CN111836682A - 聚合物珠粒 - Google Patents
聚合物珠粒 Download PDFInfo
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- CN111836682A CN111836682A CN201880077903.6A CN201880077903A CN111836682A CN 111836682 A CN111836682 A CN 111836682A CN 201880077903 A CN201880077903 A CN 201880077903A CN 111836682 A CN111836682 A CN 111836682A
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- 239000011324 bead Substances 0.000 title claims abstract description 86
- 229920000642 polymer Polymers 0.000 title claims description 91
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000005349 anion exchange Methods 0.000 claims abstract description 8
- 125000003277 amino group Chemical group 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 42
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 27
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 23
- 229920002554 vinyl polymer Polymers 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 61
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 48
- 239000011347 resin Substances 0.000 description 47
- 229920005989 resin Polymers 0.000 description 47
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 17
- 238000000034 method Methods 0.000 description 15
- 239000002245 particle Substances 0.000 description 15
- 239000011651 chromium Substances 0.000 description 14
- 229910052804 chromium Inorganic materials 0.000 description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000003957 anion exchange resin Substances 0.000 description 11
- 239000011550 stock solution Substances 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 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
- 150000002500 ions Chemical class 0.000 description 7
- 239000003361 porogen Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- 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 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000012527 feed solution Substances 0.000 description 3
