CN116891303A - Method for recycling high barium sulfate wastewater by reverse osmosis - Google Patents
Method for recycling high barium sulfate wastewater by reverse osmosis Download PDFInfo
- Publication number
- CN116891303A CN116891303A CN202310334105.XA CN202310334105A CN116891303A CN 116891303 A CN116891303 A CN 116891303A CN 202310334105 A CN202310334105 A CN 202310334105A CN 116891303 A CN116891303 A CN 116891303A
- Authority
- CN
- China
- Prior art keywords
- acid
- water
- sulfate
- barium sulfate
- barium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 title claims abstract description 229
- 238000000034 method Methods 0.000 title claims abstract description 146
- 238000001223 reverse osmosis Methods 0.000 title claims description 20
- 238000004064 recycling Methods 0.000 title claims description 9
- 239000002351 wastewater Substances 0.000 title description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 172
- 239000008235 industrial water Substances 0.000 claims abstract description 74
- 239000000203 mixture Substances 0.000 claims abstract description 68
- 239000000498 cooling water Substances 0.000 claims abstract description 56
- 238000001816 cooling Methods 0.000 claims abstract description 47
- 239000012736 aqueous medium Substances 0.000 claims abstract description 42
- 239000013078 crystal Substances 0.000 claims abstract description 37
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 34
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 34
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 26
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims abstract description 23
- 229910001626 barium chloride Inorganic materials 0.000 claims abstract description 23
- 229910000358 iron sulfate Inorganic materials 0.000 claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 13
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 13
- 229910052788 barium Inorganic materials 0.000 claims description 32
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 32
- 238000001914 filtration Methods 0.000 claims description 28
- 239000011148 porous material Substances 0.000 claims description 27
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 26
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 26
- 150000003839 salts Chemical class 0.000 claims description 26
- 239000002270 dispersing agent Substances 0.000 claims description 20
- 239000002455 scale inhibitor Substances 0.000 claims description 19
- 239000012528 membrane Substances 0.000 claims description 16
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 15
- -1 pentamethylene phosphonic acid Chemical compound 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 13
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- IQEKRNXJPCBUAT-UHFFFAOYSA-N 2-[hydroperoxy(hydroxy)phosphoryl]acetic acid Chemical compound OOP(O)(=O)CC(O)=O IQEKRNXJPCBUAT-UHFFFAOYSA-N 0.000 claims description 11
- 229940120146 EDTMP Drugs 0.000 claims description 10
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 10
- 229920000805 Polyaspartic acid Polymers 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 10
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 10
- YAWYUSRBDMEKHZ-UHFFFAOYSA-N [2-hydroxyethyl(phosphonomethyl)amino]methylphosphonic acid Chemical compound OCCN(CP(O)(O)=O)CP(O)(O)=O YAWYUSRBDMEKHZ-UHFFFAOYSA-N 0.000 claims description 10
- KIDJHPQACZGFTI-UHFFFAOYSA-N [6-[bis(phosphonomethyl)amino]hexyl-(phosphonomethyl)amino]methylphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCCCCCN(CP(O)(O)=O)CP(O)(O)=O KIDJHPQACZGFTI-UHFFFAOYSA-N 0.000 claims description 10
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 10
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 10
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 10
- 108010064470 polyaspartate Proteins 0.000 claims description 10
- 229920001529 polyepoxysuccinic acid Polymers 0.000 claims description 10
- 238000011282 treatment Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 8
- 159000000014 iron salts Chemical class 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 6
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- KKSNTCYLMGYFFB-UHFFFAOYSA-N (prop-2-enoylamino)methanesulfonic acid Chemical group OS(=O)(=O)CNC(=O)C=C KKSNTCYLMGYFFB-UHFFFAOYSA-N 0.000 claims description 5
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 5
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 5
- SYPKYPCQNDILJH-UHFFFAOYSA-N 2-methyl-2-(prop-2-enoylamino)butane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(C)(CC)NC(=O)C=C SYPKYPCQNDILJH-UHFFFAOYSA-N 0.000 claims description 5
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 claims description 5
- XCJGLBWDZKLQCY-UHFFFAOYSA-N 2-methylpropane-2-sulfonic acid Chemical compound CC(C)(C)S(O)(=O)=O XCJGLBWDZKLQCY-UHFFFAOYSA-N 0.000 claims description 5
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 5
- UCNUAGQCOCSQMY-UHFFFAOYSA-N 2-phosphanylbutanedioic acid Chemical compound OC(=O)CC(P)C(O)=O UCNUAGQCOCSQMY-UHFFFAOYSA-N 0.000 claims description 5
- XOQMWEWYWXJOAN-UHFFFAOYSA-N 3-methyl-3-(prop-2-enoylamino)butanoic acid Chemical compound OC(=O)CC(C)(C)NC(=O)C=C XOQMWEWYWXJOAN-UHFFFAOYSA-N 0.000 claims description 5
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 claims description 5
- JOXWZEYQUIILOL-UHFFFAOYSA-N 4-prop-2-enoxybenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(OCC=C)C=C1 JOXWZEYQUIILOL-UHFFFAOYSA-N 0.000 claims description 5
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 5
- 229920001444 polymaleic acid Polymers 0.000 claims description 5
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 claims description 5
- 230000003134 recirculating effect Effects 0.000 claims description 5
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 5
- 238000001728 nano-filtration Methods 0.000 claims description 4
- TTZMPOZCBFTTPR-UHFFFAOYSA-N O=P1OCO1 Chemical compound O=P1OCO1 TTZMPOZCBFTTPR-UHFFFAOYSA-N 0.000 claims description 3
- VZNFVLWVVHHMBG-UHFFFAOYSA-N dimethyl 2-prop-2-enylpropanedioate Chemical compound COC(=O)C(CC=C)C(=O)OC VZNFVLWVVHHMBG-UHFFFAOYSA-N 0.000 claims 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 74
- 229910052742 iron Inorganic materials 0.000 abstract description 37
- 230000008569 process Effects 0.000 description 14
- 238000000108 ultra-filtration Methods 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 description 9
- 239000011707 mineral Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000012466 permeate Substances 0.000 description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 230000002427 irreversible effect Effects 0.000 description 6
- 230000000670 limiting effect Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000008213 purified water Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000003002 pH adjusting agent Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- NEYTXADIGVEHQD-UHFFFAOYSA-N 2-hydroxy-2-(prop-2-enoylamino)acetic acid Chemical compound OC(=O)C(O)NC(=O)C=C NEYTXADIGVEHQD-UHFFFAOYSA-N 0.000 description 3
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 3
- ZDZVKPXKLLLOOA-UHFFFAOYSA-N Allylmalonic acid Chemical compound OC(=O)C(C(O)=O)CC=C ZDZVKPXKLLLOOA-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000002519 antifouling agent Substances 0.000 description 3
- 159000000009 barium salts Chemical class 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229960004887 ferric hydroxide Drugs 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000013505 freshwater Substances 0.000 description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 3
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ZAWQXWZJKKICSZ-UHFFFAOYSA-N 3,3-dimethyl-2-methylidenebutanamide Chemical compound CC(C)(C)C(=C)C(N)=O ZAWQXWZJKKICSZ-UHFFFAOYSA-N 0.000 description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229960005191 ferric oxide Drugs 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000005569 Iron sulphate Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000001164 aluminium sulphate Substances 0.000 description 1
- 235000011128 aluminium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229920000141 poly(maleic anhydride) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052600 sulfate mineral Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/023—Water in cooling circuits
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Abstract
The present invention provides a method of inhibiting barium sulfate scale formation in an industrial water system, the method comprising: (i) mixing (a) barium chloride and (b) iron sulfate and/or aluminum sulfate in an aqueous medium to form a mixture comprising barium sulfate, (ii) aging the mixture to form a composition comprising barium sulfate seed crystals and one or more soluble iron and/or aluminum salts in the aqueous medium, and (iii) adding at least a portion of the composition to water of the industrial water system to inhibit barium sulfate scale formation in the industrial water system. The method of the present invention may be used to recycle the cooling water emissions from a water cooling tower.
