EP2352635A2 - Ion exchanger moulded body and method for producing same - Google Patents
Ion exchanger moulded body and method for producing sameInfo
- Publication number
- EP2352635A2 EP2352635A2 EP09744682A EP09744682A EP2352635A2 EP 2352635 A2 EP2352635 A2 EP 2352635A2 EP 09744682 A EP09744682 A EP 09744682A EP 09744682 A EP09744682 A EP 09744682A EP 2352635 A2 EP2352635 A2 EP 2352635A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- starting material
- powder
- ion exchanger
- channels
- adsorber
- 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.)
- Withdrawn
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000000465 moulding Methods 0.000 claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000007858 starting material Substances 0.000 claims abstract description 27
- 239000011230 binding agent Substances 0.000 claims abstract description 25
- 229920000620 organic polymer Polymers 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims description 51
- 229920000642 polymer Polymers 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000012856 packing Methods 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 239000004793 Polystyrene Substances 0.000 claims description 9
- 229920002223 polystyrene Polymers 0.000 claims description 9
- 238000007493 shaping process Methods 0.000 claims description 9
- 238000007306 functionalization reaction Methods 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000012190 activator Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 3
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims 3
- 101100285518 Drosophila melanogaster how gene Proteins 0.000 claims 1
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- 229920005989 resin Polymers 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 8
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000004971 Cross linker Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 230000002452 interceptive effect Effects 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920005990 polystyrene resin Polymers 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- -1 strands Substances 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 238000000110 selective laser sintering Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- 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 description 1
- OBQPKGCVMCIETH-UHFFFAOYSA-N 1-chloro-1-(1-chloroethoxy)ethane Chemical compound CC(Cl)OC(C)Cl OBQPKGCVMCIETH-UHFFFAOYSA-N 0.000 description 1
- WBHAUHHMPXBZCQ-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound COC1=CC=CC(C)=C1O WBHAUHHMPXBZCQ-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- 101100532456 Rattus norvegicus Slc28a2 gene Proteins 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003973 alkyl amines Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28042—Shaped bodies; Monolithic structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/248—Reactors comprising multiple separated flow channels
- B01J19/2485—Monolithic reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3268—Macromolecular compounds
- B01J20/327—Polymers obtained by reactions involving only carbon to carbon unsaturated bonds
-
- B01J35/56—
-
- 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
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
- B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
Definitions
- the invention relates to processes for the production of organic polymer moldings having ion exchanger or adsorber properties, moldings of this type and their use in heterogeneously catalyzed chemical reactions or as adsorbers for adsorbing ions or chemical compounds.
- Ion exchangers are substances that are capable of exchanging ions bound to them for equivalent amounts of other ions from a surrounding solution. An exchange takes place between ions of the same direction.
- Adsorber resins in contrast to the ion exchange resins, have a nonionic but, depending on the structure, a more or less polar character and non-stoichiometrically adsorb both anions, cations and uncharged compounds.
- ion exchange resins and adsorbent resins are gel-based or macroreticular, spherical, porous synthetic resins based on styrene or acrylic resin.
- three-dimensional crosslinking is achieved, typically by the inclusion of divinylbenzene.
- the most commonly used ion exchangers today are polystyrene resins which are crosslinked with divinylbenzene (DVB) and thus show a high, high-molecular, three-dimensional structure and are usually in spherical form.
- DVD divinylbenzene
- a strong acidic cation exchanger By sulfonation of the crosslinked polystyrene resin, for. As with oleum, a strong acidic cation exchanger.
- acrylic acid derivatives are cross-linked with divinylbenzene.
- Anion exchangers can also be strongly basic or weakly basic. Exchanger resins with a quaternary ammonium group show a strongly basic character, while resins with tertiary amino groups have weak basic properties.
- the ion exchangers are typically used as solid spheres, whereby flow reactors can be packed with them in the form of a fixed bed.
- the object of the present invention is to provide a process for the production of organic polymer moldings with ion exchanger or adsorber properties, which allows the production of a large number of moldings geometries in a simple manner and thus the adaptation of the ion exchanger and adsorber to the respective application.
- the object is achieved according to the invention by a process for the production of organic polymer moldings having ion exchanger or adsorber properties by means of a powder-based rapid prototyping process, in which a pulverulent organic polymer starting material or starting material mixture is applied to a substrate in a thin layer and then at selected points of that layer is added a binder and any necessary auxiliaries, or irradiated or otherwise treated, so that the powder is joined at these points, whereby the powder is bonded both within the layer and with the adjacent layers , and this process is repeated so many times that the desired shape of the shaped body is completely imaged in the powder bed formed, and subsequently the powder not bound by the binder is removed, so that the bonded powder in the desired shape z remains, wherein the starting material already exhibits the ion exchanger or adsorber properties or after shaping a corresponding functionalization of the shaped body takes place.
- the ion exchanger or adsorber can serve as a catalyst for a variety of acidic or basic heterogeneously catalyzed reactions or for the purification or separation of chemical mixtures, eg. B. for wastewater treatment or in the analysis or as a guard bed.
- the catalyst / adsorber is present in disorder in the reactor, aligned in a package and installed in the orderly manner in the reactor.
- the most widespread is the use of catalysts in the form of granules, strands, tablets, rings or SpNt, which are introduced as a bed in the reactor.
- a disadvantage of this type of use is that the beds described generally lead to a large pressure drop in the reactor.
- it can easily lead to the formation of channels and the formation of zones with stagnant gas and / or liquid movement, so that the catalyst is only very unevenly loaded.
- the required removal and installation of the moldings may be complex, for example in tube bundle reactors with a large number of tubes.
- catalysts / adsorbers can also be used in the form of monoliths with continuous channels, honeycomb or rib structure, as described, for example, in DE-A-2709003.
- the process according to the invention allows the preparation of organic polymer moldings having ion exchanger or adsorber properties in any suitable geometry. The preparation is carried out by the rapid prototyping method, which is explained below.
- RP rapid prototyping
- SLS Selective Laser Sintering
- SLA Stereolithography
- EP-A-0431 924 One of the rapid prototyping methods is described in EP-A-0431 924 and comprises the layered construction of three-dimensional components made of powder and binder. Unbound powder is removed at the end and the workpiece remains in the desired geometry.
- the object is thus achieved according to the invention by the use of moldings which are optimized in terms of their geometry for the respective flow and reaction conditions in the reactor or adsorber bed, etc.
- the reactor internals can be tailored for the application, as is not possible with conventional techniques.
- the advantage of rapid prototyping technology over conventional manufacturing techniques is that theoretically any geometry, even complex components, for example, with cavities or microchannels, computer-controlled in the corresponding three-dimensional component without previous molding in molds, without cutting, using a CAD data set, Milling, grinding, etc. can be implemented.
- the production of reactor internals possible because of their optimized geometry advantages for the mass and heat transport in chemical reactions compared to conventional reactor internals. This process intensification results in higher yields, conversions and selectivities as well as a safe reaction procedure and can lead to cost savings for existing or new processes in the chemical industry through reduced apparatus sizes or reduced amounts of catalyst.
- organic polymer moldings having ion exchanger or adsorber properties are produced. These are usually gel or macroreticular porous resins.
- the powdery starting materials are based on optionally crosslinked polystyrene, poly (meth) acrylates or poly (meth) acrylic acids.
- the synthetic resins are based on styrene or acrylic resins.
- a three-dimensional crosslinking or linking by crosslinking monomers, in particular divinylbenzene is achieved.
- the exchange resins are not deformable in the heat and at the same time free of plasticizers. The release of soluble fractions is virtually eliminated.
- B. can be crosslinked with electron radiation in the finished molding.
- Crosslinkers can already be incorporated in the polymer and be brought to harden after shaping. So can be z.
- Suitable molecular weights and the preparation of the polymer resins in particular polystyrene resins or polyacrylic resins, is known to the person skilled in the art.
- the resins used in the rapid prototyping process according to the invention do not differ in this respect from the typical ion exchanger or adsorber resins.
- Pulp-shaped starting materials which can be used with or without a binder are used in the rapid prototyping method to be used according to the invention.
- the other versions apply to both variants. Both monodisperse and polydisperse powders can be used. Naturally, thinner layers can be realized with finer particles, whereby a larger number of layers and thus a higher spatial resolution is possible for the construction of a desired shaped body than with coarser particles. Preference is given to powders having an average particle size in the range from about 0.5 ⁇ m to about 450 ⁇ m, particularly preferably from about 1 ⁇ m to about 300 ⁇ m, and very particularly preferably from 10 to 100 ⁇ m. The powder to be used, if necessary, can also be specifically pretreated, for.
- the rapid prototyping method to be used according to the invention consists of the following steps, which are repeated until the desired shaped body is completely composed of the individual layers.
- a powdery starting material or starting material mixture is applied in a thin layer on a substrate and then added at selected points of this layer with a binder and any necessary auxiliaries, or irradiated or otherwise treated, so that the powder is connected at these locations, whereby the powder is combined both within the layer and with the adjacent layers.
- the powder not bound by the binder is removed and the bonded powder remains in the desired shape.
- any material suitable for bonding together adjacent particles of the powdery starting material can be used as the binder.
- organic materials especially those which can be crosslinked or otherwise covalent bond with each other, for example, phenolic resins, polyisocyanates, polyurethanes, epoxy resins, furan resins, urea-aldehyde condensates, furfuryl alcohol, acrylic acid and Acrylate dispersions, polymeric alcohols, peroxides, carbohydrates, sugars, sugar alcohols, proteins, starch, carboxymethylcellulose, xanthan, gelatin, polyethylene glycol, poly- vinyl alcohols, polyvinylpyrrolidone or mixtures thereof.
- the binders are used in liquid form either in dissolved or dispersed form, whereby both organic solvents (eg toluene) and water can be used.
- the binder is a solvent which at least superficially dissolves the polymer starting material and thus produces a connection between the powder particles.
- the dissolved polymer particles stick together so that a firm connection is formed.
- the powdered starting material contains a reactive compound which is reacted with an applied activator compound to produce a compound of the polymer starting materials.
- the reactive compound may be, for example, a monomer which is also included in the structure of the polymer starting material. This may be, for example, styrene, acrylates or acrylic acid.
- the application of the binders takes place, for example, via a nozzle, a printhead or another apparatus which permits precise placement of the smallest possible drops of the binder on the powder layer.
- the ratio of powder amount to binder amount varies depending on the substances used, and is usually in the range of about 40:60 to about 99: 1 parts by weight, preferably in the range of about 70:30 to about 99: 1 parts by weight, especially preferably in the range of about 85:15 to about 98: 2 parts by weight.
- auxiliaries may be used which may, for example, have an influence on the crosslinking of the binders or serve as hardeners.
- the adjuvants can be applied separately, but if appropriate they can also be added to the powder bed and / or the binder or the binder solution.
- the bond by radiation treatment for. In the UV or IR range, see also the above description of the surface treatment.
- the shaping may be followed by a heat treatment in order to obtain better crosslinking or conversion of the binder.
- the polymeric starting material according to the invention can be functionalized before or after shaping with acidic groups, basic groups or chelating groups.
- the functionalization takes place in the same way as in the production of ion exchange or adsorber resins. It is thus possible to use ready-to-use ion exchange resin powders or adsorber resin powders in the rapid prototyping process, or initially unfunctionalized resins are used, and the molded articles produced are subsequently functionalized.
- Strongly acidic ion exchangers are typically based on polystyrene and are sulfonated with sulfuric acid (oleum), so that sulfonic acid groups are bound to the phenyl group in the molded body.
- the reaction with perfluorosulfonic acid is also possible, cf. Applied Catalysis A: General 221 (2001) 45-62.
- Low-acid ion exchangers are typically based on polyacrylates which have free carboxyl groups. These can be obtained by basic hydrolysis of the ester groups. Furthermore, phenol-formaldehyde gels can also be used.
- Basic ion exchangers can be distinguished into strongly basic and weakly basic ion exchanger resins, depending on the presence of the fixed ions.
- Exchanger resins with a quaternary ammonium group show a strongly basic character, while the resins with tertiary amino groups have weakly basic properties.
- Basic ion exchangers can, for. B.