- 239000012458 free base Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- -1 tin (II) ions Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000000399 optical microscopy Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000012508 resin bead Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- SYRHIZPPCHMRIT-UHFFFAOYSA-N tin(4+) Chemical compound [Sn+4] SYRHIZPPCHMRIT-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
- B01J41/04—Processes using organic exchangers
- B01J41/05—Processes using organic exchangers in the strongly basic form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3206—Organic carriers, supports or substrates
- B01J20/3208—Polymeric carriers, supports or substrates
- B01J20/321—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions involving only carbon to carbon unsaturated bonds
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- 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
- B01J20/3234—Inorganic material layers
- B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
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- 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
- B01J41/04—Processes using organic exchangers
- B01J41/07—Processes using organic exchangers in the weakly basic form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/016—Modification or after-treatment of ion-exchangers
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
提供了一种阴离子交换组合物,其包含(a)具有共价结合的胺基的聚合物珠粒以及(b)氧化锡(II)。
Description
六价铬,也称为铬(VI),广泛用于各种工业过程中。六价铬有时以不希望的污染物存在于水中。希望从水中除去六价铬的方法。
US 7,708,892描述了使用掺杂有金属的离子交换剂。根据US 7,708,892,用于掺杂的金属可以是多种金属中的任何一种。根据US 7,708,892,金属掺杂的离子交换剂可用于从水中去除多种溶解的污染物,包括同时含有氧原子和金属原子的污染物,其中金属原子可选自多种金属。希望提供一种特别有效地从水中去除六价铬的离子交换组合物。
以下是本发明的陈述。
本发明的第一方面是一种阴离子交换组合物,其包含
(a)具有共价结合的胺基的聚合物珠粒,以及
(b)氧化锡(II)。
本发明的第二方面是一种处理水的方法,包括使含有溶解的铬(VI)的水与阴离子交换组合物接触,所述阴离子交换组合物包含:
(a)具有共价结合的胺基的聚合物珠粒,以及
(b)氧化锡(II)。
以下是本发明的详细说明。
如本文所用,除非上下文另外清楚地指明,否则以下术语具有指定的定义。
如本文所用,“聚合物”是由较小化学重复单元的反应产物构成的相对大的分子。聚合物可具有为直链、支链、星形、环状、超支化、交联或它们的组合的结构;聚合物可具有单一类型的重复单元(“均聚物”)或它们可具有多于一种类型的重复单元(“共聚物”)。共聚物可具有随机、依次、嵌段、以其他排列方式排列的各种类型的重复单元、或它们的任何混合物或组合。
可彼此反应形成聚合物的重复单元的分子在本文中称为“单体”。如此形成的重复单元在本文中称为单体的“聚合单元”。
