CN101870885A - Oil desulphurization method utilizing microwave driving - Google Patents
Oil desulphurization method utilizing microwave driving Download PDFInfo
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
The invention relates to an oil desulphurization method utilizing microwave driving. The invention is characterized in that the oil desulphurization method includes the following steps: desulphurization reaction auxiliary agent and emulsifier are added into oil, emulsification is carried out on the system, so as to obtain emulsion with oil and water uniformly dispersed; the emulsion reacts under the microwave radiation; after reaction is finished, extracting agent is added into the system in steps, and oil product after desulphurization is separated. Reaction auxiliary agent is mixed aqueous solution of peroxide and acid, the volume ratio of the two is 10-1:1, the volume ratio of auxiliary agent mixed aqueous solution and oil product is 1:5-30; the peroxide is 5-30% aqueous hydrogen peroxide solution, 2-10wt% of hydrogen peroxide or chlorine dioxide aqueous solution with the concentration of 2-10g/L; and the acid is formic acid, acetic acid, dicholoroacetic acid, trifluoroacetic acid, benzoic acid, citric acid, tartaric acid, ascirbuc acid, malic acid, hydrochloric acid or phosphoric acid.
Description
Technical field
The present invention relates to a kind of method of petroleum sweetening, particularly utilize the method for the petroleum sweetening of microwave-driven.
Background technology
The existence of sulfocompound in the oil can produce corrosive nature to refining equipment in oil refining process, also can produce the influence that can not be ignored to the quality of oil refining catalyst, auxiliary agent and petroleum products.Even more serious is that the sulfurous gas that produces behind the use sour product etc. has caused the serious environmental pollution problem, greatly threatens existent environment of people and Sustainable development.Therefore, production and environment for use close friend's cleaning petroleum products has become the problem that countries in the world are generally paid attention to, and various countries' environmental regulation has all proposed more and more stricter permission sulfur-bearing standard to oil product.This also carries out deep desulfuration to us to oil and has proposed new challenge.
The catalytic desulfurhydrogenation technology is the at present industrial petroleum sweetening technology of generally using, most of sulfocompound all there is removal effect preferably, but carrying out along with hydrogenation process, desulfurization rate sharply descends, desulfurization is difficult to deeply, rely on hydrofining to realize that the low sulfurized difficulty of petroleum products is increasing, therefore, press for us and seek new sulfur method to satisfy the petroleum products cleanliness standard that improves day by day.
Many non-hydrodesulfurizationprocess process of research mainly contain biological desulphurization, acid-alkali refining desulfurization, adsorption desulfurize, chemical oxidation desulfurization etc. at present.Biological desulfurizing technology is always by extensive concern, and in the petroleum sweetening field, by means of the develop rapidly of life science in recent years, the research of biological desulfurizing technology obtains paying attention to more widely.But that is that all right at present is ripe for biological desulfurization process, and also there are some bottlenecks technically in large-scale commercial applications.At first, the present desulfuration efficiency of biological desulfurizing technology is not high, bacterial classification is few and development difficulty is big, the poor selectivity of desulfurization, also can produce Degradation to hydrocarbon compound in the oil product, reduce former oil quality, so how further to optimize bacterial classification, perhaps develop the better biological catalyst of selectivity effect, also need to carry out a large amount of research.Secondly, because microorganism generally is present in water, how strengthening between water-oil phase, the material transfer between liquid phase and microbial film, also is one of urgent problem in the biological desulfurizing technology.Alkali cleaning is refining to be a kind of traditional sulfur method, and after the various improvement of process, this method still is extensive use of at each refinery at present, and the straight-run diesel oil of each refinery of China and catalytic diesel oil are most to carry out desulfurization with alkali wash.The main weak point of alkali cleaning process for purification is that desulfuration efficiency is low, and can bring serious environmental problem, and the use of a large amount of alkali inevitably can bring some secondary pollutions.In addition, the alkali lye that remains in the oil product can make the quality of oil reduce, and the emulsification problem of oil-alkali also is one of difficult problem that is faced.The ultimate principle of absorption method desulfurization is to utilize sorbent material that the sulfocompound in the oil is carried out selective adsorption, thereby with its method of from oil product, removing.The key of adsorption desulfurize is in the selection and preparation of sorbent material.Along with the raising day by day of performance of the adsorbent and the maturation gradually of absorbing process, adsorption desulfurize becomes the focus of Recent study gradually.But the present sorbent material cost that uses is higher, and recycles comparatively complexity, remains further to be studied.Chemical oxidization method is a kind of method of the petroleum sweetening that merits attention.In general because the continuous adding of chemical agent, though its desulfuration efficiency is higher, the cost of chemical oxidization method desulfurization is higher and can reduce the quality of oil.A kind of report that hypergravity is used for oil desulfurization that is called is also arranged recently, and the in theory comparatively environmental protection of this method need not add chemical reagent, but its cost is high, is difficult to carry out actual industrial applicability.
