CN104629927B - One kind peels off cleansing composition and its application method - Google Patents
One kind peels off cleansing composition and its application method Download PDFInfo
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Abstract
The invention discloses one kind to peel off cleansing composition and its application method, wherein, said composition contains D limonenes, polyethylene glycol and Determination of Polyoxyethylene Non-ionic Surfactants, and the weight ratio of the D limonenes, the polyethylene glycol and the Determination of Polyoxyethylene Non-ionic Surfactants is 1：1‑3：0.15‑1.5.Both there is the efficiency of greasy filth cleaning using the stripping cleansing composition of the present invention, the efficiency with sludge stripping, applied to circulation, especially in the presence of the circulation of oil product leakage, cleaning performance is good, and cost is low, dosage is few, and it is excellent to peel off cleaning performance.
Description
Technical field
The present invention relates to a kind of recirculated water stripping cleansing composition and its application method.
Background technology
Water resource has turned into an important factor for restricting petroleum chemical enterprise's development, and water conservation is very urgent.Circulation is
One with water rich and influential family, at present, it is that recirculated water is most direct, maximally effective water-saving method to improve cycles of concentration.But if recirculated water
System leak material not only wastes substantial amounts of fresh water, and the dosage of water treatment agent, it is necessary to the displacement of substantial amounts of fresh water
Also roll up, cost increases substantially.
Oil leak is a kind of situation that petroleum chemical enterprise's circulation often occurs.Performance of the oil leak in recirculated water
For：When the oil content increase of system, second, bacterial number is significantly exceeded.Its endanger have it is following some：First, it is bacterial growth
Nutrition is provided, makes bacterium raised growth, the suspension and material in the bacterium and recirculated water of growth form biological clay, are deposited on
In heat transmission equipment, heat transfer effect is influenceed, causes corrosion；Second, leakage material cause bactericide to fail, material directly and chlorine
Reacted with non oxidizing bactericide, the effect of bactericide is influenceed, so that bacterium raised growth；Third, some materials, such as heavy oil
Leakage, is adhered on tube wall, cooling tower or heat transmission equipment, influences to conduct heat and cool down；Fourth, bacterium raised growth, to inhibition, resistance
Dirty agent has degradation, so as to influence the inhibition of system and scale inhibition effect.
At present, the method for solving the leakage of circulation oil product is mostly low cycles of concentration operation, large excretion and large complement, is added simultaneously
Peeling off cleaning agent reduces the various adverse effects that oil leak is brought to circulation and heat exchanger surface.Low cycles of concentration
Operation can waste a large amount of fresh waters, the oily substance remained in circulation, equally can give circulation and heat exchanger
Adverse effect is brought on surface, and circulation treatment effect cannot ensure.
Therefore, it is a kind of to be applied to oil leak circulation, have excellent stripping, cleaning and the stripping of dispersive property clear
Lotion is urgently developed.
The content of the invention
When solving the leakage of circulation oil product it is an object of the invention to overcome in the prior art water resource waste it is big and
The halfway weakness of cleaning performance, and the method revealed due to solving circulation oil product in the prior art is mostly low concentration
Multiple is run, first, substantial amounts of fresh water is wasted, second, the oily substance and biological clay of heat exchanger surface residual, can bring corruption
Lose, ineffective and microbial growth of conducting heat the defects of, there is provided one kind peels off cleansing composition and its application method.
The invention provides one kind peel off cleansing composition, wherein, said composition contain D- limonenes, polyethylene glycol and
Determination of Polyoxyethylene Non-ionic Surfactants, and the D- limonenes, the polyethylene glycol and the polyoxyethylene-type nonionic
The weight ratio of surfactant is 1：1-3：0.15-1.5.
Present invention also offers a kind of application method for peeling off cleansing composition, the application method is：By the stripping
Cleansing composition adds blowdown after circulation 12-48 hours in circulation, and mends with fresh water until the circulation
Turbidity value and add it is described peel off cleansing composition before turbidity value difference between ± 10%.
