CN100441531C - Sulfate dispersion chromate reducer - Google Patents
Sulfate dispersion chromate reducer Download PDFInfo
- Publication number
- CN100441531C CN100441531C CNB2004800344494A CN200480034449A CN100441531C CN 100441531 C CN100441531 C CN 100441531C CN B2004800344494 A CNB2004800344494 A CN B2004800344494A CN 200480034449 A CN200480034449 A CN 200480034449A CN 100441531 C CN100441531 C CN 100441531C
- Authority
- CN
- China
- Prior art keywords
- composition
- cement
- tin sulphate
- chromium
- water
- 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.)
- Expired - Fee Related
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 14
- 239000006185 dispersion Substances 0.000 title description 34
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 title description 16
- 239000003638 chemical reducing agent Substances 0.000 title description 13
- 239000000203 mixture Substances 0.000 claims abstract description 97
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 claims abstract description 90
- 239000004568 cement Substances 0.000 claims abstract description 89
- 239000007788 liquid Substances 0.000 claims abstract description 78
- 239000011651 chromium Substances 0.000 claims abstract description 61
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 43
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 25
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 230000009467 reduction Effects 0.000 claims description 38
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 22
- 239000003963 antioxidant agent Substances 0.000 claims description 21
- 229940123973 Oxygen scavenger Drugs 0.000 claims description 20
- 239000011790 ferrous sulphate Substances 0.000 claims description 20
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 19
- 230000003078 antioxidant effect Effects 0.000 claims description 18
- 230000000694 effects Effects 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 15
- 150000004676 glycans Chemical class 0.000 claims description 14
- 229920001282 polysaccharide Polymers 0.000 claims description 14
- 239000005017 polysaccharide Substances 0.000 claims description 14
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 14
- 239000003292 glue Substances 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 229920001285 xanthan gum Polymers 0.000 claims description 7
- 239000000230 xanthan gum Substances 0.000 claims description 7
- 235000010493 xanthan gum Nutrition 0.000 claims description 7
- 229940082509 xanthan gum Drugs 0.000 claims description 7
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 6
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 229960004418 trolamine Drugs 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- CICKVIRTJQTMFM-UHFFFAOYSA-N sulfuric acid;tin Chemical compound [Sn].OS(O)(=O)=O CICKVIRTJQTMFM-UHFFFAOYSA-N 0.000 claims description 3
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000011343 solid material Substances 0.000 abstract 1
- 239000000654 additive Substances 0.000 description 48
- 230000000996 additive effect Effects 0.000 description 47
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 29
- 150000001875 compounds Chemical class 0.000 description 24
- 230000002829 reductive effect Effects 0.000 description 20
- 235000006708 antioxidants Nutrition 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- -1 Polyethylene Polymers 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 239000003513 alkali Substances 0.000 description 14
- 229910052723 transition metal Inorganic materials 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000012530 fluid Substances 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 150000003624 transition metals Chemical class 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000003082 abrasive agent Substances 0.000 description 8
- 239000010440 gypsum Substances 0.000 description 8
- 229910052602 gypsum Inorganic materials 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000002893 slag Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 150000002083 enediols Chemical class 0.000 description 6
- 238000007669 thermal treatment Methods 0.000 description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 5
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 5
- 150000000994 L-ascorbates Chemical class 0.000 description 5
- 239000011398 Portland cement Substances 0.000 description 5
- 241000350481 Pterogyne nitens Species 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 239000011505 plaster Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229920002310 Welan gum Polymers 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000004567 concrete Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
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- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000002000 scavenging effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910001428 transition metal ion Inorganic materials 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- SRUQARLMFOLRDN-UHFFFAOYSA-N 1-(2,4,5-Trihydroxyphenyl)-1-butanone Chemical compound CCCC(=O)C1=CC(O)=C(O)C=C1O SRUQARLMFOLRDN-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical class CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229920002148 Gellan gum Polymers 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
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- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
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- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 1
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 1
- 229940043253 butylated hydroxyanisole Drugs 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229960000355 copper sulfate Drugs 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 235000019316 curdlan Nutrition 0.000 description 1
- 229940078035 curdlan Drugs 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N dodecahydrosqualene Natural products CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000013924 ferrous gluconate Nutrition 0.000 description 1
- 239000004222 ferrous gluconate Substances 0.000 description 1
- 229960001645 ferrous gluconate Drugs 0.000 description 1
- 229960001781 ferrous sulfate Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000010492 gellan gum Nutrition 0.000 description 1
- 239000000216 gellan gum Substances 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- ZGCHATBSUIJLRL-UHFFFAOYSA-N hydrazine sulfate Chemical compound NN.OS(O)(=O)=O ZGCHATBSUIJLRL-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- GTUJJVSZIHQLHA-XPWFQUROSA-N pApA Chemical compound C1=NC2=C(N)N=CN=C2N1[C@@H]([C@@H]1O)O[C@H](COP(O)(O)=O)[C@H]1OP(O)(=O)OC[C@H]([C@@H](O)[C@H]1O)O[C@H]1N1C(N=CN=C2N)=C2N=C1 GTUJJVSZIHQLHA-XPWFQUROSA-N 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 229940097411 palm acid Drugs 0.000 description 1
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 235000010378 sodium ascorbate Nutrition 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 229960005055 sodium ascorbate Drugs 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 229940031439 squalene Drugs 0.000 description 1
- TUHBEKDERLKLEC-UHFFFAOYSA-N squalene Natural products CC(=CCCC(=CCCC(=CCCC=C(/C)CCC=C(/C)CC=C(C)C)C)C)C TUHBEKDERLKLEC-UHFFFAOYSA-N 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- SYRHIZPPCHMRIT-UHFFFAOYSA-N tin(4+) Chemical compound [Sn+4] SYRHIZPPCHMRIT-UHFFFAOYSA-N 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
A chromium VI reducing composition comprising particles of solid material selected from the group consisting of iron (II) sulfate and tin sulfate, the particles being substantially uniformly dispersed within a liquid carrier. Methods for modifying hydratable cementitious materials using the chromium reducing composition are also disclosed and provide advantages over dry powder or dissolved forms of sulfate compositions when used in cement manufacturing.
Description
Technical field
The present invention relates to the reductive agent of sexavalent chrome (VI), relate more particularly to cement additire, and be used for reducing the method for chromic salt of cement, described method relates to the solid sulphuric acid salt particle that is dispersed in the liquid vehicle.
