CN103145534A - Method for deeply removing sulfides in gasoline additive, namely methyl tert-butyl ether - Google Patents
Method for deeply removing sulfides in gasoline additive, namely methyl tert-butyl ether Download PDFInfo
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- CN103145534A CN103145534A CN2013100970982A CN201310097098A CN103145534A CN 103145534 A CN103145534 A CN 103145534A CN 2013100970982 A CN2013100970982 A CN 2013100970982A CN 201310097098 A CN201310097098 A CN 201310097098A CN 103145534 A CN103145534 A CN 103145534A
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- butyl ether
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Abstract
The invention discloses a method for deeply removing sulfides in a gasoline additive, namely methyl tert-butyl ether. The desulfurization process is as follows: firstly loading nitrates of metal elements Cu, Ag and Ni onto an adsorbent by adopting an immersion method, then heating and drying at the temperature of 100 DEG C-120 DEG C, loading a nitric acid solution on the adsorbent after drying under the condition of stirring at room temperature, and enabling the adsorbent after the completion of loading to react with the methyl tert-butyl ether at the temperature of 15 DEG C-40 DEG C for 20-90 minutes so as to deeply remove the sulfides in the methyl tert-butyl ether. The adsorbent can be recycled after adopting nitrogen to heat, blow-off, dry and regenerate. By adopting the method disclosed by the invention, the sulfides in the methyl tert-butyl ether can be fast, effectively and deeply removed, the adsorbent can be reused after regeneration, and the method has the characteristics of low investment and low operation cost.
Description
Technical field:
The present invention relates to the Petroleum Processing Technology field, relate in particular to a kind of method of deep removal methyl tertiary-butyl ether medium sulphide content.
Technical background:
Along with continuing to increase of vehicle guaranteeding organic quantity, automotive emission has become one of main source of urban air pollution, and the motor spirit quality standard is constantly upgraded, and is more and more stricter to the restriction of content of sulfur in gasoline.Methyl tertiary butyl ether, english abbreviation are MTBE (methyl-tert-butyl ether), and methyl tertiary butyl ether is good gasoline high-octane rating additive and octane promoter.Methyl tertiary butyl ether and gasoline component can dissolve each other and demixing phenomenon not occur by arbitrary proportion, when being in harmonious proportion with gasoline component, good Blending effect are arranged, and are in harmonious proportion octane value higher than its clear octane number.Methyl tertiary butyl ether stable chemical nature, oxygen level are relatively high, can significantly reduce the content of carbon monoxide in tail gas, and gasoline combustion efficient are high, can suppress the generation of ozone.95% methyl tertiary butyl ether is approximately arranged now as containing the oxygen agent in octane enhancer and gasoline.In addition, methyl tertiary butyl ether is also a kind of important industrial chemicals, as the production of Methylacrylaldehyde and methacrylic acid.The ratio of methyl tertiary butyl ether in the gasoline concoction component is generally 8%～15%.At present, the raw material of methyl tertiary butyl ether mainly comes the C4 component in catalytic cracking, coking.In production, the sulphur massfraction of methyl tert-butyl ether product changes greatly, is generally 80～3000 μ g/g.During producing country V motor spirit, even adopt hydrogen addition technology that the sulphur massfraction of catalytic gasoline is reduced to below 10 μ g/g, still sulphur content in methyl tertiary butyl ether need be reduced, the sulphur content index of state V motor spirit could be satisfied.Along with closing on of state V motor spirit standard implementation, more and more urgent to the demand of low-sulfur methyl tertiary butyl ether production technology.It is larger that the target control value of methyl tertiary butyl ether sulphur content is affected by the catalytically cracked gasoline sulphur content, methyl tertiary butyl ether raw material or methyl tert-butyl ether product are made with extra care, make the sulphur massfraction in methyl tertiary butyl ether reach 15～30 μ g/g, still need control the massfraction of