According to stripping cleansing composition provided by the invention and its application method, on the one hand, the inventors discovered that D- lemons
Though lemon alkene is not soluble in water, can be dissolved each other after surfactant is added with water with arbitrary proportion, it is possible thereby to apply in aqueous phase,
The greasy filth of clean cycle water system heat exchanger surface, the circulation that oil product leakage be present is can be applicable to, solve heat exchanger table
The problems such as corrosion and unfavorable heat transfer that face oil product is adhered to and brought；On the other hand, the present invention is non-by D- limonenes, polyoxyethylene-type
, can be with the foundry loam of loose heat exchanger surface together with ionic surface active agent compounds with polyethylene glycol, and it is taken away by current,
Solves the problems such as corrosion and scaling and microbial growth that biological clay is brought to circulation.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is 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 invention provides one kind peel off cleansing composition, wherein, said composition contain D- limonenes, polyethylene glycol and
Determination of Polyoxyethylene Non-ionic Surfactants, and the D- limonenes, the polyethylene glycol and the polyoxyethylene-type nonionic
The weight ratio of surfactant can be 1：1-3：0.15-1.5.
In the case of, according to the invention it is preferred to, the D- limonenes, the polyethylene glycol and the polyoxyethylene-type nonionic
The weight ratio of surfactant can be 1：0.75-2.5：0.25-1.
According to the present invention, the Determination of Polyoxyethylene Non-ionic Surfactants is formula（I）Shown long-chain fatty alcohol polyoxy
Vinethene and/or formula（II）Shown APES；
Formula（I）,Formula（II）,
Wherein, in formula（I）Middle R3Can be C12~C18 alkyl, polymerization degree n can be 8-40 integer, preferably 8-
35 integer；It is highly preferred that the long-chain fatty alcohol APEO can be ethoxylated dodecyl alcohol（n=9）And/or whale
Ceryl alcohol APEO（n=13）.
Wherein, in formula（II）In, R4Can be with C8~C12 alkyl, degree of polymerization m can be 3~30 integer；Preferably, R4
Can be C8, C9 or C12 alkyl, degree of polymerization m can be 9~12 integer, it is highly preferred that the APES
OPEO can be selected from（m=9）, NPE（m=9）With dodecyl phenol polyethenoxy ether（m=
9）In one or more.
According to the present invention, the polyethylene glycol can be selected from one kind in PEG-400, PEG-600 and PEG-800 or more
Kind.
It is described to peel off the form that cleansing composition is the aqueous solution, and D- lemons described in the aqueous solution according to the present invention
The total concentration of alkene, the polyethylene glycol and the Determination of Polyoxyethylene Non-ionic Surfactants can be 25-75 weight %, preferably
For 30-55 weight %.
Present invention also offers a kind of application method for peeling off cleansing composition, the application method is：By the stripping
Cleansing composition adds blowdown after circulation 12-48 hours in circulation, and mends with fresh water until the circulation
Turbidity value and add it is described peel off cleansing composition before turbidity value difference between ± 10%.
According to the present invention, the dosage for peeling off cleansing composition can be 10-50mg/L.It is described under preferable case
The dosage for peeling off cleansing composition can be 10-30mg/L.
The present invention will be described in detail by way of examples below.
In following examples and comparative example, stripping cleansing composition progress performance is prepared to the method using the present invention and is commented
Certain Circulating Water Field used by valency experiment（Hereinafter referred to as " six follow "）System outline be shown in Table 1.
Table 1
| Project | Numerical value |
| Cycles of concentration | N≥3 |
| Possess water m3 | 6000 |
| Quantity of circulating water m3/h | 12000 |
| Water amount of blowdown m3/h | 13.3 |
| Other drainage amount m3/h | 382 |
| The temperature difference DEG C | 5 |
| The main material of equipment | Carbon steel, copper |
Six follow and oil leak be present, and six, which follow water quality situation, is shown in Table 2.
