CN1284540A - Method of reducing olefin and benzene content in gasoline - Google Patents
Method of reducing olefin and benzene content in gasoline Download PDFInfo
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- CN1284540A CN1284540A CN 00118949 CN00118949A CN1284540A CN 1284540 A CN1284540 A CN 1284540A CN 00118949 CN00118949 CN 00118949 CN 00118949 A CN00118949 A CN 00118949A CN 1284540 A CN1284540 A CN 1284540A
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Abstract
By using the ionic liquid catalyst, comprising alkyl pyridine, imidazole or trimethylamine and metal or non-metal halide, in the amount of 5-30 wt% of gasoline and through the reaction at room temp. to 120 deg.C and inert or reductant gas pressure of 0.1-1.0 MPa for 10-90 min, olefin and benzene in gasoline is reduced to proper level through alkylation and isomerization while the octane number remains unchanged. The present invention features the controllable alkylation and isomerization, mild and simple reaction condition and operation, and catalyst being easy to separate from gasoline, non-sensitive to organic sulfide, capable of reducing C4 and C5 components in gasoline and reusable.
Description
The present invention relates to a kind of method by excessive alkene and benzene in catalytic alkylation and the isomery reduction gasoline.
Along with the increasingly stringent of environmental protection requirement and improving constantly of the performance of automobile own, with domestic quality of gasoline is also being formulated more strict specification index abroad, this just requires suitably to adjust existing gasoline and forms.Compare with existing specification gasoline, reformulated gasoline is formed following characteristics (Environmental Catalysis edited by F.J.J.G.Janssen and R.A.van Santen, Imperical College Press, London, 1999): benzene content (volume fraction) is not higher than 1%, total aromaticity content is not higher than 35%, olefin(e) centent is not higher than 20%, oxygenatedchemicals (massfraction) is more than or equal to 2%, sulphur content is lower than 150ppm, reduce the content of low boiling component as far as possible, octane value is equal to or higher than existing gasoline.Wherein,, can regulate and control the selectivity of its products distribution, realize alkene or benzene content in the direct reduction gasoline by improving the performance of catalytic cracking catalyst for reaching the excessive alkene that reduces in the gasoline and the purpose of benzene content.But, reduce the content of alkene in the gasoline greatly, because it is limited to improve the leeway of existing catalytic cracking catalyst performance, so method remains at present in very big difficulty.Another possible method is by shortening excessive alkene or benzene in the gasoline to be reduced to proper level alkene, again by catalytic isomerization, with the issuable straight-chain paraffin isomery of shortening collateralization, to reduce the fall of octane value as far as possible.But, this method relative complex, facility investment and production cost are than higher.
The purpose of this invention is to provide a kind of more convenient and effective means, can be under the reaction conditions of gentleness, by alkylation and isomery, when being reduced to suitable level, keep octane value constant substantially the excessive alkene in the gasoline and benzene.
Further aim of the present invention provides a kind of more convenient and effective means, can be under the reaction conditions of gentleness, the excessive alkene in the gasoline and benzene by alkylation and isomery, when being reduced to suitable level, are further suitably reduced the C in the gasoline
4-C
5Light constituent and the organic sulfur content that may exist.
The present invention realizes by following measure:
Catalyzer of the present invention is made of the ionic-liquid catalyst of alkyl pyridine, alkyl imidazole or trimethylamine hydrochloride nitrogenous compound and metal or non-metallic halide gained.Wherein, alkyl pyridine, alkyl imidazole compound can be halogenated alkyl pyridine or halogenation 1, and 3-alkyl imidazole salt, alkyl chain length wherein are C
1-C
4Metal or non-metallic halide are aluminum chloride, iron trichloride, cupric chloride, boron trifluoride, phosphorus pentafluoride; The mol ratio of metal or non-metallic halide and alkyl pyridine, imidazoles or trimethylamine hydrochloride nitrogenous compound 4: 1 to 1: 1.The weight ratio 5-30% of catalyzer and gasoline, temperature of reaction room temperature-120 ℃, inertia or reducing gas pressure 0.1-1.0MPa, under the reaction times 10-90 minute condition, by alkylation between alkene and alkene, alkene and alkane and alkene and the aromatic hydrocarbons and corresponding isomerization reaction process, making the conversion of olefines in the gasoline is corresponding alkylbenzene, naphthenic hydrocarbon or branched paraffin with the alkene in the gasoline.Thereby realize that alkene is to suitable level in the reduction gasoline.Simultaneously, owing to being converted into corresponding alkylbenzene, reduces benzene.
