CN1335353A - Comprehensive acid sludge and caustic sludge treating process - Google Patents
Comprehensive acid sludge and caustic sludge treating process Download PDFInfo
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- CN1335353A CN1335353A CN 00110701 CN00110701A CN1335353A CN 1335353 A CN1335353 A CN 1335353A CN 00110701 CN00110701 CN 00110701 CN 00110701 A CN00110701 A CN 00110701A CN 1335353 A CN1335353 A CN 1335353A
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- acid sludge
- acid
- sludge
- alkaline residue
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Abstract
The present invention relates to the comprehensive treating process of acid sludge and caustic sludge. The acid sludge is cracked at middle temperature into gas containing SO2, the gas is used in neutralizing treatment of caustic sludge, and organic components difficult to recover or with no recovery value in caustic sludge are replenished to acid sludge. The comprehensive treatment of difficult-to-treat acid sludge and caustic sludge reaches the aim of utilizing waste to treat waste, has no secondary pollution, and may be used widely in oil refinery and chemical plant.
Description
The present invention relates to a kind of oil refining, chemical environment improvement technology, relate in particular to the integrated conduct method of a kind of acid sludge, alkaline residue.
In refining of petroleum and petrochemical process, relate to many devices that utilize acid, alkali as catalyzer or refining reagent, adopt the vitriol oil as catalyzer as most of alkylation process, to discharge a large amount of spent acid in process of production; In the acid of various petrochemicals, soda finishing process, also to discharge a large amount of acid sludges and alkaline residue.
Alkyl plant is discharged acid sludge and is contained 80～85% sulfuric acid and 8～14% organism approximately, and organic major ingredient is polymer alkene, hexene hydrocarbon, alkylsulphonic acid and dissolved small molecules sulfide; The refining acid sludge of kerosene contains 86～88% H approximately
2SO
4With 4～6% organism, organic major ingredient is alkene, Phenylsulfonic acid, alkylsulphonic acid, thiophene, aromatic hydrocarbons and naphthenic hydrocarbon etc.; The lube oil finishing acid sludge contains 30% H approximately
2SO
4With 60% organism, organic major ingredient is organic sulfide, naphthenic acid and colloid etc.
In petroleum refining process, can discharge alkaline residue with sodium hydroxide solution detergent preparing petroleum products, according to the difference of institute's purified oil product, alkaline residue can be further divided into normal top gasoline alkaline residue, a normal line alkaline residue, normal two wires alkaline residue, atmosphere 3rd side cut alkaline residue, catalytic gasoline alkaline residue, catalytic diesel oil alkaline residue, liquid hydrocarbon alkaline residue etc.In these alkaline residues, mainly form by free alkali, neutral oil, sodium napthionate, phenol sodium, sulfide etc., wherein sodium napthionate mainly is distributed in a normal line alkaline residue, normal two wires alkaline residue, the atmosphere 3rd side cut alkaline residue, phenol sodium mainly is distributed in normal top gasoline alkaline residue and catalytic gasoline alkaline residue, the catalytic diesel oil alkaline residue, and sulfide then concentrates in normal top gasoline alkaline residue, catalytic gasoline alkaline residue, catalytic diesel oil alkaline residue and the liquid hydrocarbon alkaline residue.From these alkaline residues, acid sludge composition as can be known, if they are not dealt carefully with, will produce serious environmental and pollute.
The treatment process of acid sludge is a lot of in the prior art, as hydrolysis method, oxidation style, extraction process, pyrolysis method etc.Wherein pyrolysis method comprise high temperature pyrolytic cracking (HTP) and in warm method, introduced the results of laboratory of low temperature pyrolyzer in the acid sludge as the 47th～50 page of 1991 " refining of petroleum " the 10th phase, the resulting sulfur dioxide gas that contains can be used to produce sulfuric acid, or produces liquid sulfur dioxide and produce S-WAT etc.Because the resulting impurity such as containing more water vapor, hydro carbons, solid dust in the sulfur dioxide gas that contains of low temperature pyrogenation further uses the purifying treatment that needs the process complexity.Because the amount of acid sludge is generally less, can not form scale and benefit in addition.
Existing alkaline residue treatment technology mainly contains sulfuric acid neutralisation and carbonic acid gas neutralisation.In neutralizing treatment technology, the expense of sulfuric acid or carbonic acid gas account for bigger ratio in total processing costs, and when handling normal top gasoline alkaline residue, catalytic gasoline alkaline residue and catalytic diesel oil alkaline residue, the stink of the crude phenols of recovery is bigger, and product quality is reclaimed in influence.The way of using acid sludge and the direct combination treatment of alkaline residue is arranged in the prior art, but, can make the naphthenic acid and the thick deterioration in quality of phenols of recovery, make the further refining difficulty more that reclaims owing to contain the large amount of complex organism in the acid sludge.
