CN104629920A - Biological slime stripping agent and method for stripping biological slime in circulating cooling water system - Google Patents
Biological slime stripping agent and method for stripping biological slime in circulating cooling water system Download PDFInfo
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- CN104629920A CN104629920A CN201310556790.7A CN201310556790A CN104629920A CN 104629920 A CN104629920 A CN 104629920A CN 201310556790 A CN201310556790 A CN 201310556790A CN 104629920 A CN104629920 A CN 104629920A
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Abstract
The invention discloses a biological slime stripping agent and a method for stripping biological slime in a circulating cooling water system. The biological slime stripping agent provided by the invention includes an agent A and an agent B, wherein the agent A is a metal borohydride and an aminopolycarboxylicacid salt, the agent B is a quaternary phosphorus salt, and the agent A and the agent B are preserved independently. The method for stripping biological slime in circulating cooling water system provided by the invention includes adding the agent A and the agent B of the biological slime stripping agent provided by the invention into the circulating cooling water of the circulating cooling water system. Through the technological scheme, the biological slime stripping agent and the method provided by the invention can realize effective stripping of the biological slime in the circulating cooling water system at a low dosage.
Description
Technical field
The present invention relates to the method for biological clay in a kind of biological clay stripper and strip cycles cooling water system, particularly, relate to a kind of biological clay stripper and utilize the method for biological clay in biological clay stripper strip cycles cooling water system.
Background technology
Corrosion and scaling and microorganism are three large problems of recirculating cooling water system.Along with the raising of water technology, the corrosion of most of water coolant and scale problems obtain good control, but the foundry loam of system and bacterium algae problem more outstanding, especially when material from leakage, foundry loam often controls bad.Microorganism viscosity mud, once be formed in a large number, not only can reduce the heat transfer effect of interchanger and cooling tower, and Stickydeposit also can cause underdeposit corrosion at heat exchanger surface, and serious also can make heat transfer tube corrosion failure, causes stopping production.In addition Stickydeposit also can hinder corrosion inhibiting and descaling agent because of cannot contact heat-exchanging device surface and be difficult to play effect.In many factories cooling water system, mud becomes one of subject matter.Attract great attention to the control of mud in recent years, although biocide kind is more, its sludge stripping performance and environmental benefit still can not meet the requirement of current water treatment.Studying the water conditioner of mainly research environment friendly, biodegradation type, low cost in sludge stripping abroad.
CN1853473A proposes a kind of for the effective Biocidal algae-killing agent of the sludge stripping containing microorganism, and it contains isothiazolinone, dodecyl dimethyl benzyl ammonium chloride, polyacrylic acid.Its shortcoming is that Biocidal algae-killing agent of the present invention 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 suitable in subalkaline recirculated cooling water.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of can with the method for biological clay in the new bio adhesive mud remover used compared with low dosage and strip cycles cooling water system.
To achieve these goals, the present inventor has carried out large quantity research, found that: use metal borohydride, aminopolycanboxylic acid's salt and quaternary alkylphosphonium salt can biological clay effectively in strip cycles cooling water system successively.
Therefore, on the one hand, the invention provides a kind of biological clay stripper, wherein, this biological clay stripper comprises A agent and B agent, and described A agent is metal borohydride and aminopolycanboxylic acid's salt, and described B agent is quaternary alkylphosphonium salt, and A agent and B agent are independently preserved separately.
On the other hand, the invention provides the method for biological clay in a kind of strip cycles cooling water system, wherein, the method comprises in the recirculated cooling water of recirculating cooling water system, to add A agent in the invention described above biological clay stripper and B agent successively.
By technique scheme, the present invention can to realize effective stripping of biological clay in recirculating cooling water system compared with low dosage.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
Biological clay stripper provided by the invention comprises A agent and B agent, and described A agent is metal borohydride and aminopolycanboxylic acid's salt, and described B agent is quaternary alkylphosphonium salt, and A agent and B agent are independently preserved separately.
A preferred embodiment of the invention, the weight ratio of described metal borohydride, aminopolycanboxylic acid's salt and quaternary alkylphosphonium salt is 2-30:5-30:0.5-10.
According to another kind of preferred implementation of the present invention, the weight ratio of described metal borohydride, aminopolycanboxylic acid's salt and quaternary alkylphosphonium salt is 5-20:8-20:1-4.
