CN108929714B - Sodium removing agent suitable for organic sodium salt in crude oil - Google Patents
Sodium removing agent suitable for organic sodium salt in crude oil Download PDFInfo
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- CN108929714B CN108929714B CN201810879166.3A CN201810879166A CN108929714B CN 108929714 B CN108929714 B CN 108929714B CN 201810879166 A CN201810879166 A CN 201810879166A CN 108929714 B CN108929714 B CN 108929714B
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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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/02—Non-metals
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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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
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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
- 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
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- 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 sodium removing agent suitable for organic sodium salt in crude oil comprises 5-80 parts of organic ammonium salt and 20-95 parts of inorganic ammonium salt; the sodium removing agent also comprises the following components: 5-80 parts of organic ammonium salt, 20-95 parts of inorganic ammonium salt, 0.5-5 parts of transfer aid and deionized water, wherein the organic ammonium salt, the inorganic ammonium salt and the transfer aid are effective components of the crude oil sodium removal agent, and the concentration of the effective components in the deionized water is 1% -80%. The crude oil sodium removal agent is a neutral aqueous solution, does not corrode equipment, and does not have adverse effects on the crude oil processing process and sewage treatment. The sodium removing agent has good water solubility and removing capability to organic sodium salt in crude oil, is convenient to use, and can completely realize effective removal of the organic sodium salt by means of a conventional crude oil electric desalting device.
Description
Technical Field
The invention belongs to the field of petroleum processing, and mainly relates to a sodium removal agent suitable for removing oil-soluble organic sodium salt in crude oil.
Background
At present, main oil fields in China enter the later stage of secondary oil recovery, and in order to improve the recovery ratio of crude oil, a tertiary oil recovery technology which is characterized by a chemical compound flooding technology is widely applied. Among chemical compound flooding technologies, three-element compound flooding (alkali, surfactant and high molecular polymer) is a new technology developed in the last 80 th century and is widely adopted in domestic oil fields. In the ternary combination flooding technology, the anionic surfactant petroleum sodium sulfonate is widely adopted due to the characteristics of strong interfacial activity, good oil displacement effect, low price and the like. The average carbon atom number of the oleophilic group of the petroleum sodium sulfonate used in the tertiary oil recovery process is more than 23, the affinity with the crude oil is strong, and the oleophilic group is more easily dissolved in the crude oil and is a main reason for the increase of the organic sodium content of the crude oil.
Because of strong surface activity and poor water solubility of the long-carbon-chain sodium petroleum sulfonate, the oil-water separation is difficult, water is severely cut, an electric desalting tank frequently trips, and the organic sodium content of the desalted crude oil is high, so that the subsequent processing of the crude oil is influenced.
Sodium is one of the toxic and harmful metals in crude oil processing. Sodium is a strong alkali metal and its effect on the catalyst mainly comprises 3 aspects: firstly, the hydrothermal stability of the catalyst is reduced; secondly, the acid center of the catalyst is neutralized, so that the activity of the catalyst is reduced or the catalyst is permanently inactivated; thirdly, pore channels of the catalyst are blocked, the contact probability of the catalyst and materials is reduced, and finally, the product distribution is deteriorated, and the economic benefit of a refinery is influenced. The sodium salt is easy to deposit on the inner walls of equipment such as a heat exchanger, a heating furnace, a tower tray and the like to form salt scale, so that under-scale corrosion is caused, the heat transfer efficiency and the product quality are influenced, raw material coking is promoted, pipelines and equipment are blocked when the raw material coking is serious, and safety accidents are caused. Therefore, the effective removal of sodium content from crude oil is a major objective of electric crude oil desalting plant in refineries.
The sodium in crude oil has been mainly present in the form of inorganic sodium salt, such as NaCl, Na2CO3And the like, these inorganic sodium salts are readily soluble in water and can be effectively removed by an electro-desalting process. After the common medium and light crude oil is subjected to two-stage electric desalting, the salt content of the desalted crude oil can reach below 3mgNaCl/l, and the technical requirement of deep desalting is met. However, as crude oil resources become heavier and tertiary oil recovery techniques are commonly used, the organic sodium salt content of crude oilAdditionally, these sodium salts are poorly soluble in water and are difficult to remove during the electrodesalting process, resulting in the spread of the sodium hazard throughout petroleum processing.