Background technology
Chromium is the inevitable trace element in raw materials used when making cement clinker, and cement clinker is through grinding to make cement.Especially, sexavalent chrome (" Cr VI ") can form under the condition of the oxidation of cement kiln and alkaline sintering.Cr VI compound is classified as has utmost point toxicity, because their high oxidation gesture and can penetrate the ability of people tissue, thereby cause sensitization of skin, anaphylaxis and eczema.Because Cr VI compound has high-dissolvability and is released when cement and water are mixed together, so they tend to touch people's skin in handling wet cement and mortar process.
Hope is reduced to trivalent chromium (Cr III) with sexavalent chrome (Cr VI).This is because Cr III tends to come out as stable complex compound sediment from solution, thereby reduces the danger as serious skin irritant.In fact, known many reductive agents.Yet they tend in low pH level effective, and validity is relatively poor under the high pH environment of cementing compositions.
Ferrous sulfate (II) is generally used for reducing the chromium in the bonding system.In the process of reduction chromium, iron (Il) is oxidized to iron (III).Yet the actual dose of the ferrous sulfate (II) that the chromium reduction is required is required stoichiometric 10 times.This part ground be since ferrous sulfate (II) usually with dried forms, be added into to the dosage of 0.5 weight % with 0.3 weight % of cement, and can be by airborne this fact of moisture oxidation.In addition, the ferrous sulfate of this a large amount of adding dried forms (II) is in-problem.At first, in the cement operating process, be difficult to accurately add drying material.They also bring unmanageable dirt problems in the logistics, and cause the worry to the health risk that is caused by dust.
It is also important that excessive ferrous sulfate is unfavorable for bonding system,, and prolong setting time because increased the water requirement of workability.
Typically, exsiccant ferrous sulfate (II) can not be added in the cement under being higher than 80 ℃ temperature, otherwise has by the danger of a large amount of oxidations.When cement is discharged from grinding machine and is transported to temperature when surpassing 80 ℃ storer in the temperature that is up to 130 ℃, ferrous sulfate (II) must be added in the latter half of cement manufacturing and distribution process.The most normally, ferrous sulfate (II) must be about to add before the packaged transportation at cement.The other quality control step of these needs is used for checking the chromium content in the cement, and this increases trouble and cost to cement manufacturers.
As the surrogate of ferrous sulfate (II), can use tin sulphate as chromium reducing agent.The dosage of required solid sulphuric acid tin is than the dosage of ferrous sulfate II much lower (cement～0.02 weight %).When with process of lapping in cement when combination, believe tin sulphate how many easier uses and more heat-resisting and storage-stable.Yet the logistics that still exists similar tin sulphate with dry powder form to join in the cement operation is worried.
Although tin sulphate is water miscible, when being added in the cement as the aqueous solution, it loses dose effect rapidly.The actual requirement of tin sulphate is 2 times of aequum when tin sulphate is added into powder type at least.This discordance has considered to hinder the tin sulphate that uses the solution form from the economics viewpoint.
Therefore, consider above-mentioned shortcoming, the inventor believes to be needed new chromium reducing agent, this reductive agent to need low relatively dosage adding rate and can liquid form sends and distribute.
The invention summary
Compare with tin sulphate with the ferrous sulfate (II) of solubilized form that uses in the prior art or dry powder form, the invention provides a large amount of solid sulphuric acid salt particles, it is believed that its oxidation-resistance of being more convenient for distributing and having more.Therefore exemplary composition of the present invention comprises a large amount of solids, and described solids comprise ferrous sulfate (II), tin sulphate or its mixture, and described particle is dispersed in the liquid vehicle basically equably.
In a preferred composition, liquid vehicle is the water dispersion that comprises sulphate particles (as tin sulphate) and viscosity modifier (VMA).The example of VMA comprises welan gum (welan gum), xanthan gum, You Tan (diutan) glue and ether of cellulose.In another preferred composition, liquid vehicle can comprise alkanolamine, as the form of trolamine, tri-isopropanolamine, diethanolamine and salt thereof; And liquid vehicle can randomly comprise water.It is believed that in liquid composition of the present invention to comprise a large amount of vitriol, because when introducing water, in vitriol can be included in solids and two kinds of forms of dissolving simultaneously as liquid vehicle or as liquid vehicle a part of.
When comparing, use liquid vehicle that bigger tolerance range and accessibility is provided with drying material.In addition, liquid product provides bigger advantage in environmental health and secure context, because it has eliminated the possibility that the people sucks chemical dust.In addition, the dose effect when using liquid vehicle to cause the dose effect of tin sulphate to be not less than the tin sulphate that adds dried forms, the advantage that provides liquid to add simultaneously to tin sulphate.
The present invention is used for reducing the illustrative methods of cement chromium and comprises introduce the liquid composition that above-mentioned comprising is dispersed in the sulphate particles in the liquid vehicle in the mutual grinding operation of cement clinker.Or sulfate dispersion of the present invention can be added in cement and cementing compositions such as concrete, masonry mortar, gypsum, the sprayed concrete etc. with the form of adulterant composition.The present invention also provides the cementing compositions that comprises hydratability cement and aforesaid liquid composition.
Other illustrative methods of the present invention and composition also can comprise optional viscosity modifier, at least a or multiple following material except sulphate particles sexavalent chrome (" CrVI ") reductive agent: (A) at least a other hexavalent chrome reduction agent (as metal-salt); (B) be total to additive, comprise antioxidant, oxygen scavenger or its mixture; (C) at least a cement additire (as alkanolamine); Or (D) aforementioned any mixture.
Further advantages of the invention and feature will describe in further detail hereinafter.
Description of drawings
Fig. 1 uses various forms of tin sulphates for expression and reduces the legend of chromium, and described various forms comprises 20% solution (prior art), dry powder form (prior art) and two kinds of liquid vehicle dispersion forms of the present invention.
The detailed description of exemplary
Therefore, generalized as preceding institute, but the present invention relates to the chromium reducing composition of liquid dispersion, be used for reducing the method for chromium of matrix material and matrix material by using described chromium reducing composition to make.