sulphur in catalytically cracked gasoline lower than 8～9 μ g/g, just can concoct out in theory qualified state V gasoline.And the sulphur content of reduction catalytically cracked gasoline can cause the decline of octane value.In actual production, also need further to reduce sulphur massfraction in methyl tertiary butyl ether lower than 10 μ g/g, just can reach the mediation requirement.Contain mercaptan, thioether, disulphide and a small amount of thiophene sulfides after refining in C4, in sulfide, Main Components is the neutral sulphur such as thioether and disulphide.Neutral sulphur and alkene and methyl tertiary butyl ether polarity differ little, adopt the loss of liquid-liquid extraction method methyl tert-butyl ether product larger.Due to alkene and the methyl tertiary butyl ether molecular structure unstable, the carbon-sulfur bond bond energy is much larger than the carbon-oxygen bond bond energy, the selectivity of hydrogenating desulfurization is difficult to be guaranteed.And adopting the method for distillation (or extractive distillation) to realize that sulphur further falls in methyl tertiary butyl ether, facility investment and energy consumption are larger.Non-hydrodesulfurizationprocess process energy consumption is low, and the another kind that becomes deep desulfuration is selected.Oxidation style usually adopt mass concentration be 30% hydrogen peroxide as oxygenant, because the oxygenant water content is larger, under normal temperature, sweetening effectiveness is relatively poor, and can a small amount of moisture of dissolving in methyl tert-butyl ether product, causes deterioration in quality.The sorbent material method operates at normal temperatures and pressures, does not consume hydrogen, and the by product after desulfurization also is adsorbed in the hole of sorbent material, and is very little on the impact of the quality of methyl tertiary butyl ether, be a kind of novelty, efficiently, clean gasoline additive process for deep desulphurization fast.
Summary of the invention:
A kind of method that the purpose of this invention is to provide deep removal methyl tertiary-butyl ether medium sulphide content.
The process of deep removal methyl tertiary-butyl ether medium sulphide content of the present invention is as follows:
At first the aqueous solution of the nitrate of preparing metal element Cu, Ag, Ni, nitrate shared massfraction in solution is 0.05%～35%, then add sorbent material in this solution, then sorbent material dipping 30～90 minutes is dried to constant weight at 100 ℃～120 ℃ temperature.Obtain the sorbent material of the nitrate of containing metal element Cu, Ag, Ni after drying, the nitrate of load and the mass ratio of sorbent material are 0.05: 1～0.2: 1.Then load on sorbent material adding under mass concentration 40%～68% salpeter solution stirring at room, the salpeter solution of load and the mass ratio of sorbent material are 0.05: 1～0.25: 1.Sorbent material after load and methyl tertiary butyl ether be 15 ℃～40 ℃ reactions, the sulfide in can the deep removal methyl tertiary butyl ether.Sorbent material can be recycled after adopting the dry regeneration of nitrogen heating stripping.
Advantage of the present invention:
The method of deep removal methyl tertiary butyl ether medium sulphide content of the present invention, operation at normal temperatures and pressures, the by product after desulfurization also is adsorbed in the hole of sorbent material, and is very little on the quality impact of MTBE, has less investment, the characteristics that running cost is low.
Embodiment:
1. embodiment 1
At first prepare the aqueous solution 10g of the cupric nitrate of mass concentration 35%, add silica gel absorber 2g, flooded 90 minutes, the sorbent material that contains cupric nitrate after filtration is dried to constant weight under 120 ℃.The mass ratio of nitrate and sorbent material 0.2: 1.Load on above-mentioned sorbent material adding under mass concentration 68% salpeter solution stirring at room, the mass ratio of salpeter solution and sorbent material is 0.25: 1.Sorbent material and sulphur content be the methyl tertiary butyl ether of 253 μ g/g according to mass ratio 0.02: 1,40 ℃ of reactions 20 minutes, can make the sulphur content in methyl tertiary butyl ether be reduced to 3 μ g/g.Reacted sorbent material can recycle after adopting 60 ℃ of dry regeneration of heating stripping of nitrogen.
