CN1132641C - Process for comprehensive treatment of acid and alkali dregs - Google Patents
Process for comprehensive treatment of acid and alkali dregs Download PDFInfo
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- CN1132641C CN1132641C CN 00110593 CN00110593A CN1132641C CN 1132641 C CN1132641 C CN 1132641C CN 00110593 CN00110593 CN 00110593 CN 00110593 A CN00110593 A CN 00110593A CN 1132641 C CN1132641 C CN 1132641C
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Abstract
The present invention relates to a method for the comprehensive treatment of acid sludge and caustic sludge. The schizolysis of the acid sludge is carried out to form gas containing sulfur dioxide, and the neutralization oxidation treatment of the caustic sludge is carried out by the gas. The method of the present invention can carry out comprehensive treatment for the acid sludge and the caustic sludge which are difficult to treat to reach the purpose of controlling waste by the waste without secondary pollution, and the present invention can be widely used for controlling the acid sludge and the caustic sludge in an oil refinery and a 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.
Be that acid sludge is carried out thermo-cracking is SO at present to effective, the most most economical treatment process of acid sludge
2, produce sulfuric acid with contact process then.As " refining of petroleum " periodical, 1991, the fifth phase, the 62nd, 63 page of method that discloses a kind of " pyrolysis method processing waste sulfuric acid from alkylation ".It is that spent acid is being burnt more than 1000 ℃ with auxiliary fuel, and sulfuric acid and sulfonic acid group are decomposed into SO
2And H
2O, wherein oil and acid esters are oxidized to H
2O and CO
2The SO that contains that burns and generate
2Gas enters sulfuric acid apparatus through waste heat boiler and removes to produce sulfuric acid.This method is applicable to the producer with sulfuric acid production plant, and will carry out bigger transformation to the ortho-sulfuric acid production equipment, invests bigger.If set up sulfuric acid production plant separately, then be difficult to reach the certain economic scale.And when using acid sludge splitting gas system sulfuric acid, this splitting gas needs dedusting, dewaters, and has increased facility investment and process cost.
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, in total processing costs, account for bigger ratio, and when handling normal top gasoline alkaline residue, catalytic gasoline alkaline residue and catalytic diesel oil alkaline residue, the stink of the crude phenols that reclaim and the sour water of discharge is bigger, product quality is reclaimed in influence, and Working environment and atmosphere are polluted.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 plant investment is few, processing costs is low, reclaim quality product height, the acid sludge that does not produce new pollution, alkaline residue integrated conduct method.
The inventive method may further comprise the steps:
(1) acid sludge in pyrolyzer pyrolytic decomposition for containing SO
2Gas;
(2) step (1) obtains contains SO
2Gas contacts with alkaline residue;
(3) tail gas of discharging in the step (2) contacts with fresh alkaline residue, and the alkaline residue of discharge enters step (2).
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.The acid sludge cracking produces contains SO
2Gas can contain SO with other approach obtains
2Gas mixes use, and other contains the S material as containing H can also to add some
2S and/or SO
2And the gas of organic sulfide, as the stripping gas of sulfur recovery facility tail gas, acidic water stripping device, these gases contain SO through burning to produce
2Mixed gas.These contain the S material and also can directly enter the cracking simultaneously of acid sludge pyrolyzer and obtain containing SO
2Gas.
The service temperature of acid sludge pyrolyzer is generally 850～1200 ℃, and coefficient of excess air is 1.1～3, and what obtain with this understanding contains SO
2By volume contains SO in the gas
2Can reach 3～15%, be generally 4～10%, contain O
2Can reach 2～15%, be generally 3～12%, the gas that produces can cool to 350～1000 ℃ by waste heat boiler, be preferably 400～600 ℃.Gas content among the present invention is in butt.
Step (2) is the gas-liquid two-phase reaction, the gas phase reactor of being back to back, and liquid phase can enter continuously, outflow reactor, also can react by intermittent type, and when liquid phase during continuously into and out of reactor, gas-liquid two-phase can adopt counter current contact or and stream contact.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 temperature of reaction in this step is controlled to be 30～180 ℃, is preferably 40～120 ℃, and its reaction pressure is the pressure that remains liquid phase.The consumption volume ratio of gas and alkaline residue is 20～3000, is preferably 200～2000, and the reaction time of alkaline residue in reactor is 0.05～30h.The pH of the final liquid phase of successive reaction liquid effluent and rhythmic reaction is controlled to be 3～8, is preferably 4～6.
