WO2017001957A1 - Additive composition for demulsification of water-in-oil emulsion, and method of use thereof, and method of demulsification - Google Patents

Additive composition for demulsification of water-in-oil emulsion, and method of use thereof, and method of demulsification Download PDF

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Publication number
WO2017001957A1
WO2017001957A1 PCT/IB2016/053481 IB2016053481W WO2017001957A1 WO 2017001957 A1 WO2017001957 A1 WO 2017001957A1 IB 2016053481 W IB2016053481 W IB 2016053481W WO 2017001957 A1 WO2017001957 A1 WO 2017001957A1
Authority
WO
WIPO (PCT)
Prior art keywords
phenol
formaldehyde
demulsification
oxyalkylated
cardanol
Prior art date
Application number
PCT/IB2016/053481
Other languages
English (en)
French (fr)
Inventor
Mahesh Subramaniyam
Original Assignee
Dorf Ketal Chemicals (India) Private Limited
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
Priority to US15/576,573 priority Critical patent/US10815435B2/en
Priority to ES16738219T priority patent/ES2791977T3/es
Application filed by Dorf Ketal Chemicals (India) Private Limited filed Critical Dorf Ketal Chemicals (India) Private Limited
Priority to BR112017027499-0A priority patent/BR112017027499B1/pt
Priority to MYPI2017001963A priority patent/MY193752A/en
Priority to PL16738219T priority patent/PL3316982T3/pl
Priority to EP16738219.1A priority patent/EP3316982B1/en
Priority to CN201680039404.9A priority patent/CN107735154B/zh
Priority to JP2017567648A priority patent/JP6715869B2/ja
Priority to KR1020187002430A priority patent/KR102181878B1/ko
Priority to AU2016286418A priority patent/AU2016286418B2/en
Priority to CA2991178A priority patent/CA2991178C/en
Publication of WO2017001957A1 publication Critical patent/WO2017001957A1/en
Priority to PH12018500017A priority patent/PH12018500017B1/en
Priority to CONC2018/0000254A priority patent/CO2018000254A2/es
Priority to ZA2018/00406A priority patent/ZA201800406B/en
Priority to HRP20200810TT priority patent/HRP20200810T1/hr

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G33/00Dewatering or demulsification of hydrocarbon oils
    • C10G33/04Dewatering or demulsification of hydrocarbon oils with chemical means
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D17/00Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02Separation of non-miscible liquids
    • B01D17/04Breaking emulsions
    • B01D17/047Breaking emulsions with separation aids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G31/00Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/08Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2256/00Main component in the product gas stream after treatment
    • B01D2256/24Hydrocarbons
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/80Water

