CN103771593B - Remover for removing biological slime in recirculated cooling water and method for removing biological slime in recirculated cooling water system - Google Patents
Remover for removing biological slime in recirculated cooling water and method for removing biological slime in recirculated cooling water system Download PDFInfo
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Abstract
The invention discloses a remover for removing biological slime in recirculated cooling water. The remover contains a polyoxyethylene ether-type nonionic surfactant, a biosurfactant and an osmotic agent. The invention also provides a method for removing biological slime in a recirculated cooling water system by the remover. The method comprises putting the remover into the recirculated cooling water. The remover effectively removes biological slime deposited on the equipment and pipes of the recirculated cooling water system, utilizes the biodegradable environmentally-friendly biosurfactant to replace a part of synthetic surfactants, reduces a synthetic surfactant use amount, has good biological slime removal effects and reduces secondary pollution on the environment.
Description
Technical field
The present invention relates to the method for foundry loam in a kind of biological clay stripper and strip cycles cooling water system, particularly, relate to a kind of be suitable for recirculated cooling water can foundry loam effectively in strip cycles cooling water system and the biological clay stripper of environmental protection and by the method for foundry loam in its strip cycles cooling water system.
Background technology
In the process of industrial colling, often run into corrosion and scaling, foundry loam problem.Along with the raising of water technology, inhibition, the scale inhibition problem of most of water coolant obtain good solution, but the foundry loam of system and bacterium algae problem more outstanding, especially when material from leakage, foundry loam is often peeled off bad.Microorganism viscosity mud is once be formed in a large number, not only can reduce the cooling effect of interchanger and cooling tower, worsen water quality, but also the corrosion of equipment in cooling water system can be caused and reduce inhibition, the scale inhibition of water quality stabilizer and the effect of killing livestock, directly affect and endanger production, bringing financial loss.In many factories cooling water system, mud becomes one of subject matter.
In recent years the stripping of mud is attracted great attention.At present, although adhesive mud remover kind is more, its sludge stripping performance and environmental benefit still can not meet the requirement of current water treatment.The external water conditioner research in adhesive mud remover direction mainly being laid particular emphasis on to development environment friendly, biodegradation type, low cost.
Domestic cycle water adhesive mud remover mostly is cationic surfactant, and its peeling effect is pretty good, but there are some defects, such as, in use can have an impact to other water conditioner, simultaneously, also there is consumption large, and easily secondary pollution problems is caused to environment.Along with the enhancing of mankind's environmental consciousness and the progress of modern biotechnology, bio-surfactant industrial expansion receives great promotion, and development is more and more rapider, and has the trend of progressively substituted chemistry synthetic surfactant.
Bio-surfactant is microorganism oozy product with certain surface activity in metabolic process, has unique amphiphile, amphiphilic molecule structure.Bio-surfactant is similar to synthetic surfactant performance, and it has the performance of the reduction surface interface tension force identical with synthetic surfactant, wetting and penetrance, emulsifying dispersivity etc.In addition, bio-surfactant, compared with synthetic surfactant, also has many advantages, such as, biodegradable, can not cause and pollute; Nontoxic or low toxicity; Can produce with industrial waste, be conducive to environmental pollution improvement; There is better Environmental compatibility etc.Bio-surfactant substitutes synthetic surfactant and is applied to industrial circulating cooling water sludge stripping, has broad application prospects.
CN1853473A proposes a kind of Biocidal algae-killing agent that can carry out effectively peeling off for microorganism viscosity mud, and it contains isothiazolinone, dodecyl dimethyl benzyl ammonium chloride, polyacrylic acid.This Biocidal algae-killing agent is chemosynthesis medicament, and generally uses with higher dosage.
