CN118420136A - Preparation method of compound phosphorus-free environment-friendly scale inhibitor - Google Patents
Preparation method of compound phosphorus-free environment-friendly scale inhibitor Download PDFInfo
- Publication number
- CN118420136A CN118420136A CN202410882144.8A CN202410882144A CN118420136A CN 118420136 A CN118420136 A CN 118420136A CN 202410882144 A CN202410882144 A CN 202410882144A CN 118420136 A CN118420136 A CN 118420136A
- Authority
- CN
- China
- Prior art keywords
- parts
- scale inhibitor
- preparation
- polycarboxylic
- stirring
- 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.)
- Granted
Links
- 239000002455 scale inhibitor Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 150000001875 compounds Chemical class 0.000 title claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 66
- 235000019426 modified starch Nutrition 0.000 claims abstract description 39
- 229920001612 Hydroxyethyl starch Polymers 0.000 claims abstract description 38
- 229920001577 copolymer Polymers 0.000 claims abstract description 38
- 229940050526 hydroxyethylstarch Drugs 0.000 claims abstract description 38
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 229920000881 Modified starch Polymers 0.000 claims abstract description 23
- 239000004368 Modified starch Substances 0.000 claims abstract description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 90
- 238000003756 stirring Methods 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 27
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 18
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical group Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 58
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 238000001879 gelation Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 description 20
- 238000005260 corrosion Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 14
- 239000012086 standard solution Substances 0.000 description 14
- 229910000975 Carbon steel Inorganic materials 0.000 description 11
- 229910001424 calcium ion Inorganic materials 0.000 description 11
- 239000010962 carbon steel Substances 0.000 description 11
- 229910021645 metal ion Inorganic materials 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000012085 test solution Substances 0.000 description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 5
- 239000001110 calcium chloride Substances 0.000 description 5
- 229960002713 calcium chloride Drugs 0.000 description 5
- 229910001628 calcium chloride Inorganic materials 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 4
- 229960005069 calcium Drugs 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 230000003068 static effect Effects 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 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- LGGXTTVQTBPPLC-ULAWRXDQSA-N (4r,5s,6r,7r)-1,4,5,6,7,8-hexahydroxyoctan-3-one Chemical compound OCCC(=O)[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO LGGXTTVQTBPPLC-ULAWRXDQSA-N 0.000 description 2
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 125000003636 chemical group Chemical group 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920001444 polymaleic acid Polymers 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920000805 Polyaspartic acid Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 1
- 229940052299 calcium chloride dihydrate Drugs 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 1
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
- C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- General Chemical & Material Sciences (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention belongs to the field of environmental protection water treatment, and relates to a preparation method of a compound phosphorus-free environment-friendly scale inhibitor, in particular to a preparation method of a modified starch polymer and a polycarboxylic sulfonic acid copolymer, wherein the finally obtained scale inhibitor comprises a hydroxyethyl starch and polycarboxylic sulfonic acid copolymer, and the existence of sulfonic groups in the copolymer can ensure that the scale inhibitor has better water solubility and prevent gelation of the scale inhibitor. The finally obtained compound phosphorus-free environment-friendly scale inhibitor can obviously play the synergistic effect of two polymers, improve the efficiency of the scale inhibitor, reduce the use amount of the scale inhibitor and reduce the scale inhibition cost of enterprises.
Description
Technical Field
The invention belongs to the field of environmental protection water treatment, and relates to a preparation method of a compound phosphorus-free environment-friendly scale inhibitor containing hydroxyethyl starch and a polycarboxylic sulfonic acid copolymer, wherein the scale inhibitor is a phosphorus-free high polymer copolymer and belongs to the environment-friendly scale inhibitor.
Background
With the rapid development of the industry in China, the use amount of industrial cooling water is greatly increased. The biggest problem faced in the use of cooling water is scale deposition. Along with the continuous flow of water in the cooling circulation system, calcium, magnesium and iron plasma in the water gradually deposit on the inner wall of the cooling circulation system equipment, so that scale is formed, the cooling efficiency is reduced, the equipment is corroded, and the consumption of the cooling water is greatly increased. Therefore, the scale inhibitor is added into the circulating water system, so that ion deposition can be effectively prevented, and equipment corrosion and cooling efficiency reduction are avoided.
Conventional scale inhibitors generally contain a large amount of phosphate, and although the scale inhibitor has very high scale inhibition efficiency, the large amount of phosphate ions can cause eutrophication of water, so that algae microorganisms in water are excessively propagated, and ecological balance is seriously damaged. In order to solve the above problems, the art has also developed organic polyacrylic acid and polymaleic acid scale inhibitors, which do not contain nitrogen and phosphorus elements, do not cause eutrophication of water, and a large amount of carboxyl groups can be chelated with metal ions such as calcium, magnesium, iron and the like to damage the lattice structure of the surface of the scale, so that the scale on the inner wall of a pipeline can be removed. However, the scale inhibition efficiency is limited due to the single function of the carboxylic acid group, and a large amount of carboxylic acid groups are easy to form gel with metal ions, so that the scale inhibition effect is reduced. In addition, compared with inorganic phosphate scale inhibitors, the organic scale inhibitors have lower efficiency and high production cost, and bring great economic burden to enterprises.
