CN101353593A - Desulphurization method by irradiating oil with high-energy electron beam - Google Patents
Desulphurization method by irradiating oil with high-energy electron beam Download PDFInfo
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Abstract
The invention discloses a desulphurization method by using a high-power electron beam for irradiating oils, which is characterized by comprising the following steps: a. the high-power electron beam is used for irradiating air so as to lead the air to contain high-concentration ozone; b. the air after the irradiation is input to an irradiation reactor for fully contacting with the oil products; and c. the high-power electron beam is used for irradiating the oils and the air, and the ozone in the air leads the organic sulfur in the oils to generate oxidation reaction and be oxidized to sulfur-contained organic matter of sulfones, sulfoxides and sulfoacids. The method of the invention has simple technique, just needs the main technical process of irradiation, has small initial aggregate investment, low energy consumption, operation cost rather lower than that of the prior art, is beneficial to protecting environment, greatly reduces environment pollution without secondary pollution and can more greatly decrease the sulfur content in the oil products by adding the species and amount of the accessory constituent, thus improving the product quality.
Description
Technical field
The present invention relates to a kind of method that oil product is carried out desulfurization, particularly adopt high-power electron beam that oil product is carried out the sulfur method of irradiation, belong to the application category of civilian non-power nuclear technique at petrochemical industry.
Background technology
Petroleum products all contains sulphur in various degree, and the harm of sulphur is many-sided.The petroleum products sulfur-bearing not only influences existing oil refining process (as equipment anticorrosion, the performance of catalyzer etc.), the quality of oil product and performance (as stability etc.), and in recent years, automobile increases, the tail gas that gives off also increases, because the acid rain that the oil product sulfur-bearing is caused also has influence on the environment of human survival gradually, so people must constantly seek the higher desulfuration method.
The crude oil in China sulphur content is lower, but oil reserve descends at present, and imported crude oil will become the main raw material sources in refinery.Mostly sulphur content is higher for external crude oil, and especially the middle-eastern crude sulphur content is very high, removes the wherein sulphur of hazardness, improves sulfur removal technology, improves desulfuration efficiency to greatest extent, also requires to develop better desulfurizing oil novel process.
Sulphur mainly contains two kinds of existence forms in the oil product: active sulphur and inactive sulfur, and the former comprises elementary sulfur, hydrogen sulfide and mercaptan, direct easily and metal reacts; The latter comprises thioether, disulphide, thiophene etc., is not easy to react with metal.For a long time, petroleum refining industry generally adopts the way of alkali cleaning to remove sulfide in the oil product, and this method is comparatively simple, but remains in problems, and serious as environmental pollution, desulfuration efficiency is low.By alkali cleaning, can remove most of sulfide in the oil product, but produce a large amount of sulfur-containing waste waters, as not dealt carefully with, quite serious to the harm of environment.In addition,, also contain organic sulfide in various degree in the oil product,, can have a strong impact on its use value as further not carrying out refinement treatment because alkali cleaning is not high to the decreasing ratio of organic sulfide.Hydrodesulfurization also is a kind of traditional desulfurization technology, and its application time is longer, and desulfurization depth is bigger, and at present both at home and abroad still in a large amount of uses, and each oil refining enterprise continues to optimize the operational condition of device, improves desulfuration efficiency.But shortcomings such as one-time investment is big, running cost height that this method has.And along with the harshness day by day of environmental standard, existing hydrogenating desulfurization technology often can not satisfy the needs (as removing the dibenzothiophene in the diesel oil) of deep desulfuration.People have also developed novel sulfur removal technologies such as catalytic oxidation desulfurization, catalysis adsorption desulfurize, catalytic cracking and desulfurizing, abstraction desulfurization, biological desulphurization, microwave desulfurization now, but these technologies are because self more existing shortcoming, and reasons such as, work-ing life not high as needs catalyzer, energy consumption height, desulfuration efficiency can not large-scale promotion and application.