The disclosure of the Invention of CN99804475.X a kind of petroleum products contact a kind of method of carrying out desulfurization with acid organic polymer.Though this method does not need to use hydrogen, institute is the acid organic polymer of perfluorination preferably, because the organic polymer molecular weight is big, indissoluble is separated, and the accumulation of organic product can hinder contacting of acid organic polymer catalyzer and raw material on the acidic organic compound surface, thereby slows down sweetening process, and reaction can not be finished, organic polymer is difficult in addition separates, and can adsorb oil, and fluorochemicals is also unfriendly to environment.A kind of method of adsorption desulfurize has been introduced in the invention of CN200710027226.0, this method technology is simple, easy and simple to handle, but sorbent material is difficult to regeneration, the sorbent material making is numerous and diverse, cost is higher, and the desulfuration selectivity of sorbent material is low, and desulfurization time is long, efficient is low and loading capacity is little, is difficult to carry out industrialization.2002 the 21st the 8th phases of volume chemical industry progress goes up " biocatalysis petroleum sweetening technical progress " and has reported biocatalysis petroleum sweetening technology, this technology can be operated under low-temp low-pressure, do not need hydrogen, cost is low, can handle various oils, handiness is good, pollution-free, environmentally friendly, but activity at biological catalyst, there are many obstacles in selectivity and stability and fermentation production rate aspect, selection at bacterial classification, also there are numerous present insurmountable difficult problems in aspects such as the production of biological catalyst and regeneration, and the technology of biocatalysis technology and engineering problem, comprise the design of new-type bioreactor, isolation technique, the processing of byproduct and as why not reduce problem such as oil quality and all also be in the laboratory study stage.
Generally speaking, though more than each technical scheme on sweetening effectiveness, obtained some progress, does not still have at present the desulfurization technology that higher desulfuration efficiency is arranged and can not reduce oil quality simultaneously, and generally input cost is big, still is in conceptual phase, technology is immature.How overcoming problems of the prior art, has been to need one of problem that solves in the current desulfurization technology field.
Summary of the invention
The objective of the invention is to be to provide a kind of with the novel non-hydrotreated petroleum desulfurization technology of microwave as driving means, make petroleum oil product and reaction promoter form mixed system comparatively uniformly by physical treatment, driving effect at microwave issues biochemical desulphurization reaction then, to reach the effect that efficiently removes sulfocompound in the oil.
Technical scheme of the present invention is: utilize the method for the petroleum sweetening of microwave-driven, the method for described petroleum sweetening comprises the steps:
1) in oil, adds desulphurization reaction auxiliary agent and emulsifying agent, and system is carried out emulsification, obtain the finely dispersed emulsion of profit;
2) emulsion in the step 1) is positioned under the microwave radiation reacts;
3) after reaction finished, gradation added extraction agent in system, isolated oil product after the desulfurization.