Definitions

  • Additive composition for demulsification of water-in-oil emulsion, and method of use thereof, and method of demulsification are added to water-in-oil emulsion, and method of use thereof, and method of demulsification.
  • the present invention relates to additive composition for demulsification of water-in-oil emulsion.
  • the present invention relates to additive composition for demulsification of water-in-oil emulsion caused by mixing of wash water and crude oil.
  • the present invention relates to additive composition for demulsification of water-in-oil emulsion caused by mixing of wash water and crude oil in the desalter unit of the refinery.
  • the present invention relates to additive composition for demulsification of water-in-oil emulsion caused by mixing of wash water and crude oil in the desalter unit of the refinery, wherein the additive composition comprises:
  • a a compound selected from the group comprising glyoxal, neutralized glyoxal and mixture thereof;
  • the present invention relates to a method of demulsification of water-in-oil emulsions, particularly of water-in-oil emulsions caused by mixing of wash water and crude oil, more particularly of water-in-oil emulsions caused by mixing of wash water and crude oil in the desalter unit of the refinery.
  • the present invention relates to a method of using the additive composition of the present invention for demulsification of water-in-oil emulsions, particularly of water-in-oil emulsions caused by mixing of wash water and crude oil, more particularly of water-in-oil emulsions caused by mixing of wash water and crude oil in the desalter unit of the refinery.
  • the water-in-oil emulsions are formed in various industrial operations, and are responsible for substantial loss of various industrial ingredients including difficulties in separation of oil. Therefore, breaking of water-in-oil emulsions during the processing of oil is the requirement of the industry, particularly of the crude oil refinery industry wherein the wash water gets mixed with crude oil in the desalter unit of the refinery and forms water-in-oil emulsion.
  • the water-in-oil emulsion caused by mixing of wash water and crude oil is broken by addition of demulsifier to the wash water.
  • the main problem of using the demulsifiers is that these are to be used in higher amounts and required continuously through the processing of crude oil, which results in substantial increase in cost of processing of crude oil.
  • demulsifiers are expensive, which also results in substantial increase in cost of processing of crude oil.
  • demulsifiers are condensation product of nonyl phenols, and presently, there is a need to reduce consumption of nonyl phenols in view of their cost and environmental adverse effects.
  • the present invention aims at providing a solution to above-described existing industrial problems by providing:
  • Hi method for demulsification of water-in-oil emulsions by employing the additive composition.
  • the main object of the present invention is to provide:
  • an additive composition for demulsification of water-in-oil emulsions particularly of water-in-oil emulsions caused by mixing of wash water and crude oil, more particularly of water-in-oil emulsions caused by mixing of wash water and crude oil in the desalter unit of the refinery.
  • the other object of the present invention is to provide:
  • a method of demulsification of water-in-oil emulsions by employing an additive composition of the present invention particularly of water-in-oil emulsions caused by mixing of wash water and crude oil, more particularly of water-in-oil emulsions caused by mixing of wash water and crude oil in the desalter unit of the refinery.
  • Another object of the present invention is to provide:
  • Hi a method of using the additive composition of the present invention for demulsification of water-in-oil emulsions, particularly of water-in-oil emulsions caused by mixing of wash water and crude oil, more particularly of water-in-oil emulsions caused by mixing of wash water and crude oil in the desalter unit of the refinery.
  • an object of the present invention is to provide an additive composition for demulsification of water-in-oil emulsions, which is preferably caused by mixing of wash water and crude oil, more preferably for demulsification of the water-in-oil emulsions caused by mixing of wash water and crude oil in the desalter unit of the refinery so as to reduce the amount of the presently used demulsifiers, which are condensation product of nonyl phenols, and hence, to reduce consumption of nonyl phenols, and thereby to reduce cost of processing and associated environmental adverse effects.
  • the inventor has found that when a compound selected from the group comprising glyoxal, neutralized glyoxal, glyoxal derivative and a mixture thereof is added to one or more demulsifiers, the said compound, surprisingly and unexpectedly, results in substantial improvement of demulsification efficiency of the demulsifier, and thereby, results in substantial reduction of requirement of amount of the demulsifier, which results in substantial decrease in cost of processing of crude oil, and associated environmental adverse effects.
