CN1227165C - Water treating corrosion and scale inhibitor and its prepn. - Google Patents
Water treating corrosion and scale inhibitor and its prepn. Download PDFInfo
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- CN1227165C CN1227165C CN02112951.7A CN02112951A CN1227165C CN 1227165 C CN1227165 C CN 1227165C CN 02112951 A CN02112951 A CN 02112951A CN 1227165 C CN1227165 C CN 1227165C
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- Prior art keywords
- epoxy
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- acid
- salt
- propanesulfonic acid
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000005260 corrosion Methods 0.000 title claims abstract description 20
- 230000007797 corrosion Effects 0.000 title claims abstract description 20
- 239000002455 scale inhibitor Substances 0.000 title claims abstract description 10
- 239000004593 Epoxy Substances 0.000 claims abstract description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 239000011734 sodium Substances 0.000 claims abstract description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 239000008235 industrial water Substances 0.000 claims abstract description 6
- 229920001577 copolymer Polymers 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- AIIAHNREQDTRFI-UHFFFAOYSA-N oxiran-2-ylmethanesulfonic acid Chemical class OS(=O)(=O)CC1CO1 AIIAHNREQDTRFI-UHFFFAOYSA-N 0.000 claims description 4
- DDLBHIIDBLGOTE-UHFFFAOYSA-N 3-chloro-2-hydroxypropane-1-sulfonic acid Chemical class ClCC(O)CS(O)(=O)=O DDLBHIIDBLGOTE-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims 1
- DCEMCPAKSGRHCN-UHFFFAOYSA-N oxirane-2,3-dicarboxylic acid Chemical class OC(=O)C1OC1C(O)=O DCEMCPAKSGRHCN-UHFFFAOYSA-N 0.000 abstract description 23
- -1 3-chloro-2-hydroxyl propyl sulfonate Chemical compound 0.000 abstract description 17
- 239000002253 acid Substances 0.000 abstract description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- DIORMHZUUKOISG-UHFFFAOYSA-N sulfoformic acid Chemical compound OC(=O)S(O)(=O)=O DIORMHZUUKOISG-UHFFFAOYSA-N 0.000 abstract 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 2
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 239000003112 inhibitor Substances 0.000 abstract 1
- 239000003456 ion exchange resin Substances 0.000 abstract 1
- 229920003303 ion-exchange polymer Polymers 0.000 abstract 1
- 230000005764 inhibitory process Effects 0.000 description 27
- 239000000047 product Substances 0.000 description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 239000005864 Sulphur Substances 0.000 description 9
- 239000001506 calcium phosphate Substances 0.000 description 8
- 229910000389 calcium phosphate Inorganic materials 0.000 description 8
- 235000011010 calcium phosphates Nutrition 0.000 description 8
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 229910000975 Carbon steel Inorganic materials 0.000 description 3
- 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 3
- 239000010962 carbon steel Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- JKTORXLUQLQJCM-UHFFFAOYSA-N 4-phosphonobutylphosphonic acid Chemical compound OP(O)(=O)CCCCP(O)(O)=O JKTORXLUQLQJCM-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241001677188 Coccus viridis Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MCCWPEKYUVRUEE-UHFFFAOYSA-N [Ca].C(C1CO1)S(=O)(=O)O.[Ca].[Ca] Chemical compound [Ca].C(C1CO1)S(=O)(=O)O.[Ca].[Ca] MCCWPEKYUVRUEE-UHFFFAOYSA-N 0.000 description 1
- MAHGVKZSJAYDIT-UHFFFAOYSA-N [Ca].ClCC(CS(=O)(=O)O)O Chemical compound [Ca].ClCC(CS(=O)(=O)O)O MAHGVKZSJAYDIT-UHFFFAOYSA-N 0.000 description 1
- JBXUGRHBMXRXSQ-UHFFFAOYSA-N [K].C(C1CO1)S(=O)(=O)O.[K].[K] Chemical compound [K].C(C1CO1)S(=O)(=O)O.[K].[K] JBXUGRHBMXRXSQ-UHFFFAOYSA-N 0.000 description 1
- WMSPCVPOPKNEQI-UHFFFAOYSA-N [NH4+].OC(CCl)CS([O-])(=O)=O Chemical compound [NH4+].OC(CCl)CS([O-])(=O)=O WMSPCVPOPKNEQI-UHFFFAOYSA-N 0.000 description 1
