CN108117209B - Comprehensive treatment method and device for alkaline residue waste liquid - Google Patents
Comprehensive treatment method and device for alkaline residue waste liquid Download PDFInfo
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- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
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Abstract
The invention relates to a treatment method of alkaline residue waste liquid, which comprises the steps of (1) using sulfuric acid to carry out acidification treatment on the alkaline residue waste liquid, introducing inert gas, and stopping acidification when the pH value reaches 2-6; (2) the acidified tail gas enters a tail gas treatment unit, and sulfides are recovered; (3) settling the acidified waste liquid, and recovering an oil phase; (4) and recovering the oil phase, performing single-stage continuous evaporation and crystallization on the acidified wastewater, performing dephenolization treatment on the generated steam, introducing the dephenolized steam into a steam compressor, and performing centrifugal separation on the generated crystal slurry to obtain the sodium sulfate. The method provided by the invention can be used for efficiently treating high-concentration sulfides and COD in the alkaline residue and recovering useful substances in the alkaline residue waste liquid, so that the acidified tail gas can be discharged up to the standard, especially, the use amount of a medicament in the treatment process is reduced, the quality of sodium sulfate crystal salt is improved, and the generated condensed water can be discharged up to the standard or recycled.
Description
Technical Field
The invention belongs to the technical field of environment-friendly wastewater treatment, and particularly relates to a comprehensive treatment method and a comprehensive treatment device for alkali residue waste liquid, which are suitable for comprehensive treatment of oil refining alkali residue waste liquid, petrochemical sodium sulfide-containing alkali residue waste liquid and organic acid salt alkali residue waste liquid.
Background
In the process of refining oil alkali in an oil refinery, alkaline waste liquid containing high-concentration pollutants is generated, the discharge amount of COD, sulfide and phenol accounts for a great proportion of the discharge amount of the pollutants in the oil refinery, and the alkaline waste liquid mainly comprises normal-pressure diesel oil alkaline residue, catalytic gasoline alkaline residue, catalytic diesel oil alkaline residue, liquid hydrocarbon alkaline residue and the like. If the alkaline residue waste liquid is directly discharged, the environment can be seriously polluted; if the sewage treatment plant is sent to the sewage treatment plant, the normal operation of the sewage treatment plant is seriously influenced, the sewage is difficult to discharge after reaching the standard, and the equipment is seriously corroded. The caustic sludge problem is prevalent in oil refineries. In recent years, as national environmental regulations and standards become complete and strict and the demand for improving the environmental quality becomes higher and higher, the treatment of the caustic sludge is more and more emphasized. Among the alkaline residues, the alkaline residues with the highest contents of petroleum acids such as sulfide, phenol and the like are catalytic gasoline and diesel oil alkaline residues and liquid hydrocarbon alkaline residues, wet oxidation treatment is generally used at present, oxidation waste liquid is neutralized by sulfuric acid, phenol and petroleum acid are recovered, alkaline residue neutralization water is generated, the COD is still high and can reach 30000-60000mg/L, a large amount of salt is generated in the oxidation and neutralization processes, and the impact on a sewage treatment field of a refining enterprise is large. The normal pressure diesel oil alkaline residue mainly contains petroleum acid, which is generally treated by neutralizing and recovering naphthenic acid with sulfuric acid to generate diesel oil alkaline residue neutralizing water, wherein COD is relatively low, but salt concentration is very high, and the diesel oil alkaline residue can enter a sewage treatment field after being diluted in a large amount.
Aiming at the treatment of the high-sulfur high-COD alkaline residue waste liquid, some patents propose different treatment methods and devices.
CN200720169916.5 discloses an alkali dreg wastewater's processing apparatus, includes: a biochemical treatment unit, a micro-electrolysis treatment unit or/and a coagulating sedimentation treatment unit; the micro-electrolysis treatment unit consists of a water distribution tank and an electrolytic tank, the coagulating sedimentation treatment unit consists of a coagulating tank and a sedimentation tank, and the biochemical treatment unit consists of a water inlet tank and a multi-stage aeration biological filter; the biological aerated filter is provided with a biological packed bed, the interior of the packed bed is divided into a plurality of space units by a separation net, each space unit is filled with active biological packing, and an aeration pipeline is arranged below the packed bed. The device is suitable for the treatment of high-concentration alkaline residue wastewater, and has the characteristics of good treatment effect on COD, ammonia nitrogen and sulfides, high petroleum tolerance, impact resistance and the like. This patent does not consider the recovery of petroleum acids such as phenol, and is not economical.