Term used herein " cement " is meant the Portland cement (Portlandcement) that is used for building commerce, it is meant that described cement clinker is made up of the calcium sulfate that contains one or more forms (ASTM type i, II, III, IV or V) as levigate adulterating agent usually by grinding or grinding the hydratability cement that cement clinker is made mutually." bonding " material is such material, and they have when water exists individually solidifies and the hardened hydraulicity or hydratability cementing property.Matrix material comprises grinding granulated blast furnace slag (though some air cooled slag also can be considered to agglutinating) and Roman cement (as usual Portland cement)." bonding " material also can comprise gypsum (as calcium sulfate hemihydrate), aluminate cement, ceramic cement, oilwell drilling cement, reach other.
Solids sulfate dispersion of the present invention can be used in the cement manufactory, as directly being used in shredder (as ball mill, roll mill), separator, the classifier, or is used in bag technology of the package.Dispersion also can be used on cement neutralization after the manufacturing and is used in cementing compositions such as concrete, masonry mortar (mortar masonry), gypsum fire prevention body, sprayed concrete and other composition.
Except that Portland cement, the term " cement " that the present invention uses can comprise volcanic ash, its be have seldom or do not have cementing value (promptly, as tackiness agent) the material of siliceous or silicon-aluminum containing, but when water exists, the volcanic ash of form in small, broken bits and the calcium hydroxide generation chemical reaction that discharges by the Portland cement hydration, thus material formed with cementing property.For example referring to Dodson, V.,
Concrete Admixtures(Van Nostrand Reinhold, New York1990), 159 pages.Diatomite, Wingdale, clay (as metakaolin), shale, flying dust, siliceous smog and blast-furnace slag also are that some belong to the material in the known volcanic ash.Some grinds granular blast-furnace slag and high calcium flying dust and had not only had and coagulate rigid but also have cohesiveness.
The invention provides and comprise the liquid composition that is dispersed in the solid sulphuric acid salt particle in the liquid vehicle.It is believed that described vitriol based additive can be reduced into chromium III with chromium VI effectively, and it can be known as " chromium reducing agent " in this article sometimes.Illustrative methods of the present invention is included in and adds described liquid composition (sulphate particles chromium reducing agent) in the process of mutual grinding cement clinker in cement clinker, thereby makes hydratability cement.
An illustrative methods making described liquid composition merges as the water dispersion with at least a viscosity modifier (VMA) with liquid vehicle for the vitriol (as tin sulphate, ferrous sulfate (II)) with the solids form.VMA makes and might produce the concentration sulfate dispersion of homogeneous basically, even also be like this afterwards in the quite long shelf lives (as 28 days).Viscosity modifier (VMA) should provide the absolute dilution (sheerthinning) of being convenient to pumping liquid dispersion of the present invention feature.In addition, VMA should not can hinder the effect of cement admixture composition in the end using.
Term viscosity modifier used herein (" VMA ") is meant the reagent of dried enriched material form, or when it is dispersed in the water and become the reagent of high viscosity liquid thus.The suitable VMA of high viscosity liquid form it is believed that and be particularly suitable for purpose of the present invention, and it can be available from GraceConstruction Products, Cambridge, and Massachuetts, commodity are by name to be V-MAR
3.This VMA is based on outstanding smooth glue (available from CP Kelco), and contains water and dispersion agent, as can be available from the commodity of Grace ADVA by name
Those dispersion agents.
The present invention can use other viscosity modifier (VMA).They include but not limited to: (a) biological polymer polysaccharide is selected from welan gum, outstanding smooth glue, xanthan gum, sandlwood carbohydrate gum (rhamsan), gellan gum (gellan), dextran, amylopectin, heat polysaccharide (curdlan) and derivative thereof with fixed attention; (b) ocean glue is selected from phycocolloid, agar, carrageenin and derivative thereof; (c) plant secretion thing is selected from Viscogum BE, Sudan Gum-arabic, kuteera gum, yellow work glue, dawa gum (Ghatti) and derivative thereof; (d) seed glue is selected from guar gum, Viscogum BE, gumbo glue, plantago mucilage, mesquite gum and derivative thereof; (e) starch-based glue class is selected from ether, ester and derivative thereof (for example referring to US 6,1110,271, the 3 hurdles, 38-46 is capable); With their mixture; And (f) relevant thickening material, be selected from the urethane copolymers of the expandable acrylic copolymer of alkali, the hydrophobically modified of hydrophobically modified, based on the relevant thickening material of urethane, Mierocrystalline cellulose (for example Natvosol, carboxymethyl hydroxyethyl cellulose), polyacrylic ester and polyethers.
Tin sulphate is 330g/l (for example referring to Encyclopedia ofChemical Technology, the 4th edition .24 volume, the 129th page) 25 ℃ solubleness.The invention enables the concentration that will be loaded into the tin sulphate in the liquid vehicle to be higher than usually by described vitriol being dissolved in resulting concentration in the independent water.For example, when in the mixture that the solids tin sulphate is dispersed in water and viscosity modifier, might obtain to account for the tin sulphate dispersion of gross weight 56%, wherein 35% tin sulphate will be as solid dispersed, and 21% tin sulphate will be dissolved in the solution.On behalf of the amount of the tin sulphate of carrying with liquid form, this surprising increase is arranged.
Other the exemplary liquid vehicle of tin sulphate or ferrous sulfate of being used to suspend comprises alkanolamine, it can be nonaqueous, if or used water, then described liquid vehicle to be essentially the part water-based in addition.Exemplary alkanolamine comprises the form of trolamine, tri-isopropanolamine, diethanolamine and salt thereof.
Exemplary chromate reduction liquid composition of the present invention comprises: the chromate reduction active substance of solid sulphuric acid tin particulate forms (mean particle size is 0.001 to 1.0 micron), and its content is 40-70% based on the dry weight of composition; Water, its content is 5%-50% based on the gross weight of liquid composition; With biological polymer polysaccharide viscosity modifier, it is selected from outstanding smooth glue and xanthan gum, and the content of described biological polymer polysaccharide is 0.1%-10% based on the gross weight of liquid composition.
Other exemplary composition of the present invention except comprising ferrous sulfate (II) or tin sulphate (II), can further comprise other chromium reducing agent (as metal-salt), includes but not limited to tin protochloride, manganous sulfate, iron sulphide and/or iron protochloride.
