EP3802435A1 - Verfahren zum recycling von extraktwasser bei der polyamid 6-herstellung - Google Patents
Verfahren zum recycling von extraktwasser bei der polyamid 6-herstellungInfo
- Publication number
- EP3802435A1 EP3802435A1 EP18729922.7A EP18729922A EP3802435A1 EP 3802435 A1 EP3802435 A1 EP 3802435A1 EP 18729922 A EP18729922 A EP 18729922A EP 3802435 A1 EP3802435 A1 EP 3802435A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- extract water
- cation
- unit
- ion
- exchanger
- 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.)
- Pending
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 39
- 229920002292 Nylon 6 Polymers 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000004064 recycling Methods 0.000 title claims abstract description 14
- 238000005342 ion exchange Methods 0.000 claims abstract description 31
- 150000001768 cations Chemical class 0.000 claims abstract description 28
- 150000001450 anions Chemical class 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- 238000005341 cation exchange Methods 0.000 claims abstract description 7
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 69
- 150000002500 ions Chemical class 0.000 claims description 41
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 22
- 239000003957 anion exchange resin Substances 0.000 claims description 21
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 20
- 239000003729 cation exchange resin Substances 0.000 claims description 18
- 238000001704 evaporation Methods 0.000 claims description 17
- 230000008020 evaporation Effects 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 239000012535 impurity Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 125000004122 cyclic group Chemical group 0.000 claims description 11
- 238000004332 deodorization Methods 0.000 claims description 11
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 11
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229940043430 calcium compound Drugs 0.000 claims description 5
- 150000001674 calcium compounds Chemical class 0.000 claims description 5
- 235000019827 calcium polyphosphate Nutrition 0.000 claims description 5
- 238000010276 construction Methods 0.000 claims description 5
- 150000002697 manganese compounds Chemical class 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229920002842 oligophosphate Polymers 0.000 claims description 5
- 150000003112 potassium compounds Chemical class 0.000 claims description 5
- 150000003377 silicon compounds Chemical class 0.000 claims description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 150000003609 titanium compounds Chemical class 0.000 claims description 4
- 230000001877 deodorizing effect Effects 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 239000002351 wastewater Substances 0.000 claims 1
- 238000005349 anion exchange Methods 0.000 abstract description 4
- 239000003456 ion exchange resin Substances 0.000 description 11
- 229920003303 ion-exchange polymer Polymers 0.000 description 11
- 239000000243 solution Substances 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- -1 amine compounds Chemical class 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 150000003388 sodium compounds Chemical class 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 230000009965 odorless effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- MXRGSJAOLKBZLU-UHFFFAOYSA-N 3-ethenylazepan-2-one Chemical compound C=CC1CCCCNC1=O MXRGSJAOLKBZLU-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000009935 nitrosation Effects 0.000 description 1
- 238000007034 nitrosation reaction Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/02—Column or bed processes
- B01J47/026—Column or bed processes using columns or beds of different ion exchange materials in series
- B01J47/028—Column or bed processes using columns or beds of different ion exchange materials in series with alternately arranged cationic and anionic exchangers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/04—Processes using organic exchangers
- B01J39/05—Processes using organic exchangers in the strongly acidic form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/04—Processes using organic exchangers
- B01J39/07—Processes using organic exchangers in the weakly acidic form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/02—Column or bed processes
- B01J47/04—Mixed-bed processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
- C02F1/004—Processes for the treatment of water whereby the filtration technique is of importance using large scale industrial sized filters
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/427—Treatment of water, waste water, or sewage by ion-exchange using mixed beds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/38—Polymers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/04—Flow arrangements
- C02F2301/043—Treatment of partial or bypass streams
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/02—Odour removal or prevention of malodour
Definitions
- the present invention relates to a process for the recycling of extract water resulting from the production of polyamide 6 or its copolymers (PA6 / 66), an apparatus for recycling in the production of
- Polyamide or its copolymers (PA6 / 66) accumulating extract water and the use of this device for recycling of resulting in the production of polyamide 6 or its copolymers (PA6 / 66) extracting water.
- caprolactam present in the crude product after the polymerization and cyclic and linear oligomers of caprolactam must be removed after the polymerization. This usually happens with hot water.
- the resulting extract waters typically contain from 5 to 20 percent by weight of organic fractions which must be reused from an economic point of view. These are these concentrated and recycled as raw material of the polyamide 6 synthesis, while the condensed distillate is used again for the extraction.