CN200920199634.9 discloses a treatment device for caustic sludge generated by light oil product desulfurization, which comprises a light oil product input pipe, a carbon dioxide tank, a mixer, a fiber membrane contactor, a settling tank, an alkali liquor circulating pipe,The device comprises an alkali liquor input pipe, a dilution water input pipe and a waste liquid output pipe, wherein the alkali liquor input pipe is connected with an alkali liquor oxidation tower, a gas distributor and a heater are arranged in the alkali liquor oxidation tower, an air input pipe is arranged at the lower part of the alkali liquor oxidation tower, an alkali residue input pipe is arranged at the upper part of the alkali liquor oxidation tower, and a tail gas pipe is arranged at the top of the alkali liquor oxidation tower; the device lets the caustic sludge oxidize into sodium hydroxide, disulfide, sulphate etc. with sodium thiolate, sodium sulfide in alkali lye oxidation tower like this, and sodium hydroxide is carbonized into sodium bicarbonate and oil separation at the fibrous membrane contactor, dissolves in waste liquid, consequently this utility model is an environmental protection processing apparatus of the caustic sludge of light oil desulfurization production, makes the waste liquid reach the emission requirement of going biological pond to handle after handling, and can improve the quality of the light oil of extraction. The tail gas containing sulfide generated by the device is incinerated to generate SO2The exhaust gas of (2) requires further treatment. The organic matter in the process of extracting and acidifying light oil is used, but with the increasing strictness of the quality of the oil, the problem that the quality of the oil does not reach the standard can be faced.
CN200520145126.4 discloses a sequencing batch type high-sulfur-content wastewater and alkaline residue waste liquid treatment device, wherein a first desulfurization area, a second desulfurization area, a desalination area, a deamination area and an intermediate water tank are sequentially arranged in a device main body, and the deamination area and the intermediate water tank can be arranged above the desalination area or can be arranged along the length direction or the width direction; the two desulfurization areas are respectively provided with an alkaline residue wastewater inlet pipe, a medicament adding port, a compressed air inlet, a gas collecting port and a decanter, and the middle water tank is provided with a circulating water pump and a water outlet; a water outlet and a sludge discharge pipe of the device are arranged on the desalting zone; the first desulfurization zone, the second desulfurization zone, the desalination zone and the intermediate water tank are respectively provided with a device emptying pipe; the deamination area is provided with a gas inlet, a spraying inlet and a gas discharge outlet. The device converts sulfide in the waste water into sulfate through air oxidation under the action of the iron-containing salt solution or other iron-containing compounds, and the sulfate is precipitated from water by adding lime milk, so that the sulfide in the waste water is thoroughly removed, and ammonia in the waste water is effectively treated. This patent does not consider the recovery of petroleum acids such as phenol, and is not economical.
CN02100855.8 discloses a desulfurization, deamination, dephenolization treatment device for petrochemical industry acid water and caustic sludge, which comprises a desulfurization device and an air supply type biological tower filter, wherein, the desulfurization device carries out desulfurization by adding ferric salt and compressed air, the air supply type biological tower filter is filled with compressed air, and microorganisms in the air supply type biological tower filter are utilized to carry out deamination and dephenolization. The invention does not consider the recovery of petroleum acid substances such as phenol and the like, does not relate to the problem of treating tail gas generated in the treatment process, and has poor environmental benefit and economic benefit.
CN201620017047.3 relates to a comprehensive treatment device of caustic sludge waste liquid, including acidizing subsides unit, oil phase recovery unit, tail gas processing unit and single-stage continuous evaporation crystallization separation unit, wherein single-stage continuous evaporation crystallization separation unit includes neutralization water adjusting tank, single-stage continuous evaporation crystallization system and centrifuge, and neutralization water adjusting tank is used for collecting and adjusting pH with the acid waste liquid of acidizing subsides equipment lower part and oil phase storage tank bottom, specifically is after adjusting acid water pH to 6-8 with NaOH, sends to single-stage continuous evaporation crystallization unit and carries out the evaporation crystallization. The device can efficiently remove petroleum acids such as high-concentration sulfides, phenols and the like in the alkali residue waste liquid, reduce the salt content of neutralized water, but before the waste liquid enters the evaporation crystallization unit, the pH value of acidified waste water needs to be adjusted to 6-8, a large amount of alkali liquor needs to be consumed, and part of phenol in the adjusted waste liquid exists in a sodium phenolate form, so that the quality of sodium sulfate crystallization and crystallized salt can be influenced; and a small amount of organic matters such as phenol and the like in the waste liquid enter steam during evaporation, and cavitation and corrosion are generated on a subsequent steam compressor. In addition, the neutralized water does not meet the discharge requirement after desalting, and needs to be sent to a biochemical treatment tank for further treatment.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a comprehensive treatment method and a comprehensive treatment device for caustic sludge waste liquid. The method provided by the invention can be used for efficiently treating high-concentration sulfides and COD in the alkaline residue and recovering useful substances in the alkaline residue waste liquid, so that the acidified tail gas can be discharged up to the standard, especially, the use amount of a medicament in the treatment process is reduced, the quality of sodium sulfate crystal salt is improved, and the generated condensed water can be discharged up to the standard or recycled. The method is suitable for the alkali residue waste liquid with high sulfide and organic pollutant content, and realizes the energy-saving and high-efficiency treatment of the alkali residue waste liquid.