The purpose of this invention is to provide that a kind of less energy consumption, processing cost are low, the simple acid sludge of method, alkaline residue integrated conduct method.
The inventive method may further comprise the steps:
(1) acid sludge 200～650 ℃ of following pyrolysis for containing SO
2Gas;
(2) step (1) obtains contains SO
2Gas and alkaline residue carry out neutralization reaction;
(3) liquid phase after step (2) neutralization reaction finishes is carried out oily water separation.
Acid sludge described in the above-mentioned steps (1) can be the acid sludge that comes from alkyl plant, it also can be the acid sludge that produces in the oil acid treating process, as kerosene acid treating acid sludge, lubricating oil acid treating acid sludge etc., its main ingredient is a sulfuric acid, also contains some complicated organism in addition.Organic content is controlled at 28～80w% in the acid sludge, preferably is controlled at 35～60w%, and the acid sludge of Chan Shenging has only the organism in the lubricating oil acid treating acid sludge can reach above-mentioned requirements in process of production, and the acid sludge of other type then should suitably add partial organic substances.When handling the lower acid sludge of organic content, can use in the alkaline residue and after the oil phase that obtains is all or part of directly adds in the acid sludge, after also can isolating the composition of easily making with extra care recovery in the oil phase, the part of no recovery value is added in the acid sludge, like this, both satisfied acid sludge pyrolytic condition, and also made the part of no recovery value in the alkaline residue oil phase obtain handling and utilizing.Also can add recovery value is low in some factories organic waste such as oil trap oil slick etc., make it to obtain to handle and utilize.
Warm pyrolytic temperature is generally 200～650 ℃ in the acid sludge, is preferably 300～500 ℃, and it is 0.5～5 hour constantly that reaction stops, and is preferably 1～3 hour, and pyrolysis reactor can adopt moving-bed or fluidized-bed, and batch operation also can adopt fixed bed.Pyrolysis product is high density sulfur dioxide gas and low-sulfur solid coke.Low sulfur coke wherein is a fine fuel, and warm pyrolytic origin of heat in can be used as also can be used as it and uses.
The reaction of step (2) acid-base neutralisation can be adopted conventional continous way or batch operation.In reactor, can adopt gas phase is that external phase, liquid phase are the spray ways of contact of disperse phase, and also can adopt liquid phase is that external phase, gas phase are the bubbling ways of contact of disperse phase.For control reaction temperature or improve gas, liquid contact effect, can adopt the liquid phase part circulation.The reactor of step (2) can adopt empty cartridge reactor or dose filler to increase contact area.The neutralization reaction temperature does not need special control, and its reaction pressure gets final product for the pressure that keeps gas, liquid proper flow.The pH of the final liquid phase of neutralization reaction is controlled to be 3～8, is preferably 4～6.For reducing the content of the objectionable constituent such as sulfurous gas in the neutralization reaction tail gas, can adopt fresh alkaline residue or other basic solution that tail gas is held back, thoroughly the contaminated solution problem.
In the alkaline residue and after through quiescent settling, be separated into oil phase and water, if oil phase is no recovery value, or refining comparatively difficulty then can all be added in the acid sludge usefulness of confession acid sludge pyrolysis to.Oil phase can further be made with extra care and obtain product if recovery value is arranged, and the unworthy byproduct that produces in the treating process can add in the acid sludge.Aqueous phase still contains a certain amount of organism, needs further processing just can discharge.
Acid of the present invention, alkaline residue comprehensive processing method, principle in line with the treatment of wastes with processes of wastes against one another, two kinds of refuses of different nature are carried out combined governance, reduced the reagent expense of present alkaline residue neutralizing treatment on the one hand, saved the facility investment and the working cost of system sulfuric acid after the acid sludge cracking or other products on the other hand, reached the treatment of wastes with processes of wastes against one another, made full use of the target of resource.Discharging waste gas after the inventive method is handled is sulfurous pollutants such as sulfide hydrogen, sulfurous gas, mercaptan, thioether not substantially, also seldom contain organic pollutants such as volatile phenol, hydrocarbon, and owing to content of sulfur dioxide in warm the venting one's spleen in the acid sludge is higher, the tail gas amount is less, has therefore controlled pollution problem from concentration and total amount two aspects.The organism of no recovery value can add in the acid sludge as pyrolysis feed in the alkaline residue, has solved the limited shortcoming of its market.Can also add the low organic waste of recovery value in some factories.The low sulfur coke that pyrolysis obtains can be used as the pyrolytic energy derive, does not need to add supplementing energy.The plant investment of the inventive method is few, energy consumption is low, do not consume chemical reagent substantially, is the effective ways of acid, the alkaline residue comprehensive regulation.
