Remove the method for sulfide in the oil products with high aromatic hydrocarbon content
Technical field
The invention belongs to the desulfurization technology field of petrochemical complex, particularly relate to the method that removes sulfide in the oil products with high aromatic hydrocarbon content.
Background technology
Along with the heaviness and poor qualityization of petroleum, the aromaticity content in petroleum and the product increases gradually.Because aromatic hydrocarbons is important chemical material, for example, C9 aromatic fuel oil is important gasoline dope, and organic solvent also is to produce resin and sooty important source material.So remove the sulfide in the aromatic hydrocarbons oil product and keep aromaticity content to become the emphasis that the scientific research personnel pays close attention to gradually, but also be not directed against the sulfur method efficiently of C9 aromatic hydrocarbons at present.
At present, the technology of producing the low-sulfur petroleum products mainly is a hydrogenating desulfurization technology (HDS), under the condition of HTHP, uses catalyzer to carry out hydrogenation, and the organosulfur behind the hydrogenation in the petroleum products is converted into hydrogen sulfide.The limit that removes the sulfide of domestic now hydrogenating desulfurization technology can not satisfy external and be about to the new standard requirement of implementation at home.If will increase the degree of depth of hydrogenating desulfurization, certainly will to increase service temperature and pressure, the development new catalyst, thus cause the investment of petroleum products processing to increase greatly.Thereby the price of its product can not let numerous human consumers accept, if can not develop the cheap desulfurization technology of novel and effective as early as possible, the production of ultra-low sulfur petroleum products will certainly shortage, and then causes the crisis of big bulge in price.In addition, hydrogenation process may reduce the content of aromatic hydrocarbons in the oil product significantly, and is unfavorable to the production of high aromaticity content product.
Oxidative desulfurization techniques research has obtained people's attention gradually; Oxidation sweetening is promptly under the effect of oxygenant and catalyzer; Organosulfur in the petroleum products is oxidized to sulfone or sulfoxide, and the polarity of sulfide increases, and the mode that is beneficial to extraction or absorption removes sulfide.To common model compound, such as thionaphthene (BT), the research of dibenzothiophene (DBT) is comparative maturity, and the mode desulfurization degree through oxidation sweetening reaches more than 90%.
In recent years, made significant headway to the research of further raising oxidation sweetening rate.Such as phase-transfer catalysis (PTC), promptly use the quaternary amine neutral compound that polarity is higher and be extracted in the organic phase, to reach the purpose of desulfurization; Also has the catalysis of complicated transition metal complex, such as H
3PM
12O
40(M=Mo W), has improved the oxidation activity of hydrogen peroxide greatly.Hyperacoustic use has also increased the speed of reaction and the desulfuration efficiency of oxidation sweetening greatly.Patent CN1412280A uses UW-phase-transfer catalysis-transition metal complex catalysis (mainly being phospho-wolframic acid) recently, and the desulfuration efficiency with oxidation of success is brought up to about 98%.With do not use ultrasonic comparing, oxidation system has has just met or exceeded the sweetening effectiveness that does not have ultrasonic down reaction several hrs in tens fens very short clock times under action of ultrasonic waves.
But, in being directed against the research of actual petroleum products, oxidation sweetening, especially the ultrasonic oxidation desulfurization technology has exposed a lot of problems.The probe type ultrasonic wave producer that existing ultrasonic oxidation reaction is all used, there is extremely strong scale effect in such reaction unit, is unfavorable for industriallization.The step of existing ultrasonic oxidation desulfurization is very complicated, and oxygenant and catalyst structure are complicated, with high difficult recovery of mutual solubility of oil product.Along with the increase of aromaticity content in the petroleum products, desulfurization degree is the trend that glides significantly.Because of aromaticity content is too high, oil quality is poor, and the reaction preference of oxygenant and catalyzer is poor, and the desulfurization degree of the BO of present high aromaticity content has only 11%.Simultaneously, side-reaction consumes a large amount of reaction reagents, can't reclaim after causing having reacted, aromatic hydrocarbons and numerous extraction agent mutual solubility are higher in addition, are difficult to select to be suitable for the extraction agent of industrial application.Because of quantitative responses such as oxygenant and oil products, make that the reaction reagent cost is higher.At present, to the direct abstraction desulfurization of C9 aromatic hydrocarbons, desulfurization degree does not reach 50% yet.Cause research and production cost all to improve greatly, hindered further developing of deep desulfuration technology.
