CN110921953B - Resource treatment process and device for coking desulfurization waste liquid - Google Patents
Resource treatment process and device for coking desulfurization waste liquid Download PDFInfo
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- CN110921953B CN110921953B CN201911237777.9A CN201911237777A CN110921953B CN 110921953 B CN110921953 B CN 110921953B CN 201911237777 A CN201911237777 A CN 201911237777A CN 110921953 B CN110921953 B CN 110921953B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Abstract
The invention discloses a resource treatment process and a resource treatment device for coking desulfurization waste liquid, wherein the process is to pretreat the desulfurization waste liquid and adjust the pH value of the desulfurization waste liquid to 4.0-5.5. And then carrying out filtration operation and pressurization treatment on the desulfurization waste liquid, and then carrying out heat exchange with the desulfurization waste liquid after heating treatment and catalytic oxidation. And (3) evaporating and concentrating the desulfurized liquid after heat exchange, wherein the condensate is directly subjected to biochemical treatment, the concentrated liquid is subjected to catalytic conversion treatment, an ammonium sulfate solution is obtained by filtering, and the ammonium sulfate solution enters an ammonium sulfate mother liquid tank to recover an ammonium sulfate product. The invention converts ammonium thiocyanate and ammonium thiosulfate into ammonium sulfate, realizes the mild conversion of salt and solves the problem of overstocked ammonium thiocyanate; after the desulfurization waste liquid is subjected to salt extraction, water can directly enter biochemical treatment, and the problems of liquid expansion, water balance and the like of a system are solved; reduces the pollution to the environment and realizes the resource treatment of the desulfurization waste liquid.
Description
Technical Field
The invention relates to a resource treatment process and a resource treatment device for coking desulfurization waste liquid, and belongs to the field of coking.
Background
In the desulfurization process of the coke oven gas, inorganic salts such as ammonium thiosulfate, ammonium thiocyanate, ammonium sulfate and the like can be generated due to side reactions. When the inorganic salt is accumulated to a certain concentration, the desulfurization efficiency is reduced, and in order to ensure the desulfurization efficiency of the system, fresh desulfurization solution needs to be periodically supplemented, and the desulfurization waste liquid needs to be periodically discharged outwards. Because the content of the desulfurization by-products in the desulfurization waste liquid is relatively high, the direct discharge not only causes serious pollution to the environment, but also causes waste of resources. Therefore, an effective method is urgently needed to solve the problem.
In the prior art, enterprises generally add desulfurized waste liquid to coking coal and pyrolyze it in a coke oven. The method not only increases the energy consumption in the coking process, but also influences the quality of the coke.
Chinese patent CN 102795643A discloses a method for extracting ammonium thiocyanate from coking desulfurization waste liquid, which utilizes the solubility difference of ammonium thiosulfate, ammonium sulfate and ammonium thiocyanate in methanol along with the temperature change to evaporate the desulfurization waste liquid to obtain mixed salt, add methanol to stir, filter, freeze at low temperature, filter to obtain 87-94% ammonium thiocyanate crystals, and add the mixed salt into the filtrate for cyclic operation. The purity of the ammonium thiocyanate crystal obtained by the method is not high, ammonium thiosulfate and ammonium sulfate in the filtrate are not effectively utilized, and the economic benefit is low.
Chinese patent CN 104071807A discloses a new process for extracting ammonium thiocyanate from coking desulfurization waste liquid, which comprises adding activated carbon into the desulfurization waste liquid for decolorization, filtering, evaporating and crystallizing to obtain mixed salt, extracting with ethanol, introducing nitrogen gas for pressure filtration, crystallizing and centrifuging to obtain ammonium thiocyanate crystals, drying the filter residue at low temperature, adding lignite powder, monoammonium phosphate, potassium chloride and organic feed liquid, stirring, and granulating to obtain organic fertilizer. The method realizes the recycling of ammonium thiosulfate and ammonium sulfate, but the method can generate a large amount of condensed liquid which is difficult to treat, and has more complex operation procedures and more process investment.
Chinese patent CN109534540A discloses a method for decoloring desulfurized waste liquid and a method for extracting salt from desulfurized waste liquid, which aim at different desulfurized waste liquids, adjust the pH value by using dilute sulfuric acid, and add active carbon for vacuum decoloring. And evaporating and concentrating the decolorized waste liquid, cooling, crystallizing, filtering to obtain ammonium sulfate, and evaporating and crystallizing the filtrate again to obtain ammonium thiocyanate. The method has stable decolorizing effect, but the condensate water obtained by evaporation operation contains more impurities, can not be biochemically treated, and can only circulate in the system, thus causing the liquid expansion of the system and the problem of water balance.