Table 2
| Project | Scope | Average value |
| PH value | 8.7~8.4 | 8.5 |
| Hardness/(mg/L) | 1628~1342 | 1469 |
| Ca2+/(mg/L) | 1135~862 | 1012 |
| Total alkalinity/(mg/L) | 324~178 | 253 |
| Total iron/(mg/L) | 1.7~0.6 | 1.0 |
| Zn2+/(mg/L) | 3.2~1.6 | 2.5 |
| Total phosphorus/(mg/L) | 6.5~5.7 | 6.2 |
| Chlorine residue/(mg/L) | 1.0~0.1 | 0.4 |
| COD/(mg/L) | 135~109 | 127 |
| Turbidity/(mg/L) | 25.8~13.7 | 18.4 |
| Heterotroph/(individual/mL) | 6.0×104~1.2 × 105 | 8.1×104 |
| Cycles of concentration | 6.3~2.8 | 4.1 |
In the present invention, reference《Boiler feed water and cooling water quality analysis method national standard》GB/T12151-1989 points
Light photometry determines turbidity value；
Reference《Industrial circulating cooling water water analysis method》GB/T14643.1-1993 standard plate counts method measure is different
Bacteria content.
The laboratory evaluation method of sludge stripping performance uses Extracellular polymers method.
Extracellular polymers are the important components of activated sludge, and its main organic principle is carbohydrate, nucleic acid and protein.
After adhesive mud remover acts on activated sludge, the organic principle such as polysaccharide and nucleic acid is scattered in recirculated cooling water, according to more
The organic component content such as sugar and nucleic acid is evaluated the peeling effect of adhesive mud remover.Concrete operation step is as follows：
（1）Activated sludge be placed on centrifuge with 7000r/min centrifuge 5min, abandoning supernatant, with distilled water repeatedly from
The heart cleans 3 times, obtains standby foundry loam.
（2）The above-mentioned foundry loams of 10g/L, various concentrations adhesive mud remover are added in conical flask, with distilled water diluting, is being turned round
With 150r/min 27 DEG C of revolution 24h of rotating speed constant temperature on instrument.
（3）Above-mentioned mixed liquor filtering is taken out, determines polysaccharide and nucleic acid content in filtrate.Measurement of the polysaccharide content uses anthrone
Sulfuric acid process, the measure of nucleic acid content use fixing phosphorus method.
D- limonenes used are purchased from Ji'an City Tian Yuan medicinal oils factory in following examples and comparative example, and polyethylene glycol is purchased from
Jinan City Licheng District all Hue work business departments, Determination of Polyoxyethylene Non-ionic Surfactants and myristyl benzyl dimethyl chlorine
Change ammonium and be purchased from Luoyang imperial fine chemistry industry head factory by force.
Embodiment 1
Prepare and peel off cleansing composition Q1, wherein, the stripping cleansing composition contains 20 weight % D- limonenes,
10 weight % NPE（m=9）, 20 weight % PEG-400 and 50 weight % deionized water；
The stripping cleansing composition 30mg/L of above-mentioned preparation is added in circulation, is recycled to blowdown after 24h, and
Mend with fresh water until the turbidity value of the circulation and the turbidity value difference before the addition stripping cleansing composition
Between ± 10%；
The turbidity and heterotroph numerical value tested before and after the stripping in the stripping cleansing composition Q1 clean cycle water systems,
It the results are shown in Table 3.
Embodiment 2
Prepare and peel off cleansing composition Q2, wherein, the stripping cleansing composition contains 10 weight % D- limonenes,
15 weight % OPEO（m=9）, 25 weight % PEG-600 and 50 weight % deionized water；
The stripping cleansing composition 30mg/L of above-mentioned preparation is added in circulation, is recycled to blowdown after 24h, and
Mend with fresh water until the turbidity value of the circulation and the turbidity value difference before the addition stripping cleansing composition
Between ± 10%；
The turbidity and heterotroph numerical value tested before and after the stripping in the stripping cleansing composition Q2 clean cycle water systems,
It the results are shown in Table 3.