Therefore, aiming at the problems faced by the existing polyacrylic acid and polymaleic acid scale inhibitors, the development of a novel high-molecular polymer scale inhibitor is urgently needed, the efficiency of the scale inhibitor is improved, the use amount of the scale inhibitor is reduced, and the scale inhibition cost of enterprises is reduced.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a compound phosphorus-free environment-friendly scale inhibitor, which is characterized in that a modified starch polymer and a polycarboxylic sulfonic acid copolymer are compounded, and the finally obtained scale inhibitor comprises a copolymer of hydroxyethyl starch and polycarboxylic sulfonic acid, wherein the existence of sulfonic groups in the copolymer can ensure that the scale inhibitor has better water solubility and prevent gelation of the scale inhibitor. The finally obtained compound phosphorus-free environment-friendly scale inhibitor can obviously play the synergistic effect of two polymers, improve the efficiency of the scale inhibitor, reduce the use amount of the scale inhibitor and reduce the scale inhibition cost of enterprises.
The invention aims to achieve the aim, and the aim is achieved by the following technical scheme:
the preparation method of the compound phosphorus-free environment-friendly scale inhibitor comprises the following specific preparation steps of hydroxyethyl starch and a polycarboxylic sulfonic acid copolymer: wherein the weight parts of the components are as follows,
(1) Preparation of hydroxyethyl starch derivatives containing propenyl groups:
Adding 10-20 parts of hydroxyethyl starch into 50-200 parts of solvent, stirring for 10-30 minutes at 10-40 ℃, then adding 4-7 parts of acrylic acid and 11-19 parts of condensing agent, maintaining the temperature of the mixed solution at 10-40 ℃, adding 0.1-0.5 part of 4-dimethylaminopyridine, and continuously stirring for 4-10 hours; then the reaction solution is poured into 500-2000 parts of methanol, stirred for 20-40 minutes, filtered, and the solid is respectively washed three times by 50-80 parts of methanol, and dried to obtain the hydroxyethyl starch derivative containing propenyl.
(2) Preparation of modified starch polymer:
Adding the hydroxyethyl starch derivative containing the propenyl, 18-26 parts of acrylic acid and 5-8 parts of maleic anhydride prepared in the step (1) into 100-150 parts of deionized water, introducing argon for 10-30 minutes under the stirring condition, then adding 0.3-0.7 part of potassium peroxodisulfate, heating to 70-90 ℃, and stirring for 2-4 hours; cooling to 10-30 ℃, pouring the reaction liquid into 800-2000 parts of methanol, filtering, washing the solid with 100-150 parts of methanol for three times respectively, and drying to obtain a modified starch polymer;
In the step, the structure of hydroxyethyl starch is modified by acrylic acid, and the obtained acrylic acid modified starch is copolymerized with acrylic acid and maleic anhydride to obtain a modified starch polymer, wherein the polymer contains a large number of hydroxyethyl glucose structural units and a large number of oxygen atoms and can coordinate with a plurality of metal ions to form chelate, so that various metal ions can be effectively removed. The polymer is a hyperbranched polymer, can form a hyperbranched network structure, has a more stable structure after metal ions are chelated with the polymer, and can remarkably improve the efficiency and the capability of removing the metal ions of the scale inhibitor.
(3) Preparation of a polycarboxylic sulfonic acid copolymer:
Adding 16-19 parts of 2-acrylamide-2-methylpropanesulfonic acid, 10-14 parts of acrylic acid and 12-16 parts of maleic anhydride into 130-180 parts of deionized water, introducing argon for 10-30 minutes under the stirring condition, adding 0.5-0.9 part of potassium persulfate, heating to 70-90 ℃, and stirring for 2-4 hours; cooling to 10-30 ℃, pouring the reaction solution into 1200-2200 parts of methanol, filtering, washing the solid with 150-200 parts of methanol for three times respectively, and drying to obtain the polycarboxylic sulfonic acid copolymer;
The polycarboxylic sulfonic acid copolymer of the 2-acrylamide-2-methylpropanesulfonic acid obtained in the step has a large amount of sulfonic acid groups, and the solubility of the sulfonic acid groups after being combined with metal ions is good; after being compounded with other components, the anti-scaling agent can improve the solubility of the anti-scaling agent, and meanwhile, the acrylic acid and the starch compounds can be prevented from being chelated with metal ions to form gel.
(4) Preparation of a compound environment-friendly phosphorus-free scale inhibitor containing hydroxyethyl starch and a polycarboxylic sulfonic acid copolymer:
And (3) directly blending the modified starch polymer prepared in the step (2) and the polycarboxylic acid copolymer prepared in the step (3) to obtain the compound phosphorus-free scale inhibitor containing hydroxyethyl starch and the polycarboxylic acid copolymer.
The modified starch polymer and the polycarboxylic sulfonic acid copolymer are blended, so that the production cost is low, the synergistic effect of the modified starch polymer and the polycarboxylic sulfonic acid copolymer can be remarkably exerted, the efficiency of the scale inhibitor is improved, the use amount of the scale inhibitor is reduced, and the scale inhibition cost of enterprises is reduced.
Preferably, in the preparation method, the following steps are adopted:
in the step (1), the solvent is dimethyl sulfoxide or N, N-dimethylformamide.
In the step (1), the condensing agent is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride or dicyclohexylcarbodiimide.
In the step (2), potassium persulfate is added in two batches, wherein 0.1-0.4 part of potassium persulfate is added in the first batch and 0.2-0.3 part of potassium persulfate is added in the second batch. The two batches are separated by at least 30 minutes, which prevents the presence of unreacted monomers in the system, resulting in an insufficient final degree of polymerization.