- JMTIXSZQYHAMLY-UHFFFAOYSA-N [P].[Zn] Chemical compound [P].[Zn] JMTIXSZQYHAMLY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- UBMXFGVZFUYLSN-UHFFFAOYSA-N azanium;propane-1-sulfonate Chemical compound [NH4+].CCCS([O-])(=O)=O UBMXFGVZFUYLSN-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920001529 polyepoxysuccinic acid Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- XCEQEKOYONQLOF-UHFFFAOYSA-M sodium 3-chloro-2-hydroxypropanoate Chemical compound [Na+].ClCC(C(=O)[O-])O XCEQEKOYONQLOF-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The present invention relates to a novel corrosion and scale inhibitor of epoxy succinic acid-2, 3-epoxy propyl sulfonic acid copolymers and salt-poly epoxy sulfo-carboxylic acid and salts for water treatment. The present invention has the general structural formula of H[OCH(CH2SO3M)]n [OCH(CO2M)CHCO2M]mOH, wherein M represents H<+>, Na<+>, K<+>, NH4<+> and 1/2Ca<2+>, and m and n represent integers of 1 to 40. The preparation method of the present invention comprises that 3-chloro-2-hydroxyl propyl sulfonate adopted as a raw material is firstly used for generating 2, 3-epoxy propyl sulfonate under the action of the alkalis of sodium hydroxide, potassium hydroxide and calcium hydroxide or ammonia water, and is further copolymerized with salts of epoxy succinic acid to obtain poly epoxy sulfo-carboxylate in the presence of the alkalis of the sodium hydroxide, the potassium hydroxide and the calcium hydroxide or the ammonia water; finally, the 3-chloro-2-hydroxyl propyl sulfonate reacts with H type positive ion series ion exchange resin to obtain poly epoxy sulfo-carboxylic acid. The present invention also discloses the purposes of the poly epoxy sulfo-carboxylic acid and the salts as corrosion inhibitors, scale inhibitors and dispersing agents in industrial water treatment.
Description
One, technical field
The present invention relates to a kind of novel water treating corrosion and scale inhibitor and preparation method thereof.
Two, background technology
Because the shortage day by day of Freshwater resources, and metallic corrosion etc. has brought enormous economic loss [Shi Shengtai etc. for the industrial production of countries in the world, corrosion and protection, 1990,11 (4): 1], industrial cycle water treatment medicament more and more is subject to people's attention [Jiang Liren, corrosion and protection, 1984, (1)].The organic multicomponent phosphonic acids is a present widely used class water conditioner [GWofford, C Slezak, M Bukay.Industrial Water Treatment, 1991], and they have solved the problem of system's generation calcium carbonate scale, and are more high temperature resistant.Its defective is that organic phospho acid can not suppress phosphorus system effectively and phosphorus zinc is calcium phosphate scale, zinc dirt and the ferric oxide deposition problems that produces in the water treatment prescription.The eighties, the co-polymer of sulfonate that contains of domestic and international Application and Development had good restraining ability to calcium phosphate scale, and dispersing iron oxide effectively, stablize zine ion, thereby developing [A Pryor rapidly, M Bukay.Industry Water Treatment, 1991], the polyethylene polyamine polymethylene sulfonate that meanwhile contains single sulfonic acid group obtain research [Yao Cheng etc. Treatment of Industrial Water, 1998, (5): 18], and in the organic phospho acid molecule, introduce sulfonic acid group also obtain research [Han Yinglin etc. Nanjing University of Chemical Technology's journal, 1997, (3): 7].As everyone knows, contain phosphonate group and carboxylic acid group in the molecule of phosphine carboxylic acid compound, it is the inhibiter