CN1600835A - Method for preparing multifunctional deemulsifying agent of crude oil and products thereof - Google Patents
Method for preparing multifunctional deemulsifying agent of crude oil and products thereof Download PDFInfo
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- CN1600835A CN1600835A CN03134878.5A CN03134878A CN1600835A CN 1600835 A CN1600835 A CN 1600835A CN 03134878 A CN03134878 A CN 03134878A CN 1600835 A CN1600835 A CN 1600835A
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- crude oil
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- halogen
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Abstract
This invention provides a method for preparing crude oil demulsification agent for crude oil pretreatment in refinery plant. Said multi-functional demulsification agent has betaine structure, being of amphoteric-ion surfactant. Organic amine is used as initiator, and epoxy propane and epoxy ethane are polymerized to produce polyether, then reacting with alpha-halogenated carboxylic acid to produce said betaine structure product. This produced has advantages of: excellent emulsification ability and dewater ability, on the molecule there are quaternary amido and carboxy group, so having excellent wetting function, and having good complexation stability to alkaline earth metals in crude-oil, being of calcium-disperser, and having excellent function for removing magnesium and iron.
Description
Technical field
The present invention relates to a kind of multifunctional crude oil demulsifying agent preparation method who is used for the refinery crude oil upgrading and products thereof.
Background technology
Crude oil electric desalting is the important preprocessing means of refinery crude oil processing, and crude oil processing whole process and product performance are had material impact.In recent years, along with crude oil becomes the situation heavily and the development of crude oil deep processing technology day by day, particularly heavy oil fluid catalytic cracking and hydrocracking increase, make crude oil electric desalting by the past single becoming as anti-corrosion measure prevent poisoning of catalyst, the alleviator fouling, reduce the important preprocessing technology of ash in residual oil, the refinery coke, this just has higher requirement to electric desalting technology.These metal components in the crude oil, behind atmospheric and vacuum distillation, major part enters the residual oil fraction, and rest part is scattered in other each fraction oil.Salt is too high in the crude oil, and through interchanger and process furnace heating, metallic impurity are in interchanger and the fouling of furnace tubing inwall deposition, and not only influence is conducted heat and flow velocity, and causes that settling decomposes, and produces acid attack.The distillate (particularly residual oil) that contains these metallic impurity is during as catalytically cracked material, on the catalyzer rapidly absorption go up a large amount of metallic impurity, catalyzer is poisoned rapidly.For protecting certain catalyst activity, just must increase the magnitude of recruitment of live catalyst and the quantity discharged of decaying catalyst, cause material consumption increase and environmental pollution.
When the distillate of containing metal impurity was used as hydrocracking raw material, these metallic impurity particularly calcium, iron etc. formed the sulfide deposition on beds, and these settlings not only influence the catalytic activity of hydrogenation catalyst; And seriously stop up the bed hole, and hinder oil stream normally passing through on beds, cause the hydrogenation catalyst unit consumption to strengthen, shortened the device cycle of operation.
When residual oil was used as the raw material of producing refinery coke, metallic impurity wherein can increase the ash in the refinery coke, have a strong impact on quality product.
Remove in the hydro carbons the useful pyrrolidone-alcohol mixture of the method for metal or with a kind of preferable C/H than and preferred molecular weight fused-ring aromatic compound and with the method for some high dielectric strength organic compound by complexometric extraction, can partly remove the metallic impurity in the hydrocarbon ils, use di-carboxylic acid, ethylenediamine tetraacetic acid (EDTA) and salt thereof also can remove the metallic impurity in the part hydrocarbon ils.
At present, refinery's widespread use is electric desalting crude oil upgrading technology.Principle is that crude oil demulsifier and metal remover are dissolved in respectively in the electric desalting water filling, water filling and crude oil are behind the mixing tank thorough mixing, water is dispersed into very little water droplet in crude oil, organometallic compound effect in water-oil interface metal remover soluble in water and crude oil, make metal ion free, or form complex compound, throw out is dissolved in or be dispersed in the water.Water droplet is under the acting in conjunction of electric field and emulsion splitter, and is rapidly coalescent and separate from crude oil, reaches dehydrating of crude oil, demetalization purpose.
At present, crude oil demulsifier and metal remover, precipitation agent mostly are and are used.Use separately the alkaline-earth metal of crude oil demulsifier in can not effective elimination crude oil; And decalcifying agent itself does not have the breakdown of emulsion function.
Summary of the invention
The objective of the invention is: prepare a kind of multifunctional crude oil demulsifying agent, this emulsion splitter has stronger surfactivity and good wettability, and enough flocculations and agglutinating power, has efficient breakdown of emulsion and dewatering.
