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WO2016113987A1 - Procédé de séparation huile-eau pour goudron de houille contenant de l'eau et agent de séparation huile-eau - Google Patents

Procédé de séparation huile-eau pour goudron de houille contenant de l'eau et agent de séparation huile-eau Download PDF

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Publication number
WO2016113987A1
WO2016113987A1 PCT/JP2015/081433 JP2015081433W WO2016113987A1 WO 2016113987 A1 WO2016113987 A1 WO 2016113987A1 JP 2015081433 W JP2015081433 W JP 2015081433W WO 2016113987 A1 WO2016113987 A1 WO 2016113987A1
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WO
WIPO (PCT)
Prior art keywords
water
oil
coal tar
tar
water separation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/081433
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English (en)
Japanese (ja)
Inventor
洋平 宮▲崎▼
たかし 吉川
毅 土岐
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kurita Water Industries Ltd
Original Assignee
Kurita Water Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kurita Water Industries Ltd filed Critical Kurita Water Industries Ltd
Publication of WO2016113987A1 publication Critical patent/WO2016113987A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C1/00—Working-up tar
    • C10C1/02—Removal of water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C1/00—Working-up tar
    • C10C1/20—Refining by chemical means inorganic or organic compounds

Definitions

  • the present invention relates to an oil-water separation method and an oil-water separation agent for hydrous coal tar.
  • Coal tar (hereinafter also referred to as “tar”) is a by-product generated from a coke oven and is produced as follows. Aqueous water (ammonia water) is sprayed on the gas generated in the coke oven and cooled, and the resulting condensate is allowed to stand in a tar decanter together with the water to separate it into a water layer and a tar layer. Put in tar tank (crude refined product storage tank after separation of decanter), extract water and put into water tank.
  • tar crude product storage tank after separation of decanter
  • coal tar forms an emulsion in a water-containing state
  • oil-water separation is required in a tar decanter, a tar tank, a centrifuge (super decanter) or the like in the production and purification process of coal tar.
  • heavy oil in coal tar has a large specific gravity, a high affinity with water, and forms a strong emulsion in a water-containing state, so that separation is not easy even with a centrifugal separation method.
  • a heavy oil mainly composed of coal tar contains water-containing waste oil containing water, an alkyl allyl sulfonate, an alkane sulfonate, a higher alcohol sulfate, a polyoxyethylene alkylphenyl sulfate salt, and a polyoxyethylene alkyl.
  • Patent Document 2 describes a method of separating oil and water by adding a cationic surfactant mainly composed of quaternary ammonium salt or imidazole derivative to tar-based hydrous waste oil.
  • a cationic surfactant mainly composed of quaternary ammonium salt or imidazole derivative
  • the oil / water separation effect was not sufficient.
  • an anionic surfactant does not show a good separation effect, and the difference between the place of addition of these drugs in the coal tar production process and the oil-water separation effect was not described.
  • Patent Document 3 discloses that when a tar decanter is used to separate coal tar and aqueous water, a small amount of a lipophilic demulsifier such as a mixture of an alkylphenol formalin condensate and a polymerized ether is added to the tar decanter. Describes a method for removing wrinkles suspended in aqueous water by breaking the emulsion at the interface. However, no mention is made of the effect of reducing moisture in tar.
  • a lipophilic demulsifier such as a mixture of an alkylphenol formalin condensate and a polymerized ether
  • An object of the present invention is to provide an oil / water separation method and an oil / water separation agent excellent in the oil / water separation effect of hydrous coal tar.
  • One or more interfaces selected from the group consisting of a nonionic surfactant having a Griffin method HLB value of 6.5 or more and an anionic surfactant having a Davis method HLB value of 45 or more in order to solve the above problems
  • the present inventors have found that an excellent oil-water separation effect can be exhibited by adding an activator to a hydrous coal tar containing 1 part by weight of moisture with respect to 1 part of coal tar.
  • the present invention provides the following oil-water separation method and oil-water separation agent.
  • One or more surfactants selected from the group consisting of a nonionic surfactant having a Griffin method HLB value of 6.5 or more and an anionic surfactant having a Davis method HLB value of 45 or more are treated with coal tar 1
  • An oil-water separation method of hydrous coal tar wherein oil-water separation is carried out by adding water to hydrous coal tar containing 1 part by weight or less of water with respect to parts.
  • a nonionic surfactant having a Griffin method HLB value of 6.5 or more and an anionic surfactant having a Davis method HLB value of 45 or more Oil / water separator.
  • the oil-water separation effect of the hydrous coal tar is excellent, and the moisture of the coal tar can be sufficiently reduced to obtain a stable quality tar product. It becomes.
  • the addition part should just be a part with much coal tar content rather than a water
  • the present invention relates to an oil-water separation method and an oil-water separation agent for hydrous coal tar.
  • the hydrous coal tar oil / water separating agent used in the present invention is selected from the group consisting of a nonionic surfactant having a Griffin method HLB value of 6.5 or more and an anionic surfactant having a Davis method HLB value of 45 or more.
  • One or more surfactants exhibiting a sufficient oil / water separation effect with respect to hydrous coal tar containing one part by weight of water in a mass ratio of 1 part or less, particularly hydrous coal tar at the outlet of the tar decanter.
  • “moisture” is a concept including industrial water and clean water used for washing in order to extract salt from crude tar, in addition to safe water.
  • the nonionic surfactant used in the present invention requires a Griffin method HLB value of 6.5 or more, and preferably 7.0 or more.
  • the type is not limited as long as it has an HLB value, but polyoxyalkylene alkyl ethers and polyoxyethylene polyoxypropylene block polymers are preferably used.
  • the polyoxyalkylene alkyl ether having such a Griffin method HLB value is usually an alkyl group having 8 to 12 carbon atoms, the polyoxyalkylene is polyoxyethylene, and the number of moles of ethylene oxide added is in the range of 16 to 25. Obtained from.
