CN113599761B - Petrochemical alkaline residue treatment system and treatment method - Google Patents

Petrochemical alkaline residue treatment system and treatment method Download PDF

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CN113599761B
CN113599761B CN202110797562.3A CN202110797562A CN113599761B CN 113599761 B CN113599761 B CN 113599761B CN 202110797562 A CN202110797562 A CN 202110797562A CN 113599761 B CN113599761 B CN 113599761B
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sintering
flue gas
petrochemical
alkaline
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CN113599761A (en
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万新宇
许海川
张俊
王海风
高建军
王�锋
武兵强
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Central Iron and Steel Research Institute
CISRI Sunward Technology Co Ltd
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CISRI Sunward Technology Co Ltd
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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/40—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by heating to effect chemical change, e.g. pyrolysis
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/36—Detoxification by using acid or alkaline reagents
    • C—CHEMISTRY; METALLURGY
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    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/40—Inorganic substances
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Abstract

The invention relates to a system and a method for treating petrochemical alkaline residues, belongs to the technical field of treatment of the petrochemical alkaline residues, and solves the technical problems that the conventional method for treating the petrochemical alkaline residues is complex, energy consumption is approximate, economical efficiency is poor, and environmental friendliness is poor. The treatment system comprises a sintering flue gas acidification unit, a desulfurization ash calcification unit and a sintering machine detoxification unit which are connected in sequence; the sintering flue gas acidification unit is communicated with the sintering flue gas main pipeline and is also communicated with a sintering flue gas treatment system; introducing the petrochemical alkaline residue into a sintering flue gas acidification unit for acidification treatment; the desulfurization ash calcification unit is used for carrying out calcification reaction on the acidified waste liquid; carrying out solid-liquid separation on the calcified product, sending the solid precipitate into a lime kiln, and sending the alkaline residue liquid into a detoxification unit of a sintering machine; the detoxification unit of the sintering machine is used for carrying out high-temperature detoxification on the residual neutral oil and organic acidic substances in the alkaline residue liquid. The invention achieves 100 percent treatment of the petrochemical alkaline residue and realizes the aim of zero emission.

Description

Petrochemical alkaline residue treatment system and treatment method
The invention relates to the technical field of petrochemical alkaline residue waste liquid treatment, in particular to a system and a method for treating petrochemical alkaline residue waste liquid.
Background
Gasoline, diesel oil, liquefied gas and other products produced in the petroleum processing industry contain a lot of acidic non-hydrocarbon compounds, and indexes such as sulfur content, corrosion, acidity and the like of oil products are easy to exceed standards. In order to ensure the stability of oil products, acidic substances in the oil products are generally removed by an alkaline washing process, and a solution after the alkaline washing is waste alkali liquor commonly called caustic sludge. The main components of the caustic sludge are high-concentration sulfides, part of neutral oil substances brought by emulsification in the caustic washing process, mercaptan and thiophenol, and the COD content in each liter of the caustic sludge can reach hundreds of thousands of milligrams. The caustic sludge with such complex components can seriously pollute the environment if being directly discharged; if the sewage treatment system is sent to a sewage treatment plant, the normal operation of the sewage treatment system can be seriously influenced.
In recent years, with the increasing environmental protection requirements and the strict control requirements on the migration and flow of hazardous wastes, some refinery enterprises even set up a strict policy of "hazardous wastes do not leave factory". Therefore, how to economically and effectively complete the harmless treatment of the petrochemical alkaline residues becomes a problem which needs to be solved by each refining enterprise.
In the existing petrochemical alkaline residue treatment methods, some incinerators are used for incineration, so that the energy consumption is high and the economical efficiency is poor; some H produced by flue gas acidification method2S gas can not be harmlessly treated, so that the subsequent flue gas treatment cost is increased, in addition, the corrosion resistance requirement of equipment is strict, the process flow is complex, and the economy of caustic sludge treatment is poor.
Disclosure of Invention
In view of the above analysis, the present invention is directed to a system and a method for treating petrochemical alkaline residue waste liquid, so as to solve the technical problems of complicated treatment method, low economical efficiency due to energy consumption, and poor environmental protection in the conventional petrochemical alkaline residue waste liquid treatment method.