- the organic polymers preferably have surface areas in the range from 5 to 200 m 2 / g, more preferably 10 to 100 m 2 / g, in particular 20 to 70 m 2 / g.
- the average pore diameter is preferably 2 to 200 nm, in particular 10 to 100 nm.
- In a functionalization are preferably 0.1 to 15 eq / kg, more preferably 0.5 to 10 eq / kg, especially 1 to 7 eq / kg, especially 2 to 6 eq / kg of functional or ionic groups.
- the degree of functionalization determines inter alia the total capacity of the ion exchanger resins. Geometry of the moldings
- the geometry of the shaped body depends on the requirements of the respective field of application and can be varied within wide limits due to the flexibility of the powder-based rapid prototyping method.
- the organic polymer moldings having ion exchanger or adsorber properties can have one or more channels extending through the mold body and open to the outside.
- an ion exchange medium can flow through these channels.
- Such a shaped body preferably has from two to 100, particularly preferably from 4 to 50, channels. The channels pass through the molding and are open at the entrance and exit points.
- the organic polymer shaped body having ion exchanger or adsorber properties may alternatively or additionally have a surface / volume ratio which is at least twice as large, preferably at least three times as large as the surface area / volume ratio of a sphere of the same volume , So far, organic ion exchangers were usually used in spherical form.
- the moldings according to the invention allow a substantially improved ion exchange by increasing the surface available for the exchange.
- the organic polymer moldings having ion exchanger or adsorber properties can also be in the form of a monolith through which a fluid medium can flow, the monoliths having channels which are at an angle in the range of 0 ° to 70 °, preferably 30 ° to 60 ° inclined to the main flow direction.
- the monoliths may additionally have the specified number of channels and the specified surface / volume ratio.
- the packs may preferably be embodied as multi-channel packs which have channels in which the chemical reaction preferably takes place and additionally contain channels in which the convective heat transport preferably takes place.
- the channels for the heat transport are preferably more inclined and preferably have a hydraulic diameter which is larger by a factor of 2 to 10 than the diameter of the channels for catalysis. But even monolithic structures with advantageously arranged holes and / or openings, which connect the individual channels together and thus intensify cross-mixing, have significant advantages over the existing forms. Installation of the moldings in reactors, adsorption beds, cleaning beds The moldings used according to the invention are used as reactor internals.
- the moldings used according to the invention can extend to the edge of the (column-shaped) reactor.
- the incorporation of the structured catalysts in the reactor can be carried out in various ways, for. B. in a tube (bundle) reactor by arranging the cylindrical components on top of each other, wherein not necessarily all catalyst parts have the same shape, structure, functionalization, etc., but also vertical / longitudinal segmentation are possible.
- installation may also be segmented in the transverse direction (such as with pie chunks through 4 quarter cylinders or through a number of hexagonal honeycomb-like components placed side by side).
- Each packing element may be constructed of a plurality of longitudinally oriented layers, each layer containing closely spaced channels, the channels of adjacent layers crossing each other and the channels within a packing element having side walls which are permeable or impermeable to the fluids.
- the packs are preferably either a) equipped with an edge seal to ensure a uniform flow over the entire packing cross-section to suppress the Randauerkeit, or b) preferably have a structure that has no higher porosity at the edge.
- the invention also relates to corresponding packing elements.
- Suitable forms or structures of the moldings used according to the invention are described, for example, in the following documents by the companies Montz and Sulzer.
- the structures which are described in WO 2006/056419, WO 2005/037429, WO 2005/037428, EP-A-1 362 636, WO 01/52980 and EP-B-1 251 958, respectively A-38 18 917, DE-A-32 22 892, DE-A-29 21 270, DE-A-29 21 269, CA-A-10 28 903, CN-A-1 550 258, GB-A- 1 186 647, WO 97/02880, EP-A-1 477 224, EP-A-1 308 204, EP-A-1 254 705, EP-A-1 145 761, US 6,409,378, EP-A-1 029 588, EP-A-1 022 057 and WO 98/55221.
- Another suitable molding is in the form of a cross-channel packing, the packing being composed of vertical layers consisting of corrugated or pleated metal oxides forming flow channels, the flow channels of adjacent layers crossing open, and the angle between the intersecting channels being less than about 100 ° is.
- a cross-channel package is described for example in EP-A-1 477 224, see also the angle definition there.
- packs which can be used as moldings are Sulzer BX tissue packs, Sulzer lamellar packs Mellapak, high-performance packs such as Mellapak Plus, structured packings from Sulzer (Optiflow), Montz (BSH) and Kühni (Rombopak) and packs from Emitec (www.emitec.com).
- the moldings may, for example, have the shape of the packing types A3, B1, BSH, C1 and M of Montz.
- the packing bodies are composed of corrugated webs (lamellae). The waves are inclined to the vertical and form with the adjacent lamellae intersecting flow channels.
- Monolith sizes can be chosen freely. Typical preferred monolith sizes are in the range of 0.5 to 20 cm, in particular 1 to 10 cm. It is also possible to produce larger monolith monoliths.
- the moldings of the invention are particularly preferably applicable when the available from known ion exchangers balls are too small, too large pressure losses or bypasses occur.
- the ion exchangers or adsorbers produced according to the invention can be used in a large number of applications. First, they can be used as adsorber for a variety of different ions and chemical compounds. All metal ions contained in aqueous or organic liquid systems can be bound here, for example alkali metal or alkaline earth metal ions or heavy metal ions, but also metal ions, ammonium ions or anions.
- the adsorber resins can be used for the purification of waste water.
- the geometry is chosen so that an optimal adsorption of the metal ions from the flowing through solution is achieved at an optimum throughput. The adsorption properties can change with the pH.
- the ion exchangers can also be used to reduce the water hardness.
- Anion exchangers can be used to remove unwanted anions from liquid systems, for example sulfates, nitrates, halides such as chlorides or iodides.
- Trace enrichment is possible with the help of chelating ion exchangers.
- the total salt content of solutions and waters can be determined, interfering cations or anions can be removed with cation or anion exchangers, and chromatographic separation is possible.
- the shaped bodies can be used to break up poorly soluble compounds.
- the molded article After ion exchange, the molded article is typically washed and regenerated or eluted to be usable for other applications.
- Preferred areas of application are water treatment such as water softening, desalination, partial desalination, the separation of rare earths, the separation of amino acids and their use in analytics.
- the separation of high molecular weight organic compounds or dyes is preferred.
- Other preferred applications are the purification and recovery of antibiotics, vitamins and alkaloids, the purification of enzymes and the adsorption of dyes.
- the isolation and determination of acids and alkalis as well as the removal of interfering cations and anions is a preferred field of application.
- mineral acids such as hydrochloric or sulfuric acid and alkalis, such as caustic soda and potassium hydroxide solution for the catalysis of esterifications, saponifications, condensations, rearrangements, hydrolyses, polymerizations, dehydration or Cyclizations has long been known. Due to the moldings according to the invention, products are available which, as carriers of exchangeable counterions as well as mineral acids or alkali solutions, contain catalytically active hydrogen or hydroxyl ions and likewise exhibit an immediate catalytic activity.
- strongly acidic cation exchangers in the H + form can be used. In the case of base-catalyzed reactions, strongly basic ion exchangers in the OH " form can be used.
- the present as a shaped body catalysts have many advantages over homogeneous acid or base catalysts: they can be easily separated from the reaction product, since they are present as moldings. They can be reused immediately without regeneration in most cases. Selectivity for large or small molecules is possible. Their use in continuous reaction is possible. They prevent the entrainment of foreign ions in the reaction product. They avoid interfering secondary or secondary reactions, so that the product purity increases.
- the novel moldings are particularly preferably used as catalysts in esterifications, saponifications, dehydration, hydration, dehydration, aldol condensation, polymerizations, di- and oligomerization, alkylation.
- cyanohydrin syntheses acetate formation, acylation, nitration, epoxidation, sugar inversion, rearrangement, isomerization, etherification, crosslinking.
- the reaction is preferably follows at a temperature of up to 180 0 C, in particular at most 150 0 C.
- the moldings of the invention can also be used as a guard bed to remove unwanted impurities from fluids.
- Polymer powders having a mean particle size in the range from about 0.5 .mu.m to about 450 .mu.m, particularly preferably from about 1 .mu.m to about 300 .mu.m, and very particularly preferably from 10 to 100 .mu.m, are used for producing the shaped bodies according to the invention.
- the powder may, as described, additionally contain one or more activators.
- connection between the polymer powder particles may be by treatment with a solvent, by irradiation, or by applying a reactive compound which is applied as an activator compound to produce a compound of the polymer particles.
- the functionalization of the resulting resin moldings can be carried out both in the starting powder and in the molding. In this case, for example, a sulfonation, as described above, carried out. Accordingly, the polymer is functionalized before or after shaping with acidic groups, basic groups or chelating groups.
- the invention also relates to organic polymer moldings having ion exchanger or adsorber properties which can be prepared by the process described.
- the organic moldings are preferably used as reactor internals in heterogeneously catalyzed chemical reactions or as adsorbers for adsorbing ions or chemical compounds.
- a three-dimensionally structured "cross-channel structure" of polystyrene spheres is produced according to FIG. 1.
- the length of the polymer moldings is 50 mm, the diameter is 14 mm.
- the shaping takes place as three-dimensional printing on the ProMetal RCT S15 (ProMetal RCT GmbH, 86167 Augsburg). After printing, the green compact is blown free from unbonded polystyrene beads and the polystyrene molded body is then treated with oleum to give a strongly acidic ion exchanger.
- a three-dimensionally structured "cross-channel structure" of polystyrene is produced as shown in Figure 2.
- the length is 100 mm, the diameter is 80 mm, and shaping by means of rapid prototyping takes place on the ProMetal RCT S15 (ProMetal RCT GmbH, 86167 Augsburg) Blowing is treated with oleum to produce a strong acid ion exchanger of the polystyrene moldings.
Abstract
The production of organic polymer moulded bodies with ion exchanger or ion adsorber properties is carried out by means of a powder-based rapid prototyping method, according to which a powdery organic polymer starting material or starting material mixture is applied to a base in a thin layer and mixed with a binding agent and optionally required auxiliary agents in selected areas of said layer, or irradiated or treated in another way, such that the powder is bound to these areas, both inside the layer and also to adjacent layers, and said process is repeated until the desired form of the moulded body is completely reproduced in the formed powder bed. The powder which is not bound by the binding agent is then removed such that the bound powder remains in the desired form, the starting material already comprising the ion exchanger or ion adsorber properties or, following the moulding, a corresponding functionalisation of the moulded body is carried out.
Description
lonentauscher-Formkörper und Verfahren zu ihrer Herstellung Ion exchange molded body and process for its preparation
Beschreibung Die Erfindung betrifft Verfahren zur Herstellung von organischen Polymer-Formkörpern mit lonentauscher- oder Adsorbereigenschaften, derartige Formkörper und ihre Verwendung in heterogen katalysierten chemischen Reaktionen oder als Adsorber zum Adsorbieren von Ionen oder chemischen Verbindungen.The invention relates to processes for the production of organic polymer moldings having ion exchanger or adsorber properties, moldings of this type and their use in heterogeneously catalyzed chemical reactions or as adsorbers for adsorbing ions or chemical compounds.
lonen(aus)tauscher sind Stoffe, die befähigt sind, Ionen, die an sie gebunden sind, gegen äquivalente Mengen anderer Ionen aus einer sie umgebenden Lösung auszutauschen. Dabei erfolgt ein Austausch zwischen Ionen gleichsinniger Ladung. Adsor- berharze besitzen im Gegensatz zu den lonenaustauscherharzen einen nichtionischen, jedoch je nach Aufbau mehr oder weniger polaren Charakter und adsorbie- ren nicht-stöchiometrisch sowohl Anionen, Kationen als auch ungeladene Verbindungen.Ion exchangers are substances that are capable of exchanging ions bound to them for equivalent amounts of other ions from a surrounding solution. An exchange takes place between ions of the same direction. Adsorber resins, in contrast to the ion exchange resins, have a nonionic but, depending on the structure, a more or less polar character and non-stoichiometrically adsorb both anions, cations and uncharged compounds.