Description
Background
Because of mineral scaling (e.g., barium sulfate scaling) and subsequent scaling of the purification system, purification of high hardness wastewater by reverse osmosis processes may often be a limiting step in wastewater recirculation in industrial water systems (e.g., cooling water systems).
More specifically, the cooling water discharge (or bleed) is the discharge portion of the used cooling system water that is simultaneously replaced with fresh water. This discharge and replacement process reduces the concentration of minerals and other system contaminants that steadily increase due to evaporation of water in the system. Cooling water evaporation is typically the major part of fresh water consumption in industrial plants, and cooling water discharge is typically the major part of wastewater discharge. The cooling water effluent contains not only high concentrations of minerals, but also sludge, rust, microorganisms and other foulants. To reduce the concentration of scale, it is known in the art to recycle a portion of the discharge water through a filtration process including Reverse Osmosis (RO). The recycling process typically includes a chemical pretreatment including an anti-fouling agent, a dispersant, and a coagulant.
However, because of the formation of large amounts of barium sulfate (a particular mineral), this barium sulfate scale is often a limiting factor or bottleneck in filtration and reverse osmosis processes. To help reduce the concentration of barium sulfate, conventional chemical pretreatment may include seeding with barium sulfate to induce crystallization, precipitation, and removal of sparingly soluble barium salts. However, the barium sulfate powders currently commercially available have proven ineffective as crystallization promoters in the presence of scale inhibitors and/or dispersants that are typically included to combat other fouling.
Accordingly, there remains a need for improved methods of inhibiting barium sulfate scale formation in industrial water systems, and more particularly, methods of recycling the cooling water emissions of water cooling towers. The present invention provides such a method. These and other advantages of the invention, as well as additional inventive features, will be apparent from the description of the invention provided herein.
Disclosure of Invention
The present invention provides a method of inhibiting barium sulfate scale formation in an industrial water system, the method preferably comprising: (i) Mixing (a) barium chloride and (b) iron sulfate and/or aluminum sulfate in an aqueous medium to form a mixture comprising barium sulfate; (ii) Aging the mixture containing barium sulfate to form a composition comprising barium sulfate seed crystals and one or more soluble iron and/or aluminum salts in the aqueous medium; and (iii) adding at least a portion of the composition comprising the barium sulfate seed crystal and one or more soluble iron and/or aluminum salts in the aqueous medium to water of the industrial water system to form treated water, thereby inhibiting barium sulfate scaling in the industrial water system.
The present invention also provides a method of recirculating the cooling water effluent of a water cooling tower, the method preferably comprising: (i) Mixing (a) barium chloride and (b) iron sulfate and/or aluminum sulfate in an aqueous medium to form a mixture comprising barium sulfate; (ii) Aging the mixture containing barium sulfate to form a composition comprising barium sulfate seed crystals and one or more soluble iron and/or aluminum salts in the aqueous medium; and (iii) adding at least a portion of the composition comprising the barium sulfate seed crystal and one or more soluble iron and/or aluminum salts in the aqueous medium to the cooling water effluent to form a treated cooling water effluent, thereby inhibiting barium sulfate scaling in the water cooling tower.
Drawings
FIG. 1 depicts an exemplary flow chart of a method of inhibiting barium sulfate scale in an industrial water system.
Detailed Description
The present invention provides a method of inhibiting barium sulfate scale formation in an industrial water system, the method preferably comprising: mixing (a) barium chloride and (b) iron sulfate and/or aluminum sulfate in an aqueous medium to form a mixture comprising barium sulfate; aging the mixture containing barium sulfate to form a composition comprising barium sulfate seed crystals and one or more soluble iron and/or aluminum salts in the aqueous medium; and adding at least a portion of the composition comprising the barium sulfate seed crystal and one or more soluble iron and/or aluminum salts in the aqueous medium to water of the industrial water system to form treated water to inhibit barium sulfate scaling in the industrial water system.
The methods described herein may be used to inhibit barium sulfate scaling in industrial water systems. As used herein, the term "scale" or "scaling" may refer to any salt or mineral deposit (e.g., barium deposit and/or sulfate deposit) that accumulates on surfaces in industrial water systems. The methods described herein may be used to inhibit scale deposits (e.g., barium deposits and/or sulfate deposits) that form on surfaces in industrial water systems due to evaporation of water and/or concentration of salts or minerals in industrial water systems, which may include, for example, cooling systems, boiler systems, heating systems, membrane systems, papermaking processes, or any other system that moves or circulates water as part of an industrially or industrially applicable process. The concentration of salts or minerals (e.g., barium sulfate) in the water of the industrial water system may cause the salts or minerals (e.g., barium sulfate) in the water to become supersaturated. Thus, in some embodiments, the present invention may be used to inhibit scaling in water of an industrial water system by supersaturating barium sulfate in water of the industrial water system prior to treatment with a composition comprising barium sulfate seed crystals and one or more soluble iron salts, aluminum salts, or a combination thereof in an aqueous medium. The formation of scale (e.g., barium deposits and/or sulfate deposits) can cause fouling of filters or reverse osmosis devices, thereby inhibiting or reducing the efficiency of purification and recirculation of feed water in industrial water systems.
In some embodiments, the methods of the present invention comprise mixing (a) barium chloride and (b) ferric sulfate and/or aluminum sulfate in an aqueous medium to form a mixture comprising barium sulfate. The barium chloride and the iron sulfate and/or aluminum sulfate may be mixed in any suitable form and by any suitable means. For example, barium chloride and ferric sulfate and/or aluminum sulfate may be added to the mixture as a solid, an aqueous solution, an aqueous dispersion, or any suitable combination thereof. In some embodiments, barium chloride and iron sulfate and/or aluminum sulfate are mixed together as an aqueous solution of barium chloride and an aqueous solution of iron sulfate and/or aluminum sulfate.
The iron sulphate may be present in any suitable form. For example, the iron sulfate may be ferric sulfate, polymeric Ferric Sulfate (PFS), or any suitable combination thereof. In some embodiments, the iron sulfate comprises iron (III) sulfate (i.e., ferric sulfate). Thus, for example, the method may comprise, for example, the addition of iron (III) sulfate. In some embodiments, the method may additionally or alternatively include adding Polymeric Ferric Sulfate (PFS).
The aluminium sulphate may be present in any suitable form. In some embodiments, the method includes adding an aluminum sulfate, such as, for example, aluminum sulfate, polyaluminum sulfate (PAS), or any suitable combination thereof. In some embodiments, the method comprises adding polyaluminium sulfate (PAS).
The barium chloride and iron sulfate and/or aluminum sulfate may be combined in any suitable manner and in any suitable amount/concentration and in any suitable ratio as desired to produce barium sulfate seed crystals effective to promote precipitation of barium salts in the system. For example, barium chloride may be mixed with a molar excess of iron sulfate and/or aluminum sulfate, iron sulfate and/or aluminum sulfate may be mixed with a molar excess of barium chloride, or barium chloride may be mixed with iron sulfate and/or aluminum sulfate in a 1:1 molar ratio. In some embodiments, barium chloride is mixed with a molar excess of ferric sulfate and/or aluminum sulfate.