Embodiment 3
Prepare and peel off cleansing composition Q3, wherein, the stripping cleansing composition contains 30 weight % D- limonenes, and 5
Weight % dodecyl phenol polyethenoxy ether（m=9）, 15 weight % PEG-800 and 50 weight % deionized water；
The stripping cleansing composition 30mg/L of above-mentioned preparation is added in circulation, is recycled to blowdown after 24h, and
Mend with fresh water until the turbidity value of the circulation and the turbidity value difference before the addition stripping cleansing composition
Between ± 10%；
The turbidity and heterotroph numerical value tested before and after the stripping in the stripping cleansing composition Q3 clean cycle water systems,
It the results are shown in Table 3.
Embodiment 4
Prepare and peel off cleansing composition Q4, wherein, the stripping cleansing composition contains 25 weight % D- limonenes,
15 weight % ethoxylated dodecyl alcohol（n=9）, 10 weight % PEG-400 and 50 weight % deionized water；
The stripping cleansing composition 30mg/L of above-mentioned preparation is added in circulation, is recycled to blowdown after 24h, and
Mend with fresh water until the turbidity value of the circulation and the turbidity value difference before the addition stripping cleansing composition
Between ± 10%；
The turbidity and heterotroph numerical value tested before and after the stripping in the stripping cleansing composition Q4 clean cycle water systems,
It the results are shown in Table 3.
Embodiment 5
Prepare and peel off cleansing composition Q5, wherein, the stripping cleansing composition contains 15 weight % D- limonenes, and 5
Weight % cetanol APEO（n=13）, 30 weight % PEG-600 and 50 weight % deionized water；
The stripping cleansing composition 30mg/L of above-mentioned preparation is added in circulation, is recycled to blowdown after 24h, and
Mend with fresh water until the turbidity value of the circulation and the turbidity value difference before the addition stripping cleansing composition
Between ± 10%；
The turbidity and heterotroph numerical value tested before and after the stripping in the stripping cleansing composition Q5 clean cycle water systems,
It the results are shown in Table 3.
Embodiment 6
Prepare and peel off cleansing composition Q6, wherein, the stripping cleansing composition contains 20 weight % D- limonenes,
10 weight % dodecyl phenol polyethenoxy ether（m=9）, 20 weight % PEG-800 and 50 weight % deionized water；
The stripping cleansing composition 10mg/L of above-mentioned preparation is added in circulation, is recycled to blowdown after 24h, and
Mend with fresh water until the turbidity value of the circulation and the turbidity value difference before the addition stripping cleansing composition
Between ± 10%；
The turbidity and heterotroph numerical value tested before and after the stripping in the stripping cleansing composition Q6 clean cycle water systems,
It the results are shown in Table 3.
Embodiment 7
Prepare and peel off cleansing composition Q7, wherein, the stripping cleansing composition contains 20 weight % D- limonenes,
10 weight % NPE（m=9）, 20 weight % PEG-400 and 50 weight % deionized water；
The stripping cleansing composition 50mg/L of above-mentioned preparation is added in circulation, is recycled to blowdown after 24h, and
Mend with fresh water until the turbidity value of the circulation and the turbidity value difference before the addition stripping cleansing composition
Between ± 10%；
The turbidity and heterotroph numerical value tested before and after the stripping in the stripping cleansing composition Q1 clean cycle water systems,
It the results are shown in Table 3.
Embodiment 8
Prepare and peel off cleansing composition Q8, wherein, the stripping cleansing composition contains 20 weight % D- limonenes,
10 weight % OPEO（m=9）, 20 weight % PEG-600 and 50 weight % deionized water；
The stripping cleansing composition 30mg/L of above-mentioned preparation is added in circulation, is recycled to blowdown after 12h, and
Mend with fresh water until the turbidity value of the circulation and the turbidity value difference before the addition stripping cleansing composition
Between ± 10%；
The turbidity and heterotroph numerical value tested before and after the stripping in the stripping cleansing composition Q8 clean cycle water systems,
It the results are shown in Table 3.