For the same reason, in the step (3), potassium persulfate is added in three batches, wherein the first batch is added with 0.2-0.3 part, the second batch is added with 0.2-0.3 part, and the third batch is added with 0.1-0.3 part. The batch interval is also 30 minutes or more.
Compared with the prior art, the invention has the following beneficial effects:
The modified starch polymer is prepared by modifying the structure of hydroxyethyl starch by acrylic acid, preparing hydroxyethyl starch derivative containing propenyl, and further copolymerizing acrylic acid and maleic anhydride, and contains a large number of hydroxyethyl glucose structural units and a large number of oxygen atoms, and has good chelation effect on a large number of metal ions. And after the acrylic acid reacts with the hydroxyethyl starch, the acrylic acid and the maleic anhydride are further copolymerized to generate a hyperbranched structure, and a large amount of metal ions can be filled in the hyperbranched network structure, so that the efficiency and the capability of removing the metal ions of the scale inhibitor can be obviously improved.
The invention also prepares the polycarboxylic sulfonic acid copolymer containing 2-acrylamide-2-methylpropanesulfonic acid, and the existence of sulfonic acid groups can ensure that the scale inhibitor has better water solubility and prevent the scale inhibitor from gelation. According to the invention, the modified starch polymer and the polycarboxylic sulfonic acid copolymer are compounded, so that the synergistic effect of the two polymers can be remarkably exerted, the efficiency of the scale inhibitor is improved, the use amount of the scale inhibitor is reduced, and the scale inhibition cost of enterprises is reduced.
Detailed Description
The invention will be further explained below with reference to specific embodiments, which are only suitable for a further, completely clear explanation of the invention, the described embodiments being only some, but not all, of the embodiments of the invention. All other embodiments created based on this invention are within the scope of this invention. The following examples and experimental examples are all conventional techniques using instruments, reagents, etc.
Example 1: the preparation method of the compound phosphorus-free environment-friendly scale inhibitor comprises the following specific preparation steps: wherein the weight parts of the components are as follows,
(1) Preparation of hydroxyethyl starch derivatives containing propenyl groups:
Adding 10 parts of hydroxyethyl starch into 50 parts of dimethyl sulfoxide, stirring for 10 minutes, adding 4 parts of acrylic acid and 11 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, maintaining the temperature of the mixed solution at 10 ℃, adding 0.1 part of 4-dimethylaminopyridine, continuously stirring for 4 hours, pouring the reaction solution into 500 parts of methanol, stirring for 20 minutes, filtering, washing the solid with 50 parts of methanol for three times, and drying to obtain the hydroxyethyl starch derivative containing propenyl;
(2) Preparation of modified starch polymer:
Adding the hydroxyethyl starch derivative containing the propenyl, 18 parts of acrylic acid and 5 parts of maleic anhydride prepared in the step (1) into 100 parts of deionized water, introducing argon for 10 minutes under the stirring condition, adding potassium peroxodisulfate in two batches, adding 0.1 part in the first batch and 0.2 part in the second batch, heating to 70 ℃ at intervals of 30 minutes, stirring for 2 hours, cooling to 10 ℃, pouring the reaction solution into 800 parts of methanol, filtering, washing the solid with 100 parts of methanol for three times, and drying to obtain a modified starch polymer;
(3) Preparation of a polycarboxylic sulfonic acid copolymer:
adding 16 parts of 2-acrylamide-2-methylpropanesulfonic acid, 10 parts of acrylic acid and 12 parts of maleic anhydride into 130 parts of deionized water, introducing argon for 10 minutes under the stirring condition, adding potassium peroxodisulfate in three batches, adding 0.2 part in the first batch, 0.2 part in the second batch, 0.1 part in the third batch, heating to 70 ℃ at intervals of 30 minutes, stirring for 2 hours, cooling to 10 ℃, pouring the reaction solution into 1200 parts of methanol, filtering, washing the solid with 150 parts of methanol for three times, and drying to obtain a polycarboxylic sulfonic acid copolymer;
(4) Preparation of a compound phosphorus-free scale inhibitor containing hydroxyethyl starch and a polycarboxylic sulfonic acid copolymer:
and (3) blending the modified starch polymer prepared in the step (2) and the polycarboxylic acid copolymer prepared in the step (3) to obtain the compound phosphorus-free scale inhibitor containing hydroxyethyl starch and the polycarboxylic acid copolymer.