The treatment method of the oil refining alkaline residue waste liquid comprises the following steps:
(1) acidizing the alkali residue waste liquid by using sulfuric acid, introducing inert gas, and stopping acidizing when the pH value reaches 2-6;
(2) acidified tail gas generated by acidification enters a tail gas treatment unit, and sulfide is recovered;
(3) settling the acidified waste liquid after the acidification treatment, and recovering an oil phase;
(4) and (3) carrying out single-stage continuous evaporation and crystallization on the acidified wastewater after the oil phase is recovered, carrying out dephenolization treatment on the generated secondary steam, introducing the dephenolized steam into a steam compressor, and carrying out centrifugal separation on the generated crystal slurry to obtain sodium sulfate.
In the invention, the sulfuric acid used in the step (1) is preferably concentrated sulfuric acid, and the acidification treatment is stopped when the pH value of the alkaline residue waste liquid reaches 2-4. Inert gases such as nitrogen and the like are introduced in the acidification treatment, so that on one hand, the more thorough removal of sulfides is facilitated, and on the other hand, the separation of petroleum acids such as phenol and the like from a water phase is facilitated. And (2) the acidification treatment in the step (1) can remove more than 99.9 percent of sulfide in the alkaline residue waste liquid.
In the invention, the acidified tail gas generated by acidification in the step (2) can be treated by combining organic amine absorption and distillate oil absorption. Organic amine absorption is used for removing H in tail gas2S, gas discharged from the top of the acidification reaction settler, the oil phase storage tank and the like enters from the bottom of the organic amine washing tower and is in countercurrent contact with organic amine absorption liquid sprayed from the top to remove H in tail gas2And S. The organic amine absorption liquid is preferably MDEA (N-methyldiethanolamine), and the rich absorption liquid is returned to an MDEA regeneration system of a refinery. The distillate oil is used for absorbing organic sulfide in tail gas, the distillate oil is diesel oil, crude diesel oil, etc., and the liquid-gas ratio is controlled to be 80-100L/m3The absorption temperature is 5-35 ℃, the absorption pressure is 50-150kPaG, organic sulfide and organic matter in the tail gas are removed, and the rich absorption oil is subjected to hydrofining treatment. After treatment, H can be2S and organic sulfide are effectively recycled.
In the present invention, the oil phase in step (3) is mainly a petroleum acid such as phenol, and the petroleum acid can be further recovered. After the oil phase is recovered, the removal rate of COD can reach more than 85 percent.
In the invention, the secondary steam generated by the single-stage continuous evaporative crystallization in the step (4) is subjected to dephenolization treatment, the phenol contained in the steam mainly comprises phenol, cresol, xylenol and the like, the dephenolization treatment can adopt an adsorption method, a membrane separation method and the like, the adsorption method can adopt adsorbents such as activated carbon, resin, molecular sieves and the like, and the membrane separation method can adopt reverse osmosis membrane separation.
In the invention, the compressed steam generated by the steam compressor in the step (4) is firstly used for heating the acidified wastewater, the generated high-temperature condensed water is used for preheating the acidified wastewater, and finally the generated condensed water reaches the standard and is discharged or recycled.
In the invention, the solid phase obtained by centrifugal separation in the step (4) is sodium sulfate crystal salt, and the liquid phase obtained by centrifugal separation is mixed with evaporative crystallization mother liquor, then is heated together with preheated acidified wastewater, and then is circularly subjected to single-stage continuous evaporative crystallization.
