CN106348466B - A kind of water treatment agent and preparation method thereof - Google Patents
A kind of water treatment agent and preparation method thereof Download PDFInfo
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- CN106348466B CN106348466B CN201610858650.9A CN201610858650A CN106348466B CN 106348466 B CN106348466 B CN 106348466B CN 201610858650 A CN201610858650 A CN 201610858650A CN 106348466 B CN106348466 B CN 106348466B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 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 claims abstract description 50
- 239000011734 sodium Substances 0.000 claims abstract description 50
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920000141 poly(maleic anhydride) Polymers 0.000 claims abstract description 13
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 13
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 13
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims abstract description 12
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 9
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 239000011265 semifinished product Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims 2
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 19
- 230000007797 corrosion Effects 0.000 abstract description 19
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 abstract description 13
- 239000004021 humic acid Substances 0.000 abstract description 13
- 230000005764 inhibitory process Effects 0.000 abstract description 12
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 229960001484 edetic acid Drugs 0.000 abstract description 6
- 230000002401 inhibitory effect Effects 0.000 abstract description 6
- 241000894006 Bacteria Species 0.000 abstract description 5
- 241000195493 Cryptophyta Species 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004061 bleaching Methods 0.000 abstract description 2
- 230000009920 chelation Effects 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 238000004448 titration Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 229910001424 calcium ion Inorganic materials 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- DEGAKNSWVGKMLS-UHFFFAOYSA-N calcein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(CN(CC(O)=O)CC(O)=O)=C(O)C=C1OC1=C2C=C(CN(CC(O)=O)CC(=O)O)C(O)=C1 DEGAKNSWVGKMLS-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 229960002378 oftasceine Drugs 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical group C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- FENRSEGZMITUEF-ATTCVCFYSA-E [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].OP(=O)([O-])O[C@@H]1[C@@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H]1OP(=O)([O-])[O-] Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].OP(=O)([O-])O[C@@H]1[C@@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H]1OP(=O)([O-])[O-] FENRSEGZMITUEF-ATTCVCFYSA-E 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 238000013215 result calculation Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- 229940083982 sodium phytate Drugs 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000005791 algae growth Effects 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- 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
- C02F5/105—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 combined with inorganic substances
-
- 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
- C02F5/14—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 containing phosphorus
- C02F5/145—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 containing phosphorus combined with inorganic substances
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention belongs to chemical fields, it is related to water treatment agent, more particularly to a kind of water treatment agent and preparation method thereof, the water treatment agent includes following raw material: sodium humate, ethylenediamine tetra-acetic acid, calgon, zinc sulfate, sodium hypochlorite, 1-hydroxy ethylidene-1,1-diphosphonic acid, polymaleic anhydride and water.The preparation method of the water treatment agent is on the basis of humic acid sodium type, carry out grafting chelation reaction, inhibiting group is accessed, reach the corrosion inhibitive function of the medicament, compounding reaction filtering adsorption bleaching is carried out again, reaches the problem of solving the problems, such as humic acid sodium type water treatment agent seriously corroded and making recirculated water blackening, and humic acid sodium type water treatment agent is made to reach good scale inhibition, slow dirt, the effect for inhibiting bacterium algae to breed, without a large amount of drainings.
Description
Technical field
The invention belongs to chemical fields, are related to water treatment agent, and in particular to a kind of water treatment agent and preparation method thereof.
Background technique
Energy conservation and environmental protection are two issues that need special attentions of the world today, therefore, efficient, novel and green environment-friendly type
Product has become one of the emphasis direction of scientists from all over the world's research.Water is the most excellent carrier of industrial heat exchange.In order to save water
Cooling water is recycled in resource, enterprise.But industrial circulating water easy fouling during cycle heat exchange.Recirculated water knot
Heat transfer rate is low caused by dirt, equipment is corroded and microbial growth is to perplex three problems of enterprise.Solution is now
Phosphorous water treatment agent is added in recirculated water to achieve the purpose that alleviate corrosion and scale inhibition, then solves micro- life by the way that fungicide is added
Object growth problems.But create the problem that 1, the type inorganic agent is phosphorous again in such treatment process, cause circulation Shuifu County
Nutrient laden, bacterium algae are bred more serious；2, the type medicament can only in divergent cyclical water at dirt matter, scale inhibition performance is on 85% left side
The right side, cycles of concentration are more than that 3 times or more pharmacy effects substantially reduce, it is necessary to which a large amount of draining control cycles of concentration are at 3 times hereinafter, ability
Enough reach scale inhibition effect, results in water resource waste in this way；3, fungicide must be added individually, cause recirculated water largely useization
Chemical product, polluted-water increase cost and workload.
Sodium humate is high-molecular compound, has the multiple functions such as demineralized water, antiscale, anticorrosion and scale removal, and rotten
Sodium phytate is cheap, nontoxic, and chemical stability is good, can deposit use for a long time.Sodium humate is a kind of good scale remover, humic acid
The scale effect mechanism of sodium is not stablized calcium and magnesium ion in water not instead of merely, generates grain slag (not forming hard scale), passes through
Blowdown reaches scale inhibition effect, and at this moment calcium and magnesium ion concentration variation contains the grain slag amount that a part does not generate scale, and rotten
Sodium phytate can also be adsorbed on metal surface, prevent fouling.So sodium humate is industrial inevitable requirement as scale remover, still
The corrosion inhibition of sodium humate is less desirable.
Data of publication of application is on September 14th, 2005, and publication No. is the Chinese invention patent application of CN1666963A, is disclosed
A kind of scale preventing and removing agent for Treatment of Industrial Water, it by sodium humate 15-30%, sodium carbonate 65-75%, starch 2-10%,
Calgon 1.2-2% composition.
Authorized announcement date is on March 26th, 2014, and the Chinese invention patent of notification number CN103172183B discloses one kind
Water treatment corrosion inhibitors and water treatment agent containing corrosion inhibiter, including humic acid and corrosion inhibiter, the corrosion inhibiter is by sodium metasilicate, oleic acid
Sodium, neopelex and hexamethylenetetramine form, and the additional amount of each component is humic acid in every liter of water to be processed
Sodium 0.025g, sodium metasilicate 0.1-2g, enuatrol 0.02-2g, neopelex 0.1-2g, hexamethylenetetramine 0.05-
2g is 8.0-9.0 with sodium hydroxide tune pH value.
Two kinds of water treatment agents disclosed above solve recirculated water fouling, bacterium algae growth and drainage problem, but increase
The problem of equipment corrosion and recirculated water are turned into black.During popularization and use, enterprise is not easily accepted by.
So in order to solve the above technical problems, needing to improve water treatment agent in the prior art.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of water treatment agents, to solve water treatment agent pair in the prior art
The problem of corrosion of equipment and circulation are turned into black.Meanwhile the present invention also provides the preparation methods of above-mentioned water treatment agent.
In order to solve the above-mentioned technical problem, the technical solution of the present invention is as follows:
A kind of water treatment agent, including following raw material: sodium humate, ethylenediamine tetra-acetic acid, calgon, zinc sulfate, secondary
Sodium chlorate, 1-hydroxy ethylidene-1,1-diphosphonic acid, polymaleic anhydride and water.
The preparation method of above-mentioned water treatment agent the following steps are included:
S1, reaction kettle is added in sodium humate, is that water is added in 1:2~8 by the weight ratio of sodium humate and water, heating is stirred
It mixes, is completely dissolved sodium humate；Preferably, the weight ratio of the sodium humate and water is 1:2~5；It is further preferred that institute
The weight ratio for stating sodium humate and water is 1:3.
S2, by above-mentioned sodium humate solution keep 35~60 DEG C of temperature, under stirring conditions, by weight be added 1~
8% ethylenediamine tetra-acetic acid reacts 4~36h；Preferably, above-mentioned sodium humate solution is kept for 35~50 DEG C of temperature, stirred
Under conditions of, by weight the ethylenediamine tetra-acetic acid for being added 1~3%, react 4~30h；It is further preferred that by above-mentioned rotten plant
Acid sodium solution keep 40 DEG C of temperature, under stirring conditions, by weight be added 2% ethylenediamine tetra-acetic acid, reaction 6~for 24 hours.
S3, it is cooled to room temperature, by weight the zinc sulfate that 5~20% calgons and 1~10% are added, mixing is equal
It is even, 70~95 DEG C are heated to, 2~10h is reacted；Preferably, it is cooled to room temperature, by weight 8~15% calgons of addition
Zinc sulfate with 2~6%, is uniformly mixed, and is heated to 75~90 DEG C, reacts 2~6h；It is further preferred that being cooled to room temperature, press
The zinc sulfate of 10% calgon and 3% is added in weight ratio, is uniformly mixed, and is heated to 80 DEG C, reacts 4h.
S4, it is cooled to room temperature, filters, obtain filtrate, 8~20% are added into filtrate by the weight of step S3 acquired solution
Sodium hypochlorite decolourizes to get colourless semi-finished product；Preferably, 10 are added into filtrate by the weight of step S3 acquired solution~
18% sodium hypochlorite；It is further preferred that 15% sodium hypochlorite is added into filtrate by the weight of step S3 acquired solution.
S5,2~10% 1-hydroxy ethylidene-1,1-diphosphonic acid and 2~10% poly is added into semi-finished product by weight
Acid anhydride is uniformly mixed to get water treatment agent；Preferably, by weight the 1-hydroxy ethylidene-1,1-diphosphonic acid that 3~7% are added into semi-finished product
With 3~7% polymaleic anhydride；It is further preferred that by weight into semi-finished product be added 5% 1-hydroxy ethylidene-1,1-diphosphonic acid and
5% polymaleic anhydride.
By adopting the above technical scheme, due to carrying out grafting chelation reaction on the basis of humic acid sodium type water treatment agent, into
It has gone modification, has reached the corrosion inhibitive function of the medicament, then carried out compounding reaction filtering adsorption bleaching, reached and solve humic acid sodium type water
Treatment agent seriously corroded and the problem of making recirculated water blackening, make humic acid sodium type water treatment agent reach good scale inhibition, slow dirt,
The effect for inhibiting bacterium algae to breed, without a large amount of drainings.
The water treatment agent scale inhibition performance obtained by above-mentioned technical proposal reaches 96% or more, enhances than effect before improving
10%；Solve the problems, such as that existing water treatment agent keeps recirculated water colored and corrosion equipment.Rate of corrosion is down to 0.005g/m2A with
Under, it promotes recirculated water cycles of concentration to 10 times or more from 3 times or less, without a large amount of drainings, has saved water resource.List is not needed
Sterilization algae removal processing solely is carried out to recirculated water, medicament itself has the function of to inhibit bacterium algae, mitigates cycle water pollution.
Specific embodiment
The invention will be further described With reference to embodiment.It should be noted that for these realities
The explanation for applying mode is used to help understand the present invention, but and does not constitute a limitation of the invention.In addition, this hair disclosed below
Technical characteristic involved in bright each embodiment can be combined with each other as long as they do not conflict with each other.
A kind of water treatment agent, including following raw material: sodium humate, ethylenediamine tetra-acetic acid, calgon, zinc sulfate, secondary
Sodium chlorate, 1-hydroxy ethylidene-1,1-diphosphonic acid, polymaleic anhydride and water.
Embodiment 1
A kind of preparation method of water treatment agent, includes the following steps:
S1, reaction kettle is added in 10kg sodium humate, then 50kg water is added into reaction kettle, heating stirring makes humic acid
Sodium is completely dissolved；
S2, above-mentioned sodium humate solution is kept for 35 DEG C of temperature, under stirring conditions, 4.8kg ethylenediamine tetrem is added
Acid reacts 36h；
S3, it is cooled to room temperature, 3.24kg calgon and 6.48kg zinc sulfate is added, stirs evenly, is heated to 70 DEG C,
React 10h；
S4, it is cooled to room temperature, filters, obtain filtrate, 5.96kg sodium hypochlorite is added into filtrate, decoloration is to get colourless half
Finished product；
S5,1.61kg 1-hydroxy ethylidene-1,1-diphosphonic acid and 8.05kg polymaleic anhydride are added into semi-finished product, be uniformly mixed to get
Water treatment agent.
Embodiment 2
A kind of preparation method of water treatment agent, includes the following steps:
S1, reaction kettle is added in 10kg sodium humate, then 80kg water is added into reaction kettle, heating stirring makes humic acid
Sodium is completely dissolved；
S2, above-mentioned sodium humate solution is kept into temperature 60 C, under stirring conditions, 5.4kg ethylenediamine tetrem is added
Acid, reaction is for 24 hours；
S3, it is cooled to room temperature, 19.08kg calgon and 9.54kg zinc sulfate is added, be uniformly mixed, be heated to 95
DEG C, react 2h；
S4, it is cooled to room temperature, filters, obtain filtrate, 24.80kg sodium hypochlorite is added into filtrate, decoloration is to get colourless half
Finished product；
S5,14.88kg 1-hydroxy ethylidene-1,1-diphosphonic acid and 2.98kg polymaleic anhydride are added into semi-finished product, are uniformly mixed, i.e.,
Obtain water treatment agent.
Embodiment 3
A kind of preparation method of water treatment agent, includes the following steps:
S1, reaction kettle is added in 10kg sodium humate, then 30kg water is added into reaction kettle, heating stirring makes humic acid
Sodium is completely dissolved；
S2, above-mentioned sodium humate solution is kept for 40 DEG C of temperature, under stirring conditions, 0.8kg ethylenediamine tetrem is added
Acid reacts 6h；
S3, it is cooled to room temperature, 4.08kg calgon and 1.22kg zinc sulfate is added, be uniformly mixed, be heated to 80 DEG C,
React 4h；
S4, it is cooled to room temperature, filters, obtain filtrate, 6.92kg sodium hypochlorite is added into filtrate, decoloration is to get colourless half
Finished product；
S5,2.65kg 1-hydroxy ethylidene-1,1-diphosphonic acid and 2.65kg polymaleic anhydride are added into semi-finished product, be uniformly mixed to get
Water treatment agent.
Embodiment 4
A kind of preparation method of water treatment agent, includes the following steps:
S1, reaction kettle is added in 10kg sodium humate, then 30kg water is added into reaction kettle, heating stirring makes humic acid
Sodium is completely dissolved；
S2, above-mentioned sodium humate solution is kept for 65 DEG C of temperature, under stirring conditions, 0.4kg ethylenediamine tetrem is added
Acid reacts 12h；
S3, it is cooled to room temperature, 6.06kg calgon and 2.02kg zinc sulfate is added, be uniformly mixed, be heated to 90 DEG C,
React 8h；
S4, it is cooled to room temperature, filters, obtain filtrate, 4.85kg sodium hypochlorite is added into filtrate, decoloration is to get colourless half
Finished product；
S5,3.20kg 1-hydroxy ethylidene-1,1-diphosphonic acid and 4.27kg polymaleic anhydride are added into semi-finished product, be uniformly mixed to get
Water treatment agent.
Test example
Water treatment agent obtained by embodiment 1 to 4 and the (weight of the water treatment agent before improvement is added into circulation respectively
Amount proportion is 1-hydroxy ethylidene-1,1-diphosphonic acid: acrylamide: polymaleic anhydride=4:3:3), the additional amount of water treatment agent is 30ppm,
Circulation is run 2 months under conditions of 35 DEG C, calculates concentration rate, scale inhibition performance and rate of corrosion.
Used reagent in test:
Hydrochloric acid, potassium hydroxide, calcein, phenolphthalein, potassium chloride, EDTA, nitric acid, sodium hydroxide, silver nitrate and potassium chromate
It is that analysis is pure, the production of Solution on Chemical Reagents in Shanghai factory.Stainless steel test piece is produced by Jiangsu Gaoyou Electronic Instruments Plant.
1, EDTA titration measuring calcium ion content
1.1 reagents and instrument
1+1 hydrochloric acid solution, 20% potassium hydroxide solution, calcein phenolphthalein mixed indicator (calcein 0.2g is weighed,
Phenolphthalein 0.07g is placed in mortar, adds 20g potassium chloride, and finely ground mixing is stored in wide-mouth bottle), 0.01mol/LEDTA standard
Solution, 25mL buret, 5mL pipette.
1.2 analytical procedure
The water sample 50mL filtered through Medium speed filter paper is drawn, is moved into 250mL conical flask, 1+1 hydrochloric acid 3 is added to drip, is mixed, heating
Half a minute is boiled, 50 DEG C or less plus 5mL20% potassium hydroxide solution, then plus about 80mg calcein phenolphthalein mixing instruction are cooled to
Agent is titrated to the yellowish green decoloration of fluorescent with 0.01mol/L EDTA standard solution, occurs red being terminal.
1.3 Analysis result calculation
Calcium ion content X (mg/L, in terms of CaCO3) in water sample, is calculated as follows:
In formula: EDTA standard solution consumes volume, mL when V-titration；
M-EDTA concentration of standard solution, mol/L；
Vw-volume of water sample, mL；
100.08-calcium carbonate molal weights, g/mol.
2, precipitation titration measures chloride ion content
2.1 reagent
Nitric acid solution (1+300), sodium hydroxide (2g/L), silver nitrate standard titration solution (0.01mol/L), potassium chromate refers to
Show agent (50g/L), phenolphthalein indicator (10g/L ethanol solution).
2.2 analytical procedure
In water sampling 25ml to 250mL conical flask, 2 drop phenolphthalein indicators are added, with sodium hydroxide solution or nitric acid solution
The pH for adjusting water sample makes red just become colorless.
1.0mL potassium chromate indicator is added, in the case where continuous shake, best silver nitrate under the conditions of white background
Standard titration solution titration, until appearance is brick-red.Blank test is done simultaneously.
2.3 Analysis result calculation
Calcium ion content X (mg/L) in water sample, is calculated as follows:
In formula: V1Sample consumes the numerical value of silver nitrate standard titration solution, mL；
V0Blank test consumes the numerical value of the volume of silver nitrate standard titration solution, mL；
The numerical value of V- volume of sample, mL；
The exact value of c- silver nitrate standard titration solution concentration, mol/L；
The numerical value of the molal weight of M- oxygen, g/mol (35.45).
3, rate of corrosion measurement (lacing film is stainless steel test piece)
New lacing film is immersed in dehydrated alcohol and is cleaned twice with absorbent cotton, then moves into clean dehydrated alcohol and impregnates again
For a moment, it is placed on clean filter paper, cold wind drying is wrapped with filter paper, set in drier, is weighed after 24 hours stand-by；Lacing film is hung
Into circulation water station monitor heat exchanger, runs 2 months, fetch lacing film；It is reprocessed after observing and recording surface appearance, it is heavy to corrosion
The unconspicuous part of product, is wiped with rubber, it is made to expose metal true qualities, is then immersed in dehydrated alcohol and is cleaned two with absorbent cotton
Time, then immerse and impregnated in clean dehydrated alcohol a moment, taking-up is placed on clean filter paper, and cold wind drying is wrapped with filter paper, is placed in
It in drier, weighs after 24 hours, obtains weightlessness, calculate rate of corrosion.
W1- standard lacing film weight, g；
Lacing film weight after W2- corrosion, g；
S- lacing film area, m2；
T- hanging test time, a.
According to said determination institute value, scale inhibition performance and rate of corrosion are calculated:
1, table test measures cycles of concentration, scale inhibition performance and rate of corrosion
It can be seen that, by the chelating inhibiting group on sodium humate, solve recirculated water to equipment by the above test data
Etching problem；Concentration rate is higher, and scale inhibition effect is better.
Water treatment agent provided by the invention solves the problems, such as that medicament dyes recirculated water by decolorization；It enhances
Scale prevention ability has saved 30% water resource without a large amount of drainings.
Above the embodiments of the present invention are described in detail, but the present invention is not limited to described embodiments.It is right
For those skilled in the art, in the case where not departing from the principle of the invention and spirit, these embodiments are carried out more
Kind change, modification, replacement and modification, still fall in protection scope of the present invention.
Claims (3)
1. a kind of preparation method of water treatment agent, which comprises the steps of:
S1, reaction kettle is added in sodium humate, is that water is added in 1:2~8 by the weight ratio of sodium humate and water, heating stirring makes
Sodium humate is completely dissolved；
S2, sodium humate solution is kept for 35~60 DEG C of temperature, under stirring conditions, by weight the second two for being added 1~8%
Amine tetraacethyl reacts 4~36h；
S3, it is cooled to room temperature, by weight 5~20% calgon and 1~10% zinc sulfate is added, is uniformly mixed,
70~95 DEG C are heated to, 2~10h is reacted；
S4, it is cooled to room temperature, filters, obtain filtrate, 8~20% time is added into filtrate by the weight of acquired solution in step S3
Sodium chlorate decolourizes to get colourless semi-finished product；
S5,2~10% 1-hydroxy ethylidene-1,1-diphosphonic acid and 2~10% polymaleic anhydride is added into semi-finished product by weight, mixes
It closes uniformly to get water treatment agent.
2. the preparation method of water treatment agent according to claim 1, which comprises the steps of:
S1, reaction kettle is added in sodium humate, is that water is added in 1:2~5 by the weight ratio of sodium humate and water, heating stirring makes
Sodium humate is completely dissolved；
S2, sodium humate solution is kept for 35~50 DEG C of temperature, under stirring conditions, by weight the second two for being added 1~3%
Amine tetraacethyl reacts 4~30h；
S3, it is cooled to room temperature, by weight 8~15% calgon and 2~6% zinc sulfate is added, is uniformly mixed,
75~90 DEG C are heated to, 2~6h is reacted；
S4, it is cooled to room temperature, filters, obtain filtrate, 10~18% are added into filtrate by the weight of acquired solution in step S3
Sodium hypochlorite decolourizes to get colourless semi-finished product；
S5,3~7% 1-hydroxy ethylidene-1,1-diphosphonic acid and 3~7% polymaleic anhydride, mixing is added into semi-finished product by weight
Uniformly to get water treatment agent.
3. the preparation method of water treatment agent according to claim 2, which comprises the steps of:
S1, reaction kettle is added in solid sodium humate, is that water is added in 1:3 by the weight ratio of sodium humate and water, heating stirring makes
Sodium humate is completely dissolved；
S2, sodium humate solution is kept for 40 DEG C of temperature, under stirring conditions, by weight the ethylenediamine tetrem for being added 2%
Acid, reaction 6~for 24 hours；
S3, it is cooled to room temperature, by weight 10% calgon and 3% zinc sulfate is added, is uniformly mixed, is heated to 80
DEG C, react 4h；
S4, it is cooled to room temperature, filters, obtain filtrate, 15% secondary chlorine is added into filtrate by the weight of acquired solution in step S3
Sour sodium decolourizes to get colourless semi-finished product；
S5,5% 1-hydroxy ethylidene-1,1-diphosphonic acid and 5% polymaleic anhydride is added into semi-finished product by weight, is uniformly mixed, i.e.,
Obtain water treatment agent.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1068802A (en) * | 1991-07-13 | 1993-02-10 | 牡丹江市洗涤原料厂 | Multifunctional water treating agent contg. organic phosphine |
| CN101125715A (en) * | 2007-08-16 | 2008-02-20 | 樊桂修 | Composite corrosion-retarding antisludging agent for treating high-concentration multiple circulating water |
| AU2008202311A1 (en) * | 2008-05-22 | 2009-12-10 | Al-Samadi, Riad Dr | High Water Recovery Single Stage Membrane Process |
| CN102276069A (en) * | 2011-05-06 | 2011-12-14 | 河北科技大学 | Reinjection water treatment agent for oil well |
| CN103739096A (en) * | 2014-01-26 | 2014-04-23 | 刘晓萍 | Corrosion and scale inhibitor for boiler |
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- 2016-09-28 CN CN201610858650.9A patent/CN106348466B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1068802A (en) * | 1991-07-13 | 1993-02-10 | 牡丹江市洗涤原料厂 | Multifunctional water treating agent contg. organic phosphine |
| CN101125715A (en) * | 2007-08-16 | 2008-02-20 | 樊桂修 | Composite corrosion-retarding antisludging agent for treating high-concentration multiple circulating water |
| AU2008202311A1 (en) * | 2008-05-22 | 2009-12-10 | Al-Samadi, Riad Dr | High Water Recovery Single Stage Membrane Process |
| CN102276069A (en) * | 2011-05-06 | 2011-12-14 | 河北科技大学 | Reinjection water treatment agent for oil well |
| CN103739096A (en) * | 2014-01-26 | 2014-04-23 | 刘晓萍 | Corrosion and scale inhibitor for boiler |
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