Patent CN101040033 provides a kind of method that removes the sulfur in heavy oil thing, although can obviously prolong life of catalyst, the method for cut back product obviously is not suitable for large-scale production.Patent 03133543.8,01134272.2 and 200610012777.5 provides the method for desulfurizing and dearomatizing efficiently.But aromatic hydrocarbons loses in a large number in the process of hydrogenation.Recently, patent 200510055621.0 provides a kind of method of oxidation sweetening, utilizes the katalysis of MOXs such as Mn, Sb, W, Ce, Sn, Mo, V or Cr to remove the sulfide in the product, and aromatic hydrocarbons is formed not influence.Although this patent provides a kind of relatively method of highly selective; But only be applicable to the oil product that aromaticity content is lower; For unsaturated hydrocarbons content such as aromatic hydrocarbons up to the oil product more than 70% even 98%; Because the aromaticity content height has quite high solvability to reaction solvent and follow-up extraction agent, so this technology still can not be suitable for for the oil product of high aromaticity content.The present invention has developed a kind of sulfur method that is applicable to the oil product that aromaticity content is high first.
Summary of the invention
Remove the method for sulfide in the oil products with high aromatic hydrocarbon content of the present invention, concrete steps are following:
1) the configuration sour hydrogen salt with mineral acid or sulfuric acid hydrogen salt or phosphoric acid of the organic low charcoal of monobasic commonly used is that 1:4~9:2 forms mixed solution with the molar concentration rate; With joining mixing acid and oxygenant according to the mixed of volume ratio 10:1~1:5, mixed solution and raw oil mix according to the volume ratio of 1:8~9:1 and form the profit two-phase medium; The profit two-phase medium under stirring and ultrasound-enhanced acting in conjunction, is realized profit two emulsification fully mutually; With the most of sulfide oxidation in the oil product is sulfone class or sulfoxide;
2) phase-splitting behind the breakdown of emulsion;
3) adopt with the composite extractant of the immiscible polar solvent of aromatic hydrocarbons with the water composition oil product after oxidation is extracted, polar solvent mixes according to volume ratio 2:1-1:4 with water and obtains mixed extractant, removes the sulfide in the oil product, obtains low sulfur product.
Breakdown of emulsion adopts common breaking method, comprises that normal temperature leaves standstill, the method for low temperature (3~15 ℃), high temperature (70~95 ℃), perhaps carries out centrifugally with 100~20000 rev/mins rotating speed, and chemical demulsifying process is carried out phase-splitting behind the breakdown of emulsion to reacted emulsion.Chemical demulsifying process comprises the anaerobic hydrochlorate or the oxygen acid salt of the non-sulfur-bearing that adds Na, K.Concentration is approximately 0.04-2%;
Use common solvent to comprise the monohydroxy-alcohol of acetonitrile, C1-C4 and divalent alcohol, ketone; And common organic solvent comprises N; Dinethylformamide (DMF), N-Methyl pyrrolidone etc., polar solvent mix according to volume ratio 1:10~10:1 with water and obtain mixed extractant.
Said organic acid comprises formic acid, acetate or isopropylformic acid; Mineral acid comprises sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid; Hydrogen salt comprises sulfuric acid hydrogen salt or the corresponding class of phosphoric acid hydrogen salt,
Described mineral acid is arranged is phosphoric acid, and preferred concentration is 0.4mol/L; Organic acid is a formic acid, and concentration is 0.4mol/L.
Described oxygenant comprises H
2O
2Solution, dioxide peroxide, ozone, air or oxygen; Preferred oxygenant is H
2O
2Solution, concentration between 5-30%, preferred 30% concentration.
Said ultrasonic output frequency 20-1000kHz, suitable time 5-30 minute, preferred 20 minutes.
The inventive method of introduction of the present invention can be used in the sweetening process of heavy oil and high aromaticity content oil product, and cost is low, and method is simple, and desulfurization effect does not produce secondary pollution in the process, reached the requirement of green chemical industry process.In the sweetening process of C9 aromatic hydrocarbons oil product, this method obviously is superior to other sulfur methods that existing document is introduced.
The present invention has overcome higher BO weak effect of present aromaticity content and the high shortcoming of cost in the following aspects:
1. use cheap oxygenant, catalyzer and extraction agent,, reduce production costs in conjunction with the traditional technology method.
2. designed a kind of method of practicable deep oxidation desulfurization, reaction conditions is gentle, compares with existing oxidation desulfurizing method, and this method steps is simple, is easy to carry out suitability for industrialized production.
3. applicable object is mainly the higher heavy oil product of aromaticity content, is particularly suitable for using in the oil of heaviness and the Chemical Manufacture day by day now.
Embodiment
Adopt C9 aromatic fuel oil that the present invention is done further explain below in conjunction with embodiment, but the present invention is not limited to this.
The C9 aromaticity content is higher than 50% in the raw material C9 aromatic hydrocarbons oil product.
