CN112011362A - Method for removing sodium salt from hydrocarbon oil - Google Patents

Method for removing sodium salt from hydrocarbon oil Download PDF

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Publication number
CN112011362A
CN112011362A CN201910466079.XA CN201910466079A CN112011362A CN 112011362 A CN112011362 A CN 112011362A CN 201910466079 A CN201910466079 A CN 201910466079A CN 112011362 A CN112011362 A CN 112011362A
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sodium
oil
hydrocarbon
quaternary phosphonium
phosphonium salt
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CN201910466079.XA
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CN112011362B (en
Inventor
沈明欢
于丽
王振宇
秦冰
张峰
苗杰
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G33/00—Dewatering or demulsification of hydrocarbon oils
    • C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G33/00—Dewatering or demulsification of hydrocarbon oils
    • C10G33/02—Dewatering or demulsification of hydrocarbon oils with electrical or magnetic means
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1033—Oil well production fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

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

Abstract

A method for removing sodium salts from hydrocarbon oils, comprising: the hydrocarbon raw oil, the quaternary phosphonium salt sodium removal auxiliary agent, the demulsifier and water are mixed in a mixer and enter an electric desalting device for desalting treatment, so that the hydrocarbon oil with the remarkably reduced sodium content is obtained. The quaternary phosphonium salt is represented by the general formula [ R1P+(R2)3]nXn‑Wherein R is1Is C8‑C22Alkyl or alkoxy of (a); r2Is C1‑C4Alkyl or hydroxyalkyl, phenyl or benzyl; n is an integer from 1 to 3 and X is an anionic group. The method can effectively solve the problem of metal sodium pollution of the oil refining catalytic cracking unit catalyst caused by the oilfield chemical agent, and greatly reduce the risk of sodium poisoning of the catalytic cracking catalyst.