Further specify the concrete operation method and the condition of the inventive method below by embodiment.
Embodiment 1
The weight of the acid sludge of alkyl plant consists of: sulfuric acid 83%, oil 3%, water and other organic impurity 14%.Mixing alkaline residue consists of: free sodium hydroxide 4%, neutral oil 7%, naphthenic acid 11%, sulfide 500mg/L, volatile phenol 310mg/L.
The neutralization reactor operating method adopts gas phase to feed continuously, and alkaline residue intermittently enters reactor, and type of reactor is the void tower structure.The neutralization reaction at the end water layer pH value of liquid phase is 4.2, and through settlement separate, remaining material adds in the acid sludge behind the oil phase recovery part naphthenic acid, makes the organic content of acid sludge reach 30%.The acid sludge pyrolysis temperature is 400 ℃, and reaction time is 3.5 hours.The discharging tail gas of neutralization reactor further absorbs with fresh alkaline residue.
Embodiment 2
The weight of the acid sludge of alkyl plant consists of: sulfuric acid 83%, oil 3%, water and other organic impurity 14%.The atmosphere 3rd side cut alkaline residue consists of: free sodium hydroxide 3%, neutral oil 5%, naphthenic acid 14%, sulfide 60mg/L, volatile phenol 915mg/L, COD
Cr300000mg/L.
The neutralization reactor operating method adopts gas phase to feed continuously, and alkaline residue intermittently enters reactor, and type of reactor is the void tower structure.The neutralization reaction at the end water layer pH value of liquid phase is 5, and through settlement separate, remaining material adds in the acid sludge behind the oil phase recovery part naphthenic acid, makes the organic content of acid sludge reach 40%.The acid sludge pyrolysis temperature is 450 ℃, and reaction time is 3 hours.The discharging tail gas of neutralization reactor further absorbs with fresh alkaline residue.
Embodiment 3
The lubricating oil acid sludge, free sulfuric acid 38%, moisture 5%, organism 57%.Mixing alkaline residue consists of: free sodium hydroxide 2%, neutral oil 1%, naphthenic acid 8%, sulfide 20mg/L, volatile phenol 570mg/L.
The neutralization reactor operating method adopts gas phase to feed continuously, and alkaline residue enters reactor continuously, and type of reactor is a packing tower.The pH value of discharging liquid phase is 5, and through settlement separate, oil phase reclaims naphthenic acid.The acid sludge pyrolysis temperature is 550 ℃, and reaction time is 2 hours.The discharging tail gas of neutralization reactor further absorbs with fresh alkaline residue.
Embodiment 4
Mixing acid sludge consists of: free sulfuric acid 70%, oil 4%, water and other impurity 26%.Mixing alkaline residue consists of: free sodium hydroxide 8%, neutral oil 5%, naphthenic acid 0.2%, sulfide 1000mg/L, volatile phenol 15%.
The neutralization reactor operating method adopts gas phase to feed continuously, and alkaline residue intermittently enters reactor, and type of reactor is the void tower structure.The neutralization reaction at the end water layer pH value of liquid phase is 6.5, and through settlement separate, remaining material adds in the acid sludge behind the oil phase recovery part phenol, makes the organic content of acid sludge reach 65%.The acid sludge pyrolysis temperature is 250 ℃, and reaction time is 4.5 hours.The discharging tail gas of neutralization reactor further absorbs with fresh alkaline residue.
Embodiment 5
Mixing acid sludge consists of: free sulfuric acid 75%, oil 4%, water and other impurity 21%.Mixing alkaline residue consists of: free sodium hydroxide 5%, neutral oil 3%, naphthenic acid 0.2%, sulfide 1000mg/L, volatile phenol 7%.
The neutralization reactor operating method adopts gas phase to feed continuously, and alkaline residue intermittently enters reactor, and type of reactor is the void tower structure.The neutralization reaction at the end water layer pH value of liquid phase is 6.5, and through settlement separate, oil phase all adds in the acid sludge, makes the organic content of acid sludge reach 35%.The acid sludge pyrolysis temperature is 400 ℃, and reaction time is 4 hours.The discharging tail gas of neutralization reactor further absorbs with 10% sodium hydroxide solution.
