CN104629920B - The method of biological clay in a kind of biological clay remover and strip cycles cooling water system - Google Patents
The method of biological clay in a kind of biological clay remover and strip cycles cooling water system Download PDFInfo
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Abstract
The invention discloses a kind of method of biological clay in biological clay remover and strip cycles cooling water system.The biological clay remover of the present invention includes A agent and B agent, and the A agent is metallic boron hydrides and aminopolycanboxylic acid's salt, and the B agent is quaternary alkylphosphonium salt, and A agent and B agent are each independently preserved.The method of biological clay includes adding the A agent and B agent in biological clay remover of the present invention successively into the recirculated cooling water of recirculating cooling water system in strip cycles cooling water system in the present invention.By above-mentioned technical proposal, the present invention can realize being effectively peeled off for biological clay in recirculating cooling water system with relatively low-dose.
Description
Technical field
The present invention relates to a kind of method of biological clay in biological clay remover and strip cycles cooling water system, specifically
Ground, is related to a kind of biological clay remover and the side using biological clay in biological clay remover strip cycles cooling water system
Method.
Background technology
Corrosion and scaling and microorganism are the three major issues of recirculating cooling water system.With the raising of water technology, big portion
The corrosion and scale problems for dividing cooling water have obtained preferable control, but the foundry loam and bacterium algae problem of system are more prominent, especially exist
In the case of material from leakage, foundry loam often controls bad.Microorganism viscosity mud can not only reduce heat exchanger and cold once a large amount of form
But the heat transfer effect of tower, and Stickydeposit can also cause underdeposit corrosion in heat exchanger surface, serious can also make heat exchanger tube rotten
Eating thrown hole, causes to stop production.In addition Stickydeposit can also hinder corrosion inhibiting and descaling agent because that can not be difficult to play contact heat-exchanging device surface
Effect.In many factory's cooling water systems, sludge turns into one of subject matter.The control to sludge has caused height in recent years
Pay attention to, although biocide kind is more, but its sludge stripping performance and environmental benefit can not still meet the requirement of current water process.
It is external to be mainly research environment friendly, biodegradation type, the water treatment agent of low cost in terms of sludge stripping is studied.
CN1853473A proposes a kind of for the effective Biocidal algae-killing agent of the sludge stripping containing microorganism, and it contains different
Thiazolinone, dodecyl dimethyl benzyl ammonium chloride, polyacrylic acid.Its shortcoming be the Biocidal algae-killing agent of the present invention it is general with
Higher dosage is used.
CN101849547A discloses a kind of efficient germicide, be containing OIT, trishydroxymethylnitromethane and
The aqua product of three kinds of key components of dibromoethyl alcohol, there is good microorganism killing and sludge stripping to imitate in low dosage
Really, can be in the two different field applications of industrial circulating water and Membrane cleaning.Its shortcoming is trishydroxymethylnitromethane in alkalescence
Formaldehyde can be slowly decomposed to give off in solution, service life shortens, so not being suitable in subalkaline recirculated cooling water.
The content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art there is provided a kind of new bio that can be used with relatively low-dose
The method of adhesive mud remover and biological clay in strip cycles cooling water system.
To achieve these goals, the present inventor has carried out numerous studies, as a result finds：Metal boron is used successively
Hydride, aminopolycanboxylic acid's salt and quaternary alkylphosphonium salt can be efficiently peeled off the biological clay in recirculating cooling water system.
Therefore, on the one hand, the invention provides a kind of biological clay remover, wherein, the biological clay remover include A
Agent and B agent, the A agent are metallic boron hydrides and aminopolycanboxylic acid's salt, and the B agent is quaternary alkylphosphonium salt, and A agent and B agent are each independent
Preserve.
On the other hand, the invention provides a kind of method of biological clay in strip cycles cooling water system, wherein, the party
Method include toward the A agent added successively in the recirculated cooling water of recirculating cooling water system in the invention described above biological clay remover with
B agent.
By above-mentioned technical proposal, the present invention can realize having for biological clay in recirculating cooling water system with relatively low-dose
Effect is peeled off.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The biological clay remover that the present invention is provided includes A agent and B agent, and the A agent is that metallic boron hydrides and amino are more
Carboxylate, the B agent is quaternary alkylphosphonium salt, and A agent and B agent are each independently preserved.
