CN105623866A - Peeling cleaning agent composition and use method thereof - Google Patents
Peeling cleaning agent composition and use method thereof Download PDFInfo
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- CN105623866A CN105623866A CN201410610785.4A CN201410610785A CN105623866A CN 105623866 A CN105623866 A CN 105623866A CN 201410610785 A CN201410610785 A CN 201410610785A CN 105623866 A CN105623866 A CN 105623866A
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Abstract
The present invention discloses a peeling cleaning agent composition and a use method thereof, the peeling cleaning agent composition contains D-limonene, polyethylene glycol and an anionic surfactant, the weight ratio of D-limonene to polyethylene glycol to anionic surfactant is 1: 0.25-3: 0.1-1.5, and the anionic surfactant is a fatty alcohol polyoxyethylene phosphonate. The peeling cleaning agent composition has both oil sludge cleaning effect and sticky sludge pilling effect, can be used in circulating water systems, especially in circulating water systems with leaked oil, and is good in cleaning effect, low in cost, less in dosage and excellent in pilling cleaning performance.
Description
Technical field
The present invention relates to a kind of recirculated water and peel off cleansing composition and using method thereof.
Background technology
Water resource has become the key factor of restriction petroleum chemical enterprise development, and water conservation is very urgent. Circulation is one and uses water rich and influential family, and at present, improving cycles of concentration is recirculated water water-saving method the most direct, maximally effective. But, if circulation leaked substance, it is necessary to replacing with substantial amounts of fresh water, not only waste substantial amounts of fresh water, and the consumption of water treatment agent also rolls up, cost would increase substantially.
Oil leak is a kind of situation that petroleum chemical enterprise's circulation often occurs. Oil leak in recirculated water show themselves in that one be system oil content increase, two is that bacterial number exceeds standard significantly. Its harm have following some: one is provide nutrition for bacterial growth, makes antibacterial raised growth, and float in the antibacterial of growth and recirculated water and material form biological clay, are deposited in heat transmission equipment, affect heat transfer effect, cause corrosion; Two is that the material of leakage causes that antibacterial lost efficacy, and material directly reacts with chlorine and non oxidizing bactericide, affects the effect of antibacterial, so that antibacterial raised growth; Three is some material, such as heavy oil spill, adheres on tube wall, cooling tower or heat transmission equipment, impact heat transfer and cooling; Four is antibacterial raised growth, and inhibition, antisludging agent are had Degradation, thus the inhibition of influential system and scale inhibition effect.
At present, the method solving the leakage of circulation oil product mostly is the operation of low cycles of concentration, large excretion and large complement, adds simultaneously and peels off the various adverse effects that abluent reduction oil leak brings to circulation and heat exchanger surface. Low cycles of concentration operation can waste a large amount of fresh water, the oily substance of residual in circulation, brings adverse effect, circulation treatment effect to can not get ensureing can to equally circulation and heat exchanger surface.
Therefore, a kind of suitable in oil leak circulation, the stripping abluent with excellent stripping, cleaning and dispersive property is urgently developed.
Summary of the invention
It is an object of the invention to overcome water resource waste when solving the leakage of circulation oil product in prior art big and the halfway weakness of cleaning performance, and the method owing to solving the leakage of circulation oil product in prior art mostly is low cycles of concentration and runs, one is waste substantial amounts of fresh water, two is oily substance and the biological clay of heat exchanger surface residual, the defects such as the burn into ineffective and microbial growth of heat transfer can be brought, it is provided that a kind of peel off cleansing composition and using method thereof.
The invention provides a kind of stripping cleansing composition, wherein, said composition contains D-limonene, Polyethylene Glycol and anion surfactant, and the weight ratio of described D-limonene, described Polyethylene Glycol and described anion surfactant is 1:0.25-3:0.1-1.5, described anion surfactant is aliphatic alcohol polyoxyvinethene phosphate salt anionic surfactant.
Present invention also offers a kind of using method peeling off cleansing composition, this using method is: described stripping cleansing composition adds in circulation blowdown after circulation 12-48 hour, and mends with fresh water until the difference of turbidity value before the turbidity value of this circulation and the described stripping cleansing composition of addition is between �� 10%.