Typischerweise handelt es sich bei Ionenaustauscher- und Adsorberharzen um gelför- mige oder makroretikulare, sphärische, poröse Kunstharze auf Styrol- oder Acrylharz- basis. In der Regel wird eine dreidimensionale Vernetzung, typischerweise durch Mitverwendung von Divinylbenzol, erreicht. Damit sind die Austauscherharze in der Wärme nicht verformbar, frei von Weichmachern, und die Abgabe von löslichen Anteilen ist praktisch ausgeschaltet.Typically, ion exchange resins and adsorbent resins are gel-based or macroreticular, spherical, porous synthetic resins based on styrene or acrylic resin. Typically, three-dimensional crosslinking is achieved, typically by the inclusion of divinylbenzene. Thus, the exchange resins are not deformable in the heat, free of plasticizers, and the release of soluble fractions is virtually eliminated.
Die heute gebräuchlichsten Ionenaustauscher sind Polystyrolharze, die mit Divinylbenzol (DVB) vernetzt sind und dadurch einen hohen hochmolekularen dreidimensionalen Aufbau zeigen und meist in kugeliger Form vorliegen.The most commonly used ion exchangers today are polystyrene resins which are crosslinked with divinylbenzene (DVB) and thus show a high, high-molecular, three-dimensional structure and are usually in spherical form.
Durch Sulfonierung des vernetzten Polystyrolharzes, z. B. mit Oleum, entsteht ein stark saurer Kationenaustauscher. Zur Herstellung von schwach sauren Kationenaustauschern werden anstelle des Styrols Acrylsäure-Derivate mit Divinylbenzol vernetzt. Auch Anionenaustauscher können stark basisch oder schwach basisch sein. Austauscherharze mit quaternärer Ammoniumgruppe zeigen einen stark basischen Charakter, während Harze mit tertiären Aminogruppen schwach-basische Eigenschaften aufwei- sen. Die lonentauscher werden typischerweise als Feststoffkugeln eingesetzt, wobei Durchflussreaktoren mit ihnen in Form eines Festbetts gepackt werden können.By sulfonation of the crosslinked polystyrene resin, for. As with oleum, a strong acidic cation exchanger. For the preparation of weakly acidic cation exchangers, instead of styrene, acrylic acid derivatives are cross-linked with divinylbenzene. Anion exchangers can also be strongly basic or weakly basic. Exchanger resins with a quaternary ammonium group show a strongly basic character, while resins with tertiary amino groups have weak basic properties. The ion exchangers are typically used as solid spheres, whereby flow reactors can be packed with them in the form of a fixed bed.
Damit sind die Geometrien der lonentauscher- und Adsorberharze sehr stark eingeschränkt, und sie können nur in beschränktem Umfang an die jeweiligen Anforderun- gen angepasst werden, beispielsweise bezüglich des Durchflusswiderstandes, der O- berfläche usw.
Aufgabe der vorliegenden Erfindung ist die Bereitstellung eines Verfahrens zur Herstellung von organischen Polymer-Formkörpern mit lonentauscher- oder Adsorbereigen- schaften, das die Herstellung einer Vielzahl von Formkörpergeometrien in einfacher Weise erlaubt und damit die Anpassung der lonentauscher und Adsorber an die jewei- lige Anwendung.Thus, the geometries of the ion exchanger and adsorber resins are very limited, and they can be adapted only to a limited extent to the respective requirements, for example with regard to the flow resistance, the O berberfläche etc. The object of the present invention is to provide a process for the production of organic polymer moldings with ion exchanger or adsorber properties, which allows the production of a large number of moldings geometries in a simple manner and thus the adaptation of the ion exchanger and adsorber to the respective application.
Die Aufgabe wird erfindungsgemäß gelöst durch ein Verfahren zur Herstellung von organischen Polymer-Formkörpern mit lonentauscher- oder Adsorbereigenschaften mittels eines pulverbasierten Rapid-Prototyping-Verfahrens, bei dem ein pulverförmi- ges organisches Polymer-Ausgangsmaterial oder Ausgangsmaterialgemisch in einer dünnen Schicht auf eine Unterlage aufgetragen und anschließend an ausgewählten Stellen dieser Schicht mit einem Bindemittel und eventuell erforderlichen Hilfsmitteln versetzt wird, oder bestrahlt oder auf andere Art behandelt wird, so dass das Pulver an diesen Stellen verbunden wird, wodurch das Pulver sowohl innerhalb der Schicht als auch mit den angrenzenden Schichten verbunden wird, und dieser Vorgang so oft wiederholt wird, dass die gewünschte Form des Formkörpers vollständig in dem gebildeten Pulverbett abgebildet ist, und nachfolgend das nicht durch das Bindemittel verbundene Pulver entfernt wird, so dass das verbundene Pulver in der gewünschten Form zurückbleibt, wobei das Ausgangsmaterial bereits die lonentauscher- oder Adsorberei- genschaften aufweist oder nach der Formgebung eine entsprechende Funktionalisie- rung des Formkörpers erfolgt.The object is achieved according to the invention by a process for the production of organic polymer moldings having ion exchanger or adsorber properties by means of a powder-based rapid prototyping process, in which a pulverulent organic polymer starting material or starting material mixture is applied to a substrate in a thin layer and then at selected points of that layer is added a binder and any necessary auxiliaries, or irradiated or otherwise treated, so that the powder is joined at these points, whereby the powder is bonded both within the layer and with the adjacent layers , and this process is repeated so many times that the desired shape of the shaped body is completely imaged in the powder bed formed, and subsequently the powder not bound by the binder is removed, so that the bonded powder in the desired shape z remains, wherein the starting material already exhibits the ion exchanger or adsorber properties or after shaping a corresponding functionalization of the shaped body takes place.
Die lonen(aus)tauscher oder Adsorber können dabei für eine Vielzahl von sauer oder basisch heterogen katalysierten Reaktionen als Katalysator dienen oder zur Reinigung oder Stofftrennung chemischer Gemische, z. B. zur Abwasseraufbereitung oder in der Analytik oder als Guard Bed.The ion exchanger or adsorber can serve as a catalyst for a variety of acidic or basic heterogeneously catalyzed reactions or for the purification or separation of chemical mixtures, eg. B. for wastewater treatment or in the analysis or as a guard bed.
Aufgrund der Vielfalt der Adsorberanwendungen bzw. heterogen katalysierten Reaktionen kommen verschiedene Bauformen in Betracht, welche für die jeweilige Anwendung einen optimalen Stoff- und Wärmetransport gewährleisten sollen. In Schüttungen liegt der Katalysator/Adsorber ungeordnet im Reaktor vor, in einer Packung ausgerichtet und geordnet in den Reaktor eingebaut. Am weitesten verbreitet ist die Verwendung von Katalysatoren in Form von Granulaten, Strängen, Tabletten, Ringen oder SpNt, welche als Schüttung in den Reaktor eingebracht werden. Nachteilig bei dieser Art der Verwendung ist jedoch, dass die beschriebenen Schüttungen in der Regel zu einem starken Druckverlust im Reaktor führen. Außerdem kann es leicht zur Bildung von Kanälen sowie zur Ausbildung von Zonen mit stagnierender Gas- und/oder Flüssigkeitsbewegung kommen, so dass der Katalysator nur sehr ungleichmäßig belastet wird. Daneben kann auch der erforderliche Aus- und Einbau der Formkörper aufwändig sein, beispielsweise bei Rohrbündelreaktoren mit einer großen Anzahl an Rohren.
Für bestimmte Anwendungen können Katalysatoren/Adsorber auch in Form von Monolithen mit durchgehenden Kanälen, Waben- oder Rippenstruktur eingesetzt werden, wie sie beispielsweise in DE-A-2709003 beschrieben sind. Das erfindungsgemäße Verfahren erlaubt die Herstellung organischer Polymerformkörper mit lonentauscher- oder Adsorbereigenschaften in beliebiger geeigneter Geometrie. Die Herstellung erfolgt dabei durch das Rapid-Prototyping-Verfahren, welches nachstehend erläutert ist.Due to the variety of adsorber applications or heterogeneously catalyzed reactions, various types are contemplated which should ensure optimal material and heat transport for the respective application. In beds, the catalyst / adsorber is present in disorder in the reactor, aligned in a package and installed in the orderly manner in the reactor. The most widespread is the use of catalysts in the form of granules, strands, tablets, rings or SpNt, which are introduced as a bed in the reactor. A disadvantage of this type of use, however, is that the beds described generally lead to a large pressure drop in the reactor. In addition, it can easily lead to the formation of channels and the formation of zones with stagnant gas and / or liquid movement, so that the catalyst is only very unevenly loaded. In addition, the required removal and installation of the moldings may be complex, for example in tube bundle reactors with a large number of tubes. For certain applications, catalysts / adsorbers can also be used in the form of monoliths with continuous channels, honeycomb or rib structure, as described, for example, in DE-A-2709003. The process according to the invention allows the preparation of organic polymer moldings having ion exchanger or adsorber properties in any suitable geometry. The preparation is carried out by the rapid prototyping method, which is explained below.
Fertigungsverfahren „Rapid Prototyping"Manufacturing process "Rapid Prototyping"
Dem Fachmann ist unter dem Begriff „Rapid Prototyping" (RP) ein Fertigungsverfahren für Musterbauteile bekannt, mit dem auch sehr detailreiche Werkstücke nahezu beliebiger Geometrie aus vorhandenen CAD-Daten möglichst ohne manuelle Umwege oder Formen direkt und schnell hergestellt werden können. Das Prinzip des Rapid Prototyping beruht auf dem schichtweisen Aufbau von Bauteilen unter Nutzung physikalischer und/oder chemischer Effekte. Dabei haben sich zahlreiche Verfahren wie z. B. das Selective Laser Sintering (SLS) oder die Stereolithographie (SLA) etabliert. Die Verfahren an sich unterscheiden sich in Bezug auf das Material, mit welchem die Schichten aufgebaut werden (Polymere, Harze, Papierbahnen, Pulver etc.) und die Methode, mit welcher diese Materialien verbunden werden (Laser, Heizung, Binder oder Bindersys- teme etc.). Die Verfahren sind in zahlreichen Veröffentlichungen beschrieben.The person skilled in the art is known by the term "rapid prototyping" (RP) a production method for sample components with which even highly detailed workpieces of almost any geometry can be produced directly and quickly from existing CAD data without manual detours or forms Prototyping is based on the layered build-up of components using physical and / or chemical effects, with numerous techniques such as Selective Laser Sintering (SLS) or Stereolithography (SLA) being established on the material with which the layers are built up (polymers, resins, paper webs, powders, etc.) and the method by which these materials are joined (laser, heating, binder or binder systems, etc.) Publications described.
Eines der Rapid Prototyping Verfahren ist in EP-A0431 924 beschrieben und umfasst den schichtweisen Aufbau von dreidimensionalen Bauteilen aus Pulver und Bindemittel. Nicht gebundenes Pulver wird am Ende entfernt und es bleibt das Werkstück in der gewünschten Geometrie zurück.One of the rapid prototyping methods is described in EP-A-0431 924 and comprises the layered construction of three-dimensional components made of powder and binder. Unbound powder is removed at the end and the workpiece remains in the desired geometry.
Aus WO 2004/112988 ist bekannt, dass auch mehr als ein pulverförmiges Ausgangsmaterial verwendet werden kann, und US 2005/0017394 offenbart die Verwendung von Aktivierungsmitteln, welche die Aushärtung des Binders induzieren.It is known from WO 2004/112988 that more than one powdered starting material can also be used, and US 2005/0017394 discloses the use of activating agents which induce the curing of the binder.