Example 2: the preparation method of the compound phosphorus-free environment-friendly scale inhibitor comprises the following specific preparation steps: wherein the weight parts of the components are as follows,
(1) Preparation of hydroxyethyl starch derivatives containing propenyl groups:
Adding 20 parts of hydroxyethyl starch into 200 parts of N, N-dimethylformamide, stirring for 30 minutes, adding 7 parts of acrylic acid and 19 parts of dicyclohexylcarbodiimide, maintaining the temperature of the mixed solution at 40 ℃, adding 0.5 part of 4-dimethylaminopyridine, continuously stirring for 10 hours, pouring the reaction solution into 2000 parts of methanol, stirring for 40 minutes, filtering, washing the solid with 80 parts of methanol for three times, and drying to obtain a hydroxyethyl starch derivative containing propenyl;
(2) Preparation of modified starch polymer:
Adding the hydroxyethyl starch derivative containing the propenyl, 26 parts of acrylic acid and 8 parts of maleic anhydride prepared in the step (1) into 150 parts of deionized water, introducing argon for 30 minutes under the stirring condition, adding potassium peroxodisulfate in two batches, adding 0.4 part of potassium peroxodisulfate in the first batch, adding 0.3 part of potassium peroxodisulfate in the second batch, heating to 90 ℃ at intervals of 35 minutes, stirring for 4 hours, cooling to 30 ℃, pouring the reaction liquid into 2000 parts of methanol, filtering, washing the solid with 150 parts of methanol for three times, and drying to obtain a modified starch polymer;
(3) Preparation of a polycarboxylic sulfonic acid copolymer:
Adding 19 parts of 2-acrylamide-2-methylpropanesulfonic acid, 14 parts of acrylic acid and 16 parts of maleic anhydride into 180 parts of deionized water, introducing argon for 30 minutes under the stirring condition, adding potassium peroxodisulfate in three batches, adding 0.3 part in the first batch, adding 0.3 part in the second batch, adding 0.3 part in the third batch, heating to 90 ℃ at intervals of 35 minutes, stirring for 4 hours, cooling to 30 ℃, pouring the reaction solution into 2200 parts of methanol, filtering, washing the solid with 200 parts of methanol for three times, and drying to obtain a polycarboxylic sulfonic acid copolymer;
(4) Preparation of a compound phosphorus-free scale inhibitor containing hydroxyethyl starch and a polycarboxylic sulfonic acid copolymer:
and (3) blending the modified starch polymer prepared in the step (2) and the polycarboxylic acid copolymer prepared in the step (3) to obtain the compound phosphorus-free scale inhibitor containing hydroxyethyl starch and the polycarboxylic acid copolymer.
Example 3: the preparation method of the compound phosphorus-free environment-friendly scale inhibitor comprises the following specific preparation steps: wherein the weight parts of the components are as follows,
(1) Preparation of hydroxyethyl starch derivatives containing propenyl groups:
adding 16 parts of hydroxyethyl starch into 110 parts of dimethyl sulfoxide, stirring for 20 minutes, adding 5.4 parts of acrylic acid and 15 parts of dicyclohexylcarbodiimide, maintaining the temperature of the mixed solution at 25 ℃, adding 0.31 part of 4-dimethylaminopyridine, continuously stirring for 6 hours, pouring the reaction solution into 1200 parts of methanol, stirring for 30 minutes, filtering, washing the solid with 65 parts of methanol for three times, and drying to obtain the hydroxyethyl starch derivative containing propenyl;
(2) Preparation of modified starch polymer:
Adding the hydroxyethyl starch derivative containing the propenyl, 22 parts of acrylic acid and 6.4 parts of maleic anhydride prepared in the step (1) into 122 parts of deionized water, introducing argon for 20 minutes under the stirring condition, adding potassium persulfate in two batches, adding 0.25 part in the first batch and 0.25 part in the second batch, heating to 80 ℃ at intervals of 30 minutes, stirring for 3 hours, cooling to 20 ℃, pouring the reaction solution into 1200 parts of methanol, filtering, washing the solid with 130 parts of methanol for three times, and drying to obtain a modified starch polymer;
(3) Preparation of a polycarboxylic sulfonic acid copolymer:
Adding 17 parts of 2-acrylamide-2-methylpropanesulfonic acid, 12 parts of acrylic acid and 14 parts of maleic anhydride into 160 parts of deionized water, introducing argon for 20 minutes under the stirring condition, adding potassium peroxodisulfate in three batches, adding 0.25 part in the first batch, 0.25 part in the second batch, adding 0.15 part in the third batch, heating to 80 ℃ at intervals of 30 minutes, stirring for 3 hours, cooling to 20 ℃, pouring the reaction solution into 1700 parts of methanol, filtering, washing the solid with 170 parts of methanol for three times, and drying to obtain a polycarboxylic sulfonic acid copolymer;
(4) Preparation of a compound phosphorus-free scale inhibitor containing hydroxyethyl starch and a polycarboxylic sulfonic acid copolymer:
and (3) blending the modified starch polymer prepared in the step (2) and the polycarboxylic acid copolymer prepared in the step (3) to obtain the compound phosphorus-free scale inhibitor containing hydroxyethyl starch and the polycarboxylic acid copolymer.
Comparative example: the composite scale inhibitor was prepared according to the method described in example 2 in the method for producing the composite scale inhibitor of polyaspartic acid and polyacrylic acid under the patent name of application number CN 201410672769.8:
Adding 30 parts of maleic anhydride and 52 parts of ammonia water into a reaction kettle, starting stirring, adding 2 parts of a mixture of ferric oxide and nickel oxide when the temperature is raised to 55 ℃, stopping stirring uniformly, standing at a constant temperature for 1.1 hours, starting stirring, adding 6 parts of deionized water, stopping heating, reducing the reaction temperature to 25 ℃ under the stirring condition, adjusting the pH value of the reaction solution to 9-10 by using a 1M sodium hydroxide aqueous solution, adding 10 parts of polyacrylic acid, and stirring for 30 min to obtain the carboxylic acid scale inhibitor.
Experimental example 1: and (3) testing the scale inhibition performance of the calcium carbonate:
Preparing a sodium bicarbonate standard solution with the concentration of bicarbonate ions of 18.3 mg/mL, a calcium chloride standard solution with the concentration of calcium ions of 6.0 mg/mL, an EDTA standard solution with the concentration of 0.01 mol/L, a potassium hydroxide solution with the mass fraction of 200 g/L and a calcium-carboxylic acid indicator.
