CN115537230A - Online petroleum acid removing process - Google Patents
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- CN115537230A CN115537230A CN202211253375.XA CN202211253375A CN115537230A CN 115537230 A CN115537230 A CN 115537230A CN 202211253375 A CN202211253375 A CN 202211253375A CN 115537230 A CN115537230 A CN 115537230A
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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
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
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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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
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Abstract
The invention discloses an on-line deacidification process and method for crude oil, crude oil distillate oil and crude oil products containing petroleum acid in the processes of petroleum pretreatment, gathering, transportation, storage and refining, which mainly comprises the following steps: before crude oil enters a distillation treatment process, raw materials to be entered are mixed with a petroleum acid remover, and the obtained mixture and raw oil to be processed containing petroleum acid are jointly subjected to process treatment. The invention discloses an on-line deacidification process method for reducing acid value and removing petroleum acid in crude oil, crude oil distillate oil and crude oil products in the processes of petroleum pretreatment, gathering, transportation, storage and transportation and petroleum refining, and a petroleum acid remover.
Description
Technical Field
The invention relates to the technical field of petroleum exploitation, storage and transportation and petroleum refining processing. The invention relates to an on-line deacidification process for removing petroleum acid, in particular to an on-line deacidification process technology and method for crude oil, crude oil distillate oil and crude oil products containing the petroleum acid, which can remove the petroleum acid under the existing process conditions of crude oil extraction and pretreatment, gathering and transportation, refining and processing and the like, greatly reduce the investment of equipment and the like and do not add load to the existing process.
Background
With the increasing exhaustion and increasing exploitation degree of petroleum resources, a large amount of high acid value crude oil is exploited, and the yield of the high acid value crude oil in the world currently accounts for about 5% of the total yield annually and also increases at a speed of 0.3% annually. The high-acid crude oil has high viscosity, high density, more colloid, high acid value and high carbon residue. The world has about 9000 million tons of high acid value crude oil resources and about 1800 million tons of recoverable quantity. The high acid value crude oil resources in China are also rich and are mainly distributed in Liaohe, victory, xinjiang and other oil fields. The acid value of the crude oil reflects the amount of naphthenic acid, fatty acid, phenols and other petroleum acids in the crude oil. When the acid value (measured in terms of KOH, the same shall apply hereinafter) of crude oil is more than 0.5mg/g, corrosion of equipment can be caused, so that crude oil with an acid value of more than 0.5mg/g is generally called high acid value crude oil. Processing highly acidic crude oil according to conventional crude oil processing techniques will cause corrosion of the heating furnace, the fractionating tower and the equipment pipelines, affecting the product quality. Therefore, the refining enterprises do not favor processing the acid-containing crude oil, especially the high-acid crude oil, so that the acid-containing crude oil is over-supplied and over-demanded in the international crude oil market and the price is generally lower. The successful research and development of the new deacidification process of the acid-containing crude oil can generate better economic benefit, so that the method for more effectively removing the naphthenic acid and other petroleum acids from the crude oil has very important significance.
The independent deacidification technologies mainly studied at present are roughly divided into the following types:
the first method is to destroy the organic acid in the crude oil by thermal decomposition, and decompose the organic acid at high temperature to reduce the acidity of the crude oil, but the high energy consumption has a limit to the decomposition of naphthenic acid, and is not suitable for industrial application.
The second method is to add the extractant to distill, including solvent extraction, etc., add the extractant to the crude oil and mix thoroughly, react for 4-5 hours at about 200 ℃ to obtain crude oil and methanol, reduce the acidity of crude oil but consume huge energy, and is difficult to popularize in industry.
In the third method, crude oil or distillate oil is subjected to hydrogenation decomposition of petroleum acid by using a catalyst at the temperature of between 100 and 300 ℃ at the bar of between l and 50bar, but the implementation process conditions are very harsh, the application and popularization difficulty is high, a plurality of technical difficulties need to be broken through if industrial amplification application is carried out, and the operation cost is very high.