According to the present invention, described metal borohydride can be the various metal borohydrides that can decompose generation hydrogen in water, is preferably alkali metal borohydride, is more preferably sodium borohydride and/or POTASSIUM BOROHYDRIDE.
According to the present invention, described aminopolycanboxylic acid's salt can be the various common aminopolycanboxylic acid's salt as complexing agent, be preferably aminopolycanboxylic acid's sodium salt and/or aminopolycanboxylic acid's sylvite, be more preferably selected from least one of nitrilotriacetic acid trisodium salt, disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate and diethylene triamine pentacetic acid (DTPA) five in sodium.
According to the present invention, the various quaternary alkylphosphonium salts with biological clay stripping effect that described quaternary alkylphosphonium salt can be commonly used for this area, can be selected from general formula is R
1r
2r
3r
4pX and (R
1r
2r
3r
4p)
2sO
4compound at least one, wherein R
1, R
2, R
3or R
4for the hydroxyalkyl of carbonatoms to be the alkyl of 1-8 or carbonatoms be 1-8 and R
1, R
2, R
3and R
4identical or different, X is chlorine or bromine.
Preferably, described quaternary alkylphosphonium salt is at least one in tetramethyl phosphonium chloride phosphorus, tetrakis hydroxymetyl phosphonium sulfuric and Tetrakis hydroxymethyl phosphonium chloride.
In strip cycles cooling water system provided by the invention, the method for biological clay comprises add A agent and B agent successively in the recirculated cooling water of recirculating cooling water system, and described A agent is metal borohydride and aminopolycanboxylic acid's salt, and described B agent is quaternary alkylphosphonium salt.
According to the present invention, to the not special requirement of the consumption of metal borohydride, under preferable case, relative to the recirculated cooling water of 1L, the consumption of metal borohydride is 20-300mg, is more preferably 50-200mg.
According to the present invention, described metal borohydride can be the various metal borohydrides that can decompose generation hydrogen in water, is preferably alkali metal borohydride, is more preferably sodium borohydride and/or POTASSIUM BOROHYDRIDE.
According to the present invention, to the consumption of aminopolycanboxylic acid's salt, there is no particular limitation, and under preferable case, relative to the recirculated cooling water of 1L, the consumption of aminopolycanboxylic acid's salt is 50-300mg, is more preferably 80-200mg.
According to the present invention, described aminopolycanboxylic acid's salt can be the various common aminopolycanboxylic acid's salt as complexing agent, is preferably selected from least one of nitrilotriacetic acid trisodium salt, disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate and diethylene triamine pentacetic acid (DTPA) five in sodium.
According to the present invention, have no particular limits the consumption of quaternary alkylphosphonium salt, under preferable case, relative to the recirculated cooling water of 1L, the consumption of quaternary alkylphosphonium salt is 5-100mg, is more preferably 10-40mg.
According to the present invention, the various quaternary alkylphosphonium salts with biological clay stripping effect that described quaternary alkylphosphonium salt can be commonly used for this area, can be selected from general formula is R
1r
2r
3r
4pX and (R
1r
2r
3r
4p)
2sO
4compound at least one, wherein R
1, R
2, R
3or R
4for the hydroxyalkyl of carbonatoms to be the alkyl of 1-8 or carbonatoms be 1-8 and R
1, R
2, R
3and R
4identical or different, X is chlorine or bromine.
Preferably, described quaternary alkylphosphonium salt is at least one in tetramethyl phosphonium chloride phosphorus, tetrakis hydroxymetyl phosphonium sulfuric and Tetrakis hydroxymethyl phosphonium chloride.
According to the present invention, as long as add A agent successively in order and B agent can realize object of the present invention, but the timed interval adding A agent and B agent is preferably 5-30h, is more preferably 8-24h.Be preferably 0.5-30h the working time added after B agent, be more preferably 1-24h.Adding after B agent runs for some time (preferred 0.5-30h, more preferably 1-24h), A agent (namely repeating to add successively in the inventive method the step of A agent and B agent) can be added with the biological clay in lasting strip cycles cooling water system.The present inventor finds, the time controlling to add A agent and B agent can obtain better peeling effect in above-mentioned preferable range.
Biological clay stripper of the present invention or method are applicable to various recirculating cooling water system, and peeling effect is remarkable.
