CN102442738B - Treatment process of alkaline residue during sweetening of light hydrocarbon - Google Patents
Treatment process of alkaline residue during sweetening of light hydrocarbon Download PDFInfo
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- CN102442738B CN102442738B CN 201010506825 CN201010506825A CN102442738B CN 102442738 B CN102442738 B CN 102442738B CN 201010506825 CN201010506825 CN 201010506825 CN 201010506825 A CN201010506825 A CN 201010506825A CN 102442738 B CN102442738 B CN 102442738B
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- alkaline residue
- gasoline
- liquid
- mercaptan
- phenol
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Abstract
A treatment process of alkaline residue during sweetening of light hydrocarbon is provided, comprising the steps of inputting alkaline residue during alkali wash of gasoline or liquefied gas to an alkaline residue tank (A); filling alkali wash water of liquefied gas to mix and dilute the alkaline residue; using a pump to introduce the mixture to an upper end of the fiber bundle in a fiber membrane mass-transfer reactor (B); introducing carbon dioxide to the top of the fiber membrane mass-transfer reactor (B); reacting the diluted alkaline residue liquid with the carbon dioxide so as to enable phenoxide and mercaptide in the alkaline residue liquid to transform to phenol and mercaptan and enable sodium hydroxide to transform to sodium bicarbonate, meanwhile, introducing desulphurized gasoline liquid to the fiber membrane mass-transfer reactor (B) so as to enable the generated phenol and mercaptan to enter to gasoline phase after being extracted by the gasoline liquid; using a pump to circulate the gasoline liquid to the top of the fiber membrane mass-transfer reactor (B); when the phenol and mercaptan in the gasoline arrive at a certain concentration, discharging the phenol and mercaptan to a hydrogen desulfurization system; using a circulating pump to circulate the alkaline liquid continuously till that pH of the alkaline residue is 6-8, and then discharging the neutral brine formed by the alkaline residue. The process disclosed by the invention has high efficiency and saves water resource.
Description
Technical field
The present invention relates to the treatment process of a kind of alkaline waste water of desulfurization of petroleum products technical field.
Technical background
The low sulfuration of refined oil product is a kind of development trend, is the more and more tighter and people of the environmental regulation inevitable outcomes more and more higher to the requirement of environmental quality of surviving.Particularly the trend of the low sulfuration of gasoline and liquefied gas is had higher requirement to the desulfurization of oil refining enterprise product.
Along with the rapid growth of China's economy, the energy demand sharp increase, the crude oil import amount also increases year by year, and wherein major part is Middle East sulfur-bearing and high-sulpur crude.So the ratio of China's oil refining enterprise processing sulfur-bearing and high-sulpur crude is more and more high, because the difference according to work flow in Crude Oil Processing of the sulphur in crude oil is distributed in (as LPG, dry gas, virgin naphtha, pressure naphtha, straight-run spirit, catalytic gasoline, kerosene, diesel oil, fuel wet goods) in product by certain transformation rule, for the sulphur content that makes these products reaches related standards, just must improve the sweetening power of refinery, this has just proposed challenge to sulfur removal technology, equipment and the production management of oil refining enterprise.
Therefore, the Petroleum ﹠ Petrochemical Enterprises of China must be in the face of from the challenge of two aspects: be on the one hand the mean content of sulfur of raw material improving, be that the sulphur content of product will reduce on the other hand.This just requires to have efficiently, less energy-consumption, the sulfur removal technology of low emission and the requirement that equipment satisfies these two aspects.Simultaneously the spent lye treatment of desulfurization discharging is had higher requirement.
The present invention is exactly the novel process of the processing of a kind of light hydrocarbon mercaptan removal alkaline waste water of developing in order to adapt to this requirement.
Summary of the invention
The waste lye that liquefied gas and gasoline desulfur form also contains Sulfothiorine (Na except containing alkali (NaOH)
2S
2O
3), sodium mercaptides (NaSR), sodium sulphite, phenol sodium (RONa), sodium carbonate, sodium napthionate and catalyzer.
Contain alkali (NaOH) 7-10%, Sulfothiorine (Na in typical liquefied gas alkaline mud
2S
2O
3) 3-5%, sodium mercaptides (NaSR) 200-300ppm, phenol sodium (RONa)＜0.02%.