  • glyoxal and neutralized glyoxal are less expensive than the demulsifiers, it further results in substantial decrease in cost of processing of the crude oil.
  • the present invention relates to a demulsification composition for demulsification of water-in-oil emulsion caused due to wash water in the crude oil, wherein the composition comprises: a. a compound selected from the group comprising glyoxal, neutralized glyoxal, glyoxal derivative and a mixture thereof; and
  • the neutralized glyoxal is glyoxal having pH neutral to basic.
  • the inventor has observed that the glyoxal is very acidic, and therefore, it may cause corrosion. Accordingly, neutralizing the glyoxal till its pH is neutral to basic avoids corrosion of crude oil processing unit, and still improves demulsification efficiency of the demulsifier.
  • the neutralized glyoxal is obtained by neutralizing the glyoxal with an amine or alkaline medium.
  • the amine may include (or comprises) triethanol amine (TEA).
  • TAA triethanol amine
  • the alkaline medium may include (or comprises) sodium hydroxide aqueous solution.
  • the neutralized glyoxal may also include (or comprise) neutralized derivative of glyoxal. Therefore, in the present invention, the term “neutralized glyoxal” or the term “neutralized derivative of glyoxal” have one and same meaning unless otherwise explicitly described.
  • the pH neutral to basic includes a pH varying from about 7 to about 12.
  • the glyoxal derivative may include (or comprise) methanol, ethanol, butanol, ethylene glycol derivatives of glyoxal, or a mixture thereof.
  • the demulsifier is selected from the group comprising condensation product of:
  • the demulsifier is selected from the group comprising condensation product of: i) cardanol, nonyl phenol and amyl phenol, and formaldehyde;
  • the above-described condensation product is oxyalkylated.
  • the demulsifier is selected from the group comprising oxyalkylated condensation product of:
  • the demulsifier is selected from the group comprising oxyalkylated condensation product of:
  • the above-described condensation products is oxyalkylated with ethylene oxide, propylene oxide, butylene oxide or their mixtures to result in oxyalkylated copolymers or oxyalkylated polymers thereof. Therefore, in accordance with one of the embodiments of the present invention, the demulsifier is selected from the group comprising:
  • the demulsifier may be selected from a group comprising:
  • copolymer means a polymer made from two different phenols and the term “polymer” means a polymer made from one phenol.
  • the molecular weight of the demulsifier of the present invention may vary from about 2000 to about 20000 daltons as measured by Gel Permeation Chromatography using the tetrahydro furan (THF) as solvent.
  • the composition comprises:
  • the composition may comprise: a) about 0.1 ppm to about 1000 ppm of the compound selected from the group comprising glyoxal, neutralized glyoxal, glyoxal derivative and a mixture thereof; and
  • the additive composition may be added to the crude oil phase or to the desalter wherein wash water is mixed with crude oil and forms a water-in-oil emulsion.
  • the present invention relates to
  • the present demulsification composition comprising:
  • a a compound selected from the group comprising glyoxal, neutralized glyoxal, glyoxal derivative and a mixture thereof;
  • the present invention relates to
  • a a compound selected from the group comprising glyoxal, neutralized glyoxal, glyoxal derivative and a mixture thereof;
  • the 'blank' is without any additive
  • compound 'A' is demulsifier, which is base catalysed nonylphenol formaldehyde resin and used for comparison;
  • compositions comprise
  • compositions comprise:
  • ⁇ ' a compound selected from glycolic acid, glyoxylic acid, DL-malic acid, benzaldehyde, or glutaraldehyde.
  • the compound 'A' (the demulsifier) is 50% active, the glyoxal is 40% active, the neutralized glyoxal comprises 40% active glyoxal neutralized with 100% active triethanol amine (TEA); the glycolic acid, the glyoxylic acid and the DL-malic acid are 40% active.
  • TEA triethanol amine
  • the present additive composition and the prior art or comparative additive composition was added to the water-in-oil emulsion of water and crude oil formed after mixing of water and crude oil.
  • test was carried out in portable electric desalter (PED) or electrostatic separator at 130°C, with water-in-oil emulsion comprising 5% by vol of wash water (pH of wash water was 6.6), and 95% by vol of crude oil from Western part of India.
  • PED portable electric desalter
  • electrostatic separator at 130°C
  • the second component which is either the glyoxal or the neutralized glyoxal (as per the present invention); or the glycolic acid, the glyoxylic acid; the DL-malic acid; the benzaldehyde; or the glutaraldehyde (for the purpose of comparison).
  • the present compositions are more economical and environmental friendly.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Colloid Chemistry (AREA)
  • Detergent Compositions (AREA)
PCT/IB2016/053481 2015-07-01 2016-06-13 Additive composition for demulsification of water-in-oil emulsion, and method of use thereof, and method of demulsification WO2017001957A1 (en)