CN101849547A discloses a kind of efficient germicide, it is the aqua product containing isothiazolinone, trishydroxymethylnitromethane and dibromoethyl alcohol three kinds of main ingredients, there is when low dosage good microorganism killing and sludge stripping effect, can in industrial circulating water and Membrane cleaning two different field application.Its shortcoming is that trishydroxymethylnitromethane can slowly decompose in micro alkaline solution and releases formaldehyde, and work-ing life shortens, so be not too applicable in subalkaline recirculated water.
Existing adhesive mud remover is in order to remove the foundry loam in recirculating cooling water system, need to use a large amount of synthetic surfactants, but also serious pollution is caused to environment, along with the enhancing of mankind's environmental consciousness, need badly develop a kind of can foundry loam effectively in strip cycles cooling water system and the adhesive mud remover of environmental protection.
Summary of the invention
The object of the invention is to overcome the above-mentioned problems in the prior art, a kind of adhesive mud remover of the biological clay that can the e-quipment and pipe inwall of effective strip cycles cooling water system deposit is provided.
For achieving the above object, the invention provides one and being suitable for biological slime of circulating cooling water stripper, comprising Polyoxyethylene Ether Nonionic Surfactant, bio-surfactant and permeate agent.
In addition, the present invention also provides a kind of method utilizing foundry loam in biological slime of circulating cooling water stripper strip cycles cooling water system of the present invention, and the method comprises to be put into described biological slime of circulating cooling water stripper in recirculated cooling water.
Biological clay stripper of the present invention carries out biological clay stripping by the synergy of Polyoxyethylene Ether Nonionic Surfactant and bio-surfactant, and the potent osmosis of the permeate agent of interpolation can strengthen the sludge stripping effect of Polyoxyethylene Ether Nonionic Surfactant and bio-surfactant.By the combined action of three, make the stripping of biological clay more thorough, thus reduce the deposition of biological clay on the e-quipment and pipe inwall of recirculating cooling water system.
Embodiment
According to biological slime of circulating cooling water stripper of the present invention, wherein, described biological clay stripper contains Polyoxyethylene Ether Nonionic Surfactant, bio-surfactant and permeate agent.
According to biological slime of circulating cooling water stripper of the present invention, wherein, with the gross weight of described biological clay stripper for benchmark, the content of described Polyoxyethylene Ether Nonionic Surfactant is 10-30 % by weight; The content of described bio-surfactant is 30-60 % by weight; The content of described permeate agent is 20-40 % by weight.Preferably, with the gross weight of described biological clay stripper for benchmark, the content of described Polyoxyethylene Ether Nonionic Surfactant is 12-29 % by weight; The content of described bio-surfactant is 32-58 % by weight; The content of described permeate agent is 22-39 % by weight.
The type of service of the present invention to Polyoxyethylene Ether Nonionic Surfactant, bio-surfactant and permeate agent does not specially require, and can be solution form, also can be solidapowder form.According to biological slime of circulating cooling water stripper of the present invention, wherein, described Polyoxyethylene Ether Nonionic Surfactant is the tensio-active agent of chemosynthesis, preferably, described Polyoxyethylene Ether Nonionic Surfactant is long-chain fat polyoxyethylenated alcohol and/or alkylphenol polyoxyethylene; The general formula of described long-chain fat polyoxyethylenated alcohol is R
1o (CH
2cH
2o)
mh, wherein R
1for C
10-C
20alkyl, m is the integer of 6-40, preferred R
1for C
12-C
18alkyl, m is the integer of 8-35.The specific examples of fatty alcohol-polyoxyethylene ether can be, but not limited to as paregal O-8(C
12-C
18aliphatic alcohol polyethenoxy (8) ether), paregal O-10(C
12-C
18aliphatic alcohol polyethenoxy (10) ether), paregal O-15(C
12-C
18aliphatic alcohol polyethenoxy (15) ether), paregal O-20(C
12-C
18aliphatic alcohol polyethenoxy (20) ether), paregal O-30(C
12-C
18aliphatic alcohol polyethenoxy (30) ether) etc.; The general formula of described alkylphenol polyoxyethylene is R
2c
6h
4o (CH
2cH
2o)
nh, wherein, R
2for C
6-C
14alkyl, n is the integer of 3-30, preferred R
2for C
8-C
12alkyl, n is the integer of 10-20.The specific examples of described alkylphenol polyoxyethylene can be, but not limited to as OP-3(sim alkylphenol polyoxyethylene (3) ether), OP-6(sim alkylphenol polyoxyethylene (6) ether), OP-10(sim alkylphenol polyoxyethylene (10) ether), OP-20(sim alkylphenol polyoxyethylene (20) ether), OP-30(sim alkylphenol polyoxyethylene (30) ether), NP-4(nonyl phenol polyethenoxy (4) ether), NP-6(nonyl phenol polyethenoxy (6) ether), NP-10(nonyl phenol polyethenoxy (10) ether), NP-21(nonyl phenol polyethenoxy (21) ether), NP-30(nonyl phenol polyethenoxy (30) ether).