Contain alkali (NaOH) 3-4%, Sulfothiorine (Na in alkaline residue after typical gasoline (catalysis) alkali cleaning
2S
2O
3) 8-9%, sodium mercaptides (NaSR) 1000-2000ppm, phenol sodium (RONa) 6-7.5%.
Sodium mercaptides in these waste lyes (NaSR) and phenol sodium (RONa) are extremely harmful to environment, must remove, and the method that removes is exactly with the carbonic acid gas neutralization, namely leads to people's carbonic acid gas in alkali lye, and the sodium mercaptides (NaSR) in alkaline residue is neutralized into NaHCO at this moment
3With mercaptan, phenol sodium (ArONa) is neutralized into phenol and NaHCO
3, NaOH is neutralized into NaHCO
3And water.Main chemical reaction is as follows:
1） NaOH+CO
2→NaHCO
3+H
2O
2） NaSR+ CO
2+H
2O→NaHCO
3+RSH
3） ArONa+CO
2+H
2O→NaHCO
3+ArOH
Phenol in these alkaline residues, mercaptan (RSH) are taken away with solvent extraction, made alkaline residue become neutral salt solution.
Due to sodium bicarbonate (NaHCO
3) solubleness in water is smaller, in order not make sodium bicarbonate (NaHCO
3) precipitate in water, can dilute with liquefied gas alkali cleaning after washing water, contain alkali (NaOH) 30～60 ppm in liquefied gas alkali cleaning after washing water, contain Sulfothiorine (Na
2S
2O
3) 40～60 ppm, be also a kind of alkaline waste water of lower concentration, do with it the consumption that dilution water had both been saved water, reduce the consumption of water, liquefied gas alkali cleaning after washing water is fully used, reduce the discharging of alkaline waste water.
Technical scheme of the present invention is as follows:
A kind of light hydrocarbon mercaptan removal alkaline residue harmless treatment process, its flow process as shown in Figure 1, it comprises the following steps:
Step 1. is with the alkaline residue of Alkali cleaning of gasoline or the alkaline residue input alkaline residue tank (A) of liquefied gas alkali cleaning, inject the liquefied gas soda-wash water and carry out mixed diluting, alkaline residue concentration after dilution depending on alkaline residue temperature at that time and the solubleness of sodium bicarbonate, in general, the soda-wash water add-on of dilution is greater than the alkaline residue amount, when liquefied gas soda-wash water quantity not sufficient, add fresh water and regulate, do not separate out to guarantee sodium bicarbonate;
alkaline residue liquid after the dilution that step 2. obtains step 1 is introduced the upstream extremity of the interior fibrous bundle of tunica fibrosa mass transfer reaction device (B) with pump, the structure of tunica fibrosa mass transfer reaction device (B) and reaction principle are referring to patent US 3992156, carbonic acid gas is introduced the top of tunica fibrosa mass transfer reaction device (B), alkaline residue liquid and carbonic acid gas after dilution react, make phenates and thiolate in alkaline residue liquid be converted into phenol and mercaptan, sodium hydroxide is converted into sodium bicarbonate, the top of simultaneously stream of the gasoline liquid after desulfurization being introduced tunica fibrosa mass transfer reaction device (B), its entrance is lower than the entrance of alkaline residue liquid, form carbonic acid gas, gasoline and alkaline residue liquid three-phase forward flow down along fiber surface, make the phenol of generation be entered gasoline mutually with mercaptan by the extraction of gasoline liquid stream, the amount that enters the carbonic acid gas of reactor is controlled with automatic pH value control system, to guarantee that the discharging Alkali Waste pH Value is as 6 ~ 8,
The gasoline liquid stream that step 3. will flow into the gravity separator bottom tunica fibrosa mass transfer reaction device (B) loops back the top of tunica fibrosa mass transfer reaction device with pump, be disposed to gasoline and be in harmonious proportion system when the concentrations of mercaptans in gasoline reaches 8ppm, the alkaline residue liquid that flows into the gravity separator bottom of tunica fibrosa mass transfer reaction device (B) bottom constantly is circulated to Alkali Waste pH Value 6 ~ 8 o'clock with recycle pump in reactor, alkaline residue becomes neutral brine discharge.