Once combined in the aqueous medium, the barium chloride and iron sulfate and/or aluminum sulfate are preferably aged to form a composition comprising barium sulfate seed crystals and one or more soluble iron and/or aluminum salts in the aqueous medium. As used herein, the term "aging" the mixture may refer to mixing the mixture (e.g., stirring, shaking, stirring, inverting, etc.), allowing the mixture to stand, heating the mixture, cooling the mixture, or any suitable combination thereof, thereby allowing the formation of barium sulfate seed crystals and one or more soluble iron and/or aluminum salts in an aqueous medium. As used herein, "one or more soluble iron and/or aluminum salts in an aqueous medium" may refer to one or more iron and/or aluminum salts and/or one or more iron and/or aluminum salts that are partially soluble in the aqueous medium (i.e., aqueous solution) such that at least a portion of such salts may precipitate out of the aqueous medium (i.e., form an aqueous slurry or dispersion containing such salts). The mixture may be aged for any suitable period of time such that the aging provides a composition comprising the barium sulfate seed and one or more soluble iron and/or aluminum salts in an aqueous medium. The aging time may be adjusted in any suitable manner to promote and/or optimize seed formation based on variables that may affect the rate and quality of seed formation produced in a particular system, such as, for example, the concentration of added reagent, the purity of water used, temperature, etc. In some embodiments, the mixture may be aged for at least 5 minutes, at least 10 minutes, at least 15 minutes, at least 30 minutes, at least 1 hour, at least 2 hours, at least 5 hours, or at least 10 hours. In some embodiments, the mixture of barium chloride and iron sulfate and/or aluminum sulfate may be aged for a period of time ranging from about 5 minutes to about 10 hours, from about 5 minutes to about 5 hours, from about 5 minutes to about 2 hours, from about 5 minutes to about 1 hour, from about 5 minutes to about 30 minutes, from about 10 minutes to about 10 hours, from about 10 minutes to about 5 hours, from about 10 minutes to about 2 hours, from about 10 minutes to about 1 hour, from about 10 minutes to about 30 minutes, from about 15 minutes to about 10 hours, from about 15 minutes to about 5 hours, from about 15 minutes to about 2 hours, from about 15 minutes to about 1 hour, from about 15 minutes to about 30 minutes, from about 30 minutes to about 10 hours, from about 30 minutes to about 5 hours, from about 30 minutes to about 2 hours, or from about 30 minutes to about 1 hour.
The methods described herein may further comprise adding at least a portion of a composition comprising barium sulfate seed and one or more soluble iron and/or aluminum salts in an aqueous medium to water of an industrial water system to form treated water. The composition comprising the barium sulfate seed crystal and one or more soluble iron and/or aluminum salts in an aqueous medium may be added to the water of the industrial water system by any suitable means. For example, the composition may be added to the water of an industrial water system by pouring, injection, spraying, or the like, to introduce barium sulfate seed crystals into the water of the industrial water system. Without wishing to be bound by any particular theory, it is believed that the barium sulfate seed precipitates supersaturated barium sulfate already present in the feed water system, which reduces the soluble barium concentration, thereby alleviating the bottleneck caused by barium sulfate scaling in the downstream process. It is also believed that after the solution is introduced into the feed water, the aqueous iron and/or aluminum salts may form iron and/or aluminum hydroxide, wherein the formed iron and/or aluminum hydroxide agglomerate barium sulfate crystals in situ to form larger, easily filterable particles or crystals, improving the efficiency of the filtration process by preventing smaller barium sulfate particles (e.g., nanoparticles) from entering the membrane pores, thereby limiting irreversible fouling.
In some embodiments, the invention comprises adding a composition comprising barium sulfate seed crystals and one or more soluble iron and/or aluminum salts in an aqueous medium to water of an industrial water system in an amount sufficient to provide the following iron or aluminum dosages: from about 5ppm to about 500ppm, from about 5ppm to about 250ppm, from about 5ppm to about 100ppm, from about 5ppm to about 50ppm, from about 5ppm to about 20ppm, from about 10ppm to about 500ppm, from about 10ppm to about 250ppm, from about 10ppm to about 100ppm, from about 10ppm to about 50ppm, from about 10ppm to about 20ppm, from about 15ppm to about 500ppm, from about 15ppm to about 250ppm, from about 15ppm to about 100ppm, from about 15ppm to about 50ppm, from about 15ppm to about 20ppm, from about 20ppm to about 500ppm, from about 20ppm to about 250ppm, from about 20ppm to about 100ppm, or from about 20ppm to about 50ppm.
The process of the present invention is particularly useful for inhibiting barium sulfate scale. As used herein, "barium sulfate scale" may refer to the formation of barium sulfate on a surface or the formation of barium minerals and sulfate minerals on a surface due to the presence of barium sulfate. Without wishing to be bound by any particular theory, it is believed that the freshly generated barium sulfate precipitate (e.g., by mixing/aging (a) barium chloride and (b) iron sulfate and/or aluminum sulfate) as described herein has a greater and/or effective active surface area for promoting barium salt precipitation than conventional (e.g., commercially available) barium sulfate powders. More specifically, it is believed that the immediate generation of barium sulfate seed crystals prior to addition to the water of the industrial water system according to the present invention results in more efficient removal of barium sulfate, for example by precipitation of barium sulfate, which may be highly concentrated or even in a supersaturated state in the water of the industrial water system, in particular in the presence of an anti-fouling agent and/or a dispersant.
The barium sulfate seed crystals of the present invention may be prepared shortly or immediately (e.g., at the point of use) prior to addition to the water of the industrial water system. "immediately or immediately (e.g., at the point of use) prior to addition to the water of the industrial water system" includes cases in which the barium sulfate seed crystal is prepared about 5 hours or less prior to addition to the water of the industrial water system, e.g., about 2 hours or less, about 1 hour or less, about 30 minutes or less, about 20 minutes or less, about 10 minutes or less, about 5 minutes or less, about 1 minute or less, about 45 seconds or less, about 30 seconds or less, or about 10 seconds or less prior to addition to the water of the industrial water system. Barium sulfate seed crystals may also be prepared within 100m of the point of use, for example within 50m of the point of use, within 10m of the point of use, or even within 1m of the point of use. As used herein, "point of use" refers to the point or physical location of adding barium sulfate seed crystals relative to the point or physical location of the water of the industrial water system.
In some embodiments, the methods of the present invention may further comprise filtering the treated water to remove suspended particles (e.g., barium sulfate, ferric hydroxide, and/or aluminum hydroxide) to form filtered treated water. The treated water may be filtered (e.g., contacted with and/or passed through a suitable filter medium, or decanted) by any suitable means to remove at least a portion of suspended particles (e.g., barium sulfate, ferric hydroxide, and/or aluminum hydroxide) from the treated water. In some embodiments, the method comprises filtering the treated water with one or more filters having a pore size of about 10 μm to about 100 μm, one or more microfilters having a pore size of about 0.1 μm to about 10 μm, one or more nanofilters having a pore size of about 1nm to about 0.1 μm, or a combination thereof. For example, the treated water may be sequentially filtered with one or more filters having sequentially decreasing pore sizes (e.g., with a filter having a pore size of about 10 μm to about 100 μm, a microfilter having a pore size of about 0.1 μm to about 10 μm, and a nanofilter having a pore size of about 1nm to about 0.1 μm) to avoid filter fouling. Alternatively, the treated water may be filtered through any filter having a pore size of about 10 μm to about 100 μm, a microfilter having a pore size of about 0.1 μm to about 10 μm, and/or a nanofilter having a pore size of about 1nm to about 0.1 μm. In some embodiments, the treated water is filtered with at least one microfilter having a pore size of about 0.1 μm to about 10 μm.