Description

Method for removing sodium salt from hydrocarbon oil
Technical Field
The invention relates to a method for demetallizing hydrocarbon oil, in particular to a method for removing metal sodium salt from hydrocarbon raw oil.
Background
In recent years, with increasing weight and deterioration of petroleum resources and the use of a large amount of oilfield chemicals in the oil extraction and gathering processes, the proportion of pollutants in crude oil processed by refineries is increased, wherein metal pollutants have increasingly negative effects on the catalytic cracking process, and the pollution elements mainly comprise nickel, vanadium, iron, calcium, sodium and the like, are continuously deposited on a catalyst in the catalytic cracking reaction process, cause catalyst poisoning by destroying the crystal structure, blocking pore channels, covering active sites and the like, and the process is generally irreversible.
In order to improve the recovery ratio of crude oil, the application of tertiary oil recovery technology tends to be wide, the ternary combination flooding technology is further developed on the basis of great success of polymer flooding of domestic main oil fields such as Daqing oil fields, and the like, and the heavy alkylbenzene sulfonate and the alkali solution are compounded for use, so that the interfacial tension of the crude oil can be reduced to an ultralow value within a wide concentration range, and the oil recovery ratio is obviously improved. The petroleum sulfonate, the heavy alkylbenzene sulfonate and other oil extraction additives have good interfacial activity and emulsifying property, but the problems of difficult demulsification, high crude sodium content, catalyst poisoning and the like are easily caused while the crude oil recovery rate is improved, the normal and stable operation of a catalytic cracking device of a refinery is influenced, and the agent consumption and the production cost are increased.
Aiming at the problem of metal pollution on a catalytic cracking balancing agent, a catalyst with strong metal resistance is selected and a metal passivator is added in the industry, but the methods have high cost and low efficiency, and the effect of reducing the metal content in the raw materials from the source is achieved with half the effort. The electric desalting is used as a main anti-corrosion measure of a refinery, generally, the first operation step of removing solid particles, toxic and harmful substances and soluble pollutants in crude oil by enterprises is the first operation step, at present, the electronic desalting platform is used for removing nickel, vanadium, iron and calcium in raw materials, and an acidic demetallizing agent is mainly used.
CN108929714A discloses a sodium removing agent suitable for organic sodium salt in crude oil, which comprises 5-80 parts of organic ammonium salt, 20-95 parts of inorganic ammonium salt and 0.5-5 parts of transfer aid. The organic ammonium salt is one or a mixture of more of ammonium acetate, ammonium salicylate, ammonium benzoate, ammonium oxalate, ammonium citrate, ammonium hexahydroxy antimonate and ammonium acrylate; the inorganic ammonium salt is one or a mixture of more of ammonium carbonate, ammonium bicarbonate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium chloride, ammonium sulfate, ammonium bisulfate and ammonium nitrate. The sodium removing agent has complex components and low sodium removing efficiency, and the maximum removing rate of organic sodium is only 82 percent.
Disclosure of Invention
Aiming at the problem of catalyst organic sodium poisoning caused by ternary combination flooding surfactant petroleum sulfonate, heavy alkylbenzene sulfonate and the like, the invention provides a method for removing organic sodium salt from hydrocarbon raw oil so as to realize source treatment of pollutants.
The inventor of the application unexpectedly finds that organic sodium salt can be removed very effectively by using quaternary phosphonium salt as a sodium removal auxiliary agent, and the effect of the quaternary ammonium salt is far better than that of quaternary ammonium salt with similar structure.
The method comprises the following steps: the hydrocarbon raw oil, the quaternary phosphonium salt sodium removal auxiliary agent, the demulsifier and water are mixed in a mixer and enter an electric desalting device, and the hydrocarbon oil with the significantly reduced sodium content is obtained after treatment.
The quaternary phosphonium salt is represented by the general formula [ R1P+(R2)3]nXn-Wherein R is1Is C8-C22Is preferably C10-C18An alkyl group or an alkoxy group, more preferably an alkoxy group having an acetal or polyether structure; r2Is C1-C4Alkyl of (C)1-C4Hydroxyalkyl, phenyl or benzyl of (a); n is an integer from 1 to 3 and X is an anionic group. Wherein, when n is 1, X is a monovalent anion such as Cl-、Br-Or HCOO-When n is 2, X is a divalent anion, e.g. SO4 2-(ii) a When n is 3, X is a trivalent anion, e.g. PO4 3-。
According to the inventionIn one embodiment, the quaternary phosphonium salt is preferably dodecyl tributyl phosphonium chloride, hexadecyl trihydroxypropyl phosphonium bromide, dodecyl oxymethyl tributyl phosphonium chloride, having the structure C12H25OCH2OCH2CH2P(C6H5)3Acetal modified quaternary phosphonium salt of Cl, having the structure of C10H21O(CH2CH2O)2CH2CH2P(C6H5)3One or more of Cl polyether modified quaternary phosphonium salts.
The dosage of the sodium removal auxiliary agent can be 5-500ug/g, preferably 10-300ug/g, more preferably 20-200ug/g based on the mass of the hydrocarbon raw oil.
The hydrocarbon raw oil is abbreviated as hydrocarbon oil and includes but is not limited to: crude oil, residual oil, refinery waste oil, and the like.
The content of metallic sodium in the hydrocarbon feedstock oil may be 1-200mg/kg, preferably 5-50mg/kg, based on the mass of the hydrocarbon oil.
