the amount corresponding approximately to 7 mass % relative to the epsilon-caprolactams containing byproduct of reaction the mixing gas of supply from the second row outlet 15 being connected with tower bottom with LCV, for mixing the remainder of gas, while make the amount in mean temperature 184 DEG C condensation extract from the first row outlet 14 being connected with top of tower on the internal reflux limit of distillation column 11.Then, it is 2 × 10 by what be converted into the radial direction of the first packed layer 12 by the flow of liquid4kg/m2The circulation fluid of the flow of/h is supplied to supply line 18.As circulation fluid, the liquid extraction obtained solid constituent being filtered device filtration via the filter screen being arranged at second row outlet 15 as the second filter house 17 uses to circular route 158.
By above-mentioned condition, after the removing carrying out distillation and impurity in about 30 days, blocking as the filter screen of the second filter house 17 setting frequently occurs, all unstable from the valve opening of the amount of the liquid of second row outlet 15 extraction and LCV, it was shown that there occurs attachment and the blocking of solid constituent in the inside of distilling apparatus 8.Speculating this is because the removing as the solid constituent of impurity becomes insufficient, and polymerizable component is not rinsed and is attached to each position, inside of distillation column 11 and is polymerized, the amount of polymer increases, and thus, the total amount of solid constituent dramatically increases.
[comparative example 2]
It is used under the coexisting of lower alcohol use solid acid catalyst and is generated, by cyclohexanone-oxime, the mixing gas obtained in epsilon-caprolactams reaction, when using the distilling apparatus shown in Fig. 4 to separate the epsilon-caprolactams as goal object, carry out the removing of impurity by existing method.Specific as follows.
Distilling apparatus 9 shown in Fig. 4 is following composition, namely, in the distilling apparatus 8 shown in Fig. 3, the midway of supply line 18 arrange the second cooler 150 (after, in order to distinguish with the second cooler 150, the cooler 140 being arranged at first row outlet 14 is called " the first cooler 140 "), the supply line 18 of circular route 158 with distillation column 11 side (downstream) of the second cooler 150 is connected.That is, in distilling apparatus 9, circular route 158 contacts with circulation fluid with the cooled mixing gas before being supplied to the inside of distillation column 11, mixes the mode that gas is further cooled and is connected with supply line 18.It addition, the second cooler 150 and the first cooler 140 are identical.In addition, distilling apparatus 9 is identical with the distilling apparatus 8 shown in Fig. 3.
The methanol as lower alcohol, pentasil type zeolite catalysts as solid acid catalyst is used to react respectively.Then, the mixing gas obtained contains the epsilon-caprolactams containing byproduct of reaction containing the noble gas of water, about 36 mass % of the methanol of about 61 mass %, about 3 mass % respectively mean temperature 387 DEG C.
With the second cooler 150 of the indirect heat exchange formula of the high-temperature gas employing 160 DEG C, above-mentioned mixing gas is cooled to average 320 DEG C, then makes it contact with circulation fluid described later.Then, the mixing gas of cooling is supplied to the inside of the distillation column 11 being set as pressure 97.3kPa (730Torr), temperature 200～220 DEG C, extract the liquid relative to the amount corresponding approximately to 7 mass % containing the epsilon-caprolactams of byproduct of reaction the mixing gas of supply with LCV from the second row outlet 15 being connected with tower bottom, for mixing the remainder of gas, while make the amount in mean temperature 185 DEG C condensation extract from the first row outlet 14 being connected with top of tower on the internal reflux limit of distillation column 11.Then, it is 2 × 10 by what be converted into the radial direction of the first packed layer 12 by the flow of liquid4kg/m2The circulation fluid of the flow of/h is supplied to supply line 18.As circulation fluid, the liquid extraction obtained solid constituent being filtered device filtration via the filter screen being arranged at second row outlet 15 as the second filter house 17 uses to circular route 158, makes this circulation fluid contact with the mixing gas cooled down with cooler 150.
By above-mentioned condition, after the removing carrying out distillation and impurity in about 30 days, blocking as the filter screen of the second filter house 17 setting frequently occurs in the same manner as the situation of comparative example 1, all unstable from the valve opening of the amount of the liquid of second row outlet 15 extraction and LCV, it was shown that there occurs attachment and the blocking of solid constituent in the inside of distilling apparatus 9.
[embodiment 2]
It is used under the coexisting of lower alcohol use solid acid catalyst and is generated, by cyclohexanone-oxime, the mixing gas obtained in the reaction of epsilon-caprolactams, when using the distilling apparatus shown in Fig. 2 to separate the epsilon-caprolactams as goal object, carry out the removing of impurity.Specific as follows.