Preparation of catalysts process of the present invention is:
Get an amount of solid metal halogenide, as aluminum trichloride (anhydrous) and solid-state alkyl pyridine, alkyl imidazole or trimethylamine hydrochloride, as chlorinated butyl pyridine or 1-methyl, 3-butyl imidazole nitrogen-containing heterocycle compound quaternary ammonium salt, after mechanically mixing under the normal temperature, promptly form at room temperature a kind of or near the limpid liquid that is in a liquid state under the room temperature, i.e. ionic liquid.Wherein, the mol ratio of metal or non-metallic halide and alkyl pyridine, alkyl imidazole nitrogen-containing heterocycle compound is 4: 1-1: 1.
Typical implementation process of the present invention is: add above-mentioned catalyzer 5-60 gram in 1 liter high-pressure reactor of stirring, thermometer is housed, adds gasoline 50-200 milliliter, sealing.Introduce nitrogen or hydrogen to pressure and be 1.0MPa to the maximum.Stir down, room temperature or be heated to certain temperature (being no more than 120 ℃) keeps reaction 10-90 minute, stops heating.Because alkylation process is thermopositive reaction, so-called temperature of reaction is a room temperature, and actual being meant no longer heated reactor in reaction process.Reactor cooling is opened reactor to room temperature.Gasoline and catalyzer natural layering through alkylation and isomery.Collect upper strata gasoline, sampling is carried out qualitative and quantitative analysis with U.S. HP6890/5973GC-MS combined instrument.Remaining ionic-liquid catalyst can reuse.After repeatedly using, can be under 100-120 ℃ with this catalyzer, standard machinery pump depletion 30 minutes is removed possible volatile impurity such as organosulfur, to recover its optimum performance.
Because ionic-liquid catalyst is insoluble with gasoline, and gasoline is relative with the duration of contact of catalyzer shorter, in actual application, the operator scheme of reaction both can be an intermittent type, also can be continuous flowing type.
With the gasoline before and after the reaction treatment, press the GB5487 method and measure research octane number (RON) RON, press the GB503 method and measure motor-method octane number MON.
Substantive distinguishing features of the present invention is: under quite gentle condition, can realize the isomery of alkylation and alkane to the alkene in the gasoline or benzene 1..2. each component in the gasoline and catalyzer is insoluble and AUTOMATIC ZONING makes sepn process become more easy.Liquid catalyst vapour pressure under employed condition is extremely low, is difficult for running off.3. catalyzer is insensitive to the organosulfur that may exist in the gasoline, and promptly anti-sulfur poisonous performance is strong.Simultaneously, because ionic-liquid catalyst has good dissolving power to organosulfur, thereby can further reduce organic sulfur content possible in the gasoline.4. the content of the lower boiling light constituent in the gasoline can be suitably reduced, thereby the volatility of gasoline can be suitably reduced.5. catalyst activity is stable, and is reusable.
Below among each embodiment used gasoline all take from Fushun oil branch office without the catalytic gasoline that is in harmonious proportion.
Embodiment 1-2:
Get 30 milliliters of ionic liquids that are made of Aluminum chloride anhydrous and chlorinated butyl pyridine, wherein the mol ratio of aluminum chloride and chlorinated butyl pyridine is 2: 1.Put into the 1 liter high-pressure reactor that stirring, thermometer are housed.Add 200 milliliters in gasoline, airtight.Wherein the volume ratio of ionic-liquid catalyst and gasoline is 15/100.Embodiment 1: the nitrogen that charges in reactor is warming up to 100 ℃ to 0.5MP, stirs to keep reaction 1 hour down.Reaction finishes the back sampling analysis and the results are shown in table 1.Embodiment 2: stirring reaction is 0.5 hour under normal pressure, the room temperature.Reaction finishes the back sampling analysis and the results are shown in table 2.