The purpose of the invention is mainly realized by the following technical scheme:
on one hand, the invention provides a petrochemical alkaline residue treatment system, which comprises a sintering flue gas acidification unit, a desulfurization ash calcification unit and a sintering machine detoxification unit which are sequentially connected;
the sintering flue gas acidification unit is communicated with a sintering flue gas main pipeline, and sintering flue gas enters the sintering flue gas acidification unit through the sintering flue gas main pipeline; the sintering flue gas acidification unit is also communicated with the sintering flue gas treatment system, the petrochemical alkaline residues are introduced into the sintering flue gas acidification unit, the acidified tail gas generated after the petrochemical alkaline residues are acidified is introduced into the sintering flue gas treatment system, and the generated acidified waste liquid enters the desulfurization ash calcification unit;
introducing the desulfurized ash generated in the sintering process into acidified waste liquid in a desulfurized ash calcification unit for calcification reaction, then carrying out solid-liquid separation on the obtained calcification product to obtain solid precipitate and alkali slag waste liquid, sending the solid precipitate into a lime kiln, and then sending the alkali slag liquid into a detoxification unit of a sintering machine after batching;
the detoxification unit of the sintering machine is used for carrying out high-temperature detoxification on the residual neutral oil and organic acidic substances in the alkaline residue liquid.
In one possible design, the sintering flue gas acidification unit comprises a first reactor;
the desulfurization ash calcification unit comprises a second reactor and a separation tank;
the sintering machine detoxification unit comprises a sintering mixer and a sintering machine.
On the other hand, the invention also provides a petrochemical alkaline residue processing method, which adopts the alkaline residue processing system and comprises the following steps:
step 1, adding liquid petrochemical alkaline residues to be treated into a first reactor, and then introducing sintering flue gas into the first reactor through a main sintering flue gas pipeline for acidification treatment; obtaining acidified tail gas and acidified waste liquid;
step 2, adding the acidified waste liquid into a second reactor, adding sintered desulfurized ash into the second reactor for re-reaction, introducing the solution obtained by re-reaction into a separation tank, and performing solid-liquid separation to obtain alkali residue waste liquid Na2SO4Regenerating the solution, and separating the obtained solid precipitate into calcium carbonate precipitate;
step 3, adding Na2SO4The regeneration solution is mixed into a sintering mixer and enters a sintering machine along with the sintering mixture for roasting, so that high-temperature digestion and detoxification are realized.
Further, in step 1, the acidification pressure is equal to the pressure of the sintering flue gas; the acidification treatment temperature is 85-95 ℃; the acidification treatment time is 70-120 min; the heat source for heating the petrochemical alkaline residue is provided by the waste heat of the sintering flue gas.
Further, in step 1, the acidified waste liquid after the acidification treatment contains Na2CO3And NaHCO3。
Further, in the step 2, the mass ratio of the acidified waste liquid to the sintering desulfurization ash is 1: 1.0-1.8.
Further, in step 2, standing the reaction product obtained by re-reaction in a separation tank for more than or equal to 3 hours, carrying out solid-liquid separation after layering, and separating to obtain Na2SO4The concentration of the regeneration solution is 5.0-6.0 wt%.
Further, in step 2, the calcium carbonate precipitate obtained by the solid-liquid separation is sent to a lime kiln to be calcined, and CaO produced by the calcination is used as a sintering flux.
Further, in step 3, Na2SO4The solution is mixed into the sintering mixture according to a certain proportion;
the temperature in the sintering machine is 950-1350 ℃.
Further, in step 1, the petrochemical caustic sludge comprises pre-caustic washing caustic sludge obtained after desulfurization and dephenolization of gasoline, naphtha or aromatic hydrocarbon; and/or liquefied gas desulfurization pre-caustic washing caustic sludge; and/or catalyst-containing caustic sludge obtained by desulfurizing gasoline, naphtha, aromatic hydrocarbon or liquefied gas; and/or caustic sludge waste liquid generated in the process of alkaline washing and refining catalytic gasoline and catalytic diesel.
Compared with the prior art, the invention can realize at least one of the following beneficial effects:
(1) the petrochemical alkaline residue treatment system comprises a sintering flue gas acidification unit and desulfurization ashCompared with the prior art, the invention utilizes the sintering flue gas generated in the steel industry to be introduced into the petrochemical alkaline residue and utilizes CO in the sintering flue gas2、SO2、O2The gas neutralizes the alkaline residue, the sulfide and COD in the alkaline residue are efficiently removed, and the acidified tail gas directly enters the existing sintering flue gas treatment system.
(2) After the sintering desulfurization ash is subjected to calcification reaction, part of calcium carbonate is discharged, and the rest alkaline residue enters a detoxification unit of a sintering machine for high-temperature detoxification and digestion. The invention can realize low-cost and harmless treatment of the caustic sludge which is highly difficult to treat, and greatly reduces the environmental pollution.
(3) The invention takes the waste flue gas and the desulfurized ash generated in the sintering process as the raw materials for treating the petrochemical alkaline residue, thereby not only realizing the utilization of the sintering solid waste, but also achieving the purpose of treating the petrochemical alkaline residue.