250ML of water was added to a 500 mL volumetric flask, a volume of calcium chloride standard solution was added with a burette, a quantity of the sample solutions of examples 1-3 and comparative example was added with a pipette, and shaking was performed. Then adding 20mL borax buffer solution, and shaking uniformly. Slowly adding a certain volume of sodium bicarbonate standard solution into a burette, shaking uniformly, dripping, diluting to scale with water, and shaking uniformly. And simultaneously, a blank experiment without adding a scale inhibitor is carried out.
The conical flask containing the blank and reagent solution was immersed in a constant temperature water bath at 80 c, the reagent solution level was not higher than the water bath level, the solution was placed at constant temperature for 10h, and the solution was filtered while hot with medium speed quantitative filter paper, after the filtrate was cooled, 25.0 filtrate mL was removed, placed in a 250mL conical flask, water was added to 80 mL, and 5mL potassium hydroxide solution and about 0.1g of calcium-carboxylic acid indicator were added. And titrating the solution from purple to bright blue by using an ethylenediamine tetraacetic acid disodium standard solution to obtain the final point. The mass concentration of the calcium ions in the test solution and the blank test solution are calculated according to the following formula.
The concentration of calcium ions in the aqueous solution, ρ, is expressed in mg/mL:
ρ=V1CM/V
Wherein:
the mass concentration of rho-calcium ions is mg/mL;
V 1 -the value of the volume of the disodium ethylenediamine tetraacetate standard solution consumed in titration is in mL;
accurate value of actual concentration of disodium C-ethylenediamine tetraacetate in mol/L, (c=0.01)
The molar mass of M-calcium ions is given in g/mol (M=40.08)
V-the value of the volume of the standard solution of calcium chloride taken, in mL, (V=25)
Scale inhibition performance of the water treatment agent is calculated by eta, and the numerical value is expressed as percent:
η=（ρ3-ρ2）/（ρ1-ρ2 ）×100
Wherein:
ρ 3 -the numerical value of the mass concentration of calcium ions after the test of adding the water treatment agent into the test solution is mg/mL;
ρ 2 -the numerical value of the mass concentration of calcium ions after the blank test solution without the water treatment agent is tested, and the unit is mg/mL;
ρ 1 -the value of the mass concentration of calcium ions in water under actual working conditions or in formulated water, the unit is mg/mL.
TABLE 1 calculation results of scale inhibition ratio for calcium carbonate
。
As shown in the results of Table 1, the scale inhibitor of the invention in example 2 shows a good scale inhibition efficiency for calcium carbonate, the scale inhibition efficiency can reach 89.96% when the concentration of the scale inhibitor is 15 mg/mL, the scale inhibition efficiency can reach 94.85% when the concentration of the scale inhibitor is 20 mg/mL, the concentration of the scale inhibitor is continuously increased, the scale inhibition efficiency tends to be stable, and the use amount of the scale inhibitor can not be increased any more for controlling the cost. And the scale inhibition rate of the examples is obviously better than that of the comparative examples, and has very remarkable progress.
Experimental example 2: calcium sulfate scale inhibition performance test:
Preparing a sodium sulfate standard solution with sulfate ion concentration of 18.3 mg/mL, a calcium chloride standard solution with calcium ion concentration of 6.0 mg/mL, an EDTA standard solution with concentration of 0.01mol/L, a potassium hydroxide solution with mass fraction of 200 g/L and a calcium-carboxylic acid indicator.
250 ML of water was added to a 500 mL volumetric flask, a volume of a standard solution of calcium chloride was added with a burette, a quantity of the sample solutions of examples 1-3 and comparative example was added with a pipette, and shaking was performed. Slowly adding a certain volume of sodium sulfate standard solution by using a burette, shaking uniformly, dripping, diluting to a scale by using water, and shaking uniformly. And simultaneously, a blank experiment without adding a scale inhibitor is carried out.
Immersing the conical flask containing the blank and the reagent solution in a constant temperature water bath at 60 ℃, keeping the liquid level of the reagent solution not higher than the liquid level of the water bath, standing at a constant temperature for 6h, filtering with medium-speed quantitative filter paper while the reagent solution is hot, taking 25.0 of mL of the filtrate after the filtrate is cooled, placing the filtrate in a conical flask at 250 mL, adding water to 80mL, adding 5mL of potassium hydroxide solution and about 0.1 g of calcium-carboxylic acid indicator. And titrating the solution from purple to bright blue by using an ethylenediamine tetraacetic acid disodium standard solution to obtain the final point. The mass concentrations of the calcium ions in the test solution and the blank test solution were calculated respectively according to the formula in experimental example 1.
TABLE 2 calculation of the scale inhibition ratio of calcium sulfate
。
As shown in Table 2, the scale inhibitor of example 2 of the present invention also shows excellent scale inhibition efficiency for calcium sulfate, the scale inhibition efficiency can reach 98.89% when the concentration of the scale inhibitor is 5 mg/mL, and the scale inhibition efficiency reaches 100% when the concentration of the scale inhibitor is more than 10 mg/mL. And the scale inhibition rate of the examples is obviously better than that of the comparative examples, and has very remarkable progress.
Experimental example 3: static scale inhibition experiment and rotary hanging piece corrosion inhibition experiment for circulating water
Simulated circulating water was formulated to test the scale and corrosion inhibition rates of examples 1,2, 3 and comparative examples. Wherein, the pH of the solution=8.0, the total hardness is 500.0 mg/L, the alkalinity is 300.0 mg/L and the Cl - 1348.82 mg/L,SO4 2- 1143.2 mg/L.