According to biological slime of circulating cooling water stripper of the present invention, described bio-surfactant comprises many different kinds.Chemical constitution according to them can be divided into the five large classes such as glycolipid, lipopeptid and lipoprotein, lipid acid and phosphatide, polymkeric substance and full cellular surface lipid.Bio-surfactant in the present invention mainly plays a part to peel off, disperse biological clay.Because glycolipid bio-surfactant has good perviousness, dispersiveness and bacteriostasis property, therefore, the present invention preferably uses glycolipid bio-surfactant.The specific examples of described glycolipid bio-surfactant has: rhamnolipid, marine alga glycolipid, sophorolipid, mannosylerythritol lipid, cellobiose fat, that is, can be selected from one or more in above-mentioned bio-surfactant.More preferably, described glycolipid bio-surfactant is selected from one or more in rhamnolipid, marine alga glycolipid, sophorolipid and mannosylerythritol lipid.
According to biological slime of circulating cooling water stripper of the present invention, permeate agent can improve sludge stripping effect, gives full play to the synergistic effect between each component of adhesive mud remover.Consider and the interaction of bio-surfactant and osmotic effect, permeate agent of the present invention is preferably the permeate agent of not cation, and preferably, described permeate agent is selected from sodium diethylhexyl sulfosuccinate and/or water-solubleazone.
Those skilled in the art is well known that, trade name is rhamnolipid, the tensio-active agent of marine alga glycolipid, sophorolipid and mannosylerythritol lipid is the product that effective constituent is rhamnolipid, marine alga glycolipid, sophorolipid and mannosylerythritol lipid separately, and the content of effective constituent is wherein different because the difference of manufacturer exists height.The product of trade name is penetrant t to be effective constituent be sodium diethylhexyl sulfosuccinate, the content of effective constituent is wherein different because the difference of manufacturer exists height.The product of water-solubleazone to be effective constituent be 1-orthododecyl nitrogen heterocyclo heptane-2-ketone, the content of effective constituent is wherein different because the difference of manufacturer exists height.Though the height of the effective constituent in above-mentioned commercial products which kind of there is is different, the Polyoxyethylene Ether Nonionic Surfactant in the present invention, bio-surfactant and permeate agent all measure its percentage composition at biological slime of circulating cooling water stripper with effective constituent wherein.
The present invention also provides the method for foundry loam in a kind of strip cycles cooling water system, and the method comprises to be put into biological slime of circulating cooling water stripper provided by the invention in recirculated cooling water.
According to method of the present invention, described biological slime of circulating cooling water stripper can directly be put in recirculated cooling water, if the active constituent content in the Polyoxyethylene Ether Nonionic Surfactant be commercially available, bio-surfactant and permeate agent commodity is too high and not easily mixed by various composition, can add after a certain amount of water makes each component mix and put into again in recirculated cooling water, like this, described biological clay stripper can be made to be distributed to equably rapidly in described recirculated cooling water.Wherein, the consumption for the described water dissolving each component can adjust according to actual needs, is not particularly limited.In addition, according to method of the present invention, described water is had no particular limits, can be various forms of water conventional in this area, such as: tap water, pure water, distilled water, deionized water etc., consider that the composition in biological clay stripper described in ion pair contained in described water may have an impact, in the present invention, preferably use deionized water.