Multifunctional crude oil demulsifying agent of the present invention has the trimethyl-glycine molecular structure, belongs to zwitterionics, its molecular formula
Wherein, R
1=(C
3H
6O)
y(C
2H4O)
xH, x=5-30; Y=15-50; Q=1-15; R=1-2
Invention has the crude oil demulsifier preparation process as follows, with a certain amount of organic amine is initiator, these initiators can be quadrols, diethylenetriamine, triethylene tetramine, polyethylene polyamine, and their mixture, and propylene oxide (PO) polymerization, be catalyzer with sodium hydroxide or potassium hydroxide, temperature of reaction 90-150 ℃, reaction pressure is 0.15-0.45MPa.Treat to feed oxyethane (EO) again after PO absorbs fully, EO is polyethers after absorbing fully.Get a certain amount of above-mentioned polyethers, generate the betaine type molecular structure with the alpha-halogenated carboxylic acids reacting by heating again, add a certain amount of solvent and be finished product.Alpha-halogenated carboxylic acids is alpha-halogen acetate, alpha-halogen propionic acid, alpha-halogen higher fatty acid, alpha-halogen Succinic Acid, alpha-halogen propanedioic acid.
The multifunctional crude oil demulsifying agent of invention has the trimethyl-glycine molecular structure, belong to zwitterionics, owing to have above-mentioned molecular structure, this emulsion splitter has stronger surfactivity and good wettability, and enough flocculations and agglutinating power, have efficient breakdown of emulsion and dewatering.Amido and quaternary amine base are strong absorption bases, the emulsion splitter molecule is adsorbed on the water-oil interface rapidly by these groups, have the active oxyethane of good interface, propylene oxide chain and quaternary amine base and be connected and move freely and stay on the interface, make break down of boundary film, milk sap generation breakdown of emulsion.This crude oil demulsifier and other emulsion splitter commonly used and chemical formula agent have excellent compatibility.Wider to all kinds of crude oil emulsion adaptability.
Simultaneously, this emulsion splitter has better water solubility, and carboxyl and quaternary amine base and deposit on the molecule have fabulous wetting effect, it is good calcium dispersion agent that alkaline-earth metal in the crude oil is had fabulous complexing stabilising effect, and the magnesium in the crude oil, iron are also had removal effect preferably.
Embodiment
Embodiment 1
1. propylene oxide (PO), oxyethane (EO) block co-polyether
In the 500ml autoclave of electric mixer is housed, add 23.0g diethylenetriamine and 80ml Mixed XYLENE, adding 0.2g potassium hydroxide is catalyzer, under the condition of heating and stirring, feed 70.0gPO and 15.0gEO successively, range of reaction temperature 120-140 ℃, reaction pressure is 0.45MPa, and decompression steams dimethylbenzene and promptly gets required polyethers after the absorption fully.
2. the betaine type crude oil demulsifier is synthetic
In the 500ml there-necked flask of band stirring, thermometer, prolong, add 1 polyethers 54.0g and 220ml95% ethanol, carefully add 36.0g alpha-halogen acetate in three batches, reinforced Bi Huiliu 3 hours, heat filtering is removed white solid in the solution, steams the product that the ethanol in the filtrate obtains then and is finished product.
Dehydration test is carried out (bottle examination method) according to ordinary method.Under the room temperature condition, add xinjiang crude oil (moisture 0.6%) 50.0g in the tapered test tube of 100ml tool plug band scale, add the 12.0g deionized water, the crude oil demulsifier of metering is put into water bath with thermostatic control and is taken out after 15 minutes, vibration is 5 minutes on vibrator, put back in the water bath with thermostatic control, time recording is deviate from the water body product again.The oil sample water ratio is 20%; 90 ± 1 ℃ of bath temperatures; Demulsifier concentration 100ppm.
| Emulsion splitter | Add-on ppm | Dehydration rate amount ml | Dehydration rate % | The sewage color | ||||
| Dewatering time min | ?10 | ?20 | ?30 | ?60 | 90 | |||
| Blank | 0 | ?2.7 | ?3.8 | ?5.9 | ?6.4 | No change | 52 | The interface is unclear |
| Blank | 0 | ?3.2 | ?4.2 | ?6.2 | ?6.7 | No change | 59 | The interface is unclear |
| Example 1 | 100 | ?8.1 | ?10.1 | ?10.7 | ?11.0 | No change | 89 | The interface is clear |
| Example 1 | 100 | ?8.5 | ?10.6 | ?11.0 | ?11.3 | No change | 92 | The interface is clear |
Embodiment 2
Method with embodiment 1 prepares block co-polyether, in the autoclave of electric mixer is housed, adds 23.0g triethylene tetramine and 80ml Mixed XYLENE, and adding 0.2g sodium hydroxide is catalyzer.Under the condition of heating and stirring, feed 70.0gPO and 15.0gEO successively, range of reaction temperature 90-120 ℃, reaction pressure is 0.45MPa, and decompression steams dimethylbenzene and promptly gets required polyethers after the absorption fully.