For example, chinese patent application publication No. CN1827744a discloses a method for directly processing high acid crude oil by using a conventional riser catalytic cracking technology, the processing technology is not different from conventional catalytic cracking, and the catalyst has no special requirement, the high acid crude oil directly enters the bottom of the riser after being preheated to 200 ℃ and is in contact reaction with a high temperature regenerated catalyst, however, the high acid crude oil directly contacts with a high temperature regenerant, which causes over-cracking of middle distillate, affects product distribution of the device, and loses straight-run diesel oil fraction with better quality, so the method cannot be applied in actual production, and refining and processing of the high acid crude oil all the time can only adopt a mode of blending the high acid crude oil with other crude oil.
For the petroleum exploitation and petroleum refining industries at home and abroad, at present, no mature technology and application example for on-line petroleum acid removal exist, the method is only limited to laboratory research and paper publication for a long time, and the method cannot be applied to the industry and does not research and develop an on-line deacidification technology combined with the field process condition. The main producing areas of the crude oil containing acid and high acid in China are concentrated in Sinkiang oil fields, victory oil fields and Liaohe oil fields, and the research and the application of petroleum acid online removal technology combined with the production process of crude oil mining gathering, crude oil refining and the like are not available at present.
Disclosure of Invention
The invention aims to provide an on-line petroleum acid removal process, in particular to an on-line deacidification process and method for crude oil, crude oil distillate oil and crude oil products containing petroleum acid, which have the advantages of good deacidification effect, higher deacidification efficiency, more applicable industrial application scenes, easier industrial application and popularization, and lower energy consumption and cost.
To achieve these objects and advantages in accordance with the present invention, as embodied and broadly described herein, the present invention provides an on-line deacidification process of crude oil, crude oil distillate, crude oil product containing petroleum acid, comprising the steps of: before crude oil enters a distillation treatment process, raw materials to be entered are mixed with a petroleum acid remover, the obtained mixture and raw oil containing petroleum acid are jointly subjected to subsequent process treatment, and the petroleum acid is directly removed on line by utilizing the existing process conditions.
Preferably, for crude oil containing petroleum acid, the process location of the added petroleum acid removal agent is after the production well of the crude oil, including before and during the processes of storage, pretreatment, sedimentation separation, dehydration demulsification, transportation and gathering of the crude oil, such as before a sedimentation separation tank, before electric dehydration demulsification, during storage and transportation of the crude oil, and the like.
Preferably, for crude oils containing petroleum acids, the process location for the addition of the petroleum acid removal agent is located prior to the crude oil entering the distillation tower, including the process locations and positions prior to the flash tower, the de-watering and desalting process, the preliminary tower, the atmospheric furnace, the atmospheric tower, and the like.
Preferably, for crude oil distillate and crude oil products containing petroleum acid, the process position of the added petroleum acid removing agent is located before or during the process of crude oil distillate treatment, including before a vacuum furnace, before a vacuum tower, a normal slag line, a slag reducing line, a side line of an atmospheric tower, a side line of a vacuum tower and other crude oil distillate systems and pipelines needing deacidification treatment.
Preferably, for crude oil distillate and crude oil products containing petroleum acid, the process position of the added petroleum acid removing agent is before or in the process of crude oil distillate treatment, including before each device reactor such as a catalytic cracking reactor, a hydrofining reactor and a hydrocracking reactor, or before a heating furnace, before a fractionating tower side line, a residual oil line, the bottom of the fractionating tower, before the device feeding and the like.
Preferably, the filling process and position for setting the petroleum acid removing agent can be one-point filling or simultaneous filling in a plurality of process procedures, the using and filling dosage of the petroleum acid removing agent is not less than 10PPM of the weight of crude oil, crude oil distillate oil, crude oil products and the like needing to remove the petroleum acid, and the dosage of the solution formed after the petroleum acid removing agent is diluted in the solvent is enlarged according to the dilution ratio.