(4) The waste gas generated by the whole treatment method is directly discharged into the existing sintering treatment system, and a flue gas treatment device is not required to be additionally built, so that the investment is saved; in addition, the treated alkaline residue residual liquid enters a sintering machine in a form of moisture, and the high-temperature detoxification of toxic substances (neutral oil and organic acidic substances (such as creosote, mercaptan and thiophenol)) is realized by utilizing the high-temperature characteristic of the sintering machine, so that the 100% treatment of petrochemical alkaline residue is realized, and the zero emission target is realized.
In the invention, the technical schemes can be combined with each other to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
FIG. 1 is a process flow diagram of petrochemical caustic sludge provided by the present invention.
Detailed Description
The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, which form a part hereof, and which together with the embodiments of the invention serve to explain the principles of the invention and not to limit its scope.
The invention provides a petrochemical alkaline residue treatment system, which comprises a sintering flue gas acidification unit, a desulfurization ash calcification unit and a sintering machine detoxification unit which are sequentially connected, as shown in figure 1; the sintering flue gas acidification unit is communicated with a sintering flue gas main pipeline, and sintering flue gas enters the sintering flue gas acidification unit through the sintering flue gas main pipeline; the sintering flue gas acidification unit is also communicated with the sintering flue gas treatment system, the petrochemical alkaline residues are introduced into the sintering flue gas acidification unit, the acidified tail gas generated after the petrochemical alkaline residues are acidified is introduced into the sintering flue gas treatment system, and the generated acidified waste liquid enters the desulfurization ash calcification unit; introducing the desulfurized ash generated in the sintering process into acidified waste liquid in a desulfurized ash calcification unit for calcification reaction, then carrying out solid-liquid separation on the obtained calcification product to obtain solid precipitate and alkali slag waste liquid, sending the solid precipitate into a lime kiln, and then sending the alkali slag liquid into a detoxification unit of a sintering machine after batching; the detoxification unit of the sintering machine is used for carrying out high-temperature detoxification on the residual neutral oil and organic acidic substances in the alkaline residue liquid.
It should be noted that the treatment system of the present invention is directed to petrochemical caustic sludge comprising: the alkaline washing caustic sludge after gasoline, naphtha or arene desulfurization and dephenolization, the liquefied gas desulfurization alkaline washing caustic sludge, the catalyst-containing caustic sludge after gasoline, naphtha, arene or liquefied gas desulfurization (mercaptan), and the caustic sludge waste liquid generated in the alkaline washing refining process of catalytic gasoline and catalytic diesel, or the mixed caustic sludge after the above caustic sludge is mixed.
In the petrochemical alkaline residue, the main components comprise: the COD content range is 6 multiplied by 104～1×105mg/L, phenol content range is 5X 103～3×105mg/L，S2-In the range of 2X 103～2×105mg/L, pH 8-15, oil content 1 × 102～1×105mg/L。
The prior petrochemical alkaline residue treatment method and the technical problems thereof are as follows: (1) in the process, the caustic sludge is directly fed into an incinerator without being pretreated, so that volatile organic matters and sulfides with foul odor in the caustic sludge are greatly emitted in the evaporation process, the concentration of pollutants in the gas-phase condensate is higher and higher, and the recycling of the gas-phase condensate is influenced. In addition, the energy consumption of the evaporation process and the incinerator is large, and the economical efficiency is poor. (2) The alkaline residue treatment process belongs to a flue gas acidification method and has certain defects: firstly, the optimal temperature of the flue gas neutralization reaction is 30-70 ℃, and the temperature of the regenerated flue gas of the fluidized catalytic cracking device is as high as 600-700 ℃, so that the flue gas needs to be purified and cooled before the caustic sludge treatment, the waste heat energy is not fully utilized, and the process flow of the treatment process is prolonged; secondly, the main component in the regenerated flue gas of the fluid catalytic cracking unit is CO2、SO2And NOx, containing no O2So that H generated by the neutralization reaction in the alkaline residue2S gas cannot be harmlessly treated, so that the subsequent flue gas treatment cost is increased; finally, the method for treating the caustic sludge can form high-salt caustic sludge neutralizing water and still cause impact on a sewage treatment plant. (3) Treating alkaline residue with SO by flue gas acidification method2The gas is used as the main raw material for acidification. SO required for the process2The gas source is unstable, the requirement on the corrosion resistance of equipment is strict, the process flow is complex, and the economy of alkali residue treatment is poor.