The methanol as lower alcohol, pentasil type zeolite catalysts as solid acid catalyst is used to react respectively.Then, the mixing gas obtained contains the epsilon-caprolactams containing byproduct of reaction containing the noble gas of water, about 31 mass % of the methanol of about 61 mass %, about 8 mass % respectively mean temperature 376 DEG C.
In distilling apparatus 2, as the packing material of the first packed layer 12, use specific surface area is 90m2/m3Packing material (Sulzer company " Mellagrid90X "), as the packing material of the second packed layer 13, use specific surface area is 125m2/m3Packing material (Sulzer company " Mellapak125X "), make the height H of the first packed layer 121Height H relative to distillation column 110It is 25%, makes the height H of the second packed layer 132Height H relative to distillation column 110It is 20%.
Above-mentioned mixing gas is supplied to the inside of the distillation column 11 being set as pressure 96.1kPa (721Torr), temperature 200～220 DEG C, extract the liquid of the amount corresponding approximately to 8 mass % relative to the epsilon-caprolactams containing byproduct of reaction the mixing gas of supply from the second row outlet 15 being connected with tower bottom with LCV, for mixing the remainder of gas, while make the amount in mean temperature 185 DEG C condensation extract from the first row outlet 14 being connected with top of tower on the internal reflux limit of distillation column 11.Making the circulation fluid of the radial direction of the first packed layer 12 and the total flow of backflow is 2.9 × 104kg/m2/ h.As circulation fluid, the liquid extraction obtained solid constituent being filtered device filtration via the filter screen being arranged at second row outlet 15 as the second filter house 17 uses to circular route 151.
Its result, through more than 120 days, the amount of liquid and the valve opening of LCV extracted from second row outlet 15 were stablized, and almost no solids observed composition is in the attachment of the inside of distilling apparatus 2, it is possible to confirm to inhibit blocking.The data of the valve opening of LCV now are shown in Fig. 5.In Fig. 5, transverse axis represents the days of operation of distilling apparatus 2, and the longitudinal axis represents the valve opening of the LCV of any time after operation start of distilling apparatus 2 and the difference ([valve opening of the LCV of any time after operation start]-[valve opening of the LCV of the operating first day]) of the valve opening of the LCV of the operating first day.In such manner, it is possible to make distilling apparatus 2 stably continuously run.
[embodiment 3]
The mixing gas obtained in the reaction of the epsilon-caprolactams being used under the coexisting of lower alcohol use solid acid catalyst and being generated by cyclohexanone-oxime, when using the distilling apparatus shown in Fig. 1 to separate the epsilon-caprolactams as goal object, carries out the removing of impurity.Specific as follows.
The methanol as lower alcohol, pentasil type zeolite catalysts as solid acid catalyst is used to react respectively.Then, the mixing gas obtained contains the epsilon-caprolactams containing byproduct of reaction containing the noble gas of water, about 31 mass % of the methanol of about 60 mass %, about 9 mass % respectively mean temperature 378 DEG C.
In distilling apparatus 1, as the packing material of the first packed layer 12 and the second packed layer 13, using specific surface area respectively is 90m2/m3Packing material (Sulzer company " Mellgrid90X "), make the height H of the first packed layer 121Height H relative to distillation column 110It is 25%, makes the height H of the second packed layer 132Height H relative to distillation column 110It is 20%.
Above-mentioned mixing gas is supplied to the inside of the distillation column 11 being set as pressure 92.0kPa (690Torr), temperature 200～220 DEG C, extract the liquid of the amount corresponding approximately to 9 mass % relative to the epsilon-caprolactams containing byproduct of reaction the mixing gas of supply from the second row outlet 15 being connected with tower bottom with LCV, for mixing the remainder of gas, while make the amount in mean temperature 184 DEG C condensation extract from the first row outlet 14 being connected with top of tower on the internal reflux limit of distillation column 11.Making the circulation fluid of the radial direction of the first packed layer 12 and the total flow of backflow is 3.1 × 104kg/m2/ h, as circulation fluid, uses the liquid extraction extracted from second row outlet 15 to circular route 151.
Its result, through more than 150 days, the amount of liquid and the valve opening of LCV extracted from second row outlet 15 were stablized, and almost no solids observed composition is in the attachment of the inside of distilling apparatus 2, it is possible to confirm to inhibit blocking.The data of the valve opening of LCV now are shown in Fig. 5.In such manner, it is possible to make distilling apparatus 2 stably continuously run.