Table 1. catalytic alkylation and isomerization reduce content of olefin in gasoline result's front and back contrast significantly
*Comprise: butane, Trimethylmethane, butylene, iso-butylene, pentane, iso-pentane, amylene and isopentene.
| Volumn concentration, % | C 4-C 5Light constituent * | Total normal paraffin | Total isoparaffin | Total olefin | Naphthenic hydrocarbon | Benzene | Aromatic hydrocarbons |
| Before the reaction | 15.9???? | ?5.2 | ?26.1 | ?43.7 | ?7.2 | ?0.5 | ?17.3 |
| After the reaction | 7.0 | ?7.0 | ?54.4 | ?0.8 | ?16.1 | ?0.2 | ?21.5 |
The front and back contrast that catalytic alkylation and isomerization gasoline are formed under table 2. normal temperature and pressure
Embodiment 3-4:
| Volumn concentration, % | C 4-C 5Light constituent | Total normal paraffin | Total isoparaffin | Total olefin | Naphthenic hydrocarbon | Benzene | Aromatic hydrocarbons |
| Before the reaction | 15.9 | ?5.2 | ?26.1 | ?43.7 | ?7.2 | ?0.5 | ?17.3 |
| After the reaction | 9.9 | ?4.6 | ?37.6 | ?24.8 | ?12.9 | ?0.2 | ?20.0 |
Get 30 milliliters of ionic liquids that are made of Aluminum chloride anhydrous and chlorinated butyl pyridine, wherein the mol ratio of aluminum chloride and chlorinated butyl pyridine is 2: 1.Put into the 1 liter high-pressure reactor that stirring, thermometer are housed.Add 200 milliliters in gasoline, sealing.Stirring reaction is 15 minutes under normal pressure, the room temperature.After reaction finishes, the gasoline that reacted is taken out, the sample thief analysis, embodiment 3.Add gasoline again and use this catalyzer reaction repeated for 200 milliliters, and repeat this process four times again, embodiment 4.The results are shown in table 3.
Table 3. reduces alkylation and gasoline composition contrast of isomery front and back and catalyst system repetition performance under the reaction times
| Volumn concentration, % | C 4-C 5Light constituent | Total normal paraffin | Total isoparaffin | Total olefin | Naphthenic hydrocarbon | Benzene | Aromatic hydrocarbons |
| Before the reaction | 15.9 | ?5.2 | ?26.1 | ?43.7 | ?7.2 | ?0.5 | ?17.3 |
| 1 secondary response, example 3 | ?11.2 | ?4.7 | ?38.0 | ?29.9 | ?9.8 | ?0.4 | ?17.2 |
| 2 secondary responses, example 4 | ?11.4 | ?4.9 | ?36.8 | ?30.2 | ?9.7 | ?0.4 | ?18.0 |
| 3 secondary responses, example 4 | ?11.2 | ?4.0 | ?39.6 | ?28.4 | ?10.4 | ?0.4 | ?17.2 |
| 4 secondary responses, example 4 | ?11.3 | ?4.7 | ?37.4 | ?30.3 | ?9.6 | ?0.4 | ?17.6 |
| 5 secondary responses, example 4 | ?11.4 | ?4.5 | ?36.9 | ?30.6 | ?9.8 | ?0.4 | ?17.8 |
With gasoline before the reaction and the gasoline of handling through embodiment 3, carry out octane number determination, the result is as shown in table 4.
The comparison of gasoline modified front and back octane value data under table 4. embodiment 3 conditions
| Research octane number (RON) RON | Motor-method octane number MON | |
| Before the reaction | ????91.9 | ????79.1 |
| After the reaction, example 3 | ????91.2 | ????79.8 |
Gasoline before will reaction and the gasoline of handling through embodiment 3 carry out simulation distil experiment with vapor-phase chromatography, relatively react front and back gasoline required time when distillating the same amount cut, and the result is as shown in table 5.The chromatogram simulated conditions: when chromatographic column temperature was 40 ℃, sample introduction kept this column temperature after 20 minutes, was warming up to cut with 5 ℃/minute speed and finished.At this moment, the corresponding temperature that gasoline fraction finishes before the reaction is 135 ℃; Reacted is 155 ℃.