Compared with the prior art, the invention injects untreated petrochemical alkaline residues into the sintering flue gas acidification unit, injects sintering flue gas introduced through the main sintering flue gas pipeline into the sintering flue gas acidification unit, and carries out acidification treatment on petrochemical alkaline residue waste liquid, specifically: the method comprises the following steps that (1) neutralization reaction is carried out on sintering flue gas, sulfide, sodium phenolate, sodium naphthenate and residual alkaline solution in petrochemical alkaline residues, generated acidified tail gas enters a flue gas treatment system of a sintering machine, obtained acidified waste liquid enters a desulfurization ash calcification unit, desulfurization ash generated in a sintering process is introduced into the desulfurization ash calcification unit, the acidified waste liquid is subjected to calcification reaction by using the desulfurization ash, then obtained calcification products are subjected to solid-liquid separation, solid precipitates and alkaline residue waste liquid are obtained, the solid precipitates (calcium carbonate) are transported to a self-prepared lime kiln of a steel enterprise to be calcined, and generated CaO is used as a sintering flux; then, the caustic sludge liquid is proportioned to a proper concentration and then sintered in a mixer, and the mixture is sent to a detoxification unit of a sintering machine; the detoxification unit of the sintering machine is used for carrying out high-temperature detoxification on the neutral oil and the organic acidic substances (such as the impure phenol, the mercaptan and the thiophenol) remained in the alkaline residue liquid.
It should be noted that the sintering flue gas acidification unit comprises a first reactor which is a packed tower, an impinging stream reactor and other equipment. The desulfurization ash calcification unit comprises a second reactor and a separation tank; the sintering machine detoxification unit comprises a sintering mixer and a sintering machine.
Compared with the prior art, the invention puts the petrochemical alkaline residues into the sintering process of the steel industry for coupling treatment, and utilizes CO in the sintering flue gas2、SO2、O2Neutralizing the alkaline residue with gas, efficiently removing sulfides and COD in the alkaline residue, and directly feeding the acidified tail gas into the existing sintering flue gas treatment system; after the sintering desulfurization ash is subjected to calcification reaction, part of calcium carbonate is discharged, and the rest alkaline residue enters a sintering system for high-temperature detoxification and digestion. The invention can realize low-cost and harmless treatment of the caustic sludge which is highly difficult to treat, and greatly reduces the environmental pollution.
The invention also provides a petrochemical alkaline residue treatment method, which adopts the alkaline residue treatment system and comprises the following steps:
step 1, adding liquid petrochemical alkaline residues to be treated into a first reactor, and then introducing sintering flue gas into the first reactor through a main sintering flue gas pipeline for acidification treatment; obtaining acidified tail gas and acidified waste liquid, wherein the components of the acidified waste liquid contain Na2CO3And NaHCO3；
Step 2, adding the acidified waste liquid into a second reactor, and adding sintered desulfurization ash into the second reactor for re-reaction, wherein the mass ratio of the acidified waste liquid to the sintered desulfurization ash is 1: 1.0-1.8; introducing the solution obtained by the re-reaction into a separation tank, carrying out solid-liquid separation, and separating the alkali residue wasteThe liquid is Na2SO4Regenerating the solution, and separating the obtained solid precipitate into calcium carbonate precipitate;
step 3, adding Na2SO4The regeneration solution is mixed into a sintering mixer and enters a sintering machine along with the sintering mixture for roasting, so that high-temperature digestion and detoxification are realized.
In the step 1, the sintering flue gas generated by the steel enterprises is characterized in that: the flue gas temperature is high, generally 80-180 ℃, the water content is 10-13%, the oxygen content is 15-18%, the carbon dioxide content is 10-15%, and the concentration of sulfur dioxide is about 600-900 mg/m3，NOXThe concentration of (A) is about 200-310 mg/m3The sintering flue gas amount is large, and the flue gas produced by each ton of sintering ore is 4000-6000 m3. The sintering flue gas contains CO2、SO2And O2The three smoke components can simultaneously carry out acidification and oxidation reactions on the petrochemical alkaline residue.
In the step 1, the acidification treatment pressure is equal to the pressure of the sintering flue gas; the acidification treatment temperature is 85-95 ℃; the acidification treatment time is 70-120 min; the heat source for heating the petrochemical alkaline residue is provided by the waste heat of the sintering flue gas.