2. embodiment 2
At first prepare the aqueous solution 10g of the Silver Nitrate of mass concentration 0.05%, add SBA-15 sorbent material 2g, flooded 30 minutes, the sorbent material that contains Silver Nitrate after filtration is dried to constant weight under 100 ℃.The mass ratio of nitrate and sorbent material 0.05: 1.Load on above-mentioned sorbent material adding under mass concentration 40% salpeter solution stirring at room, the mass ratio of salpeter solution and sorbent material is 0.05: 1.Sorbent material and sulphur content be the methyl tertiary butyl ether of 128 μ g/g according to mass ratio 0.25: 1,15 ℃ of reactions 90 minutes, can make the sulphur content in methyl tertiary butyl ether be reduced to 5 μ g/g.Reacted sorbent material can recycle after adopting 90 ℃ of dry regeneration of heating stripping of nitrogen.
3. embodiment 3
At first prepare the aqueous solution 10g of the nickelous nitrate of mass concentration 25%, add MCM-41 sorbent material 2g, flooded 60 minutes, the sorbent material that contains nickelous nitrate after filtration is dried to constant weight under 110 ℃.The mass ratio of nitrate and sorbent material 0.1: 1.Load on above-mentioned sorbent material adding under mass concentration 68% salpeter solution stirring at room, the mass ratio of salpeter solution and sorbent material is 0.15: 1.Sorbent material and sulphur content be the methyl tertiary butyl ether of 217 μ g/g according to mass ratio 0.15: 1,30 ℃ of reactions 60 minutes, can make the sulphur content in methyl tertiary butyl ether be reduced to 2 μ g/g.Reacted sorbent material can recycle after adopting 80 ℃ of dry regeneration of heating stripping of nitrogen.
Claims (6)
1. the method for a deep removal methyl tertiary-butyl ether medium sulphide content, is characterized in that, process is as follows:
(1) aqueous solution of the nitrate of preparing metal element Cu, Ag, Ni, nitrate shared massfraction in solution is 0.05%～35%, then add sorbent material in this solution, sorbent material dipping 30～90 minutes, filter to isolate sorbent material, then sorbent material is dried to constant weight at 100 ℃～120 ℃ temperature.
(2) obtain the sorbent material of the nitrate of containing metal element Cu, Ag, Ni after drying, will load on sorbent material under mass concentration 40%6～68% salpeter solution stirring at room.
(3) sorbent material after load is completed and methyl tertiary butyl ether be 15 ℃～40 ℃ reactions, the sulfide in can the deep removal methyl tertiary butyl ether.Sorbent material can recycle after adopting 60 ℃～90 ℃ dry regeneration of heating stripping of nitrogen.
2. metallic element nitrate according to claim 1, is characterized in that, described nitrate is cupric nitrate, Silver Nitrate, nickelous nitrate.
3. the method for deep removal methyl tertiary-butyl ether medium sulphide content according to claim 1, is characterized in that, described sorbent material is silica gel, SBA series and MCM Series Molecules sieve adsorbant.
4. the method for deep removal methyl tertiary-butyl ether medium sulphide content according to claim 1, is characterized in that, the nitrate of described load and the mass ratio of sorbent material are 0.05: 1～0.2: 1.
5. the method for deep removal methyl tertiary-butyl ether medium sulphide content according to claim 1, is characterized in that, the salpeter solution of described load and the mass ratio of sorbent material are 0.05: 1～0.25: 1.
6. the method for deep removal methyl tertiary-butyl ether medium sulphide content according to claim 1, it is characterized in that, described sorbent material and sulfur methyl tertiary butyl ether were according to mass ratio 0.02: 1～0.25: 1, reacted 20～90 minutes at 15 ℃～40 ℃ temperature, obtain the methyl tert-butyl ether product of deep desulfuration.
