CN1062007C - Process for regenerating aromatic hydrocarbon extraction solvent - Google Patents
Process for regenerating aromatic hydrocarbon extraction solvent Download PDFInfo
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- CN1062007C CN1062007C CN97120270A CN97120270A CN1062007C CN 1062007 C CN1062007 C CN 1062007C CN 97120270 A CN97120270 A CN 97120270A CN 97120270 A CN97120270 A CN 97120270A CN 1062007 C CN1062007 C CN 1062007C
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Abstract
The present invention relates to a method of regenerating aromatic hydrocarbon extraction solvent. The method is characterized in that system circulating water the quantity of which is 50 to 400% of solvent quantity is added to solvent to be regenerated, and the processes of mechanical filtering or bed-filtering and decolouring and cleaning treatment by adsorption bed are adopted to implement the regeneration of the aromatic hydrocarbon extraction solvent. The regenerated solvent is clear and transparent.
Description
The invention belongs to the renovation process of used solvent, more particularly, is a kind of purifying method of relevant aromatic hydrocarbon extraction solvent.
In order to obtain the aromatic hydrocarbons of required purity from oil, petroleum refining industry adopts liquid-liquid method for extracting promptly to utilize hydro carbons difference of solubleness in solvent to reach the purpose of aromatics separation and non-aromatics to cracking hydrogenated gasoline or reformed oil usually.Because solvent is in the medium-term and long-term cycle operation of device, a small amount of solvent inevitably can oxidized generation acidic substance, add the influence of the resistance to acid material monoethanolamine of contained trace amounts of olefin in the extracting raw material and adding, make the color of circulating solvent more and more dark, superpolymer and acidic substance constantly accumulate, gradually influence extraction procedure, when serious even influence the quality of extracting product.Therefore, must regenerate to circulating solvent.
Existing renovation process is to adopt underpressure distillation (Hou Xianglin chief editor, " Chinese oil Refining Technologies ", Sinopec press, P185,1991.12. first version).This method troublesome poeration, solvent loss is big, the energy consumption height, the coking of regenerator column reboiler is remarkable, especially higher solvent such as Tetraglycol 99 to boiling point, its coking and solvolysis problem are more outstanding.U.S. Pat 2878812 once proposed to adopt ion exchange resin that glycol ether and triglycol are carried out absorption regeneration, but the solvent after lacking the work-ing life of this method resin, regenerating still is yellow, and particularly regeneration of resin need be used alkaline solution.Early seventies, U.S. Pat 3595781 has been invented a kind of renovation process of extraction solvent, this method is to treat that the regenerated circulating solvent mixes with raffinating oil, 0.7～100 times the water that adds the regenerated solvent amount, utilize the affinity of solvent and water, make organic impurity, painted thing priority enrichment in raffinating oil, to reach the purpose of purifying solvent.The shortcoming of this method is that the product of raffinating oil can be subjected to a certain degree pollution.Recently, U.S. Pat 4919816 proposes the renovation process of tetramethylene sulfone extraction system recirculated water, and this method can be removed the acidic substance in the recirculated water effectively, reduces the corrosion of equipment, but can't remove the pollutent of solvent systems, outstanding shortcoming still is that regeneration of resin need be used alkaline solution.
The objective of the invention is to overcome the defective of existing reclaiming process, propose a kind of simple to operate, solvent loss is few, the renovation process of the aromatic hydrocarbon extraction solvent of non-environmental-pollution.
Realize the main technical schemes of the object of the invention: in treating the regenerated aromatic hydrocarbon extraction solvent, add systemic circulation water, do decolouring by filtration, adsorption bed and handle.
Specific embodiment of the present invention is followed successively by:
(1) arene extracting process treat in the regenerated solvent add systemic circulation water and thorough mixing, the amount of described recirculated water is to treat 100～400% of regenerated solvent amount, preferably 100～200%;
(2) treated the mixture of regenerated solvent and recirculated water is by mechanical filter or bed filtration, 30～100 ℃ of bed filtration temperature, air speed 0.1～3.0h (1) step
-1, to remove various mechanical impuritys;
(3) by the material after the filtration of (2) step, at 30～100 ℃ of temperature, air speed 0.1～5.0h
-1, handle through the adsorption bed decolorizing purification under 1: 5～1: 20 condition of bed blade diameter length ratio.
The pressure reduction of above-mentioned filtration or adsorption bed surpasses 1. 0kg/cm
2The time, adopt usual method backwash or switching, to remove filter residue.Described mechanical filter method comprises that plate basket filter filters, whizzer filters, by the cylindrical or plate shaped millipore filter filtration that the sintering such as powder of pottery, stainless steel, copper or nickel form, its aperture is 3～30 μ m.The medium that described bed filtration adopts comprises 20～80 purpose quartz sands, sand, pearlstone.