Embodiment 9
Prepare and peel off cleansing composition Q9, wherein, the stripping cleansing composition contains 20 weight % D- limonenes,
10 weight % dodecyl phenol polyethenoxy ether（m=9）, 20 weight % PEG-800 and 50 weight % deionized water；
The stripping cleansing composition 30mg/L of above-mentioned preparation is added in circulation, is recycled to blowdown after 48h, and
Mend with fresh water until the turbidity value of the circulation and the turbidity value difference before the addition stripping cleansing composition
Between ± 10%；
The turbidity and heterotroph numerical value tested before and after the stripping in the stripping cleansing composition Q9 clean cycle water systems,
It the results are shown in Table 3.
Comparative example 1
Using compound method and application method same as Example 1, difference is, stripping cleaning agent combination
Thing contains 5 weight % D- limonenes, 20 weight % NPE（n=10）, 35 weight % PEG-400 and 40 weights
Measure % deionized water；
The turbidity and heterotrophism bacterium number tested before and after the stripping in the stripping cleansing composition DQ1 clean cycle water systems
Value, the results are shown in Table 3.
Comparative example 2
Using compound method and application method same as Example 1, difference is, stripping cleaning agent combination
Thing contains 40 weight % D- limonenes, 15 weight % NPE（n=10）, 5 weight % PEG-400 and 40 weights
Measure % deionized water；
The turbidity and heterotrophism bacterium number tested before and after the stripping in the stripping cleansing composition DQ2 clean cycle water systems
Value, the results are shown in Table 3.
Comparative example 3
Using application method same as Example 1, difference is, adds 100mg/L's in circulation
Myristyl benzyl dimethyl ammonium chloride（1427）.
Test the greasy filth cleansing composition（Myristyl benzyl dimethyl ammonium chloride, i.e., 1427）Clean cycle water system
In greasy filth before and after oil content and heterotroph numerical value, the results are shown in Table 3.
Table 3
The stripping cleansing composition using the present invention is can be seen that from above example 1-9 and comparative example 1-3 data
Applied in the circulation that oil product leakage be present, turbidity value increase, peculiar bacterium number also increases, and shows the stripping using the present invention
The excellent effect cleaned from cleansing composition to the greasy filth in circulation.Therefore, using the stripping cleaning agent of the present invention
Composition is applied to the circulation that oil product leakage be present, the excellent stripping cleaning used in comparative example of greasy filth cleaning performance
Agent composition.
To the embodiment 1-5 stripping cleansing compositions prepared and the foundry loam of the stripping cleaning agent used in comparative example 3
Stripping performance is evaluated, and the concentration of stripping cleansing composition prepared by embodiment 1-5 is 30mg/L, is used in comparative example 3
1427 concentration that adds be 100mg/L, as a result as shown in table 4.
Table 4
| Embodiment | Polyoses content/(mg/L) | Nucleic acid content/(mg/L) |
| Embodiment 1（Peel off cleansing composition Q1） | 23.64 | 3.982 |
| Embodiment 2（Peel off cleansing composition Q2） | 28.51 | 4.820 |
| Embodiment 3（Peel off cleansing composition Q3） | 19.74 | 3.338 |
| Embodiment 4（Peel off cleansing composition Q4） | 17.85 | 3.066 |
| Embodiment 5（Peel off cleansing composition Q5） | 35.44 | 6.008 |
| Comparative example 3（Peel off cleaning agent 1427） | 13.08 | 2.161 |
It is even clear in the stripping prepared using embodiment 1-5 it was found from the data of above example 1-5 and comparative example 3
The concentration of detergent composition is 30mg/L, in the case of the use of the concentration of stripping cleaning agent 1427 in comparative example 3 being 100mg/L,
That is the amount of the stripping cleaning agent used in comparative example 3 is more than this feelings of amount that cleansing composition is peeled off in embodiment 1-5
Under condition, using the present invention strippings cleansing composition be applied to exist oil product reveal circulation in, polyoses content with
And the value of nucleic acid content is still better than the polyoses content for peeling off cleansing composition and nucleic acid content used in comparative example 3
Value, show to peel off excellent effect of the cleansing composition to the stripping in circulation using the present invention.