The ammonium thiocyanate and other secondary salts extracted by the process have small market demand, so that the problems of product overstock and difficult sale are very prominent. In addition, the method can generate a large amount of condensed liquid, namely COD and NH in the condensed liquid3The content of N and sulfide is high, liquid expansion is easily caused when the sulfur is returned to a desulfurization system, and the biochemical system of an enterprise cannot process the sulfur.
Therefore, a resource treatment process of coking desulfurization waste liquid is urgently needed by coking enterprises. The method has the advantages that the ammonium thiocyanate, ammonium thiosulfate and other secondary salts in the coking desulfurization waste liquid are efficiently recovered and converted, and the problems that the ammonium thiocyanate is small in market demand and difficult to sell are solved. Meanwhile, water in the desulfurization waste liquid is effectively treated, so that the water subjected to salt extraction by the desulfurization waste liquid can enter biochemical treatment, and the problems of liquid expansion of a system and the like are solved; the method has important significance for improving the benefits of coking enterprises, reducing the pollution to the environment and realizing the efficient utilization of resources.
Disclosure of Invention
The invention aims to provide a resource treatment process of coking desulfurization waste liquid, obtain a high-quality ammonium sulfate product, solve the problem that ammonium thiocyanate is difficult to sell, and realize resource treatment of coking desulfurization waste liquid.
The main organic matters in the desulfurization waste liquid are phenol substances, and the invention realizes the effective degradation of phenol by utilizing oxygen in the air through a catalytic wet oxidation technology, so that the water quality in the desulfurization waste liquid meets the requirements of biochemical treatment. Aiming at the mixed salt of ammonium thiosulfate and ammonium thiocyanate in the desulfurization waste liquid, the mixed salt is respectively converted into a single product of ammonium sulfate by adopting a pretreatment and catalytic conversion mode. The reaction equation is:
the invention provides a resource treatment process of coking desulfurization waste liquid, which comprises the following steps:
(1) pretreating the desulfurization waste liquid;
(2) filtering the pretreated desulfurization waste liquid;
(3) pressurizing the filtrate;
(4) introducing the desulfurization solution obtained in the step (3) into a heat exchanger, and exchanging heat with the desulfurization solution after catalytic oxidation reaction;
(5) introducing the desulfurized liquid after heat exchange into a heater for heating treatment;
(6) introducing the desulfurization solution obtained in the step (5) into a catalytic oxidation reactor for catalytic oxidation treatment; returning the liquid after the catalytic oxidation reaction to the heat exchanger, and exchanging heat with the pressurized desulfurization liquid in the step (3);
(7) introducing the liquid subjected to heat exchange in the step (4) into an evaporator for evaporation and concentration;
(8) introducing the concentrated solution generated in the step (7) into a catalytic conversion reactor for conversion treatment;
(9) filtering the liquid after the catalytic conversion reaction; introducing the filtered filtrate into an ammonium sulfate mother liquor tank to obtain ammonium sulfate; and (4) recycling the filtered solid or treating the filtered solid with coal.
The specific process of the above technical scheme is further explained as follows:
in the step (1), the desulfurization waste liquid is stirred by a stirring kettle, and the pH value of the desulfurization waste liquid is adjusted to 4.0-5.5 by dilute sulfuric acid. And introducing acid gas generated in the pretreatment process into a scrubber, washing by using a desulfurization solution, discharging the gas after washing, and returning the liquid to a desulfurization solution tank for recycling.
In the step (2), the filtrate obtained by filtering is subjected to pressure treatment, and the solid obtained by filtering can be directly sold in an external mode in a sulfur paste mode or sold in an external mode after being subjected to melting treatment.
And (3) pressurizing the filtrate obtained in the step (2) by using a pressurizing pump, wherein the pressure is 0.3-3 MPa.
In the step (5), a heater is adopted to heat the desulfurization solution, the heating temperature is 80-160 ℃, and the heating heat source is supplied by burning steam, heat-conducting oil or coal gas.
In the step (6), the oxidant is air or oxygen in the oxidation process, and the catalyst is a heterogeneous wet oxidation catalyst taking transition metals such as copper and iron and precious metals such as platinum as active components; the reaction temperature in the catalytic oxidation process is 80-160 ℃, the pressure is 0.3-3 MPa, the reaction time is 5-30 min, the gas-liquid ratio (volume ratio) is 100-1000, and the liquid airspeed is 2-30 h-1。
In the step (7), the main heat of evaporation in the evaporator is derived from the sensible heat of the desulfurization waste liquid after wet oxidation, and steam or heat conducting oil can be introduced in an auxiliary manner. And (4) carrying out biochemical treatment on the condensate generated in the evaporation process, and introducing the condensate into a catalytic conversion reactor for conversion treatment.
In the step (8), 30-90% by mass of sulfuric acid is added in the conversion process, and the volume ratio of the sulfuric acid to the desulfurization waste liquid is 1: 1-1: 10. The conversion reaction temperature is 70-95 ℃, the reaction time is 5-60 min, the used catalyst is a carbon-based catalyst, the catalyst takes wheat straws as raw materials, copper, iron and manganese as active components, precursor selective complexation is carried out, and the wheat straw carbon-based catalyst is obtained after carbonization and activation. The conversion reactor can be a kettle type or a fixed bed type, and when the kettle type reactor is used, the using amount of the catalyst is 50-100 g/L. When the reactor is a fixed bed, the liquid airspeed is 5-50 h-1And introducing the acidic gas generated in the conversion process into a scrubber, washing by using a desulfurization solution, discharging the gas after washing, and returning the washing solution to the desulfurization solution tank for recycling.
In the step (9), the filtered solids are treated in different ways according to different reactors used in the conversion process in the step (8), if the reactors are kettle-type, part of the filtered solids are returned to the conversion reactor for recycling, and part of the filtered solids are treated by blending coal. If the reactor is fixed bed type, the coal blending treatment is carried out on all the filtered solids.
The invention provides a device for recycling coking desulfurization waste liquid, which comprises a preprocessor, a filter, a heat exchanger, a heater, a catalytic oxidation reactor, an evaporator, a catalytic conversion reactor, a scrubber, a desulfurization liquid tank, a second filter and an ammonium sulfate mother liquid tank, wherein the preprocessor is connected with the filter;
the desulfurization waste liquid is introduced into a preprocessor, a gas outlet of the preprocessor is connected with the bottom of a scrubber, a gas outlet and a desulfurization liquid inlet are arranged above the scrubber, and the bottom of the scrubber is connected with a desulfurization liquid tank; a liquid outlet of the preprocessor is connected with a filter, a solid outlet is arranged at the bottom of the filter, a liquid outlet above the filter is connected with a heat exchanger, and the heat exchanger is connected with the bottom of the catalytic oxidation reactor; a liquid outlet of the heat exchanger is connected with a heater, the other end of the heater is connected with a catalytic oxidation reactor, a catalyst inlet is formed in the middle of the catalytic oxidation reactor, an oxygen or air feeding hole is formed in the bottom of the catalytic oxidation reactor, and a solution outlet after oxidation reaction is formed in the solution after oxidation reaction from the bottom of the catalytic oxidation reactor; a liquid outlet of the heat exchanger is connected with an evaporator, a condensate outlet generated in the evaporator leads to a biochemical treatment process, a concentrated solution outlet of the evaporator is connected with a catalytic conversion reactor, and a dilute sulfuric acid and carbon-based catalyst feeding hole is formed above the catalytic conversion reactor; an acid gas outlet above the catalytic conversion reactor is connected with the bottom of the scrubber; and a liquid outlet of the catalytic conversion reactor is connected with a second filter, a liquid outlet above the second filter is connected with an ammonium sulfate mother liquor tank, and a solid outlet is arranged below the second filter.
The invention has the beneficial effects that:
(1) compared with the prior art, the invention converts ammonium thiocyanate and ammonium thiosulfate into ammonium sulfate, thereby realizing the full utilization of the desulfurization waste liquid;
(2) after the desulfurization waste liquid is subjected to salt extraction, water can directly enter biochemical treatment, and the problems of liquid expansion, water balance and the like of a system are solved; realizes the resource treatment of the desulfurization waste liquid.
Drawings
FIG. 1 is a flow chart of the process using a tank reactor in example 1.
FIG. 2 is a process flow diagram of example 2 using a fixed bed reactor.
In the figure: 1-a preprocessor; 2-a filter; 3-external pin; 4-a heat exchanger; 5-a heater; 6-a catalytic oxidation reactor; 7-an evaporator; 8-biochemical treatment; 9-a kettle type catalytic conversion reactor; 10-a scrubber; 11-a desulfurization liquid tank; 12-a second filter; 13-ammonium sulfate mother liquor tank; 14-recycling or coal blending treatment; 15-fixed bed catalytic conversion reactor; a-desulfurization waste liquid; b-dilute sulfuric acid; c-sulfur paste or molten sulfur; a D-catalyst; e-oxygen or air; f-condensate; h-concentrated solution; i-a carbon-based catalyst; g-gas; l-liquid; s-solid; t-high temperature.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1
The waste liquid used in the embodiment is desulfurization waste liquid generated by coking gas of a coking plant, 100 mL of the desulfurization waste liquid is taken, and the main component of the desulfurization waste liquid is 150 g.L of ammonium thiocyanate-1Ammonium thiosulfate 80 g.L-1Ammonium sulfate 50 g.L-1. The catalytic conversion reactor adopts a kettle type reactor.