Step (3) adopts alkaline residue to contact with the tail gas of step (2), and used alkaline residue amount is 10～100% of the handled total alkali quantity of slag.The operating method of reactor can be identical with the operating method of reactor in the step (2), also can be different, and preferred gas-liquid two-phase counter current contact, temperature of reaction is controlled at 20～70 ℃.The purpose of this step is for unreacted sulfide in the tail gas of holding back step (2) and the organism that volatilizes etc.
Fig. 1 is the operating process synoptic diagram of a typical scenario of the present invention.
Fig. 2 is the operating process synoptic diagram of another embodiment of the invention.
Below in conjunction with one step of accompanying drawing explanation technical scheme of the present invention and effect.
Acid sludge or contain S material 6 and air 7 in pyrolysis furnace (or incinerator) 5 cracking (or oxidation) for containing SO2Gas, this mist is adjusted to needed temperature through waste heat boiler or heat exchanger, then with newly Bright alkaline residue and come the alkaline residue of autoreactor 3 to react in reactor 2, handled alkaline residue can be whole Pass through earlier reactor 3 and then enter reactor 2. When adopting continued operation, from reactor 2, discharge If reacted liquid phase temperature is too high, then can be through carrying out again the sedimentation layering after heat exchanger 4 coolings, when adopting When using intermittent operation, the sedimentation of can in reactor, lowering the temperature. Continuous from the tail gas that reactor 2 is discharged React by reactor 3 and fresh alkaline residue 1.
SO is produced in the thermal decomposition of acid sludge high temperature2The concrete steps of gas are: with alkylation acid sludge, the refining acid of kerosene Slag and lubricating oil acid sludge spray into pyrolysis oven continuously, as required, spray into simultaneously an amount of auxiliary fuel. Acid sludge heat Separating stove has vertical and horizontal two kinds, and combustion zone and the cracking zone of vertical heater separate, and acid sludge is from being installed in stove The swivel nozzle at center, top sprays in the stove, and nozzle is the rotating cup type, and acid sludge is close by the concentric cover of atomizing air Introduce in the stove at the envelope center. According to the viscosity of different load with different acid, change rotating speed with frequency converter. The rotary cup type nozzle is more superior than injection nozzle, and its inlet amount is big, need not pressurize, and droplet distribution is even, transfers Joint flexibly; Because rotation is difficult for stopping up. Pyrolysis furnace has several combustion chambers, by radiation mode heat is passed Give the acid sludge that sprays into. High-temperature combustion gas passes through cracking zone with the speed of 20 meter per seconds, mixes with acid sludge, advances The row cracking reaction. The pyrolysis furnace bottom keeps about 1000 ℃, to reach best lytic effect.
Can add some in the acid sludge pyrolysis furnace and contain the S material, as contain H2S、SO
2Sour gas or have The gas of machine sulfide also can use in addition and burn in the tail gas conduct that contains the S material and the gas of alkaline residue.
Alkaline residue comes from the waste soda residue of discharging in oil refining, the chemical industry alkali refining device, processes former according to each producer The difference of oil kind and operating procedure, it is bigger that the composition of alkaline residue also differs. Technical solution of the present invention and operation bar Part can for alkaline residue of different nature, be selected Operating condition. For sulfur compound more urge vapour alkali Slag can adopt higher neutralization reaction temperature, and improves the content that contains oxygen in the sulfur dioxide gas as far as possible, Simultaneously can prolong the reaction time, so namely can obtain faster neutralization reaction speed, can also take place In the time of neutralization reaction sulfide is carried out oxidation, make in the tail gas of discharge not sulfide hydrogen, organic sulfur compound Deng odorant pollutant, make emission reach environmental protection standard. For sulfur compound lower normal one, two, three The line alkaline residue can adopt relatively low neutral temperature, can reduce like this investment cost and the daily behaviour of device Make expense, owing to wherein contain more aphthenic acids, in order to prevent too much foam, can use liquid simultaneously Part circulates or demister is set in neutralization reactor mutually.
The inventive method will neutralize, oxidation bonding in a reactor, react needed heat basically Can be provided by air inlet, the neutralization in, with the sulfur-containing foul substance oxidation, namely simplified operating procedure, Saved equipment investment, solved again follow-up pollution problem, taken full advantage of simultaneously the heat energy of air inlet, reached The treatment of wastes with processes of wastes against one another, the target of the comprehensive regulation.