Instance 1
The molar concentration rate of configuration formic acid and phosphoric acid is the mixed solution of 1:1, and concentration is 30% H
2O
2Solution gets the catalyzed oxidation mixed solution.The catalyzed oxidation mixed solution is mixed according to the volume ratio of 1:2 with oil product; It is the groove type ultrasonic wave producer of 40kHz that reaction system is placed frequency; After reacting 20 minutes under 60 ℃; With cooling off breakdown of emulsion in 10 ℃ the water coolant, the KCl of adding 0.1% carries out breakdown of emulsion in the emulsion of handling through preliminary breakdown of emulsion then, realizes oily water separation through centrifugal back.The volume ratio of using solvent and oil product is then carried out twice extraction as the mixed extractant of 2:1, obtains the product A after the desulfurization.
Embodiment 2
Compare with embodiment 1, frequency of ultrasonic is adjusted into 80kHz, other material consumption is identical with embodiment 1 with operational condition, obtains desulfurization product B.
Embodiment 3
Compare with embodiment 1, frequency of ultrasonic is adjusted into 1000kHz, other material consumption is identical with embodiment 1 with operational condition, obtains desulfurization product C.
Embodiment 4
Compare with embodiment 1, will be adjusted into 30 minutes the treatment time, other material consumption is identical with embodiment 1 with operational condition, obtains desulfurization product D.
Embodiment 5
Compare with embodiment 1, change the volume ratio of oxygenant and raw oil into 1:4, other material consumption is identical with embodiment 1 with operational condition, obtains desulfurization product E.
Embodiment 6
Compare with embodiment 1, oxygenant is adjusted into dioxide peroxide, other material consumption is identical with embodiment 1 with operational condition, obtains desulfurization product F.
Embodiment 7
Compare with embodiment 1, oxygenant is adjusted into ozone, other material consumption is identical with embodiment 1 with operational condition, obtains desulfurization product G.
Embodiment 8
Compare with embodiment 1, formic acid and concentration of phosphoric acid are adjusted into 7:2, other material consumption is identical with embodiment 1 with operational condition, obtains desulfurization product H.
Embodiment 9
Compare with embodiment 1, formic acid and concentration of phosphoric acid are adjusted into 1:4, other material consumption is identical with embodiment 1 with operational condition, obtains desulfurization product I.
Embodiment 10
Compare with embodiment 1, formic acid is adjusted into acetate, other material consumption is identical with embodiment 1 with operational condition, obtains desulfurization product J.
Embodiment 11
Compare with embodiment 1, phosphoric acid acid is adjusted into hydrochloric acid, other material consumption is identical with embodiment 1 with operational condition, obtains desulfurization product K.
Embodiment 12
Compare with embodiment 1, phosphoric acid is adjusted into potassium primary phosphate, other material consumption is identical with embodiment 1 with operational condition, obtains desulfurization product L.
Embodiment 13
Embodiment 1 compares, and phosphoric acid is adjusted into sodium pyrosulfate, and other material consumption is identical with embodiment 1 with operational condition, obtains desulfurization product M.
Embodiment 14
Compare with embodiment 1, extraction times is adjusted into 3 times, other material consumption is identical with embodiment 1 with operational condition, obtains desulfurization product N.
Embodiment 15
Embodiment 1 compares, and changes breakdown of emulsion salt into NaCl, and other material consumption is identical with embodiment 1 with operational condition, obtains desulfurization product O.
Embodiment 16
Compare with embodiment 1, change breakdown of emulsion salt into potassium primary phosphate, other material consumption is identical with embodiment 1 with operational condition, obtains desulfurization product P.
Embodiment 17
Compare with embodiment 1, change the volume ratio of methyl alcohol and water into 1:1, other material consumption is identical with embodiment 1 with operational condition, obtains desulfurization product Q.
Embodiment 18
Compare with embodiment 1, change methyl alcohol into ethanol, other material consumption is identical with embodiment 1 with operational condition, obtains desulfurization product R.
The product desulfurization degree that each embodiment obtains is as described in Table 1
Table 1 sweetening effectiveness relatively
Visible by above result, when formic acid and concentration of phosphoric acid ratio were 7:2, the desulfurization degree of C9 aromatic hydrocarbons oil product can reach 70%, showed that organic acid and inorganic acid concentration ratio have fundamental influence to sweetening effectiveness.Sweetening effectiveness is best when the volume ratio of methyl alcohol and water is 4:1, and follow-up extraction step also has material impact to sweetening effectiveness.
Visible through above-mentioned comparison, the said method of this patent has remarkable advantages for the higher oil product of aromaticity content.This method can be used in the sweetening process of heavy oil and high aromaticity content oil product, and cost is low, and process is simple, has the remarkable economical social value.
Obviously, the foregoing description only is giving an example of doing in order to be illustrated more clearly in, and is not the qualification to embodiment.Those of ordinary skill for affiliated field can also be made other multi-form variation or change on the basis of above-mentioned explanation.Here need not also can't give exhaustive to all embodiments.And conspicuous variation of being amplified out thus or change still are among the protection domain of the invention.