In the step 1, CO in the sintering flue gas is treated in an acidification process2The alkaline solution and sulfide, sodium phenolate, sodium naphthenate and residual alkaline solution in the alkaline residue are subjected to acidification reaction, and the specific acidification principle is as follows:
2ArONa (sodium phenolate) + CO2+H2O＝2ArOH+Na2CO3 (1)
2RCOONa (sodium naphthenate) + CO2+H2O＝2RCOOH+Na2CO3 (2)
Na2S+CO2+H2O＝Na2CO3+H2S (3)
2NaOH+CO2＝Na2CO3+H2O (4)
Na2CO3+CO2+H2O＝2NaHCO3 (5)
2NaHS+CO2+H2O＝Na2CO3+2H2S (6)
In addition, O in the sintering flue gas2With sulfide and CO in petrochemical alkaline residue2H produced by acidification2S is oxidized to generate SO2The concrete principle is as follows:
Na2S+1.5O2＝Na2O+SO2 (7)
H2S+O2＝2S+2H2O (8)
H2S+1.5O2＝2SO2+H2O (9)
2Na2S+2O2+H2O＝Na2S2O3+2NaOH (10)
Na2S2O3+2NaOH+2O2＝2Na2SO4+H2O (11)
2NaSR+H2O+1/2O2＝RSSR+2NaOH (12)
the main component of the acidified tail gas (acidified reaction flue gas) generated by the acidification treatment is SO2And residual CO in the sintering flue gas2、NOXAnd the acidified tail gas does not need an additional treatment device and is directly connected into the original flue gas treatment system of the sintering machine from the exhaust pipeline of the first reactor.
It should be noted that the sintering flue gas contains O2Can improve the removal effect of sulfide in the caustic sludge, compared with other alkaline sludge without O2The sintering flue gas does not need additional supplementary air or oxygen.
In the step 1, in the acidification treatment process, the operation pressure is the same as the sintering flue gas pressure, the sintering flue gas pressure is micro negative pressure, and the pressure is increased to 1.0-3.5 kpa after passing through a booster fan; the acidification treatment temperature is controlled to be 85-95 ℃, a heat source for heating the caustic sludge is mainly provided by the waste heat of sintering flue gas, no extra heat is needed, the acidification treatment time is controlled to be 70-120 min, and high COD (chemical oxygen demand) removal rate and phenol and sulfide removal rate in the caustic sludge treatment process can be ensured.
The acidification treatment equipment adoptsAt present, the caustic sludge treatment is commonly carried out by equipment, such as a packed tower, an impinging stream reactor and the like. After acidification treatment, the COD removal rate of the alkaline residue waste liquid can reach more than 99 percent, and organic sulfide and H2The removal rate of S is more than 99 percent, and the removal rate of volatile phenol is more than 96 percent.
In the step 2, the main component of the acidified petrochemical alkaline residue is Na2CO3And NaHCO3Directly adding the sintered desulfurized ash for re-reaction, wherein the reaction mechanism is as follows:
Na2CO3+CaSO4＝Na2SO4+CaCO3 (13)
Na2CO3+Ca(OH)2＝2NaOH+CaCO3 (14)
NaHCO3+Ca(OH)2＝NaOH+CaCO3+H2O (15)
Na2CO3+CaSO3＝Na2SO3+CaCO3 (16)
after the sintering desulfurization ash treatment, over 97 wt% of carbonate and bicarbonate ions can be removed, and CaCO is used3Discharging the precipitate to obtain a solution mainly containing Na2SO4The regenerated solution is kept still in a separation tank for more than or equal to 3 hours, solid-liquid separation is carried out after layering, and separated CaCO3The precipitate is directly sent to a lime roasting workshop (lime kiln) of a steel plant for calcination, CaO obtained by calcination is used as a sintering flux, and Na obtained by separation2SO4The concentration of the regeneration solution is 5.0-6.0 wt%.
General CO2Sodium carbonate generated by the acidification neutralization process is easy to cause the emulsification phenomenon of a system, so that crude phenol and naphthenic acid in the system cannot be completely separated. The main component is CaSO due to weak acidity of phenol and naphthenic acid4And CaSO3Addition of desulfurized fly ash with Na2CO3Reaction takes place to form CaCO which is easy to precipitate3The method solves the problem that crude phenol and naphthenic acid can not be completely separated, and simultaneously solves the problem of utilization of a desulfurization byproduct, namely solid waste.
It should be noted that, in the step 2, the sintered desulfurized ash according to the present invention may be one or more of the sintered ashes produced by the wet desulfurization process, the semi-dry desulfurization process or the dry desulfurization process. Wherein, the wet desulphurization product mainly contains CaSO4The dry and semi-dry desulfurization products are mainly CaSO4And CaSO3The latter content is relatively high; in addition, the product contains free CaO and Ca (OH)2。
In the above step 3, Na having a concentration of 5.0 to 6.0 wt% obtained by solid-liquid separation is added2SO4The regeneration solution is mixed into a sintering mixer, and the Na is added2SO4The proportion of the addition mass of the regeneration solution to the total mass of the sintering mixture is less than 0.5 percent, and Na2SO4The regeneration solution enters the sintering along with the sintering mixture to be subjected to high-temperature digestion and detoxification, the temperature in the sintering machine is 950-1350 ℃, the neutral oil and organic acidic substances (such as the impure phenol, the mercaptan and the thiophenol) remained in the alkaline residue can completely realize high-temperature detoxification, and no secondary pollution, no odor and no discharged sewage are generated.