乙烯基单体具有结构其中R1、R2、R3、和R4各自独立地为氢、卤素、脂族基团(例如像烷基基团)、取代的脂族基团、芳基基团、取代的芳基基团、另一取代或未取代的有机基团、或它们的任何组合。乙烯基单体能够自由基聚合以形成聚合物。一些乙烯基单体具有结合到R1、R2、R3和R4中的一者或多者中的一个或多个可聚合的碳-碳双键;此类乙烯基单体在本文中称为多官能乙烯基单体。具有恰好一个可聚合的碳-碳双键的乙烯基单体在本文中称为单官能乙烯基单体。
苯乙烯类单体为如下的乙烯基单体,其中R1和R2各自为氢、R3为氢或烷基并且-R4具有以下结构
其中R5、R6、R7、R8、和R9各自独立地为氢、卤素、脂族基团(例如像烷基基团或乙烯基基团)、取代的脂族基团、芳基基团、取代的芳基基团、另一取代或未取代的有机基团、或它们的任何组合。
单体之间形成一种或多种聚合物的反应在本文中称为聚合过程。
在本文中聚合物被认为含有用于制备聚合物的单体的聚合单元,即使在聚合后,通过加入一种或多种官能团改变了一些或所有这些聚合单元。例如,由苯乙烯和DVB以90:10的苯乙烯:DVB的重量比制备的共聚物被认为具有90重量%的苯乙烯聚合单元。如果该共聚物随后通过与硫酸反应以用磺酸基团替换芳族环上的一些氢原子而被改变,则所得官能化聚合物仍被认为具有90重量%的苯乙烯聚合单元。
大孔聚合物珠粒具有平均孔径为20nm或更大的多孔结构。孔径是使用Brunauer-Emmett-Teller(BET)方法用氮气测量的。大孔聚合物珠粒通常通过将致孔剂掺入单体液滴中来制备。致孔剂可溶于单体,但聚合物不溶于致孔剂,因此随着聚合物的形成,致孔剂的相分离域得以保留。聚合后,通过蒸发或通过用溶剂洗涤除去致孔剂。聚合物珠粒的多孔结构是当致孔剂从其相分离域除去时留下的空的空间。
凝胶型聚合物珠粒的制备不使用致孔剂。凝胶型聚合物珠粒中的孔是聚合物珠粒的缠结的、可能是交联的聚合物链中的原子之间的自由体积。凝胶型聚合物珠粒中的孔小于20nm。在一些情况下,凝胶型树脂中的孔太小而无法使用BET法检测。
如本文所用,离子交换是其中使溶液与离子交换树脂接触的方法。在与溶液接触之前,离子交换树脂具有某一电荷的官能团,并具有与官能团缔合的相反电荷的离子。当使溶液与离子交换树脂接触时,溶液中的一些离子通过与离子交换树脂上的官能团缔合的相同电荷的离子交换位置而附着到离子交换树脂上。
聚合物珠粒是含有基于颗粒重量的90重量%或更多的有机聚合物的颗粒。聚合物珠粒为球形或接近球形。聚合物珠粒的特征在于其半径。如果珠粒不是球形的,则在本文中将珠粒的半径取为“参考球”的半径,所述“参考球”是与所述珠粒具有相同体积的假想球。
如本文所用,“环境温度”与“室温”同义,并且为约23℃。
颗粒的集合体可以通过体积平均直径来表征。
比率在本文中如下进行表征。例如,如果认为比率为5:1或更高,则意味着所述比率可为5:1或6:1或100:1,但不可以为4:1。为了以一般方式陈述这种表征,如果认为比率为X:1或更高,则比率为Y:1,其中Y大于或等于X。类似地,例如,如果认为比率为2:1或更低,则意味着所述比率可为2:1、或1:1、或0.001:1,但不可以为3:1。为了以一般方式陈述这种表征,如果认为比率为Z:1或更低,则比率为W:1,其中W小于或等于Z。
本发明的阴离子交换组合物含有聚合物珠粒的集合体。聚合物珠粒含有聚合物。聚合物珠粒是在25℃下为固体的颗粒,并且含有聚合物,其量为基于聚合物颗粒重量的90重量%或更多;更优选地95重量%或更多。
本发明的阴离子交换组合物还含有氧化锡(II)。优选地,以阴离子交换组合物的总重量的百分比计,聚合物珠粒和氧化锡(II)的重量的总和为90%或更高;更优选地95%或更高;更优选地99%或更高。
聚合物珠粒可以是大孔珠粒或凝胶珠粒。优选的是大孔珠粒。
聚合物颗粒中的优选聚合物是通过自由基聚合乙烯基单体形成的聚合物。
优选的乙烯基单体为苯乙烯类单体、丙烯酸类单体及其混合物。优选地,所用的所有单体选自苯乙烯类单体、丙烯酸类单体及其混合物;更优选地选自苯乙烯类单体。更优选地,所用的所有单体选自苯乙烯类单体。乙烯基单体优选地包括一种或多种单官能乙烯基单体。优选的单官能乙烯基单体为丙烯酸类和苯乙烯类单官能单体;更优选的为单官能苯乙烯类单体;更优选的为苯乙烯。乙烯基单体优选地包括一种或多种多官能乙烯基单体。优选的多官能乙烯基单体为多官能苯乙烯类单体;更优选的为二乙烯基苯。
聚合物颗粒中优选的聚合物含有苯乙烯类单体的聚合单元,其量为基于聚合物重量的5重量%或更多;更优选地25重量%或更多;更优选地50重量%或更多;更优选地75重量%或更多;更优选地95重量%或更多。
优选的聚合物具有多官能乙烯基单体的聚合单元,其量为基于聚合物重量的1重量%或更多;更优选地1.5重量%或更多;更优选地2重量%或更多。优选的聚合物具有多官能乙烯基单体的聚合单元,其量为基于聚合物重量的25重量%或更少;更优选地20重量%或更少;更优选地15重量%或更少;更优选地11重量%或更少;更优选地6%或更少。