Adopting high energy particle that material is handled or processed is a kind of high-tech method, compares it with existing technology and has lot of advantages, and simple as technology, easy to operate, energy consumption is low, and is very little to environmental influence, can not bring environmental pollution etc.Some the processing aspect that high energy particle is used in organic materials has some researchs and report, is exactly to adopt high-energy electron beam irradiation cracked method to reduce the food fibre that the polymerization degree of lacking lint cellulose prepares different cellulosic components as CN101194684A.CN1560201A adopts gamma-rays that oil product is carried out the mercaptan removal deodorizing and handles.CN1544129A adopts electron beam deep oxidation purifying flue gas.But adopt high-power electron beam that oil product is carried out irradiation desulfurization technology aspect and do not see relevant report and research.
Summary of the invention
The object of the present invention is to provide a kind of high-power electron beam that adopts that oil product is carried out the sulfur method of irradiation, its high-power electron beam that adopts the rumbatron source to provide carries out the irradiation desulfurization to oil product, and technology is simple, and energy consumption is low, desulfuration efficiency height, compliance with environmental protection requirements.
Technical scheme of the present invention is: a kind of high-power electron beam that adopts carries out the sulfur method of irradiation to oil product, it is characterized in that: have following steps:
A. utilize high-power electron beam that air is carried out irradiation, make and contain high-concentrated ozone in the air;
B. the air behind the irradiation is input to the irradiation reaction device, takes place fully to contact with oil product;
C. with high-power electron beam oil product and air are carried out irradiation, the ozone of air makes the organosulfur generation oxidizing reaction in the oil product, is oxidized to the sulfurous organic compound of sulfone class, sulfoxide class and sulfonic acid class.
Aforesaid employing high-power electron beam carries out the sulfur method of irradiation to oil product, it is characterized in that: from irradiation reaction device output oil product after oxidation, adopt traditional polar solvent extract way that its sulfurous organic compound is wherein carried out solvent extraction, obtain high sulfur-bearing extractum and low sulfur-bearing and raffinate oil, extraction solvent recycling use from high sulfur-bearing extractum; High sulfur-bearing extractum obtains the sulfur-bearing byproduct through chemical process or biological degradation, the low sulfur-bearing further processing sweet oil of raffinating oil then.
Aforesaid employing high-power electron beam carries out the sulfur method of irradiation to oil product, it is characterized in that: high-energy electron beam energy 0.2-5MeV in the irradiation reaction device, absorption dose 1-60kGy, absorbed dose rate 0.1-30kGy/s, temperature 0-200 ℃, pressure is 0-5atm.
Aforesaid employing high-power electron beam carries out the sulfur method of irradiation to oil product, and it is characterized in that: oil product is one or more in gasoline, diesel oil, boat kerosene, heavy oil, residual oil and the crude oil.
Aforesaid employing high-power electron beam carries out the sulfur method of irradiation to oil product, and it is characterized in that: high-power electron beam is provided by the high-energy electron accelerator source.
Aforesaid employing high-power electron beam carries out the sulfur method of irradiation to oil product, it is characterized in that: before the high-energy electron beam irradiation oil product, add the auxiliary substance with catalytic activity in the irradiation reaction device, it is selected in titanium cyanines cobalt class catalyzer, heteropolyacid catalyst or loading transition metallic catalyst.
Principle of work of the present invention is: the high-power electron beam that employing rumbatron source provides is to oil product (various gasoline, diesel oil, the boat coal, heavy oil, the dregs of fat or even crude oil) carry out the irradiation desulfurization, high-power electron beam at first carries out irradiation to air molecule, make airborne part oxygen generate ozone, ozone has very strong oxygenizement, when under radiation environment, contacting with the oil product molecule, can be the sulphur oxidation in the oil product, sulfurous organic compound generates the compound of the sulphur that conventional polar solvent can extract at last, by solvent extraction, obtain low sulfur-bearing and raffinate oil and high sulfur-bearing extractum, solvent is then recyclable to be recycled.For the sulphur content that reduces in the oil product can be added some auxiliary substances, regulate and control product yield and quality by the consumption and the kind of CONTROL PROCESS condition and auxiliary substance.