According to stripping cleansing composition provided by the invention and using method thereof, on the one hand, though the inventors discovered that D-limonene is water insoluble, but can dissolve each other with arbitrary proportion with water after adding anion surfactant, thus can be applied in aqueous phase, the greasy filth of clean cycle water system heat exchanger surface, is especially applicable in and there is the circulation that oil product is revealed, and solves heat exchanger surface oil product and adheres to and the corrosion that brings and the problem such as unfavorable of conducting heat; On the other hand, the present invention is by together with composite with Polyethylene Glycol to D-limonene, aliphatic alcohol polyoxyvinethene phosphate salt anionic surfactant, can be loosened the foundry loam of heat exchanger surface, and make it be taken away by current, solve the problems such as corrosion and scaling and microbial growth that biological clay brings to circulation.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the specific embodiment of the present invention is described in detail. It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
The invention provides a kind of stripping cleansing composition, wherein, said composition contains D-limonene, Polyethylene Glycol and anion surfactant, and the weight ratio of described D-limonene, described Polyethylene Glycol and described anion surfactant can be 1:0.25-3:0.1-1.5, described anion surfactant is aliphatic alcohol polyoxyvinethene phosphate salt anionic surfactant.
According to the invention it is preferred in situation, the weight ratio of described D-limonene, described Polyethylene Glycol and described aliphatic alcohol polyoxyvinethene phosphate salt anionic surfactant can be 1:0.75-2.5:0.25-1.
According to the present invention, described aliphatic alcohol polyoxyvinethene phosphate salt anionic surfactant selected from structural formula is: RO (C2H4O)mPO3 2-(M+)2, wherein, R is C12��C13Alkyl, the numerical value of degree of polymerization m is 2��3, it is preferable that degree of polymerization m is 2 or 3, M+For H+��Na+��K+Or organoammonium ions;
Preferably, described aliphatic alcohol polyoxyvinethene phosphate salt anionic surfactant is alkylpolyoxyethylene phosphate ester and/or Sodium Trideceth sodium phosphate, wherein, and degree of polymerization m=2.
According to the present invention, described Polyethylene Glycol can be selected from one or more in PEG-400, PEG-600 and PEG-800.
According to the present invention, described stripping cleansing composition is the form of aqueous solution, and the total concentration of D-limonene described in this aqueous solution, described Polyethylene Glycol and described aliphatic alcohol polyoxyvinethene phosphate salt anionic surfactant can be 25-75 weight %, it is preferred to 30-55 weight %.
Present invention also offers a kind of using method peeling off cleansing composition, this using method is: described stripping cleansing composition adds in circulation blowdown after circulation 12-48 hour, and mends with fresh water until the turbidity value difference before the turbidity value of this circulation and the described stripping cleansing composition of addition is between �� 10%.
According to the present invention, the consumption of described stripping cleansing composition can be 10mg/L-50mg/L. Under preferable case, the consumption of described stripping cleansing composition can be 10mg/L-30mg/L.
Hereinafter will be described the present invention by embodiment.
In following example and comparative example, cleansing composition is peeled off in the method preparation adopting the present invention and carries out the system outline of certain Circulating Water Field (hereinafter referred to as " six follow ") that benchmark test adopts in Table 1.
Table 1
| Project | Numerical value |
| Cycles of concentration | N��3 |
| Possess water yield 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 there is oil leak, and six follow water quality situation in Table 2.
Table 2
| Project | Scope | Meansigma methods |
| 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 ferrum/(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 |
| Heterotrophic bacteria/(individual/mL) | 6.0��104��1.2 �� 105 | 8.1��104 |
| Cycles of concentration | 6.3��2.8 | 4.1 |
In the present invention, with reference to " boiler feed water and cooling water quality analyze method national standard " GB/T12151-1989 spectrophotometry turbidity value;
In the present invention, heterotrophic bacteria content is measured with reference to " industrial circulating cooling water water analysis method " GB/T14643.1-1993 SPC method.
In the present invention, the laboratory evaluation method of sludge stripping performance adopts Extracellular polymers method.
In the present invention, Extracellular polymers is the important component part of activated sludge, and its predominantly organic composition is saccharide, 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 the organic component content such as polysaccharide and nucleic acid, the peeling effect of adhesive mud remover is evaluated. Concrete operation step is as follows:
(1) activated sludge is placed on centrifuge with the centrifugal 5min of 7000r/min, abandoning supernatant, with distilled water eccentric cleaning 3 times repeatedly, obtains standby foundry loam.
(2) in conical flask, add the above-mentioned foundry loam of 10g/L, variable concentrations adhesive mud remover, with distilled water diluting, free gyroscope turns round 24h with the rotating speed constant temperature 27 DEG C of 150r/min.
(3) take out above-mentioned mixed liquor to filter, measure polysaccharide 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.
D-limonene used in following example and comparative example is purchased from Ji'an City Tian Yuan medicinal oil factory, Polyethylene Glycol is purchased from Licheng District, Jinan City all Hue works business department, and described aliphatic alcohol polyoxyvinethene phosphate salt anionic surfactant and myristyl benzyl dimethyl ammonium chloride are all purchased from Luoyang dragon fine chemistry industry head factory by force.