Preferably, the petroleum acid remover has one or more of functions and types including but not limited to deacidification catalyst, alkali, alcohol, ether, phenol, aldehyde, amide, imidazole, chelating agent, complexing agent, surfactant, ammonia and organic amine, and can be a single functional single component or a compound with multiple functions of two or more components.
The preparation method of the deacidification catalyst comprises the following steps:
step one, drying nano silicon dioxide in vacuum, dispersing the nano silicon dioxide in toluene for ultrasonic dispersion, adding dilute hydrochloric acid and methacrylic acid, heating, filtering and washing to obtain a nano silicon dioxide carrier, wherein the weight ratio of the methacrylic acid to the nano silicon dioxide is (8-20): 1;
step two, mixing the nano silicon dioxide carrier with acrylamide and dimethyl diallyl ammonium chloride according to the weight ratio of 1: (4-10): (1-5) dissolving in an organic solvent, introducing nitrogen, heating to 60-80 ℃, adding an initiator in batches, and reacting for 8-12 h to obtain a mixture solution;
step three, pouring the mixture solution into acetone for soaking, performing suction filtration, washing and drying to obtain the deacidification catalyst, wherein the chemical structural formula of the deacidification catalyst is as follows:
preferably, the organic solvent in the second step is N, N-dimethylformamide.
Preferably, the initiator in the second step is azobisisobutyronitrile.
Preferably, the weight percentage of the azobisisobutyronitrile in the nano silica carrier is 0.2-1%.
Preferably, the grafting density of the nano silicon dioxide carrier in the petroleum acid online removal process is 0.15-0.3 chain/nm 2 。
The invention at least comprises the following beneficial effects:
first, the process and the method for removing the petroleum acid disclosed by the invention can be suitable for the technological processes of crude oil extraction, treatment, gathering and transportation and the like, can also be used for the technological processes of crude oil processing, refining and the like, have a wide application range and have good industrial popularization and application prospects.
Secondly, the on-line deacidification process and the petroleum acid removing agent can effectively utilize the field process condition to set the filling process and fill the petroleum acid removing agent with the crude oil, crude oil distillate oil and crude oil products needing to be subjected to the petroleum acid removal under the condition of not greatly increasing the cost and the investment, reduce the acid value to remove the petroleum acid, ensure that the deacidification rate is averagely more than 30 percent, and have higher input-output ratio and use value.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Detailed Description
The present invention is further described in detail below with reference to specific embodiments so that those skilled in the art can practice the invention with reference to the description.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or combinations thereof.
It is to be noted that the experimental methods described in the following embodiments are all conventional methods unless otherwise specified, and the reagents and materials, if not otherwise specified, are commercially available; in the description of the present invention, it should be noted that unless otherwise explicitly stated or limited, the terms "mounted," "connected" and "disposed" are to be construed broadly and can be, for example, fixedly connected, disposed, detachably connected, disposed or integrally connected and disposed. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art. The terms "transverse," "longitudinal," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used in the indicated orientations and positional relationships to indicate orientations and positional relationships based on those shown, merely to facilitate description of the invention and to simplify description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be construed as limiting the present invention.
The invention discloses an on-line deacidification process and method for crude oil, crude oil distillate oil and crude oil products containing petroleum acid in the processes of petroleum exploitation, storage, transportation, refining and processing, according to one aspect of the invention, the process mainly comprises the following steps: before crude oil enters a distillation treatment process, raw materials to be entered are mixed with a petroleum acid remover, and the obtained mixture and the crude oil containing the petroleum acid are jointly subjected to process treatment.