Below will be described the present invention by embodiment.In following examples, the laboratory evaluation method of biological clay stripping performance adopts Extracellular polymers method (namely being evaluated the biological clay stripping performance of the inventive method by analysis polysaccharide content and nucleic acid content), Extracellular polymers is the important component part of active sludge, its main organic composition is carbohydrate, nucleic acid and protein, Extracellular polymers is conducive to microorganism cells cohesion, important effect is played in formation stabilate film and anaerobic grain sludge, the organic constituent of Extracellular polymers can change the surface property of bacterium flco and the physical property of granule sludge, promote the stable of intercellular cohesion and structure, after biological clay stripper acts on active sludge, Extracellular polymers is destroyed, the organic composition such as polysaccharide and nucleic acid is scattered in recirculated cooling water, thus realize the stripping of biological clay.Therefore, can evaluate according to the peeling effect of the organic component content such as polysaccharide and nucleic acid to adhesive mud remover, after adding chemicals treatment, the organic component content such as polysaccharide and nucleic acid is higher, illustrates that the biological clay stripping performance of medicament is higher.In embodiment, revolution uses gyrostat (HYG-III rotary type constant temperature speed governing shaking flask cabinet, the Shanghai complete factory of nova automation control appliance) to operate, and to control pivotal rotating speed be 150r/min, and temperature is 27 DEG C.
The method of sampling analysis polysaccharide equal size is: get mixed solution and filter, measure polysaccharide content and nucleic acid content in filtrate, measurement of the polysaccharide content adopts anthrone-sulphuric acid method, and the mensuration of nucleic acid content adopts fixing phosphorus method.
The preparation method of biological clay solution is: be placed on whizzer active sludge (taking from Sinopec Beijing Yanshan Mountain branch office West secondary sedimentation tank of sewage treatment work) with the centrifugal 5min of 7000r/min, abandoning supernatant, by distilled water eccentric cleaning 3 times repeatedly, obtain biological clay for subsequent use, biological clay for subsequent use and distilled water are mixed to get the biological clay solution that biological clay concentration is 10g/L.
Embodiment 1
In the Erlenmeyer flask containing 1L biological clay solution, add sodium borohydride 50mg, nitrilotriacetic acid trisodium salt 200mg, revolution 8h, the tetramethyl phosphonium chloride phosphorus then adding 10mg continues revolution 24h, and sampling analysis polysaccharide content and nucleic acid content, the results are shown in Table 1.
Embodiment 2
In the Erlenmeyer flask containing 1L biological clay solution, add POTASSIUM BOROHYDRIDE 200mg, disodium ethylene diamine tetraacetate 80mg, revolution 24h, the tetrakis hydroxymetyl phosphonium sulfuric then adding 40mg continues revolution 1h, and sampling analysis polysaccharide content and nucleic acid content, the results are shown in Table 1.
Embodiment 3
Sodium borohydride 100mg, diethylene triamine pentacetic acid (DTPA) five sodium 150mg is added in the Erlenmeyer flask containing 1L biological clay solution, revolution 16h, then the Tetrakis hydroxymethyl phosphonium chloride adding 20mg continues revolution 16h, and sampling analysis polysaccharide content and nucleic acid content, the results are shown in Table 1.
Embodiment 4
In the Erlenmeyer flask containing 1L biological clay solution, add POTASSIUM BOROHYDRIDE 150mg, tetrasodium ethylenediamine tetraacetate 100mg, revolution 12h, the tetramethyl phosphonium chloride phosphorus then adding 30mg continues revolution 16h, and sampling analysis polysaccharide content and nucleic acid content, the results are shown in Table 1.
Embodiment 5
Sodium borohydride 120mg, nitrilotriacetic acid trisodium salt 90mg is added in the Erlenmeyer flask containing 1L biological clay solution, revolution 14h, the tetrakis hydroxymetyl phosphonium sulfuric of the tetramethyl phosphonium chloride phosphorus and 5mg that then add 15mg continues revolution 16h, and sampling analysis polysaccharide content and nucleic acid content, the results are shown in Table 1.
Embodiment 6
POTASSIUM BOROHYDRIDE 70mg, diethylene triamine pentacetic acid (DTPA) five sodium 160mg is added in the Erlenmeyer flask containing 1L biological clay solution, revolution 20h, the Tetrakis hydroxymethyl phosphonium chloride of the tetrakis hydroxymetyl phosphonium sulfuric and 10mg that then add 15mg continues revolution 14h, sampling analysis polysaccharide content and nucleic acid content, the results are shown in Table 1.