For alkaline residue of different nature, adopt Operating condition in the methods of the invention, make wherein each Plant pollutant and all obtain administering comparatively thoroughly, after using the more fresh alkaline residue of free alkali content and neutralizing Emission further contacts, and makes the noxious pollutant in the emission be retained down further processing, row Put tail gas and thoroughly administered, fully meet the requirement of environmental protection.
Acid of the present invention, alkaline residue comprehensive processing method are in line with the principle of the treatment of wastes with processes of wastes against one another, to two kinds of heterogeneitys Refuse carry out combined governance, reduced on the one hand the reagent expense of present alkaline residue neutralisation treatment, on the other hand Saved equipment investment and the operating cost of sulfuric acid processed after the acid sludge cracking, reached the treatment of wastes with processes of wastes against one another, taken full advantage of The target of resource, recovery valuable product. Discharging waste gas after the inventive method is processed is Containing Sulfur not substantially The sulfurous pollutants such as hydrogen, sulfur dioxide, mercaptan, thioether also seldom contain the organic contaminations such as volatile phenol, hydrocarbon Thing meets environmental requirement. The thick product phenol or the aphthenic acids quality that reclaim are higher, not the malodorant such as sulfur compound Matter is conducive to further refinement treatment. Sulfide in the sewage after the processing and CODCrContent falls greatly Low, can carry out again biochemical treatment etc. to reach discharge standard, also can directly enter the sewage-farm, no Can impact to the sewage-farm. The plant investment of the inventive method is few, energy consumption is low, chemical reagent consumption Less, reclaim the product quality height, do not produce new pollution, be 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%, and oil 3%, water and other impurity 14% add fuel gas and carry out scission reaction under 1000 ℃, and coefficient of excess air is 1.4.Cracking tail gas reclaims heat through waste heat boiler, and the boiler export flue-gas temperature is 630 ℃, contains sulfurous gas 6%, oxygen 10%.
Catalytic gasoline soda finishing waste soda residue consists of: free sodium hydroxide 8%, neutral oil 0.2%, sulfide 2.615%, volatile phenol 10%, COD
Cr535750mg/l.
Adopt gas phase to feed continuously in answering device 2, the alkaline residue of being discharged by reactor 3 intermittently passes in and out reactor, and the reaction time of alkaline residue in reactor is 5 hours, gas-liquid consumption volume ratio is 750, temperature of reaction is 160 ℃, and reaction pressure is 0.8MPa, and type of reactor is the void tower structure.The water layer pH value that liquid phase is discharged in reaction is 4.2, the COD of the sour water after the sedimentation layering
CrFor 1850mg/L and there is not stink, organic layer does not have the sulfide stink.
The tail gas of discharging from reactor 2 enters reactor 3, contacts with handled whole alkaline residues, and reactor 3 adopts gas, the reverse Continuous Contact of liquid, and temperature of reaction is 40 ℃.Reactor 3 discharge tail gas do not have sulfurous pollutants, and volatile phenol content is 3 μ L/L.
Embodiment 2
The weight of the acid sludge of alkyl plant consists of: sulfuric acid 83%, and oil 3%, water and other impurity 14% add the sour gas of sulfide hydrogen 8% simultaneously, add fuel gas and carry out cracking and combustion reactions under 1200 ℃, and coefficient of excess air is 1.2.Cracking tail gas reclaims heat through waste heat boiler, and the boiler export flue-gas temperature is 520 ℃, contains sulfurous gas 7%, oxygen 4%.
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.
In answering device 2, adopt gas phase to feed continuously, enter reactor continuously from the fresh alkaline residue of reactor 3 effusive alkaline residues and 60%, adopt the mode of reverse spray, the residence time of alkaline residue in reactor is 0.1 hour, gas-liquid consumption volume ratio is 380, temperature of reaction is 90 ℃, and reaction pressure is a normal pressure, and type of reactor is the void tower structure.The water layer pH value that liquid phase is discharged in reaction is 6.5, the COD of the sour water after the sedimentation layering
CrBe 2250mg/L, sulfide does not detect, and organic layer does not have the sulfide stink.
The tail gas of discharging from reactor 2 enters reactor 3, contacts with 40% of processing alkaline residue, and reactor 3 adopts gas, the reverse continuous spray contact of liquid, and temperature of reaction is 60 ℃.Reactor 3 discharge tail gas detect less than sulfurous pollutants, and volatile phenol content is 3 μ L/L.
Embodiment 3
The weight of the acid sludge of alkyl plant consists of: sulfuric acid 83%, and oil 3%, water and other impurity 14% add fuel gas and carry out scission reaction under 900 ℃, and coefficient of excess air is 1.9.Cracking tail gas reclaims heat through waste heat boiler, and the boiler export flue-gas temperature is 350 ℃, contains sulfurous gas 4%, oxygen 12%.