  • Specific examples of the polyoxyalkylene alkyl ether used in the present invention include, for example, a polyoxyalkylene alkyl ether having an HLB value of 11 (trade name “Sannonic SS-50”, manufactured by Sanyo Chemical Industries, Ltd.).
  • Polyoxyethylene polyoxypropylene block polymer is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer obtained by polymerizing ethylene oxide to polypropylene glycol obtained by polymerization of propylene oxide.
  • Polyethylene oxide, polypropylene oxide The HLB value varies depending on the degree of polymerization (usually several tens of each).
  • Specific examples of the polyoxyethylene polyoxypropylene block polymer used in the present invention include, for example, a polyoxyethylene polyoxypropylene block polymer having an HLB value of 7 (trade name “New Pole PE-74”, Sanyo Chemical Industries, Ltd. And a polyoxyethylene polyoxypropylene block polymer having a HLB value of 16 (trade name “New Pole PE-78”, manufactured by Sanyo Chemical Industries, Ltd.).
  • a nonionic surfactant having a Griffin method HLB value of less than 6.5 as used in Comparative Examples 13 and 14 described below has a poor oil-water separation effect, and the Griffin method HLB value is 6.5 or more. Even if a nonionic surfactant is used, the oil-water separation effect is poor for a mixture of coal tar and water having a moisture content higher than that of coal tar.
  • the anionic surfactant used in the present invention requires an HLB value calculated by the Davis method of 45 or more, and preferably 54 or more.
  • the Davis is used as such an anionic surfactant.
  • Polyoxyalkylene alkyl sulfosuccinates and sulfosuccinic acid alkyl salts having a method HLB value are preferably used.
  • the polyoxyalkylene of the polyoxyalkylene alkyl group is polyoxyethylene or polyoxypropylene, and the average addition mole number thereof is preferably about 1 to 2, and the polyoxyalkylene alkyl group alkyl Has a carbon number of 10 to 18, preferably 12 to 14, and the sulfosuccinic acid salt is a sulfosuccinic acid dialkali metal salt or a sulfosuccinic acid diammonium salt.
  • polyoxyalkylene alkyl sulfosuccinate used in the present invention include, for example, polyoxyethylene (about 2) alkyl (12 to 14) disodium sulfosuccinate having a HLB value of 56 (trade name “View” Light ESS ", manufactured by Sanyo Chemical Industries, Ltd.) and the like.
  • the alkyl group has 10 to 18, preferably 12 to 14 carbon atoms
  • the sulfosuccinic acid salt is a sulfosuccinic acid dialkali metal salt or a sulfosuccinic acid diammonium salt.
  • Specific examples of the sulfosuccinic acid alkyl salt used in the present invention include, for example, disodium lauryl sulfosuccinate having a Davis method HLB value of 54 (trade name “Burelite SSS”, manufactured by Sanyo Chemical Industries, Ltd.). .
  • Davis method HLB value of sodium dodecyl sulfate which is a typical anionic surfactant is 40.
  • the total amount of one or more surfactants selected from the group consisting of a nonionic surfactant having a Griffin method HLB value of 6.5 or more and an anionic surfactant having a Davis method HLB value of 45 or more is The content is preferably 0.005 to 1% by mass, more preferably 0.01 to 0.1% by mass with respect to the minute.
  • the addition amount is 70 mass% or more in all the surfactants.
  • the above surfactants may be added as they are, such as disodium polyoxyethylene sulfosuccinate or disodium lauryl sulfosuccinate. However, in consideration of mixing and homogenization with the target hydrous coal tar, It is desirable to dilute and add as a liquid.
  • the oil / water separation method and the oil / water separation agent of the present invention are used in a process for producing coal tar, and the oil / water separation agent may be added at a location where there is more coal tar than moisture, It is preferable to add water to water-containing coal tar containing 0.7 parts by weight or less, especially for coal tar separated by tar decanter, suitable as a method for promoting dehydration in super decanter (centrifuge) ing.
  • coal tar retains moisture as a W / O type emulsion, it is necessary to break the emulsion in order to separate coal tar and water.
  • a specific surfactant that is an oil-water separator when added, it acts on the interface forming the emulsion and makes it impossible to maintain the emulsion, so water is combined and separated into water and tar. It is done.
  • a nonionic surfactant having a Griffin method HLB value of 6.5 or more and an anionic surfactant having a Davis method HLB value of 45 or more are easily soluble in water, but are difficult to dissolve and diffuse in tar.
  • coal tar was collected in a sample bottle, and 40 g, 144 g and 464 g of hydrous coal tar and pure water to which pure water was not added were added.
  • Hydrous coal tar (a mixture of coal tar and water) was prepared (the tar: water ratios were 1: 0.2, 1: 0.7, 1: 1.9, and 1: 5.7, respectively).
  • a predetermined amount of a surfactant was added to the resulting coal tar and water mixture with a micropipette. The mixture was stirred for 1 minute with a spatula and allowed to stand for 3 hours in a constant temperature bath at 70 ° C.
  • Examples 1 to 10 (a specific surfactant was added to hydrous coal tar containing 1 part by weight of water in a mass ratio of 1 part or less), a remarkable oil-water separation effect was observed. Since the surfactant used here is easily soluble in water and difficult to dissolve and diffuse in tar, it is thought that it was able to concentrate on moisture present as an emulsion in the tar and its interface. However, these surfactants also greatly reduced the oil-water separation effect in the tar / water mixtures of Comparative Examples 1 to 10 having a large water content. The ratio of the surfactant to water was reduced, and the amount of surfactant acting on the water in the emulsion was reduced. Therefore, it is considered that the oil-water separation effect was lowered.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Working-Up Tar And Pitch (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un procédé de séparation huile-eau pour goudron de houille contenant de l'eau qui excelle en matière d'effets de séparation huile-eau. Le procédé de séparation huile-eau pour goudron de houille contenant de l'eau sépare l'huile de l'eau par addition, à un goudron de houille contenant de l'eau qui contient, dans un rapport en masse, tout au plus une partie d'eau par rapport à une partie du goudron de houille, d'au moins un tensioactif choisi dans le groupe constitué par un tensioactif non ionique présentant une valeur de balance-hydrophile-lipophile (HLB) selon la méthode Griffin d'au moins 6,5 et d'un tensioactif anionique présentant une valeur HLB selon la méthode Davies d'au moins 45.
PCT/JP2015/081433 2015-01-13 2015-11-09 Procédé de séparation huile-eau pour goudron de houille contenant de l'eau et agent de séparation huile-eau Ceased WO2016113987A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-004431 2015-01-13
JP2015004431A JP5962784B2 (ja) 2015-01-13 2015-01-13 含水コールタールの油水分離方法および油水分離剤