that a class has scale-inhibiting properties concurrently, many distinctive features are arranged in water quality stabilizer, developed PBTCA (2-phosphonic acid butane-1 both at home and abroad at present, 2, the 4-tricarboxylic acid) and HPA (2-hydroxyl phosphine acetate) [Ji Yongliang, Treatment of Industrial Water, 1995, (6): 1], and the polyamine compounds [Wang Jintang of phosphonic, sulfonic and carboxylic radicals, Hongjun ZHU, Yu Bin etc. the polyamine compounds of phosphonic, sulfonic and carboxylic radicals contains and preparation method thereof, Chinese patent 99114320.5].These phosphorated water conditioners are because of it has the nutrient laden effect, are thrown into to promote the bacterium algae propagation easily behind the waters and form " red tide ", cause public hazards.Along with the reinforcement of environmental protection and consciousness of saving water, the notion of " green corrosion inhibiting and descaling agent " is suggested, and becomes the developing direction of 21 century water conditioner.Therefore, water treatment agent without phosphorus changes into one of focus into people's research.Poly-epoxy succinic acid (the PESA that U.S. Betz company will develop in the nineties in 20th century seventies, polyepoxysuccinic acid) [Tillmon H pearson etc.US3776850] is used for water treatment and developed a kind of phosphate-free water treatment agent [Brown JM, McDowell JF.US5062962, US5147555], it has the favorable biological degradability energy, have the scale inhibitor dual-use function concurrently, and be applicable to the novel green Scale inhibitors [Xiong Rongchun of characteristics such as high-alkali high solid water system, Treatment of Industrial Water, 1999,19 (3): 11].
But the texture ratio of this class water conditioner of poly-epoxy succinic acid (PESA) is more single, and is better to the effect of calcium carbonate scale, then poor to the effect of calcium phosphate etc.Therefore demand urgently this structure is modified or transformed, to invent out the green water conditioner of novel texture, more excellent performance.
Three, summary of the invention
Technical problem to be solved by this invention is to overcome the more single shortcoming of poly-epoxy succinic acid texture ratio, and the structure of poly-epoxy succinic acid is modified, and invents a kind of good water conditioner of multiple functional group, corrosion and scale inhibition performance and preparation method thereof that has.
Product of the present invention is Epoxysuccinic acid and epoxy propanesulfonic acid multipolymer and salt---poly-epoxy sulphur carboxylic acid and salt.Its general structure is H[OCH
2A CH (mistake! It is invalid to link.SO
3M)]
n[OCH(CO
2M)CHCO
2M]
mOH，M＝H
+，Na
+，K
+，NH
4 +，1/2Ca
2+；m，n＝1～40。
Preparation method of the present invention is as follows:
Under agitation to a certain amount of 3-chloro-2-hydroxy-propanesulfonic acid salt ClCH
2CH (OH) CH
2SO
3Add a certain amount of alkali sodium hydroxide, potassium hydroxide, calcium hydroxide or ammonia soln in the M solution, 0～100 ℃ of reaction 0～24h generation 2 down, 3-epoxy propanesulfonic acid salt adds a certain amount of alkali sodium hydroxide, potassium hydroxide, calcium hydroxide or ammonia soln and a certain amount of epoxy succinic hydrochlorate again
React 1～24h down at 0～100 ℃, underpressure distillation dewaters and obtains poly-epoxy sulphur carboxylate salt---epoxy succinic hydrochlorate-2,3-epoxy propanesulfonic acid salt copolymer, and its general structure is: H[OCH
2CH (CH
2SO
3M)]
n[OCH (CO
2M) CHCO
2M]
mOH, above-mentioned middle M=Na
+, K
+, NH
4 +, 1/2Ca
2+M, n=1～40 then obtain poly-epoxy sulphur carboxylic acid H[OCH with this salt and the effect of H type Zeo-karb
2CH (CH
2SO
3H)]
n[OCH (CO
2H) CHCO
2H]
mOH, m, n=1～40.