Die Aufgabe wird somit erfindungsgemäß gelöst durch die Verwendung von Formkörpern, welche hinsichtlich ihrer Geometrie für die jeweiligen Strömungs- und Reaktionsbedingungen im Reaktor bzw. Adsorberbett usw. optimiert sind. Entsprechend den erforderlichen Reaktionsbedingungen können die Reaktoreinbauten für die Anwendung maßgeschneidert hergestellt werden, wie es mit herkömmlichen Techniken nicht möglich ist. Der Vorteil der Rapid-Prototyping-Technologie gegenüber dieser konventionellen Fertigungstechniken besteht darin, dass theoretisch jede beliebige Geometrie, auch komplexe Bauteile beispielsweise mit Hohlräumen oder Mikrokanälen, mittels eines CAD-Datensatzes computergesteuert in das entsprechende dreidimensionale Bauteil ohne vorherige Abformung in Gussformen, ohne Ausschneiden, Ausfräsen, Schleifen etc. umgesetzt werden kann. Auf diese Weise ist die Herstellung von Reaktoreinbauten
möglich, die aufgrund ihrer optimierten Geometrie Vorteile für den Stoff- und Wärmetransport bei chemischen Reaktionen gegenüber herkömmlicher Reaktoreinbauten bieten. Diese Prozessintensivierung bringt höhere Ausbeuten, Umsätze und Selektivitäten sowie eine sichere Reaktionsführung mit sich und kann durch verringerte Appara- tegrößen oder gesenkte Katalysatormengen zu Kosteneinsparungen für bestehende oder neue Verfahren in der chemischen Industrie führen.The object is thus achieved according to the invention by the use of moldings which are optimized in terms of their geometry for the respective flow and reaction conditions in the reactor or adsorber bed, etc. According to the required reaction conditions, the reactor internals can be tailored for the application, as is not possible with conventional techniques. The advantage of rapid prototyping technology over conventional manufacturing techniques is that theoretically any geometry, even complex components, for example, with cavities or microchannels, computer-controlled in the corresponding three-dimensional component without previous molding in molds, without cutting, using a CAD data set, Milling, grinding, etc. can be implemented. In this way, the production of reactor internals possible because of their optimized geometry advantages for the mass and heat transport in chemical reactions compared to conventional reactor internals. This process intensification results in higher yields, conversions and selectivities as well as a safe reaction procedure and can lead to cost savings for existing or new processes in the chemical industry through reduced apparatus sizes or reduced amounts of catalyst.
Erfindungsgemäß werden organische Polymer-Formkörper mit lonentauscher- oder Adsorbereigenschaften hergestellt. Dabei handelt es sich in der Regel um gelförmige oder makroretikulare poröse Kunstharze. Typischerweise basieren die pulverförmigen Ausgangsmaterialien auf, gegebenenfalls vernetztem, Polystyrol, Poly(meth)acrylaten oder Poly(meth)acrylsäuren. Typischerweise basieren die Kunstharze auf Styrol- oder Acrylharzen. In der Regel wird eine dreidimensionale Vernetzung oder Verknüpfung durch vernetzende Monomere, insbesondere Divinylbenzol, erreicht. Damit sind die Austauscherharze in der Wärme nicht verformbar und gleichzeitig frei von Weichmachern. Die Abgabe von löslichen Anteilen ist praktisch ausgeschaltet. Es können aber auch unvernetzte Polymere eingesetzt werden, die sich nachträglich durch Einbringen geeigneter Vernetzer oder durch Bestrahlung z. B. mit Elektronenstrahlung im fertigen Formkörper vernetzen lassen. Vernetzer können bereits in das Polymer eingearbeitet sein und nach der Formgebung zum Aushärten gebracht werden. So lassen sich z. B. Silane als Vernetzer in das Polymer einbringen.According to the invention, organic polymer moldings having ion exchanger or adsorber properties are produced. These are usually gel or macroreticular porous resins. Typically, the powdery starting materials are based on optionally crosslinked polystyrene, poly (meth) acrylates or poly (meth) acrylic acids. Typically, the synthetic resins are based on styrene or acrylic resins. As a rule, a three-dimensional crosslinking or linking by crosslinking monomers, in particular divinylbenzene, is achieved. Thus, the exchange resins are not deformable in the heat and at the same time free of plasticizers. The release of soluble fractions is virtually eliminated. However, it is also possible to use uncrosslinked polymers which are subsequently oxidized by introducing suitable crosslinkers or by irradiation, for example. B. can be crosslinked with electron radiation in the finished molding. Crosslinkers can already be incorporated in the polymer and be brought to harden after shaping. So can be z. B. introduce silanes as crosslinkers in the polymer.
Geeignete Molekulargewichte und die Herstellung der Polymerharze, insbesondere Polystyrolharze oder Polyacrylharze, ist dem Fachmann bekannt. Die im erfindungs- gemäß eingesetzten Rapid-Prototyping-Verfahren eingesetzten Harze unterscheiden sich in dieser Hinsicht nicht von den typischen Ionenaustauscher- oder Adsorberhar- zen.Suitable molecular weights and the preparation of the polymer resins, in particular polystyrene resins or polyacrylic resins, is known to the person skilled in the art. The resins used in the rapid prototyping process according to the invention do not differ in this respect from the typical ion exchanger or adsorber resins.
Pulverformpowder form
In dem erfindungsgemäß zu verwendenden Rapid-Prototyping-Verfahren werden pul- verförmige Ausgangsmaterialien eingesetzt, die mit oder ohne Bindemittel eingesetzt werden können. Die weiteren Ausführungen gelten für beide Varianten. Es können sowohl monodisperse wie auch polydisperse Pulver eingesetzt werden. Dabei können mit feineren Teilchen naturgemäß dünnere Schichten realisiert werden, wodurch für den Aufbau eines gewünschten Formkörpers eine größere Anzahl von Schichten und damit eine höhere räumliche Auflösung möglich ist als mit gröberen Teilchen. Bevorzugt werden Pulver mit einer mittleren Teilchengröße im Bereich von etwa 0,5 μm bis etwa 450 μm, besonders bevorzugt von etwa 1 μm bis etwa 300 μm und ganz beson- ders bevorzugt von 10 bis 100 μm. Das einzusetzende Pulver kann, wenn dies erforderlich ist, auch gezielt vorbehandelt werden, z. B. durch mindestens einen der Schritte
Kompaktieren, Mischen, Granulieren, Sieben, Agglomerieren oder Mahlen auf eine bestimmte Teilchengrößenfraktion oder durch Einbringen von Additiven, wie Vernetzern, Oberflächenbehandlung zur Verbesserung der Adhäsion beim Binden, z. B. durch Plasma-Behandlung, Corona-Behandlung, Säurebehandlung (HNO3, H2SO4), Ozon, UV etc. oder auch Einbringen von Rußen zur besseren Aufnahme von IR- Strahlung. Geeignete Polymermaterialien sind beispielsweise in WO 2005/010087, WO 03/106148, EP-A-O 995 763 und US 7,049.363 beschrieben.Pulp-shaped starting materials which can be used with or without a binder are used in the rapid prototyping method to be used according to the invention. The other versions apply to both variants. Both monodisperse and polydisperse powders can be used. Naturally, thinner layers can be realized with finer particles, whereby a larger number of layers and thus a higher spatial resolution is possible for the construction of a desired shaped body than with coarser particles. Preference is given to powders having an average particle size in the range from about 0.5 μm to about 450 μm, particularly preferably from about 1 μm to about 300 μm, and very particularly preferably from 10 to 100 μm. The powder to be used, if necessary, can also be specifically pretreated, for. By at least one of the steps Compacting, mixing, granulating, sieving, agglomerating or milling to a particular particle size fraction or by incorporating additives such as crosslinkers, surface treatment to improve adhesion in binding, e.g. As by plasma treatment, corona treatment, acid treatment (HNO 3 , H 2 SO 4 ), ozone, UV, etc. or introduction of carbon blacks for better absorption of IR radiation. Suitable polymer materials are described, for example, in WO 2005/010087, WO 03/106148, EP-AO 995 763 and US Pat. No. 7,049,363.
Herstellungmanufacturing
Das erfindungsgemäß zu verwendende Rapid-Prototyping-Verfahren besteht bekanntermaßen aus den folgenden Schritten, die so oft zu wiederholen sind, bis der gewünschte Formkörper vollständig aus den einzelnen Schichten aufgebaut ist. Ein pul- verförmiges Ausgangsmaterial oder Ausgangsmaterialgemisch wird in einer dünnen Schicht auf eine Unterlage aufgetragen und anschließend an ausgewählten Stellen dieser Schicht mit einem Bindemittel und eventuell erforderlichen Hilfsmitteln versetzt, oder bestrahlt oder auf andere Art behandelt, so dass das Pulver an diesen Stellen verbunden wird, wodurch das Pulver sowohl innerhalb der Schicht als auch mit den angrenzenden Schichten verbunden wird. Nachdem dieser Vorgang so oft wiederholt wurde, dass die gewünschte Form des Werkstücks vollständig in dem gebildeten Pulverbett abgebildet ist, wird das nicht durch das Bindemittel verbundene Pulver entfernt, und es bleibt das verbundene Pulver in der gewünschten Form zurück.As is known, the rapid prototyping method to be used according to the invention consists of the following steps, which are repeated until the desired shaped body is completely composed of the individual layers. A powdery starting material or starting material mixture is applied in a thin layer on a substrate and then added at selected points of this layer with a binder and any necessary auxiliaries, or irradiated or otherwise treated, so that the powder is connected at these locations, whereby the powder is combined both within the layer and with the adjacent layers. After this process has been repeated so many times that the desired shape of the workpiece is completely imaged in the powder bed formed, the powder not bound by the binder is removed and the bonded powder remains in the desired shape.
Zur Anwendung können insbesondere das SoluPor®-Verfahren oder das PolyPor®- Verfahren kommen. Beim SoluPor®-Verfahren werden die Polymerpartikel an den gewünschten Stellen rein physikalisch verklebt. Das Lösemittel wird nach dem schichtweisen Aufbau der Form wieder ausgetrieben. Beim PolyPor®-Verfahren werden die Polymerpartikel an den gewünschten Stellen von einem Reaktivlöser angelöst, der anschließend durch einen freigesetzten Initiator polymerisiert. Das Restmonomer wird ausgetrieben.To apply the Solupor ® process or PolyPor ® can in particular - Method arrive. In the SoluPor ® process, the polymer particles are physically bonded at the desired locations. The solvent is expelled again after the layered structure of the mold. When PolyPor ® process, the polymer particles in the desired areas are dissolved by a reactive solvent, which is then polymerized by a released initiator. The residual monomer is expelled.
Bindemittel und HilfsmittelBinders and auxiliaries
Als Bindemittel kann generell jedes Material verwendet werden, welches geeignet ist, benachbarte Partikel des pulverförmigen Ausgangsmaterials fest miteinander zu verbinden. Bevorzugt sind hierbei organische Materialien, besonders solche, die sich vernetzen lassen oder auf andere Art und Weise eine kovalente Bindung miteinander eingehen können, beispielsweise Phenolharze, Polyisocyanate, Polyurethane, Epoxyhar- ze, Furanharze, Harnstoff-Aldehyd-Kondensate, Furfurylalkohol, Acrylsäure- und Acry- latdispersionen, polymere Alkohole, Peroxide, Kohlenhydrate, Zucker, Zuckeralkohole, Proteine, Stärke, Carboxymethylcellulose, Xanthan, Gelatine, Polyethylenglycol, PoIy-
vinylalkohole, Polyvinylpyrrolidon oder Mischungen davon. Die Bindemittel werden flüssig entweder in gelöster oder dispergierter Form eingesetzt, wobei sowohl organische Lösungsmittel (z. B. Toluol) als auch Wasser verwendet werden können. Gemäß einer Ausführungsform der Erfindung ist das Bindemittel ein Lösungsmittel, das das Polymer-Ausgangsmaterial zumindest oberflächlich anlöst und damit eine Verbindung zwischen den Pulverteilchen herstellt. Die angelösten Polymerteilchen verkleben miteinander, so dass eine feste Verbindung entsteht. Gemäß einer anderen Ausführungsform enthält das pulverförmige Ausgangsmaterial eine reaktionsfähige Verbindung, die mit einer aufgetragenen Aktivatorverbindung zur Reaktion gebracht wird und damit eine Verbindung der Polymer-Ausgangsmaterialien herstellt. Die reaktionsfähige Verbindung kann beispielsweise ein Monomer sein, das auch in der Struktur des Polymer- Ausgangsmaterials enthalten ist. Es kann sich damit beispielsweise um Styrol, Acrylate oder Acrylsäure handeln.In general, any material suitable for bonding together adjacent particles of the powdery starting material can be used as the binder. Preference is given here to organic materials, especially those which can be crosslinked or otherwise covalent bond with each other, for example, phenolic resins, polyisocyanates, polyurethanes, epoxy resins, furan resins, urea-aldehyde condensates, furfuryl alcohol, acrylic acid and Acrylate dispersions, polymeric alcohols, peroxides, carbohydrates, sugars, sugar alcohols, proteins, starch, carboxymethylcellulose, xanthan, gelatin, polyethylene glycol, poly- vinyl alcohols, polyvinylpyrrolidone or mixtures thereof. The binders are used in liquid form either in dissolved or dispersed form, whereby both organic solvents (eg toluene) and water can be used. According to one embodiment of the invention, the binder is a solvent which at least superficially dissolves the polymer starting material and thus produces a connection between the powder particles. The dissolved polymer particles stick together so that a firm connection is formed. In another embodiment, the powdered starting material contains a reactive compound which is reacted with an applied activator compound to produce a compound of the polymer starting materials. The reactive compound may be, for example, a monomer which is also included in the structure of the polymer starting material. This may be, for example, styrene, acrylates or acrylic acid.