Mixing alkaline residue consists of: free sodium hydroxide 4%, neutral oil 7%, naphthenic acid 11%, sulfide 500mg/L, volatile phenol 310mg/L, COD
Cr450000mg/L.
In answering device 2, adopt gas phase to feed continuously, come the alkaline residue of autoreactor 3 and 20% fresh alkaline residue intermittently to pass in and out reactor, the reaction time of alkaline residue in reactor is 15 hours, gas usage and alkaline residue volume ratio are 1100, temperature of reaction is 110 ℃, reaction pressure is 0.2MPa, and type of reactor is the void tower structure, at the top of reactor 2 demister is set.The water layer pH value that liquid phase is discharged in reaction is 5.5, the COD of the sour water after the sedimentation layering
CrBe 2870mg/L, sulfide does not detect, and organic layer does not have the sulfide stink.
The tail gas of discharging from reactor 2 enters reactor 3, contacts with 80% of processing alkaline residue, and reactor 3 employing gas phases intermittently enter reactor by, liquid phase continuously, and temperature of reaction is 45 ℃.Reactor 3 discharge tail gas do not have sulfurous pollutants, and volatile phenol content is 2 μ L/L.
Embodiment 4
The weight of the acid sludge of alkyl plant consists of: sulfuric acid 82%, and oil 3%, water and other impurity 15% add fuel gas and carry out scission reaction under 1100 ℃, and coefficient of excess air is 1.4.Cracking tail gas reclaims heat through waste heat boiler, and the boiler export flue-gas temperature is 400 ℃, contains sulfurous gas 5%, oxygen 7%.
Mixing alkaline residue consists of: free sodium hydroxide 8%, neutral oil 5%, naphthenic acid 0.2%, sulfide 1000mg/L, volatile phenol 15%, COD
Cr550000mg/L.
In reactor 2, adopt gas phase to feed continuously, come the fresh alkaline residue of the alkaline residue 30% of autoreactor 3 to enter reactor continuously, gas, liquid two-phase adopt and the stream mode contact, two-phase all enters from reactor lower part, flows out from top, and the residence time of alkaline residue in reactor 2 is 8 hours, gas-liquid consumption and alkaline residue volume ratio are 2500, temperature of reaction is 150 ℃, and reaction pressure is 0.7MPa, and type of reactor is the void tower structure.The water layer pH value that liquid phase is discharged in reaction is 4.5, the COD of the sour water after the sedimentation layering
CrBe 4250mg/L, sulfide does not detect, and organic layer does not have the sulfide stink.
The tail gas of discharging from reactor 2 enters reactor 3, contacts with 70% of processing alkaline residue, and reactor 3 gas phases are passed through continuously, and the alkaline residue intermittent type enters reactor 3, and temperature of reaction is 55 ℃.Reactor 3 discharge tail gas do not have sulfurous pollutants, and volatile phenol content is 5 μ L/L.
Embodiment 5
The weight of the acid sludge of alkyl plant consists of: sulfuric acid 86%, and oil 4%, water and other impurity 10% add fuel gas and carry out scission reaction under 1250 ℃, and coefficient of excess air is 1.2.Cracking tail gas reclaims heat through waste heat boiler, and the boiler export flue-gas temperature is 950 ℃, contains sulfurous gas 15%, oxygen 3%.
Mixing alkaline residue consists of: free sodium hydroxide 6%, neutral oil 3%, naphthenic acid 5.1%, sulfide 120mg/L, volatile phenol 0.1%, COD
Cr150000mg/L.
In reactor 2, adopt gas phase to feed continuously, come the fresh alkaline residue of the alkaline residue 60% of autoreactor 3 to enter reactor continuously, gas, liquid two-phase adopt and the stream mode contact, and two-phase all enters from reactor lower part, flows out from top, the residence time of alkaline residue in reactor 2 is 0.5 hour, gas-liquid consumption and alkaline residue volume ratio are 200, and temperature of reaction is 95 ℃, and reaction pressure is a normal pressure, type of reactor is the void tower structure, and cat head is established scum dredger.The water layer pH value that liquid phase is discharged in reaction is 6.8, the COD of the sour water after the sedimentation layering
CrBe 3250mg/L, sulfide does not detect, and organic layer does not have the sulfide stink.