Wherein, the petroleum acid remover comprises a deacidification catalyst, and the preparation method comprises the following steps:
step one, drying nano silicon dioxide in vacuum, dispersing the nano silicon dioxide in toluene for ultrasonic dispersion, adding dilute hydrochloric acid and methacrylic acid, heating, filtering and washing to obtain a nano silicon dioxide carrier, wherein the weight ratio of the methacrylic acid to the nano silicon dioxide is (8-20): 1;
step two, mixing the nano silicon dioxide carrier with acrylamide and dimethyl diallyl ammonium chloride according to the weight ratio of 1: (4-10): (1-5) dissolving in an organic solvent, introducing nitrogen, heating to 60-80 ℃, adding an initiator in batches, and reacting for 8-12 h to obtain a mixture solution;
step three, pouring the mixture solution into acetone for soaking, performing suction filtration, washing and drying to obtain the deacidification catalyst, wherein the chemical structural formula of the deacidification catalyst is as follows:
the invention can be used for a plurality of processes of crude oil extraction and crude oil processing and refining, and one process flow of the crude oil processing and refining mainly comprises the following steps: after crude oil reaches an atmospheric and vacuum distillation device of a petrochemical company or an oil refinery, process positions such as inlets, outlets or distillation line outlets of a tower side line before a dehydration desalting process, a fractionating tower, an atmospheric tower, a vacuum tower and the like are combined, a filling process and filling equipment are set according to field production process conditions, and a petroleum acid remover is injected into crude oil, distillate oil, side distillate, a tower bottom residue oil line and the like at one or more positions, so that the petroleum acid remover participates in the atmospheric and vacuum distillation process for refining crude oil, can react with petroleum acid in crude oil, distillate oil, side distillate or residual oil, achieves the purposes of reducing the acid value of the crude oil, the distillate oil, the side distillate, the residual oil and the like and removing the petroleum acid, and plays roles of optimizing subsequent production and refining processes, reducing the production operation difficulty, saving energy, reducing consumption, inhibiting corrosion, reducing potential safety hazards and the like. The process for adding the petroleum acid removing agent is to select the process position for adding the petroleum acid removing agent to be better as the distance from the process and equipment to be participated is longer before the crude oil is dehydrated and desalted, before the inlets of a fractionating tower, an atmospheric tower, a vacuum tower and the like, and the positions of a tower outlet, a tower bottom residual oil line, a tower side line outlet and the like, so that the better mixing uniformity degree of the petroleum acid removing agent and the raw oil is ensured, the removal rate and the removal effect of the petroleum acid are improved, and the process position can be set by simultaneously arranging the adding process and facilities at one position or a plurality of points.
The on-line deacidification process is arranged, and the processes of adding the petroleum acid remover into the injection facility, the petroleum acid remover and the like and the petroleum acid remover can effectively reduce the acid values of crude oil, crude oil distillate oil, crude oil products and the like and remove the petroleum acid in the processes of crude oil exploitation, treatment, storage and transportation, gathering, transportation, processing, refining, optimizing subsequent production processes, saving energy, reducing consumption, inhibiting corrosion, reducing potential safety hazards and the like, and has good industrial application prospect. The petroleum acid on-line removal process can reduce the acid value and simultaneously achieve the effects of reducing water, viscosity, condensation point, metal ion and salt content, inhibiting corrosion, preventing coke scale and the like if being matched with the processes of demulsification, dehydration, desalination, demetallization, viscosity reduction and pour point reduction, corrosion prevention and scale inhibition in the processes of crude oil pretreatment, dehydration demulsification, gathering and transportation, storage and transportation or refining. The deacidification catalyst utilizes nano silicon dioxide to carry out graft modification on the nano silicon dioxide, so that the nano silicon dioxide has ammonia and organic amine components, can effectively reduce the acid value, remove petroleum acid and inhibit corrosion, has the effect of reducing the viscosity of crude oil, and is beneficial to storage, transportation, energy conservation and consumption reduction of the crude oil.
In one embodiment, the organic solvent in the second step is N, N-dimethylformamide.
In one embodiment, the initiator in the second step is azobisisobutyronitrile.
In one embodiment, the weight percentage of the azobisisobutyronitrile to the nano silica carrier is 0.2 to 1%.