Publications (1)

Publication Number Publication Date
WO2016113987A1 true WO2016113987A1 (fr) 2016-07-21

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JP (1) JP5962784B2 (fr)
TW (1) TWI658134B (fr)
WO (1) WO2016113987A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7360648B2 (ja) * 2019-06-24 2023-10-13 株式会社片山化学工業研究所 タール粘度低減剤、タール粘度低減剤を含むタール及びタール粘度低減方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4139451A (en) * 1977-12-12 1979-02-13 Nalco Chemical Company Method for dewatering coke tar-water mixtures
JPH0119439B2 (fr) * 1980-10-24 1989-04-11 Domutaa Inc
JP2000230177A (ja) * 1999-02-15 2000-08-22 Dai Ichi Kogyo Seiyaku Co Ltd 石炭タール水分離用乳化破壊剤
CN102839007A (zh) * 2011-06-24 2012-12-26 上海宝钢化工有限公司 酸性乳化焦油的破乳、中和、脱水处理方法
JP2014104392A (ja) * 2012-11-26 2014-06-09 Kurita Water Ind Ltd 油及び／又は油状成分と水の分離方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001162107A (ja) * 1999-12-10 2001-06-19 Lion Corp 油水分離剤
CN102432741B (zh) * 2011-09-05 2013-11-27 陕西驭腾实业有限公司 一种焦化油水分离剂及其制备方法和使用方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4139451A (en) * 1977-12-12 1979-02-13 Nalco Chemical Company Method for dewatering coke tar-water mixtures
JPH0119439B2 (fr) * 1980-10-24 1989-04-11 Domutaa Inc
JP2000230177A (ja) * 1999-02-15 2000-08-22 Dai Ichi Kogyo Seiyaku Co Ltd 石炭タール水分離用乳化破壊剤
CN102839007A (zh) * 2011-06-24 2012-12-26 上海宝钢化工有限公司 酸性乳化焦油的破乳、中和、脱水处理方法
JP2014104392A (ja) * 2012-11-26 2014-06-09 Kurita Water Ind Ltd 油及び／又は油状成分と水の分離方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KAIMEN KASSEIZAI NYUMON, 11 June 2007 (2007-06-11), pages 140 - 147 *

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JP5962784B2 (ja) 2016-08-03
JP2016130284A (ja) 2016-07-21
TWI658134B (zh) 2019-05-01
TW201625778A (zh) 2016-07-16

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