优选的聚合物具有单官能乙烯基单体的聚合单元,其量为基于聚合物重量的99重量%或更少;更优选地98.5重量%或更少;更优选地98重量%或更少;更优选地98.5重量%或更少。优选的聚合物具有单官能乙烯基单体的聚合单元,其量为基于聚合物重量的75重量%或更多;更优选地80重量%或更多;更优选地85重量%或更多;更优选地89重量%或更多;更优选地94重量%或更多。
优选地,在单体共聚之后,将聚合物进行转化过程以产生阴离子交换树脂。阴离子交换树脂分为以下几类。弱碱阴离子交换树脂具有伯、仲或叔侧氨基团。强碱阴离子交换树脂具有侧季铵基团。当这些侧基官能团中的任何一个已经附接到聚合物珠粒上时,所述珠粒称为“官能化树脂”。
通常,在由聚合物珠粒(诸如交联的聚苯乙烯珠粒)制备阴离子交换树脂时,有利地将珠粒卤烷基化,优选地卤甲基化,最优选地氯甲基化,并且随后将离子活性交换基团附接到卤烷基化共聚物上。通常,卤代烷基化反应包括使交联的加成共聚物与卤代烷基化剂溶胀,并且然后在Friedel-Crafts催化剂的存在下使共聚物与卤代烷基化剂反应。通常,通过使卤烷基化的共聚物与氨、伯胺或仲胺反应来制备弱碱阴离子交换树脂。通常,通过使卤烷基化的共聚物与叔胺反应来制备强碱阴离子交换树脂。
本发明的聚合物珠粒的集合体还含有氧化锡(II)。可以通过任何方法将氧化锡(II)引入聚合物珠粒的集合体中。优选的方法是提供阴离子交换树脂聚合物珠粒,并使所述珠粒与含有溶解的锡(II)离子的水溶液例如像氯化锡(II)的水溶液接触。优选地,从含有锡(II)离子的溶液中移出珠粒之后,然后使珠粒与pH高于8的水溶液例如像氢氧化钠水溶液接触。从pH高于8的溶液中移出珠粒后,优选用水洗涤珠粒。
优选地,聚合物珠粒的集合体的体积平均直径为200微米或更大;更优选400微米或更大,更优选600微米或更大。优选地,聚合物珠粒的集合体的体积平均直径为1,500微米或更小;更优选1,000微米或更小。
除聚合物之外,聚合物珠粒的集合体正常还包含水。预期水被吸附到官能化的聚合物珠粒中。通过除去液态水(如果有的话与聚合物珠粒接触)并且然后在23℃下使珠粒与100%相对湿度的空气达到平衡来评估水的量。珠粒中水的量,基于官能化的聚合物珠粒的总重量(包括珠粒和吸附的水两者),优选为30重量%或更多;更优选地50重量%或更多;更优选地60重量%或更多;更优选地70重量%或更多。珠粒中水的量,基于官能化的聚合物珠粒的集合体的总重量,优选为90%重量或更少。
聚合物珠粒的集合体中锡的量的表征为元素锡的重量占阴离子交换组合物总重量的百分比。优选地,锡的量为0.5%或更多;更优选地1%或更多;更优选地2%或更多;更优选地3%或更多。优选地,锡的量为25%或更少;更优选地20%或更少;更优选地15%或更少;更优选地10%或更少。
优选地,存在于聚合物珠粒的集合体中的大部分或全部锡以氧化锡(II)的形式存在。优选地,以氧化锡(II)的形式存在的锡的量,以全部存在的锡的摩尔百分比,为90%或更多;更优选地95%或更多;更优选地99%或更多。
优选的是,大部分或全部的氧化锡(II)存在于聚合物珠内部或聚合物珠表面处或这两者的混合中,而不存在于聚合物珠粒之间的间隙中。优选地,基于氧化锡(II)的总重量,90重量%或更多的氧化锡(II)位于聚合物珠粒内部。优选地,基于氧化锡(II)的总重量,80重量%或更多的氧化锡(II)处于颗粒的形式,其直径为小于100微米;更优选5微米或更小;更优选2微米或更小;更优选1微米或更小。
表征较不优选的氧化锡(II)形式是有用的,本文标记为“外部”氧化锡(II),其是位于聚合物珠粒之间的间隙中具有10微米或更大的任何尺寸颗粒形式的氧化锡(II),无论这种氧化锡(II)颗粒是否与一个或多个聚合物珠粒的表面接触。优选地,外部氧化锡(II)的量占全部氧化锡(II)的摩尔百分比为10%或更低;更优选地5%或更低;更优选地2%或更低;更优选地1%或更低;更优选零。
优选地,聚合物珠粒除锡(II)以外几乎不含或不含金属。优选地,作为元素金属的所有金属的总重量与元素锡(II)的重量之比为0.5:1或更小;更优选地0.2:1或更小;更优选地0.1:1或更小;更优选地0.05:1或更小;更优选地0.02:1或更小;更优选地0.01:1或更小。
本发明的聚合物珠粒的优选用途是处理含有溶解的铬(VI)离子的水(本文为“处理前的”水)。铬(VI)离子可以作为任何分子、离子或络合物的一部分存在,只要铬处于(VI)氧化态并且只要所述分子、离子或络合物溶解在处理前的水中。优选的是包含铬(VI)的阴离子。含有铬(VI)的阴离子的实例是HCrO4 -、CrO4 2-、和Cr2O7 2-。优选地,所述处理前的水包含的铬(VI)以原子铬的重量计,基于所述处理前的水的总重量,为0.01ppm或更高;更优选0.02ppm或更高;更优选0.05ppm或更高。优选地,所述处理前的水包含的铬(VI)以原子铬的重量计,基于所述处理前的水的总重量,为100ppm或更低;更优选50ppm或更低;更优选25ppm或更低;更优选10ppm或更低;更优选5ppm或更低;更优选2ppm或更低;更优选1ppm或更低。
