CN1168668C - Dephenolization process of alkali oil-refining waste water - Google Patents
Dephenolization process of alkali oil-refining waste water Download PDFInfo
- Publication number
- CN1168668C CN1168668C CNB021147906A CN02114790A CN1168668C CN 1168668 C CN1168668 C CN 1168668C CN B021147906 A CNB021147906 A CN B021147906A CN 02114790 A CN02114790 A CN 02114790A CN 1168668 C CN1168668 C CN 1168668C
- Authority
- CN
- China
- Prior art keywords
- waste water
- alkaline waste
- gasoline
- phenol
- dephenolize
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002351 wastewater Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000007670 refining Methods 0.000 title claims abstract description 26
- 239000003513 alkali Substances 0.000 title claims abstract description 23
- 239000003502 gasoline Substances 0.000 claims abstract description 58
- 238000000605 extraction Methods 0.000 claims abstract description 46
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 150000002989 phenols Chemical class 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000001833 catalytic reforming Methods 0.000 claims description 5
- 239000002283 diesel fuel Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000010786 composite waste Substances 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- 238000003809 water extraction Methods 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract 2
- 230000003026 anti-oxygenic effect Effects 0.000 abstract 1
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract 1
- 235000017550 sodium carbonate Nutrition 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 10
- 230000006698 induction Effects 0.000 description 7
- 238000004065 wastewater treatment Methods 0.000 description 7
- 239000000284 extract Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- -1 sulfide sodium salt Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a dephenolization method of alkali oil-refining waste water. The dephenolization method discloses semi-finished gasoline which is used as an extracting phase and phenol-containing alkali waste water are proportionally mixed by a mixer, wherein the pH value of the phenol-containing alkali waste water is adjusted, and products comprising naphthenic acid, crude phenol, Na2CO3, etc. are recovered. The mixture stands still, semi-finished gasoline is separated after layering, and thereby, phenol in the alkali waste water is eliminated. The dephenolization method has the advantages of simplicity, high extraction efficiency, small occupation area, low cost, enhanced antioxygenic property of the oil and no secondary pollution.
Description
Technical field
The present invention relates to in the crude refining process through alkali cleaning catalytically cracked gasoline, diesel oil or liquefied gas program, and reclaimed naphthenic acid, crude phenols, Na
2CO
3Deng the method that the phenol alkaline waste water carries out dephenolize that contains behind the product.
Background technology
Crude refining becomes in the product processes such as gasoline, kerosene, diesel oil and liquefied gas, adopts alkali washing process to remove the acidic impurities in the oil product usually, and deutero-contains the phenol alkaline waste water environment protection has been produced very big pressure thus.
Existing oil refining alkaline waste water treatment process generally is to adopt CO
2Or sulfuric acid acidation handles, and reclaims naphthenic acid, crude phenols, and after filtration, dry Na
2CO
3Send wastewater treatment field to handle Deng the waste liquid behind the product, phenol content reaches more than the 2000mg/L in the waste liquid, has increased the processing load in sewage-farm greatly, Na
2CO
3Product is also because to contain detrimental impurity such as phenols, organic sulfide sodium salt too high, has pungent stench and can not find outlet.Bibliographical information is arranged, adopt the technology of Wet-type oxidation sweetening and intermittent type biological treatment (SBR) dephenolize can more effectively handle alkaline waste water.As in the treatment process of Chinese patent CN1257047A about waster water of alkaline residul from oil refinery, adopt active sludge earlier through domestication in 12 to 48 days, then at steady motion period with the phenol removal more than 80%; In addition; 1996 the 1st phases " environment protection " disclose a kind of " oil refining alkaline sewage improvement technology novel process "; the main process of its method adds after 9 below to contain again and helps the extraction liquid (kerosene) of collection agent to extract for alkaline waste water being acidified to PH; extraction back water outlet can directly enter wastewater treatment field; extraction liquid is after adding alkali lye is stripped; reclaim crude phenols, extraction liquid recycles.But first method is long running period, and floor space is big, unfavorable popularization; And the second method employing adds the alkali back extraction, has increased the amount of alkaline waste water, is unfavorable for environmental protection.More than two kinds of methods all only have containing the dephenolize function of phenol alkaline waste water, what help is other indexs of oil quality do not had.
Summary of the invention
The purpose of this invention is to provide the method that a kind of oil refining contains the dephenolize of phenol alkaline waste water, its dephenolize method is simple, the extraction efficiency height, and floor space is little, and cost is low, and can improve the antioxidant property of oil product, does not cause secondary pollution.
Technical solution of the present invention be with as the work in-process gasoline of extraction agent be adjusted into weakly alkaline and reclaimed naphthenic acid, crude phenols, Na
2CO
3Contain the phenol alkaline waste water behind the product, mix through mixing tank, leave standstill thereafter with certain proportion, treat layering after, isolate work in-process gasoline, thereby remove the phenol in the alkaline waste water.
The above waste water that need adjust pH value is that alkali cleaning catalytically cracked gasoline, diesel oil or liquefied gas produced in the crude refining process contains the phenol alkaline waste water or the composite waste of these waste water.