The tail gas of discharging from reactor 2 enters reactor 3, contacts with 40% of processing alkaline residue, and reactor 3 gas phases are passed through continuously, and the alkaline residue intermittent type enters reactor 3, and temperature of reaction is 25 ℃.Reactor 3 discharge tail gas do not have sulfurous pollutants, and volatile phenol content is 3 μ L/L.
Embodiment 6
The weight of the acid sludge of alkyl plant consists of: sulfuric acid 84%, and oil 3%, water and other impurity 13% add fuel gas and carry out scission reaction under 900 ℃, and coefficient of excess air is 1.1.Cracking tail gas reclaims heat through waste heat boiler, and the boiler export flue-gas temperature is 450 ℃, contains sulfurous gas 12%, oxygen 2%.
Mixing alkaline residue consists of: free sodium hydroxide 2%, neutral oil 1%, naphthenic acid 8%, sulfide 20mg/L, volatile phenol 570mg/L, COD
Cr260000mg/L.
In answering device 2, adopt gas phase to feed continuously, come the alkaline residue of autoreactor 3 and 70% fresh alkaline residue to enter reactor continuously, two anti-phase contacts, the reaction time of alkaline residue in reactor is 2 hours, gas usage and alkaline residue volume ratio are 120, and temperature of reaction is 80 ℃, and reaction pressure is a normal pressure, type of reactor is the void tower structure, and 40% of neutralization back alkaline residue circulates.The water layer pH value that liquid phase is discharged in reaction is 7.5, the COD of the sour water after the sedimentation layering
CrBe 4720mg/L, sulfide does not detect, and organic layer does not have the sulfide stink.
The tail gas of discharging from reactor 2 enters reactor 3, contacts with 30% of processing alkaline residue, and reactor 3 adopts gas, liquid and flows Continuous Contact, and temperature of reaction is 30 ℃.Reactor 3 discharge tail gas do not have sulfurous pollutants, and volatile phenol content is 5 μ L/L.
Embodiment 7
The weight of the refining acid sludge of kerosene consists of: sulfuric acid 88%, and oil 5%, water and other impurity 7% add fuel gas and carry out scission reaction under 900 ℃, and coefficient of excess air is 1.4.Cracking tail gas reclaims heat through waste heat boiler, and the boiler export flue-gas temperature is 400 ℃, contains sulfurous gas 9%, oxygen 6%.
Mixing alkaline residue consists of: free sodium hydroxide 3%, neutral oil 1%, naphthenic acid 4%, sulfide 20mg/L, volatile phenol 570mg/L, COD
Cr150000mg/.
In answering device 2, adopt gas phase to feed continuously, come the alkaline residue of autoreactor 3 and 50% fresh alkaline residue to enter reactor continuously, two anti-phase contacts, the reaction time of alkaline residue in reactor is 1.5 hours, gas usage and alkaline residue volume ratio are 700, and temperature of reaction is 95 ℃, and reaction pressure is a normal pressure, type of reactor is the void tower structure, and 20% of neutralization back alkaline residue circulates.The water layer pH value that liquid phase is discharged in reaction is 7.5, the COD of the sour water after the sedimentation layering
CrBe 2200mg/L, sulfide does not detect, and organic layer does not have the sulfide stink.
The tail gas of discharging from reactor 2 enters reactor 3, contacts with 50% of whole processing alkaline residue amounts, and reactor 3 adopts gas, liquid and flows Continuous Contact, and temperature of reaction is 35 ℃.Reactor 3 discharge tail gas do not have sulfurous pollutants, and volatile phenol content is 3 μ L/L.
Embodiment 8
The weight of lube oil finishing acid sludge consists of: sulfuric acid 32%, and organism 60%, water and other impurity 8% carry out scission reaction under 1200 ℃, and coefficient of excess air is 1.1.Cracking tail gas reclaims heat through waste heat boiler, and the boiler export flue-gas temperature is 350 ℃, contains sulfurous gas 3%, oxygen 3%.
Mixing alkaline residue consists of: free sodium hydroxide 10%, neutral oil 5%, naphthenic acid 0.2%, sulfide 1000mg/L, volatile phenol 15%, COD
Cr550000mg/L.
In reactor 2, adopt gas phase to feed continuously, come the alkaline residue of autoreactor 3 to enter reactor continuously, gas, liquid two-phase adopt the countercurrent spray mode to contact, reaction times is 0.6 hour, gas-liquid consumption and alkaline residue volume ratio are 2000, temperature of reaction is 98 ℃, and reaction pressure is a normal pressure, and type of reactor is the void tower structure.The water layer pH value that liquid phase is discharged in reaction is 6.3, the COD of the sour water after the sedimentation layering
CrBe 3850mg/L, sulfide does not detect, and organic layer does not have the sulfide stink.