In the there-necked flask of band stirring, thermometer, prolong, add example 1 polyethers 54.0g and 200ml 95% ethanol, be heated to 50 ℃, slowly drip alpha-chloro propionic acid 49.0g.Dropwise, reactant refluxes and made reaction reach complete in about 2.5 hours.Remove by filter white solid, removal of solvent under reduced pressure and unreacted reactant are cooled to room temperature, add 60ml industrial alcohol or methyl alcohol and are finished product.
Test conditions is, 130 ℃ of xinjiang crude oil desalination temperature, strength of electric field are 1000V/cm, water injection rate 6%,
Total residence time 40 minutes.Metal content analysis adopts the dry ashing atomic absorption method in the crude oil.
| Example 2 emulsion splitter ppm | ?30 | ?70 | ?100 | ?150 | Take off preceding crude oil | Maximum decreasing ratio % | |
| Metal content | Ca | ?16.0 | ?13.0 | ?11.0 | ?9.4 | 52.0 | 82 |
| Mg | ?0.9 | ?0.67 | ?0.52 | ?0.45 | 1.1 | 59 | |
| Fe | ?2.1 | ?1.8 | ?1.5 | ?1.4 | 2.9 | 52 | |
This invention emulsion splitter has better breakdown of emulsion and metal removal effect, and is comparatively economical when the emulsion splitter consumption is 100ppm.
Embodiment 3
In the 500ml autoclave of electric mixer is housed, add 23.0g quadrol and 80ml Mixed XYLENE, adding 0.2g potassium hydroxide is catalyzer, under the condition of heating and stirring, feed 70.0gPO and 15.0gEO successively, range of reaction temperature 130-150 ℃, reaction pressure is 0.15MPa, and decompression steams dimethylbenzene and promptly gets required polyethers after the absorption fully.
In the 500ml there-necked flask of band stirring, thermometer, prolong, add polyethers 54.0g and 220ml95% ethanol, carefully add 36.0g alpha-halogen Succinic Acid in three batches, reinforced Bi Huiliu 3 hours, heat filtering is removed white solid in the solution, steams the product that the ethanol in the filtrate obtains then and is finished product.This invention emulsion splitter has better breakdown of emulsion and metal removal effect, and is comparatively economical when the emulsion splitter consumption is 100ppm.
Claims (4)
1. multifunctional crude oil demulsifying agent preparation method, it is characterized in that: be initiator with the organic amine, and propylene oxide (PO) polymerization, be catalyzer with sodium hydroxide or potassium hydroxide, temperature of reaction 90-150 ℃, reaction pressure is for O.15-0.45MPa, treat to feed oxyethane (EO) again after PO absorbs fully, EO is polyethers after absorbing fully, gets above-mentioned polyethers, generate the betaine type molecular structure with the alpha-halogenated carboxylic acids reacting by heating again, add solvent and be finished product.
2. multifunctional crude oil demulsifying agent preparation method according to claim 1 is characterized in that: organic amine is a quadrol, diethylenetriamine, triethylene tetramine, polyethylene polyamine, and their mixture.
3. multifunctional crude oil demulsifying agent preparation method according to claim 1 is characterized in that: alpha-halogenated carboxylic acids is alpha-halogen acetate, alpha-halogen propionic acid, alpha-halogen higher fatty acid, alpha-halogen Succinic Acid, alpha-halogen propanedioic acid.