- additives such as titanium dioxide as matting agent for textile applications can be added already during the polymerization. Consequently, these additives come in contact with water during the subsequent extraction in the process and foreign matter such as e.g. Minerals from the coating of titanium dioxide are washed out.
- the difficulty lies in the fact that the dissolved oligomers of caprolactam can precipitate at temperatures below 80 ° C and block lines. However, if the temperature is kept above 80 ° C., no anion exchangers can be used, since they rapidly degrade at temperatures above 80 ° C. and tend to liberate odorous compounds, in particular amines, and contaminate the recirculating streams ,
- No. 5,245,029 relates to an ion exchange process for purifying water caprolactam solutions in a process for the preparation of caprolactam and laurolactam, in which a mixture of cyclohexanone oxime and cyclodeodecanoxime in the presence of sulfuric acid and fuming sulfuric acid is subjected to a Beckman reaction. Rearrangement is subjected. The process comprises, after neutralization of the reaction products from the rearrangement, a first extraction with an organic solvent and a second extraction of the first extract with water to obtain a second extract of an aqueous caprolactam solution.
- aqueous caprolactam solution obtained by extraction with a water immiscible organic solvent is treated with a strongly acidic cation exchange resin followed by a weakly basic anion exchange resin or further with a strongly basic anion exchange resin to remove surfactants such as alkyl sulfate , GB 762,879 describes a process for the removal of organic impurities from lactams, which describes the conduction of lactam in aqueous solution via anion and cation exchangers, which can be arranged in any order.
- GB 1 175,279 relates to processes for the purification of e-caprolactam obtained by nitrosation of cyclohexyl compounds and containing volatile amide-based bases.
- the e-caprolactam is treated with an alkaline reagent in the presence of water and a halogen or an alkali metal hypohalide to convert the volatile amide-based bases to amine compounds.
- These amine compounds are separated from the e-caprolactam, for example by a cation exchanger.
- No. 5,225,524 relates to a process for rendering odorless polymer solutions containing amino groups.
- a solution of terpolymers of vinylpyrrolidone, vinylcaprolactam and dimethylaminoethyl methacrylate is treated with from 0.1 to 10% by weight of an acidic compound or an acidic anion exchange resin in order to render it predominantly odorless.
- a further object of the present invention is to provide a device for the purification of extract water resulting from the production of polyamide 6 or its copolymers. This object is achieved by the method according to independent claim 1, which comprises the following steps:
- ion exchanger module comprising at least the following ion exchanger units: i) at least one cation exchanger unit, ii) at least one anion exchanger unit, wherein the extract water contains the ion exchanger units in c) deodorizing the extract water from step b) by iii) at least one cation exchanger unit or a mixed ion exchanger unit which comprises at least one anion exchanger and at least one cation exchanger, and wherein the extract water during the entire process Method has a temperature in the range of 80 to 100 ° C.
- the independent claim 12 relates to a device for cleaning and deodorization of Kapolactam-containing extract water obtained in the polyamide 6 preparation, comprising an extractor upstream and downstream of this an evaporation plant, between which in the flow path at least one filtration unit and an ion exchange module are positioned, wherein the ion exchange module contains at least the following ion exchange units: i) at least one cation exchanger unit, ii) at least one anion exchanger unit, iii at least one cation exchanger unit or a mixed ion exchanger unit which comprises at least one anion exchanger and at least one cation exchanger, the ion exchanger units being arranged in the flow direction of the extract water in the order i-ii-ii ,
- a preferred embodiment of the device according to the invention is specified in dependent claim 13.
- Claims 14 to 16 relate to uses of the device according to the invention for the recycling of extracting water resulting from the production of polyamide 6.
- Recycling of extract water in the context of the present invention is understood to mean that a concentrate of the extract water is returned to the polymerization reactor for the production of polyamide 6.
- the "purification” in the context of the present invention relates to the removal of soluble and insoluble impurities from the extract water.
- deodorization is understood to mean the removal of odor-intensive substances from the extract water which have arisen during the "purification” or which have not been removed during the purification step.
- Ion exchange resins have functional groups such as, for example, sulfonic acid groups, trimethylammonium groups or amino groups.
- a functional group-based ion exchange resin is understood to mean that the functionality of the ion exchange resin is based on this group.