Principal feature of the present invention is to have used the tunica fibrosa mass transfer reaction device of three-phase following current.In reactor B, water (alkali lye) and oil phase (gasoline) and gas phase (carbonic acid gas) enter forward from the top of reactor simultaneously and flow down, and neutralization reaction and solvent extraction are all occured on the tunica fibrosa surface, have improved greatly the efficient of reactor.
Second characteristic of the present invention are the alkaline residues with liquefied gas alkali cleaning after washing water dilution Alkali cleaning of gasoline (or liquefied gas alkali cleaning), have both saved the consumption of water, and liquefied gas alkali cleaning after washing water is fully used, and have reduced discharge of wastewater.
The 3rd characteristics of the present invention are the amounts of the carbonic acid gas that enters reactor of controlling with automatic pH value control system, and discharging alkaline residue pH is controlled in 6 ~ 8 scope.Because the pH value is processed whole alkaline residue, be no matter except phenol and in and the sodium ion influential effect very large, so pH need control very well.
The 4th characteristics of the present invention be with the stream extraction of the gasoline liquid after desulfurization with in carbonic acid gas with alkaline residue after the phenol and the mercaptan that generate, do not allow these organism entered environments, environmental contamination reduction allows these organism be fully used in the subsequent technique process simultaneously.
Description of drawings
Fig. 1 is the schematic flow sheet of light hydrocarbon mercaptan removal alkaline residue harmless treatment process of the present invention, and wherein: A is the alkaline residue tank; B is tunica fibrosa mass transfer reaction device; 1 is the alkaline residue liquid front pump after dilution; 2 is alkaline residue liquid recycle pump; 3 are gasoline liquid stream recycle pump.
Embodiment
Embodiment 1.Light hydrocarbon mercaptan removal alkaline residue harmless treatment process
The alkaline residue of liquefied gas alkali cleaning and Alkali cleaning of gasoline advances alkaline residue tank (A) and carries out mixed diluting with the liquefied gas soda-wash water by 1:1.then inject with the amount of 3 tons/hour tunica fibrosa mass transfer reaction device (B) (the reactor diameter 500mm that processes alkaline waste liquor with pump, high 5000mm), with the carbonic acid gas that enters reactor (about 0.39 ton/hour, control with automatic pH=6-8 value control system and react, gasoline liquid stream (2 tons/hour) extraction that the phenol that reaction generates and mercaptan are entered after the desulfurization of reactor simultaneously enters gasoline mutually, gasoline liquid stream goes back to the top of tunica fibrosa mass transfer reaction device with pump circulation (8.5 tons/hour of internal circulating loads), when reaching finite concentration, the phenol in gasoline and mercaptan is disposed to hydrodesulfurizationsystem system (2 tons/hour).Alkaline residue liquid with recycle pump constantly in reactor the circulation (9.8 tons/hour of internal circulating loads) to alkaline residue pH value 6 ~ 8, contain NaHCO
37～9%, Na
2S
2O
33.5～4.5%, phenol 0.1%, Na
2S＜20PPm, detection does not contain mercaptan, becomes neutral brine discharge (2.9 tons/hour).
Claims (2)
1. a light hydrocarbon mercaptan removal alkaline residue harmless treatment process, is characterized in that it comprises the following steps:
Step 1. is injected the alkaline residue of Alkali cleaning of gasoline or the alkaline residue input alkaline residue tank (A) of liquefied gas alkali cleaning the liquefied gas soda-wash water and is carried out mixed diluting, when liquefied gas soda-wash water quantity not sufficient, adds fresh water and regulates, and does not separate out to guarantee sodium bicarbonate;
alkaline residue liquid after the dilution that step 2. obtains step 1 is introduced the upstream extremity of the interior fibrous bundle of tunica fibrosa mass transfer reaction device (B) with pump, carbonic acid gas is introduced the top of tunica fibrosa mass transfer reaction device (B), alkaline residue liquid and carbonic acid gas after dilution react, make phenates and thiolate in alkaline residue liquid be converted into phenol and mercaptan, sodium hydroxide is converted into sodium bicarbonate, the top of simultaneously stream of the gasoline liquid after desulfurization being introduced tunica fibrosa mass transfer reaction device (B), its entrance is lower than alkaline residue liquid entrance, form carbonic acid gas, gasoline and alkaline residue liquid three-phase forward flow down along fiber surface, make the phenol of generation be entered gasoline mutually with mercaptan by the extraction of gasoline liquid stream,
The gasoline liquid stream that step 3. will flow into the gravity separator bottom tunica fibrosa mass transfer reaction device (B) loops back the top of tunica fibrosa mass transfer reaction device with pump, be disposed to gasoline and be in harmonious proportion system when the concentrations of mercaptans in gasoline reaches 8ppm, the alkaline residue liquid that flows into the gravity separator bottom of tunica fibrosa mass transfer reaction device (B) bottom constantly is circulated to Alkali Waste pH Value 6 ~ 8 o'clock with recycle pump in reactor, alkaline residue becomes neutral brine discharge.