Biological slime of circulating cooling water stripper provided by the invention can be applied in various recirculating cooling water system, and under preferable case, it is 7-9 that biological clay stripper of the present invention is specially adapted to pH value; Being preferably pH value is in the weakly alkaline recirculating cooling water system of 7.5-8.5, for carrying out effective biological clay stripping to the e-quipment and pipe of recirculating cooling water system.
According to the method for foundry loam in strip cycles cooling water system of the present invention, the input amount of the present invention to biological clay stripper does not specially require, preferably, with the recirculated cooling water of often liter for benchmark, the input amount of described biological clay stripper is 10-80mg, more preferably 20-50mg.
Measurement of the polysaccharide content adopts anthrone-sulphuric acid method, concrete operation step is as follows: draw 1mL solution to be measured and be placed in test tube, be dipped in frozen water and cool, then (take anthrone 0.2g, to add 100mL concentration be the concentrated sulfuric acid dissolution of 98.08 % by weight and get final product to add 4mL anthrone reagent.The same day, preparation used), boil 10min in boiling water bath, taking-up measures absorbancy with after tap water cooling at the wavelength place of 620nm, is then calculated the polysaccharide content of solution to be measured by typical curve according to the absorbance recorded.
The mensuration of nucleic acid content adopts fixing phosphorus method, and its principle contains a certain proportion of organophosphorus according in nucleic acid molecule, just can be tried to achieve the amount of nucleic acid by the amount measuring organophosphorus in nucleic acid.Organic phosphorous content is the difference of total phosphorous and positive phosphorus content.Wherein, the mensuration of total phosphorous is carried out according to boiler feed water and water coolant analytical procedure GB/T 6913.2-1986, and the mensuration of positive phosphorus content is carried out according to boiler feed water and water coolant analytical procedure GB/T 6913.1-1986.
The all ingredients used in the embodiment of the present invention is as shown in table 1 below:
Table 1
Embodiment 1-10 and comparative example 1-6
Under normal temperature (25 DEG C), the blending ratio of the formula of according to the form below 2 gets each component, is uniformly mixed, and namely obtains biological slime of circulating cooling water stripper provided by the invention.
Table 2
Application examples 1 laboratory test
Should use-case for illustration of the sludge stripping effect of the biological clay stripper of embodiment 1-10 and comparative example 1-6.
The laboratory evaluation method of sludge stripping performance adopts Extracellular polymers method.Extracellular polymers is the important component part of active sludge, and its main organic composition is carbohydrate, nucleic acid and protein.After adhesive mud remover acts on active sludge, the organic composition such as polysaccharide and nucleic acid is scattered in water, and the sludge stripping effect of content to adhesive mud remover according to the organic composition such as polysaccharide and nucleic acid in water is evaluated.Concrete operation step is as follows:
(1) active sludge fetched by Fangshan secondary sedimentation tank of sewage treatment work is placed in the centrifugal 5min of 7000r/min on whizzer, abandoning supernatant, by distilled water eccentric cleaning 3 times repeatedly, obtains foundry loam for subsequent use.
(2) in Erlenmeyer flask, add the above-mentioned foundry loam that step (1) obtains, and with distilled water diluting to 10g/L, and add the biological clay stripper that embodiment 1-10 and comparative example 1-6 prepares respectively, be placed in shaking flask cabinet, under 27 DEG C of constant temperature, with the rotating speed of 150r/min, rock 24h, obtain mixed solution.