- a preferred embodiment according to the present invention provides that the extract water caprolactam in monomeric form and / or cyclic and / or linear oligomers of caprolactam and impurities preferably selected from the group consisting of titanium compounds, silicon compounds, manganese compounds, aluminum compounds, sodium - compounds, potassium compounds, calcium compounds, in particular calcium sulfate, calcium polyphosphates, calcium oligophosphates and mixtures thereof.
- the proportion of cyclic and / or linear oligomers of caprolactam in the extract water is 5 to 20 wt .-%, preferably 10 to 15 wt .-%, based on the total mass of the extract water.
- a particularly preferred embodiment according to the present inven tion provides that the extract water caprolactam in monomeric form and / or cyclic and / or linear oligomers of caprolactam and impurities preferably selected from the group consisting of Titanver- compounds, silicon compounds, manganese compounds, aluminum compound compounds, sodium compounds, potassium compounds, calcium compounds, in particular calcium sulfate, calcium polyphosphates, calcium oligophosphates and mixtures thereof and the proportion of cyclic and / or linear oligomers of caprolactam in the extract water 5 to 20% by weight, preferably 10 to 15 wt .-%, based on the total mass of the extract water is.
- the proportion of caprolactam in the extract water is 5 to 20 wt .-%, preferably 10 to 15 wt .-% based on the total mass of the extract water.
- the proportion of impurities in the extract water is less than 1 wt .-%, preferably less than 0.5 wt .-% based on the total mass of the extract water.
- the extract water has a temperature in the range of 83 to 95 ° C, preferably in the range of 85 to 90 ° C during the entire process. If lower temperatures were used oligomers of caprolactam would precipitate and blockage of lines would be expected.
- the filtration unit a has a filter with a pore size in the range of 0.1 to 100 ⁇ m, preferably 5 to 50 ⁇ m.
- the filtration unit allows to remove insoluble impurities and suspended solids from the extract water.
- the at least one cation exchange unit i) is formed in the form of a resin bed.
- the at least one cation exchanger unit i) contains a sulfonic acid group-based cation exchange resin.
- Cation-exchange resins based on sulfonic acid groups are highly acidic.
- the at least one anion exchange unit ii) is in the form of a resin bed.
- the at least one anion exchanger unit ii) contains a trimethylammonium-based anion exchange resin.
- Anion exchange resins based on trimethylammonium groups are counted among the type I exchangers, are strongly basic and have an increased thermal stability compared to the type II exchangers.
- Amino group-based anion exchange resins are counted among the weakly basic anion exchange resins.
- a further preferred embodiment of the present invention provides that the at least one cation exchanger unit or mixed ion exchanger unit iii) used in step c) for deodorization is formed in the form of a resin bed.
- a mixed bed is used in which the cation and anion exchange resins are distributed almost homogeneously.
- a preferred ratio of cation exchange resin to anion exchanger is 1.9: 1.3 based on the active groups.
- the ion exchanger unit iii) is present in an ion exchange module with the ion exchanger units i) and ii).
- the at least one mixed ion exchanger unit comprises a mixture of a sulfonic acid group-based cation exchange resin and an trimethylammonium group-based anion exchange resin.
- the deodorization according to step c) is ensured by at least one container filled with a cation exchange resin or mixtures of at least one cation exchange resin and at least one anion exchange resin.
- this container is preferably installed behind the ion exchanger module in the extra water circuit.
- the odorizing step c) serves to neutralize odor-intensive substances which have been newly formed by the ion exchange module, in particular the ion exchange unit ii).
- the cation exchange resin in this container is preferably based on sulfonic acid groups and the anion exchange resin on trimethylammonium groups.
- the at least one container between the ion exchanger module and the evaporation plant is attached.
- a further preferred embodiment of the present invention provides that the at least one container for deodorization between the evaporation plant and the extractor is arranged. It is particularly preferred to install the container in the condensate of the evaporation plant, since there are lower temperatures of 20 to 70 ° C, preferably 40 to 60 ° C, are present. This has the advantage that the ion exchange resins are exposed to a lower thermal load and thus longer periods of use are possible. Another reason for the preferred mounting of the container in the condensate of the evaporation plant is in the accumulation of the volatile amines, which are the odorous substances, at this position, since they evaporate with the water.
- the water which is recycled from the evaporation plant into the extractor does not constitute extract water in the sense of the present invention, since it contains no organic constituents such as caprolactam or its oligomers.
- Another preferred embodiment of the present invention provides that at least one of the ion exchanger units i), ii) and / or those for deodorization iii), preferably all ion exchanger units, contain at least one protective filter.