Die Anwendung der Bindemittel erfolgt beispielsweise über eine Düse, einen Druckkopf oder eine andere Apparatur, die eine genaue Platzierung möglichst kleiner Tropfen des Bindemittels auf der Pulverschicht erlaubt. Das Verhältnis von Pulvermenge zu Bindemittelmenge variiert in Abhängigkeit von den verwendeten Substanzen und liegt in der Regel im Bereich von etwa 40 : 60 bis etwa 99 : 1 Gewichtsteilen, bevorzugt im Be- reich von etwa 70 : 30 bis etwa 99 : 1 Gewichtsteilen, besonders bevorzugt im Bereich von etwa 85 : 15 bis etwa 98 : 2 Gewichtsteilen.The application of the binders takes place, for example, via a nozzle, a printhead or another apparatus which permits precise placement of the smallest possible drops of the binder on the powder layer. The ratio of powder amount to binder amount varies depending on the substances used, and is usually in the range of about 40:60 to about 99: 1 parts by weight, preferably in the range of about 70:30 to about 99: 1 parts by weight, especially preferably in the range of about 85:15 to about 98: 2 parts by weight.
Des Weiteren können gegebenenfalls ein oder mehrere Hilfsmittel zum Einsatz kommen, die beispielsweise einen Einfluss auf die Vernetzung der Bindemittel haben kön- nen oder als Härter dienen. Die Hilfsmittel können separat appliziert werden, sie können aber gegebenenfalls auch dem Pulverbett und/oder dem Bindemittel bzw. der Bindemittel-Lösung zugesetzt werden. Zudem kann die Bindung durch Strahlungsbehandlung, z. B. im UV- oder IR-Bereich, verbessert werden, siehe auch die vorstehende Beschreibung der Oberflächenbehandlung.Furthermore, optionally one or more auxiliaries may be used which may, for example, have an influence on the crosslinking of the binders or serve as hardeners. The adjuvants can be applied separately, but if appropriate they can also be added to the powder bed and / or the binder or the binder solution. In addition, the bond by radiation treatment, for. In the UV or IR range, see also the above description of the surface treatment.
An die Formgebung kann sich noch eine Wärmebehandlung anschließen, um eine bessere Vernetzung oder Umsetzung der Bindemittel zu erhalten. Das polymere Ausgangsmaterial kann erfindungsgemäß vor oder nach der Formgebung mit sauren Gruppen, basischen Gruppen oder chelatisierenden Gruppen funktionalisiert werden. Die Funktionalisierung erfolgt dabei in gleicher Weise, wie sie bei der Herstellung von Ionenaustauscher- oder Adsorberharzen erfolgt. Damit ist es möglich, fertige lonenaus- tauscherharzpulver oder Adsorberharzpulver im Rapid-Prototyping-Verfahren einzusetzen, oder zunächst noch nicht funktionalisierte Harze werden eingesetzt, und die hergestellten Formkörper werden nachfolgend funktionalisiert.
Stark saure lonentauscher basieren typischerweise auf Polystyrol und werden mit Schwefelsäure (Oleum) sulfoniert, so dass im Formkörper Sulfonsäuregruppen an der Phenylgruppe gebunden, vorliegen. Auch die Umsetzung mit Perfluorsulfonsäure ist möglich, vergleiche Applied Catalysis A: General 221 (2001 ) 45 - 62. Schwächer saure lonentauscher basieren typischerweise auf Polyacrylaten, die freie Carboxylgruppen aufweisen. Diese können durch basische Hydrolyse der Estergruppen erhalten werden. Ferner können auch Phenol-Formaldehyd-Gele eingesetzt werden.The shaping may be followed by a heat treatment in order to obtain better crosslinking or conversion of the binder. The polymeric starting material according to the invention can be functionalized before or after shaping with acidic groups, basic groups or chelating groups. The functionalization takes place in the same way as in the production of ion exchange or adsorber resins. It is thus possible to use ready-to-use ion exchange resin powders or adsorber resin powders in the rapid prototyping process, or initially unfunctionalized resins are used, and the molded articles produced are subsequently functionalized. Strongly acidic ion exchangers are typically based on polystyrene and are sulfonated with sulfuric acid (oleum), so that sulfonic acid groups are bound to the phenyl group in the molded body. The reaction with perfluorosulfonic acid is also possible, cf. Applied Catalysis A: General 221 (2001) 45-62. Low-acid ion exchangers are typically based on polyacrylates which have free carboxyl groups. These can be obtained by basic hydrolysis of the ester groups. Furthermore, phenol-formaldehyde gels can also be used.
Basische lonentauscher können in stark basische und schwach basische lonentau- scherharze unterschieden werden, je nach vorhandenen Festionen. Austauscherharze mit quaternärer Ammoniumgruppe zeigen einen stark basischen Charakter, während die Harze mit tertiären Aminogruppen schwach basische Eigenschaften aufweisen. Beispielsweise geeignete basische Gruppen sind -N+(CH3)2(CH2OH), -N+(CH3)3, -N(R)2 mit R = Alkyl wie -N(CH3)2, -NH-CH2-CH2-NH2. Basische lonentauscher können z. B. ausgehend von Polystyrol durch Umsetzung mit Methyl-Chlormethyl-ether und nachfolgende Umsetzung der erhaltenen -CH2CI-Gruppen mit sekundären oder tertiären Alkylaminen erhalten werden. Es ist auch möglich, in den lonentauschern Thio- harnstoffgruppen oder Metallionen bindende oder chelatisierende Gruppen vorzusehen. Allgemein wird mit den aktiven Zentren das Polymer modifiziert, und so werden die Adsorptions- oder lonentauschereigenschaften eingestellt.Basic ion exchangers can be distinguished into strongly basic and weakly basic ion exchanger resins, depending on the presence of the fixed ions. Exchanger resins with a quaternary ammonium group show a strongly basic character, while the resins with tertiary amino groups have weakly basic properties. For example, suitable basic groups are -N + (CH 3 ) 2 (CH 2 OH), -N + (CH 3 ) 3 , -N (R) 2 with R = alkyl such as -N (CH 3 ) 2 , -NH- CH 2 -CH 2 -NH 2 . Basic ion exchangers can, for. B. starting from polystyrene by reaction with methyl chloromethyl ether and subsequent reaction of the obtained -CH 2 CI groups with secondary or tertiary alkylamines. It is also possible to provide thionourea groups or metal ion-binding or chelating groups in the ion exchangers. Generally, with the active sites, the polymer is modified, and thus the adsorption or ion exchange properties are adjusted.
Die organischen Polymere weisen vorzugsweise Oberflächen im Bereich von 5 bis 200 m2/g, besonders bevorzugt 10 bis 100 m2/g, insbesondere 20 bis 70 m2/g auf. Der mittlere Porendurchmesser beträgt vorzugsweise 2 bis 200 nm, insbesondere 10 bis 100 nm. Bei einer Funktionalisierung liegen vorzugsweise 0,1 bis 15 eq/kg, besonders bevorzugt 0,5 bis 10 eq/kg, insbesondere 1 bis 7 eq/kg, speziell 2 bis 6 eq/kg an funktionellen oder ionischen Gruppen vor.The organic polymers preferably have surface areas in the range from 5 to 200 m 2 / g, more preferably 10 to 100 m 2 / g, in particular 20 to 70 m 2 / g. The average pore diameter is preferably 2 to 200 nm, in particular 10 to 100 nm. In a functionalization are preferably 0.1 to 15 eq / kg, more preferably 0.5 to 10 eq / kg, especially 1 to 7 eq / kg, especially 2 to 6 eq / kg of functional or ionic groups.
Durch den Funktionalisierungsgrad wird unter anderem die Gesamtkapazität der lonen- tauscherharze bestimmt. Geometrie der FormkörperThe degree of functionalization determines inter alia the total capacity of the ion exchanger resins. Geometry of the moldings
Die Geometrie der Formkörper richtet sich nach den Erfordernissen des jeweiligen Anwendungsgebiets und kann aufgrund der Flexibilität des pulverbasierten Rapid- Prototyping-Verfahrens in weiten Bereichen variiert werden. Beispielsweise können die organischen Polymer-Formkörper mit lonentauscher- oder Adsorber-Eigenschaften einen oder mehrere durch den Formkörper verlaufende und nach außen offene Kanäle aufweisen. Durch diese Kanäle kann beispielsweise ein lonentauschermedium strömen. Bevorzugt weist ein derartiger Formkörper zwei bis 100, besonders bevorzugt 4 bis 50 Kanäle auf. Die Kanäle durchziehen den Formkörper und sind an der Eintrittsund Austrittsstelle offen.
Der organische Polymer-Formkörper mit lonentauscher- oder Adsorber-Eigenschaften kann alternativ oder zusätzlich ein Oberflächen/Volumen-Verhältnis aufweisen, das mindestens doppelt so groß, bevorzugt mindestens dreimal so groß ist wie das Ober- flächen/Volumen-Verhältnis einer Kugel mit gleichem Volumen. Bisher wurden organische lonentauscher in der Regel in Kugelform eingesetzt. Die erfindungsgemäßen Formkörper erlauben einen wesentlich verbesserten lonenaustausch durch Erhöhung der für den Austausch zur Verfügung stehenden Oberfläche.The geometry of the shaped body depends on the requirements of the respective field of application and can be varied within wide limits due to the flexibility of the powder-based rapid prototyping method. For example, the organic polymer moldings having ion exchanger or adsorber properties can have one or more channels extending through the mold body and open to the outside. For example, an ion exchange medium can flow through these channels. Such a shaped body preferably has from two to 100, particularly preferably from 4 to 50, channels. The channels pass through the molding and are open at the entrance and exit points. The organic polymer shaped body having ion exchanger or adsorber properties may alternatively or additionally have a surface / volume ratio which is at least twice as large, preferably at least three times as large as the surface area / volume ratio of a sphere of the same volume , So far, organic ion exchangers were usually used in spherical form. The moldings according to the invention allow a substantially improved ion exchange by increasing the surface available for the exchange.
Die organischen Polymer-Formkörper mit lonentauscher- oder Adsorbereigenschaften können auch die Form eines Monolithen aufweisen, der von einem fluiden Medium durchströmt werden kann, wobei die Monolithen Kanäle aufweisen, die in einem Winkel im Bereich von 0 ° bis 70 °, bevorzugt 30 ° bis 60 ° gegen die Hauptströmungsrichtung geneigt sind. Die Monolithen können dabei zusätzlich die angegebene Anzahl an Ka- nälen und das angegebene Oberflächen/Volumen-Verhältnis aufweisen.The organic polymer moldings having ion exchanger or adsorber properties can also be in the form of a monolith through which a fluid medium can flow, the monoliths having channels which are at an angle in the range of 0 ° to 70 °, preferably 30 ° to 60 ° inclined to the main flow direction. The monoliths may additionally have the specified number of channels and the specified surface / volume ratio.