Filtering the treated water to remove suspended particles (e.g., barium sulfate, ferric hydroxide, and/or aluminum hydroxide) may provide any suitable concentration of barium in the filtered treated water. For example, filtering the treated water may result in a barium concentration in the filtered treated water of less than about 0.12mg/L, a barium concentration in the filtered treated water of less than about 0.1mg/L, or a barium concentration in the filtered treated water of less than about 0.08mg/L. In some embodiments, the methods of the present invention can reduce the barium concentration in the water of an industrial water system from supersaturated (prior to treatment) with barium sulfate to, for example, less than about 0.12mg/L barium concentration in the treated water after filtration, less than about 0.1mg/L barium concentration in the treated water after filtration, or less than about 0.08mg/L barium concentration in the treated water after filtration.
In some embodiments, the methods of the present invention can further comprise purifying the filtered water (i.e., the filtered treated water) by reverse osmosis to provide purified treated water. For example, if filtering the treated water to remove suspended particles does not provide water of sufficient purity to be recycled back into the industrial water system of a particular system, the filtered water (i.e., the filtered treated water) may be purified by reverse osmosis.
The method of the present invention may further comprise recycling the treated water back to the industrial water system. The treated water may be recycled back to the industrial water system for further use as (i) at least a portion of the composition comprising the barium sulfate seed and the one or more soluble iron and/or aluminum salts in the aqueous medium is added to the water of the industrial water system to form treated water, (ii) the treated water is filtered to remove suspended particles, thereby forming filtered treated water, and/or (iii) the filtered water is optionally purified by reverse osmosis to provide purified treated water.
An exemplary flow chart of a method of inhibiting barium sulfate scale in an industrial water system is depicted in fig. 1. Fig. 1 depicts combining ferric sulfate and barium chloride in an aqueous medium to form a mixture containing barium sulfate, and combining the mixture with feed water in a mixing tank. After combining the mixture containing barium sulfate and feed water in the mixing tank, the resulting composition is filtered using Ultrafiltration (UF) (e.g., using a microfilter) to form a concentrate, the concentrate is removed to form a permeate, the permeate is Reverse Osmosis (RO) to form a concentrate, the concentrate is removed to form a permeate, and the permeate can be recycled back to the industrial water system.
In some embodiments, the water of the industrial water system may further comprise a scale inhibitor. As mentioned herein, conventional (e.g., commercially available) barium sulfate powders may not perform particularly well when used in combination with scale inhibitors (e.g., polymer-based scale inhibitors). Thus, the method of the present invention may be particularly suitable for industrial water systems in which one or more additional scale inhibitors (e.g., polymer-based scale inhibitors) are present. Scale inhibitors that may be present in the water of the industrial water system may include, but are not limited to, for example, polymaleic acid, poly (meth) acrylic acid, polyepoxysuccinic acid (PESA), polyaspartic Acid (PASP), aminotrimethylene phosphonic Acid (AMP), 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDP), 2-phosphonobutane-1, 2, 4-tricarboxylic acid (PBTC), polyaminopolyether methylene phosphonate (PAPEMP), ethylenediamine tetramethylene phosphonic acid (EDTMPA), diethylenetriamine pentamethylene phosphonic acid (DTPMPA), hexamethylenediamine tetramethylene phosphonic acid (HMDTMPA), bis (hexamethylenetriamine pentamethylene phosphonic acid) (bhmtpmmp), hydroxyethylamino bis (methylenephosphonic acid) (HEMPA), hydroxyphosphonoacetic acid (HPA), phosphinosuccinic acid oligomers (PSO), salts thereof, or combinations thereof. Alternatively or additionally, the scale inhibitor may comprise a polymer and/or copolymer comprising one or more monomers selected from the group consisting of: (meth) acrylic acid, (meth) acrylamide, hydroxypropyl acrylate, 2-acrylamido-2-methylpropane sulfonate, maleic anhydride, sulfonated styrene, t-butyl acrylamide, salts thereof, and combinations thereof. For example, the scale inhibitor may include polymaleic anhydride, poly (meth) acrylic acid, poly (meth) acrylamide, alkyl epoxycarboxylate, salts thereof, or combinations thereof. The scale inhibitor may further comprise a copolymer comprising monomers selected from the group consisting of: (meth) acrylic acid, (meth) acrylamide, hydroxypropyl acrylate, 2-acrylamido-2-methylpropane sulfonate, maleic anhydride, sulfonated styrene, t-butyl acrylamide, salts thereof, and combinations thereof. For example, the scale inhibitor may include (meth) acrylic acid/(meth) acrylamide copolymer (AA/AM), (meth) acrylic acid/hydroxypropyl acrylate copolymer (AA/HPA), (meth) acrylic acid/2-acrylamido-2-methylpropanesulfonate copolymer (AA/AMPS), maleic anhydride/sulfonated styrene copolymer (MA/SS), (meth) acrylic acid/(meth) acrylamide/t-butylacrylamide copolymer (AA/AM/t-BAM), (meth) acrylic acid/2-acrylamido-2-methylpropanesulfonate/t-butylacrylamide copolymer (AA/AMPS/t-BAM), (meth) acrylic acid/sulfonated styrene/2-acrylamido-2-methylpropanesulfonate copolymer (AA/SS/AMPS), 2-acrylic acid/(meth) acrylamide/aminomethylsulfonate copolymer (AA/AM/AMs), copolymers of 2-acrylic acid and alpha-2-propenyl-omega-hydroxypoly (oxy-1, 2-ethanediyl) (e.g., PAP-sodium), salts thereof, or combinations thereof.
In some embodiments, the water of the industrial water system may further comprise a polymeric dispersant. As mentioned herein, conventional (e.g., commercially available) barium sulfate powders may not perform particularly well when used in combination with polymeric dispersants. Thus, the process of the present invention may be particularly suitable for industrial water systems in which one or more polymeric dispersants are present. The polymeric dispersant may comprise at least one monomer component that is acrylamidomethanesulfonic acid, (dimethyl (2-oxobut-3-en-1-yl) ammonio) methanesulfonate, allyloxy polyethoxy (10) sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, acrylamide t-butylsulfonate, 4- (allyloxy) benzenesulfonic acid, styrenesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allylhydroxypropane sulfonic acid, salts thereof, or combinations thereof. Alternatively or additionally, the polymeric dispersant may comprise at least one monomer component that is (meth) acrylamide, (meth) acrylic acid, itaconic acid, maleic anhydride, crotonic acid, acrylamidoglycolic acid, salicylacrylamidoglycolic acid, allylmalonic acid dimethyl ester, 2-carboxyethyl acrylate, 3-acrylamido-3-methylbutanoic acid, salts thereof, or combinations thereof.
In some embodiments, the methods described herein may further comprise adjusting the pH of the water, treated water, filtered water, and/or purified water of the industrial water system with a pH adjuster. The pH of the water, treated water, filtered water, and/or purified water of the industrial water system may be adjusted to any suitable pH, for example, to help inhibit barium sulfate scale formation in the industrial water system. For example, the water of the industrial water system, the treated water, the filtered water, and/or the purified water may have a pH of about 4 to about 12. In some embodiments, the water, treated water, filtered water, and/or purified water of the industrial water system may have a pH of about 4 to about 12, about 5 to about 12, about 4 to about 11, about 5 to about 11, about 4 to about 10, about 5 to about 10, about 4 to about 9, about 5 to about 9, about 4 to about 8, about 5 to about 8, about 6 to about 12, about 6 to about 11, about 6 to about 10, about 6 to about 9, about 6 to about 8, about 7 to about 12, about 8 to about 12, about 9 to about 12, about 7 to about 10, or about 8 to about 10. The pH adjuster may be an acidic or basic pH adjuster, or the pH adjuster comprises an acidic, basic or a combination of acidic and basic pH adjusters, such as a buffer. In some embodiments, the pH adjustor can comprise, for example, sulfuric acid, acetic acid, citric acid, nitric acid, propionic acid, tartaric acid, fumaric acid, phosphoric acid, salts thereof, or combinations thereof.