It should be noted that the blending mass of the alkaline residue waste liquid is less than 0.5% of the total amount of the sintering mixture, because the Na element contained in the alkaline residue waste liquid affects the quality of the sintered ore and the smooth operation of the blast furnace after being blended into the sintering machine, the single blending proportion should be reduced as much as possible, and the principle of 'small quantity for multiple times' is followed.
In summary, the invention uses untreated petrochemical alkaline residues to be injected into a first reactor, the sintering flue gas introduced through a main sintering flue gas pipeline is injected into the first reactor (for example, a packed tower, an impinging stream reactor and other devices) to acidify the alkaline residue waste liquid, the alkaline residue waste liquid is subjected to neutralization reaction with sulfides, sodium phenolate, sodium naphthenate and residual alkaline solution in the petrochemical alkaline residues, the generated acidified waste gas enters a flue gas treatment system of a sintering machine (the sintering flue gas treatment system originally arranged in a steelmaking enterprise), the obtained acidified waste liquid enters a separation device (a separation tank), sintering desulfurization ash is used for calcification, precipitates generated by calcification are mainly calcium carbonate, after solid-liquid separation, the calcium carbonate is transported to a self-provided lime kiln of the steel enterprise to be calcined, CaO generated by calcination is used as a sintering flux, and the residual separation liquid is blended to an appropriate concentration and then enters a sintering mixer to be calcined with the mixture, the residual neutral oil and organic acidic substances (such as hetero-phenol, mercaptan and thiophenol) in the alkaline residue can be completely detoxified at high temperature.
Compared with the prior art, the waste gas generated by the whole treatment method is directly discharged into the existing sintering treatment system, and a flue gas treatment device is not required to be additionally built, so that the investment is saved; in addition, the treated alkaline residue residual liquid enters a sintering machine in a form of water, and the high-temperature detoxification of toxic substances is realized by utilizing the high-temperature characteristic of the sintering machine, so that the 100% treatment of petrochemical alkaline residue is realized, and the aim of zero emission is realized.
Example 1
The liquid hydrocarbon alkaline residue of a petrochemical enterprise has COD of 4.13 × 105mg/L, volatile phenols of 0.1 wt%, sodium methyl mercaptide of 3.6 wt%, Na2S is 0.2 wt% and pH is 11.67.
The method shown in figure 1 is adopted for treatment, liquid hydrocarbon alkaline residue to be treated is added into a reaction tank, flue gas of a sintering machine is introduced into the reaction tank, the temperature of the alkaline residue in a first reactor (the reaction tank) is adjusted to be 85 ℃ by controlling the flow of the flue gas, the acidification reaction time is controlled to be 100min, sodium naphthenate, sodium phenolate and sodium sulfide in the alkaline residue are converted into sodium carbonate, naphthenic acid and phenol in the acidification process, and hydrogen sulfide is oxidized to generate SO2The gas enters a sintering flue gas treatment device. Adding the acidified alkaline residue into sintered desulfurized ash for calcification treatment, and controlling Na2CO3And CaSO4In a molar ratio of 1: 1.2, the settling time is 3 hours.
The pH value of the alkaline residue after the acidification treatment is 7.9, the removal rate of sulfide is 99.1%, the removal rate of phenols is 96.8%, and the removal rate of COD is 99.2%. Using sintered desulfurized ash to calcify the acidizing fluid, precipitating carbonate with the concentration of more than 96 percent, and finally obtaining Na with the concentration of 5.0 weight percent2SO4Solutions, CaCO produced by calcification3Feeding into a lime kiln for calcination, taking the obtained CaO as a sintering flux, and carrying out solid-liquid separation on the residual Na2SO4The solution is prepared to proper concentration and then mixed with the mixtureAfter the mixture is mixed, the mixture enters a sintering machine for high-temperature detoxification and digestion, and 100% utilization of the residual separation liquid is realized.
Example 2
The liquid hydrocarbon alkaline residue of a petrochemical enterprise has COD of 4.13 × 105mg/L, volatile phenols of 0.1 wt%, sodium methyl mercaptide of 3.6 wt%, Na2S is 0.2 wt% and pH is 11.67.