Priority Applications (15)

Application Number Priority Date Filing Date Title
KR1020187002430A KR102181878B1 (ko) 2015-07-01 2016-06-13 유중수적형 에멀젼의 해유화를 위한 첨가제 조성물, 이의 사용 방법, 및 해유화 방법
JP2017567648A JP6715869B2 (ja) 2015-07-01 2016-06-13 油中水型エマルションの解乳化のための添加剤組成物、及びその使用方法、及び解乳化の方法
BR112017027499-0A BR112017027499B1 (pt) 2015-07-01 2016-06-13 Composição aditiva para a demulsificação de uma emulsão água-em-óleo, seu método de uso e o método de demulsificação
ES16738219T ES2791977T3 (es) 2015-07-01 2016-06-13 Composición aditiva para demulsificación de emulsión de agua en petróleo, y procedimiento de uso de la misma, y procedimiento de demulsificación
PL16738219T PL3316982T3 (pl) 2015-07-01 2016-06-13 Kompozycja dodatku do demulgacji emulsji typu woda w oleju i sposób jej stosowania i sposób demulgacji
EP16738219.1A EP3316982B1 (en) 2015-07-01 2016-06-13 Additive composition for demulsification of water-in-oil emulsion, and method of use thereof, and method of demulsification
AU2016286418A AU2016286418B2 (en) 2015-07-01 2016-06-13 Additive composition for demulsification of water-in-oil emulsion, and method of use thereof, and method of demulsification
US15/576,573 US10815435B2 (en) 2015-07-01 2016-06-13 Additive composition for demulsification of water-in-oil emulsion, and method of use thereof, and method of demulsification
MYPI2017001963A MY193752A (en) 2015-07-01 2016-06-13 Additive composition for demulsification of water-in-oil emulsion, and method of use thereof, and method of demulsification
CN201680039404.9A CN107735154B (zh) 2015-07-01 2016-06-13 用于油包水乳液的破乳的添加剂组合物及其使用方法,以及破乳方法
CA2991178A CA2991178C (en) 2015-07-01 2016-06-13 Additive composition for demulsification of water-in-oil emulsion, and method of use thereof, and method of demulsification.
PH12018500017A PH12018500017B1 (en) 2015-07-01 2018-01-03 Additive composition for demulsification of water-in-oil emulsion, and method of use thereof, and method of demulsification
CONC2018/0000254A CO2018000254A2 (es) 2015-07-01 2018-01-12 Composición aditiva para demulsificación de emulsión de agua en petróleo, y método de uso de la misma, y método de demulsificación
ZA2018/00406A ZA201800406B (en) 2015-07-01 2018-01-19 Additive composition for demulsification of water-in-oil emulsion, and method of use thereof, and method of demulsification
HRP20200810TT HRP20200810T1 (hr) 2015-07-01 2020-05-18 Smjesa dodataka za deemulzifikaciju emulzije vode u ulju, i postupak za njezinu upotrebu, i postupak deemulzifikacije

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN2515/MUM/2015 2015-07-01
IN2515MU2015 2015-07-01

Publications (1)

Publication Number Publication Date
WO2017001957A1 true WO2017001957A1 (en) 2017-01-05

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PCT/IB2016/053481 WO2017001957A1 (en) 2015-07-01 2016-06-13 Additive composition for demulsification of water-in-oil emulsion, and method of use thereof, and method of demulsification

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US (1) US10815435B2 (US20090163788A1-20090625-C00002.png)
EP (1) EP3316982B1 (US20090163788A1-20090625-C00002.png)
JP (1) JP6715869B2 (US20090163788A1-20090625-C00002.png)
KR (1) KR102181878B1 (US20090163788A1-20090625-C00002.png)
CN (1) CN107735154B (US20090163788A1-20090625-C00002.png)
AU (1) AU2016286418B2 (US20090163788A1-20090625-C00002.png)
BR (1) BR112017027499B1 (US20090163788A1-20090625-C00002.png)
CA (1) CA2991178C (US20090163788A1-20090625-C00002.png)
CO (1) CO2018000254A2 (US20090163788A1-20090625-C00002.png)
ES (1) ES2791977T3 (US20090163788A1-20090625-C00002.png)
HR (1) HRP20200810T1 (US20090163788A1-20090625-C00002.png)
HU (1) HUE049869T2 (US20090163788A1-20090625-C00002.png)
MY (1) MY193752A (US20090163788A1-20090625-C00002.png)
PE (1) PE20180154A1 (US20090163788A1-20090625-C00002.png)
PH (1) PH12018500017B1 (US20090163788A1-20090625-C00002.png)
PL (1) PL3316982T3 (US20090163788A1-20090625-C00002.png)
WO (1) WO2017001957A1 (US20090163788A1-20090625-C00002.png)
ZA (1) ZA201800406B (US20090163788A1-20090625-C00002.png)