Bevorzugt ist eine Form anzustreben, bei deren Verwendung als Adsorber oder Katalysator in heterogen katalysierten chemischen Reaktionen es zu einer möglichst hohen Quervermischung sowie zu einem möglichst geringen Druckverlust im Reaktor, außer- dem zu einer nur geringen Rückvermischung entgegen der Strömungsrichtung und zu einem ausreichend großen Massen- und Wärmetransport kommt, einschließlich des Wärmetransports nach außen. Vorteilhafte Formen können sich beispielsweise an der aus der Destillationstechnik bekannten Packungen in Kreuzkanalstrukturen orientieren, die dem Fachmann bekannt sind und von Herstellern wie Montz, Sulzer oder Kühni angeboten werden. Die Kanäle können eine beliebige Querschnittsform aufweisen, wobei quadratische, rechteckige oder runde Querschnittsformen bevorzugt sind.It is preferable to aim for a form which, when used as an adsorber or catalyst in heterogeneously catalyzed chemical reactions, leads to the highest possible cross-mixing and to the lowest possible pressure loss in the reactor, and also to only little backmixing against the flow direction and to a sufficiently large mass - And heat transport comes, including the heat transport to the outside. Advantageous forms can be based, for example, on the packings known from the distillation technology in cross-channel structures which are known to the person skilled in the art and are offered by manufacturers such as Montz, Sulzer or Kühni. The channels may have any cross-sectional shape, with square, rectangular or circular cross-sectional shapes being preferred.
Die Packungen können bevorzugt als Mehrkanalpackungen ausgeführt sein, die Kanäle aufweisen, in denen bevorzugt die chemische Reaktion stattfindet, und zusätzlich Kanäle beinhalten, in denen bevorzugt der konvektive Wärmetransport stattfindet. Die Kanäle für den Wärmetransport sind bevorzugt stärker geneigt und weisen bevorzugt einen hydraulischen Durchmesser auf, der um den Faktor 2 - 10 größer ist als der Durchmesser der Kanäle für die Katalyse. Aber auch monolithische Strukturen mit vorteilhaft angeordneten Löchern und/oder Öffnungen, welche die einzelnen Kanäle miteinander verbinden und somit eine Quervermischung intensivieren, haben gegenüber den existierenden Formen entscheidende Vorteile. Einbau der Formkörper in Reaktoren, Adsorptionsbetten, Reinigungsbetten
Die erfindungsgemäß verwendeten Formkörper werden als Reaktoreinbauten verwendet. Dabei können sie in unausgerichteter Form als Schüttung oder in räumlich ausgerichteter Form, beispielsweise als Packung in einem kolonnenförmigen Reaktor vorliegen, wie es prinzipiell von Monolithen bekannt ist. Dabei können die erfindungsgemäß eingesetzten Formkörper bis an den Rand des (kolonnenförmigen) Reaktors reichen. Der Einbau der strukturierten Katalysatoren in den Reaktor kann auf verschiedene Weise erfolgen, z. B. in einen Rohr(bündel)reaktor durch Anordnen der zylinderförmigen Bauteile übereinander, wobei nicht notwendigerweise alle Katalysatorteile die gleiche Form, Struktur, Funktionalisierung etc. aufweisen müssen, sondern auch vertika- le/longitudinale Segmentierungen möglich sind. Außerdem kann der Einbau auch segmentiert in der Querrichtung erfolgen (wie z. B. bei Tortenstückchen durch 4 Viertel- Zylinder oder durch eine Anzahl von sechseckigen, honigwabenähnlichen Bauteilen, die man nebeneinander anordnet).The packs may preferably be embodied as multi-channel packs which have channels in which the chemical reaction preferably takes place and additionally contain channels in which the convective heat transport preferably takes place. The channels for the heat transport are preferably more inclined and preferably have a hydraulic diameter which is larger by a factor of 2 to 10 than the diameter of the channels for catalysis. But even monolithic structures with advantageously arranged holes and / or openings, which connect the individual channels together and thus intensify cross-mixing, have significant advantages over the existing forms. Installation of the moldings in reactors, adsorption beds, cleaning beds The moldings used according to the invention are used as reactor internals. They may be in unoriented form as a bed or in spatially oriented form, for example as a packing in a column-shaped reactor, as is known in principle from monoliths. In this case, the moldings used according to the invention can extend to the edge of the (column-shaped) reactor. The incorporation of the structured catalysts in the reactor can be carried out in various ways, for. B. in a tube (bundle) reactor by arranging the cylindrical components on top of each other, wherein not necessarily all catalyst parts have the same shape, structure, functionalization, etc., but also vertical / longitudinal segmentation are possible. In addition, installation may also be segmented in the transverse direction (such as with pie chunks through 4 quarter cylinders or through a number of hexagonal honeycomb-like components placed side by side).
Jedes Packungselement kann aus einer Mehrzahl von longitudinal ausgerichteten Lagen aufgebaut sein, wobei jede Lage dicht angeordnete Kanäle enthält, die Kanäle benachbarter Lagen sich kreuzen und die Kanäle innerhalb eines Packungselements seitliche Wände aufweisen, die für die Fluide durchlässig oder undurchlässig sind.Each packing element may be constructed of a plurality of longitudinally oriented layers, each layer containing closely spaced channels, the channels of adjacent layers crossing each other and the channels within a packing element having side walls which are permeable or impermeable to the fluids.
Die Packungen werden bevorzugt zur Unterdrückung der Randgängigkeit entweder a) mit einer Randabdichtung ausgestattet, um eine gleichmäßige Durchströmung über den gesamten Packungsquerschnitt zu gewährleisten, oder b) besitzen bevorzugt eine Struktur, die keine höhere Porosität am Rand aufweist.The packs are preferably either a) equipped with an edge seal to ensure a uniform flow over the entire packing cross-section to suppress the Randgängigkeit, or b) preferably have a structure that has no higher porosity at the edge.
Die Erfindung betrifft auch entsprechende Packungselemente.The invention also relates to corresponding packing elements.
Beispiele für GeometrieExamples of geometry
Geeignete Formen bzw. Strukturen der erfindungsgemäß eingesetzten Formkörper sind beispielsweise in folgenden Schriften von den Firmen Montz und Sulzer beschrieben . Beispielsweise sind die Stru kturen zu nen nen , die in WO 2006/056419, WO 2005/037429, WO 2005/037428, EP-A-1 362 636, WO 01/52980 bzw. EP-B-1 251 958, DE-A-38 18 917, DE-A-32 22 892, DE-A-29 21 270, DE-A-29 21 269, CA-A-10 28 903, CN-A-1 550 258, GB-A-1 186 647, WO 97/02880, EP-A-1 477 224, EP-A-1 308 204, EP-A-1 254 705, EP-A-1 145 761 , US 6,409,378, EP-A-1 029 588, EP-A-1 022 057 und WO 98/55221 beschrieben sind. Ein weiterer geeigneter Formkörper liegt in Form einer Kreuzkanalpackung vor, wobei die Packung aus vertikalen Lagen zusammengesetzt ist, die aus gewellten oder plissierten, Strömungskanäle bildenden Metalloxiden bestehen, die Strömungskanäle benachbarter Lagen sich offen kreuzen und der Winkel zwischen den sich kreuzenden Kanälen kleiner als rund 100 °
ist. Eine derartige Kreuzkanalpackung ist beispielsweise in der EP-A-1 477 224 beschrieben, siehe auch die dortige Winkeldefinition.Suitable forms or structures of the moldings used according to the invention are described, for example, in the following documents by the companies Montz and Sulzer. For example, the structures which are described in WO 2006/056419, WO 2005/037429, WO 2005/037428, EP-A-1 362 636, WO 01/52980 and EP-B-1 251 958, respectively A-38 18 917, DE-A-32 22 892, DE-A-29 21 270, DE-A-29 21 269, CA-A-10 28 903, CN-A-1 550 258, GB-A- 1 186 647, WO 97/02880, EP-A-1 477 224, EP-A-1 308 204, EP-A-1 254 705, EP-A-1 145 761, US 6,409,378, EP-A-1 029 588, EP-A-1 022 057 and WO 98/55221. Another suitable molding is in the form of a cross-channel packing, the packing being composed of vertical layers consisting of corrugated or pleated metal oxides forming flow channels, the flow channels of adjacent layers crossing open, and the angle between the intersecting channels being less than about 100 ° is. Such a cross-channel package is described for example in EP-A-1 477 224, see also the angle definition there.
Beispiele der als Formkörper verwendbarer Packungen sind Sulzer Gewebepackungen BX, Sulzer Lamellenpackungen Mellapak, Hochleistungspackungen wie Mellapak Plus, Strukturpackungen von Sulzer (Optiflow), Montz (BSH) und Kühni (Rombopak) sowie Packungen von Emitec (www.emitec.com).Examples of packs which can be used as moldings are Sulzer BX tissue packs, Sulzer lamellar packs Mellapak, high-performance packs such as Mellapak Plus, structured packings from Sulzer (Optiflow), Montz (BSH) and Kühni (Rombopak) and packs from Emitec (www.emitec.com).
Die Formkörper können beispielsweise die Form der Packungstypen A3, B1 , BSH, C1 und M von Montz aufweisen. Dabei sind die Packungskörper aus gewellten Bahnen (Lamellen) zusammengesetzt. Die Wellen verlaufen geneigt zur Vertikalen und bilden mit den benachbarten Lamellen sich kreuzende Strömungskanäle.The moldings may, for example, have the shape of the packing types A3, B1, BSH, C1 and M of Montz. The packing bodies are composed of corrugated webs (lamellae). The waves are inclined to the vertical and form with the adjacent lamellae intersecting flow channels.
Monolithgrößen können frei gewählt werden. Typische bevorzugte Monolithgrößen liegen im Bereich von 0,5 bis 20 cm, insbesondere 1 bis 10 cm. Es ist auch möglich, größere Monolithe aus Monolithsegmenten herzustellen.Monolith sizes can be chosen freely. Typical preferred monolith sizes are in the range of 0.5 to 20 cm, in particular 1 to 10 cm. It is also possible to produce larger monolith monoliths.
Die erfindungsgemäßen Formkörper sind insbesondere dann bevorzugt anwendbar, wenn die von bekannten lonentauschern verfügbaren Kugeln zu klein sind, zu große Druckverluste oder Bypässe auftreten.The moldings of the invention are particularly preferably applicable when the available from known ion exchangers balls are too small, too large pressure losses or bypasses occur.
Anwendungenapplications
Die erfindungsgemäß hergestellten lonen(aus)tauscher oder Adsorber können bei ei- ner Vielzahl von Anwendungen eingesetzt werden. Zum einen können sie als Adsorber für eine Vielzahl unterschiedlicher Ionen und chemischen Verbindungen eingesetzt werden. Es können dabei alle in wässrigen oder organischen flüssigen Systemen enthaltenen Metallionen gebunden werden, beispielsweise Alkali- oder Erdalkali- Metallionen oder Schwermetallionen, aber auch Metallionen, Ammoniumionen oder Anionen. Die Adsorberharze können dabei zur Reinigung von Abwässern eingesetzt werden. Die Geometrie wird dabei so gewählt, dass eine optimale Adsorption der Metallionen aus der durchströmenden Lösung bei einem optimalen Durchsatz erreicht wird. Die Adsorptionseigenschaften können sich dabei mit dem pH-Wert ändern.The ion exchangers or adsorbers produced according to the invention can be used in a large number of applications. First, they can be used as adsorber for a variety of different ions and chemical compounds. All metal ions contained in aqueous or organic liquid systems can be bound here, for example alkali metal or alkaline earth metal ions or heavy metal ions, but also metal ions, ammonium ions or anions. The adsorber resins can be used for the purification of waste water. The geometry is chosen so that an optimal adsorption of the metal ions from the flowing through solution is achieved at an optimum throughput. The adsorption properties can change with the pH.
Die lonentauscher können auch zur Verminderung der Wasserhärte eingesetzt werden. Anionentauscher können eingesetzt werden, um unerwünschte Anionen aus flüssigen Systemen zu entfernen, beispielsweise Sulfate, Nitrate, Halogenide wie Chloride oder lodide.The ion exchangers can also be used to reduce the water hardness. Anion exchangers can be used to remove unwanted anions from liquid systems, for example sulfates, nitrates, halides such as chlorides or iodides.