Its synthetic route is as follows:
Novel water treatment agent PECS of the present invention and salt have very significant advantage:
1) prepared product has been introduced poly-epoxy propanesulfonic acid structure in poly-epoxy succinic acid, contain polyethers, sulfonic acid group and hydroxy-acid group in the molecular structure simultaneously, not phosphorous, have the favorable biological degradability energy, so product of the present invention is a kind of novel green water conditioner.
2) utilize " synergistic effect " between polyethers, sulfonic group and the carboxylic acid group simultaneously, make its inhibition, scale inhibition, dispersing property better.Poly-epoxy sulphur carboxylic acid and salt even can be used as the corrosion inhibiting and descaling agent of cycles of concentration up to 3～4.5 o'clock, the scale inhibition performance of resistance calcium carbonate scale can reach 98%, and the scale inhibition performance of resistance calcium phosphate scale can reach 90%, can reach 89.6% to the corrosion inhibition rate of carbon steel.Can in handling, industrial circulating cooling water be extensive use of.
3) synthetic route is simple, and raw material is easy to get, and cost is low, is suitable for suitability for industrialized production.
Four, embodiment
Embodiment 1
Under agitation in the 3-chloro-2-hydroxypropionate sodium 50g aqueous solution (concentration is 40%), add 40% sodium hydroxide solution 11g, behind 40 ℃ of reaction 30min, the sodium hydroxide solution 12g that adds Epoxysuccinic acid hydrogen sodium 16.4g and 40% again, react 2h down at 100 ℃, underpressure distillation removes certain water after-filtration and obtains poly-epoxy sulphur carboxylic acid sodium 28.2g (epoxy succinic acid disodium-2,3-epoxy propanesulfonic acid sodium multipolymer, PECS-1), yield is 84.5%.Obtain poly-epoxy sulphur carboxylic acid (PECS-1h) after the PECS-1 aqueous solution handled with acidic cation-exchange resin.Its IR data: 3493cm
-1(OH stretching vibration); 2928cm
-1, 2850cm
-1(C-H stretching vibration); 1604cm
-1(stretching vibration of C=O); 1200cm
-1, 1047cm
-1(RSO
3M, C-O); 619cm
-1(RSO
3M).Its
1HNMR data and ownership see Table 1, can get n: m=1 by table 1: 1.4, and measure through Small angle X diffraction and to learn that its weight-average molecular weight is 2075, n=9 then, m=6.4.
Table 1 PECS-1h's
1HNMR (D
2O makes solvent)
| Sequence number | Chemical shift (ppm) | Peak area | Ownership |
| 1 2 3 4 5 6 | 4.70 4.17 4.08 3.98 3.47 3.18 | 208.88 14.29 2.00 4.55 28.66 4.64 | 1、HDO 5、 62 10 3、 7、 8、 9 4 |
This product is through static-state scale inhibition test, and the result shows under 2ppm concentration, can reach 98.4% to the scale inhibition performance of calcium carbonate scale, and the scale inhibition performance of calcium phosphate scale be can be 80.4%; Corrosion inhibition test shows that the concentration of this product in tap water is 10ppm, is 88.4% to the carbon steel corrosion inhibition rate.
Embodiment 2
Under agitation to 53g 2, the potassium hydroxide solution 30g of adding 40% in the 3-epoxy propanesulfonic acid aqueous solutions of potassium (concentration is 40%), add epoxy succinic potassium hydrogen phthalate 17.0g again, react 2h down at 20 ℃, underpressure distillation removes certain water after-filtration and obtains poly-epoxy sulphur carboxylic acid potassium 34.3g (Epoxysuccinic acid dipotassium-2,3-epoxy propanesulfonic acid potassium multipolymer, PECS-2), yield is 80.6%.Obtain poly-epoxy sulphur carboxylic acid (PECS-2h) after the PECS-2 aqueous solution handled with H type 732 cationic exchange coloums, with embodiment 1 measure polymerization degree n: m=1: 1.35, weight-average molecular weight is 2300, n=10.8, m=8.This product is through static-state scale inhibition test, and the result shows under 2ppm concentration, can reach 98.6% to the scale inhibition performance of calcium carbonate scale; Scale inhibition performance to calcium phosphate scale can reach 78.4%; Corrosion inhibition test shows that the concentration of this product in tap water is that 5ppm is 91.4% to the carbon steel corrosion inhibition rate.