The invention also provides a device for comprehensively treating the alkali residue waste liquid, which mainly comprises an acidification settling unit, an oil phase recovery unit, a tail gas treatment unit and an evaporation crystallization unit, wherein:
(1) the acidification settling unit mainly comprises material conveying equipment, a pipeline mixer and an acidification reaction settler, wherein the material conveying equipment is used for conveying the alkali residue waste liquid, the sulfuric acid and the inert carrier gas into the acidification reaction settler, the pipeline mixer is used for fully mixing the alkali residue waste liquid and the sulfuric acid, and the acidification reaction settler is used for acidification reaction settling of the alkali residue waste liquid;
(2) the oil phase recovery unit mainly comprises an oil phase storage tank and oil phase refining equipment, wherein the oil phase storage tank is used for storing petroleum acids such as phenol and the like discharged by the acidification and sedimentation equipment, and the oil phase refining equipment is used for refining and recovering the discharged oil phase;
(3) the tail gas treatment unit mainly comprises an organic amine washing tower and a diesel oil absorption tower, wherein the organic amine washing tower is used for removingRemoving H in tail gas2S, the diesel oil absorption tower is used for absorbing organic sulfides;
(4) the evaporative crystallization unit mainly comprises a preheater, a forced circulation pump, an evaporator, a crystallizer, dephenolization equipment, a steam compressor and a centrifugal separator, acidified wastewater firstly enters the preheater for preheating, preheated waste liquid is sent to the evaporator through the forced circulation pump to be heated and then enters the crystallizer, materials form flash evaporation in the crystallizer, generated secondary steam enters the dephenolization equipment, dephenolized steam enters the steam compressor for reuse, crystallized slurry is centrifugally separated to obtain crystallized salt with a solid phase mainly comprising sodium sulfate, and a liquid phase obtained after centrifugal separation and crystallized mother liquid are sent to the evaporator through the forced circulation pump to be continuously heated, so that the density of the crystallized slurry in the crystallizer is adjusted.
In the device, an inverted U-shaped backflow preventing pipe or a one-way valve is arranged on the inert carrier gas conveying pipeline to prevent the waste liquid from flowing backwards.
In the device, a pipeline is arranged between the acidification reaction settler and the oil phase storage tank for connection, and the oil phase can flow into the oil phase storage tank by the pressure of the acidification reaction settler and then is pumped to oil phase refining equipment for recovery. The oil phase refining equipment is mainly used for refining crude phenol, so that the additional value of the alkali residue waste liquid treatment is improved, and the treatment cost is reduced.
In the device, the top of the organic amine washing tower is provided with a defoaming facility to prevent foams and liquid from being carried.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method can efficiently treat high-concentration sulfides and COD in the alkaline residue, simultaneously recover useful substances in the alkaline residue waste liquid as much as possible, realize the standard-reaching discharge of the acidified tail gas in the whole treatment process, effectively treat and utilize steam generated in the treatment process, and has good environmental benefit and economic benefit.
(2) The method does not need to consume a large amount of alkali liquor to carry out neutralization treatment on the acidified wastewater, reduces the using amount of the medicament and reduces the treatment cost.
(3) The method avoids the influence on the sodium sulfate crystallization and the quality of the crystallized salt caused by the fact that part of phenol exists in the form of sodium phenolate in the traditional alkali residue neutralization water evaporation crystallization process, and can obtain relatively pure sodium sulfate salt, thereby improving the quality of the sodium sulfate crystallized salt.
(4) By directly carrying out evaporative crystallization on the acidified wastewater and carrying out dephenolization treatment on the secondary steam, cavitation and corrosion on a steam compressor are effectively avoided.
(5) The condensate water finally produced by the method meets the standard discharge or recycling requirement, no secondary sewage is produced, and zero discharge of the alkaline residue waste liquid is realized.
Drawings
FIG. 1 is a process flow diagram of the treatment method and apparatus of the present invention;
wherein: 1-an alkali residue pump, 2-a sulfuric acid pump, 3-a pipeline mixer, 4-an acidification reaction settler and 5-pH monitoring of acidification waste liquid; 6-oil phase storage tank, 7-oil phase delivery pump and 8-oil phase refining equipment; 9-organic amine washing tower, 10-organic amine rich delivery pump, 11-defoaming facility, 12-diesel oil absorption tower, 13-organic amine rich absorption liquid regeneration system and 14-diesel oil hydrofining unit; 15-a preheater, 16-an evaporator, 17-a crystallizer, 18-a centrifugal separator, 19-a forced circulation pump, 20-a dephenolizing device, 21-a steam compressor and 22-a mirabilite refining unit;
101-alkaline residue waste liquid, 102-sulfuric acid, 103-acidified waste water, 104-petroleum acid such as phenol and the like, 105-preheated acidified waste water, 106-heated acidified waste water, 107-crystal slurry, 108-sodium sulfate, 109-liquid phase obtained by centrifugal separation, 110-secondary steam, 111-purified steam, 112-compressed steam, 113-high-temperature condensed water, 114-crystallization mother liquor and 115-condensed water;
201-inert carrier gas, 202-acidified Tail gas (containing H)2S and organosulfide), 203-poor organoamine absorbent, 204-rich organoamine absorbent, 205-removal of H2The tail gas after S acidification (containing organic sulfide), 206-purified gas, 207-poor diesel oil absorption liquid and 208-rich diesel oil absorption liquid.