所述处理前的水任选地包含一种或多种额外的溶解的化合物。优选的额外的溶解的化合物是无机盐。优选地,基于所述水的总重量(包括溶解的化合物),所有溶解的化合物的总量是1重量%或更少;更优选地0.3重量%或更少;更优选地0.1重量%或更少。
优选地,通过使处理前的水与本发明的聚合物珠粒接触来处理所述处理前的水。接触可以通过任何方法进行,包括例如批次法和柱法。
在批次法中,将处理前的水和聚合物珠粒放置在容器中并且任选地机械搅拌。优选地,然后例如通过包括倾析或过滤或它们的组合的方法将水(现在在本文中称为“处理后的水”)与聚合物珠粒分离。在批次法中,有用的是将比率“R1”定义为以克计聚合物珠粒的重量(以不存在大体积水的湿珠粒测量)与批次中以克计原子铬(VI)的总重量之比。
在柱法中,将聚合物珠粒的集合体放置在将聚合物珠粒捕获在适当位置的容器中,该容器具有用于水进入容器的入口和具有用于水离开容器的出口,该入口允许水流过容器,同时与聚合物珠粒紧密接触。处理前的水通过入口引入,在重力或泵或它们的组合作用下被强制流过柱,并且然后通过出口离开柱。离开柱之后,在本文中水标记为“处理后的水”。
在柱法中,比率R1如下表征。使用潮湿但不存在大体积水的珠粒,以克计测量聚合物珠粒的集合体的重量。使处理前的水流过所述柱,并且然后停止流动。铬(VI)的重量被认为是进入柱的所有处理前的水中所有原子铬(VI)的总重量,以克计。然后比率R1是聚合物珠粒的集合体的重量与铬(VI)的重量之比。
不管使用的方法是批次法还是柱法,R1优选为300:1或更大;更优选450:1或更大;更优选900:1或更大。优选地,R1为10,000:1或更小。
以下是本发明的实例。
以下特性用于表征聚合物珠粒的集合体。“VMD”是颗粒的基于体积的平均直径,以微米(μm)计。“EQ-水”是在将珠粒暴露于液体水,除去过量的液体水并使珠粒与空气在100%相对湿度23℃下达到平衡之后,在聚合物珠粒的集合体中发现的水的量;然后将珠粒称重,干燥并再次称重;并且重量差为“EQ-水”,表示为水的重量占珠粒初始总重量(包括水)的百分比。
以下实例中使用以下缩写。
DI=去离子的
ND=未检出-铬的检出限为0.05μg/g
Sty/DVB=苯乙烯、二乙烯基苯和乙基乙烯基苯的共聚物
polycond=缩聚物
使用了四种树脂。在引入氧化锡(II)之前,这四种树脂具有以下特性:
(1)对比
(2)季铵
(3)大孔的
使用了以下锡储备溶液:
锡(II)储备溶液:35g氯化锡(II)/1000mL DI水
锡(IV)储备溶液:45g氯化锡(IV)/1000mL Di水
制备了以下进料溶液(即“处理前的水”):
<u>CrO<sub>3</sub></u> | <u>NaCl</u> | <u>Na<sub>2</sub>SO<sub>4</sub></u> | <u>CaCl<sub>2</sub></u> | <u>MgCl<sub>2</sub></u> | <u>DI水</u> | |
进料A | 0.014g | 1.05g | 0.35g | -- | -- | 7L |
进料B | 0.10g | 1.5g | 0.5g | -- | -- | 10L |
进料C | 0.102g | 1.5g | 0.493g | 0.749g | 0.745g | 10L |
进料D | 0.250g | 1.5g | 0.503 | 0.404 | 0.352 | 10L |
实例1:将锡装载到树脂上
将锡装载到树脂上如下进行。将树脂离心以除去大体积的水,得到“湿”树脂。将1L树脂与2L的储备溶液混合。将混合物搅拌4小时,然后倒出。取出少量树脂样品进行分析。将剩余的树脂与1.5L的1.0NNaOH水溶液混合。将混合物搅拌约14小时,然后倒析。用DI水充分洗涤树脂。
使用感应耦合等离子体(ICP)发射光谱法测量树脂的锡含量。锡的检出限为按重量计5ppm。将树脂样品分三个阶段进行测试:在暴露于储备溶液之前(“Cl”或“游离碱”阶段),暴露于储备溶液之后立即(“SnCl2”或“SnCl4”阶段)以及从NaOH溶液中倾析后的树脂(“NaOH”阶段)。锡的量报告为元素锡的重量占树脂总重量(即聚合物珠粒的集合体的总重量)的百分比。结果如下:
<u>实例类型</u> | <u>树脂</u> | <u>储备溶液</u> | <u>阶段</u> | <u>锡wt%</u> |
制备 | SBA-MP | 无 | Cl | ND |
制备 | SBA-MP | Sn(II) | SnCl<sub>2</sub> | 0.3 |
工作 | SBA-MP | Sn(II) | NaOH | 4.4 |