The method shown in figure 1 is adopted for treatment, liquid hydrocarbon alkaline residue to be treated is added into a reaction tank, flue gas of a sintering machine is introduced into a first reactor (the reaction tank), the temperature of the alkaline residue in the reaction tank is adjusted to be 90 ℃ by controlling the flow of the flue gas, the acidification reaction time is controlled to be 110min, sodium naphthenate, sodium phenolate and sodium sulfide in the alkaline residue are converted into sodium carbonate, naphthenic acid and phenol in the acidification process, and hydrogen sulfide is oxidized to generate SO2The gas enters a sintering flue gas treatment device. Adding the acidified alkaline residue into sintered desulfurized ash for calcification treatment, and controlling Na2CO3And CaSO4In a molar ratio of 1: 1.5, the settling time is 4 hours.
The pH value of the alkaline residue after the acidification treatment is 7.5, the removal rate of sulfide is 99.3%, the removal rate of phenols is 97.2%, and the removal rate of COD is 99.5%. After the acidizing fluid is calcified by using sintered desulfurized ash, carbonate with the concentration of more than 97 percent is precipitated, and finally Na with the concentration of 5.8 weight percent is obtained2SO4Solutions, CaCO produced by calcification3Feeding into a lime kiln for calcination, taking the obtained CaO as a sintering flux, and carrying out solid-liquid separation on the residual Na2SO4After the solution is prepared to the proper concentration, the solution is mixed with the sintering mixture and then enters a sintering machine for high-temperature detoxification and digestion, so that 100% utilization of the residual separation liquid is realized.
Example 3
The liquid hydrocarbon alkaline residue of a petrochemical enterprise has COD of 4.13 × 105mg/L, volatile phenols of 0.1 wt%, sodium methyl mercaptide of 3.6 wt%, Na2S is 0.2 wt% and pH is 11.67.
The method shown in figure 1 of the invention is adopted for treatment, liquid hydrocarbon alkaline residue to be treated is added into a first reactor (reaction tank), flue gas of a sintering machine is introduced into the reaction tank, and the reaction is adjusted by controlling the flow of the flue gasThe temperature of the alkaline residue in the tank is 95 ℃, the acidification reaction time is controlled to be 120min, sodium naphthenate, sodium phenolate and sodium sulfide in the alkaline residue are converted into sodium carbonate, naphthenic acid and phenol in the acidification process, and hydrogen sulfide is oxidized to generate SO2The gas enters a sintering flue gas treatment device. Adding the acidified alkaline residue into sintered desulfurized ash for calcification treatment, and controlling Na2CO3And CaSO4In a molar ratio of 1: 1.8, the settling time is 5 hours.
The pH value of the alkaline residue after the acidification treatment is 7.2, the removal rate of sulfide is 99.8%, the removal rate of phenols is 98.6%, and the removal rate of COD is 99.8%. After the acidizing fluid is calcified by using sintered desulfurized ash, more than 98 percent of carbonate is precipitated, and finally Na with the concentration of 5.3 weight percent is obtained2SO4Solutions, CaCO produced by calcification3Feeding into a lime kiln for calcination, taking the obtained CaO as a sintering flux, and carrying out solid-liquid separation on the residual Na2SO4After the solution is prepared to the proper concentration, the solution is mixed with the sintering mixture and then enters a sintering machine for high-temperature detoxification and digestion, so that 100% utilization of the residual separation liquid is realized.
Compared with the prior art, the invention introduces the sintering process of the steel industry into the harmless treatment process of the petrochemical alkaline residue, and embeds the treatment of the petrochemical alkaline residue in the existing sintering process, and the design idea of the invention is as follows: three main treatment parts of 'sintering flue gas acidification-desulfurization ash calcification-sintering machine detoxification'. The waste flue gas and the desulfurized ash generated in the sintering process are used as raw materials for treating the petrochemical alkaline residue, so that the utilization of sintering solid waste is realized, and the purpose of treating the petrochemical alkaline residue is achieved. Waste gas generated in the whole process is directly discharged into the existing sintering treatment system, and a flue gas treatment device does not need to be additionally built, so that the investment is saved; in addition, the treated alkaline residue residual liquid enters a sintering machine in a form of water, and high-temperature detoxification of toxic substances is realized by the high-temperature characteristic of the alkaline residue residual liquid, so that the aims of 100% treatment and zero emission of petrochemical alkaline residue are fulfilled.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.