Work in-process gasoline as extraction agent of the present invention is catalytically cracked gasoline, or catalytic reforming gasoline.
More than the alkaline waste water of required adjustment pH value of the present invention, be to adopt CO
2Or sulfuric acid is adjusted the pH value that contains the phenol alkaline waste water that produced after the alkali cleaning program in the crude refining process in the scope of 7-10.5.
The alkaline waste water of required adjustment pH value of the present invention is to adopt CO
2Or sulfuric acid to adjust the pH value that contains the phenol alkaline waste water that is produced after the alkali cleaning program in the crude refining process be 7.5-9.5.
More than the work in-process gasoline as extraction agent of the present invention be 1: 1 to 3: 1 with having adjusted the volume ratio that contains the phenol alkaline waste water behind the pH value.
Work in-process gasoline as extraction agent of the present invention is 1: 1 with having adjusted the volume ratio that contains the phenol alkaline waste water behind the pH value.
More than mixing tank of the present invention be static mixer, or tower mixing tank.
The work in-process gasoline extraction that the present invention is used as extraction agent alkali cleaning program and reclaimed naphthenic acid, crude phenols, Na in the crude refining process
2CO
3Produced behind the product to contain phenol alkaline waste water extraction progression be more than 2.
As extraction agent, purpose at first is the phenol in the extraction alkaline waste water with work in-process gasoline in the present invention, reaches with the waste water behind the assurance extraction phenol to enter the requirement that handle in the sewage-farm again, improves the sewage disposal qualification rate.Its two, adopt the phenol in the work in-process gasoline extraction alkaline waste water to be to utilize aldehydes matter can improve the antioxidant property of gasoline, and need not again gasoline to be stripped.Its three, be the processed oil blend component as catalytically cracked gasoline, the catalytic reforming gasoline of work in-process gasoline, in use, phenol can burn with gasoline, can not cause secondary pollution.Its four, the induction period of gasoline of extraction behind the phenol obviously improves, and that is to say and improved the gasoline stability in storage.
Alkali cleaning program and reclaimed naphthenic acid, crude phenols, Na in the crude refining process
2CO
3What produced behind the product contains in the phenol alkaline waste water, and contained phenol is that the form with phenol sodium exists, and its content is more than 2000mg/L.So big content is not enough by single extraction only, generally extracts progression more than 2.Also be extract reaches concentration balance in extraction agent and this two-phase of stoste after, this two is separated with extraction agent and stoste, and promptly extracting progression is 1.Add fresh extraction agent again, separate, promptly extracting progression is 2.
Induction period of gasoline is not less than 480 minutes by motor spirit (GB17930-1999), and inductive phase, corresponding the raising helped the stability that gasoline stores, i.e. oxidation-resistance.Breakdown time is a kind of index of describing the gasoline stability in storage, is meant that specifically gasoline is stored into the time that oxygen bomb pressure obviously descends and experienced under 100 ℃ of constant temperature in being full of the oxygen bomb of oxygen, generally with a minute expression.The present invention can adjust the phenol that contains in the phenol alkaline waste water behind the pH value by the work in-process gasoline extraction is improved induction period of gasoline.
Advantage of the present invention is that the dephenolize method is simple, the extraction efficiency height, and floor space is little, and cost is low, and can improve the antioxidant property of oil product, does not cause secondary pollution.
Embodiment
Example 1
To use CO
2Transferring pH value is 9.45, and has reclaimed naphthenic acid, crude phenols, Na
2CO
3Mixed-alkali waste water behind the product, with catalytically cracked gasoline with the direct hybrid extraction of 1: 2 ratio of volume ratio, the extraction progression be 2.After the extraction, the phenol content of alkaline waste water drops to 386mg/L by 2200mg/L, can in line wastewater treatment field.Extraction back induction period of gasoline rises to 720min by 600min, will extract back gasoline and Q-grade gasoline and be in harmonious proportion at 1: 10 with volume ratio.
Example 2
To use CO
2Transferring pH value is 9.45, and has reclaimed naphthenic acid, crude phenols, Na
2CO
3Mixed-alkali waste water behind the product, with catalytically cracked gasoline with the direct hybrid extraction of 1: 1 ratio of volume ratio, the extraction progression be 2.After the extraction, the phenol content of alkaline waste water drops to 538mg/L by 2200mg/L, can in line wastewater treatment field.Extraction back induction period of gasoline rises to 680min by 600min, will extract back gasoline and Q-grade gasoline and be in harmonious proportion at 1: 10 with volume ratio.
Example 3
To use CO
2Transferring pH value is 9.45, and has reclaimed naphthenic acid, crude phenols, Na
2CO
3Mixed-alkali waste water behind the product, with catalytic reforming gasoline with the direct hybrid extraction of 1: 2 ratio of volume ratio, the extraction progression be 2.After the extraction, the phenol content of alkaline waste water drops to 356mg/L by 2200mg/L, can in line wastewater treatment field.Extraction back induction period of gasoline rises to 711min by 600min, will extract back gasoline and Q-grade gasoline and be in harmonious proportion at 1: 10 with volume ratio.