[embodiment 4]
It is used under the coexisting of lower alcohol use solid acid catalyst and is generated, by cyclohexanone-oxime, the mixing gas obtained in the reaction of epsilon-caprolactams, when using the distilling apparatus shown in Fig. 2 to separate the epsilon-caprolactams as goal object, carry out the removing of impurity.Specific as follows.
The methanol as lower alcohol, pentasil type zeolite catalysts as solid acid catalyst is used to react respectively.Then, the mixing gas obtained contains the epsilon-caprolactams containing byproduct of reaction containing the noble gas of water, about 35 mass % of the methanol of about 60 mass %, about 5 mass % respectively mean temperature 375 DEG C.
In distilling apparatus 2, as the packing material of the first packed layer 12 and the second packed layer 13, using specific surface area respectively is 257m2/m3Packing material, make the height H of the first packed layer 121Height H relative to distillation column 110It is 22%, makes the height H of the second packed layer 132Height H relative to distillation column 110It is 22%.
Above-mentioned mixing gas is supplied to the inside of the distillation column 11 being set as pressure 97.3kPa (730Torr), temperature 200～220 DEG C, extract the liquid of the amount corresponding approximately to 16 mass % relative to the epsilon-caprolactams containing byproduct of reaction the mixing gas of supply from the second row outlet 15 being connected with tower bottom with LCV, for mixing the remainder of gas, while make the amount in mean temperature 174 DEG C condensation extract from the first row outlet 14 being connected with top of tower on the internal reflux limit of distillation column 11.Making the circulation fluid of the radial direction of the first packed layer 12 and the total flow of backflow is 2.6 × 104kg/m2/ h, as circulation fluid, the liquid extraction obtained solid constituent being filtered device filtration via the filter screen being arranged at second row outlet 15 as the second filter house 17 uses to circular route 151.
Its result, through more than 80 days, almost no solids observed composition was in the attachment of the inside of distilling apparatus 2, it is possible to confirm to inhibit blocking.During this period, repeatedly there occurs the rising to the attachment of the first packed layer 12 or the second packed layer 13 and the valve opening of avalanche and this LCV together thereof of some solid constituents, but hinder continuously running of distilling apparatus 2.The data of the valve opening of LCV now are shown in Fig. 5.
Industrial applicability
The present invention can be used in by distilling the refining step separating goal object from mixing gas overall.
Symbol description
1,2 ... distilling apparatus, 11 ... distillation column, 111 ... gas supply part, 12 ... the first packed layer, 13 ... the second packed layer, 14 ... first row outlet, 141 ... return wire, 15 ... second row outlet, 151 ... circular route, 16 ... the first filter house, 17 ... the second filter house, Z ... the short transverse of distillation column
Claims (5)
1. the method removing impurity, it is characterized in that, be pass through to distill from maybe can pass through containing solid constituent to be polymerized the composition forming solid constituent as the mixing gas of impurity separate epsilon-caprolactams time, the method that described impurity is removed from the inside of distillation column carrying out distilling
Described distillation column has: the packed layer filled with packing material of the one layer～three layers arranged in the short transverse of described distillation column,
It is arranged at the gas supply part at the position of the lower section of the described packed layer of foot,
It is arranged at the first extract part of the top of the described packed layer of topmost, and
It is arranged at the second extract part of the lower section of described gas supply part,
The specific surface area of the packing material in the packed layer of described foot is 70～300m2/m3,
The method of described removing impurity includes: at the position of lower section of the described packed layer of foot, and from described distillation column, described mixing gas is externally supplied to inside,
Described distillation column distills, the gas containing epsilon-caprolactams is extracted from described first extract part of the top of the described packed layer being arranged at topmost the outside of described distillation column,
Liquid containing described impurity is extracted from the second extract part of the lower section being arranged at described gas supply part the outside of described distillation column,
Using at least some of packed layer being supplied from above described foot as circulation fluid of the liquid of described extraction, described circulation fluid and the backflow from the top of described distillation column is utilized to rinse the described impurity caught by the packed layer of described foot, obtain the liquid containing described impurity, and
Liquid containing described impurity is extracted from described second extract part the outside of described distillation column,
Described mixing gas is under the coexisting of the alcohol that carbon number is 1～6, uses solid acid catalyst, cyclohexanone-oxime generate the gas obtained in the gas-phase reaction of epsilon-caprolactams.
2. the method for removing impurity according to claim 1, wherein, the described circulation fluid in arbitrary face that the short transverse with described distillation column of the packed layer of described foot is vertical is 1.5 × 10 with the total flow of described backflow4～1.2 × 105kg/m2/h。
3. the method for removing impurity according to claim 1, farther includes: the part cooling of the gas containing epsilon-caprolactams will extracted from described first extract part so that it is be condensed into liquid, and makes described liquid from the upper return of described distillation column.