In the step 1), reaction promoter is superoxide and sour mixed aqueous solution, and the add-on volume ratio of two materials is 10: 1～1: 1 in this mixed solution, and the volume ratio of auxiliary agent mixed aqueous solution and oil product is 1: 5～1: 30; Described superoxide is 5%～30% aqueous hydrogen peroxide solution, and the content of amounting to into hydrogen peroxide is 2-10wt% or aqueous solution of chlorine dioxide, and concentration is the 2-10 grams per liter; Acid can be organic acids such as formic acid, acetate, dichloro acetic acid, trifluoroacetic acid, phenylformic acid, citric acid, tartrate, xitix, oxysuccinic acid, can certainly adopt mineral acid, if corrosion resistant requirement of equipment and aftertreatment also have higher requirements can, hydrochloric acid, phosphoric acid etc. are better.
In the step 1), the emulsification means are that ultrasonic wave or high-speed physical stir shearing action, and wherein, shearing rotating speed is 3000～23000 rev/mins; The emulsive time is 3～8 minutes.Emulsifying agent adopts conventional tensio-active agent, as SP-80, TW-60, NP-4, NP-10, sodium dodecyl benzenylsulfonate etc.
Step 2) in, the described microwave exposure reaction times is 3～10 minutes, the frequency 500～3000MHz of microwave, and temperature of reaction is 50～90 ℃, pressure is normal pressure.
In the step 3), carry out the breakdown of emulsion layering after the microwave exposure reaction is finished, emulsion splitter can be series such as TA, AR, PFA, DPA, SDT, AE, AP, SP, BP, US; Also can adopt method of extraction to separate: described extraction agent is a basic solution, adopts yellow soda ash or the sodium bicarbonate aqueous solution of 5%～10wt%, or adopts the aqueous sodium hydroxide solution of 0.3～1wt%; The volume ratio of aqueous sodium carbonate, sodium bicarbonate aqueous solution or aqueous sodium hydroxide solution and oil product is 1: 2～1: 10.Can also be when adopting the technology of basic solution extraction in the microwave irradiating and the processing condition of standing demix in addition, the microwave irradiating time is standing demix after 1～10 minute.
Step 1) and 2) can circulate and carry out, promptly design the defeated recycle system of a pump and made emulsification and microwave-driven handle and to carry out circularly continuously, improve efficient.
The present invention compared with prior art beneficial effect is: 1) the present invention is that a kind of physics and chemical means of combining is in the petroleum sweetening means of one, by the high efficiency drive effect of microwave and the chemical reaction effect of desulfurizing assistant agent, finally make the sulfocompound in the oil be converted into the material of removing easily, again by simple separation means, realize the purpose of desulfurization, especially the removal effect of the sulfocompounds such as thiophene-based that are difficult to remove for additive method is obvious especially; 2) the microwave-driven means of the present invention's employing, make the reaction times shorten greatly, on principle, mainly be to utilize the microwave of special frequency channel less to hydrocarbons (specific inductivity is generally less) effect nonpolar in the oil sample system or that polarity is less, and to there being the auxiliary agent (mostly be aqueous systems, specific inductivity is bigger) in materials such as certain polarity sulfocompound and the adding system to have stronger action effect.Can not destroy whole structured oil phase like this, can handle targetedly S-contained substance again, play the effect of selectively acting, usefulness is higher than other supplementary meanss far away; 3) the auxiliary agent utilization ratio height among the present invention is little to environmental influence.Because the reaction times is short and reactive system is capable of circulation carrying out, greatly improved the utilization ratio of reagent, and desulfurization product generally is the bigger sulfone compound of polarity, can remove by adding extraction agent separation such as the soda ash aqueous solution, and it is recyclable, harmless substantially to environment, positive effect has been played in environment protection and green production; 4) the present invention is easy to operate, and cost is lower, has higher popularization and application values.