2. light hydrocarbon mercaptan removal alkaline residue harmless treatment process according to claim 1, it is characterized in that: the amount that enters the carbonic acid gas of reactor is controlled with automatic pH value control system, and controlling alkaline residue liquid pH value is 6-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010506825 CN102442738B (en) | 2010-10-14 | 2010-10-14 | Treatment process of alkaline residue during sweetening of light hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010506825 CN102442738B (en) | 2010-10-14 | 2010-10-14 | Treatment process of alkaline residue during sweetening of light hydrocarbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102442738A CN102442738A (en) | 2012-05-09 |
| CN102442738B true CN102442738B (en) | 2013-06-19 |
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|---|---|---|---|
| CN 201010506825 Expired - Fee Related CN102442738B (en) | 2010-10-14 | 2010-10-14 | Treatment process of alkaline residue during sweetening of light hydrocarbon |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102671907B (en) * | 2012-05-31 | 2014-09-03 | 中国石油化工股份有限公司 | Combination method and device of caustic sludge desulfuration and dephenolization neutralization and tail gas desulphurization processing |
| CN106745442B (en) * | 2015-11-19 | 2019-09-10 | 中国石油化工股份有限公司 | A kind of refinery basic sewage acidification reaction device and acidization tool |
Citations (6)
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|---|---|---|---|---|
| CN1335353A (en) * | 2000-07-24 | 2002-02-13 | 中国石油化工股份有限公司 | Comprehensive acid sludge and caustic sludge treating process |
| CN101077984A (en) * | 2007-07-25 | 2007-11-28 | 中国石油大学(北京) | Deep desulfurization method for liquefied petroleum gas |
| CN101343554A (en) * | 2007-07-09 | 2009-01-14 | 中国石油化工股份有限公司 | Process for preparing light-end product |
| CN101418229A (en) * | 2008-11-14 | 2009-04-29 | 中国石油化工集团公司 | Mercaptans removal apparatus for light oil and mercaptans removal method thereof |
| CN101475831A (en) * | 2008-12-08 | 2009-07-08 | 中国石化扬子石油化工有限公司 | Method for plasma removing thiol in liquefied petroleum gas |
| CN201579249U (en) * | 2009-11-05 | 2010-09-15 | 宁波中一石化科技有限公司 | Device for treating alkaline residue generated by desulfurizing light oil |
-
2010
- 2010-10-14 CN CN 201010506825 patent/CN102442738B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1335353A (en) * | 2000-07-24 | 2002-02-13 | 中国石油化工股份有限公司 | Comprehensive acid sludge and caustic sludge treating process |
| CN101343554A (en) * | 2007-07-09 | 2009-01-14 | 中国石油化工股份有限公司 | Process for preparing light-end product |
| CN101077984A (en) * | 2007-07-25 | 2007-11-28 | 中国石油大学(北京) | Deep desulfurization method for liquefied petroleum gas |
| CN101418229A (en) * | 2008-11-14 | 2009-04-29 | 中国石油化工集团公司 | Mercaptans removal apparatus for light oil and mercaptans removal method thereof |
| CN101475831A (en) * | 2008-12-08 | 2009-07-08 | 中国石化扬子石油化工有限公司 | Method for plasma removing thiol in liquefied petroleum gas |
| CN201579249U (en) * | 2009-11-05 | 2010-09-15 | 宁波中一石化科技有限公司 | Device for treating alkaline residue generated by desulfurizing light oil |
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|---|---|
| CN102442738A (en) | 2012-05-09 |
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