Claims (9)

1. The system for treating petrochemical alkaline residues is characterized by comprising a sintering flue gas acidification unit, a desulfurization ash calcification unit and a sintering machine detoxification unit which are sequentially connected;
the sintering flue gas acidification unit is communicated with a sintering flue gas main pipeline, and the sintering flue gas enters the sintering flue gas acidification unit through the sintering flue gas main pipeline; the sintering flue gas acidification unit is also communicated with a sintering flue gas treatment system, the petrochemical alkaline residues are introduced into the sintering flue gas acidification unit, acidified tail gas generated after the petrochemical alkaline residues are acidified is introduced into the sintering flue gas treatment system, and the generated acidified waste liquid enters the desulfurization ash calcification unit;
introducing desulfurized ash generated in the sintering process into acidified waste liquid in a desulfurized ash calcification unit for calcification reaction, then carrying out solid-liquid separation on the obtained calcification product to obtain solid precipitate and alkali residue waste liquid, sending the solid precipitate into a lime kiln, and then sending the alkali residue liquid into a detoxification unit of a sintering machine after batching;
the sintering machine detoxification unit is used for carrying out high-temperature detoxification on residual neutral oil and organic acidic substances in the alkaline residue liquid;
the petrochemical alkaline residue comprises pre-alkaline washing alkaline residue obtained by desulfurizing and dephenolizing gasoline, naphtha or aromatic hydrocarbon; and/or liquefied gas desulfurization pre-caustic washing caustic sludge; and/or catalyst-containing caustic sludge obtained by desulfurizing gasoline, naphtha, aromatic hydrocarbon or liquefied gas; and/or alkaline residue waste liquid generated in the process of alkaline washing and refining catalytic gasoline and catalytic diesel oil;
the sintering flue gas contains CO2、SO2And O2Three smoke components.
2. The system for treating petrochemical alkaline residues according to claim 1, wherein the sintering flue gas acidification unit comprises a first reactor;
the desulfurization ash calcification unit comprises a second reactor and a separation tank;
the sintering machine detoxification unit comprises a sintering mixer and a sintering machine.
3. A petrochemical alkaline residue processing method, characterized in that the alkaline residue processing system of claim 2 is adopted, and the processing method comprises the following steps:
step 1, adding liquid petrochemical alkaline residues to be treated into a first reactor, and then introducing sintering flue gas into the first reactor through a main sintering flue gas pipeline for acidification treatment; obtaining acidified tail gas and acidified waste liquid;
step 2, adding the acidified waste liquid into a second reactor, adding sintered desulfurized ash into the second reactor for re-reaction, introducing the solution obtained by re-reaction into a separation tank, and performing solid-liquid separation to obtain alkali residue waste liquid Na2SO4Regenerating the solution, and separating the obtained solid precipitate into calcium carbonate precipitate;
step 3, adding Na2SO4The regeneration solution is mixed into a sintering mixer and enters a sintering machine along with the sintering mixture for roasting, so that high-temperature digestion and detoxification are realized.
4. The process for the treatment of petrochemical alkaline residues according to claim 3, wherein in said step 1, the pressure of said acidification treatment is equal to the pressure of sintering fumes; the acidification treatment temperature is 85-95 ℃; the acidification treatment time is 70-120 min; the heat source for heating the petrochemical alkaline residue is provided by the waste heat of the sintering flue gas.
5. The method for treating petrochemical alkaline residue according to claim 4, wherein the acidified waste liquid after acidification in step 1 contains Na2CO3And NaHCO3。
6. The method for treating petrochemical alkaline residue according to claim 3, wherein in the step 2, the mass ratio of the acidified waste liquid to the sintered desulfurized ash is 1: 1.0-1.8.
7. The method for treating petrochemical alkaline residue according to claim 3, wherein in the step 2, the reaction product obtained by the re-reaction is kept standing in a separation tank for at least 3 hours, solid-liquid separation is performed after layering, and the separated Na is obtained2SO4The concentration of the regeneration solution is 5.0-6.0wt%。
8. The method for treating petrochemical alkaline residue according to claim 7, wherein in the step 2, calcium carbonate precipitate obtained by solid-liquid separation is sent to a lime kiln for calcination, and CaO generated by calcination is used as a sintering flux.
9. The method for treating petrochemical alkaline residue according to claim 8, wherein in the step 3, the Na is added2SO4The solution is mixed into the sintering mixture according to a certain proportion; the Na is2SO4The ratio of the addition mass of the solution to the total mass of the sintering mixture is less than 0.5 percent;
the temperature in the sintering machine is 950-1350 ℃.
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CN112225239A (en) * 2020-09-10 2021-01-15 河南华慧有色工程设计有限公司 Method for producing and co-processing flue gas desulfurization waste liquid by sodium-alkali method through aluminum oxide

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007175675A (en) * 2005-12-28 2007-07-12 Shionome Block Kk Detoxification process of composite industrial waste
CN202744500U (en) * 2012-05-30 2013-02-20 中国石油化工股份有限公司 Treatment device for light oil deodorizing caustic sludge
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