The tail gas of discharging from reactor 2 enters reactor 3, contacts with whole handled alkaline residues, and reactor 3 gas phases are passed through continuously, and the alkaline residue intermittent type enters reactor 3, and temperature of reaction is 55 ℃.Reactor 3 discharge tail gas do not have sulfurous pollutants, and volatile phenol content is 5 μ L/L.
Claims (22)
1, the integrated conduct method of a kind of acid sludge, alkaline residue may further comprise the steps:
(1) acid sludge in pyrolyzer pyrolytic decomposition for containing SO
2Gas;
(2) step (1) obtains contains SO
2Gas contacts with alkaline residue;
(3) tail gas of discharging in the step (2) contacts with fresh alkaline residue, and the alkaline residue of discharge enters step (2);
Wherein to come from the vitriol oil be acid sludge, boat coal acid treating acid sludge and the lubricating oil acid treating acid sludge of the alkyl plant of catalyzer to the acid sludge described in the step (1); Described alkaline residue comes from the waste soda residue of discharging in oil refining, the Chemicals soda finishing device.
2,, it is characterized in that the described SO of containing according to the method for claim 1
2By volume contains SO in the gas
2Be 3～15%, temperature is 350～1000 ℃.
3,, it is characterized in that the described SO of containing according to the method for claim 1
2By volume contains O in the gas
2Be 2～15%.
4,, it is characterized in that the described SO of containing according to the method for claim 1 or 2
2By volume contains SO in the gas
2Be 4～10%, temperature is 400～600 ℃.
5,, it is characterized in that the described SO of containing according to the method for claim 1 or 3
2By volume contains O in the gas
2Be 3～12%.
6, according to the method for claim 1, the service temperature that it is characterized in that the acid sludge pyrolyzer described in the step (1) is 850～1200 ℃, and coefficient of excess air is 1.1～3.
7,, it is characterized in that step (2) adopts gas, the liquid two-phase reactor of being back to back according to the method for claim 1.
8,, it is characterized in that gas, the contact of liquid two phase countercurrent flow according to the method for claim 7.
9,, it is characterized in that gas, liquid two-phase and stream contact according to the method for claim 7.
10,, it is characterized in that step (2) adopts liquid phase intermittently to pass in and out reactor, the gas phase reactor of being back to back according to the method for claim 1.
11,, it is characterized in that the liquid phase part circulation according to the method for claim 10.
12, according to the method for claim 7 or 10, the temperature of reaction that it is characterized in that step (2) is 30～180 ℃.
13,, it is characterized in that described temperature of reaction is 40～120 ℃ according to the method for claim 12.
14,, it is characterized in that its reaction pressure is for keeping the pressure of liquid phase according to the method for claim 7 or 10.
15, according to the method for claim 7 or 10, the pH that it is characterized in that successive reaction liquid effluent or the final liquid phase of rhythmic reaction is 3～8.
16,, it is characterized in that described pH value is for being controlled at 4～6 according to the method for claim 15.
17,, it is characterized in that the total consumption volume ratio of gas-liquid of described reaction is 20～3000 according to the method for claim 7 or 10.
18, according to the method for claim 7 or 10, the reaction times that it is characterized in that described alkaline residue is 0.05～30h.
19,, it is characterized in that gas and alkaline residue counter current contact in the step (3) according to the method for claim 1.
20,, it is characterized in that step (3) adopting gas, liquid two-phase to be back to back reactor or liquid phase intermittently pass in and out reactor and the operating method of gas phase is back to back reactor according to the method for claim 1.
21,, it is characterized in that the alkaline residue that enters step (3) accounts for 10～100% of the total alkali slag weight of handling according to the method for claim 1.
22, according to the method for claim 1, the temperature of reaction that it is characterized in that step (3) is 20～70 ℃.
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| CN104607435B (en) * | 2013-11-05 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of comprehensive processing method of sulfur-bearing alkaline residue |
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| CN110228866B (en) * | 2019-06-10 | 2024-02-09 | 赤峰中色锌业有限公司 | Method and equipment for treating sewage acid and sewage |
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2000
- 2000-06-28 CN CN 00110593 patent/CN1132641C/en not_active Expired - Lifetime
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| Publication number | Publication date |
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| CN1330968A (en) | 2002-01-16 |
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