As used herein, an "industrial water system" refers to any system that circulates water as part of an industrially or industrially applicable process. Non-limiting examples of "industrial water systems" include, for example, cooling systems, boiler systems, heating systems, membrane systems, papermaking processes, humidification systems, recovery systems, water purification systems, or any other system that moves or circulates water as part of an industrially or industrially applicable process. In some embodiments, the industrial water system is a cooling water system, such as, for example, an open loop cooling system, a closed loop cooling system, a passivating cooling system, or a combination thereof.
As used herein, "water" refers to any liquid that contains water as a major component. The water may include, for example, purified water, tap water, fresh water, recycled water, brine, steam, and/or any aqueous solution or aqueous blend. In some embodiments, the water of the industrial water system comprises cooling water emissions.
In some embodiments, the methods described herein are used to recycle the cooling water emissions of a water cooling tower. Accordingly, the present invention provides a method of recirculating the cooling water effluent of a water cooling tower, for example, the method preferably comprising: for example, mixing (a) barium chloride and (b) iron sulfate and/or aluminum sulfate in an aqueous medium to form a mixture comprising barium sulfate; aging the mixture containing barium sulfate to form a composition comprising barium sulfate seed crystals and one or more soluble iron and/or aluminum salts in the aqueous medium; and (iii) adding at least a portion of the composition comprising the barium sulfate seed crystal and one or more soluble iron and/or aluminum salts in the aqueous medium to the cooling water effluent to form a treated cooling water effluent, thereby inhibiting barium sulfate scaling in the water cooling tower. In some embodiments, the method may further comprise (iv) filtering the treated cooling water effluent to remove suspended particulates, thereby forming a filtered treated cooling water effluent. In some embodiments, the method may further comprise (v) purifying the filtered cooling water effluent by reverse osmosis to provide a purified treated cooling water effluent. Further details and alternatives regarding the method of recirculating the cooling water effluent of a water cooling tower will become apparent from the embodiments and/or aspects provided herein.
Description of the embodiments
Aspects (including embodiments) of the inventive subject matter described herein can be used alone or in combination with, for example, one or more other aspects or embodiments described herein. Certain non-limiting aspects of the present disclosure numbered 1-37 are provided below without limitation. As will be apparent to one of ordinary skill in the art upon reading this disclosure, each of the individually numbered aspects may be used or combined with any of the preceding or following individually numbered aspects. This is intended to provide additional support for all such combinations of aspects and is not limited to the aspects or combinations of aspects explicitly provided below:
(1) In aspect (1) a method of inhibiting barium sulfate scale formation in an industrial water system is presented, the method comprising:
(i) Mixing (a) barium chloride and (b) iron sulfate and/or aluminum sulfate in an aqueous medium to form a mixture comprising barium sulfate;
(ii) Aging the mixture comprising barium sulfate to form a composition comprising barium sulfate seed crystals and one or more soluble iron and/or aluminum salts in the aqueous medium; and
(iii) At least a portion of the composition comprising the barium sulfate seed crystal and one or more soluble iron and/or aluminum salts in the aqueous medium is added to water of the industrial water system to form treated water to inhibit barium sulfate scaling in the industrial water system.
(2) In aspect (2) there is provided the method of aspect (1), wherein the method further comprises:
(iv) The treated water is filtered to remove suspended particles, thereby forming filtered treated water.
(3) In aspect (3) there is provided the method according to aspect (2), wherein the method further comprises:
(v) The filtered treated water is purified, for example by reverse osmosis, to provide purified treated water.
(4) In aspect (4) the method of any one of aspects (1) - (3) is presented, wherein the method comprises adding an iron sulfate salt that is iron sulfate, polymeric Ferric Sulfate (PFS), or a combination thereof.
(5) In aspect (5) the method according to any one of aspects (1) - (4) is presented, wherein the method comprises adding an aluminum sulfate salt, the aluminum sulfate salt being aluminum sulfate, polyaluminum sulfate (PAS), or a combination thereof.
(6) In aspect (6) the method according to any one of aspects (1) - (5) is presented, wherein the water of the industrial water system further comprises a scale inhibitor.
(7) In aspect (7) there is provided the method according to aspect (6), wherein the scale inhibitor comprises polymaleic acid, poly (meth) acrylic acid, polyepoxysuccinic acid (PESA), polyaspartic Acid (PASP), aminotrimethylene phosphonic Acid (AMP), 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDP), 2-phosphonobutane-1, 2, 4-tricarboxylic acid (PBTC), polyaminopolyether methylenephosphonate (PAPEMP), ethylenediamine tetramethylene phosphonic acid (EDTMPA), diethylenetriamine pentamethylene phosphonic acid (DTPMPA), hexamethylenediamine tetramethylene phosphonic acid (HMDTMPA), bis (hexamethylenetriamine pentamethylene phosphonic acid) (bhmtmp), hydroxyethylamino bis (methylenephosphonic acid) (HEMPA), hydroxyphosphonoacetic acid (HPA), phosphinosuccinic acid oligomers (PSO), salts thereof, or combinations thereof.
(8) In aspect (8) the method according to any one of aspects (1) - (7) is presented, wherein the water of the industrial water system further comprises a polymeric dispersant.
(9) In aspect (9) there is provided the method according to aspect (8), wherein the polymeric dispersant comprises at least one monomer component/unit that is acrylamidomethanesulfonic acid, (dimethyl (2-oxobut-3-en-1-yl) ammonio) methanesulfonate, allyloxypolyethoxy (10) sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, acrylamide t-butyl sulfonate, 4- (allyloxy) benzenesulfonic acid, styrenesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allylhydroxypropanesulfonic acid, salts thereof, or combinations thereof.
(10) In aspect (10) there is provided the method of aspect (9), wherein the polymeric dispersant further comprises at least one monomer component/unit that is (meth) acrylamide, (meth) acrylic acid, itaconic acid, maleic anhydride, crotonic acid, acrylamidoglycolic acid, salicylacrylamidoglycolic acid, allylmalonic acid dimethyl ester, 2-carboxyethyl acrylate, 3-acrylamido-3-methylbutanoic acid, salts thereof, or combinations thereof.
(11) In aspect (11) the method according to any one of aspects (1) - (10) is presented, wherein barium sulfate in the water of the industrial water system is supersaturated prior to treatment with the composition comprising the barium sulfate seed crystal and the one or more soluble iron and/or aluminum salts.
(12) In aspect (12) there is provided the method of any one of aspects (1) - (11), comprising filtering the treated water with a filter having a pore size of about 10 μm to about 100 μm.
(13) In aspect (13) there is provided the method according to any one of aspects (1) - (12), comprising filtering the treated water with a microfilter having a pore size of about 0.1 μm to about 10 μm.
(14) In aspect (14) there is provided the method according to any one of aspects (1) - (13), comprising filtering the treated water with a nanofiltration having a pore size of about 1nm to about 0.1 μm.
(15) In aspect (15) the method according to any one of aspects (1) to (14), wherein the industrial water system comprises a cooling system, a boiler system, a heating system,
A membrane system, a papermaking process or system, a humidification system, a recovery system, or a water purification system.
(16) In aspect (16) there is provided the method according to any one of aspects (1) - (14), wherein the industrial water system comprises a cooling water system.