Embodiment 1
Cleansing composition Q1 is peeled off in preparation, and wherein, this stripping cleansing composition contains the D-limonene of 20 weight %, the alkylpolyoxyethylene phosphate ester (m=2) of 10 weight %, the deionized water of PEG-400 and the 50 weight % of 20 weight %;
The stripping cleansing composition 30mg/L of above-mentioned preparation is added in circulation, circulate to blowdown after 24h, and mend with fresh water until the turbidity value difference before the turbidity value of this circulation and the described stripping cleansing composition of addition is between �� 10%;
Testing the turbidity peeling off front and back in this stripping cleansing composition Q1 clean cycle water system and heterotrophic bacteria numerical value, result is in Table 3.
Embodiment 2
Cleansing composition Q2 is peeled off in preparation, and wherein, this stripping cleansing composition contains the D-limonene of 10 weight %, the alkylpolyoxyethylene phosphate ester (m=2) of 15 weight %, the deionized water of PEG-600 and the 50 weight % of 25 weight %;
The stripping cleansing composition 30mg/L of above-mentioned preparation is added in circulation, circulate to blowdown after 24h, and mend with fresh water until the turbidity value difference before the turbidity value of this circulation and the described stripping cleansing composition of addition is between �� 10%;
Testing the turbidity peeling off front and back in this stripping cleansing composition Q2 clean cycle water system and heterotrophic bacteria numerical value, result is in Table 3.
Embodiment 3
Cleansing composition Q3 is peeled off in preparation, and wherein, this stripping cleansing composition contains the D-limonene of 30 weight %, the alkylpolyoxyethylene phosphate ester (m=2) of 5 weight %, the deionized water of PEG-800 and the 50 weight % of 15 weight %;
The stripping cleansing composition 30mg/L of above-mentioned preparation is added in circulation, circulate to blowdown after 24h, and mend with fresh water until the turbidity value difference before the turbidity value of this circulation and the described stripping cleansing composition of addition is between �� 10%;
Testing the turbidity peeling off front and back in this stripping cleansing composition Q3 clean cycle water system and heterotrophic bacteria numerical value, result is in Table 3.
Embodiment 4
Cleansing composition Q4 is peeled off in preparation, and wherein, this stripping cleansing composition contains the D-limonene of 25 weight %, the alkylpolyoxyethylene phosphate ester (m=2) of 15 weight %, the deionized water of PEG-400 and the 50 weight % of 10 weight %;
The stripping cleansing composition 30mg/L of above-mentioned preparation is added in circulation, circulate to blowdown after 24h, and mend with fresh water until the turbidity value difference before the turbidity value of this circulation and the described stripping cleansing composition of addition is between �� 10%;
Testing the turbidity peeling off front and back in this stripping cleansing composition Q4 clean cycle water system and heterotrophic bacteria numerical value, result is in Table 3.
Embodiment 5
Cleansing composition Q5 is peeled off in preparation, and wherein, this stripping cleansing composition contains the D-limonene of 15 weight %, the alkylpolyoxyethylene phosphate ester (m=2) of 5 weight %, the deionized water of PEG-600 and the 50 weight % of 30 weight %;
The stripping cleansing composition 30mg/L of above-mentioned preparation is added in circulation, circulate to blowdown after 24h, and mend with fresh water until the turbidity value difference before the turbidity value of this circulation and the described stripping cleansing composition of addition is between �� 10%;
Testing the turbidity peeling off front and back in this stripping cleansing composition Q5 clean cycle water system and heterotrophic bacteria numerical value, result is in Table 3.
Embodiment 6
Cleansing composition Q6 is peeled off in preparation, and wherein, this stripping cleansing composition contains the D-limonene of 20 weight %, the Sodium Trideceth sodium phosphate (m=2) of 10 weight %, the deionized water of PEG-800 and the 50 weight % of 20 weight %;
The stripping cleansing composition 10mg/L of above-mentioned preparation is added in circulation, circulate to blowdown after 24h, and mend with fresh water until the turbidity value difference before the turbidity value of this circulation and the described stripping cleansing composition of addition is between �� 10%;
Testing the turbidity peeling off front and back in this stripping cleansing composition Q6 clean cycle water system and heterotrophic bacteria numerical value, result is in Table 3.