Detailed Description
The method and apparatus of the present invention will be described in detail below with reference to the accompanying drawings and examples.
The comprehensive treatment device for the alkaline residue waste liquid is shown in figure 1 and comprises an acidification settling unit, an oil phase recovery unit, a tail gas treatment unit and an evaporation crystallization unit.
The acidification settling unit mainly comprises an alkali residue pump 1, a sulfuric acid pump 2, a pipeline mixer 3 and an acidification reaction settler 4. The alkali residue waste liquid 101 is conveyed by an alkali residue pump 1, the sulfuric acid 102 is conveyed by a sulfuric acid pump 2, the alkali residue waste liquid and the sulfuric acid are fully mixed in a pipeline mixer 3 and then enter an acidification reaction settler 4, under the blowing-off of inert gases 201 such as nitrogen, sulfides are removed, and acidified tail gas 202 is formed and enters a tail gas treatment unit. The acidification reaction settler is provided with a pH monitoring device 5, and the pH of acidification liquid of the acidification sedimentation settler is controlled to be 2-6 by adjusting the amount of sulfuric acid, so that removal of sulfide and petroleum acid is facilitated. Inert carrier gas 201 such as nitrogen enters from the lower part of the acidification reaction settler to play a role in gas stripping, which is beneficial to the separation of petroleum acids such as phenol and the like from a water phase and the more thorough removal of sulfides. An inverted U-shaped backflow prevention pipe or a one-way valve is arranged on the inert carrier gas conveying pipeline to prevent the waste liquid from flowing backwards. The sulfuric acid is used for neutralizing the alkali residue waste liquid, so that petroleum acids such as sulfide, phenol and the like in the alkali residue waste liquid can be efficiently removed, and the COD of the waste liquid is reduced.
The oil phase recovery unit mainly comprises an oil phase storage tank 6, an oil phase delivery pump 7 and oil phase refining equipment 8, wherein the acidified and settled upper oil phase 104 enters the oil phase storage tank 6 and is delivered to the oil phase refining equipment 8 through the oil phase delivery pump 7 for refining treatment, and petroleum acid such as phenol is recovered. The oil phase refining equipment 8 is mainly used for refining crude phenol and improving the additional value of the treatment of the alkaline residue waste liquid. A pipeline is arranged between the acidification reaction settler 4 and the oil phase storage tank 6 for connection, and the oil phase can flow into the oil phase storage tank 6 by the pressure of the acidification reaction settler.
The tail gas treatment unit mainly comprises an organic amine washing tower 9, a diesel oil absorption tower 12, an acidification reaction settler 4 and an acidification tail gas 202 discharged from the tank top of an oil phase storage tank 6, wherein the acidification tail gas enters from the bottom of the organic amine washing tower and is in countercurrent contact with lean organic amine absorption liquid 203 sprayed from the top to remove H in the tail gas2And S. The top of the organic amine washing tower is provided with a defoaming facility 11, and the organic amine-rich absorption liquid 204 is sent to a refinery organic amine-rich absorption liquid regeneration system through an organic amine-rich delivery pump 1013. Washing acidified tail gas with organic amine to remove H2The acidified tail gas 205 containing organic sulfide after S enters a diesel oil absorption tower 12, and the purified gas 206 is discharged after the diesel oil absorbs the organic sulfide. The diesel oil 207 is selected from raw oil to be hydrotreated, and the diesel-rich absorption liquid 208 and the hydrogenated raw oil are mixed and enter the diesel oil refining unit 14.