Embodiment 3
Under agitation add 0.05mol 3-chloro-2-hydroxy-propanesulfonic acid calcium and 0.025mol calcium hydroxide, reacted 30 minutes down at 50 ℃, add 0.10mol Epoxysuccinic acid calcium then, add 0.03mol calcium hydroxide again and make catalyzer, react down at 80 ℃ and continue reaction 10 hours, get tawny thickness turbid solution, the underpressure distillation after-filtration must gather epoxy sulphur calcium carboxylates 23.2g (Epoxysuccinic acid dicalcium-2,3-epoxy propanesulfonic acid calcium multipolymer, PECS-3), yield is 89.6%.This reaction product is suitably diluted the back go up H type 732 cationic exchange coloums, receive effluent liquid underpressure distillation product (Epoxysuccinic acid-2,3-epoxy propanesulfonic acid multipolymer, PECS-3h), with embodiment 1 measure polymerization degree n: m=1: 1.9, weight-average molecular weight is 4280, n=11, m=17.9.This product is tested through static-state scale inhibition, and the result shows under 2mg/L concentration, can reach 93.2% to the scale inhibition performance of lime carbonate, and the scale inhibition performance of calcium phosphate is reached 77.5%, and the ability of dispersing iron oxide is 85.8%.
Embodiment 4
In the 1000ml three-necked flask, add 0.1mol 3-chloro-2-hydroxy-propanesulfonic acid ammonium and 0.05mol ammoniacal liquor, react 30min down at 60 ℃, add 0.05mol Epoxysuccinic acid ammonium and 0.30mol ammoniacal liquor then 60 ℃ of reactions down, continue reaction 24h, get tawny thickness turbid solution, the underpressure distillation after-filtration must gather epoxy sulphur calcium carboxylates 20.2g (Epoxysuccinic acid two ammoniums-2,3-epoxy propanesulfonic acid ammonium multipolymer, PECS-4), yield is 82.1%.This reaction product is suitably diluted the back goes up sodium type cationic exchange coloum, receive the effluent liquid evaporated under reduced pressure and get product (PECS-4h), with embodiment 1 measure polymerization degree n: m=1: 0.65, weight-average molecular weight is 2900, n=12.8, m=8.32.This product is tested through static-state scale inhibition, and the result shows under 2mg/L concentration, is 97.4% to the scale inhibition performance of lime carbonate, and the scale inhibition performance of calcium phosphate is reached 80.7%, and the ability of dispersing iron oxide is 76.8%.
The synthesis condition of other poly-epoxy sulphur carboxylic acids (PECS) sees Table 2, the scale inhibition of product disperses and corrosion inhibition sees Table 3.