In one embodiment, the grafting density of the nano-silica carrier in the petroleum acid online removal process is 0.15-0.3 chain/nm 2 。
In one embodiment, the petroleum acid remover is added before the crude oil electric dehydration demulsification process.
It is to be noted that the experimental methods described in the following embodiments are all conventional methods unless otherwise specified, and the reagents and materials are commercially available unless otherwise specified.
< example 1>
An on-line petroleum acid removing process mainly comprises the following steps: mixing high-acid crude oil to be input with a petroleum acid remover before the crude oil enters a crude oil electric dehydration demulsification system, and injecting the obtained mixture into the crude oil electric dehydration demulsification system to carry out an electric dehydration demulsification process;
the petroleum acid remover is prepared by compounding 30% of deacidification catalyst and 70% of compound organic amine as binary mixed liquid, and the preparation method of the deacidification catalyst comprises the following steps:
step one, drying nano-silica in vacuum, dispersing the nano-silica in toluene, performing ultrasonic dispersion, adding dilute hydrochloric acid and methacrylic acid, heating, filtering and washing to prepare a nano-silica carrier, wherein the weight ratio of the methacrylic acid to the nano-silica is 15;
dissolving the nano-silica carrier, acrylamide and dimethyl diallyl ammonium chloride in N, N-dimethylformamide according to a weight ratio of 1;
step three, pouring the mixture solution into acetone for soaking, performing suction filtration, washing and drying to obtain the deacidification catalyst, wherein the grafting density of the deacidification catalyst is 0.23chain/nm 2 。
< example 2>
An on-line petroleum acid removing process mainly comprises the following steps: mixing high-acid crude oil to be fed with a petroleum acid remover before the high-acid crude oil enters a crude oil electric dehydration demulsification system, injecting the obtained mixture into the crude oil electric dehydration demulsification system, and simultaneously adding a 20PPM demulsifier and a 50PPM demetallizing agent into the electric dehydration demulsification system to jointly carry out an electric dehydration, desalination and demulsification process;
the petroleum acid remover is prepared by compounding 30% of deacidification catalyst and 70% of compound organic amine as binary mixed liquid, and the preparation method of the deacidification catalyst comprises the following steps:
step one, drying nano-silica in vacuum, dispersing the nano-silica in toluene, performing ultrasonic dispersion, adding dilute hydrochloric acid and methacrylic acid, heating, filtering and washing to prepare a nano-silica carrier, wherein the weight ratio of the methacrylic acid to the nano-silica is 15;
dissolving the nano-silica carrier, acrylamide and dimethyl diallyl ammonium chloride in N, N-dimethylformamide according to a weight ratio of 1;
step three, pouring the mixture solution into acetone for soaking, performing suction filtration, washing and drying to obtain the deacidification catalyst, wherein the grafting density of the deacidification catalyst is 0.23chain/nm 2 。
< example 3>
An on-line petroleum acid removing process mainly comprises the following steps: mixing high-acid crude oil to be fed with a petroleum acid remover before the high-acid crude oil enters a crude oil electric dehydration demulsification system, and injecting the obtained mixture into the crude oil electric dehydration demulsification system;
wherein the petroleum acid remover is a compound organic amine.
< example 4>
An on-line petroleum acid removing process mainly comprises the following steps: mixing high-acid crude oil to be fed with a petroleum acid remover before the high-acid crude oil enters a crude oil electric dehydration demulsification system, injecting the obtained mixture into the crude oil electric dehydration demulsification system, and simultaneously adding a 20PPM demulsifier and a 50PPM demetallizing agent into the electric dehydration demulsification system to jointly perform an electric dehydration demulsification process;
wherein the petroleum acid remover is composite organic amine.
< comparative example 1>
The conventional crude oil electric dehydration demulsification process and scheme are adopted, no additional process and equipment are added, and the comparative example 1 is taken as a blank reference.