Gasoline modified front and back boiling range changes relatively under table 5. embodiment 3 conditions
| Quantity of distillate (%) | Time (minute) | |
| Gasoline before the reaction | Reaction back gasoline | |
| ????5 | ????1.40 | ????1.45 |
| ????10 | ????1.49 | ????1.51 |
| ????20 | ????1.85 | ????1.86 |
| ????30 | ????2.20 | ????2.32 |
| ????40 | ????2.78 | ????2.82 |
| ????50 | ????4.04 | ????4.02 |
| ????60 | ????5.35 | ????5.75 |
| ????70 | ????8.41 | ????8.41 |
| ????80 | ????17.41 | ????17.21 |
| ????90 | ????25.48 | ????26.00 |
| ????98 | ????28.12 | ????30.76 |
| ????100 | ????35.80 | ????40.89 |
Embodiment 5-6:
Get 60 milliliters of ionic liquids that are made of Aluminum chloride anhydrous and chlorinated butyl pyridine, wherein the mol ratio of aluminum chloride and chlorinated butyl pyridine is 2: 1.Put into the 1 liter high-pressure reactor that stirring, thermometer are housed.Add 200 milliliters in gasoline, sealing.Charge into nitrogen to 0.5MPa, in 100 ℃ of stirring reactions 10 minutes.After reaction finishes, the gasoline that reacted is taken out, sampling analysis, embodiment 5.
Reactions steps and condition be with embodiment 5, is that embodiment 6 behind 0.5% the thiophene but add volume fraction in gasoline.The result is shown in table 6,7.
Table 6. increases ionic liquid quantity catalytic alkylation and isomerization gasoline is formed contrast
| Volumn concentration, % | C 4-C 5Light constituent | Total normal paraffin | Total isoparaffin | Total olefin | Naphthenic hydrocarbon | Benzene | Aromatic hydrocarbons |
| Before the reaction | 15.9 | ?5.2 | ?26.1 | ?43.7 | ?7.2 | ?0.5 | ?17.3 |
| After the reaction, example 5 | ?3.7 | ?6.7 | ?42.8 | ?4.2 | ?16.6 | ?0.15 | ?29.6 |
Ionic-liquid catalyst sulfur resistance contrast when table 7. is identical with table 6 reaction conditions
Embodiment 7:
| Volumn concentration, % | C 4-C 5Light constituent | Total normal paraffin | Total isoparaffin | Total olefin | Naphthenic hydrocarbon | Benzene | Aromatic hydrocarbons | Thiophene |
| Before the reaction | 15.8 | ?5.2 | ?26.0 | ?43.5 | ?7.2 | ?0.5 | ?17.2 | ?0.5 |
| After the reaction, example 6 | ?7.2 | ?5.1 | ?52.8 | ?3.5 | ?13.6 | ?0.13 | ?24.6 | ?0.3 |
Get 60 milliliters of ionic liquids that are made of Aluminum chloride anhydrous and chlorinated butyl pyridine, wherein the mol ratio of aluminum chloride and chlorinated butyl pyridine is 2: 1.Put into the 1 liter high-pressure reactor that stirring, thermometer are housed.Add 200 milliliters in gasoline, add 4 milliliters of benzene again, sealing.Reaction is 15 minutes under normal pressure, the room temperature.After reaction finishes, the gasoline that reacted is taken out the sample thief analysis.The result is as shown in table 8.
Table 8. adds behind 2% the benzene the ionic liquid-catalyzed performance of butyl-pyridinium/aluminum chloride and gasoline and forms contrast
Embodiment 8:
| Volumn concentration, % | C 4-C 5Light constituent | Total normal paraffin | Total isoparaffin | Total olefin | Naphthenic hydrocarbon | Benzene | Aromatic hydrocarbons |
| Before the reaction | 15.5 | ?5.1 | ?25.6 | ?42.7 | ?7.0 | ?2.5 | ?16.9 |
| After the reaction | 4.4 | ?5.7 | ?37.7 | ?19.6 | ?10.1 | ?0.9 | ?26.1 |
Reactions steps is with embodiment 1, but with chlorination 1-methyl, 3 butyl imidazole replace the chlorinated butyl pyridine, wherein aluminum chloride and 1-methyl, and the mol ratio of 3 butyl imidazole is 2: 1, and the volume ratio of ionic-liquid catalyst and gasoline is 15/100, and the result is as shown in table 9.