The exemplary that the present invention is other except the sulphate particles that comprises the dispersion form, can further comprise at least a cement additire, and it comprises alkanolamine, glycol, sugar, chloride salt or its mixture.The consumption of one or more optional cement additires can be 5%-80% based on the gross weight of liquid composition.
In the present invention other exemplary composition and method, the contriver consider might with make ferrous sulfate (II) and/or tin sulphate solids more the sludge proof material coat or capsule seals described particle, these materials do not hinder described particle to be dispersed in equably in the aforesaid liquid carrier basically, and these materials do not hinder above-mentioned particle as the effect of chromium reducing agent in cementing compositions.Exemplary capsule closure material or coating material can comprise polysaccharide, starch, carbohydrate or its improved form; Polyethylene; With other polymer materials.
Other illustrative methods of the present invention, except the agent of sulfuric acid alkali hexavalent chrome reduction, further comprise and in cement clinker, introducing as the antioxidant, oxygen scavenger or its mixture that are total to additive, vitriol reagent is carried out in being introduced in before the described grinding or in the process of lapping of these materials: the ratio of additive is 99.5: 0.5 to 20: 80 altogether; More preferably ratio is 99: 1 to 50: 50; Most preferably be 95: 5 to 60: 40.
Though also inessential, preferably sulfuric acid alkali chromium reducing agent salt and optional common additive (antioxidant and/or oxygen scavenger) both are distributed in the same fluid additive composition.Not so not preferably, as before cement clinker grinds, in the process or add additive altogether afterwards discriminably.
Therefore, no matter be that combination is added or added respectively, the amount of total common additive (antioxidant and/or oxygen scavenger) should be 0.05 to 80.0% based on the gross weight of fluid additive composition, more preferably 0.5 to 50.0%, most preferably 1.0 to 30.0%.
Term used herein " antioxidant " is meant such composition, material or compound, particularly when they are incorporated in the fluid additive composition that contains above-mentioned sulfuric acid alkali chromium (VI) reductive agent, it reduces rate of oxidation or reduces unwanted oxygenizement to the hexavalent chrome reduction agent in others.For example United States Patent (USP) 5,211,875 disclose and it is believed that and be fit to antioxidant of the present invention, for example 2,6-two (tertiary butyl)-4-cresols (BHT), 2,2 '-methylene radical-two (the 6-tertiary butyl-p-cresol), the triphenyl phosphorous acid ester, three-(nonyl phenyl) phosphorous acid ester and dilauryl sulfo-malonic ester.Also it is believed that other antioxidant such as United States Patent (USP) 6,465, the sulfurous gas described in 065, THBP 2,4,5 trihydroxybutyrophenone and butylated hydroxy anisole also are fit to the present invention.Aforesaid, these antioxidants can be attached in the same fluid additive composition with vitriol, or, not so not preferably, before grinding, in the process or in cement or cement clinker, add these antioxidants afterwards respectively.The consumption of antioxidant should be preferably 0.05 to 80% based on the gross weight (if being attached in the composition) of fluid additive composition, and more preferably 0.5 to 50%, most preferably 1.0 to 30.0%.If separate adding with fluid additive, then the amount of antioxidant can be 0.1ppm to 1000ppm, more preferably 1.0-300ppm, most preferably 5-100ppm (based on the umber of per 1,000,000 parts of dry cement weight).
Term used herein " oxygen scavenger " is meant such composition, material or compound, when being comprised in the fluid additive composition that comprises sulfuric acid alkali CrVI reductive agent, they can remove deoxidation, for example (a) by staying the oxygen reaction or combine with carrying, or (b) obtain harmless product by catalytic oxidation.
Can be used as the exemplary oxygen scavenger of additive altogether of the present invention and include but not limited to that (a) contains the compound of ethylenically unsaturated hydrocarbons; (b) phenol or its salt or derivative; (d) azanol or hydrazine or derivatives thereof; (e) sulfurous acid or its salt or derivative; (f) transition metal complex; Or its mixture.
The exemplary oxygen-scavenging compositions of one class comprises ethylenically unsaturated hydrocarbons.Ethylenically unsaturated hydrocarbons can use separately or use with transition-metal catalyst.Ethylenically unsaturated hydrocarbons can be replacement or unsubstituted.As defined herein, unsubstituted ethylenically unsaturated hydrocarbons is anyly to have at least one aliphatic carbon-to-carbon double bond and comprise the carbon of 100 weight % and the compound of hydrogen.The ethylenically unsaturated hydrocarbons of the replacement of this paper definition is to have at least one aliphatic carbon-to-carbon double bond and comprise the carbon of about 50 weight %-99 weight % and the compound of hydrogen.Preferred replacement or unsubstituted ethylenically unsaturated hydrocarbons have the compound of two or more ethylenically unsaturated groups for those per molecules.
The preferred example of unsubstituted ethylenically unsaturated hydrocarbons includes but not limited to: diene polymer such as polyisoprene, (as using trans-polyisoprene), polyhutadiene (particularly 1, the 2-polyhutadiene, have more than or equal to 50% 1, the 2-microstructure), and multipolymer, as styrene butadiene.Described hydrocarbon also comprises polymer compound, as polypenthylene, poly-octene and other polymkeric substance by the olefin metathesis preparation; Diene oligomer such as squalene; And derive from Dicyclopentadiene (DCPD), norbornadiene, 5-ethylidene-2-norbornene or other contains polymer of monomers or the multipolymer that surpasses a carbon-to-carbon double bond (conjugation or unconjugated).These hydrocarbon comprise carotenoid such as β-Hu Luobusu further.
The preferred ethylenically unsaturated hydrocarbons that replaces includes but not limited to that those contain the compound of oxygen part, as ester, acid acid, aldehyde, ether, ketone, alcohol, superoxide and/or hydroperoxide.The composition that uses also can comprise the mixture of two or more above-mentioned replacements or unsubstituted ethylenically unsaturated hydrocarbons.