Embodiment 7
Biological clay stripping test is carried out according to the method for embodiment 1, unlike, the consumption of sodium borohydride is 40mg, the results are shown in Table 1.
Embodiment 8
Biological clay stripping test is carried out according to the method for embodiment 2, unlike, the consumption of POTASSIUM BOROHYDRIDE is 250mg, the results are shown in Table 1.
Embodiment 9
Biological clay stripping test is carried out according to the method for embodiment 3, unlike, the consumption of diethylene triamine pentacetic acid (DTPA) five sodium is 60mg, the results are shown in Table 1.
Embodiment 10
Biological clay stripping test is carried out according to the method for embodiment 4, unlike, the consumption of tetrasodium ethylenediamine tetraacetate is 250mg, the results are shown in Table 1.
Embodiment 11
Biological clay stripping test is carried out according to the method for embodiment 1, unlike, the consumption of tetramethyl phosphonium chloride phosphorus is 8mg, the results are shown in Table 1.
Embodiment 12
Biological clay stripping test is carried out according to the method for embodiment 2, unlike, the consumption of tetrakis hydroxymetyl phosphonium sulfuric is 80mg, the results are shown in Table 1.
Comparative example 1
Biological clay stripping test is carried out according to the method for embodiment 1, unlike, do not add sodium borohydride, the results are shown in Table 1.
Comparative example 2
Biological clay stripping test is carried out according to the method for embodiment 2, unlike, do not add disodium ethylene diamine tetraacetate, the results are shown in Table 1.
Comparative example 3
Biological clay stripping test is carried out according to the method for embodiment 3, unlike, do not add Tetrakis hydroxymethyl phosphonium chloride, the results are shown in Table 1.
Comparative example 4
In the Erlenmeyer flask containing 1L biological clay solution, add sodium borohydride 180mg, nitrilotriacetic acid trisodium salt 200mg, revolution 20h, the cats product 1227 then adding 30mg continues revolution 24h, and sampling analysis polysaccharide content and nucleic acid content, the results are shown in Table 1.
Comparative example 5
In the Erlenmeyer flask containing 1L biological clay solution, add the tetramethyl phosphonium chloride phosphorus revolution 32h of sodium borohydride 50mg, nitrilotriacetic acid trisodium salt 200mg and 10mg, sampling analysis polysaccharide content and nucleic acid content, the results are shown in Table 1.
Comparative example 6
In the Erlenmeyer flask containing 1L biological clay solution, add the tetramethyl phosphonium chloride phosphorus of 10mg, revolution 8h, then add sodium borohydride 50mg, nitrilotriacetic acid trisodium salt 200mg and continue revolution 24h, sampling analysis polysaccharide content and nucleic acid content, the results are shown in Table 1.
Table 1
| Embodiment is numbered | Polysaccharide content/(mg/L) | Nucleic acid content/(mg/L) |
| Embodiment 1 | 20.2 | 3.83 |
| Embodiment 2 | 20.5 | 3.85 |
| Embodiment 3 | 20.7 | 3.87 |
| Embodiment 4 | 20.8 | 3.89 |
| Embodiment 5 | 21.5 | 3.95 |
| Embodiment 6 | 21.6 | 3.97 |
| Embodiment 7 | 18.6 | 3.66 |
| Embodiment 8 | 18.7 | 3.67 |
| Embodiment 9 | 19.2 | 3.72 |
| Embodiment 10 | 19.1 | 3.71 |
| Embodiment 11 | 18.9 | 3.70 |
| Embodiment 12 | 18.8 | 3.69 |
| Comparative example 1 | 3.5 | 0.85 |
| Comparative example 2 | 10.7 | 1.15 |
| Comparative example 3 | 6.5 | 1.05 |
| Comparative example 4 | 16.7 | 3.11 |
| Comparative example 5 | 12.4 | 1.73 |
| Comparative example 6 | 11.8 | 1.56 |
Testing example 1
The biological clay stripping means of embodiment 1 and comparative example 1 is carried out field application test.The method of slime content in Analytical system is adopted to evaluate biological clay stripping performance.The mensuration of slime content is carried out according to industrial circulating cooling water water quality analysis method standard GB/T/T14643.1-2009.
Field application test condition: the internal circulating load 13000m of circulating water system
3/ h, power system capacity 6500m
3, cycles of concentration 3.0 ± 0.2, flow velocity 1.0m/s, temperature in 32 ± 1 DEG C, the temperature difference 6 DEG C.