The invention has the beneficial effects as follows: technology of the present invention is simple, only this main processes of irradiation need be set; Initial gross investment is little, and energy consumption is low, and process cost is well below existing technology, and is favourable to the protection environment, can largely reduce environmental pollution, and can not bring secondary pollution; Kind that can be by adding auxiliary component and quantity reduce the sulphur content in the oil product more, promote quality product.
Embodiment
Adopt high-power electron beam that the sulfur method that oil product carries out irradiation is described in detail below in conjunction with embodiment to the present invention.
Embodiment 1: the diesel oil of catalytic cracking gained at room temperature, squeeze into the irradiation reaction device by pump, by decollator mode with bubbling be dispersed in oil product from irradiation reaction device bottom through the air behind the high-energy electron beam irradiation this moment, the outlet of irradiation reaction device top is connected to condensing works, emptying, oil gas ratio is 1: 1, high-power electron beam (1.5Mev) carries out irradiation to oil product and air, irradiation reaction device internal pressure is 1.05atm, the absorption dose speed of oil product is 2kGy/s in the irradiation reaction device, and absorption dose is 20kGy.Condition to air irradiation is that absorption dose speed is 5kGy/s, and absorption dose is 20kGy.Take 50% ethanolic soln to extract than 1: 1 then by finish.Weigh the desulfurization degree of oil product with mercaptans content in the oil product, the result shows that after the radiation treatment, the mercaptan decreasing ratio is 82%, and diesel yield is 69%.
Embodiment 2: the gasoline of catalytic cracking gained at room temperature, squeeze into the inlet of irradiation reaction device by pump, the air mixed behind inlet and high-energy electron beam irradiation is passed through atomizing nozzle, in the irradiation reaction device, oil product is atomized, and simultaneously the irradiation reaction device is carried out irradiation.The outlet of irradiation reaction device top is connected to condensing works, emptying.Oil gas ratio is 1: 3, and high-power electron beam (0.8Mev) carries out irradiation to oil product and air, and irradiation reaction device internal pressure is 1.1atm, and the absorption dose speed of oil product is 2kGy/s in the irradiation reaction device, and absorption dose is 18kGy.Condition to air irradiation is that absorption dose speed is 6kGy/s, and absorption dose is 18kGy.Take 50% ethanolic soln to extract than 1: 1 then by finish.Weigh the desulfurization degree of oil product with mercaptans content in the oil product, the result shows that after the radiation treatment, the mercaptan decreasing ratio is 85%, and yield of gasoline is 65%.
Embodiment 3: the diesel oil of catalytic cracking gained under 50 ℃, squeeze into the irradiation reaction device by pump, by decollator mode with bubbling be dispersed in oil product from irradiation reaction device bottom through the air behind the high-energy electron beam irradiation this moment, the outlet of irradiation reaction device top is connected to condensing works, emptying, the ratio of oil product and air is 1: 2, adds homemade loading type Mn in oil product
2O
3-Al
2O
3Catalyzer, the ratio of catalyzer and oil product is 5: 100, and high-power electron beam (1.5Mev) carries out irradiation to oil product and air, and irradiation reaction device internal pressure is 1.05atm, and the absorption dose speed of oil product is 3kGy/s in the irradiation reaction device, absorption dose is 15kGy.Condition to air irradiation is that absorption dose speed is 5kGy/s, and absorption dose is 25kGy.Take 50% ethanolic soln to extract than 1: 1 by finish then, weigh the desulfurization degree of oil product with mercaptans content in the oil product, the result shows that after the radiation treatment, the mercaptan decreasing ratio is 93%, and diesel yield is 65%.
Claims (7)
1, a kind of high-power electron beam that adopts carries out the sulfur method of irradiation to oil product, it is characterized in that: have following steps:
A. utilize high-power electron beam that air is carried out irradiation, make and contain high-concentrated ozone in the air;
B. the air behind the irradiation is input to the irradiation reaction device, takes place fully to contact with oil product;
C. with high-power electron beam oil product and air are carried out irradiation, the ozone of air makes the organosulfur generation oxidizing reaction in the oil product, is oxidized to the sulfurous organic compound of sulfone class, sulfoxide class and sulfonic acid class.