(17) In aspect (17) the method of any one of aspects (1) - (16) is presented, wherein the water of the industrial water system comprises a cooling water discharge.
(18) The method according to any one of aspects (2) to (17) is set forth in aspect (18),
wherein the filtered treated water has a barium concentration of less than about 0.12 mg/L.
(19) In aspect (19) the method of any one of aspects (2) - (17) is presented, wherein the filtered treated water has a barium concentration of less than about 0.1 mg/L.
(20) In aspect (20) there is provided the method according to any one of aspects (1) - (19), comprising recycling the treated water back into the industrial water system.
(21) In aspect (21) there is presented a method of recirculating cooling water emissions from a water cooling tower, the method comprising:
(i) Mixing (a) barium chloride and (b) iron sulfate and/or aluminum sulfate in an aqueous medium to form a mixture comprising barium sulfate;
(ii) Aging the mixture comprising barium sulfate to form a composition comprising barium sulfate seed crystals and one or more soluble iron and/or aluminum salts in the aqueous medium; and
(iii) At least a portion of the composition comprising the barium sulfate seed crystals and one or more soluble iron and/or aluminum salts in the aqueous medium is added to the cooling water effluent to form a treated cooling water effluent in which barium sulfate scaling in the water cooling tower is inhibited.
(22) In aspect (22) there is provided the method according to aspect (21), wherein the method further comprises:
(iv) The treated cooling water effluent is filtered to remove suspended particulates, thereby forming a filtered treated cooling water effluent.
(23) In aspect (23) there is provided the method according to aspect (22), wherein the method further comprises:
(v) The filtered cooling water effluent is purified, for example by reverse osmosis, to provide a purified treated cooling water effluent.
(24) In aspect (24) the method of any one of aspects (21) - (23) is presented, wherein the method comprises adding an iron sulfate salt that is ferric sulfate, polymeric Ferric Sulfate (PFS), or a combination thereof.
(25) In aspect (25) the method according to any one of aspects (21) - (24) is presented, wherein the method comprises adding an aluminum sulfate salt, the aluminum sulfate salt being aluminum sulfate, polyaluminum sulfate (PAS), or a combination thereof.
(26) In aspect (26) there is provided the method according to any one of aspects (21) - (25), wherein the cooling water effluent further comprises a scale inhibitor.
(27) In aspect (27) there is provided the method according to aspect (26), wherein the scale inhibitor comprises polymaleic acid, poly (meth) acrylic acid, polyepoxysuccinic acid (PESA), polyaspartic Acid (PASP), aminotrimethylene phosphonic Acid (AMP), 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDP), 2-phosphonobutane-1, 2, 4-tricarboxylic acid (PBTC), polyaminopolyether methylenephosphonate (PAPEMP), ethylenediamine tetramethylene phosphonic acid (EDTMPA), diethylenetriamine pentamethylene phosphonic acid (DTPMPA), hexamethylenediamine tetramethylene phosphonic acid (HMDTMPA), bis (hexamethylenetriamine pentamethylene phosphonic acid) (bhmtmp), hydroxyethylamino bis (methylenephosphonic acid) (HEMPA), hydroxyphosphonoacetic acid (HPA), phosphinosuccinic acid oligomers (PSO), salts thereof, or combinations thereof.
(28) In aspect (28) there is provided the method of any one of aspects (21) - (27), wherein the cooling water effluent further comprises a polymeric dispersant.
(29) In aspect (29) there is provided the method of aspect (28), wherein the polymeric dispersant comprises at least one monomer component/unit that is acrylamidomethanesulfonic acid, (dimethyl (2-oxobut-3-en-1-yl) ammonio) methanesulfonate, allyloxypolyethoxy (10) sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, acrylamide t-butyl sulfonate, 4- (allyloxy) benzenesulfonic acid, styrenesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allylhydroxypropanesulfonic acid, salts thereof, or combinations thereof.
(30) In aspect (30) there is provided the method of aspect (29), wherein the polymeric dispersant further comprises at least one monomer component/unit that is (meth) acrylamide, (meth) acrylic acid, itaconic acid, maleic anhydride, crotonic acid, acrylamidoglycolic acid, salicylacrylamidoglycolic acid, allylmalonic acid dimethyl ester, 2-carboxyethyl acrylate, 3-acrylamido-3-methylbutanoic acid, salts thereof, or combinations thereof.
(31) The method of any one of aspects (21) - (30) is presented in aspect (31), wherein barium sulfate in the cooling water effluent of the water cooling tower is supersaturated prior to treatment with the composition comprising the barium sulfate seed crystal and the one or more soluble iron and/or aluminum salts.
(32) In aspect (32) there is provided the method of any one of aspects (21) - (31), comprising filtering the treated cooling water effluent with a filter having a pore size of about 10 μm to about 100 μm.
(33) In aspect (33) there is provided the method of any one of aspects (21) - (32), comprising filtering the treated cooling water effluent with a microfilter having a pore size of about 0.1 μm to about 10 μm.
(34) In aspect (34) there is provided the method of any one of aspects (21) - (33), comprising filtering the treated cooling water effluent with a nanofiltration having a pore size of about 1nm to about 0.1 μm.
(35) The method of any one of aspects (22) - (34) is set forth in aspect (35), wherein the filtered treated cooling water effluent has a barium concentration of less than about 0.12 mg/L.
(36) The method of any one of aspects (22) - (34) is set forth in aspect (36), wherein the filtered treated cooling water effluent has a barium concentration of less than about 0.1 mg/L.
(37) In aspect (37) there is provided the method of any one of aspects (23) - (36), the method comprising recycling the treated water back into the industrial water system.
Examples
The following examples further illustrate the invention but, of course, should not be construed as in any way limiting its scope.
Example 1
This example demonstrates the use of freshly generated BaSO 4 The treated cooling tower discharges barium (Ba) in solution exhibited by water 2+ ) And (3) concentration reduction.
A cooling tower discharge water sample was obtained with the following parameters: 0.2ppm of barium (Ba) 2+ ) 300ppm of sulfate radical (SO) 4 2- ) 150ppm of calcium (Ca) 2+ ) 73ppm of magnesium (Mg) 2+ ) pH 8.4, conductivity 2100 μs/cm and total alkalinity (CaCO) of 350ppm 3 Meter).
An aqueous solution of Polymeric Ferric Sulfate (PFS) containing 10 wt% iron was mixed with a solution containing 10 wt% BaCl 2 ·H 2 The aqueous solutions of O were mixed in the ratios shown in table 1. The resulting solution was stirred for 10 minutes to produce barium sulfate seed crystals and iron salts, and added to the cooling tower drain water sample such that the treated cooling tower drain water sample had an iron dosage of 20 ppm. The mixture was stirred for 10 minutes to 60 minutes to precipitate barium sulfate, and filtered using an ultrafiltration membrane having an average pore size of about 0.15 μm. The effluent barium concentration was determined by Inductively Coupled Plasma (ICP) spectroscopy and the results are shown in table 1.
2+ TABLE 1 influence of Water treatment on barium (Ba) concentration
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As is apparent from the results shown in Table 1, relative to the inclusion of BaSO 4 Control treatment 1A, dosed, comprised of Polymeric Ferric Sulfate (PFS) and BaCl 2 ·H 2 The combination of O forms in situ BaSO 4 Is processed according to the invention1B to 1M significantly reduced the concentration of barium in the effluent. In addition, table 1 shows that the composition consists of Polymeric Ferric Sulfate (PFS) and BaCl 2 ·H 2 The combination of O forms in situ BaSO 4 The inventive treatments 1B to 1M are significantly better than those comprising commercially available/conventional BaSO 4 Comparative examples of powder dosing were conducted at 1N to 1P. These results indicate that the compositions are composed of Polymeric Ferric Sulfate (PFS) and BaCl relative to the control 2 ·H 2 Freshly prepared BaSO formed in situ by the combination of O 4 The concentration of barium in the effluent is reduced more effectively and is significantly better than commercially available/conventional barium sulfate powders.