As mentioned above, ethylenically unsaturated hydrocarbons can advantageously use with transition-metal catalyst under many circumstances.Though be not bound by any particular theory, the proper metal catalyzer is those compounds of change between at least two kinds of oxidation state easily.Referring to Sheldon, R.A.; Kochi, J.K.; " Metal-Catalyzed Oxidations of Organic Compounds " (Academic Press, NeW York 1981).Preferably, transition-metal catalyst is the form of the salt that forms with the metal that is selected from the periodictable first, second or the 3rd transition series.Proper metal includes but not limited to manganese II or III, iron II or III, cobalt II or III, nickel II or III, copper I or II, rhodium II, III or IV and ruthenium.When metal is introduced in fluid additive or be introduced in the cement, the oxidation state that the oxidation state of metal need not activity form.Metal is preferably iron, nickel or copper.More preferably manganese, most preferably cobalt.The proper metal counterion includes but not limited to muriate, acetate, stearate radical, palm acid group, 2 ethyl hexanoic acid root, neodecanoic acid root or cycloalkanes acid group.
The unsaturated additive altogether of the olefinic of the replacement of preferred classes comprises enediol.The example of commercially available enediol comprises xitix and saccharosonic acid and salt (as sodium ascorbate, SODIUM ISOVITAMIN C) or derivative.Any stereoisomer of these compounds can be effective in the present invention.Xitix/the ascorbate salt of an alkali metal salt and alkaline earth salt such as potassium or sodium is preferred.
The exemplary of use enediol in addition comprises the activator of the oxygen scavenging capacity that is used to strengthen enediol.For example, United States Patent (USP) 4,524,015 discloses the particulate mixtures that uses ascorbate salt or xitix, alkaline carbonate, iron cpd, blackout and water.Therefore, these can be considered to useful enediol activator.
Illustrative methods that the present invention is other and composition can comprise the activator that is used to contain the enediol compound, as transistion metal compound, complex compound or inner complex.The more preferably transition metal of chosen from Fe, copper, cobalt or nickel.Most preferably iron or copper.Preferably supply form of transition metal is (1) compound as the ordinary salt of transition metal ion, or the poly-alkyl polyamine of (2) transition metal ion (" PAPA ") inner complex, big cyclammonium (" big ring ") inner complex or amino poly-carboxylate inner complex.Also may use other to contain the transition metal chelate of one or more amine, hydroxyl, carboxylate or sulfhedryl or its combination.
Metal catalyst can comprise simple transition metal salt such as iron protochloride or iron(ic) chloride, cuprous chloride or cupric chloride, ferrous sulfate or copper sulfate, Ferrous Gluconate, single nickel salt or cobalt chloride, and they are more preferably, most preferably copper sulfate.The transition metal amine of chelating is the metal catalyst that particularly suitable uses with ascorbate salt, because when using with suitable amount, they have oxygen scavenging matter, this has increased the oxygen scavenging matter of ascorbate salt, therefore makes metallo-chelate remove compound as second.And, but the oxygen of the transition metal ion catalysis ascorbate salt in the complex compound is removed activity.In the chelating ion complex compound, preferably poly-alkyl polyamine; More preferably those have the complex compound of the carbochain of symmetrical length between adjacent nitrogen atom, and most preferably those each described chains comprise 1-4, and the best is the complex compound of 2 carbon atoms.Also can use the transition metal chelate of ethylenediamine tetraacetic acid (EDTA) (" EDTA "), as Fe++/EDTA/ (2Na+).
Therefore other exemplary oxygen scavenger can comprise independent transition metal complex (as except with above-mentioned enediol uses).This material is by Aquanautics, Inc., Alameda, California exploitation.(referring to Packaging Technology, " OxygenEliminator Extends Shelf Life, " 1989 and " Extending the Life of a Bottleof Beer, " New York Times, Mar.29,1989).These materials (yet being not uniquely) especially are that those are at transition metal and United States Patent (USP) 4,959, the complex compound that forms between the poly-alkylamine of the what is called of describing in 135 (described document is merged in this paper as a reference), and those are at transition metal with as United States Patent (USP) 4, the complex compound that forms between " the big cyclammonium " described in 952,289 (described document is merged in this paper as a reference).
In the present invention, these transition metal complexes can and can be used as oxygen scavenger in conjunction with oxygen.These complex compounds can not form or not be activated (promptly can not or debond oxygen), are exposed to together under water or the water vapor up to amine and metal.
Do not wish to be bound by theory, the contriver believes that common additive (antioxidant and/or oxygen scavenger) can advantageously play a role by following one or more mechanism.At first; additive can be used as classical antioxidant/oxygen scavenger altogether; thereby any preferential additive reaction together of oxygenant (molecular oxygen etc.) that enters in the liquid carrier medium that contains the CrVI reductive agent, thereby protect employed sulfuric acid alkali CrVI reductive agent and any other metal-salt CrVI reductive agent.This had increased its storage life for sulfuric acid alkali CrVI reductive agent and other metal-salt reductive agent effectively before they are added into cement mill or are added in the cement of grinding.
The contriver believes that also aforementioned mechanism also works after sulfuric acid alkali CrVI reduction liquid composition has been added in the cement.When outside moisture and molecular oxygen were penetrated in the cement of processing, oxygen will be before itself and the reaction of sulfuric acid alkali CrVI reductive agent be removed by additive altogether.For this purpose, preferably sulfuric acid alkali CrVI reductive agent is pre-mixed into single fluid additive with optional additional metals salt and/or common additive (antioxidant and/or oxygen scavenger).
The contriver believes that also the common additive that contains antioxidant and/or oxygen scavenger can react, thereby the vitriol of any reduction chromium of regeneration or other metal-salt reductive agent, thereby keep the used sulfate reduction agent or the level of any other reductive agent by having decomposed with the chance reaction of foreign molecules oxygen (or other unwanted oxygenant).This mechanism can be before the fluid additive composition be added to cement, between the shelf lives of finished cement or when finished product cement is used to make mortar or concrete, play a role.
The contriver believes that further the common additive that contains antioxidant and/or oxygen scavenger can form adducts with CrVI reductive agent (sulfuric acid alkali reagent and any other metal-salt) or with its oxidised form such as tin (IV) (itself is active CrVI reductive agent).
Other embodiments comprise is of value to the agent combination that cement is made with sulfate reduction agent and above-mentioned common additive (antioxidant and/or oxygen scavenger) and one or more.These reagent comprise cement auxiliary agent such as glycol, glycerine, amine, alkanolamine and known cement quality modifying agent such as sodium-chlor, nitrocalcite, calcium nitrite, sugar, reach other.Two pure and mild glycerine are considered to improve the stability in storage of tin salt.The mechanism of this benefit is unknown, but its activity that may relate to molecular oxygen in the presence of glycol or glycerine reduces.
