CN103789024A - Hydrogen aquathermolysis method of high-acid crude oil - Google Patents
Hydrogen aquathermolysis method of high-acid crude oil Download PDFInfo
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- CN103789024A CN103789024A CN201210432652.3A CN201210432652A CN103789024A CN 103789024 A CN103789024 A CN 103789024A CN 201210432652 A CN201210432652 A CN 201210432652A CN 103789024 A CN103789024 A CN 103789024A
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Abstract
The invention provides a hydrogen aquathermolysis method of high-acid crude oil. By utilization of a characteristic that the high-acid crude oil is prone to emulsification, after water and the high-acid crude oil are uniformly mixed, hydrogen is fed into the oil-water mixture, and the mixture is fed into a hydrogen aquathermolysis reactor in a lower feeding manner. The high-acid crude oil is subjected to hydrogenation deacidification and pyrolysis at a high temperature while demulsification is performed simultaneously. Gas-liquid separation is achieved in a high-pressure separator and dehydration and desalination are achieved.
Description
Technical field
The present invention relates to a kind of high-acid crude oil treatment process, particularly adopt hydrothermal cracking method to process the method for crude oil with high acid content.
Background technology
Crude oil is a kind of non-renewable energy, and along with the fast development of world economy, people improve constantly the degree of dependence of crude oil.Through Fast Algorithm for Mining for many years, crude oil constantly presents the trend of in poor quality.
The output of world's high-acid crude oil accounts for 10% left and right of crude oil ultimate production at present, and presents the trend rising year by year.Because the acid in crude oil mainly exists with the form of naphthenic acid, naphthenic acid can react with iron at a certain temperature, causes the heavy corrosion of refining equipment.So in the course of processing of crude oil, the height of acid content is an important factor can not be ignored.Therefore, although the price of high-acid crude oil is lower on international raw oil market, its processing also has certain economic benefit, and refinery is not extremely ready to process yet.
In crude oil, how many employing acid numbers of acid content characterize, in and 1 gram of potassium hydroxide milligram number that the contained acidic substance of oil sample need.In general, it is high-acid crude oil that acid value for crude oil is greater than 1mgKOH/g, and acid number is acid-containing raw oil at 0.5～1mgKOH/g, and acid number is low sour crude oil lower than 0.5mgKOH/g.Low sour crude oil adds man-hour in refinery very little to the corrosion of equipment.
High-acid crude oil is subject to the impact of temperature larger on the corrosion condition of refining equipment.Conventionally almost there is no below corrodibility at 220 ℃, along with the rising of temperature, corrodibility strengthens gradually, and in the time that temperature is 400 ℃ of left and right, the acid in crude oil is decomposed, and corrodibility declines.
Generally, the acidic substance in high-acid crude oil easily form natural emulsifying agent, can cause emulsification serious in electric desalting process, oily water separation difficulty, and water, salt are all difficult to remove.
The working method of crude oil with high acid content mainly contains and mixes the low sour crude oil of refining, pyrolysis depickling, hydrogenation deacidification and alkali cleaning depickling etc. at present.Along with the increase gradually of high-acid crude oil output, the method for mixing the low sour crude oil of refining can not fundamentally solve the problem of high-acid crude oil processing; Pyrolysis depickling and hydrogenation deacidification all need just process electric desalting process, and tooling cost is higher; Adopt the method for alkali lye depickling can make emulsification of crude oil serious, separation difficulty, produced simultaneously sewage is also difficult to process, and brings environmental issue.
CN200910089173.4 provides a kind of device and atmospheric and vacuum distillation and atmospheric vacuum distillation method of crude oil with high acid content, the position of seriously corroded in crude oil with high acid content processing is replaced with to erosion-resisting alloy material, the method is the running period of extension fixture to a certain extent, if but the high character that contains acid starting material changes, also need a large amount of practical experience accumulation, find the new hot spot that may produce.Device design is complicated, and cost is higher, inapplicable to existing device.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method that high-acid crude oil faces hydrogen hydrothermal cracking, the inventive method is utilized the feature of the easy emulsification of high-acid crude oil, and by after water and the even mixing of high-acid crude oil, oil-water mixture passes into hydrogen, following feeding manner enters and faces hydrogen aquathermolysis device, under comparatively high temps, the cracking of high-acid crude oil hydrogenation deacidification, simultaneous breakdown of emulsion, in high-pressure separator, realize gas-liquid separation, and dehydration, desalination.