Description of drawings
Fig. 1 is the process flow diagram that the present invention utilizes the petroleum sweetening technology of microwave-driven
Embodiment
The invention will be further described below in conjunction with accompanying drawing and specific embodiment:
The petroleum sweetening method of the usefulness microwave-driven that proposes according to the present invention, at first in oil sample, add desulphurization reaction auxiliary agent and emulsifying agent, and system carried out emulsification, obtain the finely dispersed emulsion of profit two-phase, then this mix emulsion fluid is positioned over react for some time under the microwave radiation after, add a certain amount of alkaline aqueous solution again and extract and separate, can obtain the lower oil product of sulfur-bearing.
Embodiment 1:
At 300g crude oil (is respectively Liaohe Oil Field crude oil, Shengli Oil Field crude oil, United Arab Emirates Ah cloth crude oil) in, add 3mL acid (can be formic acid, acetate, dichloro acetic acid, trifluoroacetic acid, phenylformic acid, citric acid, tartrate, xitix, oxysuccinic acid etc.), 8mLH respectively
2O
2, water an amount of (50～200mL), small amounts of emulsifiers (massfraction＜0.1%); Mixed solution placed carry out emulsification 3～5 minutes under the high-shear emulsion machine, 3000～23000 rev/mins of rotating speeds; Emulsion is transferred in the special reaction flask then, reaction is 10 minutes under the microwave radiation condition, the soda ash aqueous solution (also can be 5% sodium bicarbonate aqueous solution or 1% sodium hydroxide solution) that adds 100mL5% then in the oil sample after desulfurization leaves standstill or the centrifugal oil product that can isolate after the desulfurization.In this example, utilize the microwave-driven petroleum sweetening, described microwave frequency is 2480MHz, belongs to decimetric wave, microwave input power 450W.Except that specifying, test conditions is a normal pressure in this example.Under the condition of microwave oven, the power input of the microwave radiation that every milliliter of crude oil is subjected to: 0.3-10W all can.Can adopt the industrial microwave device to carry out processing of the present invention.
The oil sample before and after handling has been carried out the mensuration of sulphur content according to ASTM 4239-2005 standard.
The sweetening effectiveness of several crude oil:
| The oil product title | Sulphur content before the desulfurization | Sulphur content after the desulfurization | Desulfurization degree |
| Liaohe Oil Field crude oil | ??1.03％ | ??0.37％ | ??64.1％ |
| Shengli Oil Field crude oil | ??0.69％ | ??0.32％ | ??53.6％ |
| United Arab Emirates Ah cloth crude oil | ??0.32％ | ??0.08％ | ??75.0％ |
Embodiment 2: microwave irradiation time is tested sweetening effectiveness
Handle according to method described in the embodiment 1, different is at microwave irradiation time is the processing of taking a sample in 1,3,5,7,10 minute, measures then.Other processing modes are all identical with reaction conditions.
The desulfurization result of different microwave irradiation times: (oil product: United Arab Emirates Ah cloth crude oil sample)
| Time/min | ??1 | ??3 | ??5 | ??7 | ??10 |
| Desulfurization degree | ??41.2％ | ??60.3％ | ??71.5％ | ??74.8％ | ??75.0％ |
Embodiment 3: the microwave radiation frequency is tested sweetening effectiveness
Handle according to method described in the embodiment 1, different is is to react under 850MHz, 1500MHz, the 2480MHz 10 minutes in the microwave radiation frequency respectively, measures then.Other processing modes are all identical with reaction conditions.
Desulfurization result under the different microwave radiation frequencies: (oil product: United Arab Emirates Ah cloth crude oil sample)
| Frequency | ??850MHz | ??1500MHz | ??2480MHz |
| Desulfurization degree | ??74.2％ | ??72.9％ | ??75.1％ |
Embodiment 4: water oil ratio is tested sweetening effectiveness
Handle according to method described in the embodiment 1, the volume ratio of different is oil phase and water different are to carry out the microwave desulfurization reaction under the condition in 9: 1,6: 1,2: 1 in water oil ratio respectively, and other processing modes are all identical with reaction conditions.