Eine Spurenanreicherung ist mit Hilfe chelatisierender lonentauscher möglich. Der Gesamtsalzgehalt von Lösungen und Wässern kann bestimmt werden, störende Kationen
oder Anionen können mit Kationen- bzw. Anionentauschern entfernt werden, und eine chromatographische Trennung ist möglich. Zudem können die Formkörper zum Auf- schluss von schwer löslichen Verbindungen eingesetzt werden.Trace enrichment is possible with the help of chelating ion exchangers. The total salt content of solutions and waters can be determined, interfering cations or anions can be removed with cation or anion exchangers, and chromatographic separation is possible. In addition, the shaped bodies can be used to break up poorly soluble compounds.
Nach dem lonenaustausch wird der Formkörper typischerweise gewaschen und regeneriert oder eluiert, um für weitere Anwendungen einsetzbar zu sein.After ion exchange, the molded article is typically washed and regenerated or eluted to be usable for other applications.
Bevorzugte Anwendungsgebiete sind die Wasseraufbereitung wie Wasserenthärtung, Entsalzung, Teilentsalzung, die Trennung seltener Erden, die Trennung von Aminosäu- ren und der Einsatz in der Analytik. Auch die Abtrennung hochmolekularer organischer Verbindungen oder Farbstoffe ist bevorzugt. Weitere bevorzugte Anwendungsgebiete sind die Reinigung und Gewinnung von Antibiotika, Vitaminen und Alkaloiden, die Reinigung von Enzymen und die Adsorption von Farbstoffen. Auch die Isolierung und Bestimmung von Säuren und Alkalien sowie die Entfernung störender Kationen und Anio- nen ist ein bevorzugtes Anwendungsgebiet.Preferred areas of application are water treatment such as water softening, desalination, partial desalination, the separation of rare earths, the separation of amino acids and their use in analytics. The separation of high molecular weight organic compounds or dyes is preferred. Other preferred applications are the purification and recovery of antibiotics, vitamins and alkaloids, the purification of enzymes and the adsorption of dyes. The isolation and determination of acids and alkalis as well as the removal of interfering cations and anions is a preferred field of application.
Ein Hauptanwendungsgebiet der lonentauscher ist die Katalyse.One main field of application of ion exchangers is catalysis.
Die Verwendung von Mineralsäuren wie Salz- oder Schwefelsäure und Laugen, wie Natronlauge und Kalilauge für die Katalyse von Veresterungen, Verseifungen, Kondensationen, Umlagerungen, Hydrolysen, Polymerisationen, Dehydratisierungen oder Cyc- lisierungen ist seit langem bekannt. Durch die erfindungsgemäßen Formkörper stehen Produkte zur Verfügung, die als Träger austauschfähiger Gegenionen ebenso wie Mineralsäuren oder Alkalilaugen katalytisch wirksame Wasserstoff- oder Hydroxylionen enthalten und ebenfalls eine unmittelbare katalytische Wirkung zeigen. So können für sauer katalysierte Reaktionen anstelle von Mineralsäuren stark saure Kationentau- scher in der H+-Form verwendet werden. Im Falle von basenkatalysierten Reaktionen können stark basische lonentauscher in der OH"-Form eingesetzt werden.The use of mineral acids such as hydrochloric or sulfuric acid and alkalis, such as caustic soda and potassium hydroxide solution for the catalysis of esterifications, saponifications, condensations, rearrangements, hydrolyses, polymerizations, dehydration or Cyclizations has long been known. Due to the moldings according to the invention, products are available which, as carriers of exchangeable counterions as well as mineral acids or alkali solutions, contain catalytically active hydrogen or hydroxyl ions and likewise exhibit an immediate catalytic activity. For acid-catalyzed reactions, instead of mineral acids, strongly acidic cation exchangers in the H + form can be used. In the case of base-catalyzed reactions, strongly basic ion exchangers in the OH " form can be used.
Die als Formkörper vorliegenden Katalysatoren weisen gegenüber homogenen Säureoder Base-Katalysatoren viele Vorteile auf: Sie können leicht vom Reaktionsprodukt abgetrennt werden, da sie als Formkörper vorliegen. Sie können in den meisten Fällen ohne Regenerierung sofort wieder verwendet werden. Eine Selektivität bezüglich großer oder kleiner Moleküle ist möglich. Ihr Einsatz in der kontinuierlichen Reaktionsfüh- rung ist möglich. Sie verhindern das Einschleppen von Fremdionen in das Reaktionsprodukt. Sie vermeiden störende Sekundär- oder Nebenreaktionen, so dass sich die Produktreinheit erhöht.The present as a shaped body catalysts have many advantages over homogeneous acid or base catalysts: they can be easily separated from the reaction product, since they are present as moldings. They can be reused immediately without regeneration in most cases. Selectivity for large or small molecules is possible. Their use in continuous reaction is possible. They prevent the entrainment of foreign ions in the reaction product. They avoid interfering secondary or secondary reactions, so that the product purity increases.
Besonders bevorzugt werden die erfindungsgemäßen Formkörper als Katalysatoren in Veresterungen, Verseifungen, Wasserabspaltungen, Hydratisierungen, Dehydratisierungen, Aldolkondensationen, Polymerisationen, Di- und Oligomerisierungen, Alkylie-
rungen, Dealkylierungen und Transalkylierungen, Cyanhydrin-Synthesen, Acetatbil- dungen, Acylierungen, Nitrierungen, Epoxidierungen, Zuckerinversionen, Umlagerungen, Isomerisierungen, Veretherungen, Vernetzungen eingesetzt. Dabei folgt die Umsetzung vorzugsweise bei einer Temperatur von maximal 180 0C, insbesondere maxi- mal 150 0C.The novel moldings are particularly preferably used as catalysts in esterifications, saponifications, dehydration, hydration, dehydration, aldol condensation, polymerizations, di- and oligomerization, alkylation. cyanohydrin syntheses, acetate formation, acylation, nitration, epoxidation, sugar inversion, rearrangement, isomerization, etherification, crosslinking. The reaction is preferably follows at a temperature of up to 180 0 C, in particular at most 150 0 C.
Geeignete Umsetzungen sind auch in Applied Catalysis A: General 221 (2001 ), 45 - 62, beschrieben.Suitable reactions are also described in Applied Catalysis A: General 221 (2001), 45-62.
Die erfindungsgemäßen Formkörper können auch als Guard Bed eingesetzt werden, um aus Fluiden unerwünschte Verunreinigungen zu entfernen.The moldings of the invention can also be used as a guard bed to remove unwanted impurities from fluids.
Herstellungmanufacturing
Die Herstellung der Formkörper erfolgt wie eingangs für das Rapid Prototyping beschrieben. Es kann auf die eingangs zitierte Literatur verwiesen werden, ferner auf Gebhardt, Rapid Prototyping, Werkzeuge für die schnelle Produktentstehung, Carl Hansa Verlag München, 2000, J. G. Heinrich.The production of the moldings is carried out as described above for rapid prototyping. Reference may be made to the literature cited above, and to Gebhardt, Rapid Prototyping, Tools for Rapid Product Development, Carl Hansa Verlag, Munich, 2000, J.G. Heinrich.
Zur Herstellung der erfindungsgemäßen Formkörper werden Polymerpulver mit einer mittleren Teilchengröße im Bereich von etwa 0,5 μm bis etwa 450 μm, besonders bevorzugt von etwa 1 μm bis etwa 300 μm und ganz besonders bevorzugt von 10 bis 100 μm eingesetzt. Das Pulver kann, wie beschrieben, zusätzlich einen oder mehrere Aktivatoren enthalten.Polymer powders having a mean particle size in the range from about 0.5 .mu.m to about 450 .mu.m, particularly preferably from about 1 .mu.m to about 300 .mu.m, and very particularly preferably from 10 to 100 .mu.m, are used for producing the shaped bodies according to the invention. The powder may, as described, additionally contain one or more activators.
Wie beschrieben kann die Verbindung zwischen den Polymerpulverteilchen durch Behandlung mit einem Lösungsmittel, durch Bestrahlen oder durch Applizieren einer reaktionsfähigen Verbindung erfolgen, die als Aktivatorverbindung aufgetragen wird und damit eine Verbindung der Polymerteilchen herstellt.As described, the connection between the polymer powder particles may be by treatment with a solvent, by irradiation, or by applying a reactive compound which is applied as an activator compound to produce a compound of the polymer particles.
Die Funktionalisierung der erhaltenen Harzformkörper kann sowohl im Ausgangspulver wie auch im Formkörper erfolgen. Dabei wird beispielsweise eine Sulfonierung, wie vorstehend beschrieben, durchgeführt. Entsprechend wird das Polymer vor oder nach der Formgebung mit sauren Gruppen, basischen Gruppen oder chelatisierenden Grup- pen funktionalisiert.The functionalization of the resulting resin moldings can be carried out both in the starting powder and in the molding. In this case, for example, a sulfonation, as described above, carried out. Accordingly, the polymer is functionalized before or after shaping with acidic groups, basic groups or chelating groups.
Die Erfindung betrifft auch nach dem beschriebenen Verfahren herstellbare organische Polymer-Formkörper mit lonentauscher- oder Adsorbereigenschaften.
Die organischen Formkörper werden bevorzugt als Reaktoreinbauten in heterogen katalysierten chemischen Reaktionen oder als Adsorber zum Adsorbieren von Ionen oder chemischen Verbindungen eingesetzt.The invention also relates to organic polymer moldings having ion exchanger or adsorber properties which can be prepared by the process described. The organic moldings are preferably used as reactor internals in heterogeneously catalyzed chemical reactions or as adsorbers for adsorbing ions or chemical compounds.
Die folgenden Beispiele sollen die Erfindung weiter erläutern, ohne sie jedoch zu limitieren.The following examples are intended to further illustrate the invention without, however, limiting it.
BeispieleExamples
Beispiel 1 :Example 1 :
Es wird eine dreidimensional strukturierte Form „Kreuzkanalstruktur" gemäß Figur 1 aus Polystyrolkugeln hergestellt. Die Länge der Polymer-Formkörper beträgt 50 mm, der Durchmesser 14 mm. Die Formgebung erfolgt als dreidimensionales Drucken auf der ProMetal RCT S15 (ProMetal RCT GmbH, 86167 Augsburg). Nach dem Druck wird der Grünling von unverbundenen Polystyrolkugeln freigeblasen. Der Polystyrol- Formkörper wird anschließend mit Oleum behandelt, wodurch ein stark saurer lonen- tauscher erhalten wird.A three-dimensionally structured "cross-channel structure" of polystyrene spheres is produced according to FIG. 1. The length of the polymer moldings is 50 mm, the diameter is 14 mm., The shaping takes place as three-dimensional printing on the ProMetal RCT S15 (ProMetal RCT GmbH, 86167 Augsburg). After printing, the green compact is blown free from unbonded polystyrene beads and the polystyrene molded body is then treated with oleum to give a strongly acidic ion exchanger.
Beispiel 2:Example 2:
Es wird eine dreidimensional strukturierte Form „Kreuzkanalstruktur" gemäß Figur 2 aus Polystyrol hergestellt. Die Länge beträgt 100 mm, der Durchmesser 80 mm. Die Formgebung mittels Rapid Prototyping erfolgt auf der ProMetal RCT S15 (ProMetal RCT GmbH, 86167 Augsburg). Nach dem anschließenden Freiblasen wird zur Herstellung eines stark sauren lonentauschers der Polystyrol-Formkörper mit Oleum behandelt.A three-dimensionally structured "cross-channel structure" of polystyrene is produced as shown in Figure 2. The length is 100 mm, the diameter is 80 mm, and shaping by means of rapid prototyping takes place on the ProMetal RCT S15 (ProMetal RCT GmbH, 86167 Augsburg) Blowing is treated with oleum to produce a strong acid ion exchanger of the polystyrene moldings.