A preferred embodiment of the invention, the metallic boron hydrides, aminopolycanboxylic acid's salt and quaternary alkylphosphonium salt
Weight ratio is 2-30:5-30:0.5-10.
According to another preferred embodiment of the present invention, the metallic boron hydrides, aminopolycanboxylic acid's salt and quaternary alkylphosphonium salt
Weight ratio be 5-20:8-20:1-4.
According to the present invention, the metallic boron hydrides can decompose the metal boron hydrogen of generation hydrogen to be various in water
Compound, preferably alkali metal borohydride, more preferably sodium borohydride and/or potassium borohydride.
According to the present invention, aminopolycanboxylic acid's salt can be various common aminopolycanboxylic acid's salt as complexing agent,
Preferably aminopolycanboxylic acid's sodium salt and/or aminopolycanboxylic acid's sylvite, are more preferably selected from nitrilotriacetic acid trisodium salt, ethylenediamine tetra-acetic acid two
At least one of sodium, tetrasodium ethylenediamine tetraacetate and the sodium of diethylene triamine pentacetic acid (DTPA) five.
According to the present invention, the quaternary alkylphosphonium salt can be the various quaternary phosphoniums with biological clay release effect commonly used in the art
Salt, can be R selected from formula1R2R3R4PX and (R1R2R3R4P)2SO4At least one of compound, wherein R1、R2、R3Or R4
Hydroxyalkyl and R that the alkyl or carbon number for being 1-8 for carbon number are 1-81、R2、R3And R4It is identical or different, X be chlorine or
Bromine.
Preferably, the quaternary alkylphosphonium salt be tetramethyl phosphonium chloride phosphorus, tetrakis hydroxymetyl phosphonium sulfuric and THPC in extremely
Few one kind.
The method of biological clay is included toward recirculating cooling water system in the strip cycles cooling water system that the present invention is provided
A agent and B agent are added in recirculated cooling water successively, the A agent is metallic boron hydrides and aminopolycanboxylic acid's salt, and the B agent is season
Microcosmic salt.
According to the present invention, the consumption of metallic boron hydrides is not required particularly, under preferable case, following relative to 1L
Ring cooling water, the consumption of metallic boron hydrides is 20-300mg, more preferably 50-200mg.
According to the present invention, the metallic boron hydrides can decompose the metal boron hydrogen of generation hydrogen to be various in water
Compound, preferably alkali metal borohydride, 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, under preferable case, following relative to 1L
Ring cooling water, the consumption of aminopolycanboxylic acid's salt is 50-300mg, more preferably 80-200mg.
According to the present invention, aminopolycanboxylic acid's salt can be various common aminopolycanboxylic acid's salt as complexing agent,
It is preferably selected from nitrilotriacetic acid trisodium salt, disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate and the sodium of diethylene triamine pentacetic acid (DTPA) five
At least one of.
According to the present invention, the consumption of quaternary alkylphosphonium salt is had no particular limits, under preferable case, the circulating cooling relative to 1L
Water, the consumption of quaternary alkylphosphonium salt is 5-100mg, more preferably 10-40mg.
According to the present invention, the quaternary alkylphosphonium salt can be the various quaternary phosphoniums with biological clay release effect commonly used in the art
Salt, can be R selected from formula1R2R3R4PX and (R1R2R3R4P)2SO4At least one of compound, wherein R1、R2、R3Or R4
Hydroxyalkyl and R that the alkyl or carbon number for being 1-8 for carbon number are 1-81、R2、R3And R4It is identical or different, X be chlorine or
Bromine.
Preferably, the quaternary alkylphosphonium salt be tetramethyl phosphonium chloride phosphorus, tetrakis hydroxymetyl phosphonium sulfuric and THPC in extremely
Few one kind.
According to the present invention, as long as adding A agent and B agent successively in order can be achieved the purpose of the present invention, still, A is added
The time interval of agent and B agent is preferably 5-30h, more preferably 8-24h.The run time preferably 0.5-30h after B agent is added,
More preferably 1-24h.Adding B agent operation a period of time（It is preferred that 0.5-30h, more preferably 1-24h）Afterwards, A agent can be added（I.e.
Repeat to add the step of A agent and B agent successively in the inventive method）With the biological clay in lasting strip cycles cooling water system.
It was found by the inventors of the present invention that control adds A agent and the time of B agent results in more preferably stripping effect in above-mentioned preferred scope
Really.