The single-stage continuous evaporative crystallization unit mainly comprises a preheater 15, an evaporator 16, a crystallizer 17, a centrifugal separator 18, a forced circulation pump 19 and a steam compressor 21, acidified wastewater 103 discharged from an acidification reaction settler 4 is mixed with acidified wastewater 103 intermittently discharged from the lower part of an oil phase storage tank by an oil phase delivery pump 7 and then is delivered to the preheater 15 for preheating, a heat source of the preheater adopts high-temperature condensed water 113 after heat exchange of the evaporator 16, the acidified wastewater 105 after preheating is delivered into the evaporator 16 by the forced circulation pump 19 for heating, the acidified wastewater 106 after heating enters the crystallizer 17 to form flash evaporation in the crystallizer, secondary steam 110 is formed and discharged from an outlet of the crystallizer and then enters a dephenolization device 20 to remove phenolic substances in the steam to obtain purified steam 111, the purified steam 111 is generated into compressed steam 112 by the steam compressor 21 and is firstly used for heating and preheating the acidified wastewater 105 by the evaporator 16, the generated high-temperature condensed water 113 enters the preheater 15 for preheating the acidified wastewater 103, and finally the generated condensed water 115 is discharged or recycled after reaching the standard. The sodium sulfate in the material in the crystallizer 17 is crystallized and grown due to the evaporation of the water, and the generated mother liquor 114 is conveyed to the evaporator through the forced circulation pump 19 to be continuously heated, evaporated and crystallized, so that the density of the crystal slurry in the crystallizer is adjusted. And (3) enabling crystal slurry 107 which is generated at the bottom of the crystallizer and meets the requirements to enter a centrifugal separator 18 for separation, conveying a liquid phase 109 obtained by centrifugal separation to an evaporator through a forced circulation pump 19 for continuous heating, evaporation and crystallization, obtaining a solid phase mainly comprising sodium sulfate 108 by centrifugal separation, and further purifying to produce anhydrous sodium sulfate or mirabilite.
Example 1
The alkaline residue waste liquid of a certain enterprise for catalyzing the mixture of gasoline alkaline residue and liquid hydrocarbon alkaline residue has COD of 3.21 × 105mg/L, sulfide 1.99 × 104mg/L, volatile phenol 1.07 × 105mg/L。
The device shown in figure 1 of the invention is adopted for treatment, the acidification reaction settler is provided with pH monitoring, the pH of the acidification wastewater in the acidification reaction settler is controlled to be 2, and nitrogen is adopted as carrier gas. The sulfuric acid acidification alkali residue waste liquid can remove sulfide, phenol and other petroleum acids in the alkali residue waste liquid, and reduce the COD of the waste liquid. And (4) allowing the acidified and settled upper oil phase to enter an oil phase storage tank, refining by using oil phase refining equipment, and recovering petroleum acids such as phenol. Acidified tail gas discharged from the top of the acidification reaction settler and the oil phase storage tank enters from the bottom of the organic amine washing tower and is in countercurrent contact with lean organic amine absorption liquid sprayed from the top to remove H in the tail gas2And S. And a defoaming facility is arranged at the top of the organic amine washing tower, and the organic amine-rich absorption liquid is sent to an organic amine absorption liquid regeneration system of a refinery through an organic amine-rich delivery pump. Washing acidified tail gas with organic amine to remove H2And (3) allowing the gas containing the organic sulfide to enter a diesel oil absorption tower, absorbing the organic sulfide by using diesel oil, and discharging the gas after reaching the standard, wherein the diesel oil is the crude diesel oil to be hydrotreated, the diesel oil absorption temperature is 30 ℃, the pressure is 80kPaG, and a diesel oil-rich absorbent is mixed with the hydrogenated raw oil for hydrotreating. The concentration of salt in acidified wastewater generated by acidification treatment reaches 15% -25%, mainly sodium sulfate enters a preheater and an evaporator of a single-stage continuous evaporative crystallization unit for heating, then enters a crystallizer, secondary steam generated by flash evaporation enters dephenolization equipment, the dephenolization treatment adopts a reverse osmosis membrane separation method to remove petroleum acids such as phenol and the like in the steam, the obtained purified steam enters the evaporator for evaporating acidified wastewater after being pressurized by a steam compressor, and then enters the preheater for preheating the acidified wastewater, and the formed condensate water reaches the standard and is discharged or recycled. And (4) centrifugally separating crystal slurry generated by crystallization to obtain high-quality sodium sulfate, and further purifying to produce anhydrous sodium sulfate or mirabilite.
After the treatment, the sulfide in the alkaline residue waste liquid is almost completely removed, the removal rate reaches more than 99.9 percent, more than 95 percent of petroleum acid such as phenol is recovered, the removal rate of the petroleum acid such as phenol dissolved in water is more than 99.5 percent, the COD (chemical oxygen demand) of condensed water is less than 50mg/L, and no further treatment is needed; improves the quality of the sodium sulfate crystal salt and eliminates the influence of impurities such as sodium phenolate and the like.