Static scale inhibition was performed according to the scale inhibition test method for calcium carbonate in the above-described test example 1.
Corrosion inhibition experiment of water treatment agent: firstly, wiping 20# carbon steel with rust-proof grease by using filter paper, then wiping the carbon steel with absorbent cotton in absolute ethyl alcohol, after wiping the carbon steel clean, sucking the carbon steel dry by using the filter paper, placing the carbon steel in a dryer for 4h, weighing (accurate to 0.2 mg), and storing the carbon steel in the dryer for standby.
Preparing water: the calcium chloride dihydrate of 7.35 g, the magnesium sulfate heptahydrate of 4.93 g and the sodium chloride of 6.58 g are weighed and dissolved in the water of about 7L, and after complete dissolution, the mixture is uniformly mixed, and the sodium bicarbonate of 1.68 g is weighed and dissolved in the water of about 1L, and after complete dissolution, the mixture is uniformly mixed. Mixing the two solutions, diluting with water to 10L, and mixing. The standard prepared water has a calcium ion concentration of 200.4 mg/L, a magnesium ion concentration of 48.62 mg/L, a chloride ion concentration of 399.1 mg/L and a bicarbonate ion concentration of 122.0 mg/L.
Finally, 2000 mL beakers are taken, 2000 mL of the preparation water is added, a certain amount of sample solutions of examples 1-3 and comparative examples are added by a pipette, the dosing concentration is 20mg/L, a certain amount of sodium bicarbonate is added, the pH is adjusted to 8.3, the solution is placed in a 45 ℃ water bath for stabilizing 2h, a weighed carbon steel hanging piece is added, a test piece is taken out after 72 h, firstly, the hanging piece is washed by tap water, secondly, about 30s is washed in an acid washing solution (10% hydrochloric acid and 0.5% hexamethylenetetramine), and the test piece is taken out. The water was quickly rinsed with tap water. Immediately immersed in sodium hydroxide solution for about 30s, taken out, rinsed with pure water, wiped with filter paper and blotted dry. Soaking in absolute ethanol for about 3 min, placing on clean filter paper, drying with filter paper, placing in a dryer for more than 4h, and weighing.
The hanger erosion rate is calculated as v in mm/a, as follows:
v=8760×（m-m0）×10/spt
Wherein:
the m-hanging piece mass loss value is expressed as g;
m 0 -the value of the mass loss average value of the hanging piece pickling blank test, wherein the unit is g;
The surface area value of the s-hanging piece is cm 2;
The density value of the p-hanging piece is expressed in g/cm 3
T-time value of experiment, the unit is h;
8760-hours corresponding to one year in h/a;
10-a number of millimeters equivalent to 1 cm in mm/cm.
The inhibition rate of the hanging piece is calculated by eta, the numerical value is expressed as percent, and the hanging piece is calculated according to the following formula:
η=(v0-v1)/v0 ×100
Wherein:
v 0 -the number of corrosion rates in mm/a for the hanging blank test;
v 1 -the value of the corrosion rate of the coupon in mm/a.
TABLE 3 calcium carbonate scale inhibition and 20# carbon steel corrosion inhibition for examples 1, 2,3 and comparative example versus circulating water
。
As shown by the results in Table 3, under the condition that the dosing concentration is 20 mg/L in the examples 1,2, 3 and comparative example, the scale inhibitor of the application in the example 2 has the scale inhibition efficiency of 98.32% on circulating water and the corrosion inhibition rate of 97.95% on carbon steel, and the scale inhibition rate of the examples is obviously better than that of the comparative example, so that the application prospect of the technical scheme of the application is very wide.
Circulating water actual condition water experiment case 1: some coking group circulating water example
The scale inhibitor prepared in experimental examples 1,2 and 3 and comparative example is tested by taking circulating water of a certain coking group in actual operation, and the dosing concentration is 20 mg/L, and the scale inhibition rate and corrosion inhibition rate of the scale inhibitor are tested. Wherein, the pH=8.46, turbidity 33.77 NTU, total hardness 483.94 mg/L, alkalinity 277.00 mg/L, calcium hardness 300.24 mg/L, cl - 1348.82 mg/L,Fe2+ 0.95 mg/L, total phosphorus 32.73 mg/L, COD 138.16 mg/L and ammonia nitrogen 1.07 mg/L of the circulating water.
Static scale inhibition was performed according to the scale inhibition test method for calcium carbonate in the above-described test example 1.
Corrosion inhibition experiments of the water treatment agent were carried out according to the hanging piece corrosion inhibition experiment method in the experiment example 3.
TABLE 4 Scale inhibition and corrosion inhibition of examples 1, 2, 3 and comparative examples on certain coking group circulating waters
。
As shown in the results of Table 4, the scale inhibitor of the invention of example 2 has a scale inhibition efficiency of 96.57% for circulating water in actual operation of a coking group, a corrosion inhibition rate of 97.39% for carbon steel, and the scale inhibition efficiency and corrosion inhibition efficiency of the examples are significantly better than those of the comparative examples.