Embodiment 7
Cleansing composition Q7 is peeled off in preparation, and wherein, this stripping cleansing composition contains the D-limonene of 20 weight %, the Sodium Trideceth sodium phosphate (m=2) of 10 weight %, the deionized water of PEG-400 and the 50 weight % of 20 weight %;
The stripping cleansing composition 50mg/L of above-mentioned preparation is added in circulation, circulate to blowdown after 24h, and mend with fresh water until the turbidity value difference before the turbidity value of this circulation and the described stripping cleansing composition of addition is between �� 10%;
Testing the turbidity peeling off front and back in this stripping cleansing composition Q1 clean cycle water system and heterotrophic bacteria numerical value, result is in Table 3.
Embodiment 8
Cleansing composition Q8 is peeled off in preparation, wherein, this stripping cleansing composition contains the D-limonene of 15 weight %, the Sodium Trideceth sodium phosphate (m=2) of 7.5 weight %, the deionized water of PEG-600 and the 62.5 weight % of 15 weight %;
The stripping cleansing composition 40mg/L of above-mentioned preparation is added in circulation, circulate to blowdown after 12h, and mend with fresh water until the turbidity value difference before the turbidity value of this circulation and the described stripping cleansing composition of addition is between �� 10%;
Testing the turbidity peeling off front and back in this stripping cleansing composition Q8 clean cycle water system and heterotrophic bacteria numerical value, result is in Table 3.
Embodiment 9
Cleansing composition Q9 is peeled off in preparation, wherein, this stripping cleansing composition contains the D-limonene of 30 weight %, the Sodium Trideceth sodium phosphate (m=2) of 15 weight %, the deionized water of PEG-400 and the 25 weight % of PEG-800 and the 15 weight % of 15 weight %;
The stripping cleansing composition 20mg/L of above-mentioned preparation is added in circulation, circulate to blowdown after 48h, and mend with fresh water until the turbidity value difference before the turbidity value of this circulation and the described stripping cleansing composition of addition is between �� 10%;
Testing the turbidity peeling off front and back in this stripping cleansing composition Q9 clean cycle water system and heterotrophic bacteria numerical value, result is in Table 3.
Comparative example 1
Adopt the compound method identical with embodiment 1 and using method, it is different in that, this stripping cleansing composition contains the D-limonene of 5 weight %, the alkylpolyoxyethylene phosphate ester (m=2) of 20 weight %, the deionized water of PEG-400 and the 40 weight % of 35 weight %;
Testing the turbidity peeling off front and back in this stripping cleansing composition DQ1 clean cycle water system and heterotrophic bacteria numerical value, result is in Table 3.
Comparative example 2
Adopt the compound method identical with embodiment 1 and using method, it is different in that, this stripping cleansing composition contains the D-limonene of 40 weight %, the alkylpolyoxyethylene phosphate ester (m=2) of 15 weight %, the deionized water of PEG-400 and the 40 weight % of 5 weight %;
Testing the turbidity peeling off front and back in this stripping cleansing composition DQ2 clean cycle water system and heterotrophic bacteria numerical value, result is in Table 3.
Comparative example 3
Adopt the using method identical with embodiment 1, be different in that, circulation adds the myristyl benzyl dimethyl ammonium chloride (1427) of 100mg/L.
Testing the oil content before and after the greasy filth in this greasy filth cleansing composition (myristyl benzyl dimethyl ammonium chloride, namely 1427) clean cycle water system and heterotrophic bacteria numerical value, result is in Table 3.
Table 3
Can be seen that from the data of above example 1-9 and comparative example 1-3, the cleansing composition of peeling off adopting the present invention is applied to exist in the circulation that oil product is revealed, turbidity value substantially increases relative to comparative example 1-3, difference bacterium number also substantially increases relative to comparative example 1-3, it was shown that adopt the present invention's to peel off the excellent effect that the greasy filth in circulation is cleaned by cleansing composition. Therefore, the cleansing composition of peeling off of the present invention is adopted to be applied to there is the circulation that oil product is revealed, the excellent stripping cleansing composition used in comparative example 1-3 of greasy filth cleaning performance.
The sludge stripping performance peeling off abluent used in cleansing composition and comparative example 3 of peeling off prepared by embodiment 1-5 is evaluated, the concentration peeling off cleansing composition prepared by embodiment 1-5 is 30mg/L, the concentration that adds of 1427 used in comparative example 3 is 100mg/L, and result is as shown in table 4.