Sweetening effectiveness under the different water oil ratio conditions: (oil product: United Arab Emirates Ah cloth crude oil sample)
Embodiment 5: different extraction agents to desulfurization after the influence of sulfocompound separating effect
Handle according to method described in the embodiment 1, different is that the extraction agent that adds is respectively 5% aqueous sodium carbonate, 5% sodium bicarbonate aqueous solution, 1% aqueous sodium hydroxide solution, other processing modes all identical with reaction conditions (the simplest method is to leave standstill after stirring).Adding basic solution satisfies under the refinery requirement pH value all can.
Different extraction agents to microwave desulfurization after the separating resulting of sulfocompound:
Can also be when adopting the technology of basic solution extraction at the microwave irradiating and the processing condition of standing demix in addition, the desulfurization degree that the microwave irradiating time is shown on standing demix slightly is better than after 1～10 minute.
Embodiment 6: the experiment that oil property changes before and after the microwave-driven petroleum sweetening
Handle according to method described in the embodiment 1, the oil product main character contrast before and after handling is as follows:
Oil product main character contrast before and after the crude Treatment: (oil product: the Shengli Oil Field crude oil sample)
Claims (8)
1. a method of utilizing the microwave-driven petroleum sweetening is characterized in that the method for described petroleum sweetening mainly comprises the steps:
1) in oil, adds desulphurization reaction auxiliary agent and emulsifying agent, and system is carried out emulsification, obtain the finely dispersed emulsion of profit;
2) emulsion in the step 1) is positioned under the microwave radiation reacts;
3) after reaction finished, gradation added extraction agent in system, isolated oil product after the desulfurization.
2. the method for utilizing the petroleum sweetening of microwave-driven according to claim 1, it is characterized in that in the described step 1), reaction promoter is superoxide and sour mixed aqueous solution, the add-on volume ratio of two materials is 10: 1～1: 1 in this mixed solution, and the volume ratio of auxiliary agent mixed aqueous solution and oil product is 1: 5～1: 30; Described superoxide is 5%～30% aqueous hydrogen peroxide solution, and the content of amounting to into hydrogen peroxide is 2-10wt% or aqueous solution of chlorine dioxide, and concentration is the 2-10 grams per liter; Acid is formic acid, acetate, dichloro acetic acid, trifluoroacetic acid, phenylformic acid, citric acid, tartrate, xitix, oxysuccinic acid, hydrochloric acid or phosphoric acid.
3. the method for utilizing the petroleum sweetening of microwave-driven according to claim 1 is characterized in that in the described step 1), and the emulsification means are that ultrasonic wave or high-speed physical stir shearing action, and wherein, shearing rotating speed is 3000～23000 rev/mins; The emulsive time is 3～8 minutes.
4. the method for utilizing the petroleum sweetening of microwave-driven according to claim 1 is characterized in that described step 2) in, the described microwave exposure reaction times is 3～10 minutes, the frequency 500～3000MHz of microwave, and temperature of reaction is 50～90 ℃, pressure is normal pressure.
5. the method for utilizing the petroleum sweetening of microwave-driven according to claim 1, it is characterized in that in the described step 3), carry out the breakdown of emulsion layering after the microwave exposure reaction is finished, emulsion splitter can be series such as TA, AR, PFA, DPA, SDT, AE, AP, SP, BP, US; Or adopt method of extraction to separate: described extraction agent is a basic solution, adopts yellow soda ash or the sodium bicarbonate aqueous solution of 5%～10wt%, or adopts the aqueous sodium hydroxide solution of 0.3～1wt%; The volume ratio of aqueous sodium carbonate, sodium bicarbonate aqueous solution or aqueous sodium hydroxide solution and oil product is 1: 2～1: 10.