In the above examples 1, 2, 3 and 4, the amount of the petroleum acid removal agent added was 500PPM;
the test conditions of the electric dehydration demulsifying device in the above examples 1, 2, 3, 4 and 1 are shown in the following table 1:
TABLE 1
< Deacidification Effect test >
Selecting a blank 10L high acid value crude oil to be processed as an index: an acid value of 2.7 (in terms of KOH) mg/g and a viscosity (50 ℃ C.) of 189.2mm 2 ·S -1 28.1mg/L of salt before dehydration, 0.22 percent of water before dehydration, 46.8 mu g/g of Ca ion content, 15.3 mu g/g of Fe ion content and 24.4 mu g/g of Ni ion, deionized water as the electro-dehydration demulsification water, the deacidification effect of the petroleum acid on-line removal process of the above examples 1-4 is tested, and the data after the crude oil electro-dehydration demulsification of the comparative example 1 is tested for comparison,the specific results are shown in the following table 2:
TABLE 2 Deacidification rate and viscosity test under 140 deg.C condition of electric dehydration demulsification (all index units are as above)
Test results show that the on-line petroleum acid removal process and method provided by the invention not only have good deacidification rate, but also have a certain viscosity reduction effect. The deacidification rate can be more than 35% by using the compound organic amine as the petroleum acid remover, and can reach more than 50% by further compounding the deacidification catalyst as the petroleum acid remover. When the on-line petroleum acid removing process and the method are applied to the demulsification, desalination and dehydration process of crude oil, the process and the demulsifier and the desalting and demetallizing agent in the process have synergistic effect, so that the demulsification and dehydration effect can be improved in an auxiliary manner, and the salt content and the metal ion content can be reduced while the acid value is reduced. Therefore, the on-line deacidification process method provided by the invention increases the on-line petroleum acid removal process and facilities, and can effectively reduce the acid value by more than 30% by adding the petroleum acid remover, and if a unique deacidification catalyst is further used in a matched manner, the method can play a good deacidification effect to improve the deacidification rate and can also obviously reduce the viscosity of the crude oil.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details and examples shown and described herein, without departing from the general concept defined by the claims and their equivalents.
Claims (15)
1. The petroleum acid on-line removal process is characterized by mainly comprising the following steps: the process comprises the steps of preparing additive facilities and processes for adding a petroleum acid remover before raw oil containing petroleum acid enters processing treatment, injecting the petroleum acid remover into the raw oil to be processed, enabling the petroleum acid remover and the raw oil to enter process equipment together for processing treatment, and removing the petroleum acid by utilizing the existing process conditions of crude oil gathering and transportation and refining.
2. The on-line petroleum acid removal process of claim 1, wherein the feedstock oil comprises crude oil, crude oil distillates, crude oil products.
3. The on-line petroleum acid removal process of claim 1, wherein the petroleum acid removal agent is added after the crude oil production well, before the processes including storage, pretreatment, sedimentation separation, dehydration demulsification, transportation and gathering of crude oil, and during the process treatment, for the processes of crude oil production, pretreatment, gathering, transportation and storage in the oil field.
4. The on-line petroleum acid removal process of claim 1, wherein the petroleum acid removal agent is added to the crude oil and the atmospheric and vacuum distillation process of the crude oil refining process at a location and location prior to the crude oil entering the distillation tower, including prior to the flash tower, prior to the dehydration and desalination, prior to the preliminary distillation tower, prior to the atmospheric furnace, and prior to the atmospheric tower.
5. The on-line petroleum acid removal process of claim 1, wherein for the atmospheric and vacuum distillation process of crude oil distillate treatment, the addition position of the petroleum acid removal agent is before or during the process of distillate treatment, including before a vacuum furnace, before a vacuum tower, a slag-constant line, a slag-reducing line, a side line of an atmospheric tower, a side line of a vacuum tower, a crude oil distillate system and a pipeline needing deacidification treatment.