Anti-incrustation corrosion inhibitor: 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP)+phosphonic acid butane-1,2,4-tricarboxylic acid (PBTCA)+zinc salt+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 and 9mg/L.
Test moisturizing water quality is in table 2, and Ca
2+, total hardness and basicity is all with CaCO
3meter, the measuring method of each parameter is as follows:
Ca
2+: reference standard GB/T6910-2006;
Total hardness: reference standard GB/T6909-2008;
Basicity: reference standard GB/T15451-2006;
Cl
-: reference standard HJ/T343-2007;
PH value: reference standard GB/T15893.2-1995;
Turbidity: reference standard GB/T15893.1-1995;
COD: reference standard GB/T11914-1989.
Table 2
Field application test the results are shown in Table 3.
Table 3
As can be seen from the result of above embodiment and testing example, biological slime of circulating cooling water stripping means of the present invention has good biological clay peeling effect.
In addition, can be found out by the results contrast of the result of embodiment 1-3 and comparative example 1-6 respectively, metal borohydride, aminopolycanboxylic acid's salt and quaternary alkylphosphonium salt add in order and to play a role and three kinds of components are indispensable.And, B agent in comparative example 4 uses cats product 1227, and the usage quantity of each component is all greater than the consumption of embodiment 1,5 and 7, but its biological clay peeling effect is not remarkable, illustrate and to compare with other nonionogenic tensides, quaternary alkylphosphonium salt and between metal borohydride and aminopolycanboxylic acid's salt, there is better synergy.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a biological clay stripper, is characterized in that, this biological clay stripper comprises A agent and B agent, and described A agent is metal borohydride and aminopolycanboxylic acid's salt, and described B agent is quaternary alkylphosphonium salt, and A agent and B agent are independently preserved separately.
2. biological clay stripper according to claim 1, wherein, the weight ratio of described metal borohydride, aminopolycanboxylic acid's salt and quaternary alkylphosphonium salt is 2-30:5-30:0.5-10.
3. biological clay stripper according to claim 1, wherein, the weight ratio of described metal borohydride, aminopolycanboxylic acid's salt and quaternary alkylphosphonium salt is 5-20:8-20:1-4.
4. according to the biological clay stripper in claim 1-3 described in any one, wherein, described metal borohydride is sodium borohydride and/or POTASSIUM BOROHYDRIDE; Described aminopolycanboxylic acid's salt is selected from least one of nitrilotriacetic acid trisodium salt, disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate and diethylene triamine pentacetic acid (DTPA) five in sodium; It is R that described quaternary alkylphosphonium salt is selected from general formula
1r
2r
3r
4pX and (R
1r
2r
3r
4p)
2sO
4compound at least one, wherein R
1, R
2, R
3or R
4for the hydroxyalkyl of carbonatoms to be the alkyl of 1-8 or carbonatoms be 1-8 and R
1, R
2, R
3and R
4identical or different, X is chlorine or bromine; Preferably, described quaternary alkylphosphonium salt is at least one in tetramethyl phosphonium chloride phosphorus, tetrakis hydroxymetyl phosphonium sulfuric and Tetrakis hydroxymethyl phosphonium chloride.
5. the method for biological clay in strip cycles cooling water system, is characterized in that, the method comprises A agent in the biological clay stripper added successively in the recirculated cooling water of recirculating cooling water system in claim 1-4 described in any one and B agent.
6. method according to claim 5, wherein, relative to the recirculated cooling water of 1L, the consumption of metal borohydride is 20-300mg, is preferably 50-200mg.
7. method according to claim 5, wherein, the timed interval adding A agent and B agent is 5-30h.
8. method according to claim 7, wherein, the timed interval adding A agent and B agent is 8-24h.
9. according to the method in claim 5-8 described in any one, wherein, adding the working time after B agent is 0.5-30h.
10. method according to claim 9, wherein, adding the working time after B agent is 1-24h.
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| CN104923078A (en) * | 2015-06-10 | 2015-09-23 | 上海丰信环保科技有限公司 | Scale inhibitor for antibacterial reverse-osmosis membrane for printing and dyeing wastewater |
| CN105236529A (en) * | 2015-10-08 | 2016-01-13 | 江海环保有限公司 | Foamless sterilization remover for air separation recirculated cooling water |
| CN106550955A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | For the efficient sterilizing remover of circulation |
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|---|---|
| CN104629920B (en) | 2017-09-29 |
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