Example 2
The alkaline residue waste liquid of a certain enterprise, which is mixed by catalytic gasoline alkaline residue, catalytic diesel oil and liquid hydrocarbon alkaline residue, wherein the COD is 2.35 × 105mg/L, sulfide 3.68 × 104mg/L, volatile phenol 5.89 × 104mg/L。
The device shown in figure 1 of the invention is adopted for treatment, the acidification reaction settler is provided with pH monitoring, the pH of the acidification wastewater in the acidification reaction settler is controlled to be 4, and nitrogen is adopted as carrier gas. The sulfuric acid acidification alkali residue waste liquid can remove sulfide, phenol and other petroleum acids in the alkali residue waste liquid, and reduce the COD of the waste liquid. And (4) the upper oil phase after acidification and sedimentation enters an oil phase storage tank, and then oil phase refining equipment is adopted for refining treatment to recover petroleum acids such as phenol and the like. Acidified tail gas discharged from the top of the acidification reaction settler and the oil phase storage tank enters from the bottom of the organic amine washing tower and is in countercurrent contact with lean organic amine absorption liquid sprayed from the top to remove H in the tail gas2And S. And a defoaming facility is arranged at the top of the organic amine washing tower, and the organic amine-rich absorption liquid is sent to an organic amine absorption liquid regeneration system of a refinery through an organic amine-rich delivery pump. Washing acidified tail gas with organic amine to remove H2And (3) allowing the gas containing the organic sulfide to enter a diesel oil absorption tower, absorbing the organic sulfide by using low-temperature diesel oil, discharging the gas after reaching the standard, selecting the diesel oil to be hydrotreated, allowing the diesel oil to have the absorption temperature of 10 ℃, allowing the diesel oil to have the pressure of 120kPaG, and mixing a diesel oil-rich absorbent with the hydrogenated raw oil for hydrotreating. The concentration of salt in acidified wastewater generated by acidification treatment reaches 15% -20%, mainly sodium sulfate enters a preheater and an evaporator of a single-stage continuous evaporative crystallization unit for heating, then enters a crystallizer, secondary steam generated by flash evaporation enters dephenolization equipment, the dephenolization treatment adopts an activated carbon adsorption method to remove petroleum acids such as phenol in the steam, the obtained purified steam enters the evaporator for evaporating acidified wastewater after being pressurized by a steam compressor, and then enters the preheater for preheating the acidified wastewater, so that formed condensate water reaches the standard and is discharged or recycled. And (4) centrifugally separating crystal slurry generated by crystallization to obtain high-quality sodium sulfate, and further purifying to produce anhydrous sodium sulfate or mirabilite.
After the treatment, the sulfide in the alkaline residue waste liquid is almost completely removed, the removal rate reaches more than 99.9 percent, more than 90 percent of petroleum acid such as phenol is recovered, the removal rate of the petroleum acid such as phenol dissolved in water is more than 99.5 percent, the COD of the purified water is less than 50mg/L, and no further treatment is needed; improves the quality of the sodium sulfate crystal salt and eliminates the influence of impurities such as sodium phenolate and the like.
Comparative example 1
The treatment process and the operating conditions were the same as in example 1. The difference lies in that: the secondary steam generated in the crystallizer of the evaporation crystallization unit is not dephenolized, directly enters a steam compressor for compression, enters an evaporator for heating and acidifying wastewater, high-temperature condensate water preheats and acidifies the wastewater, and finally formed condensate water has the volatile phenol content of thousands of mg/L and still needs to be further processed. The phenol substances contained in the secondary steam cause cavitation erosion to the steam compressor, affect the efficiency of the compressor and cause certain corrosion to the steam compressor.
Comparative example 2
The treatment process and the operating conditions were the same as in example 1. The difference lies in that: the pH value of the acidified wastewater is adjusted to 7-8 by sodium hydroxide, most of phenol enters crystal slurry during evaporation and crystallization, the quality of sodium sulfate crystal salt is greatly affected, and the formed salt cannot be refined and can only be treated according to solid waste.
Claims (10)
1. The method for treating the oil refining alkaline residue waste liquid is characterized by comprising the following steps of:
(1) acidizing the alkali residue waste liquid by using sulfuric acid, introducing inert gas, and stopping acidizing when the pH value reaches 2-6;
(2) acidified tail gas generated by acidification enters a tail gas treatment unit, and sulfide is recovered;
(3) settling the acidified waste liquid after the acidification treatment, and recovering an oil phase;
(4) carrying out single-stage continuous evaporation and crystallization on the acidified wastewater after oil phase recovery, sending the preheated acidified wastewater into an evaporator through a forced circulation pump, heating, then sending the heated acidified wastewater into a crystallizer, carrying out flash evaporation on materials in the crystallizer, carrying out dephenolization treatment on generated secondary steam, wherein the dephenolization treatment adopts an adsorption method or a membrane separation method; the dephenolized steam enters a steam compressor, and the generated crystal slurry is centrifugally separated to obtain sodium sulfate; the compressed steam generated by the steam compressor is firstly used for heating the acidified wastewater, the generated high-temperature condensed water is used for preheating the acidified wastewater, and finally the generated condensed water reaches the standard and is discharged or recycled; mixing the liquid phase obtained by centrifugal separation with the evaporative crystallization mother liquor, and heating the mixture together with preheated acidified wastewater so as to adjust the density of the crystal slurry in the crystallizer; and then circulating to carry out single-stage continuous evaporative crystallization.