6. The on-line petroleum acid removal process of claim 1, wherein the petroleum acid removal agent is added to the catalytic cracking process, gasoline and diesel hydrogenation process, lube oil hydrogenation process, wax oil hydrogenation process, heavy oil hydrogenation process, and residual oil hydrogenation process for crude oil distillate, crude oil product treatment, before the catalytic cracking reactor, the hydrofining reactor, the hydrocracking reactor, or before the heating furnace, before the fractionating tower, at the side of the fractionating tower, at the bottom of the fractionating tower, at the residual oil line, and before the feeding of the apparatus.
7. The on-line petroleum acid removal process of claim 6, wherein the hydrogenation units in the gasoline and diesel hydrogenation process, the lubricating oil hydrogenation process, the wax oil hydrogenation process, the heavy oil hydrogenation process and the residual oil hydrogenation process comprise a hydrofining unit and a hydrocracking unit.
8. The on-line petroleum acid removal process of claim 1, wherein the petroleum acid removal agent is added at one or more points, the amount of the petroleum acid removal agent used and added is not less than 10PPM of the weight of the raw oil from which the petroleum acid is to be removed, and the amount of the petroleum acid removal agent is a solution formed after the petroleum acid removal agent is diluted in a solvent, and the amount of the solution is increased according to the dilution ratio.
9. The on-line petroleum acid removal process of claim 1, wherein the petroleum acid removal agent comprises one or more of deacidification catalyst, alkali, alcohol, ether, phenol, aldehyde, amide, imidazole, chelating agent, complexing agent, surfactant, ammonia and organic amine.
10. The on-line petroleum acid removal process of claim 9, wherein the deacidification catalyst is prepared by the following steps:
step one, drying nano silicon dioxide in vacuum, dispersing the nano silicon dioxide in toluene for ultrasonic dispersion, adding dilute hydrochloric acid and methacrylic acid, heating, filtering and washing to obtain a nano silicon dioxide carrier, wherein the weight ratio of the methacrylic acid to the nano silicon dioxide is (8-20): 1;
step two, mixing the nano silicon dioxide carrier with acrylamide and dimethyl diallyl ammonium chloride according to the weight ratio of 1: (4-10): (1-5) dissolving in an organic solvent, introducing nitrogen, heating to 60-80 ℃, adding an initiator in batches, and reacting for 8-12 h to obtain a mixture solution;
step three, pouring the mixture solution into acetone for soaking, performing suction filtration, washing and drying to obtain the deacidification catalyst, wherein the chemical structural formula of the deacidification catalyst is as follows:
11. the on-line petroleum acid removal process of claim 10, wherein the organic solvent in step two is N, N-dimethylformamide.
12. The on-line petroleum acid removal process of claim 10, wherein the initiator in step two is azobisisobutyronitrile.
13. The on-line petroleum acid removal process of claim 12, wherein the azobisisobutyronitrile accounts for 0.2-1% by weight of the nano-silica carrier.
14. The on-line petroleum acid removal process of claim 10, wherein the nano-silica carrier in the deacidification catalyst has a graft density of 0.15-0.3 chain/nm 2 。
15. Use of the on-line petroleum acid removal process of any one of claims 1 to 14 for reducing acid values in crude oil, crude oil fractions, crude oil products, and in crude oil processing and refining processes in oil field for crude oil extraction, processing, storage, transportation, and gathering, and petroleum refining industries.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1465657A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | Method for reducing acid value of petroleum |
| CN103805227A (en) * | 2012-11-09 | 2014-05-21 | 长江(扬中)电脱盐设备有限公司 | Pre-treatment process method of high acid crude oil |
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2022
- 2022-10-13 CN CN202211253375.XA patent/CN115537230A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1465657A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | Method for reducing acid value of petroleum |
| CN103805227A (en) * | 2012-11-09 | 2014-05-21 | 长江(扬中)电脱盐设备有限公司 | Pre-treatment process method of high acid crude oil |
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