The synthesis condition of table 2 PECS, result
| Sequence number | M | Reaction 1 | Reaction 2 | Productive rate % | ||||
| Mole CHPS/MOH | Temperature of reaction ℃ | Reaction times h | Mole CHPS/ESA/MOH | Temperature of reaction ℃ | Reaction times h | |||
| 5 | Na + | 1∶1.0 | 60 | 2 | 1∶1.2∶0.22 | 0 | 24 | 40 |
| 6 | 1∶1.3 | 100 | 4 | 1∶1.4∶0.01 | 20 | 20 | 47 | |
| 7 | 1∶1.1 | 0 | 24 | 1.4∶1.0∶0.02 | 40 | 18 | 80 | |
| 8 | 1∶1.2 | 20 | 20 | 1∶1.05∶0.02 | 60 | 14 | 93 | |
| 9 | 1∶1.4 | 40 | 18 | 1∶1.1∶0.01 | 80 | 10 | 90 | |
| 10 | K + | 1∶1.0 | 60 | 14 | 1∶1.2∶0.02 | 100 | 6 | 91 |
| 11 | 1∶1.05 | 60 | 10 | 1∶1.4∶0.32 | 100 | 4 | 70 | |
| 12 | 1∶1.1 | 80 | 0.2 | 1∶1.0∶0.02 | 0 | 24 | 65 | |
| 13 | 1∶1.2 | 100 | 8 | 1.2∶1.0∶0.05 | 20 | 20 | 73 | |
| 14 | 1∶1.4 | 20 | 20 | 1∶1.1∶0.02 | 40 | 18 | 89 | |
| 15 | 1/2Ca 2+ | 1∶1.0 | 40 | 18 | 1∶1.27∶0.18 | 60 | 14 | 86 |
| 16 | 1∶1.1 | 60 | 14 | 1∶1.2∶0.02 | 80 | 10 | 88 | |
| 17 | 1∶1.27 | 40 | 18 | 1∶1.4∶0.02 | 100 | 8 | 82 | |
| 18 | 1∶1.2 | 100 | 0.5 | 1∶1.0∶0.06 | 100 | 0.5 | 56 | |
| 19 | 1∶1.4 | 80 | 10 | 1∶1.16∶0.02 | 0 | 24 | 64 | |
| 20 | NH 4 + | 1∶1.0 | 20 | 20 | 0.5∶1.1∶0.05 | 20 | 20 | 59 |
| 21 | 1∶1.16 | 40 | 18 | 1∶1.4∶0.04 | 40 | 18 | 68 | |
| 22 | 1∶1.1 | 60 | 14 | 1.8∶1.0∶0.1 | 60 | 14 | 70 | |
| 23 | 1∶1.2 | 80 | 16 | 1∶1.16∶0.14 | 80 | 10 | 73 | |
| 24 | 1∶1.4 | 100 | 0.2 | 1∶1.1∶0.2 | 100 | 8 | 74 | |
The performance of table 3 sintetics (PECS)
| Sequence number | Weight-average molecular weight | The polymerization degree | Corrosion inhibition rate a ％ | Scale inhibition performance b (CaCO 3) ％ | Scale inhibition performance b [Ca 3(PO 3) 2] ％ | |
| n | m | |||||
| 5 | 2910 | 9.4 | 12.1 | 89.1 | 99.3 | 89.7 |
| 6 | 5170 | 12.5 | 26 | 84.3 | 99.4 | 89.6 |
| 7 | 5200 | 24 | 14.3 | 78.8 | 98.8 | 87.8 |
| 8 | 4370 | 15.1 | 17.3 | 85.0 | 99.0 | 85.0 |
| 9 | 4750 | 16.1 | 19 | 90.8 | 99.8 | 87.8 |
| 10 | 1690 | 4.5 | 8.1 | 89.6 | 99.6 | 89.6 |
| 11 | 2010 | 4.7 | 10.3 | 79.3 | 99.1 | 89.1 |
| 12 | 2820 | 3.4 | 17.8 | 84.3 | 98.0 | 84.3 |
| 13 | 6650 | 28 | 21.1 | 88.2 | 98.8 | 88.8 |
| 14 | 2170 | 6.6 | 9.5 | 89.0 | 99.0 | 89.0 |
| 15 | 2680 | 8.4 | 11.0 | 90.8 | 99.8 | 90.8 |
| 16 | 4340 | 15.1 | 17.3 | 89.6 | 99.6 | 89.6 |
| 17 | 5130 | 16.1 | 22 | 90.4 | 99.1 | 89.1 |
| 18 | 5300 | 19 | 20.3 | 89.6 | 98.0 | 84.3 |
| 19 | 4060 | 14.7 | 15.4 | 89.1 | 99.1 | 89.6 |
| 20 | 1401 | 4.8 | 4.6 | 84.3 | 98.0 | 84.3 |
| 21 | 5990 | 14 | 30.7 | 81.8 | 98.8 | 89.8 |
| 22 | 6540 | 31.2 | 17 | 89.0 | 99.0 | 89.0 |
| 23 | 8490 | 32.7 | 30.1 | 80.7 | 98.3 | 90.6 |
| 24 | 4334 | 14.1 | 18.1 | 89.6 | 98.8 | 89.6 |
A: drug concentration is 10mg/L; B: drug concentration is 2mg/L.