Example 2
This example demonstrates that the ultrafiltration unit is using freshly generated BaSO 4 The ability to recover its initial flux after multiple filtration iterations of the treated cooling tower discharge water.
A cooling tower discharge water sample was obtained with the following parameters: 0.2ppm of barium (Ba) 2+ ) 300ppm of sulfate radical (SO) 4 2- ) 150ppm of calcium (Ca) 2+ ) 73ppm of magnesium (Mg) 2+ ) pH 8.4, conductivity 2100 μs/cm and total alkalinity (CaCO) of 350ppm 3 Meter).
With premixed BaCl 2 ·H 2 O (20 ppm) and a Polymeric Ferric Sulfate (PFS) aqueous solution containing 10 wt.% iron treat the first cooling tower discharge water sample to provide a 20ppm iron dose in the first treated cooling tower discharge water sample. The solution pH was adjusted to 7. The resulting mixture was stirred for 30 minutes and was used as feed water in the following ultrafiltration experiments under constant stirring.
With premixed BaCl 2 ·H 2 O (20 ppm) and a Polymeric Ferric Sulfate (PFS) aqueous solution containing 10 wt.% iron treat the second cooling tower discharge water sample to provide a 20ppm iron dose in the second treated cooling tower discharge water sample. After the pH was adjusted to 7 and stirred for 30 minutes, an anionic polyacrylamide solution (1 ppm) was added to flocculate the suspended solids. The resulting solution was allowed to settle for 2 hours and the resulting supernatant was used in the following ultrafiltration experiments.
Using molecular weight cut-off100kDa and an area of 40cm 2 The polyethersulfone flat membrane was subjected to ultrafiltration experiments in dead-end mode. A constant pressure of 0.1MPa was maintained and the permeate flux was calculated by weighing the filtrate with an automatic balance. A filtrate volume of 500mL was collected and the membrane was backwashed with 100mL of filtrate. The filtration/backwash process was repeated for 10 cycles. After 10 cycles, the ultrafiltration membranes were washed in the following order: backwash was performed and soaked in 500ppm sodium hypochlorite solution, deionized water, 1% citric acid solution for 10 minutes, and again in deionized water for 10 minutes. After washing, the filtration of the sample water was resumed. The ratio of the initial flux after washing to the initial flux of the original membrane was used as a measure of irreversible fouling.
Repeated ultrafiltration experiments using the first treated cooling tower discharge water sample produced an initial flux recovery of nearly 100% (> 99%). In addition, repeated ultrafiltration experiments using the second treated cooling tower drain water sample produced an initial flux recovery of 95% to 98%. Energy dispersive spectrophotometric analysis showed that 2% to 5% of fouling of ultrafiltration membranes was caused by barium, sulfur and iron as the major foulants.
These results indicate that the polymer is composed of Polymeric Ferric Sulfate (PFS) and BaCl 2 ·H 2 Freshly prepared BaSO formed in situ by the combination of O 4 Provides a minimum of irreversible fouling. In contrast, conventional methods of coagulation, flocculation, sedimentation and filtration of the supernatant can lead to significant irreversible fouling. Without wishing to be bound by any particular theory, it is believed that very fine barium sulfate crystals, which are difficult to 100% capture by conventional coagulation, flocculation and sedimentation methods, may enter the ultrafiltration membrane pores and cause irreversible membrane fouling. It is also believed that the precipitate formed in situ from the aqueous iron and/or aluminum salts after the composition is added to the feed water not only results in agglomeration of very fine barium sulfate crystals, but also prevents them from entering the membrane pores, thereby limiting irreversible fouling.
Example 3
This example demonstrates the use of freshly generated BaSO as compared to untreated cooling tower discharge water 4 Cooling of the treatmentThe Reverse Osmosis (RO) recovery limit exhibited by the column discharge water is improved.
According to the procedure described in example 2, the pre-mixed BaCl was used already according to example 2 2 ·H 2 The cooling tower effluent water from the O (20 ppm) and Polymeric Ferric Sulfate (PFS) aqueous solution treatment and the untreated cooling tower effluent water were subjected to ultrafiltration. The barium concentration of the resulting ultrafiltration effluent samples of the treated cooling tower drain water and the untreated cooling tower drain water were 0.08mg/L and 0.20mg/L, respectively, while the sulfate concentration of the two samples was about 320mg/L.
An anti-fouling agent (aminotrimethylene phosphonic Acid (ATMP); 50% aqueous solution) was added to each of the treated cooling tower effluent and the untreated cooling tower effluent at a primary dose of 5 ppm. Surface area of 310cm 2 BW30-4040RO membrane (from 1.2MPa feed pressureCommercially available) concentrate two liters each of treated cooling tower discharge water effluent and untreated cooling tower discharge water effluent. The concentration process lasted about 1 hour. After completion, permeate was collected and redirected back to the feed reservoir, allowing the RO simulation to run for an additional day in recirculation mode. RO permeate flow rate, conductivity and feed pressure were monitored during recirculation.
The results indicate that the treated cooling tower effluent water (i.e., the sample with the lower barium concentration) can be concentrated four times with a recovery of about 75% and without clogging the RO membrane. However, untreated cooling tower discharge water effluent (i.e., samples with higher barium concentrations) had significant permeate flow loss (about 10 minutes) in the recycle mode, and only a maximum recovery of about 60% could be achieved. Analysis by energy dispersive spectrophotometry showed that fouling on RO membranes was mainly the result of barium sulfate fouling.
All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.
The use of the terms "a" and "an" and "the" and "at least one" and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The term "at least one" (e.g., "at least one of a and B") as used after a list of one or more items is to be construed to refer to one item (a or B) selected from the listed items or any combination (a and B) of two or more of the listed items unless otherwise indicated herein or clearly contradicted by context. Unless otherwise indicated, the terms "comprising," "having," "including," and "containing" are to be construed as open-ended terms (i.e., meaning "including, but not limited to"). Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.
Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.
Claims (37)
1. A method of inhibiting barium sulfate scale formation in an industrial water system, the method comprising:
(i) Mixing (a) barium chloride and (b) ferric sulfate, aluminum sulfate, or a combination thereof in an aqueous medium to produce a mixture comprising barium sulfate;
(ii) Aging the mixture comprising barium sulfate to produce a composition comprising barium sulfate seed crystals and one or more soluble iron salts, aluminum salts, or combinations thereof in the aqueous medium; and
(iii) Adding at least a portion of the composition comprising the barium sulfate seed crystal and one or more soluble iron salts, aluminum salts, or combinations thereof in the aqueous medium to water of the industrial water system to form treated water to inhibit barium sulfate scaling in the industrial water system.
2. The method of claim 1, the method further comprising:
(iv) The treated water is filtered to remove suspended particles, thereby producing filtered treated water.
3. The method of claim 2, the method further comprising:
(v) Purifying the filtered water by reverse osmosis to produce purified treated water.
4. A method according to any one of claims 1-3, comprising adding an iron sulfate salt that is ferric sulfate, polymeric Ferric Sulfate (PFS), or a combination thereof.
5. The method of any one of claims 1-4, comprising adding an aluminum sulfate salt that is aluminum sulfate, polyaluminum sulfate (PAS), or a combination thereof.
6. The method of any of claims 1-5, wherein the water of the industrial water system further comprises a scale inhibitor.