对比的 | SBA-MP | Sn(IV) | SnCl<sub>4</sub> | 4.5 |
对比的 | SBA-MP | Sn(IV) | NaOH | 5.6 |
对比的 | SAC-凝胶-C | 无 | 游离碱 | ND |
对比的 | SAC-凝胶-C | Sn(II) | SnCl<sub>2</sub> | 4.3 |
对比的 | SAC-凝胶-C | Sn(II) | NaOH | 2.9 |
在上表中,由SBA-MP制成的材料(经Sn(II)储备溶液处理并且还经NaOH溶液处理)是仅有的本发明组合物的工作实例的材料。所示出的其他材料是制备的,代表制造所述工作实例的途径中的中间步骤,或者是对比实例。使用Sn(IV)或使用SAC树脂的材料不在本发明的范围内。
与SBA树脂相比,SAC树脂从储备溶液中更少吸收锡。另外,在SAC树脂中,由于NaOH处理,锡的量下降。认为在其最后阶段的SAC-凝胶-C树脂比在最后阶段的SBA-MP树脂所具有的氧化锡(II)少得多。
通过视觉观察和光学显微镜研究了三种树脂:(1)在NaOH阶段之后,具有氧化锡(II)的SBA-MP;(2)在NaOH状态后,具有氧化锡(IV)的SBA-MP,以及(3)未经锡处理的SBA-MP。对于每种树脂,将5g相应的树脂放入装有50mL浓度为0.25g/50mL的氧化铬(CrO3)溶液的60mL瓶中,并使用NaOH将pH调节至7.2。将每种树脂/CrO3溶液置于摇床上,并在室温(约23℃)下搅拌72小时。使树脂沉降,将过量的液体倾倒至废液容器,并目视检查树脂。树脂/Sn(II)混杂物和树脂对照均未示出在树脂珠粒外部金属沉淀的迹象,而树脂/Sn(IV)混杂物在树脂底部示出明显的深色颗粒状不溶性沉淀。还通过光学显微镜检查了这三种树脂。在无锡样品和氧化锡(II)样品中,未观察到除聚合物珠粒以外的颗粒。在氧化锡(IV)样品中,可以看到聚合物珠粒以外的许多外部颗粒。这些外部颗粒被识别为氧化锡(IV),并且外部颗粒覆盖了视场的大约80%。认为对树脂的观察和显微图像表明,氧化锡(II)在聚合物珠粒内部形成或直接在珠粒的表面上形成,而氧化锡(IV)则具有更大的在聚合物珠粒之间的间隙形成颗粒的趋势。
实例2:处理水
在各实验中,将一定量的树脂(见下文)放入装有1000mL进料溶液的1000mL锥形瓶中。连续搅拌混合物,并在3天和8天后测试水中的铬含量。使用ICP对铬进行了研究,以微克铬/克水(μg/g)的单位报告。检出限为0.05μg/g。结果如下:
0.75g树脂/进料A
上表中的本发明的工作实例是SBA-MP/Sn(II)/NaOH。该实例具有最佳的除铬性能,尤其是在第8天时。
树脂SBA-MP/进料B
在上表中,本发明的工作实例是三个具有Sn(II)的样品。这些样品可以很好地去除铬。
实例3:进一步装载树脂
如下向树脂装载锡。除了在每个样品中将1L的树脂与1L的储备溶液混合之外,如以上实例1装载树脂。通过上述方法测量平衡水含量和锡含量,并且结果如下。
<u>实例类型</u> | <u>树脂</u> | <u>储备溶液</u> | <u>阶段</u> | <u>EQ-水</u> | <u>锡wt%</u> |
制备 | SBA-MP | 无 | Cl | 74.5% | ND |
工作 | SBA-MP | Sn(II) | NaOH | 74.4% | 11.0 |
制备 | WBA-MP | 无 | 游离碱 | 61.6% | ND |
工作 | WBA-MP | Sn(II) | NaOH | 47.0% | 18.4 |
制备 | SBA-凝胶 | 无 | Cl | 45.0% | ND |
工作 | SBA-凝胶 | Sn(II) | NaOH | 45.0% | 6.7 |
所测试的所有三种阴离子交换树脂均示出可接受的装载氧化锡(II)的能力。
实例4:进一步处理水
如以上实例2中,测试树脂对铬(VI)的吸收。将树脂离心并倾析以除去游离水。将0.50g树脂与1000mL的进料溶液混合。然后,如上测试水的铬含量,并以微克铬/克水报告。使用进料C测试的结果如下:
0.50g树脂/进料C
在所有三种测试的阴离子交换树脂中,装载锡的树脂表现良好,并且比没有锡的相同树脂表现更好。
另外,使用上述方法用1000mL的进料D溶液测试0.50克树脂。如上测试水的铬含量,并以微克铬/克水报告。结果如下:
0.50g树脂/进料D
在所有三种测试的阴离子交换树脂中,装载锡的树脂表现良好,并且比没有锡的相同树脂表现更好。
Claims (4)
1.一种阴离子交换组合物,其包含:
(a)具有共价结合的胺基的聚合物珠粒,以及
(b)氧化锡(II)。
2.如权利要求1所述的组合物,其中,所述聚合物珠粒包含含有苯乙烯类单体的聚合单元的聚合物。
3.如权利要求1所述的组合物,其中,所述聚合物珠粒包含聚合物,所述聚合物包括一种或多种单官能乙烯基单体的聚合单元和一种或多种多官能乙烯基单体的聚合单元。