High-acid crude oil of the present invention faces the method for hydrogen hydrothermal cracking, comprises following process:
A) high-acid crude oil enters mixing tank with water and evenly mixes;
B) in the oil-water mixture that step a) obtains, pass into hydrogen;
C) profit that step b) obtains and the mixture of hydrogen react facing in hydrogen aquathermolysis device, carry out hydrogenation, depickling, cracking, breakdown of emulsion reaction under high-temperature and high-pressure conditions;
D) step c) react after logistics enter high-pressure separator, the gas of hydrogen is isolated at high-pressure separator top, reacted water is discharged in high-pressure separator bottom, generates oil and export and draw above high-pressure separator water-oil interface, realize dewater, desalination.
Step a) described crude oil with high acid content is the crude oil that acid number is greater than 0.5mgKOH/g, is preferably greater than the crude oil of 1mgKOH/g.
Step a) described even mixing process can adopt the mixing valve in technology of electric de-salting to realize, or adopts in mechanical stirring, pipeline the methods such as directly mixing.For making oil mixing with water even, can add appropriate emulsifying agent, generally select and at high temperature hold labile emulsifying agent, can in the time that finishing, reaction realize oily water separation.
The water add-on of step described in a) is 3%～50% of oil-water mixture total mass, preferably 5%～40%.
The face hydrogen aquathermolysis device of step described in c) is the known high temperature high voltage resistant reactors of oil-refining chemical those skilled in the art, is generally vertical reactor, and the mode of the following charging of mixture flow of profit and hydrogen enters faces hydrogen aquathermolysis device.
The face hydrogen hydrothermal cracking operational condition of step described in c) is: temperature of reaction is 200～420 ℃, preferably 260～380 ℃; Reaction pressure is 2.0～24.0MPa, preferably 5.0～20.0MPa; Volume space velocity is 1.0～8.0h
-1, preferably 1.5～4.0h
-1; Hydrogen to oil volume ratio is 150:1～1000:1, preferably 200:1～800:1.It is to carry out under liquid phase state that reaction pressure preferably remains on water.
Steps d) described in high-pressure separator be the known high temperature high voltage resistant separators of oil-refining chemical those skilled in the art, can be for example vertical high-pressure separator, can be also horizontal high-pressure separator.While adopting vertical high-pressure separator, after reaction, mixture flow preferably enters in high-pressure separator middle and upper part.While adopting horizontal high-pressure separator, after reaction, mixture flow preferably adopts the operating method of the right discharging of left charging or the left discharging of right charging.High-pressure separator also can operate under suitable electric field exists, to improve dewatering and desalting effect.The gas of isolated hydrogen can, for other process, also can be circulated to reactor inlet.Water after breakdown of emulsion is drawn by high-pressure separator bottom, generates oil and draw from the outlet of high-pressure separator water-oil interface top after reaction.
Steps d) described in to face reactant flow cooling temperature after hydrogen hydrothermal cracking be 120～300 ℃, preferably 160～240 ℃, so enter high-pressure separator.Pressure with face hydrogen hydrothermal cracking working pressure identical (pressure-losses is disregarded).
Under temperature of reaction and pressure, in the time that water and hydrogen exist, carboxyl and the thioether group etc. in high-acid crude oil easily ruptures, and generates H
2s, CO, CO
2deng gas, H
2can suppress the condensation reaction under high temperature, promote hydrogenation reaction, make raw material cracking.
High-acid crude oil and water evenly mix, and can remove the salt in high-acid crude oil, save the process cost of electro-dewatering desalination link.
The advantage of the pretreatment process of a kind of high-acid crude oil of the present invention is:
(1) because there is the introducing of water, on the basis of depickling, can realize the cracking of desalination and high-acid crude oil simultaneously.Both the running cost of electro-dewatering desalination in normal decompression technique can be saved, and part light Fuel can be obtained again.Facing hydrogen hydrothermal cracking working pressure protection water is to carry out under liquid-phase condition, and experiment shows, can reduce corrosion, reduces coking reaction, and favourable device is stablized long-term operation.