7. The method of claim 6, wherein the scale inhibitor comprises polymaleic acid, poly (meth) acrylic acid, polyepoxysuccinic acid (PESA), polyaspartic Acid (PASP), aminotrimethylene phosphonic Acid (AMP), 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDP), 2-phosphonobutane-1, 2, 4-tricarboxylic acid (PBTC), polyaminopolyether methylene phosphonate (PAPEMP), ethylenediamine tetramethylene phosphonic acid (EDTMPA), diethylenetriamine pentamethylene phosphonic acid (DTPMPA), hexamethylenediamine tetramethylene phosphonic acid (HMDTMPA), bis (hexamethylenetriamine pentamethylene phosphonic acid) (bhmp), hydroxyethylamino di (methylenephosphonic acid) (HEMPA), hydroxyphosphonoacetic acid (HPA), phosphinosuccinic acid oligomers (PSO), salts thereof, or combinations thereof.
8. The method of any one of claims 1-7, wherein the water of the industrial water system further comprises a polymeric dispersant.
9. The method of claim 8, wherein the polymeric dispersant comprises at least one monomer component that is acrylamidomethanesulfonic acid, (dimethyl (2-oxobut-3-en-1-yl) ammonio) methanesulfonate, allyloxypolyethoxy (10) sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, acrylamide t-butylsulfonate, 4- (allyloxy) benzenesulfonic acid, styrenesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allylhydroxypropanesulfonic acid, salts thereof, or combinations thereof.
10. The method of claim 9, wherein the polymeric dispersant further comprises at least one monomer component that is (meth) acrylamide, (meth) acrylic acid, itaconic acid, maleic anhydride, crotonic acid, acrylamidoglycolic acid salicylate, dimethyl allylmalonate, 2-carboxyethyl acrylate, 3-acrylamido-3-methylbutanoic acid, salts thereof, or combinations thereof.
11. The method of any one of claims 1-10, wherein barium sulfate in the water of the industrial water system is supersaturated prior to treatment with the composition comprising the barium sulfate seed and one or more soluble iron salts, aluminum salts, or a combination thereof in the aqueous medium.
12. The method of any one of claims 1-11, comprising filtering the treated water with a filter having a pore size of about 10 μιη to about 100 μιη.
13. The method of any one of claims 1-12, comprising filtering the treated water with a microfilter having a pore size of about 0.1 μιη to about 10 μιη.
14. The method of any one of claims 1-13, comprising filtering the treated water with a nanofiltration having a pore size of about 1nm to about 0.1 μιη.
15. The method of any one of claims 1-14, wherein the industrial water system comprises a cooling system, a boiler system, a heating system, a membrane system, a papermaking system, a humidification system, a recovery system, or a water purification system.
16. The method of any one of claims 1-14, wherein the industrial water system comprises a cooling water system.
17. The method of any one of claims 1-16, wherein the water of the industrial water system comprises a cooling water discharge.
18. The method of any one of claims 2-17, wherein the filtered treated water has a barium concentration of less than about 0.12 mg/L.
19. The method of any one of claims 2-17, wherein the filtered treated water has a barium concentration of less than about 0.1 mg/L.
20. The method of any one of claims 1-19, comprising recycling the treated water back into the industrial water system.
21. A method of recirculating cooling water emissions from a water cooling tower, the method comprising:
(i) Mixing (a) barium chloride and (b) iron sulfate and/or aluminum sulfate in an aqueous medium to form a mixture comprising barium sulfate;
(ii) Aging the mixture comprising barium sulfate to form a composition comprising barium sulfate seed crystals and one or more soluble iron salts, aluminum salts, or combinations thereof in the aqueous medium; and
(iii) At least a portion of the composition comprising the barium sulfate seed crystals and one or more soluble iron salts, aluminum salts, or combinations thereof in the aqueous medium is added to the cooling water effluent to form a treated cooling water effluent to inhibit barium sulfate scaling in the water cooling tower.
22. The method of claim 21, the method further comprising:
(iv) The treated cooling water effluent is filtered to remove suspended particulates, thereby forming a filtered treated cooling water effluent.
23. The method of claim 22, the method further comprising:
(v) Purifying the filtered cooling water effluent by reverse osmosis to provide a purified treated cooling water effluent.
24. The method of any one of claims 21-23, comprising adding an iron sulfate that is ferric sulfate, polymeric Ferric Sulfate (PFS), or a combination thereof.
25. The method of any one of claims 21-24, comprising adding an aluminum sulfate salt that is aluminum sulfate, polyaluminum sulfate (PAS), or a combination thereof.
26. The method of any one of claims 21-25, wherein the cooling water effluent further comprises a scale inhibitor.
27. The method of claim 26, wherein the scale inhibitor comprises polymaleic acid, poly (meth) acrylic acid, polyepoxysuccinic acid (PESA), polyaspartic Acid (PASP), aminotrimethylene phosphonic Acid (AMP), 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDP), 2-phosphonobutane-1, 2, 4-tricarboxylic acid (PBTC), polyaminopolyether methylene phosphonate (PAPEMP), ethylenediamine tetramethylene phosphonic acid (EDTMPA), diethylenetriamine pentamethylene phosphonic acid (DTPMPA), hexamethylenediamine tetramethylene phosphonic acid (HMDTMPA), bis (hexamethylenetriamine pentamethylene phosphonic acid) (bhmp), hydroxyethylamino di (methylenephosphonic acid) (HEMPA), hydroxyphosphonoacetic acid (HPA), phosphinosuccinic acid oligomers (PSO), salts thereof, or combinations thereof.
28. The method of any one of claims 21-27, wherein the cooling water effluent further comprises a polymeric dispersant.
29. The method of claim 28, wherein the polymeric dispersant comprises at least one monomer component that is acrylamidomethanesulfonic acid, (dimethyl (2-oxobut-3-en-1-yl) ammonio) methanesulfonate, allyloxypolyethoxy (10) sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, acrylamide t-butylsulfonate, 4- (allyloxy) benzenesulfonic acid, styrenesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allylhydroxypropanesulfonic acid, salts thereof, or combinations thereof.
30. The method of claim 29, wherein the polymeric dispersant further comprises at least one monomer component that is (meth) acrylamide, (meth) acrylic acid, itaconic acid, maleic anhydride, crotonic acid, acrylamidoglycolic acid salicylate, dimethyl allylmalonate, 2-carboxyethyl acrylate, 3-acrylamido-3-methylbutanoic acid, salts thereof, or combinations thereof.
31. The method of any one of claims 21-30, wherein barium sulfate in the cooling water effluent of the water cooling tower is supersaturated prior to treatment with the composition comprising the barium sulfate seed crystal and one or more soluble iron salts, aluminum salts, or a combination thereof in the aqueous medium.
32. The method of any one of claims 21-31, comprising filtering the treated cooling water effluent with a filter having a pore size of about 10 μιη to about 100 μιη.
33. The method of any one of claims 21-32, comprising filtering the treated cooling water effluent with a microfilter having a pore size of about 0.1 μιη to about 10 μιη.
34. The method of any one of claims 21-33, comprising filtering the treated cooling water effluent with a nanofiltration having a pore size of about 1nm to about 0.1 μιη.
35. The method of any one of claims 22-34, wherein the filtered treated cooling water effluent has a barium concentration of less than about 0.12 mg/L.
36. The method of any one of claims 22-34, wherein the filtered treated cooling water effluent has a barium concentration of less than about 0.1 mg/L.
37. The method of any one of claims 23-36, comprising recycling the treated water back into the cooling water effluent.
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| US202263326976P | 2022-04-04 | 2022-04-04 | |
| US63/326,976 | 2022-04-04 |
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