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US10815435B2 (en) 2015-07-01 2020-10-27 Dorf Ketal Chemicals (India) Private Limited Additive composition for demulsification of water-in-oil emulsion, and method of use thereof, and method of demulsification

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US10815435B2 (en) 2015-07-01 2020-10-27 Dorf Ketal Chemicals (India) Private Limited Additive composition for demulsification of water-in-oil emulsion, and method of use thereof, and method of demulsification
WO2018138595A1 (en) * 2017-01-25 2018-08-02 Dorf Ketal Chemicals (India) Private Limited Demulsification additive composition, use thereof, and method of demulsification
KR20190108577A (ko) * 2017-01-25 2019-09-24 도르프 케탈 케미칼즈 (인디아) 프라이비트 리미티드 탈유화 첨가제 조성물, 및 이의 용도, 및 탈유화 방법
CN110446773A (zh) * 2017-01-25 2019-11-12 多尔夫凯塔尔化学制品(I)私人有限公司 破乳添加剂组合物、其使用方法及破乳方法
JP2020507469A (ja) * 2017-01-25 2020-03-12 ドルフ ケタール ケミカルズ (インディア)プライヴェート リミテッド 解乳化添加剤組成物、その使用方法、及び解乳化方法
US11083981B2 (en) 2017-01-25 2021-08-10 Dorf Ketal Chemicals (India) Private Limited Demulsification additive composition, use thereof, and method of demulsification
CN110446773B (zh) * 2017-01-25 2021-09-07 多尔夫凯塔尔化学制品(I)私人有限公司 破乳添加剂组合物、其使用方法及破乳方法
KR102348954B1 (ko) 2017-01-25 2022-01-10 도르프 케탈 케미칼즈 (인디아) 프라이비트 리미티드 탈유화 첨가제 조성물, 및 이의 용도, 및 탈유화 방법
JP2022118156A (ja) * 2017-01-25 2022-08-12 ドルフ ケタール ケミカルズ (インディア)プライヴェート リミテッド 解乳化添加剤組成物、その使用方法、及び解乳化方法
US11617970B2 (en) 2017-01-25 2023-04-04 Dorf Ketal Chemicals (India) Private Limited Demulsification additive composition, use thereof, and method of demulsification

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PH12018500017A1 (en) 2018-07-09
HUE049869T2 (hu) 2020-11-30
HRP20200810T1 (hr) 2020-08-07
ES2791977T3 (es) 2020-11-06
EP3316982A1 (en) 2018-05-09
AU2016286418B2 (en) 2019-05-30
JP6715869B2 (ja) 2020-07-01
CA2991178A1 (en) 2017-01-05
US10815435B2 (en) 2020-10-27
CN107735154B (zh) 2020-06-23
BR112017027499B1 (pt) 2022-04-12
CA2991178C (en) 2019-09-10
PH12018500017B1 (en) 2018-07-09
MY193752A (en) 2022-10-27
PL3316982T3 (pl) 2020-09-21
AU2016286418A1 (en) 2018-01-25
ZA201800406B (en) 2020-10-28
BR112017027499A2 (US20090163788A1-20090625-C00002.png) 2018-08-21
KR102181878B1 (ko) 2020-11-23
PE20180154A1 (es) 2018-01-18
EP3316982B1 (en) 2020-02-19
JP2018527167A (ja) 2018-09-20
CO2018000254A2 (es) 2018-04-19
US20180163145A1 (en) 2018-06-14
KR20180021847A (ko) 2018-03-05
CN107735154A (zh) 2018-02-23

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