Table 9.1-methyl, the ionic liquid-catalyzed performance comparison of 3 butyl imidazole/aluminum chloride
| Volumn concentration, % | C 4-C 5Light constituent | Total normal paraffin | Total isoparaffin | Total olefin | Naphthenic hydrocarbon | Benzene | Aromatic hydrocarbons |
| Before the reaction | 15.9 | ?5.4 | ?24.1 | ?45.8 | ?7.1 | ?0.5 | ?17.1 |
| After the reaction | 7.1 | ?6.8 | ?53.6 | ?1.2 | ?16.5 | ?0.3 | ?18.2 |
Claims (4)
1. method that reduces alkene and benzene in the gasoline, it is characterized in that adopting the ionic-liquid catalyst that is liquid state under the room temperature that constitutes by alkyl pyridine, imidazoles or methylamine nitrogenous compound and metal or non-metallic halide or the nearly room temperature, wherein the mol ratio of metal or non-metallic halide and alkyl pyridine, imidazoles or methylamine nitrogenous compound compound is 4: 1 to 1: 1, the amount weight ratio of catalyzer and gasoline is 5-30%, in temperature of reaction is room temperature-120 ℃, rare gas element or reducing gas pressure normal pressure-1.0MPa, reaction 10-90 minute.
2. the method for claim 1 is characterized in that nitrogenous compound is alkyl pyridine, 1,3 alkyl imidazole or trimethylamine hydrochloride, and the chain length of alkyl is C
1To C
4
3. the method for claim 1 is characterized in that metal or non-metallic halide are aluminum chloride, iron trichloride, boron trifluoride, phosphorus pentafluoride.
4. the method for claim 1 is characterized in that indifferent gas or reducing gas are nitrogen, hydrogen, nitrogen and hydrogen mixture or oil refinery dry gas.
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| CN00118949A CN1098332C (en) | 2000-08-25 | 2000-08-25 | Method of reducing olefin and benzene content in gasoline |
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| CN00118949A CN1098332C (en) | 2000-08-25 | 2000-08-25 | Method of reducing olefin and benzene content in gasoline |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453524A (en) * | 2010-10-21 | 2012-05-16 | 上海欣年石化助剂有限公司 | Refining method of gasoline |
| CN102453523A (en) * | 2010-10-21 | 2012-05-16 | 上海欣年石化助剂有限公司 | Method for refining reformed gasoline |
| CN101708474B (en) * | 2009-11-11 | 2012-06-27 | 济南大学 | Ionic liquid catalyst, preparation method and application thereof |
| CN105492580A (en) * | 2013-07-04 | 2016-04-13 | 尼克森能源无限责任公司 | Olefins reduction of a hydrocarbon feed using olefins- aromatics alkylation |
| CN112958149A (en) * | 2021-02-05 | 2021-06-15 | 北京化工大学 | Composite ionic liquid catalyst, preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4897175A (en) * | 1988-08-29 | 1990-01-30 | Uop | Process for improving the color and color stability of a hydrocarbon fraction |
| CN1053691C (en) * | 1996-07-25 | 2000-06-21 | 刘世凯 | Hydrogenation technology |
-
2000
- 2000-08-25 CN CN00118949A patent/CN1098332C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101708474B (en) * | 2009-11-11 | 2012-06-27 | 济南大学 | Ionic liquid catalyst, preparation method and application thereof |
| CN102453524A (en) * | 2010-10-21 | 2012-05-16 | 上海欣年石化助剂有限公司 | Refining method of gasoline |
| CN102453523A (en) * | 2010-10-21 | 2012-05-16 | 上海欣年石化助剂有限公司 | Method for refining reformed gasoline |
| CN102453524B (en) * | 2010-10-21 | 2015-01-21 | 上海欣年石化助剂有限公司 | Refining method of gasoline |
| CN105492580A (en) * | 2013-07-04 | 2016-04-13 | 尼克森能源无限责任公司 | Olefins reduction of a hydrocarbon feed using olefins- aromatics alkylation |
| CN105492580B (en) * | 2013-07-04 | 2018-11-02 | 尼克森能源无限责任公司 | The alkene of hydrocarbon charging is reduced using alkene-aromatic alkylation |
| CN112958149A (en) * | 2021-02-05 | 2021-06-15 | 北京化工大学 | Composite ionic liquid catalyst, preparation method and application thereof |
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| CN1098332C (en) | 2003-01-08 |
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