The biological clay remover or method of the present invention is applied to various recirculating cooling water systems, and peeling effect is notable.
The present invention will be described in detail by way of examples below.In following examples, biological clay stripping performance
Laboratory evaluation method uses Extracellular polymers method（The life of the inventive method is evaluated by analyzing polyoses content and nucleic acid content
Thing sludge stripping performance）, Extracellular polymers are the important components of activated sludge, and its main organic principle is carbohydrate, nucleic acid
And protein, Extracellular polymers are conducive to microbial cell to condense, and are played in stable biomembrane and anaerobic grain sludge is formed
Important effect, the organic component of Extracellular polymers can change the surface characteristic of bacterium flco and the physics spy of granule sludge
Property, promote the stabilization of intercellular cohesion and structure, after biological clay remover acts on activated sludge, Extracellular polymers quilt
Destruction, the organic principle such as polysaccharide and nucleic acid is scattered in recirculated cooling water, so as to realize the stripping of biological clay.It therefore, it can
The peeling effect of adhesive mud remover is evaluated according to organic component contents such as polysaccharide and nucleic acid, added after chemicals treatment, it is many
The organic component content such as sugar and nucleic acid is higher, illustrates that the biological clay stripping performance of medicament is higher.In embodiment, revolution is used back
Turn instrument（The swinging constant temperature speed governing shaking flask cabinets of HYG- III, the Shanghai complete factory of nova automation control appliance）Operated, and controlled
The rotating speed of revolution is 150r/min, and temperature is 27 DEG C.
The method of sampling analysis polysaccharide equal size is：Take mixed liquor to filter, determine polyoses content and nucleic acid content in filtrate,
Measurement of the polysaccharide content uses anthrone-sulphuric acid method, and the measure of nucleic acid content uses fixing phosphorus method.
The preparation method of biological clay solution is：By activated sludge（It is derived from Sinopec Beijing Yanshan Mountain branch company West dirty
Water treatment plant's second pond）It is placed on centrifuge and 5min is centrifuged with 7000r/min, abandoning supernatant is centrifuged repeatedly clearly with distilled water
Wash 3 times, obtain standby biological clay, standby biological clay and distilled water are mixed to get the life that biological clay concentration is 10g/L
Thing foundry loam solution.
Embodiment 1
Sodium borohydride 50mg, nitrilotriacetic acid trisodium salt 200mg, revolution are added in the conical flask containing 1L biological clay solution
8h, the tetramethyl phosphonium chloride phosphorus for then adding 10mg continues to turn round 24h, sampling analysis polyoses content and nucleic acid content, the results are shown in Table
1。
Embodiment 2
Potassium borohydride 200mg, disodium ethylene diamine tetraacetate 80mg are added in the conical flask containing 1L biological clay solution,
24h is turned round, the tetrakis hydroxymetyl phosphonium sulfuric for then adding 40mg continues to turn round 1h, sampling analysis polyoses content and nucleic acid content, knot
Fruit is shown in Table 1.
Embodiment 3
Sodium borohydride 100mg, the sodium of diethylene triamine pentacetic acid (DTPA) five are added in the conical flask containing 1L biological clay solution
150mg, turns round 16h, and the THPC for then adding 20mg continues to turn round 16h, sampling analysis polyoses content and nucleic acid
Content, the results are shown in Table 1.
Embodiment 4
Potassium borohydride 150mg, tetrasodium ethylenediamine tetraacetate are added in the conical flask containing 1L biological clay solution
100mg, turns round 12h, and the tetramethyl phosphonium chloride phosphorus for then adding 30mg continues to turn round 16h, and sampling analysis polyoses content and nucleic acid contain
Amount, the results are shown in Table 1.
Embodiment 5
Sodium borohydride 120mg, nitrilotriacetic acid trisodium salt 90mg, revolution are added in the conical flask containing 1L biological clay solution
14h, the tetrakis hydroxymetyl phosphonium sulfuric of the tetramethyl phosphonium chloride phosphorus and 5mg that then add 15mg continues to turn round 16h, and sampling analysis polysaccharide contains
Amount and nucleic acid content, the results are shown in Table 1.