Example 4
To use CO
2Transferring pH value is 9.45, and has reclaimed naphthenic acid, crude phenols, Na
2CO
3Mixed-alkali waste water behind the product, with catalytic reforming gasoline with the direct hybrid extraction of 1: 1 ratio of volume ratio, the extraction progression be 2.After the extraction, the phenol content of alkaline waste water drops to 516mg/L by 2200mg/L, can in line wastewater treatment field.Extraction back induction period of gasoline rises to 692min by 600min, will extract back gasoline and Q-grade gasoline and be in harmonious proportion at 1: 10 with volume ratio.
Table 1 has been listed gasoline (after the being in harmonious proportion) quality of handling alkaline waste water.Quality of gasoline does not have big variation as can be seen from the table, reaches the gasoline request of national standard.
The gasoline of table 1, processing alkaline waste water (after being in harmonious proportion) quality
Project example 1 example 2 examples 3 examples 4 national standards
(GB17930-1999)
Sulphur content, % 0.05 0.05 0.04 0.04 is not more than 0.08
Copper corrosion 1b 1b 1a 1a is not more than 1 grade
(50℃，3h)
Inductive phase, min 620 610 600 585 is not less than 480
Aqueous fusion acid or alkali do not have
Existent gum, 3434 are not more than 5
mg/100mL
Claims (9)
1, a kind of method about oil refining alkaline waste water dephenolize, it is characterized in that as the work in-process gasoline of extraction agent be adjusted into weakly alkaline and reclaimed naphthenic acid, crude phenols, Na
2CO
3Contain the phenol alkaline waste water behind the product, mix through mixing tank, leave standstill thereafter with certain proportion, treat layering after, isolate work in-process gasoline, thereby remove the phenol in the alkaline waste water.
2, a kind of method according to claim 1 about the dephenolize of oil refining alkaline waste water, the waste water that it is characterized in that need adjusting pH value is that alkali cleaning catalytically cracked gasoline, diesel oil or liquefied gas produced in the crude refining process contains the phenol alkaline waste water or the composite waste of these waste water.
3, a kind of method about the dephenolize of oil refining alkaline waste water according to claim 1 is characterized in that the work in-process gasoline as extraction agent is catalytically cracked gasoline, or catalytic reforming gasoline.
4, a kind of method about oil refining alkaline waste water dephenolize according to claim 1 is characterized in that the alkaline waste water of required adjustment pH value, is to adopt CO
2Or sulfuric acid is adjusted the pH value that contains the phenol alkaline waste water that produced after the alkali cleaning program in the crude refining process in the scope of 7.5-10.5.
5, a kind of method about oil refining alkaline waste water dephenolize according to claim 1 is characterized in that the alkaline waste water of required adjustment pH value, is to adopt CO
2Or sulfuric acid to adjust the pH value that contains the phenol alkaline waste water that is produced after the alkali cleaning program in the crude refining process be 7.5 to 9.5.
6, a kind of method about the dephenolize of oil refining alkaline waste water according to claim 1 is characterized in that the work in-process gasoline as extraction agent is 1: 1 to 3: 1 with having adjusted the volume ratio that contains the phenol alkaline waste water behind the pH value.
7, a kind of method about the dephenolize of oil refining alkaline waste water according to claim 1 is characterized in that the work in-process gasoline as extraction agent is 1: 1 with having adjusted the volume ratio that contains the phenol alkaline waste water behind the pH value.
8, a kind of method about the dephenolize of oil refining alkaline waste water according to claim 1 is characterized in that mixing tank is a static mixer, or tower mixing tank.
9, a kind of method according to claim 1, the work in-process gasoline extraction that it is characterized in that being used as extraction agent alkali cleaning program and reclaimed naphthenic acid, crude phenols, Na in the crude refining process about oil refining alkaline waste water dephenolize
2CO
3Produced behind the product to contain phenol alkaline waste water extraction progression be more than 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021147906A CN1168668C (en) | 2002-01-28 | 2002-01-28 | Dephenolization process of alkali oil-refining waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021147906A CN1168668C (en) | 2002-01-28 | 2002-01-28 | Dephenolization process of alkali oil-refining waste water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1361068A CN1361068A (en) | 2002-07-31 |
| CN1168668C true CN1168668C (en) | 2004-09-29 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021147906A Expired - Lifetime CN1168668C (en) | 2002-01-28 | 2002-01-28 | Dephenolization process of alkali oil-refining waste water |
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| Country | Link |
|---|---|
| CN (1) | CN1168668C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613619B (en) * | 2008-06-25 | 2013-04-24 | 中国石油化工集团公司 | Method for removing phenoxy compounds in solvent oil |
| EP2948230A4 (en) * | 2013-01-28 | 2016-03-16 | Solex Water Ltd | Methods and systems for water recovery |
| CN117185566A (en) * | 2023-10-10 | 2023-12-08 | 陕西煤业化工集团神木天元化工有限公司 | A method and system for treating wastewater generated during the extraction of phenolic compounds from coal tar |
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2002
- 2002-01-28 CN CNB021147906A patent/CN1168668C/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| CN1361068A (en) | 2002-07-31 |
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Granted publication date: 20040929 |
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