(2) due to the existence of high pressure hydrogen, can suppress the condensation reaction under high temperature, reduce coking, promote the hydrocracking of high-acid crude oil, generate more light Fuel.
(3) after water and high-acid crude oil emulsification, face hydrogen hydrothermal cracking, make to have the water-oil interface place of the materials such as corrosive naphthenic acid in emulsion, be difficult for contacting with equipment, reduced corrodibility; Along with the carrying out of hydrothermal cracking, breakdown of emulsion and depickling are carried out simultaneously, and therefore after breakdown of emulsion, acid number reduces, and corrodibility is still lower.Therefore, the inventive method has solved etching problem when high-acid crude oil is processed.
(4) the method equipment is simple, and investment and running cost are lower.
Accompanying drawing explanation
Fig. 1 adopts the high-acid crude oil of vertical high-pressure separator to face hydrogen hydrothermal cracking method process schematic representation;
Fig. 2 adopts the high-acid crude oil of horizontal high-pressure separator to face hydrogen hydrothermal cracking method process schematic representation;
Wherein: 1-high-acid crude oil, 2-water, 3-oil-water mixer, 4-faces hydrogen aquathermolysis device, 5-resultant of reaction stream, water after 6-reaction, 7-circulating hydrogen, 8-generates oil, 9-high-pressure separator.
Embodiment
Below in conjunction with accompanying drawing, the pretreatment process of a kind of high-acid crude oil of the present invention is further described.
As shown in Figure 1, high-acid crude oil 1 and water 2 enter oil-water mixer 3 fully to be mixed, the oil-water mixture forming passes into circulating hydrogen 7, the mode of profit and the following charging of hydrogen mixture stream enters faces in hydrogen aquathermolysis device 4, hydrogenation under High Temperature High Pressure, depickling, cracking, breakdown of emulsion, through facing after hydrogen hydrothermal cracking, resultant of reaction stream 5 enters high-pressure separator 9, isolated circulating hydrogen 7 is circulated to reactor inlet, the rear water 6 of reaction is discharged in high-pressure separator 9 bottoms, generate oil 8 exports and draws above high-pressure separator 9 water-oil interface, realize dehydration, desalination.
For further illustrating the solution of the present invention and effect, enumerate following examples.
The present embodiment is a kind of embodiment of crude oil with high acid content processing.
Test is listed in table 1 with feedstock property.The acid number of this raw material is that 4.58 mgKOH/g belong to high-acid crude oil as shown in Table 1.Mixing valve in employing technology of electric de-salting is as oil-water mixer, and oil mixing with water condition is in table 2.
Facing hydrogen aquathermolysis device is circular straight-tube shape high temperature high voltage resistant reactor, inner reactionless device member.Face hydrogen aquathermolysis condition and the results are shown in Table 2.
The present embodiment is a kind of embodiment of crude oil with high acid content processing.
Test is listed in table 1 with feedstock property.Mixing valve in employing technology of electric de-salting is as oil-water mixer, and oil mixing with water condition is in table 2.
Facing hydrogen aquathermolysis device is circular straight-tube shape high temperature high voltage resistant reactor, inner reactionless device member.Adopt vertical high-pressure separator, face hydrogen aquathermolysis condition and the results are shown in Table 2.
Table 1 crude oil with high acid content character
| Project | Data |
| Density (20 ℃), g/cm 3 | 0.9118 |
| Acid number, mgKOH/g | 4.58 |
| Sulphur content, quality % | 0.39 |
| Nitrogen content, quality % | 0.28 |
| Salts contg, mg/L | 57 |
Table 2 experiment condition and result
| | Embodiment | 1 | |
| Oil mixing with water condition | ? | ? | |
| Water injection rate, quality % | 18.0 | 30.0 | |
| Mixture strength, MPa | 0.05 | 0.05 | |
| Face hydrogen aquathermolysis condition | ? | ? | |
| Reaction pressure, MPa | 18 | 20 | |
| Temperature of reaction, ℃ | 320 | 360 | |
| Volume space velocity, h -1 | 1.0 | 1.5 | |
| Hydrogen to oil volume ratio | 600:1 | 200:1 | |
| Generate oil nature | ? | ? | |
| Generate oleic acid value, mgKOH/g | 0.11 | 0.02 | |
| Sulphur content, quality % | 0.32 | 0.30 | |
| Nitrogen content, quality % | 0.28 | 0.26 | |
| Water-content, quality % | 0.1 | 0.1 | |
| Salts contg, mg/L | 1.8 | 1.2 |
As can be seen from Table 2, the inventive method can be carried out depickling, desalination and processed by high-acid crude oil simultaneously, has obtained good pretreating effect.