Embodiment 6
Potassium borohydride 70mg, the sodium of diethylene triamine pentacetic acid (DTPA) five are added in the conical flask containing 1L biological clay solution
160mg, turns round 20h, and the THPC of the tetrakis hydroxymetyl phosphonium sulfuric and 10mg that then add 15mg continues to turn round 14h,
Sampling analysis polyoses content and nucleic acid content, the results are shown in Table 1.
Embodiment 7
Biological clay disbonded test is carried out according to the method for embodiment 1, unlike, the consumption of sodium borohydride is 40mg,
It the results are shown in Table 1.
Embodiment 8
Biological clay disbonded test is carried out according to the method for embodiment 2, unlike, the consumption of potassium borohydride is 250mg,
It the results are shown in Table 1.
Embodiment 9
Biological clay disbonded test is carried out according to the method for embodiment 3, unlike, the sodium of diethylene triamine pentacetic acid (DTPA) five
Consumption is 60mg, the results are shown in Table 1.
Embodiment 10
Biological clay disbonded test is carried out according to the method for embodiment 4, unlike, the consumption of tetrasodium ethylenediamine tetraacetate
For 250mg, 1 the results are shown in Table.
Embodiment 11
Biological clay disbonded 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 disbonded 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 disbonded test is carried out according to the method for embodiment 1, unlike, sodium borohydride is not added with, be the results are shown in Table
1。
Comparative example 2
Biological clay disbonded test is carried out according to the method for embodiment 2, unlike, disodium ethylene diamine tetraacetate is not added with,
It the results are shown in Table 1.
Comparative example 3
Biological clay disbonded test is carried out according to the method for embodiment 3, unlike, THPC is not added with, is tied
Fruit is shown in Table 1.
Comparative example 4
Sodium borohydride 180mg, nitrilotriacetic acid trisodium salt 200mg are added in the conical flask containing 1L biological clay solution, is returned
Turn 20h, the cationic surfactant 1227 for then adding 30mg continues to turn round 24h, and sampling analysis polyoses content and nucleic acid contain
Amount, the results are shown in Table 1.
Comparative example 5
Added in the conical flask containing 1L biological clay solution sodium borohydride 50mg, nitrilotriacetic acid trisodium salt 200mg and
10mg tetramethyl phosphonium chloride phosphorus revolution 32h, sampling analysis polyoses content and nucleic acid content, the results are shown in Table 1.
Comparative example 6
10mg tetramethyl phosphonium chloride phosphorus is added in the conical flask containing 1L biological clay solution, 8h is turned round, then adds
Sodium borohydride 50mg, nitrilotriacetic acid trisodium salt 200mg continue to turn round 24h, sampling analysis polyoses content and nucleic acid content, the results are shown in Table
1。
Table 1
| Embodiment is numbered | Polyoses 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 subjected to field application test.Using raw in measurement system
The method of thing foundry loam amount evaluates biological clay stripping performance.The measure of slime content is according to industrial circulating cooling water water quality point
Analysis method standard GB/T/T14643.1-2009 is carried out.
Field application test condition：The internal circulating load 13000m of circulation3/ h, power system capacity 6500m3, cycles of concentration
3.0 ± 0.2, flow velocity 1.0m/s, 32 ± 1 DEG C of inlet temperature, 6 DEG C of the temperature difference.
Anti-incrustation corrosion inhibitor：1-hydroxy ethylidene-1,1-diphosphonic acid（HEDP）+ phosphonic acid butane -1,2,4- tricarboxylic acids（PBTCA）+ zinc salt+
Acrylic acid/2- methyl -2'- acrylamido propane sulfonic acid copolymers（AA/AMPS=7:Limiting Viscosity at 3,30 DEG C is
0.071dL/g）, valid density is respectively 4mg/L, 4mg/L, 2mg/L and 9mg/L.
Experiment moisturizing water quality is shown in Table 2, and Ca2+, total hardness and basicity is with CaCO3Meter, the assay method of each parameter is as follows：
Ca2+：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
The biological slime of circulating cooling water of the present invention is peeled off it can be seen from the result of above example and testing example
Method has good biological clay peeling effect.