6. the method for utilizing the petroleum sweetening of microwave-driven according to claim 1 is characterized in that described step 1) and 2) can circulate and carry out, promptly design the defeated recycle system of a pump and made emulsification and microwave-driven processing carry out circularly continuously.
7. the method for utilizing the petroleum sweetening of microwave-driven according to claim 1 is characterized in that emulsifying agent adopts SP-80, TW-60, NP-4, NP-10 or sodium dodecyl benzenylsulfonate.
8. the method for utilizing the petroleum sweetening of microwave-driven according to claim 5 is characterized in that adopting the technology of basic solution extraction, and the microwave irradiating time is standing demix after 1～10 minute.
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| CN103184068A (en) * | 2013-04-15 | 2013-07-03 | 淮阴师范学院 | Hydrogen peroxide-hydrochloric acid oxidation and desulfurization method |
| CN103897763B (en) * | 2014-03-27 | 2016-04-06 | 四川大学 | A kind of composite desulfuration method of high-sulfur coal and device |
| CN105820832A (en) * | 2016-01-18 | 2016-08-03 | 许裕金 | Electrochemical catalysis diesel oil desulphurization method at normal temperature and pressure |
| CN106995736A (en) * | 2017-06-08 | 2017-08-01 | 重庆科技学院 | Coal desulfurization before combustion method |
| CN107022394A (en) * | 2017-06-08 | 2017-08-08 | 重庆科技学院 | A kind of method that organic sulfur is removed in sulphur coal |
| RU182750U1 (en) * | 2018-06-20 | 2018-08-30 | Закрытое акционерное общество "Приз" | DEVICE FOR SULFURING RAW OIL IN THE FLOW |
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| CN109439366A (en) * | 2018-09-07 | 2019-03-08 | 中国石油化工股份有限公司 | A kind of method that gasoline takes off thiophene sulphur |
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| CN103184068A (en) * | 2013-04-15 | 2013-07-03 | 淮阴师范学院 | Hydrogen peroxide-hydrochloric acid oxidation and desulfurization method |
| CN103897763B (en) * | 2014-03-27 | 2016-04-06 | 四川大学 | A kind of composite desulfuration method of high-sulfur coal and device |
| CN105820832A (en) * | 2016-01-18 | 2016-08-03 | 许裕金 | Electrochemical catalysis diesel oil desulphurization method at normal temperature and pressure |
| CN106995736A (en) * | 2017-06-08 | 2017-08-01 | 重庆科技学院 | Coal desulfurization before combustion method |
| CN107022394A (en) * | 2017-06-08 | 2017-08-08 | 重庆科技学院 | A kind of method that organic sulfur is removed in sulphur coal |
| RU182750U1 (en) * | 2018-06-20 | 2018-08-30 | Закрытое акционерное общество "Приз" | DEVICE FOR SULFURING RAW OIL IN THE FLOW |
| CN108998060A (en) * | 2018-08-23 | 2018-12-14 | 中石化（洛阳）科技有限公司 | A kind of low sulfur coke production new technique |
| CN108998060B (en) * | 2018-08-23 | 2021-06-08 | 中石化（洛阳）科技有限公司 | Novel process for producing low-sulfur coke |
| CN109439366A (en) * | 2018-09-07 | 2019-03-08 | 中国石油化工股份有限公司 | A kind of method that gasoline takes off thiophene sulphur |
| CN109439366B (en) * | 2018-09-07 | 2021-06-15 | 中国石油化工股份有限公司 | Method for removing thiophene sulfur from gasoline |
| WO2020093174A1 (en) * | 2018-11-09 | 2020-05-14 | Attia Mai | Process for removing sulfur in crude oil using microwaves |
| RU2708629C1 (en) * | 2019-05-30 | 2019-12-10 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский государственный университет" (ТГУ, НИ ТГУ) | Desulfurization method of heavy oil product using microwave radiation |
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