Circulating water actual condition water experiment case 2: some group circulating water example
The scale inhibitor prepared in experimental examples 1,2 and 3 and comparative example is tested by taking circulating water of a certain group for actual operation, and the dosing concentration is 20 mg/L, and the scale inhibition rate and corrosion inhibition rate of the scale inhibitor are tested. Wherein, the pH=8.15, turbidity 5.23 NTU, total hardness 231.18 mg/L, alkalinity 99.08 mg/L, calcium hardness 185.15 mg/L, cl - 96.42 mg/L,Fe2+ 0.08.08 mg/L, total phosphorus 5.93 mg/L, COD 48.81 mg/L and ammonia nitrogen 34.34 mg/L of the circulating water.
Static scale inhibition was performed according to the scale inhibition test method for calcium carbonate in the above-described test example 1.
Corrosion inhibition experiments of the water treatment agent were carried out according to the hanging piece corrosion inhibition experiment method in the experiment example 3.
TABLE 5 Scale inhibition and corrosion inhibition for circulating water of chemical groups of examples 1, 2, 3 and comparative examples
。
As shown in the results of Table 5, the scale inhibitor of the invention of the example 2 has a scale inhibition efficiency of 99.65% for circulating water in actual operation of a chemical group, a corrosion inhibition rate of 96.91% for carbon steel, and the scale inhibition efficiency and corrosion inhibition efficiency of the example are significantly better than those of the comparative example.
Finally, it is pointed out that the above examples show and describe the basic principle of the invention, the characteristics of the product and the advantages of the method according to the invention. The present invention is not limited to the above embodiments, and various changes and modifications can be made without departing from the scope of the invention, and the invention is intended to be included in the scope of protection.
Claims (5)
1. The preparation method of the compound phosphorus-free environment-friendly scale inhibitor is characterized by comprising the following specific preparation steps: wherein the weight parts of the components are as follows,
(1) Preparation of hydroxyethyl starch derivatives containing propenyl groups:
Adding 10-20 parts of hydroxyethyl starch into 50-200 parts of solvent, stirring for 10-30 minutes at 10-40 ℃, then adding 4-7 parts of acrylic acid and 11-19 parts of condensing agent, maintaining the temperature of the mixed solution at 10-40 ℃, adding 0.1-0.5 part of 4-dimethylaminopyridine, and continuously stirring for 4-10 hours; pouring the reaction solution into 500-2000 parts of methanol, stirring for 20-40 minutes, filtering, washing the solid with 50-80 parts of methanol for three times respectively, and drying to obtain hydroxyethyl starch derivative containing propenyl;
(2) Preparation of modified starch polymer:
Adding the hydroxyethyl starch derivative containing the propenyl, 18-26 parts of acrylic acid and 5-8 parts of maleic anhydride prepared in the step (1) into 100-150 parts of deionized water, introducing argon for 10-30 minutes under the stirring condition, then adding 0.3-0.7 part of potassium peroxodisulfate, heating to 70-90 ℃, and stirring for 2-4 hours; cooling to 10-30 ℃, pouring the reaction liquid into 800-2000 parts of methanol, filtering, washing the solid with 100-150 parts of methanol for three times respectively, and drying to obtain a modified starch polymer;
(3) Preparation of a polycarboxylic sulfonic acid copolymer:
Adding 16-19 parts of 2-acrylamide-2-methylpropanesulfonic acid, 10-14 parts of acrylic acid and 12-16 parts of maleic anhydride into 130-180 parts of deionized water, introducing argon for 10-30 minutes under the stirring condition, adding 0.5-0.9 part of potassium persulfate, heating to 70-90 ℃, and stirring for 2-4 hours; cooling to 10-30 ℃, pouring the reaction solution into 1200-2200 parts of methanol, filtering, washing the solid with 150-200 parts of methanol for three times respectively, and drying to obtain the polycarboxylic sulfonic acid copolymer;
(4) Preparation of a compound environment-friendly phosphorus-free scale inhibitor containing hydroxyethyl starch and a polycarboxylic sulfonic acid copolymer:
And (3) directly blending the modified starch polymer prepared in the step (2) and the polycarboxylic acid copolymer prepared in the step (3) to obtain the compound phosphorus-free scale inhibitor containing hydroxyethyl starch and the polycarboxylic acid copolymer.
2. The method for preparing the compound phosphorus-free environment-friendly scale inhibitor, which is characterized by comprising the following steps: in the step (1), the solvent is dimethyl sulfoxide or N, N-dimethylformamide.
3. The method for preparing the compound phosphorus-free environment-friendly scale inhibitor, which is characterized by comprising the following steps: in the step (1), the condensing agent is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride or dicyclohexylcarbodiimide.
4. The method for preparing the compound phosphorus-free environment-friendly scale inhibitor, which is characterized by comprising the following steps: in the step (2), the potassium persulfate is added in two batches, wherein the first batch is added with 0.1-0.4 part, and the second batch is added with 0.2-0.3 part, and the intervals between the batches are at least 30 minutes.