In addition, respectively by embodiment 1-3 result and comparative example 1-6 results contrast can be seen that metallic boron hydrides,
Aminopolycanboxylic acid's salt and quaternary alkylphosphonium salt are added in order to play a role and three kinds of components are indispensable.Moreover, the B agent in comparative example 4
The consumption of embodiment 1,5 and 7 is all higher than using the usage amount of cationic surfactant 1227, and each component, but it is biological
Sludge stripping effect is not notable, illustrates to compare with other nonionic surfactants, quaternary alkylphosphonium salt and metallic boron hydrides and ammonia
There is preferably synergy between hydroxypolycarboxylates.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (11)
1. a kind of biological clay remover, it is characterised in that the biological clay remover includes A agent and B agent, the A agent is gold
Belong to boron hydride and aminopolycanboxylic acid's salt, the B agent is quaternary alkylphosphonium salt, and A agent and B agent are each independently preserved, wherein, the metal boron
The weight ratio of hydride, aminopolycanboxylic acid's salt and quaternary alkylphosphonium salt is 2-30:5-30:0.5-10.
2. biological clay remover according to claim 1, wherein, the metallic boron hydrides, aminopolycanboxylic acid's salt with
The weight ratio of quaternary alkylphosphonium salt is 5-20:8-20:1-4.
3. biological clay remover according to claim 1 or 2, wherein, the metallic boron hydrides be sodium borohydride and/
Or potassium borohydride；Aminopolycanboxylic acid's salt is selected from nitrilotriacetic acid trisodium salt, disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate
At least one of with the sodium of diethylene triamine pentacetic acid (DTPA) five；It is R that the quaternary alkylphosphonium salt, which is selected from formula,1R2R3R4PX and (R1R2R3R4P)2SO4At least one of compound, wherein R1、R2、R3Or R4The alkyl or carbon number for being 1-8 for carbon number are 1-8's
Hydroxyalkyl and R1、R2、R3And R4Identical or different, X is chlorine or bromine.
4. biological clay remover according to claim 1 or 2, wherein, the quaternary alkylphosphonium salt is tetramethyl phosphonium chloride phosphorus, four hydroxyls
At least one of methylsulfuric acid phosphorus and THPC.
5. a kind of method of biological clay in strip cycles cooling water system, it is characterised in that this method is included toward circulating cooling
The A agent in the biological clay remover in claim 1-4 described in any one is added in the recirculated cooling water of water system successively
With B agent.
6. method according to claim 5, wherein, the recirculated cooling water relative to 1L, the consumption of metallic boron hydrides is
20-300mg。
7. method according to claim 5, wherein, the recirculated cooling water relative to 1L, the consumption of metallic boron hydrides is
50-200mg。
8. method according to claim 5, wherein, the time interval for adding A agent and B agent is 5-30h.
9. method according to claim 5, wherein, the time interval for adding A agent and B agent is 8-24h.
10. the method according to any one in claim 5-9, wherein, the run time after B agent is added for 0.5-30h.
11. the method according to any one in claim 5-9, wherein, the run time after B agent is added for 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 |
| 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 |
| 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 |
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| US5786317A (en) * | 1996-11-22 | 1998-07-28 | Townsend; Clint E. | Stain removal compositions for carpets |
| CN1338436A (en) * | 2000-08-11 | 2002-03-06 | 中国石油化工股份有限公司 | Process for treating biological clay in circulating water system |
| CN1511791A (en) * | 2002-12-30 | 2004-07-14 | 中国石油化工股份有限公司北京燕山分 | Method for utiliznig sterilizing agent in circular cooling water |
| CN1754839A (en) * | 2004-09-29 | 2006-04-05 | 上海万森水处理有限公司 | Industrial cooling circulating water system cleaning agent |
| CN101024543A (en) * | 2007-02-05 | 2007-08-29 | 大连三达奥克化学有限公司 | High-efficiency soft-scale washing agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5786317A (en) * | 1996-11-22 | 1998-07-28 | Townsend; Clint E. | Stain removal compositions for carpets |
| CN1338436A (en) * | 2000-08-11 | 2002-03-06 | 中国石油化工股份有限公司 | Process for treating biological clay in circulating water system |
| CN1511791A (en) * | 2002-12-30 | 2004-07-14 | 中国石油化工股份有限公司北京燕山分 | Method for utiliznig sterilizing agent in circular cooling water |
| CN1754839A (en) * | 2004-09-29 | 2006-04-05 | 上海万森水处理有限公司 | Industrial cooling circulating water system cleaning agent |
| CN101024543A (en) * | 2007-02-05 | 2007-08-29 | 大连三达奥克化学有限公司 | High-efficiency soft-scale washing agent |
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