The multifunctional crude oil demulsifying agent of 4 multifunctional crude oil demulsifying agent preparation method preparations according to claim 1, it is characterized in that: molecular characterization is the trimethyl-glycine polyethers, and molecular formula is:
Wherein, R
1=(C
3H
6O)
y(C
2H4O)
xH, x=5-30; Y=15-50; Q=1-15; R=1-2
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN03134878.5A CN1283339C (en) | 2003-09-27 | 2003-09-27 | Method for preparing multifunctional deemulsifying agent of crude oil and products thereof |
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|---|---|---|---|
| CN03134878.5A CN1283339C (en) | 2003-09-27 | 2003-09-27 | Method for preparing multifunctional deemulsifying agent of crude oil and products thereof |
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|---|---|
| CN1600835A true CN1600835A (en) | 2005-03-30 |
| CN1283339C CN1283339C (en) | 2006-11-08 |
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|---|---|---|---|
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100345942C (en) * | 2005-12-12 | 2007-10-31 | 中国海洋石油总公司 | Crude oil deemulsifying agent and its preparing method |
| CN102041040A (en) * | 2010-12-27 | 2011-05-04 | 中国海洋石油总公司 | Composite raw oil demulsifier |
| US20110247966A1 (en) * | 2010-04-08 | 2011-10-13 | Nalco Company | Recovery and Separation of Crude Oil and Water from Emulsions |
| CN101473068B (en) * | 2006-04-18 | 2012-07-04 | 凯密特尔有限责任公司 | Process for the demulsifying cleaning of metallic surfaces |
| CN102558539A (en) * | 2011-12-19 | 2012-07-11 | 上海东大聚氨酯有限公司 | Method for preparing rigid foam polyether polyol by using multi-amine as initiator |
| CN101987965B (en) * | 2009-08-06 | 2013-10-16 | 中国科学院兰州化学物理研究所 | Compound desalter for crude oil |
| CN109762594A (en) * | 2019-01-18 | 2019-05-17 | 新疆科力新技术发展股份有限公司 | Low interfacial tension demulsifier and preparation method thereof |
| CN111423902A (en) * | 2020-04-20 | 2020-07-17 | 中国石油化工股份有限公司 | Demulsification synergist for thickened oil and preparation method thereof |
| CN114890921A (en) * | 2022-06-23 | 2022-08-12 | 麦加芯彩新材料科技(上海)股份有限公司 | Multi-branch sulfonated betaine ionic liquid and preparation method and application thereof |
| CN114890921B (en) * | 2022-06-23 | 2024-06-11 | 麦加芯彩新材料科技(上海)股份有限公司 | Multi-branch sulfonated betaine type ionic liquid and preparation method and application thereof |
Families Citing this family (2)
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| CN101402879B (en) * | 2008-11-14 | 2013-01-02 | 华东理工大学 | Multifunctional crude oil demulsifying agent and method of producing the same |
| CN103421533A (en) * | 2013-09-02 | 2013-12-04 | 江苏大学 | Negative ion modified polyether demulsifier and synthetic method thereof |
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2003
- 2003-09-27 CN CN03134878.5A patent/CN1283339C/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100345942C (en) * | 2005-12-12 | 2007-10-31 | 中国海洋石油总公司 | Crude oil deemulsifying agent and its preparing method |
| CN101473068B (en) * | 2006-04-18 | 2012-07-04 | 凯密特尔有限责任公司 | Process for the demulsifying cleaning of metallic surfaces |
| CN102787320A (en) * | 2006-04-18 | 2012-11-21 | 凯密特尔有限责任公司 | Process for the demulsifying cleaning of metallic surfaces |
| CN102787320B (en) * | 2006-04-18 | 2014-10-29 | 凯密特尔有限责任公司 | Process for the demulsifying cleaning of metallic surfaces |
| CN101987965B (en) * | 2009-08-06 | 2013-10-16 | 中国科学院兰州化学物理研究所 | Compound desalter for crude oil |
| US8911615B2 (en) * | 2010-04-08 | 2014-12-16 | William Marsh Rice University | Recovery and separation of crude oil and water from emulsions |
| US20110247966A1 (en) * | 2010-04-08 | 2011-10-13 | Nalco Company | Recovery and Separation of Crude Oil and Water from Emulsions |
| CN102869422A (en) * | 2010-04-08 | 2013-01-09 | 威廉马什赖斯大学 | Recovery and separation of crude oil and water from emulsions |
| CN102041040A (en) * | 2010-12-27 | 2011-05-04 | 中国海洋石油总公司 | Composite raw oil demulsifier |
| CN102041040B (en) * | 2010-12-27 | 2013-08-28 | 中国海洋石油总公司 | Composite raw oil demulsifier |
| CN102558539A (en) * | 2011-12-19 | 2012-07-11 | 上海东大聚氨酯有限公司 | Method for preparing rigid foam polyether polyol by using multi-amine as initiator |
| CN109762594A (en) * | 2019-01-18 | 2019-05-17 | 新疆科力新技术发展股份有限公司 | Low interfacial tension demulsifier and preparation method thereof |
| CN111423902A (en) * | 2020-04-20 | 2020-07-17 | 中国石油化工股份有限公司 | Demulsification synergist for thickened oil and preparation method thereof |
| CN111423902B (en) * | 2020-04-20 | 2022-04-22 | 中国石油化工股份有限公司 | Demulsification synergist for thickened oil and preparation method thereof |
| CN114890921A (en) * | 2022-06-23 | 2022-08-12 | 麦加芯彩新材料科技(上海)股份有限公司 | Multi-branch sulfonated betaine ionic liquid and preparation method and application thereof |
| CN114890921B (en) * | 2022-06-23 | 2024-06-11 | 麦加芯彩新材料科技(上海)股份有限公司 | Multi-branch sulfonated betaine type ionic liquid and preparation method and application thereof |
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