The sorbent material that described adsorption bed adopts comprises: weak base anion-exchange resin, silica gel, gac, preferably adopt the macropore weak basic anion exchange resin or 20～80 purpose granulated active carbons of phenylethylene.
Described solvent comprises glycol ether, triglycol, Tetraglycol 99, five glycol, glycol ethers, tetramethylene sulfone, N-formyl morpholine, N-Methyl pyrrolidone or its mixture.
Further describe technological process of the present invention below in conjunction with accompanying drawing.
Fig. 1 is glycols solvent extraction aromatic hydrocarbons typical process and solvent regeneration process combined process flow synoptic diagram of the present invention.
10,20,22,23,24,25,26,27 be respectively extraction tower, stripping tower among the figure, the water wash column of raffinating oil, stripping water pot, mixing tank, filtration bed, adsorption bed, backflow aromatic hydrocarbons jar.Specific operation process: raw material 1 and solvent 2 enter from the middle part and the top of extraction tower 10 respectively, at the bottom of entering extraction tower from the backwash liquor 3 at stripping tower 20 tops, oil phase is an external phase in extraction tower, solvent phase is a disperse phase, two-phase counter current contact in extraction tower is carried out heat and mass transport, cat head obtains raffinating oil 4, this is raffinated oil and enters water wash column 22 bottoms of raffinating oil, wash with water 17 counter current contact of telling from stripping tower 20 side lines, wash back water 16 and be admitted to backflow aromatic hydrocarbons jar 27, the water 15 that this jar told enters stripping water pot 23, and a part directly is used as water stripping 21, the water 8 that a part needs as solvent reclamation.Rich solvent 5 enters stripping tower 20 tops at the bottom of the extraction tower, cat head steam thing divide after the water outlet sent back to extraction tower as backwash liquor 3 at the bottom of.The mixture 13 of aromatic hydrocarbons and water vapor is extracted out from the side line of stripping tower, obtains BTX aromatics 19 after condensate cooler water outlet in 28 fens, obtains lean solvent 6 at the bottom of the tower.Tell 1～3% lean solvent and treat that promptly regenerated solvent stream strands 7 and water stream 8 from stripping water pot 23 become stream strands 9 behind mixing tank 24 thorough mixing, this stream thigh is at first by filtering bed 25 or mechanical filter, perhaps advance to filter bed 25 again through mechanical filter earlier, the bed top obtains preliminary regenerated solvent 11, further by adsorption bed 26, solvent 12 after obtaining bottom the bed to regenerate, this stream thigh mixes the back with stream thigh 21 and enters 20 ends of stripping tower as water stripping.Stream thigh 18 and 19 is sent device as non-aromatics and aromatic hydrocarbon product respectively.
Processing method of the present invention can also and other aromatic hydrocarbons extracting flow process comprise that glycols extracting five tower flow processs, tetramethylene sulfone extracting flow process unite use.
Advantage of the present invention: the solvent reclamation of present method is the normal temperature and pressure operation, has avoided the pyrolytic decomposition of solvent; Owing to no vacuum operating, alleviated the possibility of air admission system greatly, therefore the solvent protection of total system is of great benefit to; The present invention compares with vacuum distillation method, helps energy-conservationly, and solvent loss is few; Present method need not to use soda acid, and adopts systemic circulation water, therefore helps environment protection.Example 1
Raw material: the lean solvent of reformed oil Tetraglycol 99 extracting aromatic device.
Operation: add the deionized water of 200% (to Tetraglycol 99) in lean solvent, mix the back by the columniform porous filter of powder of stainless steel agglomerating, the strainer blade diameter length ratio is 1: 3, and the maximum diameter of hole is 5 μ m; Circulation speed is 1.0m
3/ m
2.h; Service temperature is 40 ℃.When strainer both sides pressure reduction surpasses 1.0kg/cm
2The time, carry out blowback with 80 ℃ hot water, blowback hot water circulation speed is 2.0m
3/ m
2.h.By 20～60 purpose active carbon beds are housed, the bed blade diameter length ratio is 1: 8 to gained filtrate again, and the operation air speed is 2.0h
-1Temperature is 40 ℃.The total treatment capacity of lean solvent is 900 times of sorbent material loading amount.The relevant table 1 that the results are shown in.Example 2
This example is the Comparative Examples of example 1.
Raw material: with example 1.
Operation: adding system recirculated water not in lean solvent, the trade mark that adsorption medium adopts Chemical Plant of Nankai Univ. to produce is the D290 macroporous anion exchange resin, and the total treatment capacity of lean solvent only is 200 times of sorbent material loading amount, and other the results are shown in Table 1 with example 1.