2. The method of claim 1, wherein: and (2) adopting concentrated sulfuric acid as sulfuric acid used in the step (1), and stopping acidification treatment when the pH value of the alkaline residue waste liquid reaches 2-4.
3. The method according to claim 1 or 2, characterized in that: the inert gas in the step (1) is nitrogen, and more than 99.9 percent of sulfide in the alkaline residue waste liquid after the acidification treatment is removed.
4. The method of claim 1, wherein: the acidified tail gas in the step (2) is treated by adopting a mode of combining organic amine absorption and distillate oil absorption, and the organic amine absorption is used for removing H in the tail gas2S, adopting MDEA as an organic amine absorption liquid, and returning rich absorption liquid to an MDEA regeneration system of a refinery; the distillate oil is used for absorbing organic sulfide in tail gas, the distillate oil is diesel oil, and the liquid-gas ratio is controlled to be 80-100L/m3The absorption temperature is 5-35 ℃, the absorption pressure is 50-150kPaG, and the rich absorption oil is subjected to hydrofining treatment.
5. The method of claim 1, wherein: the oil phase in the step (3) is phenol type petroleum acid, and after the oil phase is recovered, the removal rate of COD is more than 85%.
6. The method of claim 1, wherein: and (4) selecting active carbon, resin and a molecular sieve adsorbent by an adsorption method, and adopting a reverse osmosis membrane for separation by a membrane separation method.
7. The device for comprehensively treating the caustic sludge waste liquid by the method of any one of claims 1 to 6 is characterized by mainly comprising an acidification settling unit, an oil phase recovery unit, a tail gas treatment unit and an evaporation crystallization unit, wherein:
(1) the acidification settling unit mainly comprises material conveying equipment, a pipeline mixer and an acidification reaction settler, wherein the material conveying equipment is used for conveying the alkali residue waste liquid, the sulfuric acid and the inert carrier gas into the acidification reaction settler, the pipeline mixer is used for fully mixing the alkali residue waste liquid and the sulfuric acid, and the acidification reaction settler is used for acidification reaction settling of the alkali residue waste liquid;
(2) the oil phase recovery unit mainly comprises an oil phase storage tank and oil phase refining equipment, wherein the oil phase storage tank is used for storing phenolic petroleum acid discharged by the acidification reaction settler, and the oil phase refining equipment is used for refining and recovering the discharged oil phase;
(3) the tail gas treatment unit mainly comprises an organic amine washing tower and a diesel oil absorption tower, wherein the organic amine washing tower is used for removing H in the tail gas2S, the diesel oil absorption tower is used for absorbing organic sulfides;
(4) the evaporative crystallization unit mainly comprises a preheater, a forced circulation pump, an evaporator, a crystallizer, dephenolization equipment, a steam compressor and a centrifugal separator, acidified wastewater firstly enters the preheater for preheating, the acidified wastewater after preheating is sent to the evaporator through the forced circulation pump for heating and then enters the crystallizer, materials form flash evaporation in the crystallizer, generated secondary steam enters the dephenolization equipment, the dephenolized steam enters the steam compressor, crystallized slurry is centrifugally separated to obtain sodium sulfate crystallized salt, and liquid phase obtained after centrifugal separation and crystallized mother liquor are conveyed to the evaporator through the forced circulation pump for continuous heating, so that the density of the crystallized slurry in the crystallizer is adjusted.
8. The apparatus of claim 7, wherein: an inverted U-shaped backflow prevention pipe or a one-way valve is arranged on the inert carrier gas conveying pipeline to prevent the waste liquid from flowing backwards.
9. The apparatus of claim 7, wherein: the acidification reaction settler is connected with the oil phase storage tank through a pipeline, and the oil phase flows into the oil phase storage tank by the pressure of the acidification reaction settler and then is pumped to oil phase refining equipment.
10. The apparatus of claim 7, wherein: the top of the organic amine washing tower is provided with a defoaming facility to prevent foams and liquid from being carried.
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| CN205473138U (en) * | 2016-01-11 | 2016-08-17 | 中国石油化工股份有限公司 | Comprehensive processing apparatus of alkaline residue waste liquid |
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| CN101781038A (en) * | 2010-03-02 | 2010-07-21 | 济南冶金化工设备有限公司 | Phenol and cyanogen waste water physical chemical method control process and equipment |
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