Other exemplary common additive comprises the phenol that can be used as oxygen scavenger, as its quinone and OH-form, yet comprises and is not limited to quinhydrones (hydroquinol), pyrocatechol (neighbour-dihydroxy-benzene) and derivative thereof.
Further exemplary oxygen is removed altogether, and additive comprises azanol, hydrazine or its salt or derivative.Exemplary azanol has by structure shown in the following formula,
R wherein
1And R
2Comprise hydrogen or C separately
1-C
18Alkyl, thiazolinyl or aryl.
Exemplary hydrazine has by structure shown in the following formula:
R wherein
1, R
2, R
4And R
4Comprise hydrogen or C separately
1-C
18Alkyl, thiazolinyl or aryl.Exemplary hydroxylammonium salt comprises oxammonium hydrochloride (NH
2OHHC1) and hydroxylamine sulfate ((NH
2OH)
2H
2SO
4); And exemplary hydrazonium salt comprises hydrazine hydrochloride (N
2H
4HC1 or N
2H
42HC1) and hydrazonium sulfate (N
2H
4H
2SO
4).
Exemplary hydroxyalkyl azanol has formula HO-N-CH
2-[CH (OH)-R]
2Structure, wherein R is selected from H and C
1-C
10Alkyl; Be initial reaction rate about more than 1.5 times between the alkyl azanol of dissolved oxygen and corresponding non-hydroxylated wherein in the initial reaction rate between described hydroxyalkyl azanol and the dissolved oxygen.Another hydroxyalkyl azanol is selected from N, two (2-hydroxyethyl) azanols of N-, N, two (2-hydroxypropyl) azanol and the N of N-, two (2-hydroxybutyl) azanols of N-.
Exemplary oxygen scavenger in addition additive altogether comprises sulfurous acid or its salt, as sulphite, hydrosulphite or thiosulfite.Therefore, for example an alkali metal salt and the sulfuric acid alkali chromium reducing agent of alkali metal salt together can be attached in the fluid additive composition, the form of described an alkali metal salt is for example S-WAT or hydrosulphite or potassium sulfite or hydrosulphite.
In other exemplary of the present invention, sulphite can use with other common additive combination.For example, United States Patent (USP) 4,384,972 disclose use metal-salt, alkaloid substance, sulphite or other deliquescence compound and optional xitix or its salt.
More preferably, illustrative methods of the present invention and fluid additive composition comprise that use sulfuric acid alkali chromium reducing agent and two or more comprise the common additive of antioxidant, oxygen scavenger or its mixture.Therefore, the preferred method of the present invention is included in the mutual process of lapping of cement clinker at least two kinds of antioxidants and/or oxygen scavenger is incorporated in the cement clinker.For example, xitix and sulphite (or its salt and derivative) use capable of being combined.As another example, phenol and azanol (or its salt and derivative) use capable of being combined.Preferably, these combinations can join in the same fluid additive composition with sulfuric acid alkali chromium reducing agent, but it is believed that they also can be before the cement clinker grinding operation, in the process or be added in the cement afterwards.
Provide following examples and embodiment only to be used for illustration purpose, it is not construed as limiting scope of the present invention, and the those of ordinary skill in ability city openly can carry out various changes to it by this paper.
Embodiment 1
The preparation of tin sulphate composition of the present invention: tin sulphate particle (56gm) and outstanding smooth matrix VMA (44gm) are mixed together.Described VMA is available from Grace Construction Products, and commodity are called V-MAR
3.Other suitable VMA can comprise xanthan gum, welan gum and ether of cellulose, and the preferred dispersion agent of choosing wantonly that uses is dispersed in the water.
Performance between table 1 expression tin sulphate solid, tin sulphate dispersion and the tin sulphate solution relatively.All additives are ground mutually enter the slag cement for preparing in the ball mill of laboratory.In the cement for preparing in the laboratory, the ratio of various materials is as follows: 70% cement clinker, 25% slag, 2.8% gypsum, 1.9% plaster.Abrasive material prepares in envrionment temperature.
The additive capacity of chromate reduction additive is shown in the table 1.Give the dosage of activared carbon sulfur tin part.Provided the solvable ppm Cr (measuring) of the cold grinding material that is used to prepare with chromic salt, and at the umber of 180 ℃ of heat treated abrasive materials.The purpose of thermal treatment abrasive material is to determine the relevant antagonism of Cr reductive agent to environmental oxidation, and its validity after cement stores thus.
It is suitable with the dose effect of the tin sulphate of dry powder form that observed value with lower soluble chromium, the dose effect of the tin sulphate of dispersion form seem, and surpass the dose effect of the tin sulphate of solution form.
Measuring the cement pore water with the amount of the 1000000/chromium that a (PPM) represents by UV carries out.Dissolubility chromate can be discerned by the UV peak at 277nm and 375nm place.Calibrate by potassium bichromate solution.By preparing the ratio of cement and water wherein is that 2: 1 grout obtains the cement pore water.After mixing 9 minutes, grout is left standstill and aging 30 minutes.Grout is centrifugal, and supernatant decanted liquid also filters, and (BDL in institute's subordinate list is meant ' is lower than limit of detection ' (＜0.5ppm)) to obtain pore water.
Table 1
| The chromate reduction additive | Additive (ppm) | Tin sulphate (ppm) | Cold grinding material ppm Cr | Thermal treatment abrasive material ppm Cr | |
| Do not have | -- | -- | 8 | 9 | |
| The |
40 | 40 | 3 | 4 | |
| 56% tin sulphate dispersion | 71 | 40 | | BDL | |
| 20% tin sulphate solution | 400 | 80 | 2 | 6 | |
| The |
100 | 100 | BDL | BDL | |
| 56% tin sulphate dispersion | 179 | 100 | | BDL | |
| 20% tin sulphate solution | 1000 | 200 | BDL | 6 |
Example II
The cement that use has following composition percentage ratio carries out similar experiment: 95% cement clinker, 2.8% gypsum, 1.9% plaster.Sample chromate reduction performance separately is shown in the table 2.