The mixer can adopt a static mixer and a mixing valve used in an electric desalting device of a refinery, and can also adopt other mixing equipment.
The hydrocarbon raw oil is preferably preheated and then enters a mixer, and the preheating temperature can be 60-150 ℃.
The demulsifier needs to be screened according to the properties of the hydrocarbon oil, the screening method is well known to those skilled in the art, and the demulsifier can be a water-soluble demulsifier or an oil-soluble demulsifier, which is not described in detail herein, and is preferably a demulsifier with a thin oil-water interlayer and a low oil content in a water phase, such as BS906 and BS 01. The addition of the demulsifier can be 10-500ug/g based on the mass of the hydrocarbon raw oil.
The adding amount of the water can be 4-10 percent, preferably 6-8 percent based on the mass of the hydrocarbon raw oil.
The conditions of the electric desalting treatment are conventional in the field, and comprise the following steps: the treatment temperature is 100-150 ℃, the electric field intensity is 200-.
The method is suitable for removing organic sodium salt in hydrocarbon oil, in particular to organic sodium salt introduced by ternary complex flooding surfactant petroleum sulfonate, heavy alkylbenzene sulfonate and the like in the hydrocarbon oil. In addition, since inorganic sodium salts are more easily removed than organic sodium salts, the present invention can also remove inorganic sodium salts and other metal salts in hydrocarbon oils.
The method can be realized by utilizing the conventional electric desalting device of a refinery without modifying or newly adding related equipment, and after the sodium removal auxiliary agent is adopted to react with the residual oil field chemical agent in the hydrocarbon oil, organic sodium is converted into inorganic sodium which is easy to dissolve in water, the inorganic sodium is transferred into a water phase, and a good oil-water separation effect is achieved by combining the action of a high-efficiency demulsifier and an electrostatic field, so that qualified raw materials are provided for a subsequent processing device, the method is an effective means for solving the problem of catalytic cracking catalyst sodium poisoning, is easy to popularize and apply industrially, and has a good application prospect.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The properties of the crude oil are shown in table 1, 100g of crude oil is preheated at 60 ℃, 8g of distilled water and a quantitative demulsifier BS01 and 30ug/g of sodium removal auxiliary agent dodecyl tributyl phosphorus chloride (produced by Kent catalytic materials Co., Ltd.) are added and uniformly mixed, then the mixture is transferred to an electric desalting tank for sealing, the mixture is treated in an electrostatic field with the temperature of 120 ℃ and the electric field intensity of 500V/cm for 40min for oil-water separation, and when the temperature is reduced to about 60 ℃, an oil sample is taken for analyzing the salt content and the metallic sodium content. The results are shown in Table 2.
Example 2
Hexadecyl-trimethylolpropane phosphonium bromide (manufactured by kentuckt catalytic materials co., ltd.) was used as the sodium-removing assistant, and the operation, amount and result were as shown in table 2 in example 1.
Example 3
Alkoxy-modified quaternary phosphonium salt dodecyloxymethyltributyl phosphonium chloride (manufactured by kent catalytic materials, inc.) was used as the sodium-removing auxiliary agent, and the operation, amount and results were shown in table 2, according to the method of example 1.
Example 4
With the structure C12H25OCH2OCH2CH2P(C6H5)3Acetal-modified quaternary phosphonium salt of Cl (manufactured by Kent catalytic materials Co., Ltd.) as a sodium removal assistant was conducted in the same manner as in example 1, and the amounts and results are shown in Table 2.
Example 5
With the structure C10H21O(CH2CH2O)2CH2CH2P(C6H5)3Polyether-modified quaternary phosphonium salt of Cl (manufactured by Kent catalytic materials Co., Ltd.) as a sodium removal assistant was conducted in the same manner as in example 1, and the amounts and results thereof are shown in Table 2.
Example 6
The same as example 3, the amount of the sodium removal aid was 200 ug/g.
Example 7
The same as example 4, the amount of the sodium removal aid was 100 ug/g.
Example 8
The same as example 5, the amount of the sodium removal aid was 100 ug/g.
Comparative example 1
The procedure of example 1 was followed with the addition of the demulsifier alone and without the sodium removal aid, the amounts and results are shown in Table 2.
Comparative example 2
The procedure of example 1 was followed without the demulsifier and without the sodium removal aid, the amounts and the results are shown in Table 2.
Comparative example 3
The procedure of example 1 was followed except that the sodium removal aid was replaced with CN108929714A sodium removal aid used in example 9, namely 40 parts of ammonium acetate, 10 parts of ammonium oxalate, 10 parts of ammonium hexahydroxyantimonate, 30 parts of ammonium bicarbonate, 5 parts of ammonium sulfate, PPG-8003 parts of tert-butanol. The results are shown in Table 2.
Comparative example 4
The procedure is as in example 1 except that 1631 (cetyltrimethylammonium chloride, Shanghai Jinshan Longitude chemical plant) is added as a sodium removal aid, in amounts and results as shown in Table 2.
As can be seen from the examples and comparative examples, the use of quaternary phosphonium salt as the sodium removal aid can remove the organic sodium salt very effectively, and the effect is far better than that of the common quaternary ammonium salt.
TABLE 1 basic Properties of crude oils
Figure BDA0002079443650000061
Table 2 results of examples and comparative examples
Figure BDA0002079443650000062