Therefore, using the stripping cleansing composition of the present invention, both with excellent greasy filth cleaning performance, have again preferable
Sludge stripping performance.
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 (10)
1. one kind peels off cleansing composition, it is characterised in that said composition contains D- limonenes, polyethylene glycol and polyoxyethylene
Type nonionic surfactant, and the D- limonenes, the polyethylene glycol and the polyoxyethylene-type non-ionic surface active
The weight ratio of agent is 1：1-3：0.15-1.5,
Wherein, it is described to peel off the form that cleansing composition is the aqueous solution, and D- limonenes described in the aqueous solution, the poly- second
The total concentration of glycol and the Determination of Polyoxyethylene Non-ionic Surfactants is 25-75 weight %.
2. composition according to claim 1, wherein, the D- limonenes, the polyethylene glycol and the polyoxyethylene
The weight ratio of type nonionic surfactant is 1：1-2.5：0.25-1.
3. composition according to claim 1 or 2, wherein, the Determination of Polyoxyethylene Non-ionic Surfactants is formula (I)
APES shown in shown long-chain fatty alcohol APEO and/or formula (II)；
Wherein, R3For C12~C18 alkyl, n is 8-40 integer；R4For C8~C12 alkyl, m is 3~30 integer.
4. composition according to claim 3, wherein, n is 8-35 integer.
5. composition according to claim 3, wherein, R4For C8, C9 or C12 alkyl, m is 9~12 integer.
6. composition according to claim 1 or 2, wherein, the polyethylene glycol is selected from PEG-400, PEG-600 and PEG-
One or more in 800.
7. composition according to claim 1, wherein, D- limonenes described in the aqueous solution, the polyethylene glycol and institute
The total concentration for stating Determination of Polyoxyethylene Non-ionic Surfactants is 30-55 weight %.
8. the application method of the composition according to any one in claim 1-7, the application method are：By the stripping
Cleansing composition adds blowdown after circulation 12-48 hours in circulation, and mends with fresh water until the circulation
Turbidity value and add it is described peel off cleansing composition before turbidity value difference between ± 10%.
9. application method according to claim 8, wherein, the dosage for peeling off cleansing composition is 10-50mg/L.
10. application method according to claim 9, wherein, the dosage for peeling off cleansing composition is 10-30mg/
L。
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| CN109722673B (en) * | 2017-10-31 | 2021-03-12 | 中国石油化工股份有限公司 | Cleaning agent, cleaning agent composition, application thereof and method for treating circulating water system with leaked oil |
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| CN1789159A (en) * | 2005-12-05 | 2006-06-21 | 赵清顺 | Sterilization inhibitor for circulated cooling water treatment |
| CN102476873A (en) * | 2010-11-24 | 2012-05-30 | 中国石油化工股份有限公司 | Method for treating circulating water having light oil leaked therein |
| CN102786163A (en) * | 2011-05-18 | 2012-11-21 | 中国石油化工股份有限公司 | Circulating water processing method |
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2013
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1789159A (en) * | 2005-12-05 | 2006-06-21 | 赵清顺 | Sterilization inhibitor for circulated cooling water treatment |
| CN102476873A (en) * | 2010-11-24 | 2012-05-30 | 中国石油化工股份有限公司 | Method for treating circulating water having light oil leaked therein |
| CN102786163A (en) * | 2011-05-18 | 2012-11-21 | 中国石油化工股份有限公司 | Circulating water processing method |
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