Beispiel 3:Example 3:
Es wird eine dreidimensional strukturierte Form „Kreuzkanalstruktur" gemäß Figur 1 aus Polymethylmethacrylat-Kugeln (=PMMA) hergestellt. Die Länge der Polymer- Formkörper beträgt 50 mm, der Durchmesser 14 mm. Die Formgebung erfolgt als dreidimensionales Drucken auf der ProMetal RCT S15 (ProMetal RCT GmbH, 86167 Augsburg). Nach dem Druck wird der Grünling von unverbundenen PMMA-Kugeln freigeblasen. Der PMMA-Formkörper wird anschließend mit Natriumhydroxid-Lösung behandelt, wodurch ein schwach saurer lonentauscher erhalten wird.
A three-dimensionally structured "cross-channel structure" of polymethyl methacrylate spheres (= PMMA) is produced, the length of the polymer moldings is 50 mm, the diameter is 14 mm, and the shaping takes place as three-dimensional printing on the ProMetal RCT S15 (ProMetal RCT GmbH, 86167 Augsburg) After pressing, the green compact is blown free from unconnected PMMA spheres The PMMA molded body is then treated with sodium hydroxide solution, whereby a weakly acidic ion exchanger is obtained.
Claims
1. Verfahren zur Herstellung von organischen Polymer-Formkörpern mit lonentau- scher- oder Adsorbereigenschaften mittels eines pulverbasierten Rapid-1. A process for the production of organic polymer moldings having ion exchanger or adsorber properties by means of a powder-based rapid
Prototyping-Verfahrens, bei dem ein pulverförmiges organisches Polymer- Ausgangsmaterial oder -Ausgangsmaterialgemisch in einer dünnen Schicht auf eine Unterlage aufgetragen und anschließend an ausgewählten Stellen dieser Schicht mit einem Bindemittel und eventuell erforderlichen Hilfsmitteln versetzt wird, oder bestrahlt oder auf andere Art behandelt wird, so dass das Pulver an diesen Stellen verbunden wird, wodurch das Pulver sowohl innerhalb der Schicht als auch mit den angrenzenden Schichten verbunden wird, und dieser Vorgang so oft wiederholt wird, dass die gewünschte Form des Formkörpers vollständig in dem gebildeten Pulverbett abgebildet ist, und nachfolgend das nicht durch das Bindemittel verbundene Pulver entfernt wird, so dass das verbundene Pulver in der gewünschten Form zurückbleibt, wobei das Ausgangsmaterial bereits die lo- nentauscher- oder Adsorbereigenschaften aufweist oder nach der Formgebung eine entsprechende Funktionalisierung des Formkörpers erfolgt. Prototyping process in which a powdered organic polymer starting material or starting material mixture is applied in a thin layer on a substrate and then added at selected points of this layer with a binder and any necessary aids, or is irradiated or otherwise treated, so that the powder is joined at these points, whereby the powder is bonded both within the layer and with the adjacent layers, and this process is repeated so often that the desired shape of the shaped body is completely imaged in the formed powder bed, and subsequently the not joined by the binder powder is removed, so that the bonded powder remains in the desired shape, wherein the starting material already has the ion exchanger or adsorber or after shaping takes place a corresponding functionalization of the molding.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass das Bindemittel ein Lösungsmittel ist, das das Polymer-Ausgangsmaterial zumindest oberflächlich anlöst und damit eine Verbindung zwischen den Pulverteilchen herstellt.2. The method according to claim 1, characterized in that the binder is a solvent which dissolves the polymer starting material at least superficially and thus produces a connection between the powder particles.
3. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass durch Bestrahlen das Polymer-Ausgangsmaterial zumindest oberflächlich erweicht wird und damit eine3. The method according to claim 1, characterized in that the polymer starting material is at least superficially softened by irradiation and thus a
Verbindung zwischen den Pulverteilchen hergestellt wird.Connection is made between the powder particles.
4. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass das Polymer- Ausgangsmaterial eine reaktionsfähige Verbindung enthält, die mit einer aufge- tragenen Aktivatorverbindung zur Reaktion gebracht wird und damit eine Verbindung zwischen den Pulverteilchen des Polymer-Ausgangsmaterials herstellt.4. The method according to claim 1, characterized in that the polymer starting material contains a reactive compound which is reacted with a applied activator compound and thus produces a compound between the powder particles of the polymer starting material.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass die reaktionsfähige Verbind ung ein Monomer ist, dass auch in der Stru ktu r des Polymer- Ausgangsmaterials enthalten ist.5. The method according to claim 4, characterized in that the reactive compound is a monomer that is also contained in the stru ctu r of the polymer starting material.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das Polymer-Ausgangsmaterial auf, gegebenenfalls vor oder nach der Formgebung vernetztem, Polystyrol, Poly(meth)acrylaten oder Poly(meth)acrylsäuren basiert.6. The method according to any one of claims 1 to 5, characterized in that the polymer starting material, optionally crosslinked before or after the molding, polystyrene, poly (meth) acrylates or poly (meth) acrylic acids based.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das7. The method according to any one of claims 1 to 6, characterized in that the
Polymer-Ausgangsmaterial vor oder nach der Formgebung mit sauren Gruppen, basischen Gruppen oder chelatisierenden Gruppen funktionalisiert wird. Polymer starting material is functionalized before or after molding with acidic groups, basic groups or chelating groups.
8. Organische Polymer-Formkörper mit lonentauscher- oder Adsorbereigenschaf- ten, herstellbar nach einem Verfahren gemäß einem der Ansprüche 1 bis 7.8. Organic polymer moldings having ion exchanger or adsorber properties, preparable by a process according to one of claims 1 to 7.
9. Organische Polymer-Formkörper mit lonentauscher- oder Adsorbereigenschaf- ten, die einen oder mehrere durch den Formkörper verlaufende und nach außen offene Kanäle aufweisen.9. Organic polymer moldings with ion exchanger or adsorber properties, which have one or more through the mold body extending and outwardly open channels.
10. Organische Polymer-Formkörper mit lonentauscher- oder Adsorbereigenschaf- ten, die ein Oberflächen/Volumen-Verhältnis aufweisen, das mindestens doppelt so groß ist wie das Oberflächen/Volumen-Verhältnis einer Kugel mit gleichem10. Organic polymer moldings having ion exchanger or adsorber properties which have a surface / volume ratio that is at least twice the surface / volume ratio of a sphere with the same
Volumen.Volume.
1 1. Organische Polymer-Formkörper mit lonentauscher- oder Adsorbereigenschaf- ten, die die Form eines Monolithen aufweisen, der von einem fluiden Medium durchströmt werden kann, wobei die Monolithen Kanäle aufweisen, die von einem Reaktionsmedium durchströmt werden, wobei die Kanäle in einem Winkel im Bereich von 0 ° bis 70 °, bevorzugt 30 ° bis 60 ° gegen die Hauptströmungsrichtung geneigt sind. 1 1. Organic polymer moldings with ion exchanger or adsorber properties, which have the form of a monolith, which can be flowed through by a fluid medium, wherein the monoliths have channels through which a reaction medium, wherein the channels at an angle are inclined in the range of 0 ° to 70 °, preferably 30 ° to 60 ° to the main flow direction.
12. Verwendung von organischen Formkörpern mit lonentauscher- oder Adsorber- Eigenschaften nach einem der Ansprüche 9 bis 11 oder, erhältlich durch ein Verfahren nach einem der Ansprüche 1 bis 7, als Reaktoreinbauten in heterogen katalysierten chemischen Reaktionen oder als Adsorber zum Adsorbieren von Ionen oder chemischen Verbindungen.12. Use of organic moldings with ion exchanger or adsorber properties according to one of claims 9 to 11 or, obtainable by a process according to any one of claims 1 to 7, as reactor internals in heterogeneously catalyzed chemical reactions or as an adsorber for adsorbing ions or chemical Links.
13. Verwendung nach Anspruch 12 oder Verfahren nach einem der Ansprüche 1 bis13. Use according to claim 12 or method according to one of claims 1 to
7 oder Formkörper nach einem der Ansprüche 8 bis 1 1 , dadurch gekennzeichnet, dass die Formkörper Kanäle aufweisen, die von einem Reaktionsmedium durchströmt werden, wobei die Kanäle in einem Winkel im Bereich von 0 ° bis 70 °, be- vorzugt 30 ° bis 60 ° gegen die Hauptströmungsrichtung geneigt sind.7 or shaped body according to one of claims 8 to 1 1, characterized in that the shaped bodies have channels, which are flowed through by a reaction medium, wherein the channels at an angle in the range of 0 ° to 70 °, preferably 30 ° to 60 ° are inclined against the main flow direction.
14. Verwendung nach Anspruch 12 oder 13 oder Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass ein kolonnenförmiger Reaktor, der die Formkörper als Packungen oder Schüttung enthält, von einem Reaktionsmedium durchströmt wird, wobei die Packung aus einem Element besteht oder aus einer14. Use according to claim 12 or 13 or process according to one of claims 1 to 7, characterized in that a column-shaped reactor containing the shaped bodies as packings or bed, is flowed through by a reaction medium, wherein the packing consists of an element or from one
Mehrzahl von Elementen, die in longitudinaler Richtung angeordnete Packungsabschnitte bilden, jedes Packungs- oder Schüttungselement aus einer Mehrzahl von longitudinal ausgerichteten Lagen aufgebaut ist, jede Lage dicht angeordnete Kanäle enthält, die Kanäle benachbarter Lagen sich kreuzen und die Kanäle innerhalb eines Packungs- oder Schüttungselements seitliche Wände aufweisen, die für die Fluide durchlässig oder undurchlässig sind.A plurality of elements forming longitudinally-spaced packing sections, each packing element is constructed of a plurality of longitudinally oriented layers, each layer containing densely-disposed channels, the channels of adjacent layers crossing each other, and the channels within a packing or bedding element Have walls that are permeable or impermeable to the fluids.
15. Packungselement, wie es in Anspruch 14 definiert ist. 15. Packing element as defined in claim 14.
Priority Applications (1)
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EP09744682A EP2352635A2 (en) | 2008-10-31 | 2009-10-30 | Ion exchanger moulded body and method for producing same |
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EP08168021 | 2008-10-31 | ||
EP09744682A EP2352635A2 (en) | 2008-10-31 | 2009-10-30 | Ion exchanger moulded body and method for producing same |
PCT/EP2009/064350 WO2010049515A2 (en) | 2008-10-31 | 2009-10-30 | Ion exchanger moulded body and method for producing same |
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EP2352635A2 true EP2352635A2 (en) | 2011-08-10 |
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EP09744682A Withdrawn EP2352635A2 (en) | 2008-10-31 | 2009-10-30 | Ion exchanger moulded body and method for producing same |
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US (1) | US20110206569A1 (en) |
EP (1) | EP2352635A2 (en) |
JP (1) | JP2012506799A (en) |
KR (1) | KR20110097797A (en) |
CN (1) | CN102202870A (en) |
CA (1) | CA2742235A1 (en) |
WO (1) | WO2010049515A2 (en) |
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DE102014018579A1 (en) | 2014-12-17 | 2016-06-23 | Voxeljet Ag | Method for producing three-dimensional molded parts and adjusting the moisture content in the building material |
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FR3070874B1 (en) * | 2017-09-14 | 2022-04-22 | Black Hole Lab | FLUID DEVICE FOR CLEANING A FLUID AND ASSOCIATED CLEANING METHOD |
CN111868516A (en) * | 2018-05-17 | 2020-10-30 | 奥加诺株式会社 | Method for analyzing content of metal impurities and kit for analyzing content of metal impurities |
GB201909269D0 (en) * | 2019-06-27 | 2019-08-14 | Johnson Matthey Plc | Layered sorbent structures |
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- 2009-10-30 KR KR1020117012526A patent/KR20110097797A/en not_active Application Discontinuation
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CA2742235A1 (en) | 2010-05-06 |
CN102202870A (en) | 2011-09-28 |
US20110206569A1 (en) | 2011-08-25 |
KR20110097797A (en) | 2011-08-31 |
WO2010049515A3 (en) | 2010-12-29 |
WO2010049515A2 (en) | 2010-05-06 |
JP2012506799A (en) | 2012-03-22 |
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