Claims (9)
1, the integrated conduct method of a kind of acid sludge, alkaline residue may further comprise the steps:
(1) acid sludge 200～650 ℃ of following pyrolysis for containing SO
2Gas;
(2) step (1) obtains contains SO
2Gas and alkaline residue carry out neutralization reaction;
(3) liquid phase after step (2) neutralization reaction finishes is carried out oily water separation.
2, in accordance with the method for claim 1, it is characterized in that containing in the described acid sludge organism 28～80w%.
3,, it is characterized in that containing in the described acid sludge organism 35～60w% according to claim 1 or 2 described methods.
4, in accordance with the method for claim 1, it is characterized in that all or part of the adding in the acid sludge of oil phase that step (3) obtains.
5, in accordance with the method for claim 1, it is characterized in that warm pyrolytic temperature is 200～650 ℃ in the acid sludge, it is 0.5～5 hour constantly that reaction stops.
6, according to claim 1 or 5 described methods, it is characterized in that warm pyrolytic temperature is for being 300～500 ℃ in the acid sludge, it is 1～3 hour constantly that reaction stops.
7, in accordance with the method for claim 1, the pH that it is characterized in that the final liquid phase of the neutralization reaction described in the step (2) is controlled to be 3～8.
8,, it is characterized in that the final liquid phase PH valve of described neutralization reaction is controlled to be 4～6 according to claim 1 or 7 described methods.
9, in accordance with the method for claim 1, it is characterized in that step (2) neutralization reaction tail gas absorbs tail gas with fresh alkaline residue or other basic solution.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00110701 CN1132899C (en) | 2000-07-24 | 2000-07-24 | Comprehensive acid sludge and caustic sludge treating process |
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|---|---|---|---|
| CN 00110701 CN1132899C (en) | 2000-07-24 | 2000-07-24 | Comprehensive acid sludge and caustic sludge treating process |
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| CN1335353A true CN1335353A (en) | 2002-02-13 |
| CN1132899C CN1132899C (en) | 2003-12-31 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671061B (en) * | 2009-09-30 | 2011-11-30 | 山东海化集团有限公司 | Pretreatment method of refinery waste water |
| CN102442738A (en) * | 2010-10-14 | 2012-05-09 | 刘宽 | Treatment process of alkaline residue during sweetening of light hydrocarbon |
| CN102786176A (en) * | 2012-08-22 | 2012-11-21 | 兰州康顺石化有限责任公司 | Comprehensive utilization method of catalytic cracking gasoline sludge |
| CN103045288A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Comprehensive treatment method of high-sulphur high-COD (Chemical Oxygen Demand) caustic sludge waste liquid |
| CN103589443A (en) * | 2013-10-31 | 2014-02-19 | 吴国存 | Pollution-free purifying and efficient using method for inferior organic wastes |
| CN103769407A (en) * | 2012-10-26 | 2014-05-07 | 中国石油化工股份有限公司 | Regeneration method for sulphureous alkali residues |
-
2000
- 2000-07-24 CN CN 00110701 patent/CN1132899C/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671061B (en) * | 2009-09-30 | 2011-11-30 | 山东海化集团有限公司 | Pretreatment method of refinery waste water |
| CN102442738A (en) * | 2010-10-14 | 2012-05-09 | 刘宽 | Treatment process of alkaline residue during sweetening of light hydrocarbon |
| CN102442738B (en) * | 2010-10-14 | 2013-06-19 | 刘宽 | Treatment process of alkaline residue during sweetening of light hydrocarbon |
| CN103045288A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Comprehensive treatment method of high-sulphur high-COD (Chemical Oxygen Demand) caustic sludge waste liquid |
| CN103045288B (en) * | 2011-10-17 | 2014-12-31 | 中国石油化工股份有限公司 | Comprehensive treatment method of high-sulphur high-COD (Chemical Oxygen Demand) caustic sludge waste liquid |
| CN102786176A (en) * | 2012-08-22 | 2012-11-21 | 兰州康顺石化有限责任公司 | Comprehensive utilization method of catalytic cracking gasoline sludge |
| CN103769407A (en) * | 2012-10-26 | 2014-05-07 | 中国石油化工股份有限公司 | Regeneration method for sulphureous alkali residues |
| CN103589443A (en) * | 2013-10-31 | 2014-02-19 | 吴国存 | Pollution-free purifying and efficient using method for inferior organic wastes |
| CN103589443B (en) * | 2013-10-31 | 2015-09-09 | 唐山山岛石油化学有限公司 | The nuisanceless purification of organic waste inferior and Efficient utilization method |
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| CN1132899C (en) | 2003-12-31 |
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