- At least one, preferably all, of the ion exchange units i), ii) and iii) is bridgeable with a bypass.
- At least one, preferably all, of the ion exchanger units i), ii) and / or iii) is / are a second ion exchanger unit, which is / are preferably the same as the first ion exchanger unit in terms of construction and ion exchange material , interchangeable by a circuit.
- the temporary bridging with a bypass or the replacement by a second container or a second ion exchanger unit allows to replace the ion exchange resin without having to interrupt the operation.
- the container has at least one protective filter, wherein it is particularly preferred if both the inlet and the outlet of the container are provided with a protective filter.
- the purpose of the protective filters is to prevent the introduction of foreign substances into the ion exchange resin. Furthermore, it is particularly preferred that the last ion exchanger unit has a protective filter in the direction of flow on the outlet side, so that mechanical abrasion can be retained from the ion exchanger resin bed and its introduction into the process cycle can be prevented.
- the conductivity of the extract water after step c), which is carried out between the ion exchange module containing i) and ii) and the evaporation plant is less than 10 pS / cm, preferably is less than 5 pS / cm, more preferably less than 1 pS / cm.
- the device is designed such that the at least one cation exchange unit i) is in the form of a resin bed and / or contains a sulfonic acid group-based cation exchange resin, and / or the at least one anion exchange unit ii) is formed in the form of a resin bed and / or contains an anion exchange resin based on trimethylammonium groups, and / or contains a mixture of a sulfonic acid group-based cation exchange resin and a trimethylammonium-based anion exchange resin.
- the device according to the present invention is particularly suitable for recycling extract water resulting from polyamide 6 production.
- the apparatus is used for recycling of extract water, caprolactam in monomeric form and / or cyclic and / or linear oligomers of caprolactam and impurities preferably selected from the group consisting of titanium compounds, silicon compounds, manganese compounds , Aluminum compounds, sodium compounds, potassium compounds, calcium compounds, in particular calcium sulfate, calcium polyphosphates, calcium oligophosphates and mixtures thereof.
- the proportion of cyclic and / or linear oligomers of caprolactam is 5 to 20 wt .-%, preferably 10 to 15 wt .-%, based on the total mass of the extract water.
- the proportion of caprolactam is 5 to 20 wt .-%, preferably 10 to 15 wt .-% based on the total mass of the extract water.
- the proportion of impurities in the extract water is less than 1 wt .-%, preferably less than 0.5 wt .-% based on the total mass of the extract water.
- the device is used for recycling of extract water having a temperature in the range of 80 to 100 ° C, preferably 83 to 95 ° C and particularly preferably 85 to 90 ° C.
- FIGS. 1 to 3 serve to illustrate the invention better, but should not be construed as limiting in any way.
- FIG. 1 shows the schematic sequence of the polyamide 6 production process including the extract water cycle.
- the filtration unit (6) and the ion exchange module (7) comprising a cation ion exchanger unit i) and an anion exchange unit ii) are positioned between the extractor (4) and the evaporation plant (9).
- the units (6) and (7) ensure the filtration and purification according to process steps a) and b).
- the container (8) filled with ion exchange resin comprising a cation exchange unit or mixed ion exchanger unit iii) for the desorption according to process step c) can be arranged between the ion exchanger module (7) and the evaporation plant (8 '). However, it is preferable to position this container between the evaporation plant and the extractor. kidney, particularly preferably in the condensate of the evaporation plant (8 "). Furthermore, several containers can be used for deodorization.
- FIG. 2 schematically shows the flow of the mineral-containing extract water (15), which successively receives a filtration unit (6), a cation exchanger (7a) i) an anion exchanger (7b) ii), after which low-mineral extract water (16) is obtained which is again polyamide 6 Manufacturing process can be supplied.
- the ion exchanger unit (8) iii) comprising a mixed ion exchanger unit can be installed directly behind the ion exchange units (7a) and (7b).
- FIG. 3 a shows the bypass variant for the container for deodorization (8)
- FIG. 3 b illustrates the embodiment with a switchable second container
- FIG. 3c illustrates the embodiment with switchable identical ion exchanger units for the cation exchanger unit i), the anion exchanger unit ii) and the ion exchanger unit for the deodorizing iii).
- the ion exchange resins used in the examples were regenerated prior to use or are commercially available directly.