By table 1 data as can be known, adopt technology of the present invention, the treatment capacity of sorbent material is more much higher than the technology that does not add water, and treatment effect also clearly.Example 3
Raw material: with example 1.
Operation: the systemic circulation water of adding 350% in lean solvent, filter and adopt the bed that 20～60 order sands are housed, the bed blade diameter length ratio is 1: 10; The operation air speed is 0.3h
-1, temperature is 80 ℃, other the results are shown in table 1 with example 1.Example 4
Raw material: reformed oil triglycol extraction plant lean solvent
Operation: the trade mark that adsorption medium adopts Chemical Plant of Nankai Univ. to produce is the D290 macroporous anion exchange resin, and the bed blade diameter length ratio is 1: 15, and the operation air speed is 1.0h
-1, the total treatment capacity of lean solvent is 500 times of sorbent material loading amount, other the results are shown in table 1 with example 3.Example 5
Raw material: reformed oil tetramethylene sulfone aromatic extraction unit lean solvent
Operation: add the deionized water of 100% (to the amount of tetramethylene sulfone) in sulfolane solvent, service temperature is 70 ℃, and other is with example 1, and the total treatment capacity of solvent is 850 times of sorbent material loading amount, and the solvent quality index is listed in table 1 before and after the regeneration.Table 1 example 1～5 main operational condition and result
*Spectrophotometric determination, absorbing wavelength 420nm (as follows).
| Project | Operational condition | Result | Treatment capacity (doubly) | ||||||||||||||
| Solvent | Quantity of circulating water % | Filter | Absorption | Before the regeneration | After the regeneration | ||||||||||||
| Medium | Temperature ℃ | Air speed h -1 | Blade diameter length ratio | Sorbent material | Temperature ℃ | Air speed h -1 | Blade diameter length ratio | Outward appearance | Colourity * | The pH value | Outward appearance | Colourity * | The pH value | ||||
| Example 1 example 2 examples 3 examples 4 examples 5 | Tetraglycol 99 Tetraglycol 99 Tetraglycol 99 triglycol tetramethylene sulfone | 200 0 350 200 100 | Mechanical sand sand machinery | 40 40 80 40 70 | 1 1 0.3 1 1 | 1∶3 1∶3 1∶10 1∶8 1∶3 | Gac resin gac resin gac | 40 40 80 40 70 | 2 2 3 2 2 | 1∶8 1∶8 1∶10 1∶15 1∶8 | The muddy dark brown of the muddy dark brown dark brown of muddy dark brown dark brown | 640 640 640 320 850 | 5.8 5.8 5.8 6.5 5.0 | Limpid transparent clear transparent clear is limpid transparent | 40 60 30 65 32 | 7.1 9.0 7.8 8.8 7.5 | 900 200 800 500 850 |
Claims (7)
1. the renovation process of an aromatic hydrocarbon extraction solvent, it is characterized in that operation steps is followed successively by: (1) at recirculated water in the adding system and the thorough mixing in the regenerated solvent treated that is obtained by arene extracting process, the amount of described recirculated water is to treat 100～400% of regenerated solvent amount; (2) treated the mixture of regenerated solvent and recirculated water is by mechanical filter or bed filtration, 30～100 ℃ of bed filtration temperature, air speed 0.1～3.0h (1) step
-1, bed blade diameter length ratio 1: 5～1: 20; (3) by the material after the filtration of (2) step, at 30～100 ℃ of temperature, air speed 0.1～5.0h
-1, handle through the adsorption bed decolorizing purification under 1: 5～1: 20 the condition of bed blade diameter length ratio.
2. in accordance with the method for claim 1, it is characterized in that described solvent comprises glycol ether, triglycol, Tetraglycol 99, five glycol, glycol ethers, tetramethylene sulfone, N-formyl morpholine, N-methyl arsenic pyrrolidone or its mixture.
3. in accordance with the method for claim 1, it is characterized in that the described quantity of circulating water of step (1) is to treat 100～200% of regenerated solvent amount.
4. according to the described renovation process of claim 1, it is characterized in that the described mechanical filter of step (2) comprises that the filtration of plate basket filter, whizzer filter or filtered by the millipore filter that pottery, stainless steel, copper powder or nickel powder sintering form, its aperture is 3～30 μ m.
5. according to the described renovation process of claim 1, it is characterized in that the used filtration medium of the described bed filtration of step (2) comprises 20～80 purpose sands, quartz sand, pearlstone.
6. according to the described renovation process of claim 1, it is characterized in that the used sorbent material of the described adsorption bed of step (3) comprises gac, macroporous anion exchange resin, silica gel.