Disclosure of Invention
In order to overcome the defects in the background art, the invention aims to provide a sodium removing agent suitable for organic sodium salts in crude oil. The sodium removing agent can convert oil-soluble organic sodium salt in crude oil into water-soluble inorganic sodium salt, and is removed by means of crude oil electric desalting process, thereby solving the adverse effect of high content of organic sodium in the crude oil after being removed on the crude oil processing process.
In order to realize the purpose, the invention adopts the following technical scheme: a sodium removing agent suitable for organic sodium salt in crude oil comprises the following components in parts by weight: 5-80 parts of organic ammonium salt and 20-95 parts of inorganic ammonium salt.
In order to further improve the technical scheme, the crude oil sodium removal agent also comprises the following components: 5-80 parts of organic ammonium salt, 20-95 parts of inorganic ammonium salt, 0.5-5 parts of transfer aid and deionized water, wherein the organic ammonium salt, the inorganic ammonium salt and the transfer aid are effective components of the crude oil sodium removal agent, and the concentration of the effective components in the deionized water is 1-80%.
In order to further improve the technical scheme, the organic ammonium salt is one or a mixture of more of ammonium acetate, ammonium salicylate, ammonium benzoate, ammonium oxalate, ammonium citrate, ammonium hexahydroxyantimonate and ammonium acrylate.
In order to further improve the technical scheme, 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 hydrogen sulfate and ammonium nitrate.
In order to further improve the technical scheme, the transfer aid is one or a mixture of alcohol and a surfactant.
In order to further improve the technical scheme, the alcohol is monohydric alcohol containing 3-4 carbon atoms.
In order to further improve the technical scheme, the surfactant is a nonionic surfactant.
In order to further improve the technical scheme, the nonionic surfactant is polyethylene glycol (PEG-400-800) and polypropylene glycol (PPG-400-800) with the molecular weight of 400-800.
The preparation method of the sodium removing agent suitable for the organic sodium salt in the crude oil comprises the following steps: and (3) adding deionized water into a stirring kettle in proportion, then adding organic ammonium salt, inorganic ammonium salt and transfer aid in proportion without sequence, and stirring at normal temperature until the solid is completely dissolved.
Due to the adoption of the technical scheme, the invention has the following beneficial effects: the action mechanism of the sodium removing agent suitable for the organic sodium salt in the crude oil is mainly (1) ion exchange reaction. The organic ammonium salt and the inorganic ammonium salt are easily dissolved in water, and ammonium ions are ionized in an aqueous solution, and the ammonium ions and the organic ammonium salt (mainly sodium petroleum sulfonate, R-SO) in the crude oil3Na) to form ammonium petroleum sulfonate and transferring sodium ions to the aqueous phase. R-SO3Na+NH4 +→R-SO3NH4+Na+(ii) a (2) The difference in water solubility is utilized. For long chain petroleum sulfonates, the sodium salt is generally more water soluble than the sulfonic acid itself, and the ammonium ions in the ammonium salt hydrolyze to produce hydrogen ions which convert the sodium petroleum sulfonate to petroleum sulfonic acid. NH (NH)4 ++H2O＝NH3·H2O+H+，R-SO3Na+H+→R-SO3H+Na+(ii) a (3) And (4) carrying out precipitation reaction. The sodium ions in the petroleum sodium sulfonate are transferred to a water phase by utilizing the reaction of the sodium ions and sodium hexahydroxy antimonate to produce hydrophilic precipitate. R-SO3Na+NH4Sb(OH)6＝NaSb(OH)6↓ (white) + R-SO3NH4. Under the dual actions of a transfer aid and strong mixing, organic ammonium salt and inorganic ammonium salt are contacted with organic sodium salt in crude oil and one or more reactions are carried out, so that organic sodium ions in the crude oil are removed in the crude oil electric desalting process, and the influence of the high sodium content of the crude oil after the removal on subsequent processing is eliminated.
The sodium removing agent suitable for the organic sodium salt in the crude oil is an aqueous solution which is nearly neutral, does not corrode equipment, and does not cause adverse effects on the crude oil processing process and sewage treatment. The sodium removing agent has good water solubility and removing capability to organic sodium salt in crude oil, is convenient to use, and can completely realize effective removal of the organic sodium salt by means of a conventional crude oil electric desalting device.
The transfer aid is used for promoting organic ammonium salt and inorganic ammonium salt to fully contact with organic sodium salt in crude oil, so that the removal speed and efficiency of the organic sodium salt are improved. In this case, the crude oil sodium remover according to the present invention can be changed from an aqueous solution to a solid mixture of an organic ammonium salt and an inorganic ammonium salt, and although such a change is significantly different from the aqueous solution of the sodium remover according to the present invention in terms of morphology, the composition of the core thereof is not changed, and therefore, all changes that do not depart from the spirit of the present invention are covered by the present invention.