5. The method for preparing the compound phosphorus-free environment-friendly scale inhibitor, which is characterized by comprising the following steps: in the step (3), the potassium persulfate is added in three batches, wherein the first batch is added with 0.2-0.3 part, the second batch is added with 0.2-0.3 part, and the third batch is added with 0.1-0.3 part, and the intervals between the batches are at least 30 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410882144.8A CN118420136B (en) | 2024-07-03 | 2024-07-03 | Preparation method of compound phosphorus-free environment-friendly scale inhibitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410882144.8A CN118420136B (en) | 2024-07-03 | 2024-07-03 | Preparation method of compound phosphorus-free environment-friendly scale inhibitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN118420136A true CN118420136A (en) | 2024-08-02 |
| CN118420136B CN118420136B (en) | 2024-08-27 |
Family
ID=92335581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410882144.8A Active CN118420136B (en) | 2024-07-03 | 2024-07-03 | Preparation method of compound phosphorus-free environment-friendly scale inhibitor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118420136B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| LU62292A1 (en) * | 1970-09-28 | 1971-05-18 | ||
| US5087376A (en) * | 1990-10-15 | 1992-02-11 | Calgon Corporation | Multifunctional scale inhibitors |
| JP2004293028A (en) * | 2003-03-13 | 2004-10-21 | Hakuto Co Ltd | Scale inhibitor and scale inhibitory method for barium sulfate in water system |
| CN107902770A (en) * | 2017-10-24 | 2018-04-13 | 陈木玲 | A kind of non-phosphorus scale and corrosion inhibitor and its preparation process |
| US20230322977A1 (en) * | 2022-04-11 | 2023-10-12 | Independence Oilfield Chemicals Llc | Aqueous formulations |
-
2024
- 2024-07-03 CN CN202410882144.8A patent/CN118420136B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| LU62292A1 (en) * | 1970-09-28 | 1971-05-18 | ||
| US5087376A (en) * | 1990-10-15 | 1992-02-11 | Calgon Corporation | Multifunctional scale inhibitors |
| JP2004293028A (en) * | 2003-03-13 | 2004-10-21 | Hakuto Co Ltd | Scale inhibitor and scale inhibitory method for barium sulfate in water system |
| CN107902770A (en) * | 2017-10-24 | 2018-04-13 | 陈木玲 | A kind of non-phosphorus scale and corrosion inhibitor and its preparation process |
| US20230322977A1 (en) * | 2022-04-11 | 2023-10-12 | Independence Oilfield Chemicals Llc | Aqueous formulations |
Non-Patent Citations (3)
| Title |
|---|
| WOO, BH ET AL.: "Preparation and characterization of a composite PLGA and poly(acryloyl hydroxyethyl starch) microsphere system for protein delivery", 《PHARMACEUTICAL RESEARCH》, vol. 16, no. 11, 31 December 2001 (2001-12-31), pages 1600 - 1606 * |
| 李宇请: "聚羧酸型阻垢分散剂的研制", 《江苏化工》, no. 4, 31 December 1990 (1990-12-31), pages 14 - 16 * |
| 王超等: "酰胺类无磷缓蚀阻垢剂对稀有鮈鲫的急性毒性研究", 《广东化工》, vol. 42, no. 12, 30 June 2015 (2015-06-30), pages 49 - 50 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN118420136B (en) | 2024-08-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104891684B (en) | Without phosphorus composite slow-corrosion scale resistor for bitter recirculated water and preparation method thereof | |
| CN109019884B (en) | Composite corrosion and scale inhibition dispersant and application thereof | |
| CN107522301B (en) | Use of corrosion inhibitors or corrosion inhibitor compositions for inhibiting water corrosion | |
| CN118420136B (en) | Preparation method of compound phosphorus-free environment-friendly scale inhibitor | |
| CN114162980B (en) | Reverse osmosis membrane scale inhibitor and preparation method thereof | |
| CN107304077B (en) | Corrosion-inhibition, scale-inhibition and sterilization composition and application thereof | |
| CN117327232B (en) | Non-phosphorus non-nitrogen type green water treatment agent and preparation method and application thereof | |
| CN113789227B (en) | Calcium sulfate scale cleaning agent suitable for aluminum alloy heat transfer tube and preparation method and application thereof | |
| CN108017763B (en) | Corrosion and scale inhibition combined medicament and preparation method thereof | |
| CN116462802B (en) | Environment-friendly scale inhibition dispersing agent and preparation method thereof | |
| CN111003823A (en) | Novel efficient non-phosphorus scale and corrosion inhibitor and preparation method thereof | |
| US20210198405A1 (en) | Carboxymethyl inulin graft polymer scale and corrosion inhibitor and preparation method thereof | |
| CN111592121A (en) | Acrylic copolymer, novel environment-friendly corrosion and scale inhibitor composition and application | |
| CN116874095A (en) | Phosphorus-free mixture for boiler shutdown protection and daily operation dosing treatment | |
| CN116282599A (en) | Organic corrosion and scale inhibition water treatment agent | |
| CN113651436B (en) | Non-phosphorus non-nitrogen scale inhibition and dispersion agent and preparation method and application thereof | |
| CN114291908A (en) | Salt-making scale inhibitor and preparation method and application thereof | |
| CN115340163A (en) | Paint mist coagulant and preparation method thereof | |
| CN113428992A (en) | Environment-friendly low-corrosion scale inhibitor suitable for high-temperature geothermal and preparation method thereof | |
| CN116282596B (en) | Scale inhibition dispersing agent and preparation method thereof | |
| CN107572669B (en) | Preparation method of water treatment purifying agent | |
| CN113967411B (en) | Phosphate-free reverse osmosis membrane scale inhibitor for scale inhibition of calcium ions, magnesium ions, copper ions and barium ions and preparation method thereof | |
| CN117402290A (en) | Four-arm star polymer containing polyoxyethylene structure, and preparation method, composition and application thereof | |
| CN112176349B (en) | Non-phosphorus corrosion inhibitor composition, non-phosphorus corrosion inhibitor and application thereof | |
| CN114426341A (en) | Composition with pre-film cleaning function and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |