CN102976512B - Chemical processing method of coal chemical industry recycled circulating cooling water - Google Patents
Chemical processing method of coal chemical industry recycled circulating cooling water Download PDFInfo
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Abstract
The invention provides a chemical processing method of coal chemical industry recycled circulating cooling water. An agentia is composed of composite scale and corrosion inhibitor which is composed of 9-11 parts of polyepoxysuccinic acid, 18-22 parts of 2-phosphonobutane-1,2,4-tricarboxylic acid, 19-21 parts of methylene phosphonic acid, 25-35 parts of dirt dispersion agent, 1-3 parts of benzotriazole, and 9-18 parts of deionized water. First, adding polyepoxysuccinic acid into the 2-phosphonobutane-1,2,4-tricarboxylic acid, placing the polyepoxysuccinic acid and the 2-phosphonobutane-1,2,4-tricarboxylic acid in a container and evenly mixing, sequentially adding the methylene phosphonic acid, the dirt dispersion agent and the deionized water into the container, then stirring for 25-35 minutes, keeping the temperature at 20-35 DEG C, then adding the benzotriazole, continuously stirring for 30-60 minutes and keeping the temperature at 20-35 DEG C, and then, the composite scale and corrosion inhibitor is obtained. Dosage of the composite scale and corrosion inhibitor is 10mg/L, based on middle warmer strengthening water, total phosphorus of the circulating water is controlled to be 4-7mg/L, and a concentration ratio is controlled to be 5.0-6.0 times. The method further comprises sterilization and algae removing process and optimization of the circulating water.
Description
Technical field
Water is back to the treatment technology of recirculated cooling water in the present invention relates to, and water is back to the chemical treatment method of recirculated cooling water in the especially suitable coal chemical industrial waste water system.
Background technology
The Coal Chemical Industry water consumption is big, and the sewage characteristics of its discharging are: the waste water water yield is big, the water quality complexity, and the suspension content height, biodegradability can be poor, and toxicity is big.Waste water is back to recirculating cooling water system after advanced treatment, the potential hazard of system's maximum is that flow process is longer in the coal chemical industrial waste water advanced treatment process, and it is more influenced by uncontrollable factor, in causing during the water reuse variation water quality frequent.When harmful ion content is higher in the central water, along with constantly concentrating of recirculated water, these harmful ion content will be multiplied, and the potentially dangerous of system's corrosion and fouling increases.Middle water is that sewage carries out reuse again after biochemical treatment, and this just makes inevitably and contains a large amount of microorganisms in the water, and itself contains rich nutrient substances in addition, and therefore middle water is the ecotopia of microbial reproduction.After entering circulating water system, middle water also will inevitably bring the microorganism raised growth.Microorganism problem is another big potentially dangerous of circulating water system after the middle water reuse.
Message retrieval discloses: 1. the patent of Chinese patent ZL 03139046.3 " municipal middle water is as the deep treatment method of industrial circulating cooling water " discloses municipal middle water as the deep treatment method of industrial circulating cooling water moisturizing, the technology that special emphasis is handled at middle water depth.2. the coal chemical industrial waste water regeneration discussion of Zhang Huaibin, Liu Xiaoxi is inquired into the feasibility that coal gasification waste water is back to recirculating cooling water system, thinks and selects the materilization freatment method rate of exchange to meet the actual state of Harbin Coal Chemical Industry; But research concentrates on the research of the advanced treatment unit of waste water, does not have middle water as the chemical treatment method of recirculated cooling water moisturizing.3. people such as the Bi Yan of Inner Mongol Electric Power Research Institute roc is by corrosion inhibition test, scale-inhibiting properties test, floc test, and novel anti-incrustation corrosion inhibitor, the flocculation agent effect of water cycle water water quality in being applicable to of independent research and different steel are estimated; Result: drop into the JD-802 biological flocculant and make up water is carried out pre-treatment and added the JDZ-211 anti-incrustation corrosion inhibitor recirculated water is carried out stabilizing treatment, concentration rate is reached more than 4.0, can satisfy the engineering design requirement with this project and pertinent literature comparative analysis, both treatment process differences.
Chemical treatment method of the present invention comprises that scale inhibitor is handled, sterilization algae removal is handled, the recirculated water optimization process.Wherein, anti-incrustation corrosion inhibitor is by poly-epoxy succinic acid, 2-phosphonic acids butane-1,2,4-tricarboxylic acid, two 1,6 hexylidene triamine pentamethylene phosphonic acids, self-control dirt dispersion agent, benzotriazole, and deionized water is formed, and obtains through preparation process.The treatment process that microbiological manipulation adopts oxidizing bactericide, non-oxidizable sterilant, biological dispersion agent to combine.Full-automatic on-line control system is adopted in recirculated water optimization, guarantees security of system steady running, and improves the concentration rate of recirculated cooling water, reduces the amount of taking of fresh water, reduces discharged waste water, reaches the purpose of energy-saving and emission-reduction.Checking after testing, circulating water quality reaches the standard of GB 50050-2007 " Code for design of industrial recirculating cooling water treatment ".
Summary of the invention
The objective of the invention is to: the chemical treatment method that is provided for recirculated cooling water, by selecting of anti-incrustation corrosion inhibitor batching and synthesizing of dirt dispersion agent, make anti-incrustation corrosion inhibitor synergy, produce strong synergistic effect, guarantee the safe and stable operation of recirculating cooling water system, realize the target of energy-saving and water-saving.
The object of the present invention is achieved like this: a kind of chemical treatment method of Coal Chemical Industry reuse recirculated cooling water,
Step 1 medicament is prepared with parts by weight:
The preparation of composite scale-inhibiting corrosion inhibitor: by poly-epoxy succinic acid 9-11 part, 2-phosphonic acids butane-1,2,4-tricarboxylic acid 18-22 part, two 1,6 hexylidene triamine pentamethylene phosphonic acids 19-21 part, dirt dispersion agent 25-35 part, benzotriazole 1-3 part, deionized water 9-28 part is formed; Earlier poly-epoxy succinic acid is added 2-phosphonic acids butane-1,2, in the 4-tricarboxylic acid, place in the container, mix, add two 1,6 hexylidene triamine pentamethylene phosphonic acids, dirt dispersion agent, deionized water successively, stirred 25-35 minute, maintain the temperature at 20-35 ℃, add benzotriazole then, continue to stir 30-60 minute, maintain the temperature at 20-35 ℃, namely get composite scale-inhibiting corrosion inhibitor;
The wherein preparation of dirt dispersion agent: by maleic anhydride 480-510 part, sodium dihydrogen phosphate 200-230 part, initiator 100-120 part, deionized water 290-310 part, vinylformic acid 178-185 part are formed; Preparation:, open to stir in deionized water, the maleic anhydride sucting reaction still with pump, all dissolve to solid; Vinylformic acid, sodium dihydrogen phosphate, initiator are splashed in the reactor successively, dripped time 2.8-3.0 hour, temperature is at 60-70 ℃; Dropwise, temperature is controlled at 68-72 ℃, continues to stir 3-4 hour, is cooled to room temperature, gets the liquid of transparent thickness dirt dispersion agent, and its dirt dispersion agent solid content is 30-50%;
Wherein SODIUM PHOSPHATE, MONOBASIC is dissolved in 155 parts of deionized waters by 45 parts of sodium dihydric hypophosphites and makes;
Wherein initiator is dissolved in 100 parts of deionized waters by 10-15 part Potassium Persulphate and makes;
Step 2 sterilizing and algae-removing is handled:
1) adds sterilant at water collecting basin torrent place, 1-2 time weekly; To possess water meter, add 20-30mg/L at every turn;
2) add the modified quaternary ammonium salt series bactericidal agent at water collecting basin torrent place, every 1-2 week adds 1 time; To possess water meter, add 80-100mg/L at every turn;
3) add nonionic surface active agent at water collecting basin torrent place, add weekly 1 time; To possess water meter, add 15-30mg/L at every turn;
The optimization of step 3 recirculated water: the full-automatic total phosphorus monitoring of SYZL ∑ sigma dosing is adopted in recirculated water optimization, and the dosage 10mg/L of composite scale-inhibiting corrosion inhibitor is benchmark with bowl spares water, and control recirculated water total phosphorus is at 4-7mg/L, and concentration rate is controlled at 6.0 times; Recirculated water carries out the side filter to be handled, and is provided with the QYC-120 monitoring heat exchanger of Qingdao Hai Nuo.
Described method, the sterilant of selecting for use are bromine Chlorodimethyl glycolylurea or Surchlor GR 60 or TCCA (Trichloroisocyanuric acid).
Know-why of the present invention: the poly-epoxy succinic acid that composite scale-inhibiting corrosion inhibitor is selected for use is a kind of without phosphorus non-N structure that has, and biodegradable environmentally friendly water conditioner, poly-epoxy succinic acid has very strong alkali-resistivity, have the scale inhibitor double effects concurrently, in polymer molecule, inserted Sauerstoffatom and make its scale-inhibiting properties be better than organic phospho acid base polymer Scale inhibitors commonly used greatly.And poly-epoxy succinic acid and 2-phosphonic acids butane-1,2,4-tricarboxylic acid, two 1,6 hexylidene triamine pentamethylene phosphonic acids have good synergistic function, therefore with these several composite uses, not only scale inhibition effect is good, has also reduced the content of phosphorus in the medicament relatively, thereby has satisfied the environmental requirement of low-phosphorous discharging.Homemade dirt dispersion agent, to calcium carbonate, calcium sulfate particularly calcium phosphate scale formation and deposit good inhibition effect, ferric oxide, mud, clay and grease also there is good dispersing property, water water quality in being specially adapted to, strong shock resistance is good with organic phosphonate compatibleness and synergetic property.The treatment process of taking oxidizing bactericide, non-oxidizable sterilant, biological dispersion agent to combine can eliminate the resistance that bacterium produces certain biocide, and water microorganism is grown serious problem in controlling fully; With the control of water quality concentration rate at 5.0-6.0 doubly, can prevent that dirt from depositing at heat exchanger surface simultaneously; The control main points of the inventive method are simple, the level of automation height, and the energy-saving and cost-reducing exemplary role that provides for enterprise shows technical progress.
Embodiment
The present invention is described further in conjunction with the embodiments.
This chemical treatment method comprises composite scale-inhibiting corrosion inhibitor preparation and sterilization algae removal processing and recirculated water optimization etc.
Embodiment 1
The preparation of composite scale-inhibiting corrosion inhibitor, raw material is prepared with parts by weight: by 9 parts of poly-epoxy succinic acids, 2-phosphonic acids butane-1,2, and 18 parts of 4-tricarboxylic acid, two 1,6 19 parts of hexylidene triamine pentamethylene phosphonic acids, 25 parts of dirt dispersion agents, 1 part of benzotriazole, 9 parts of compositions of deionized water; Preparation: earlier poly-epoxy succinic acid is added 2-phosphonic acids butane-1, in 2, the 4-tricarboxylic acid, place container to mix, add two 1 successively, 6 hexylidene triamine pentamethylene phosphonic acids, dirt dispersion agent, deionized water stirred 35 minutes, maintained the temperature at 35 ℃, add benzotriazole then, continue to stir 60 minutes, maintain the temperature at 35 ℃, namely get composite scale-inhibiting corrosion inhibitor;
The wherein preparation of dirt dispersion agent: 300 parts of deionized waters and 490 parts of maleic anhydrides are successively by in the pump sucting reaction still, open and stir, all dissolve to maleic anhydride, with 180 parts of vinylformic acid, 220 parts of sodium dihydric hypophosphite solution, initiator splashes in the reactor, keep rate of addition stable, whole dropping process control is in 3 hours, temperature of reaction kettle control after all dropwising, is opened 70 ℃ of reactor cooling system and heating system control temperature below 70 ℃, stirred 3.5 hours, after be cooled to room temperature, obtaining transparent thick liquid is dirt dispersion agent, its dirt dispersion agent solid content is 50%;
Wherein sodium dihydrogen phosphate preparation: get 45 parts of sodium dihydric hypophosphites and be dissolved in 155 parts of deionized waters and make; The preparation of initiator: get 12 parts of Potassium Persulphates and be dissolved in 100 parts of deionized waters and make.
Embodiment 2
Medicament is prepared with parts by weight:
The preparation of composite scale-inhibiting corrosion inhibitor: by 11 parts of poly-epoxy succinic acids, 2-phosphonic acids butane-1,2,22 parts of 4-tricarboxylic acid, two 1,6 21 parts of hexylidene triamine pentamethylene phosphonic acids, 35 parts of dirt dispersion agents, 3 parts of benzotriazoles, 28 parts of compositions of deionized water; Earlier poly-epoxy succinic acid is added 2-phosphonic acids butane-1,2, in the 4-tricarboxylic acid, place in the container, mix, add two 1,6 hexylidene triamine pentamethylene phosphonic acids, dirt dispersion agent, deionized water successively, stirred 35 minutes, maintain the temperature at 35 ℃, add benzotriazole then, continue to stir 60 minutes, maintain the temperature at 35 ℃, namely get composite scale-inhibiting corrosion inhibitor;
The wherein preparation of dirt dispersion agent: pass through 290 kilograms of deionized waters and 500 kilograms of maleic anhydrides in the pump sucting reaction still successively, open and stir, being stirred to maleic anhydride at normal temperatures all dissolves, with 183 kilograms of vinylformic acid, 210 kilograms of sodium dihydric hypophosphite solution, 115 kilograms of initiators splash in the reactor, keep rate of addition stable, whole dropping process control was at 3 hours, temperature of reaction kettle control is at 70 ℃, and after all dropwising, the control temperature of reaction kettle is 68 ℃, stirred 4 hours, after be cooled to room temperature, obtaining transparent thick liquid is dirt dispersion agent, its dirt dispersion agent solid content is 30%;
Wherein sodium dihydrogen phosphate preparation: get 45 kilograms of sodium dihydric hypophosphites and be dissolved in 155 kilograms of deionized waters and make; Initiator preparation: get 12 kilograms of Potassium Persulphates and be dissolved in the double centner deionized water and make.
Embodiment 3
The checking of composite scale-inhibiting corrosion inhibitor test-results:
The water treatment object is the waste water of certain coal Methanol Plant processed, and the prescription of the processing of design and water quality control see Table 1, see Table 2.
Table 1 composite scale-inhibiting corrosion inhibitor prescription and code name
Water water quality control index in the table 2
Get above-mentioned water sample, test method is according to HG/T 2160-2008 " water coolant dynamic analog test method ", and experimental result is as follows:
Table 3 experiment show
Known to last table: this, composite slow-corrosion scale resistor water in Coal Chemical Industry system is back in the recirculated cooling water, and Controlling System fouling and corrosive effect are fine, and erosion rate is far controlled in GB 50050-2007 set quota scope.
Present method is used for the recirculating cooling water system of pilot scale coal Methanol Plant processed, and moisturizing is the middle water of coal chemical industrial waste water system, and composite scale-inhibiting corrosion inhibitor adopts embodiment 4 prescription B dosages to be about 12mg/L; Select bromine Chlorodimethyl glycolylurea for use by oxidizing bactericide, add weekly 2 times, add 20mg/L at every turn; Non-oxidizable sterilant is the modified quaternary ammonium salt series bactericidal agent, adds weekly 1 time, adds 80mg/L at every turn; Biological dispersion agent is nonionic surface active agent, adds weekly 1 time, each 15mg/L; Three kinds of medicament alternate intervals add, and move half a year, have effectively controlled fouling and corrosion condition, and on-the-spot service condition is good.
The full-automatic total phosphorus on-line monitoring of SYZL ∑ sigma medicine system, control recirculated water total phosphorus 4 or 7mg/L, automatic water supplement and blowdown are adopted in present method circulating water treatment; Oxidizing bactericide, non-oxidizable sterilant, biological dispersion agent adopt the artificial dosing of impact type, at water collecting basin torrent place.Calculate the dosing amount to possess the water yield; Recirculated water adopts the other filter treatment unit of Qingdao Hai Nuo and QYC-120 monitoring heat exchanger to carry out the monitoring of recirculated water operating performance, and the control concentration rate is 5.0 or 6.0.
The poly-epoxy succinic acid that present method is selected for use, 2-phosphonic acids butane-1,2,4-tricarboxylic acid, two 1,6 hexylidene triamine pentamethylene phosphonic acids, maleic anhydride are the product of Xinjiang Dean Environmental Protection Technology Co., Ltd; Benzotriazole, bromine Chlorodimethyl glycolylurea, Surchlor GR 60, TCCA (Trichloroisocyanuric acid) are commercially available general industry level product.
Claims (2)
1. the chemical treatment method of a Coal Chemical Industry reuse recirculated cooling water is characterized in that:
Step 1 medicament is prepared with parts by weight:
The preparation of composite scale-inhibiting corrosion inhibitor: by poly-epoxy succinic acid 9-11 part, 2-phosphonic acids butane-1,2,4-tricarboxylic acid 18-22 part, two 1,6 hexylidene triamine pentamethylene phosphonic acids 19-21 part, dirt dispersion agent 25-35 part, benzotriazole 1-3 part, deionized water 9-28 part is formed; Earlier poly-epoxy succinic acid is added 2-phosphonic acids butane-1,2, in the 4-tricarboxylic acid, place in the container, mix, add two 1,6 hexylidene triamine pentamethylene phosphonic acids, dirt dispersion agent, deionized water successively, stirred 25-35 minute, maintain the temperature at 20-35 ℃, add benzotriazole then, continue to stir 30-60 minute, maintain the temperature at 20-35 ℃, namely get composite scale-inhibiting corrosion inhibitor;
The wherein preparation of dirt dispersion agent: by maleic anhydride 480-510 part, sodium dihydrogen phosphate 200-230 part, initiator 100-120 part, deionized water 290-310 part, vinylformic acid 178-185 part are formed; Preparation:, open to stir in deionized water, the maleic anhydride sucting reaction still with pump, all dissolve to solid; Vinylformic acid, sodium dihydrogen phosphate, initiator are splashed in the reactor successively, dripped time 2.8-3.0 hour, temperature is at 60-70 ℃; Dropwise, temperature is controlled at 68-72 ℃, continues to stir 3-4 hour, is cooled to room temperature, gets the liquid of transparent thickness dirt dispersion agent, and its dirt dispersion agent solid content is 30-50%;
Wherein SODIUM PHOSPHATE, MONOBASIC is dissolved in 155 parts of deionized waters by 45 parts of sodium dihydric hypophosphites and makes;
Wherein initiator is dissolved in 100 parts of deionized waters by 10-15 part Potassium Persulphate and makes;
Step 2 sterilizing and algae-removing is handled:
1) adds sterilant at water collecting basin torrent place, 1-2 time weekly; To possess water meter, add 20-30mg/L at every turn;
2) add the modified quaternary ammonium salt series bactericidal agent at water collecting basin torrent place, every 1-2 week adds 1 time; To possess water meter, add 80-100mg/L at every turn;
3) add nonionic surface active agent at water collecting basin torrent place, add weekly 1 time; To possess water meter, add 15-30mg/L at every turn;
The optimization of step 3 recirculated water: adopt the dosing of the full-automatic total phosphorus supervisory system of SYZL ∑ sigma, the dosage 10mg/L of composite scale-inhibiting corrosion inhibitor is benchmark with bowl spares water, and control recirculated water total phosphorus is at 4-7mg/L, and concentration rate control at 5.0-6.0 doubly; Recirculated water carries out the side filter to be handled, and is provided with the QYC-120 monitoring heat exchanger of Qingdao Hai Nuo.
2. according to the described method of claim 1, it is characterized in that: the sterilant of selecting for use is bromine Chlorodimethyl glycolylurea or Surchlor GR 60 or TCCA (Trichloroisocyanuric acid).
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103734127B (en) * | 2014-01-08 | 2015-04-08 | 新疆德安环保科技有限公司 | Novel biologically bactericidal dispersing agent and preparation method thereof |
| CN105000685B (en) * | 2015-07-30 | 2017-01-25 | 江苏华安科研仪器有限公司 | Chemical water treatment agent |
| CN108485724B (en) * | 2018-05-30 | 2023-09-26 | 中冶京诚工程技术有限公司 | Artificial gas scale inhibition system and slow release scale removal method |
| CN108812678B (en) * | 2018-07-05 | 2020-12-25 | 河南省科学院能源研究所有限公司 | Composite corrosion-inhibiting bactericide |
| CN110026143B (en) * | 2019-05-24 | 2023-12-29 | 南京辰翌科技有限公司 | Device for developing scale and corrosion inhibitor by utilizing organic waste and process method thereof |
| CN115305465A (en) * | 2022-09-15 | 2022-11-08 | 上海高森水处理有限公司 | Circulating water phosphorus-free cleaning prefilming agent |
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