4. the method for removing impurity according to claim 1, farther includes: make described liquid from before the upper return of described distillation column, the liquid of described condensation is filtered device and filters and remove solid constituent.
5. the method for removing impurity according to claim 1, farther include: before at least some of packed layer being supplied from above described foot as circulation fluid of the liquid extracted from described second extract part, the liquid extracted from described second extract part is filtered device and filters and remove solid constituent.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-257557 | 2011-11-25 | ||
| JP2011257557 | 2011-11-25 | ||
| PCT/JP2012/080062 WO2013077319A1 (en) | 2011-11-25 | 2012-11-20 | Method for removing impurities |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103946212A CN103946212A (en) | 2014-07-23 |
| CN103946212B true CN103946212B (en) | 2016-06-29 |
Family
ID=48469763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280057251.2A Active CN103946212B (en) | 2011-11-25 | 2012-11-20 | The removing method of impurity |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2013128919A (en) |
| CN (1) | CN103946212B (en) |
| WO (1) | WO2013077319A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106251620B (en) * | 2016-09-26 | 2019-01-25 | 北京东土科技股份有限公司 | Centring system based on intelligent transportation cloud control system |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1283606A (en) * | 1999-07-06 | 2001-02-14 | 株式会社日本触媒 | Method and appts for absorbing propenoic acid compound |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2506021B2 (en) * | 1992-02-19 | 1996-06-12 | 三菱化学株式会社 | Purification method of caprolactam |
| JP3811607B2 (en) * | 2000-09-20 | 2006-08-23 | Ｙｋｋ株式会社 | Adjustable hook for clothes |
| JP4983041B2 (en) * | 2006-02-21 | 2012-07-25 | 住友化学株式会社 | Caprolactam purification method |
-
2012
- 2012-11-20 CN CN201280057251.2A patent/CN103946212B/en active Active
- 2012-11-20 WO PCT/JP2012/080062 patent/WO2013077319A1/en active Application Filing
- 2012-11-26 JP JP2012257822A patent/JP2013128919A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1283606A (en) * | 1999-07-06 | 2001-02-14 | 株式会社日本触媒 | Method and appts for absorbing propenoic acid compound |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2013077319A1 (en) | 2013-05-30 |
| JP2013128919A (en) | 2013-07-04 |
| CN103946212A (en) | 2014-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103249705B (en) | The manufacture method of acetic acid | |
| CN1926088B (en) | Control method for process of removing permanganate reducing compounds from methanol carbonylation process | |
| CN104703959B (en) | The method reclaiming permanganate reproducibility compound from acetic acid production | |
| JP4740033B2 (en) | Titanium tetrachloride purification method and purification apparatus used therefor | |
| CN102971284A (en) | Process for purifying acetic acid streams by removing permanganate reducing compounds | |
| CN103946212B (en) | The removing method of impurity | |
| TWI546113B (en) | Process and apparatus for distillative separation of a mixture of three or more components | |
| TW200800806A (en) | Method of recovering triethylamine in water | |
| CN102078702A (en) | Rectifying tower flow controllable type lateral-line extraction combined device | |
| JP6761758B2 (en) | Reduced fouling in the acetonitrile removal step of acrylonitrile recovery | |
| CN104784958A (en) | Distillation column | |
| JP2007191435A (en) | Method for producing (meth)acrylic acid | |
| EP3606903A1 (en) | Process for purifying (meth)acrylic acid including a dividing-wall distillation column | |
| KR20170110139A (en) | Methods for controlling the HI concentration in the residue stream | |
| US20140008034A1 (en) | Integrated thermosiphon reboiler-condensate pot system and process for use thereof | |
| JP5953121B2 (en) | Packed column equipped with a re-disperser for packed column and method for distillation of vinylidene chloride monomer using the same | |
| WO2015038679A1 (en) | Catalyst preparation and hydrogenation process | |
| JP2021014456A (en) | Recovery column control | |
| US20190023637A1 (en) | Hydroformylation process | |
| US20130206577A1 (en) | Process and plant for the distillation of temperature-sensitive liquids | |
| JP4802446B2 (en) | Apparatus and method for producing diphenyl carbonate or aromatic polycarbonate using the apparatus | |
| JP5175429B2 (en) | Coke oven gas cooling apparatus and method | |
| JP2016506969A (en) | Separation of acrolein from process gas of oxidation by heterogeneous catalysis of propene | |
| US9688917B2 (en) | Hydrocarbon-producing apparatus and hydrocarbon-producing method | |
| CN105777473A (en) | Online washing method for water system of methanol to olefin plant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |