CN115155311A - Regeneration process of desulfurization waste alkali - Google Patents
Regeneration process of desulfurization waste alkali Download PDFInfo
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Abstract
The invention discloses a process for regenerating desulfurized waste alkali, wherein the waste alkali enters an extraction purification unit to be fully mixed with an organic extraction solvent, organic oil substances dissolved in the waste alkali enter an organic extraction phase, an oil phase separated from the extraction unit is an extracted oil-containing extractant, a separated water phase is deoiled waste alkali, the deoiled waste alkali enters a desulfurized waste alkali regeneration unit, and the desulfurized waste alkali regeneration agent and Na in the waste alkali are utilized 2 Metathesis reaction between S to Na 2 S is converted into NaOH to generate corresponding metal sulfide precipitate, after the double decomposition reaction is finished, the alkali waste regeneration unit is a mixture consisting of original residual alkali, regenerated alkali and metal sulfide, and the cationic-anionic-amphoteric polyacrylamide flocculant is added into the mixed system to perform flocculation precipitation on various solid impurities in the system, particularly on the metal sulfide generated in the alkali waste regeneration link.
Description
Technical Field
The invention relates to the technical field of petrochemical industry environment-friendly treatment, and particularly provides a regeneration treatment process and a resource utilization treatment method of desulfurization waste alkali.
Background
The tail gas of hydrogen sulfide with a certain concentration is generated in the production processes of cracking gas or gasoline and diesel oil catalytic hydrogenation of an oil refinery, ethylene and other industries, and the hydrogen sulfide cannot be directly discharged to the atmosphere due to high toxicity, so that alkali liquor sodium hydroxide or sodium carbonate is usually adopted for absorption treatment, namely, the hydrogen sulfide is converted into sodium sulfide in a chemical absorption mode to be removed from oil gas. The main components of the desulfurization waste alkali are sodium sulfide, sodium carbonate, sodium hydroxide, organic matters, suspended matters, a small amount of mercaptan thioether and the like, and the desulfurization waste alkali contains a large amount of Chemical Oxygen Demand (COD) and has strong odor and pungent odor and cannot be directly sent to a sewage treatment plant for treatment.
At present, most of domestic enterprises adopt a high-temperature air oxidation technology to convert sodium sulfide into sodium sulfate, part of hydrocarbon substances in a solution are discharged along with tail gas, the adopted equipment is a sieve plate type or filler type oxidation reaction device, a heating medium is water vapor, air and water vapor mixed gas enters an oxidation reactor from the bottom of a tower in a parallel flow mode with waste alkali liquor, the oxidized alkali liquor is injected with sulfuric acid for neutralization treatment, and finally the oxidized alkali liquor is discharged into a sewage treatment plant, and air containing the hydrocarbon substances is discharged from the top of the tower. Although the wet oxidation technology at high temperature and high pressure can solve the problem of COD, there still exist some problems, mainly including the following points: (1) The high-temperature high-pressure wet oxidation technology has complex flow and very high requirements on equipment materials, and in a high-temperature part, hastelloy or titanium alloy materials with high corrosion resistance are used, so that the investment of treatment equipment is too high; (2) The tail gas of the tower top air has large smell, the concentration of volatile organic compounds is high, and the problem of standard exceeding emission exists; (3) the high-temperature and high-pressure operation condition has greater safety risk; (4) The subsequent addition of sulfuric acid for neutralization increases the operating cost, so that the discharged water has high salt content and high treatment difficulty; (5) The high temperature and high pressure require high temperature and high pressure, which causes high power consumption and high steam consumption, and causes over high energy consumption.
At present, the foreign alkali waste regeneration treatment mainly comprises the following two treatment methods: the first is fiber membrane extraction-oxidation regeneration technology of HOUD company in America, and the fiber membrane extraction-oxidation regeneration technology of spent caustic soda of HOUD, and the fiber membrane regeneration spent caustic soda has good effect, but has huge treatment equipment investment, high maintenance cost and poor economic benefit; the second one is the MEROX technology of U.S. UOP company, i.e. adopting catalytic alkali extraction-oxidation regeneration technology, the one-time investment and equipment maintenance cost of which are slightly lower, and it is the MEROX spent alkali desulfurization alkali regeneration technology developed in 1958 by U.S. UOP company, it extracts mercaptan with alkaline liquor to convert it into sodium mercaptide, catalytically oxidizes sodium mercaptide into disulfide, recovers polysulfide through three-phase separation, sodium sulfide is oxidized into sodium thiosulfate and sodium sulfite, the tail gas is incinerated and discharged, the method needs incineration treatment, the tail gas produced by combustion contains a large amount of SO 2 Harmful gas, and is easy to cause secondary pollution to the environment. Therefore, a new method for regenerating and treating the waste alkali is urgently needed in the technical field of treating the desulfurization waste alkali, so as to solve the problems of high investment cost, high operating cost, high safety risk and the like in the prior art.
Disclosure of Invention
The invention aims to provide a regeneration process of desulfurized spent caustic to solve the problems in the background technology.
The purpose of the invention is realized by the following technical scheme: a regeneration process of desulfurized spent caustic comprises the following steps:
firstly, the waste alkali liquor enters an extraction purification unit and is fully mixed with an organic extraction solvent;
the desulfurized waste alkali enters an extraction operation unit, is mixed and contacted with an organic solvent extracting agent, organic oil dissolved in the waste alkali liquor enters an organic phase, the organic extracting agent containing organic oil substances is separated from an oil phase of the extraction unit after extraction and separation, and the desulfurized waste alkali liquor after oil removal is separated from a water phase, so that the separation of alkali and oil is realized;
step two, organic oil substances dissolved in the waste alkali liquor enter an organic extraction phase, an oil phase separated from an extraction unit is an extracted oil-containing extractant, and a separated water phase is the deoiled waste alkali liquor;
the organic solvent extraction unit transfers the colored compounds in the waste alkali liquor into an oil phase while separating the waste alkali from the oil;
thirdly, the deoiled waste alkali liquor enters a desulfurization waste alkali liquor regeneration unit, and a desulfurization waste alkali regeneration agent and Na in the waste alkali liquor are utilized 2 Metathesis reaction between S to Na 2 S is converted into NaOH and corresponding metal sulfide precipitate is generated;
the deoiled desulfurized waste alkali liquid enters a desulfurized waste alkali liquid regeneration operation unit to react with a regenerant to enable Na 2 S is converted into NaOH and corresponding metal sulfide precipitate, so that the regeneration of the waste alkali is realized; na (Na) 2 NaOH and Na in desulfurization waste alkali in the process of converting S into NaOH 2 CO 3 The two effective alkali components are completely retained in the regenerated alkali;
fourthly, after the double decomposition reaction is finished, the waste alkali regeneration unit is a mixture consisting of original residual alkali, regenerated alkali and metal sulfide;
fifthly, adding a cationic-anionic polyacrylamide flocculant into the mixed system obtained in the fourth step to flocculate and settle various solid impurities in the system, wherein metal sulfides generated in the waste alkali regeneration link are subjected to flocculation and settling;
sixthly, the mixture from the waste alkali regeneration unit enters a filtering unit, and purified regenerated alkali liquor and metal sulfide are obtained after filtering;
and seventhly, removing the coexisting organic and inorganic impurities from the regenerated alkali liquor in the sixth step through the steps, recovering the concentration, improving the purity and reusing the regenerated alkali liquor in the desulfurization treatment.
Further, the metal sulfide separated by the filtering unit is sintered at high temperature to obtain corresponding metal oxide MeO, which can be used as a desulfurizing waste alkali solution regenerant again;
the filtering unit adopts one of a gravity filter, a vacuum filter or a pressure filter;
before the filtration process, the amphoteric polyacrylamide flocculant with the use mass concentration of 0.05-0.2mg/L is added into the desulfurization waste alkali liquor.
And further, the oil-containing extractant separated from the oil phase of the extraction unit enters an extractant regeneration process unit to be distilled at normal pressure, the organic solvent extractant is distilled for recycling, and the high-boiling-point mixed oil is left in the high-temperature kettle and is used as an oil refining raw material.
Further, an organic solvent extracting agent in the treatment process of extracting the organic oil substances in the desulfurized spent caustic soda by using the organic solvent is toluene, xylene, phosphate esters, alkyl ketones, diesel oil, kerosene, naphtha or gasoline which is used as the organic solvent extracting agent.
Further, the organic solvent extraction agent in the treatment process of extracting the organic oil substances in the desulfurized waste alkali by using the organic solvent is naphtha and gasoline.
Further, the desulfurization waste alkali regenerant is calcined magnesium oxide, calcined calcium oxide, calcined iron, calcined carbon steel scraps, calcined stainless steel scraps, calcined copper oxide, calcined zinc oxide, calcined iron oxide ore, calcined magnetite ore, calcined manganese iron ore, pyrolusite and casting molten steel dross.
Further, the desulfurization waste alkali regenerant is calcined carbon steel scraps, calcined copper scraps, calcined iron oxide ore, calcined magnetite ore, calcined manganese iron ore, calcined pyrolusite and casting molten steel dross.
Further, the mass ratio of the desulfurization waste alkali regenerant to the desulfurization waste alkali liquor is (1);
the desulfurization waste alkali regenerant adopts powder or particles, the mesh number of the powder is 10-80 meshes, and the particles are 1mm multiplied by 1mm to 10mm multiplied by 10mcm.
The application of the regeneration treatment of the desulfurization waste alkali comprises the steps of respectively taking magnetite ore powder, iron oxide ore powder and soft manganese ore powder, calcining the magnetite ore powder, the iron oxide ore powder and the soft manganese ore powder in a high-temperature resistance furnace at 1200 ℃ for 1 hour, and cooling to respectively obtain a desulfurization waste alkali magnetite ore regenerant, an iron oxide ore regenerant and a soft manganese ore regenerant;
adding 100kg of the desulfurization waste alkali magnetite ore regenerant into a 3t vertical regeneration kettle, and adding 2t of deoiled Na 2 And (3) starting a stirrer, heating to 80 ℃, keeping the temperature for 1h, and filtering to obtain regenerated alkali liquor.
The regeneration treatment application of the desulfurization waste alkali comprises the steps of collecting scum of casting molten steel, and crushing to obtain a scum regenerant of the desulfurization waste alkali casting molten steel;
100kg of the regenerating agent for the scum of the desulfurized waste alkali casting molten steel is added into a 3t vertical regeneration kettle, and 2t of deoiled Na is added 2 And (3) starting a stirrer, heating to 80 ℃, keeping the temperature for 1h, and filtering to obtain regenerated alkali liquor, wherein the content of S in the desulfurized waste alkali liquor is 2.52%.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a novel regeneration treatment technology of sulfur-containing waste alkali, which aims to solve the problems of high investment cost, high safety risk, excessive COD (chemical oxygen demand) of neutralized wastewater, high running cost and the like in the conventional treatment technology; the method can convert the dangerous waste component sodium sulfide in the desulfurized waste alkali liquor into useful sodium hydroxide, so that the concentration of the sodium hydroxide in the alkali liquor is recovered and can be recycled, and the resource utilization of the dangerous waste is realized;
the process is simple, the equipment one-time investment and maintenance cost are low, and the operability is strong, the process realizes the regeneration of the desulfurized waste alkali liquor, the alkalinity and the chromaticity of the regenerated alkali liquor meet the use requirements, the process is energy-saving and environment-friendly, no industrial wastewater is discharged except for a small amount of oil, and tail gas incineration is not needed;
the waste alkali regenerant can be used for removing Na in desulfurized waste alkali 2 S is converted into NaOH; naOH is reused for desulfurization and changed into Na 2 S; regenerating agent and then adding Na 2 S is converted into NaOH, so that a closed loop cycle is formed;
the regeneration of the waste alkali regenerant is also a closed-loop circulation: regenerants MeO and Na 2 S acts to generate NaOH and MeS; the MeS is regenerated by calcination and converted back to MeO; the MeO reacts with NaOH to generate NaOH and MeS again, thus forming closed loop circulation;
compared with the technology for treating the waste caustic sludge by using a high-temperature high-pressure wet oxidation technology, the invention does not need high-temperature high-pressure equipment, and has less one-time investment; the operation cost is low because high-temperature high-pressure steam is not needed; the operation risk is reduced because high-temperature and high-pressure operation is not carried out; due to all Na 2 The S is converted into useful NaOH, the consumption of sulfuric acid for neutralization is not needed, desalination and wastewater treatment are not needed, and the economic benefit and the environmental benefit are good.
Compared with the waste alkali regeneration treatment technology in the prior art, the invention has the following advantages: (1) reduced desulfurization and good economic benefit: the invention makes all Na in the waste alkali 2 S is converted into useful NaOH instead of sodium thiosulfate and sodium sulfite of UOP company, so that the method does not need subsequent desalination and water discharge treatment, and has better economic benefit; (2) COD reduction: the invention relates to a waste alkali regenerant and Na 2 The newly generated metal sulfide in the S reaction has large specific surface area and strong adsorption capacity, can adsorb a certain amount of organic compounds, and realizes the effects of alkali regeneration and COD reduction; (3) reducing the salt content: in the invention, na 2 The S is converted to NaOH, instead of the usual sodium thiosulfate and sodium sulfite, which remains in the lye. Therefore, the regenerated alkali obtained by treating the waste alkali by the method has lower salt content and COD; (4) the alkali recovery rate is high: the UOP spent caustic desulfurization process uses a large amount of acid to neutralize and oxidize Na 2 S and sodium mercaptide are converted into hydrogen sulfide and the resulting sulfide is incineratedAnd (3) hydrogen. Such a desulfurization process would consume all of the NaOH and sodium carbonate. The invention is used for the Na in the waste alkali 2 S is completely converted into NaOH without other losses, so the recovery rate is high; (5) low emission: in the waste alkali treatment technology, except a small amount of oil to be treated, almost no other discharge exists, and the treatment principle of solid waste reduction is met.
Drawings
FIG. 1 is a schematic flow diagram of a regeneration process framework of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
As shown in fig. 1, a process for regenerating desulfurized spent caustic comprises the following steps:
firstly, the waste alkali liquor enters an extraction purification unit and is fully mixed with an organic extraction solvent;
the desulfurized waste alkali enters an extraction operation unit, is mixed and contacted with an organic solvent extracting agent, organic oil dissolved in the waste alkali liquor enters an organic phase, the organic extracting agent containing organic oil substances is separated from an oil phase of the extraction unit after extraction and separation, and the desulfurized waste alkali liquor after oil removal is separated from a water phase, so that the separation of alkali and oil is realized;
step two, organic oil substances dissolved in the waste alkali liquor enter an organic extraction phase, an oil phase separated from an extraction unit is an extracted oil-containing extractant, and a separated water phase is the deoiled waste alkali liquor;
the organic solvent extraction unit transfers the colored compounds in the waste alkali liquor into an oil phase while separating the waste alkali from the oil;
thirdly, the deoiled waste alkali liquor enters a desulfurization waste alkali liquor regeneration unit, and a desulfurization waste alkali regeneration agent and Na in the waste alkali liquor are utilized 2 Metathesis reaction between S to Na 2 S is converted into NaOH to generate corresponding metal sulfide precipitate;
the deoiled desulfurized waste alkali liquid enters a desulfurized waste alkali liquid regeneration operation unit to react with a regenerant to enable Na 2 S is converted into NaOH and corresponding metal sulfide precipitates, so that the regeneration of the waste alkali is realized; na (Na) 2 In the process of converting S into NaOH, naOH and Na in the desulfurization waste alkali 2 CO 3 The two effective alkali components are completely retained in the regenerated alkali;
fourthly, after the double decomposition reaction is finished, the waste alkali regeneration unit is a mixture consisting of original residual alkali, regenerated alkali and metal sulfide;
fifthly, adding a cationic-anionic polyacrylamide flocculant into the mixed system obtained in the fourth step to flocculate and settle various solid impurities in the system, wherein metal sulfides generated in the waste alkali regeneration link are subjected to flocculation and settling;
sixthly, enabling the mixture from the waste alkali regeneration unit to enter a filtering unit, and filtering to respectively obtain purified regenerated alkali liquor and metal sulfide;
and seventhly, removing coexisting organic and inorganic impurities from the regenerated alkali liquor in the sixth step through the steps, recovering the concentration, improving the purity and reusing the regenerated alkali liquor in the desulfurization treatment.
As a preferred embodiment, the metal sulfide separated by the filtering unit is sintered at high temperature to obtain corresponding metal oxide MeO, which can be reused as the regenerant of the desulfurization waste lye;
the filtering unit adopts one of a gravity filter, a vacuum filter or a pressure filter;
before the filtration process, the amphoteric polyacrylamide flocculant with the mass concentration of 0.05-0.2mg/L is added into the desulfurized waste alkali liquor.
As a preferable example, the oil-containing extractant separated from the oil phase of the extraction unit enters an extractant regeneration process unit to be subjected to atmospheric distillation, the organic solvent extractant is distilled for recycling, and the high-boiling-point mixed oil is remained in the high-temperature kettle and is used as an oil refining raw material.
As a preferable example, the organic solvent extracting agent in the treatment process for extracting the organic oil substances in the desulfurized spent caustic soda by using the organic solvent is toluene, xylene, phosphate esters, alkyl ketones, diesel oil, kerosene, naphtha or gasoline as the organic solvent extracting agent.
As a preferred example, the organic solvent extracting agent in the treatment process for extracting the organic oil substances in the desulfurized spent caustic by using the organic solvent is naphtha and gasoline.
As a preferred example, the desulfurization waste alkali regenerant is calcined magnesia, calcined calcium oxide, calcined iron, calcined carbon steel scrap, calcined stainless steel scrap, calcined copper oxide, calcined zinc oxide, calcined iron oxide ore, calcined magnetite ore, calcined manganese iron ore, pyrolusite ore, molten casting steel dross.
As a preferred example, the desulfurization waste alkali regenerant is calcined carbon steel scrap, calcined copper scrap, calcined iron oxide ore, calcined magnetite ore, calcined manganese iron ore, calcined pyrolusite and molten steel dross.
As a preferable embodiment, the mass ratio of the desulfurization waste alkali regenerant to the desulfurization waste alkali liquid is 1;
the desulfurization waste alkali regenerant adopts powder or particles, the mesh number of the powder is 10-80 meshes, and the particles are 1mm multiplied by 1mm to 10mm multiplied by 10mcm.
The application of the regeneration treatment of the desulfurization waste alkali comprises the steps of respectively taking magnetite ore powder, iron oxide ore powder and soft manganese ore powder, calcining for 1h at 1200 ℃ in a high-temperature resistance furnace, and cooling to respectively obtain a desulfurization waste alkali magnetite ore regenerant, an iron oxide ore regenerant and a soft manganese ore regenerant;
adding 100kg of the desulfurization waste alkali magnetite ore regenerant into a 3t vertical regeneration kettle, and adding 2t of deoiled Na 2 And (3) starting a stirrer, heating to 80 ℃, keeping the temperature for 1h, and filtering to obtain regenerated alkali liquor.
The regeneration treatment application of the desulfurization waste alkali comprises the steps of collecting scum of casting molten steel, and crushing to obtain a regenerant of the scum of the desulfurization waste alkali casting molten steel;
100kg of the regenerating agent for the desulfurized spent caustic casting molten steel scum is added into a 3t vertical regeneration kettle, and 2t of deoiled Na is added 2 And (3) starting a stirrer, heating to 80 ℃, keeping the temperature for 1h, and filtering to obtain regenerated alkali liquor, wherein the content of S in the desulfurized waste alkali liquor is 2.52%.
The invention mainly aims to solve the technical defect problem of the existing high-temperature high-pressure wet oxidation technology for treating the desulfurization waste alkali. The invention aims to solve the technical problem of providing a regeneration process of the desulfurization waste lye, which has the advantages of simple treatment process, lower equipment one-time investment and maintenance cost and strong operability, realizes the regeneration of the desulfurization waste lye, ensures that the alkalinity and the chromaticity of the regenerated lye meet the use requirements, saves energy, protects environment, realizes zero emission of industrial wastewater except for the generation of a small amount of oil, and does not need tail gas incineration.
The technical scheme adopted by the invention is as follows: the method comprises a process unit for extracting organic oil substances in the desulfurization waste alkali by using an organic solvent, a desulfurization waste alkali regeneration process unit, a filtration process unit, a waste alkali regenerant regeneration process unit and an extractant regeneration process unit, wherein a closed-loop system is formed by combining and processing the process units.
The invention provides a regeneration treatment process of desulfurization waste alkali, which comprises the following regeneration process sequence:
the waste alkali liquor (1) enters an extraction purification unit to be fully mixed with an organic extraction solvent, organic oil substances dissolved in the waste alkali liquor (1) enter an organic extraction phase, an oil phase separated from the extraction unit is an extracted oil-containing extraction agent (2), and a separated water phase is an deoiled waste alkali liquor (3).
The deoiled waste alkali liquor (3) enters a desulfuration waste alkali liquor regeneration unit, and the desulfuration waste alkali regeneration agent (4) and Na in the waste alkali liquor are utilized 2 Metathesis reaction between S to Na 2 S is converted into NaOH and corresponding metal sulfide precipitate is generated. After the double decomposition reaction is finished, a mixture (5) consisting of original residual alkali, regenerated alkali and metal sulfide is added into an alkali waste regeneration unit, and an amphoteric polyacrylamide flocculant (6) is added into the mixed system to treat various solid impurities in the system, particularly the alkali wasteAnd performing flocculation sedimentation on the metal sulfide generated in the production link. And (3) feeding the mixture (5) from the waste alkali regeneration unit into a filtering unit, and filtering to respectively obtain purified regenerated alkali liquor (7) and metal sulfide (8). The regenerated alkali liquor (7) removes the coexisting organic and inorganic impurities through the above steps, the concentration is recovered, the purity is improved, and the regenerated alkali liquor can be reused for desulfurization treatment.
The metal sulfide (8) separated from the filtering unit is sintered at high temperature to obtain corresponding metal oxide MeO which can be reused as the regenerant of the desulfurization waste lye.
And (3) feeding the oil-containing extractant (2) separated from the oil phase of the extraction unit into an extractant regeneration process unit for atmospheric distillation, distilling out the organic solvent extractant for recycling, and taking high-boiling-point mixed oil as an oil refining raw material as high-temperature kettle residue.
(1) Process unit for extracting organic oil substances in desulfurization waste alkali by organic solvent
The separation and purification operation of separating different components of a mixture by utilizing the obviously different solubility of the different components in two solvents which are not mutually soluble in a mixed substance system is utilized, so that a method for transferring solute substances from one solvent to the other solvent is a technology for realizing separation among substances with different properties and is also a common method for substance purification.
In the invention, the desulfurized waste alkali enters an extraction operation unit and is mixed and contacted with an organic solvent extractant, organic oil dissolved in the waste alkali liquor enters an organic phase, the organic extractant containing organic oil substances is separated from an oil phase of the extraction unit after extraction and separation, and the desulfurized waste alkali liquor after oil removal is separated from a water phase, thereby realizing the separation of alkali and oil. The organic solvent extraction unit can separate the waste alkali from the oil, and simultaneously transfer colored compounds in the waste alkali to an oil phase, thereby remarkably reducing the chromaticity of the regenerated alkali.
(2) Desulfurization waste lye regeneration process unit
The deoiled desulfurized waste lye enters a desulfurized waste lye regeneration operation unit to react with the regenerant therein to make Na react 2 S is converted into NaOH and corresponding metal sulfide precipitate to realizeAnd (4) regenerating the waste alkali. Na (Na) 2 In the process of converting S into NaOH, naOH and Na originally remained in the desulfurization waste alkali 2 CO 3 The two effective alkali components are hardly lost, and are also not lost in a later process unit, all the effective alkali components are retained in regenerated alkali, and the recovery rate is close to 100 percent.
The regeneration treatment process principle of the desulfurization waste alkali liquor is as follows:
Na 2 S+MeO+H 2 O→2NaOH+MeS (1)
wherein Me may be Fe 2+ 、Fe 3+ 、Zn 2+ 、Mn 2+ 、Mn 4+ 、Cu 2+ 、Cu + And the like.
The desulfurization waste alkali regeneration treatment principle is specifically exemplified by regeneration:
MnO 2 +2Na 2 S+2H 2 O＝MnS 2 +4NaOH (1)
Fe 3 O 4 +4Na 2 S+4H 2 O＝Fe 2 S 3 +FeS+4NaOH (2)
Na 2 S+CuO+H 2 O→2NaOH+CuS (2)
Na 2 S+FeO+H 2 O→4NaOH+2FeS (3)
Na 2 S+ZnO+H 2 O→2NaOH+ZnS (4)
Na 2 S+Cu 2 O+H 2 O→2NaOH+Cu 2 S (5)
(3) Filtration process unit
And filtering the mixture of the regenerated alkali liquor and the metal sulfide, and separating the regenerated alkali liquor from the metal sulfide precipitate to obtain the regenerated alkali liquor. The concentration of the regenerated alkali liquor which is subjected to oil removal, COD removal, color removal, impurity removal and regeneration purification is recovered, and impurities are removed, so that the regenerated alkali liquor can be recycled by a desulfurization treatment process.
(4) Regeneration process unit of waste alkali regenerant
The metal-based spent caustic soda regenerant is an oxide layer formed on the surface of metal under a high-temperature calcination condition, the metal oxide layer is an effective component of the regenerant, and the oxide layer can be gradually dissolved away after a period of spent caustic soda regeneration reaction consumption, so that the metal-based spent caustic soda regenerant needs to be calcined, oxidized and regenerated again. In addition, both metal-based and metal oxide-based regenerants may have deposits or dirt adhering to their surfaces over time and also require high-temperature calcination for removal. Therefore, after a certain period of time, the spent caustic soda regenerant needs to be calcined to regenerate or expose the oxide surface.
(5) Extraction agent regeneration process unit
And the extracted organic solvent rich solution separated from the oil phase of the extraction unit enters an extraction agent normal pressure distillation regeneration unit for distillation, and separation and purification are realized by utilizing oil substances with the boiling point of the extraction agent lower than that of the extraction agent. The distilled and purified organic solvent extractant can be recycled, and high-boiling-point oils are remained in the high-temperature kettle and are used as oil refining raw materials.
(6) Regeneration treatment unit for regenerant
The metal sulfide from the filtering unit is sintered at high temperature to obtain corresponding metal oxide, which can be reused as the regenerant of the desulfurization waste lye.
The regeneration principle of the metal sulfide is high-temperature oxidation:
2MeS+3O 2 →2MeO+2SO 2
the working principle of the invention can be briefly described as follows: the desulfurization waste alkali liquor firstly enters an extraction treatment process unit, organic oil substances in the desulfurization waste alkali are extracted by an organic solvent by utilizing the extraction principle, the organic oil substances in the waste alkali liquor are extracted to an oil phase, and the organic oil substances are removed from the desulfurization waste alkali liquor; then, by a desulfurization waste alkali solution regeneration process, a desulfurization waste alkali regeneration agent and Na in the waste alkali solution are utilized 2 Reaction between S to Na 2 S is converted into NaOH and corresponding metal sulfide precipitate is generated, and the regeneration of the waste alkali is completed; finally, the regenerated alkali liquor is separated from the metal sulfide and the like through a filtering process. The regenerated alkali liquor removes coexisting organic and inorganic impurities through the above operations, the concentration is recovered, the purity is improved, and the aim of regenerating the desulfurization waste alkali is fulfilled.
The above treatment processes are repeated circularly, and the desulfurized waste alkali liquor can also be regenerated circularly.
The organic solvent extractant in the treatment process for extracting the organic oil substances in the desulfurized waste alkali by using the organic solvent can be toluene, xylene, phosphates, alkyl ketones, diesel oil, kerosene, naphtha or gasoline which is used as the organic solvent extractant. Preferred classes of organic solvents are naphtha and gasoline.
In the process for treating organic oil in organic solvent extraction desulfurization waste alkali, the extraction process can adopt equipment such as a centrifugal extractor, a mixing clarifier, a filling tower, a pulsation tower, a vibration plate tower, a fiber membrane extraction and the like. Preferably, the extraction process is a centrifugal extraction process. In order to accelerate the mass transfer rate of extraction and improve the extraction efficiency, the desulfurized waste alkali liquor needs to be heated, and the heating temperature can be between 40 and 80 ℃, and preferably between 50 and 60 ℃.
The desulfurization waste alkali regeneration process equipment can adopt an anchor stirring paddle vertical carbon steel reaction kettle, the upper part of the kettle is provided with a desulfurization waste alkali liquid feeding port, and the feeding port is connected with a discharge port of a centrifugal extractor. The lower end is provided with a discharge hole which is connected with a feed inlet of the filter; a stainless steel screen is arranged above a discharge port of the vertical carbon steel kettle, and the spent caustic soda regenerant (which can not be used when being powdery if a large-particle size regenerant is adopted) is stacked on the screen and directly contacted with the desulfurization spent caustic; the jacket of the vertical carbon steel kettle is provided with an electric heating system for heating the regeneration process of the desulfurization waste alkali liquor, the regeneration reaction temperature can be controlled between 50 ℃ and 100 ℃ according to different regenerants, and the regeneration temperature of the common desulfurization waste alkali liquor is selected from 50 ℃ to 60 ℃.
The desulfurization waste alkali regenerant in the desulfurization waste alkali regeneration process can be calcined magnesium oxide, calcined calcium oxide, calcined iron, calcined carbon steel scraps, calcined stainless steel scraps, calcined copper oxide, calcined zinc oxide, calcined iron oxide ore, calcined magnetite ore, calcined manganese iron ore, pyrolusite, molten casting steel dross and the like. Preferably calcined carbon steel scrap, calcined copper scrap, calcined iron oxide ore, calcined magnetite ore, calcined manganese iron ore, calcined pyrolusite and casting molten steel dross.
The dosage of the desulfurization waste alkali regenerant is determined by wasteIn alkali Na 2 The content of S is different, the mass ratio of the common desulfurization waste alkali regenerant to the desulfurization waste alkali liquor is 1.
The desulfurization waste alkali regenerant can adopt powder or larger particles, such as 10 meshes-80 meshes or 1mm multiplied by 1mm-10mm multiplied by 10mcm and the like.
The regeneration temperature of the desulfurization waste alkali regenerant is different according to different types, and the preferred regeneration temperature is 1000-1200 ℃.
The filtering process of the invention can adopt a gravity filter, a vacuum filter and a pressure filter, and preferably adopts a pressure filter.
Before the filtering process, the amphoteric polyacrylamide flocculant is added into the desulfurized waste alkali liquor to facilitate the filtration of suspended impurities, especially the coagulation aiding effect of the flocculant is needed for the new-generation metal sulfide, and the using mass concentration of the flocculant is 0.05-0.2mg/L, preferably 0.1mg/L.
The first embodiment is as follows:
respectively taking magnetite ore powder, iron oxide ore powder and pyrolusite ore powder, calcining for 1h in a high-temperature resistance furnace at 1200 ℃, and cooling to respectively obtain the desulfurized waste alkali magnetite ore regenerant, the iron oxide ore regenerant and the pyrolusite ore regenerant.
The second embodiment is as follows:
collecting the dross of the casting molten steel, and crushing to obtain the regenerant of the dross of the desulfurized waste alkali casting molten steel.
The third concrete embodiment:
and (3) calcining the metal cutting carbon steel scraps and the copper scraps in a high-temperature resistance furnace at 1200 ℃ and 1000 ℃ for 1h respectively, and cooling to obtain the desulfurization waste alkali calcined carbon steel scrap regenerant and the calcined copper scrap regenerant.
The fourth concrete embodiment:
100kg of the desulfurized waste alkali magnetite ore regenerant obtained in example 1 was added to a 3t vertical regeneration vessel, and 2t of deoiled Na was added 2 And (3) starting a stirrer, heating to 80 ℃, keeping the temperature for 1h, and filtering to obtain regenerated alkali liquor, wherein the content of S in the desulfurized waste alkali liquor is 3.2%. Regenerated alkali liquor Na 2 S is not detected (measured according to GB/T10500-2000 sodium sulfide industry.)) (ii) a The NaOH content was 5.9% (measured in accordance with GB/T209-2006).
The fifth concrete example:
100kg of the regenerating agent of the desulfurization waste alkali iron oxide ore in the embodiment 1 is added into a 3t vertical regeneration kettle, and 2t of deoiled Na is added 2 And (3) starting a stirrer, heating to 80 ℃, keeping the temperature for 1h, and filtering to obtain regenerated alkali liquor, wherein the content of S in the desulfurized waste alkali liquor is 2.2%. Regenerated alkali liquor Na 2 S is not detected (measured according to GB/T10500-2000 sodium sulfide industry) and the NaOH content is 5.6% (measured according to GB/T209-2006).
The sixth specific embodiment:
100kg of the regeneration agent for the desulfurized spent caustic calcined pyrolusite in example 1 was added to a 3t vertical regeneration vessel, and 2t of deoiled Na was added 2 And (3) starting a stirrer, heating to 80 ℃, keeping the temperature for 1h, and filtering to obtain regenerated alkali liquor, wherein the content of S in the desulfurized waste alkali liquor is 2.7%. The regenerated alkali liquor is not detected (measured according to GB/T10500-2000 sodium sulfide industry) and the NaOH content is 6.1% (measured according to GB/T209-2006).
The seventh specific embodiment:
100kg of the molten steel dross regenerant for the desulfurized spent caustic soda casting in example 2 was added into a 3t vertical regeneration kettle, and 2t of deoiled Na was added 2 And (3) starting a stirrer, heating to 80 ℃, keeping the temperature for 1h, and filtering to obtain regenerated alkali liquor, wherein the content of S in the desulfurized waste alkali liquor is 2.52%. Regenerated alkali liquor Na 2 S is not detected (measured according to GB/T10500-2000 sodium sulfide industry) and the NaOH content is 5.3% (measured according to GB/T209-2006).
The eighth embodiment:
100kg of the regeneration agent for the steel scraps of the desulfurized spent caustic soda calcined carbon in the embodiment 3 is added into a 3t vertical regeneration kettle, and 2t of deoiled Na is added 2 And (3) starting a stirrer, heating to 80 ℃, keeping the temperature for 1h, and filtering to obtain regenerated alkali liquor, wherein the content of S in the desulfurized waste alkali liquor is 3.0%. Regenerated alkali liquor Na 2 S is not detected (measured according to GB/T10500-2000 sodium sulfide industry) and the NaOH content is 6.8% (measured according to GB/T209-2006).
The specific embodiment is nine:
100kg of the copper scrap regenerating agent calcined by the waste desulfurized soda ash in the embodiment 3 is added into a 3t vertical regeneration kettle, and 2t of deoiled Na is added 2 And (3) starting a stirrer, heating to 80 ℃, keeping the temperature for 1h, and filtering to obtain regenerated alkali liquor. Regenerated alkali liquor Na 2 S is not detected (measured according to GB/T10500-2000 sodium sulfide industry) and the NaOH content is 5.9% (measured according to GB/T209-2006).
Two closed-loop cycles of the invention, naOH and Na are made 2 Repeatedly switching between S to repeatedly make ineffective Na 2 S is converted into useful NaOH, so that the main substances in the waste alkali system are recycled without Na 2 S neutralization and oxidation treatment are carried out, desalting is not needed, waste water is not needed to be treated, and resource utilization of hazardous waste is really achieved. The method only generates a very small amount of oil, almost has no other discharge, greatly reduces the environmental protection burden of enterprises producing the desulfurized alkali waste or enterprises treating the desulfurized alkali waste and the economic burden of waste treatment, completely accords with the treatment principle of resource reduction of solid waste, and also completely accords with the national policy of circular economy and sustainable development.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A regeneration process of desulfurization waste alkali is characterized in that: the method comprises the following steps:
firstly, the waste alkali liquor enters an extraction purification unit and is fully mixed with an organic extraction solvent;
the desulfurized waste alkali enters an extraction operation unit, is mixed and contacted with an organic solvent extractant, organic oil dissolved in the waste alkali enters an organic phase, the organic extractant containing organic oil substances is separated from an oil phase of the extraction unit after extraction and separation, and the desulfurized waste alkali is separated from a water phase of the extraction unit after oil removal, so that the separation of alkali and oil is realized;
secondly, organic oil substances dissolved in the waste alkali liquor enter an organic extraction phase, an oil phase separated from the extraction unit is an extracted oil-containing extractant, and a separated water phase is the deoiled waste alkali liquor;
the organic solvent extraction unit transfers the colored compounds in the waste alkali liquor into an oil phase while separating the waste alkali from the oil;
thirdly, the deoiled waste alkali liquor enters a desulfurization waste alkali liquor regeneration unit, and the desulfurization waste alkali regeneration agent and Na in the waste alkali liquor are utilized 2 Metathesis reaction between S to Na 2 S is converted into NaOH and corresponding metal sulfide precipitate is generated;
the deoiled desulfurized waste alkali liquid enters a desulfurized waste alkali liquid regeneration operation unit to react with a regenerant to enable Na 2 S is converted into NaOH and corresponding metal sulfide precipitate, so that the regeneration of the waste alkali is realized; na (Na) 2 NaOH and Na in desulfurization waste alkali in the process of converting S into NaOH 2 CO 3 The two effective alkali components are completely retained in the regenerated alkali;
fourthly, after the double decomposition reaction is finished, the waste alkali regeneration unit is a mixture consisting of original residual alkali, regenerated alkali and metal sulfide;
fifthly, adding a cationic-anionic polyacrylamide flocculant into the mixed system obtained in the fourth step to flocculate and settle various solid impurities in the system, wherein metal sulfides generated in the waste alkali regeneration link are subjected to flocculation and settling;
sixthly, enabling the mixture from the waste alkali regeneration unit to enter a filtering unit, and filtering to respectively obtain purified regenerated alkali liquor and metal sulfide;
and seventhly, removing coexisting organic and inorganic impurities from the regenerated alkali liquor in the sixth step through the steps, recovering the concentration, improving the purity and reusing the regenerated alkali liquor in the desulfurization treatment.
2. The process of claim 1, wherein the regeneration of the desulfurized spent caustic comprises: the metal sulfide separated by the filtering unit is sintered at high temperature to obtain corresponding metal oxide MeO which can be used as a desulfurizing waste lye regenerant again;
the filtering unit adopts one of a gravity filter, a vacuum filter or a pressure filter;
before the filtration process, the amphoteric polyacrylamide flocculant with the mass concentration of 0.05-0.2mg/L is added into the desulfurized waste alkali liquor.
3. The process of claim 1, wherein the regeneration of the desulfurized spent caustic comprises: and the oil-containing extractant separated from the oil phase of the extraction unit enters an extractant regeneration process unit to be distilled at normal pressure, the organic solvent extractant is distilled for recycling, and the high-boiling-point mixed oil is remained in the high-temperature kettle and is used as an oil refining raw material.
4. The process of claim 1, wherein the regeneration of the desulfurized spent caustic comprises: the organic solvent extracting agent in the treatment process for extracting the organic oil substances in the desulfurization waste alkali by using the organic solvent is toluene, xylene, phosphate esters, alkyl ketones, diesel oil, kerosene, naphtha or gasoline serving as the organic solvent extracting agent.
5. The process of claim 1, wherein the regeneration of the desulfurized spent caustic comprises: the organic solvent extracting agent in the treatment process for extracting the organic oil substances in the desulfurized waste alkali by using the organic solvent is naphtha and gasoline.
6. The process of claim 1, wherein the regeneration of the desulfurized spent caustic comprises: the desulfurization waste alkali regenerant is calcined magnesia, calcined calcium oxide, calcined iron, calcined carbon steel scraps, calcined stainless steel scraps, calcined copper oxide, calcined zinc oxide, calcined iron oxide ore, calcined magnetite ore, calcined manganese iron ore, pyrolusite and casting molten steel scum.
7. The process of claim 1, wherein the regeneration of the desulfurized spent caustic comprises: the desulfurization waste alkali regenerant is calcined carbon steel scraps, calcined copper scraps, calcined iron oxide ore, calcined magnetite ore, calcined manganese iron ore, calcined pyrolusite and casting molten steel scum.
8. The process of claim 1, wherein the regeneration of the desulfurized spent caustic comprises: the mass ratio of the desulfurization waste alkali regenerant to the desulfurization waste alkali liquor is 1-10;
the desulfurization waste alkali regenerant adopts powder or particles, the mesh number of the powder is 10-80 meshes, and the particles are 1mm multiplied by 1mm to 10mm multiplied by 10mcm.
9. The regeneration treatment application of the desulfurization waste alkali is characterized in that: respectively taking magnetite ore powder, iron oxide ore powder and pyrolusite ore powder, calcining for 1h at 1200 ℃ in a high-temperature resistance furnace, and cooling to respectively obtain a desulfurization waste alkali magnetite ore regenerant, an iron oxide ore regenerant and a pyrolusite ore regenerant;
adding 100kg of the desulfurization waste alkali magnetite ore regenerant into a 3t vertical regeneration kettle, and adding 2t of deoiled Na 2 And (3) starting a stirrer, heating to 80 ℃, keeping the temperature for 1h, and filtering to obtain regenerated alkali liquor, wherein the content of S in the desulfurized waste alkali liquor is 3.2%.
10. The regeneration treatment application of the desulfurization waste alkali is characterized in that: collecting dross of the casting molten steel, and crushing to obtain a dross regenerant of the desulfurized waste alkali casting molten steel;
100kg of the regenerating agent for the desulfurized spent caustic casting molten steel scum is added into a 3t vertical regeneration kettle, and 2t of deoiled Na is added 2 Desulfurized waste alkali liquor with 2.52 percent of S contentStarting the stirrer, heating to 80 ℃, keeping the temperature for 1h, and filtering to obtain regenerated alkali liquor.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5885422A (en) * | 1997-02-26 | 1999-03-23 | Stone & Webster Engineering Corporation | Spent caustic (pre)treatment process |
| CN1789162A (en) * | 2005-12-06 | 2006-06-21 | 河北工业大学 | Technique for reclaiming ethylene alkali-washing waste liquid |
| CN102815815A (en) * | 2011-06-10 | 2012-12-12 | 中国石油天然气股份有限公司 | Method for processing acid gas alkali-wash waste liquor |
| CN104071913A (en) * | 2013-03-28 | 2014-10-01 | 中国石油天然气股份有限公司 | Pollution-free processing method of sulfur-containing waste alkaline solution |
| CN111135603A (en) * | 2019-12-31 | 2020-05-12 | 大连汉诺工程技术有限公司 | Waste alkali treatment method |
-
2022
- 2022-07-11 CN CN202210809935.9A patent/CN115155311A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5885422A (en) * | 1997-02-26 | 1999-03-23 | Stone & Webster Engineering Corporation | Spent caustic (pre)treatment process |
| CN1789162A (en) * | 2005-12-06 | 2006-06-21 | 河北工业大学 | Technique for reclaiming ethylene alkali-washing waste liquid |
| CN102815815A (en) * | 2011-06-10 | 2012-12-12 | 中国石油天然气股份有限公司 | Method for processing acid gas alkali-wash waste liquor |
| CN104071913A (en) * | 2013-03-28 | 2014-10-01 | 中国石油天然气股份有限公司 | Pollution-free processing method of sulfur-containing waste alkaline solution |
| CN111135603A (en) * | 2019-12-31 | 2020-05-12 | 大连汉诺工程技术有限公司 | Waste alkali treatment method |
Non-Patent Citations (2)
| Title |
|---|
| 张秀红 等: "化学沉淀法处理乙烯裂解废碱液中的硫化物", 化学工程师, pages 41 - 44 * |
| 黄伟欣 等: "乙烯废碱液脱硫处理研究进展", 工业水处理, vol. 41, no. 4, pages 5 * |
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