Table 2
| The chromate reduction additive | Additive (ppm) | Tin sulphate (ppm) | Cold grinding material (ppm) | Thermal treatment abrasive material (ppm) |
| Cr | Cr | |||
| 56% tin sulphate dispersion | 179 | 100 | 14 | 18 |
| 56% tin sulphate dispersion | 357 | 200 | 1 | 5 |
| 20% tin sulphate solution | 1000 | 200 | 9 | 19 |
| 20% tin sulphate solution | 2000 | 400 | BDL | 1 |
EXAMPLE III
The cement that use has following composition percentage ratio carries out another test: 65% cement clinker, 7.5% slag, 15.1% Wingdale, 7.5% natural volcanic ash, 2.8% gypsum and 1.9% plaster, percentage ratio is with total weight.In this case, in heat treated cement, the tin sulphate of the 200ppm that sends in dispersion is suitable with the tin sulphate performance of the 300ppm that sends in solution.The result is as shown in table 3.
Table 3
| The chromate reduction additive | Additive (ppm) | Tin sulphate (ppm) | Cold grinding material (ppm) Cr | Thermal treatment abrasive material (ppm) Cr |
| Do not have | 8 | 8 | ||
| 56% tin sulphate dispersion | 357 | 200 | 2 | 3 |
| 20% tin sulphate solution | 1500 | 300 | 3 | 3 |
EXAMPLE IV
The cementing compositions preparation that use has following composition percentage ratio carries out another test: 96% cement clinker, 2.4% gypsum, 1.5% plaster.Compared the tin sulphate of being sent as solid, liquid and dispersion form, the performance of the tin sulphate of sending with the dispersion form equates with the performance of the tin sulphate of sending with solid form undoubtedly, and the 200ppm tin sulphate of sending in solution can not be with chromate reduction to same degree.
Table 4
| The chromate reduction additive | Additive (ppm) | Tin sulphate (ppm) | Cold grinding material (ppm) | Thermal treatment abrasive material (ppm) |
| Cr | Cr | ||||
| Do not have | 8 | 9 | |||
| 56% tin sulphate dispersion | 357 | 200 | | BDL | |
| 20% tin sulphate solution | 1000 | 200 | 5 | 8 | |
| The tin sulphate powder | 200 | 200 | BDL | BDL |
EXAMPLE V
Also tin sulphate can be suspended in the liquid vehicle that comprises at least a alkanolamine as dried particle.Find the efficient of the dose effect of tin sulphate aspect reducing chromate greater than tin sulphate solution, and roughly suitable with the dose effect of the tin sulphate of dry powder form.
Use following component preparation tin sulphate dispersion: water (20g), tin sulphate (34g) and tri-isopropanolamine (46g).Can be by replacing tri-isopropanolamine to prepare another dispersion with the di-alcohol Yi Bingchunan.
Two kinds of alkanolamines all can be used for replacing in the preparation of tin sulphate with ferrous sulfate (II), and discovery is still effective when the required dosage with ferrous sulfate reduces 20-30%, but suspension presents muddy appearance of black.
Below the table 5 expression test-results of using cement to carry out with following ratio: 96% cement clinker, 2.4% gypsum, 1.5% plaster.The preparation of this test material therefor is identical with the serial experiment of the liquid vehicle (water dispersion) of use VMA preparation with evaluation method.Observe in solution, comprise 50ppm tin sulphate and 71ppm tin sulphate sample less than the performance that is dispersed in the tin sulphate in tri-isopropanolamine (" TIPA ") (it is believed that also TIPA oneself does not have the effect of the chromate reducer separately) liquid vehicle.
Table 5
| The chromate reduction additive | Additive (ppm) | Tin sulphate (ppm) | Cold grinding material (ppm) Cr | Thermal treatment abrasive material (ppm) Cr |
| Do not have | 0 | 8 | --- | |
| Tin sulphate dispersion w/TIPA | 76 | 26 | 2 | 4 |
| Tin sulphate dispersion w/TIPA | 97 | 33 | 1 | 4 |
| Tin sulphate dispersion w/TIPA | 147 | 50 | BDL | 1 |
| 20% tin sulphate solution | 250 | 50 | 3 | 3 |
| 20% tin sulphate solution | 355 | 71 | 3 | 3 |
Example VI
Use following component preparation tin sulphate dispersion: water (20g), tin sulphate (26g) and trolamine (54g).Before just adding mixing water, this chromate reduction composition is mixed in the finished cement (making in shredder) with dried adulterant form then.Obtain the cement pore water as previously mentioned, and measure chromic salt by UV as previously mentioned.The result is shown in Figure 1.
The foregoing description and exemplary attempt to be used to illustrate the present invention, model figure of the present invention are not construed as limiting.Those of ordinary skill in the art can carry out various changes and variation to it by this paper is open.
Claims (14)
1. chromium reduction liquid composition comprises:
Contain simultaneously with solubilized form and basically homogeneous dispersive mean particle size be the water liquid carrier of the tin sulphate that exists of the solids form of 0.001-1.0 micron, the described dispersed solids of homogeneous basically particle is dispersed in the described liquid vehicle with the amount that is no more than 70% at least 40% with the dry weight based on described composition;
Described water liquid carrier comprises that the gross weight based on described liquid composition is the water of the amount of 5-50%;
Described water liquid carrier further comprises the biological polymer polysaccharide viscosity modifier that is selected from outstanding smooth glue and xanthan gum, the content of described biological polymer polysaccharide based on the gross weight of described chromium reduction liquid composition at least 0.1% to being no more than 10.0%; With
The effect of described biological polymer polysaccharide viscosity modifier provides the concentration homogeneous of described tin sulphate in described chromium reduction liquid composition, even also is like this in described chromium reduction liquid composition stores after 28 days, and provide and be convenient to the described chromium of pumping reduction liquid to the absolute dilution feature of grinding from grog the cement manufacturing processed that obtains cement, the content of tin sulphate is higher than usually the content that is reached when tin sulphate being dissolved in the independent water in the described water liquid carrier.
2. the composition of claim 1 further comprises at least a alkanolamine.
3. the composition of claim 2, wherein said alkanolamine is selected from the form of trolamine, diethanolamine, tri-isopropanolamine and salt thereof.
4. be used for the method for reduction of hexavalent chromium, comprise: the composition that grinds cement clinker and claim 1 mutually.
5. the composition that comprises the composition of hydratability matrix material and claim 1.
6. the composition of claim 1, wherein said particle is coated by the material that can make particle have more oxidation-resistance.
7. the composition of claim 1 further comprises at least a other hexavalent chrome reduction agent except described sulphate particles.