Claims (11)

1. A method for removing sodium salts from hydrocarbon oils, comprising: the hydrocarbon raw oil, the quaternary phosphonium salt sodium removal auxiliary agent, the demulsifier and water are mixed in a mixer and enter an electric desalting device for desalting treatment, so that the hydrocarbon oil with the remarkably reduced sodium content is obtained.
2. The method according to claim 1, wherein the quaternary phosphonium salt is a quaternary phosphonium salt having the general formula [ R1P+(R2)3]nXn-Wherein R is1Is C8-C22Alkyl or alkoxy of (a); r2Is C1-C4Alkyl or hydroxyalkyl, phenyl or benzyl; n is an integer from 1 to 3 and X is an anionic group.
3. The method of claim 2, wherein R1Is C10-C18Alkyl or alkoxy.
4. The method of claim 2, wherein R1Is alkoxy containing acetal or polyether structure.
5. The method of claim 2 wherein the quaternary phosphonium salt is selected from the group consisting of dodecyltributyl phosphonium chloride, hexadecyl trishydroxypropyl phosphonium bromide, alkoxy-modified quaternary phosphonium salt, dodecyloxymethyl tributyl phosphonium chloride, having the structure C12H25OCH2OCH2CH2P(C6H5)3Acetal modified quaternary phosphonium salt of Cl, having the structure of C10H21O(CH2CH2O)2CH2CH2P(C6H5)3One or more of Cl polyether modified quaternary phosphonium salts.
6. The process according to any one of claims 1 to 5, wherein the amount of the sodium removal aid is 5 to 500ug/g based on the mass of the hydrocarbon feedstock.
7. The process according to any one of claims 1 to 5, wherein the amount of the sodium removal aid is from 10 to 300ug/g based on the mass of the hydrocarbon feedstock.
8. The process according to any one of claims 1 to 5, wherein the amount of the sodium removal aid is 20 to 200ug/g based on the mass of the hydrocarbon feedstock.
9. The process according to any one of claims 1 to 5, wherein the content of metallic sodium in the hydrocarbon feedstock oil is 1 to 200mg/kg based on the mass of the hydrocarbon oil.
10. The process according to any one of claims 1 to 5, wherein the amount of water added is from 4% to 10% by mass based on the mass of the hydrocarbon feedstock.
11. A hydrocarbon oil having a significantly reduced sodium content obtainable by a process according to any one of claims 1 to 10.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102876357A (en) * 2011-07-14 2013-01-16 中国石油化工股份有限公司 Demulsifying dehydration method of oilfield produced fluid
CN105505453A (en) * 2016-01-15 2016-04-20 深圳前海新域能源科技有限公司 Water-free coal tar desalting and demetalization method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102876357A (en) * 2011-07-14 2013-01-16 中国石油化工股份有限公司 Demulsifying dehydration method of oilfield produced fluid
CN105505453A (en) * 2016-01-15 2016-04-20 深圳前海新域能源科技有限公司 Water-free coal tar desalting and demetalization method

Non-Patent Citations (2)

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Title
赵怡等: "《中国石油化工 科技信息指南》", 28 April 2002, 中国石化出版社 *
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