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Cited By (9)
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| CN103360221A (en) * | 2013-07-17 | 2013-10-23 | 凯瑞化工股份有限公司 | Method for deeply removing sulfides in MTBE |
| CN104370707A (en) * | 2013-08-14 | 2015-02-25 | 北京安耐吉能源工程技术有限公司 | Methyl tert-butyl ether crude product purification method and methyl tert-butyl ether production method |
| CN104370708A (en) * | 2013-08-14 | 2015-02-25 | 北京安耐吉能源工程技术有限公司 | Methyl tert-butyl ether crude product purification method and methyl tert-butyl ether production method |
| CN104387242A (en) * | 2014-11-06 | 2015-03-04 | 北京恩泽福莱科技有限公司 | MTBE desulfurization method and device |
| CN106542974A (en) * | 2015-09-17 | 2017-03-29 | 中国石油天然气股份有限公司 | A kind of method of sulfide in enrichment methyl tertiary-butyl ether |
| CN107469766A (en) * | 2016-06-08 | 2017-12-15 | 中国石油化工股份有限公司 | Remove adsorbent of sulfide and its preparation method and application method in MTBE |
| CN105080280B (en) * | 2014-04-15 | 2018-06-15 | 中国石油化工股份有限公司 | A kind of lighter hydrocarbons purification agent for treating waste gas and preparation method thereof |
| CN108440255A (en) * | 2018-04-25 | 2018-08-24 | 陈久仓 | A kind of synthetic method of high-purity methyl tertbutyl ether |
| CN109824487A (en) * | 2018-12-13 | 2019-05-31 | 天津康科德医药化工有限公司 | A kind of purification process of chromatographically pure methyl tertiary butyl ether(MTBE) |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103360221A (en) * | 2013-07-17 | 2013-10-23 | 凯瑞化工股份有限公司 | Method for deeply removing sulfides in MTBE |
| CN104370707A (en) * | 2013-08-14 | 2015-02-25 | 北京安耐吉能源工程技术有限公司 | Methyl tert-butyl ether crude product purification method and methyl tert-butyl ether production method |
| CN104370708A (en) * | 2013-08-14 | 2015-02-25 | 北京安耐吉能源工程技术有限公司 | Methyl tert-butyl ether crude product purification method and methyl tert-butyl ether production method |
| CN104370708B (en) * | 2013-08-14 | 2016-03-09 | 北京安耐吉能源工程技术有限公司 | The method of the thick product of a kind of purifying methyl tertiary butyl ether and the method for production methyl tertiary butyl ether |
| CN104370707B (en) * | 2013-08-14 | 2016-03-30 | 北京安耐吉能源工程技术有限公司 | The method of the thick product of purifying methyl tertiary butyl ether and the method for production methyl tertiary butyl ether |
| CN105080280B (en) * | 2014-04-15 | 2018-06-15 | 中国石油化工股份有限公司 | A kind of lighter hydrocarbons purification agent for treating waste gas and preparation method thereof |
| CN104387242A (en) * | 2014-11-06 | 2015-03-04 | 北京恩泽福莱科技有限公司 | MTBE desulfurization method and device |
| CN106542974A (en) * | 2015-09-17 | 2017-03-29 | 中国石油天然气股份有限公司 | A kind of method of sulfide in enrichment methyl tertiary-butyl ether |
| CN106542974B (en) * | 2015-09-17 | 2019-05-07 | 中国石油天然气股份有限公司 | A kind of method of sulfide in enrichment methyl tertiary-butyl ether |
| CN107469766A (en) * | 2016-06-08 | 2017-12-15 | 中国石油化工股份有限公司 | Remove adsorbent of sulfide and its preparation method and application method in MTBE |
| CN107469766B (en) * | 2016-06-08 | 2020-09-25 | 中国石油化工股份有限公司 | Adsorbent for removing sulfides in MTBE (methyl tert-butyl ether), and preparation method and application method thereof |
| CN108440255A (en) * | 2018-04-25 | 2018-08-24 | 陈久仓 | A kind of synthetic method of high-purity methyl tertbutyl ether |
| CN109824487A (en) * | 2018-12-13 | 2019-05-31 | 天津康科德医药化工有限公司 | A kind of purification process of chromatographically pure methyl tertiary butyl ether(MTBE) |
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Application publication date: 20130612 |