2, employing high-power electron beam according to claim 1 carries out the sulfur method of irradiation to oil product, it is characterized in that: from irradiation reaction device output oil product after oxidation, adopt traditional polar solvent extract way that its sulfurous organic compound is wherein carried out solvent extraction, obtain high sulfur-bearing extractum and low sulfur-bearing and raffinate oil, extraction solvent recycling use from high sulfur-bearing extractum; High sulfur-bearing extractum obtains the sulfur-bearing byproduct through chemical process or biological degradation, the low sulfur-bearing further processing sweet oil of raffinating oil then.
3, employing high-power electron beam according to claim 1 and 2 carries out the sulfur method of irradiation to oil product, it is characterized in that: high-energy electron beam energy 0.2-5MeV in the irradiation reaction device, absorption dose 1-60kGy, absorbed dose rate 0.1-30kGy/s, temperature 0-200 ℃, pressure is 0-5atm.
4, employing high-power electron beam according to claim 1 and 2 carries out the sulfur method of irradiation to oil product, and it is characterized in that: oil product is a gasoline, diesel oil, boat kerosene, one or more in heavy oil, residual oil and the crude oil.
5, employing high-power electron beam according to claim 3 carries out the sulfur method of irradiation to oil product, and it is characterized in that: high-power electron beam is provided by the high-energy electron accelerator source.
6, employing high-power electron beam according to claim 1 and 2 carries out the sulfur method of irradiation to oil product, it is characterized in that: before the high-energy electron beam irradiation oil product, add the auxiliary substance with catalytic activity in the irradiation reaction device, it is selected in titanium cyanines cobalt class catalyzer, heteropolyacid catalyst, loading transition metallic catalyst.
7, employing high-power electron beam according to claim 3 carries out the sulfur method of irradiation to oil product, it is characterized in that: before the high-energy electron beam irradiation oil product, add the auxiliary substance with catalytic activity in the irradiation reaction device, it is selected in titanium cyanines cobalt class catalyzer, heteropolyacid catalyst, loading transition metallic catalyst.
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| CNB2008101968832A CN100562557C (en) | 2008-09-08 | 2008-09-08 | A kind of sulfur method that adopts high-power electron beam oil product to be carried out irradiation |
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| CNB2008101968832A CN100562557C (en) | 2008-09-08 | 2008-09-08 | A kind of sulfur method that adopts high-power electron beam oil product to be carried out irradiation |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114132987A (en) * | 2021-11-23 | 2022-03-04 | 清华大学 | Method for removing sulfide in oil field sewage by high-energy electron beam |
| CN115582136A (en) * | 2022-10-14 | 2023-01-10 | 国能龙源环保有限公司 | Sulfoxide catalyst for desulfurization and denitrification and preparation method thereof |
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2008
- 2008-09-08 CN CNB2008101968832A patent/CN100562557C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114132987A (en) * | 2021-11-23 | 2022-03-04 | 清华大学 | Method for removing sulfide in oil field sewage by high-energy electron beam |
| CN115582136A (en) * | 2022-10-14 | 2023-01-10 | 国能龙源环保有限公司 | Sulfoxide catalyst for desulfurization and denitrification and preparation method thereof |
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Assignee: Wuhan Jiu Rui Electric Applicance Co., Ltd Assignor: Hubei Jiurui Nuclear Technology Co., Ltd. Contract record no.: 2012420000035 Denomination of invention: Desulphurization method by irradiating oil with high-energy electron beam Granted publication date: 20091125 License type: Exclusive License Open date: 20090128 Record date: 20120410 |
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Effective date of registration: 20170821 Address after: Honghu Road Development Zone in Kunshan City, Jiangsu province 215300 No. 60 room 4 Patentee after: Jiangsu new century energy Electronics Co. Ltd. Address before: 430070 Hubei city of Wuhan province East Lake Development Zone Luoshi Road No. 517 Patentee before: Hubei Jiurui Nuclear Technology Co., Ltd. |
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Granted publication date: 20091125 Termination date: 20180908 |