4.如权利要求1所述的组合物,其中,所述氧化锡(II)的存在量应使元素锡的量为基于所述组合物的重量的0.5重量%至20重量%。
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US4178270A (en) * | 1977-03-01 | 1979-12-11 | Hitachi, Ltd. | Method for supporting hydrous metal oxide on carrier |
US4284726A (en) * | 1978-05-13 | 1981-08-18 | Yasumasa Shigetomi | Composite anion adsorbent and method for making same |
US20060237371A1 (en) * | 2005-04-26 | 2006-10-26 | Paul Sylvester | Sorbent for selective removal of contaminants from fluids |
US20080035564A1 (en) * | 2006-08-09 | 2008-02-14 | Solmetex, Inc. | Sorbent For Selective Removal Of Contaminants From Fluids |
WO2017109521A1 (en) * | 2015-12-21 | 2017-06-29 | Aristotle University Of Thessaloniki - E.L.K.E. | A method for the synthesis of a bivalent tin oxy-hydroxide adsorbent for the removal of hexavalent chromium from water, particularly drinking water, the adsorbent and its use |
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JP2006263603A (ja) | 2005-03-24 | 2006-10-05 | Kurita Water Ind Ltd | ホウ素含有水の処理方法 |
DE102007020688A1 (de) | 2007-05-03 | 2008-11-06 | Lanxess Deutschland Gmbh | Konditionierung von Ionenaustauschern zur Adsorption von Oxoanionen |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4178270A (en) * | 1977-03-01 | 1979-12-11 | Hitachi, Ltd. | Method for supporting hydrous metal oxide on carrier |
US4284726A (en) * | 1978-05-13 | 1981-08-18 | Yasumasa Shigetomi | Composite anion adsorbent and method for making same |
US20060237371A1 (en) * | 2005-04-26 | 2006-10-26 | Paul Sylvester | Sorbent for selective removal of contaminants from fluids |
US20080035564A1 (en) * | 2006-08-09 | 2008-02-14 | Solmetex, Inc. | Sorbent For Selective Removal Of Contaminants From Fluids |
WO2017109521A1 (en) * | 2015-12-21 | 2017-06-29 | Aristotle University Of Thessaloniki - E.L.K.E. | A method for the synthesis of a bivalent tin oxy-hydroxide adsorbent for the removal of hexavalent chromium from water, particularly drinking water, the adsorbent and its use |
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