- a strong base Type I anion exchange resin (100 g) was refluxed overnight in water (200 g). The water subsequently smelled unpleasantly fishy and trime- thylamine was detected by gas chromatography. The resulting water was treated for 5 minutes with a mixed bed consisting of a strongly acidic and a strongly basic ion exchange resin (3 parts water to 1 part mixed bed) (duration 5 minutes), after which the odor disappeared and no trimethylamine was detectable ,
- aqueous solution with a conductivity of 32 pS / cm passed in succession through a resin bed of a strongly acidic cation exchanger and a strongly basic type I anion exchanger.
- the conductivity of the solution was reduced to 3 to 4 pS / cm.
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- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Polyamides (AREA)
Abstract
Description
Claims
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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PCT/EP2018/064503 WO2019228651A1 (de) | 2018-06-01 | 2018-06-01 | Verfahren zum recycling von extraktwasser bei der polyamid 6-herstellung |
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EP3802435A1 true EP3802435A1 (de) | 2021-04-14 |
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EP18729922.7A Pending EP3802435A1 (de) | 2018-06-01 | 2018-06-01 | Verfahren zum recycling von extraktwasser bei der polyamid 6-herstellung |
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EP (1) | EP3802435A1 (de) |
CN (1) | CN111527051B (de) |
WO (1) | WO2019228651A1 (de) |
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CN114368869A (zh) * | 2022-01-27 | 2022-04-19 | 大连海新工程技术有限公司 | 一种pa6聚合萃取水的处理装置、系统及工艺 |
Family Cites Families (15)
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---|---|---|---|---|
US3145198A (en) * | 1964-08-18 | piija | ||
GB762879A (en) | 1952-11-15 | 1956-12-05 | Stamicarbon | Process for purifying lactams |
GB867741A (en) * | 1959-02-14 | 1961-05-10 | Stamicarbon | Method of removing impurity from aqueous solutions of caprolactam containing lactam oligomers |
CH525887A (it) | 1966-07-27 | 1972-07-31 | Snia Viscosa | Procedimento di purificazione di caprolattame, in particolare ottenuto per nitrosazione di composti cicloesilici |
GB1235351A (en) * | 1968-01-01 | 1971-06-16 | Permutit Co Ltd | Fibrous cross-linked polymers |
US4380590A (en) * | 1978-09-19 | 1983-04-19 | Rohm And Haas Company | Emulsion copolymer cation exchange resins |
JP2559903B2 (ja) | 1990-11-21 | 1996-12-04 | 宇部興産株式会社 | カプロラクタム水溶液のイオン交換樹脂精製方法 |
US5225524A (en) | 1992-07-02 | 1993-07-06 | Isp Investments Inc. | Process for rendering amino-group-containing polymer solutions substantially odorless |
JPH08276180A (ja) * | 1995-04-06 | 1996-10-22 | Ngk Insulators Ltd | イオン交換純水の脱臭精製方法 |
JP2000262893A (ja) * | 1999-03-16 | 2000-09-26 | Takuma Co Ltd | 陰イオン除去剤及び陰イオン除去ケミカルフィルタ |
TW200812960A (en) * | 2006-09-04 | 2008-03-16 | China Petrochemical Dev Corp | A system and method for purification carprolactam from raw solution |
JP5720138B2 (ja) * | 2010-08-06 | 2015-05-20 | 栗田工業株式会社 | 酢酸含有排水の処理方法 |
CN103663792A (zh) * | 2013-12-12 | 2014-03-26 | 长乐恒申合纤科技有限公司 | 一种锦纶回收萃取水的过滤系统及其工艺 |
CN105801841A (zh) * | 2016-04-20 | 2016-07-27 | 温州邦鹿化工有限公司 | 一种尼龙6生产工艺及系统 |
CN105948333A (zh) * | 2016-06-30 | 2016-09-21 | 杭州聚合顺新材料股份有限公司 | 尼龙6切片萃取水中无机离子的去除方法及其去除装置 |
-
2018
- 2018-06-01 CN CN201880084887.3A patent/CN111527051B/zh active Active
- 2018-06-01 EP EP18729922.7A patent/EP3802435A1/de active Pending
- 2018-06-01 WO PCT/EP2018/064503 patent/WO2019228651A1/de unknown
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CN111527051A (zh) | 2020-08-11 |
WO2019228651A1 (de) | 2019-12-05 |
CN111527051B (zh) | 2023-03-24 |
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