Detailed Description
The present invention will be explained in detail by the following examples, which are disclosed for the purpose of protecting all technical improvements within the scope of the present invention.
Example 1
The sodium removing agent is a solid mixture of organic ammonium salt and inorganic ammonium salt, wherein the solid mixture comprises 5 parts of ammonium acetate, 35 parts of ammonium phosphate, 20 parts of diammonium hydrogen phosphate, 20 parts of ammonium nitrate and 20 parts of ammonium chloride.
Example 2
The sodium removing agent is a solid mixture of organic ammonium salt and inorganic ammonium salt, wherein the solid mixture comprises 20 parts of ammonium acetate, 30 parts of ammonium hexahydroxyantimonate, 10 parts of ammonium oxalate, 15 parts of ammonium citrate, 20 parts of ammonium acrylate and 5 parts of ammonium sulfate.
Example 3
The sodium eliminating agent for organic sodium salt in crude oil is solid mixture of organic ammonium salt and inorganic ammonium salt, and includes ammonium acetate 50 weight portions, ammonium hexahydroxy antimonate 10 weight portions, ammonium bicarbonate 20 weight portions and ammonium carbonate 20 weight portions.
Example 4
A sodium removing agent suitable for organic sodium salt in crude oil comprises 5 parts of ammonium acetate, 90 parts of ammonium carbonate, 3 parts of PEG-4003 and 2 parts of isopropanol; the effective components are stirred and dissolved in deionized water, and the total concentration of the effective component water solution is 80%.
Example 5
The sodium removing agent suitable for organic sodium salt in crude oil comprises the effective components of 60 parts of ammonium acetate, 30 parts of ammonium hexahydroxyantimonate, 5 parts of ammonium bicarbonate, 2 parts of PEG-6002 and 3 parts of tert-butyl alcohol; the effective components are stirred and dissolved in deionized water, and the total concentration of the effective component water solution is 70%.
Example 6
47 parts of ammonium acetate, 10 parts of ammonium benzoate, 5 parts of ammonium hexahydroxyantimonate, 20 parts of ammonium bicarbonate, 15 parts of ammonium dihydrogen phosphate and PEG-8003 parts of effective components of the sodium removing agent suitable for organic sodium salts in crude oil; the effective components are stirred and dissolved in deionized water, and the total concentration of the effective component water solution is 20%.
Example 7
The sodium removing agent suitable for organic sodium salt in crude oil comprises the effective components of 30 parts of ammonium acetate, 30 parts of ammonium salicylate, 20 parts of ammonium hexahydroxyantimonate, 10 parts of ammonium bicarbonate, 9 parts of ammonium phosphate and PPG-4001 parts; the effective components are stirred and dissolved in deionized water, and the total concentration of the effective component water solution is 1 percent.
Example 8
The sodium removing agent comprises the effective components of 5 parts of ammonium acetate, 5 parts of ammonium citrate, 43 parts of ammonium bicarbonate, 43 parts of diammonium hydrogen phosphate and PPG-6004 parts; the effective components are stirred and dissolved in deionized water, and the total concentration of the effective component water solution is 40%.
Example 9
The sodium removing agent comprises the effective components of 40 parts of ammonium acetate, 10 parts of ammonium oxalate, 10 parts of ammonium hexahydroxy antimonate, 30 parts of ammonium bicarbonate, 5 parts of ammonium sulfate, PPG-8003 parts of tertiary butanol and 2 parts of sodium acetate; the effective components are stirred and dissolved in deionized water, and the total concentration of the effective component water solution is 50%.
Example 10
A sodium removing agent suitable for organic sodium salt in crude oil comprises the effective components of 10 parts of ammonium acetate, 40 parts of ammonium acrylate, 35 parts of ammonium bicarbonate, 13 parts of ammonium bisulfate and 2 parts of isopropanol; the effective components are stirred and dissolved in deionized water, and the total concentration of the effective component water solution is 30 percent.
Example 11
The sodium removing agent comprises the effective components of 20 parts of ammonium acetate, 10 parts of ammonium acrylate, 10 parts of ammonium hexahydroxyantimonate, 20 parts of ammonium bicarbonate, 15 parts of ammonium dihydrogen phosphate, 20 parts of ammonium chloride and 5 parts of tert-butyl alcohol; the effective components are stirred and dissolved in deionized water, and the total concentration of the effective component aqueous solution is 65%.