(3) take out above-mentioned mixed solution to filter, measure the content of polysaccharide and nucleic acid in filtrate.The results are shown in following table 3.
Table 3
| Polysaccharide content/(mg/L) | Nucleic acid content/(mg/L) | |
| Embodiment 1 | 22.3 | 4.02 |
| Embodiment 2 | 21.8 | 3.97 |
| Embodiment 3 | 21.1 | 3.84 |
| Embodiment 4 | 22.5 | 4.06 |
| Embodiment 5 | 21.7 | 3.96 |
| Embodiment 6 | 20.8 | 3.91 |
| Embodiment 7 | 21.1 | 3.95 |
| Embodiment 8 | 21.5 | 3.92 |
| Embodiment 9 | 20.6 | 3.88 |
| Embodiment 10 | 20.9 | 3.90 |
| Comparative example 1 | 15.1 | 2.87 |
| Comparative example 2 | 16.9 | 2.92 |
| Comparative example 3 | 14.3 | 2.56 |
| Comparative example 4 | 11.4 | 2.39 |
| Comparative example 5 | 5.3 | 1.01 |
| Comparative example 6 | 11.2 | 2.47 |
As can be seen from the result of table 3, polysaccharide in the filtrate utilizing the biological clay stripper of embodiment 1-10 to obtain and the content of nucleic acid are all higher than the content of the polysaccharide in the filtrate utilizing the adhesive mud remover of comparative example 1-6 to obtain and nucleic acid, illustrate that biological clay stripper (embodiment 1-10) of the present invention is compared with the adhesive mud remover (comparative example 1-6) of prior art, there is excellent sludge stripping effect.
Application examples 2 test in place
The sludge stripping effect in recirculating cooling water system should be applied to by use-case for illustration of biological slime of circulating cooling water stripper of the present invention.
Render in the recirculating cooling water system of the same terms by the biological clay stripper of embodiment 1,4,7 and comparative example 5-6 respectively, the consumption of described biological clay stripper is as shown in table 2 respectively.
Field application test condition: the internal circulating load of circulating water system is 13000m
3/ h, power system capacity is 6500m
3/ h, controling parameters is as follows:
Cycles of concentration (saltiness of recirculated cooling water and the ratio of make up water saltiness are described): 3.0 ± 0.2;
The system flow rate of recirculated water: 1.0m/s;
Recirculated water is in the temperature at heat exchanger entrance place: 32 ± 1 DEG C;
Recirculated water imports and exports the temperature difference: 6 DEG C;
Test moisturizing water quality leading indicator is in table 4.
Table 4
The scale inhibitor medicament added in recirculated cooling water is the conventional scale inhibitor medicament used: 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP)+phosphono-containing butane-1,2,4-tricarboxylic acid (PBTCA)+Zinc vitriol+vinylformic acid/2-methyl-2'-acrylamido propane sulfonic acid multipolymer (AA/AMPS=7:3, Limiting Viscosity when 30 DEG C is 0.071dl/g), effective concentration is respectively 4mg/L, 4mg/L, 2mg/L, 9mg/L.
The biological clay stripper of embodiment 1,4,7 and comparative example 5-6 is added respectively in the recirculated water of above-mentioned condition, and the slime content measured in recirculated water, dispensing and sampling are all carry out in water collecting basin, the mensuration of slime content adopts carries out according to the biofiltration net method in industrial circulating cooling water water quality analysis method standard GB/T/T 14643.1-1993, concrete operation method is under experimental conditions, by 1m
3online foundry loam, by No. 25 plankton nets, is washed graduated cylinder, records foundry loam volume after sedimentation, it can thus be appreciated that foundry loam amount in recirculated cooling water by recirculated cooling water.Field application test the results are shown in Table 5.