Claims (3)
1. a water treating corrosion and scale inhibitor is an Epoxysuccinic acid-2,3-epoxy propanesulfonic acid multipolymer and salt, and it has following general formula: H[OCH
2CH (CH
2SO
3M)]
n[OCH (CO
2M) CHCO
2M]
mOH, wherein M=H
+, Na
+, K
+, NH
4 +, 1/2Ca
2+M, n=1～40.
2. the preparation method of a water treating corrosion and scale inhibitor is: under agitation to 1 mole 3-chloro-2-hydroxy-propanesulfonic acid salt ClCH
2CH (OH) CH
2SO
3The alkali that adds 1 mole in the M solution: sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia soln wherein a kind of, 0～100 ℃ down reaction 0～24h generate 2,3-epoxy propanesulfonic acid salt adds 1.0～2.2 moles epoxy succinic hydrochlorate again
Alkali with 0.01～0.32 mole: sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia soln wherein a kind of, react 1～24h down at 0～100 ℃, underpressure distillation dewaters and obtains epoxy succinic hydrochlorate-2,3-epoxy propanesulfonic acid salt copolymer, and its general structure is: H[OCH
2CH (CH
2SO
3M)]
n[OCH (CO
2M) CHCO
2M]
mOH, above-mentioned middle M=Na
+, K
+, NH
4 +, 1/2Ca
2+M, n=1～40 then obtain Epoxysuccinic acid-2 with this salt and the effect of H type Zeo-karb, 3-epoxy propanesulfonic acid multipolymer H[OCH
2CH (CH
2SO
3H)]
n[OCH (CO
2H) CHCO
2H]
mOH, m, n=1～40.
3. Epoxysuccinic acid-2,3-epoxy propanesulfonic acid multipolymer and salt are as inhibiter, Scale inhibitors and the dispersion agent purposes in Treatment of Industrial Water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN02112951.7A CN1227165C (en) | 2002-04-29 | 2002-04-29 | Water treating corrosion and scale inhibitor and its prepn. |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN02112951.7A CN1227165C (en) | 2002-04-29 | 2002-04-29 | Water treating corrosion and scale inhibitor and its prepn. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1375467A CN1375467A (en) | 2002-10-23 |
| CN1227165C true CN1227165C (en) | 2005-11-16 |
Family
ID=4742354
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN02112951.7A Expired - Fee Related CN1227165C (en) | 2002-04-29 | 2002-04-29 | Water treating corrosion and scale inhibitor and its prepn. |
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| Country | Link |
|---|---|
| CN (1) | CN1227165C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321077C (en) * | 2003-11-12 | 2007-06-13 | 中国石油化工股份有限公司北京燕山分公司研究院 | Composite scale-proof corrosion inbibitor containing poly epoxy succinic acid and its use |
| CN1329317C (en) * | 2004-12-23 | 2007-08-01 | 宁波大学 | High molecular water softener, synthetic method and application |
| CN100575391C (en) * | 2008-01-28 | 2009-12-30 | 同济大学 | The corrosion inhibiting and descaling agent Epoxysuccinic acid/to acid/epoxy ethylbenzene sulfonic acid copolymer and preparation method thereof |
| WO2012094816A1 (en) * | 2011-01-14 | 2012-07-19 | 南京工业大学 | Phosphorous-free corrosion and scale inhibitor and synthesis thereof |
| CN110482716A (en) * | 2019-08-31 | 2019-11-22 | 天津正达科技有限责任公司 | A kind of dedicated non-phosphorus scale dispersing agent of coal gasification buck and preparation method thereof, application |
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2002
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| Publication number | Publication date |
|---|---|
| CN1375467A (en) | 2002-10-23 |
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