In order to better illustrate the using effect of the crude oil sodium removal agent, in the experiment, the aqueous solution of the sodium removal agent is proportionally injected with the electric desalting water injection before the mixing valve, if the crude oil sodium removal agent is solid, the crude oil sodium removal agent can be firstly dissolved in the electric desalting water injection, the sodium removal agent and the organic sodium salt in the crude oil perform ion exchange reaction when an oil-water mixture enters an electric desalting tank, sodium ions are transferred from an oil phase to a water phase, oil-water separation is realized by the action of an electric field force, the oil phase flows out from the top of the electric desalting tank, and the water phase flows out from the bottom of the electric desalting tank.
The crude oil used in the test had a salt content of 12.50mg NaCl/l and an organic sodium ion content of 18.3 mg/l. All the tests have the same technological conditions, the primary and secondary water injection rates are 5%, the mixing strength is 0.8MPa, the desalting temperature is 130 ℃, and the electric field strength is 2000V/cm. The crude oil sodium removal agent disclosed by the invention is not added in a blank test, and the crude oil sodium removal agent in the embodiment 1-9 is added according to the content of an effective component of 100mg/kg (for crude oil). The test results are shown in table 1.
Table 1 test results of crude oils after two-stage stripping in examples 1 to 9
Claims (2)
1. A sodium removing agent suitable for organic sodium salt in crude oil is characterized in that: the sodium removing agent comprises the following components in parts by weight: 5-80 parts of organic ammonium salt, 20-95 parts of inorganic ammonium salt, 0.5-5 parts of transfer aid and deionized water, wherein the organic ammonium salt, the inorganic ammonium salt and the transfer aid are effective components of the sodium removing agent, and the concentration of the effective components in the deionized water is 1% -80%; the organic ammonium salt is a mixture of one or more of ammonium acetate, ammonium salicylate, ammonium benzoate, ammonium citrate and ammonium acrylate and ammonium hexahydroxy antimonate; the inorganic ammonium salt is one or a mixture of more of ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium chloride, ammonium sulfate, ammonium bisulfate and ammonium nitrate; the transfer aid is one or a mixture of alcohol and a surfactant; the alcohols are monohydric alcohols containing 3-4 carbon atoms; the surfactant is a nonionic surfactant.
2. The sodium removing agent suitable for organic sodium salt in crude oil as claimed in claim 1, which is characterized in that: the nonionic surfactant is polyethylene glycol with the molecular weight of 400-800 and polypropylene glycol with the molecular weight of 400-800.
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| CN111471485B (en) * | 2019-01-23 | 2021-12-17 | 中国石油化工股份有限公司 | Method for removing sodium salt from hydrocarbon oil |
| CN114471688B (en) * | 2020-10-28 | 2023-07-28 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst |
| CN114479912B (en) * | 2020-11-11 | 2023-12-22 | 中石油克拉玛依石化有限责任公司 | Pretreatment method of crude oil containing organic sodium |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87105145A (en) * | 1986-07-28 | 1988-04-27 | 切夫伦公司 | Staged catalyst system for removal of calcium and sodium from hydrocarbon feeds |
| CN1657593A (en) * | 2004-02-18 | 2005-08-24 | 中国石油化工股份有限公司 | Treating agent for removing metal calcium from crude oil |
| CN104004926A (en) * | 2014-06-11 | 2014-08-27 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing high-purity vanadium pentoxide through sodium polyvanadate |
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| CN1028537C (en) * | 1991-02-06 | 1995-05-24 | 中国石油化工总公司 | Removal of metals from hydrocarbon raw material with complexing agent |
| CN1760338A (en) * | 2005-11-04 | 2006-04-19 | 克拉玛依市金山石油化工有限公司 | Crude oil decalcifying agent and method for decalcifying crude oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87105145A (en) * | 1986-07-28 | 1988-04-27 | 切夫伦公司 | Staged catalyst system for removal of calcium and sodium from hydrocarbon feeds |
| CN1657593A (en) * | 2004-02-18 | 2005-08-24 | 中国石油化工股份有限公司 | Treating agent for removing metal calcium from crude oil |
| CN104004926A (en) * | 2014-06-11 | 2014-08-27 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing high-purity vanadium pentoxide through sodium polyvanadate |
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