Table 5
Experimental result as can be seen from table 5: the biological slime of circulating cooling water stripper of the present invention's (embodiment 1,4,7) is when being applied in circulating cooling system, compared with the adhesive mud remover of prior art (comparative example 5-6), the slime content stripped down is many, thus has more significant sludge stripping effect.In addition, biological slime of circulating cooling water stripper of the present invention uses biodegradable, environmentally friendly bio-surfactant Substitute For Partial synthetic surfactant, good biological clay peeling effect can be reached while minimizing synthetic surfactant consumption, the secondary pollution to environment can be reduced.
Claims (9)
1. a biological slime of circulating cooling water stripper, is characterized in that, described biological clay stripper contains Polyoxyethylene Ether Nonionic Surfactant, bio-surfactant and permeate agent; Described bio-surfactant is at least one in rhamnolipid, marine alga glycolipid, sophorolipid and mannosylerythritol lipid and cellobiose fat; Described permeate agent is selected from sodium diethylhexyl sulfosuccinate and/or water-solubleazone; With the gross weight of described biological clay stripper for benchmark, the content of described Polyoxyethylene Ether Nonionic Surfactant is 10-30 % by weight, and the content of described bio-surfactant is 30-60 % by weight, and the content of described permeate agent is 20-40 % by weight.
2. biological slime of circulating cooling water stripper according to claim 1, wherein, with the gross weight of described biological clay stripper for benchmark, the content of described Polyoxyethylene Ether Nonionic Surfactant is 12-29 % by weight; The content of described bio-surfactant is 32-58 % by weight; The content of described permeate agent is 22-39 % by weight.
3. biological slime of circulating cooling water stripper according to claim 1 and 2, wherein, described Polyoxyethylene Ether Nonionic Surfactant is long-chain fat polyoxyethylenated alcohol and/or alkylphenol polyoxyethylene.
4. biological slime of circulating cooling water stripper according to claim 3, wherein, the general formula of described long-chain fat polyoxyethylenated alcohol is R
1o (CH
2cH
2o)
mh, wherein, R
1for C
10-C
20alkyl, m is the integer of 6-40; The general formula of described alkylphenol polyoxyethylene is R
2c
6h
4o (CH
2cH
2o)
nh, wherein, R
2for C
6-C
14alkyl, n is the integer of 3-30.
5. biological slime of circulating cooling water stripper according to claim 4, wherein, R
1for C
12-C
18alkyl, m is the integer of 8-35; R
2for C
8-C
12alkyl, n is the integer of 10-20.
6. the method for foundry loam in strip cycles cooling water system, the method comprises to be put into the biological slime of circulating cooling water stripper described in any one in claim 1-5 in recirculated cooling water.
7. method according to claim 6, wherein, the recirculated cooling water relative to often liter, the input amount of described biological clay stripper is 10-80mg.
8. method according to claim 7, wherein, the recirculated cooling water relative to often liter, the input amount of described biological clay stripper is 20-50mg.
9. method according to claim 6, wherein, the pH value of described recirculated cooling water is 7-9.
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| CN104087945B (en) * | 2014-07-23 | 2016-07-27 | 广东省石油化工研究院 | A kind of bioantifouling agent |
| CN105776453A (en) * | 2014-12-26 | 2016-07-20 | 上海洗霸科技股份有限公司 | Bactericidal stripping agent, and preparation method and application thereof |
| CN105273741B (en) * | 2015-01-22 | 2017-02-22 | 上海良田化工有限公司 | Ethylene device gasoline stripping tower scale inhibitor, preparation method and usage method |
| CN105886132A (en) * | 2016-05-07 | 2016-08-24 | 毛祝新 | Antibacterial biological sticky mud stripping agent and preparation method thereof |
| CN110301437A (en) * | 2019-07-11 | 2019-10-08 | 北京中天兰清环境科技有限公司 | A kind of sterilization synergy remover for circulating water treatment |
| CN114804375B (en) * | 2021-01-29 | 2023-03-24 | 中国石油化工股份有限公司 | Biological slime dispersion inhibitor and preparation method and application thereof |
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