Table 4
| Embodiment | Polyoses content/(mg/L) | Nucleic acid content/(mg/L) |
| Embodiment 1 (peeling off cleansing composition Q1) | 22.69 | 3.823 |
| Embodiment 2 (peeling off cleansing composition Q2) | 27.37 | 4.627 |
| Embodiment 3 (peeling off cleansing composition Q3) | 18.95 | 3.204 |
| Embodiment 4 (peeling off cleansing composition Q4) | 17.14 | 2.943 |
| Embodiment 5 (peeling off cleansing composition Q5) | 34.02 | 5.768 |
| Comparative example 3 (peeling off abluent 1427) | 12.56 | 2.075 |
Data from above example 1-5 and comparative example 3, even if being 30mg/L using the embodiment 1-5 concentration peeling off cleansing composition prepared, using stripping abluent 1427 concentration in comparative example 3 is in 100mg/L situation, that is, the amount peeling off abluent used in comparative example 3 is more than peeling off the amount of cleansing composition in embodiment 1-5 in this case, the cleansing composition of peeling off adopting the present invention is applied to exist in the circulation that oil product is revealed, the value of polyoses content and nucleic acid content is still better than the value of the polyoses content peeling off cleansing composition used in comparative example 3 and nucleic acid content, show to adopt the present invention's to peel off the cleansing composition excellent effect to the stripping in circulation.
Therefore, adopt the stripping cleansing composition of the present invention, both there is excellent greasy filth cleaning performance, there is again good sludge stripping performance.
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the technology concept of the present invention; technical scheme can being carried out multiple simple variant, these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, it is possible to be combined by any suitable mode.
Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (8)
1. peel off cleansing composition for one kind, it is characterized in that, said composition contains D-limonene, Polyethylene Glycol and anion surfactant, and the weight ratio of described D-limonene, described Polyethylene Glycol and described anion surfactant is 1:0.25-3:0.1-1.5, described anion surfactant is aliphatic alcohol polyoxyvinethene phosphate salt anionic surfactant.
2. compositions according to claim 1, wherein, the weight ratio of described D-limonene, described Polyethylene Glycol and described aliphatic alcohol polyoxyvinethene phosphate salt anionic surfactant is 1:0.75-2.5:0.25-1.
3. compositions according to claim 1 and 2, wherein, the structural formula of described aliphatic alcohol polyoxyvinethene phosphate salt anionic surfactant is RO (C2H4O)mPO3 2-(M+)2, wherein, R is C12��C13Alkyl, the numerical value of degree of polymerization m is 2��3, M+For H+��Na+��K+Or organoammonium ions;
Preferably, described aliphatic alcohol polyoxyvinethene phosphate salt anionic surfactant is alkylpolyoxyethylene phosphate ester and/or Sodium Trideceth sodium phosphate, wherein, and degree of polymerization m=2.
4. compositions according to claim 1 and 2, wherein, described Polyethylene Glycol is selected from one or more in PEG-400, PEG-600 and PEG-800.
5. the compositions according to any one in claim 1-4, wherein, described stripping cleansing composition is the form of aqueous solution, and the total concentration of D-limonene described in this aqueous solution, described Polyethylene Glycol and described aliphatic alcohol polyoxyvinethene phosphate salt anionic surfactant is 25-75 weight %, it is preferred to 30-55 weight %.
6. the using method of the compositions according to any one in claim 1-5, this using method is: described stripping cleansing composition adds in circulation blowdown after circulation 12-48 hour, and mends with fresh water until the difference of turbidity value before the turbidity value of this circulation and the described stripping cleansing composition of addition is between �� 10%.
7. using method according to claim 6, wherein, the consumption of described stripping cleansing composition is 10mg/L-50mg/L.
8. using method according to claim 7, wherein, the consumption of described stripping cleansing composition is 10mg/L-30mg/L.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH03243700A (en) * | 1990-02-20 | 1991-10-30 | Nippon Oil & Fats Co Ltd | Detergent composition |
| CN102786163A (en) * | 2011-05-18 | 2012-11-21 | 中国石油化工股份有限公司 | Circulating water processing method |
| CN103787515A (en) * | 2012-10-26 | 2014-05-14 | 中国石油化工股份有限公司 | Method for peeling biological slime in circulating cooling water system |
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2014
- 2014-11-03 CN CN201410610785.4A patent/CN105623866B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03243700A (en) * | 1990-02-20 | 1991-10-30 | Nippon Oil & Fats Co Ltd | Detergent composition |
| CN102786163A (en) * | 2011-05-18 | 2012-11-21 | 中国石油化工股份有限公司 | Circulating water processing method |
| CN103787515A (en) * | 2012-10-26 | 2014-05-14 | 中国石油化工股份有限公司 | Method for peeling biological slime in circulating cooling water system |
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| 秦国治等: "《工业清洗及应用实例》", 31 January 2007, 北京：化学工业出版社 * |
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