7. according to the described method of claim 1, it is characterized in that the used sorbent material of the described adsorption bed of step (3) is 20～80 purpose granulated active carbons or phenylethylene macropore basic anion exchange resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97120270A CN1062007C (en) | 1997-11-11 | 1997-11-11 | Process for regenerating aromatic hydrocarbon extraction solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97120270A CN1062007C (en) | 1997-11-11 | 1997-11-11 | Process for regenerating aromatic hydrocarbon extraction solvent |
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|---|---|
| CN1217367A CN1217367A (en) | 1999-05-26 |
| CN1062007C true CN1062007C (en) | 2001-02-14 |
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|---|---|---|---|
| CN97120270A Expired - Lifetime CN1062007C (en) | 1997-11-11 | 1997-11-11 | Process for regenerating aromatic hydrocarbon extraction solvent |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003512145A (en) * | 1999-10-15 | 2003-04-02 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | Treatment of extraction solvents to remove acidic contaminants |
| CN101172927B (en) * | 2006-10-31 | 2010-06-30 | 北京金伟晖工程技术有限公司 | Improved raffinate processing system and method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0107908D0 (en) * | 2001-03-29 | 2001-05-23 | Bp Oil Int | Decolourisation method |
| EP1650287B1 (en) * | 2003-07-04 | 2012-03-28 | Beijing Grand Golden-Bright Engineering & Technologies Co. Ltd. | A method for recombining catalytic hydrocarbons |
| CN100378197C (en) * | 2003-11-07 | 2008-04-02 | 丁冉峰 | Catalytic hydrocarbon recombinant treating method |
| CN100377758C (en) * | 2003-10-24 | 2008-04-02 | 北京金伟晖工程技术有限公司 | Water soluble solvent vegenerating system and method |
| CN102659758A (en) * | 2012-06-01 | 2012-09-12 | 唐山中润煤化工有限公司 | Regeneration and purification method of sulfolane in crude benzene hydrofining |
| CN102731472B (en) * | 2012-06-28 | 2015-01-07 | 中国石油化工股份有限公司 | Apparatus for reducing arene extraction solvent sulfolane, and application thereof |
| CN113149955A (en) * | 2016-12-31 | 2021-07-23 | 光华（营口）化工技术服务有限公司 | Regeneration method of inferior sulfolane solvent |
| CN108929187A (en) * | 2017-05-27 | 2018-12-04 | 中国石油化工股份有限公司 | A method of the separation of extractive distillation target product from hydrocarbon mixture |
| CN110604967A (en) * | 2019-10-15 | 2019-12-24 | 北京宝晨能源工程技术有限公司 | Sulfolane regeneration device and method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3492222A (en) * | 1967-11-14 | 1970-01-27 | Universal Oil Prod Co | Solvent recovery process |
| US3595781A (en) * | 1967-12-06 | 1971-07-27 | Inst Francais Du Petrole | Solvent extraction of aromatic hydrocarbons |
| JPS62246992A (en) * | 1986-04-18 | 1987-10-28 | Mitsubishi Petrochem Co Ltd | Solvent recovering process |
| US5008004A (en) * | 1988-10-03 | 1991-04-16 | Uop | Aromatics extraction process having improved water stripper |
| CN1059851A (en) * | 1991-11-08 | 1992-04-01 | 中国石油化工总公司 | Method for recovering solvents in the hydro carbons process |
-
1997
- 1997-11-11 CN CN97120270A patent/CN1062007C/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3492222A (en) * | 1967-11-14 | 1970-01-27 | Universal Oil Prod Co | Solvent recovery process |
| US3595781A (en) * | 1967-12-06 | 1971-07-27 | Inst Francais Du Petrole | Solvent extraction of aromatic hydrocarbons |
| JPS62246992A (en) * | 1986-04-18 | 1987-10-28 | Mitsubishi Petrochem Co Ltd | Solvent recovering process |
| US5008004A (en) * | 1988-10-03 | 1991-04-16 | Uop | Aromatics extraction process having improved water stripper |
| CN1059851A (en) * | 1991-11-08 | 1992-04-01 | 中国石油化工总公司 | Method for recovering solvents in the hydro carbons process |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003512145A (en) * | 1999-10-15 | 2003-04-02 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | Treatment of extraction solvents to remove acidic contaminants |
| JP4892150B2 (en) * | 1999-10-15 | 2012-03-07 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | Treatment of extraction solvents to remove acidic contaminants |
| CN101172927B (en) * | 2006-10-31 | 2010-06-30 | 北京金伟晖工程技术有限公司 | Improved raffinate processing system and method thereof |
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| CN1217367A (en) | 1999-05-26 |
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