Claims (10)
1. high-acid crude oil faces a method for hydrogen hydrothermal cracking, it is characterized in that comprising following process:
A) high-acid crude oil enters mixing tank with water and evenly mixes;
B) in the oil-water mixture that step a) obtains, pass into hydrogen;
C) profit that step b) obtains and the mixture of hydrogen react facing in hydrogen aquathermolysis device, carry out hydrogenation, depickling, cracking, breakdown of emulsion reaction under high-temperature and high-pressure conditions;
D) step c) react after logistics enter high-pressure separator, the gas of hydrogen is isolated at high-pressure separator top, reacted water is discharged in high-pressure separator bottom, generates oil and export and draw above high-pressure separator water-oil interface, realize dewater, desalination.
2. method according to claim 1, is characterized in that: step a) described crude oil with high acid content is the crude oil that acid number is greater than 0.5mgKOH/g, is preferably greater than the crude oil of 1mgKOH/g.
3. method according to claim 1, is characterized in that: step a) middle high-acid crude oil is mixed employing mixing valve or adopted direct blending means in mechanical stirring, pipeline with water.
4. according to the method described in claim 1 or 3, it is characterized in that: step a) middle oil mixing with water process adds emulsifying agent.
5. method according to claim 1, is characterized in that: step a) in water add-on be 3%～50% of oil-water mixture total mass, preferably 5%～40%.
6. method according to claim 1, is characterized in that: the face hydrogen aquathermolysis device of step described in c) is vertical reactor, and the mode of the following charging of mixture flow of profit and hydrogen enters faces hydrogen aquathermolysis device.
7. method according to claim 1, is characterized in that: the face hydrogen hydrothermal cracking operational condition of step described in c) is: temperature of reaction is 200～420 ℃, preferably 260～380 ℃; Reaction pressure is 2.0～24.0MPa, preferably 5.0～20.0MPa; Volume space velocity is 1.0～8.0h
-1, preferably 1.5～4.0h
-1; Hydrogen to oil volume ratio is 150:1～1000:1, preferably 200:1～800:1.
8. method according to claim 7, is characterized in that: facing hydrogen aquathermolysis pressure, to remain on water be to carry out under liquid phase state.
9. method according to claim 1, is characterized in that: steps d) described in high-pressure separator for adopting vertical high-pressure separator, or adopt horizontal high-pressure separator; The gas circulation of the isolated hydrogen of high-pressure separator is to reactor inlet; Water after breakdown of emulsion is drawn by high-pressure separator bottom, generates oil and draw from the outlet of high-pressure separator water-oil interface top after reaction.
10. according to the method described in claim 1 or 9, it is characterized in that: steps d) described in to face reactant flow cooling temperature after hydrogen hydrothermal cracking be 120～300 ℃, preferably 160～240 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030062163A1 (en) * | 2001-09-17 | 2003-04-03 | Southwest Research Institute | Pretreatment processes for heavy oil and carbonaceous materials |
| US20090166261A1 (en) * | 2007-12-28 | 2009-07-02 | Chevron U.S.A. Inc. | Upgrading heavy hydrocarbon oils |
| CN101580733A (en) * | 2008-05-14 | 2009-11-18 | 中国石油化工股份有限公司 | Processing method of highly acidic crude oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030062163A1 (en) * | 2001-09-17 | 2003-04-03 | Southwest Research Institute | Pretreatment processes for heavy oil and carbonaceous materials |
| US20090166261A1 (en) * | 2007-12-28 | 2009-07-02 | Chevron U.S.A. Inc. | Upgrading heavy hydrocarbon oils |
| CN101580733A (en) * | 2008-05-14 | 2009-11-18 | 中国石油化工股份有限公司 | Processing method of highly acidic crude oil |
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