8. the composition of claim 7, wherein said at least a other hexavalent chrome reduction agent is a metal-salt.
9. the composition of claim 1 further comprises ferrous sulfate.
10. the composition of claim 1 further comprises antioxidant, oxygen scavenger or its mixture.
11. the composition of claim 1, wherein said tin sulphate particle is dispersed in the described liquid vehicle to the amount that is no more than 60% at least 50% with the dry weight based on described composition.
12. the composition of claim 1 further comprises at least a cement additire.
13. chromium reduction liquid composition comprises:
Contain simultaneously with solubilized form and basically homogeneous dispersive median size be the water liquid carrier of the tin sulphate that exists of the solids form of 0.001-1.0 micron, described solid sulphuric acid tin particle is at least 40% to be dispersed in substantially equably in the described liquid vehicle to the amount that is no more than 70% with the dry weight based on described composition;
Described water liquid carrier comprises that the gross weight based on described liquid composition is the water of the amount of 5-50%;
Described water liquid carrier further comprises antioxidant, oxygen scavenger or its mixture;
Described water liquid carrier comprises the biological polymer polysaccharide viscosity modifier that is selected from outstanding smooth glue and xanthan gum, the content of described biological polymer polysaccharide based on the gross weight of described chromium reduction liquid composition at least 0.1% to being no more than 10.0%; With
The effect of described biological polymer polysaccharide viscosity modifier provides the concentration homogeneous of described tin sulphate in described chromium reduction liquid composition, even also is like this in described chromium reduction liquid composition stores after 28 days, and provide and be convenient to the described chromium of pumping reduction liquid to the absolute dilution feature of grinding from grog the cement manufacturing processed that obtains cement, the content of tin sulphate is higher than usually the content that is reached when tin sulphate being dissolved in the independent water in the described water liquid carrier.
14. chromium reduction liquid composition comprises:
Contain simultaneously with solubilized form and basically homogeneous dispersive median size be the water liquid carrier of the tin sulphate that exists of the solids form of 0.001-1.0 micron, the described dispersed solids of homogeneous basically tin sulphate particle is at least 40% to be dispersed in the described liquid vehicle to the amount that is no more than 70% with the dry weight based on described composition;
Described water liquid carrier comprises that the gross weight based on described liquid composition is the water of the amount of 5-50%;
Described water liquid carrier further comprises at least a cement additire that is selected from alkanolamine, glycol, sugar and chloride salt; With
Described water liquid carrier comprises the biological polymer polysaccharide viscosity modifier that is selected from outstanding smooth glue and xanthan gum, the content of described biological polymer polysaccharide based on the gross weight of described chromium reduction liquid composition at least 0.1% to being no more than 10.0%; With
The effect of described biological polymer polysaccharide viscosity modifier provides the concentration homogeneous of described tin sulphate in described chromium reduction liquid composition, even also is like this in described chromium reduction liquid composition stores after 28 days, and provide and be convenient to the described chromium of pumping reduction liquid to the absolute dilution feature of grinding from grog the cement manufacturing processed that obtains cement, the content of tin sulphate is higher than usually the content that is reached when tin sulphate being dissolved in the independent water in the described water liquid carrier.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US52412503P | 2003-11-21 | 2003-11-21 | |
| US60/524,125 | 2003-11-21 | ||
| US60/541,842 | 2004-02-04 |
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| SG190815A1 (en) * | 2010-12-08 | 2013-07-31 | Denki Kagaku Kogyo Kk | Cement admixture, cement composition, and hexavalent chromium reduction method using same |
| CN102266650B (en) * | 2011-05-05 | 2012-07-25 | 中国地质大学（武汉） | A Method for Detoxification and Solidification of Cr(Ⅵ) Using Metakaolin-based Mineral Polymer Added FeCl2·6H2O |
| CN104496251B (en) * | 2014-11-25 | 2017-03-22 | 中国建筑材料科学研究总院 | Liquid hexavalent chromium reducing agent and preparation method thereof, cement and preparation method thereof |
| CN106830725B (en) * | 2017-02-21 | 2020-12-11 | 辽宁天宝华瑞建材有限公司 | Hexavalent chromium reducing agent for cement |
| CN113620365A (en) * | 2020-05-06 | 2021-11-09 | 中国石油化工股份有限公司 | Deoxidant and application thereof |
| CN113060948A (en) * | 2021-04-01 | 2021-07-02 | 重庆康尼睿能商贸有限公司 | Cement raw meal and preparation method of cement |
| CN114989371B (en) * | 2022-06-29 | 2023-10-03 | 江苏万邦新材料科技有限公司 | High-stability reducing agent for building concrete and preparation method thereof |
| CN115231847B (en) * | 2022-08-15 | 2023-05-23 | 辽宁天宝华瑞建材有限公司 | Cement chromium remover and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4209335A (en) * | 1977-05-25 | 1980-06-24 | Kabushiki Kaisha Takenaka Komuten | Method and composition, including particular additive for hydraulic cement, for fixing waste matter |
| US4784691A (en) * | 1980-12-17 | 1988-11-15 | Aktieselskabet Aalborg Portland - Cement - Fabrik | Dry cement composition |
| EP0960865A1 (en) * | 1998-05-25 | 1999-12-01 | Chemische Werke Zell-Wildshausen GMBH | Agent for the reduction of chromium (VI) ions in cement |
| EP0976695A1 (en) * | 1998-07-25 | 2000-02-02 | Economic Versicherungs-Vermittlung GmbH | Grinding aid for cement |
-
2004
- 2004-07-13 CN CNB2004800344494A patent/CN100441531C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4209335A (en) * | 1977-05-25 | 1980-06-24 | Kabushiki Kaisha Takenaka Komuten | Method and composition, including particular additive for hydraulic cement, for fixing waste matter |
| US4784691A (en) * | 1980-12-17 | 1988-11-15 | Aktieselskabet Aalborg Portland - Cement - Fabrik | Dry cement composition |
| EP0960865A1 (en) * | 1998-05-25 | 1999-12-01 | Chemische Werke Zell-Wildshausen GMBH | Agent for the reduction of chromium (VI) ions in cement |
| EP0976695A1 (en) * | 1998-07-25 | 2000-02-02 | Economic Versicherungs-Vermittlung GmbH | Grinding aid for cement |
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