As shown in fig. 1, a device for recycling coking desulfurization waste liquid comprises a preprocessor 1, a filter 2, a heat exchanger 4, a heater 5, a catalytic oxidation reactor 6, an evaporator 7, a catalytic conversion reactor, a scrubber 10, a desulfurization liquid tank 11, a second filter 12 and an ammonium sulfate mother liquid tank 13;
the desulfurization waste liquid is introduced into a preprocessor 1, a gas outlet of the preprocessor 1 is connected with the bottom of a scrubber 10, a gas outlet and a desulfurization liquid inlet are arranged above the scrubber 10, and the bottom of the scrubber 10 is connected with a desulfurization liquid tank 11; a liquid outlet of the preprocessor 1 is connected with the filter 2, a solid outlet is arranged at the bottom of the filter 2, a liquid outlet above the filter 2 is connected with the heat exchanger 4, and the heat exchanger is connected with the bottom of the catalytic oxidation reactor 6; a liquid outlet of the heat exchanger 4 is connected with a heater 5, the other end of the heater 5 is connected with a catalytic oxidation reactor 6, a catalyst D inlet is formed in the middle of the catalytic oxidation reactor 6, an oxygen or air E feeding hole is formed in the bottom of the catalytic oxidation reactor 6, and a solution outlet after oxidation reaction is formed in the bottom of the catalytic oxidation reactor 6 for a solution after oxidation reaction; a liquid outlet of the heat exchanger 4 is connected with an evaporator 7, a condensate F outlet generated in the evaporator 7 leads to a biochemical treatment 8 process, a concentrated solution outlet of the evaporator 7 is connected with a catalytic conversion reactor, and a dilute sulfuric acid B and a carbon-based catalyst I feeding hole are formed above the catalytic conversion reactor; an acid gas outlet above the catalytic conversion reactor is connected with the bottom of the scrubber 10; the liquid outlet of the catalytic conversion reactor 9 is connected with a second filter 12, the liquid outlet above the second filter 12 is connected with an ammonium sulfate mother liquor tank 13, and a solid outlet is arranged below the second filter 12.
The process flow is as follows: and introducing the desulfurization waste liquid into a preprocessor 1 for preprocessing, discharging the generated gas from the upper part of a scrubber 10 after washing after the generated gas enters the bottom of the scrubber 10, introducing the desulfurization liquid from the upper part of the scrubber 10, washing the gas, and returning the desulfurization liquid from the bottom of the scrubber 10 to a desulfurization liquid tank 11 for recycling after washing. The pretreated solution is passed through a filter 2 for filtration, and the resulting solids are removed from the bottom of the filter 2 for export 3 in the form of sulfur paste or molten sulfur C. The liquid enters the heat exchanger 4 from the upper part of the filter 2 to exchange heat with the desulfurization liquid after catalytic oxidation reaction. And introducing the desulfurization solution subjected to heat exchange into a heater 5 for heating treatment. And introducing the heated desulfurization solution into a catalytic oxidation reactor 6 for catalytic oxidation treatment, introducing a catalyst D from a feed inlet in the middle of the catalytic oxidation reactor 6, introducing oxygen or air E from a feed inlet in the bottom of the catalytic oxidation reactor 6, and introducing the solution after the oxidation reaction into a heat exchanger 4 from the bottom of the catalytic oxidation reactor 6 for heat exchange with the pressurized desulfurization solution. Introducing the liquid after heat exchange into an evaporator 7 for evaporation and concentration, performing biochemical treatment 8 on condensate F generated in the evaporator 7, introducing the concentrated solution into a kettle type catalytic conversion reactor 9 for conversion treatment, and introducing dilute sulfuric acid B and a carbon-based catalyst I from a feed inlet above the kettle type catalytic conversion reactor 9; acid gas generated in the conversion process enters the bottom of the scrubber 10 from the upper part of the kettle type catalytic conversion reactor 9, is discharged from the upper part of the scrubber 10 after being washed, desulfurization liquid enters from the upper part of the scrubber 10 to wash the gas, and the desulfurization liquid returns to the desulfurization liquid tank 11 from the bottom of the scrubber 10 for recycling after being washed. And (3) introducing the liquid converted by the catalytic conversion reactor 9 into a filter 12 for filtering, introducing the liquid into an ammonium sulfate mother liquor tank 13 from the upper part of the filter 12, and taking out the solid from the lower part of the filter 12 for recycling or coal blending treatment 14.
Firstly, introducing the desulfurization waste liquid into a stirring kettle for stirring, adding dilute sulfuric acid to adjust the pH value of the desulfurization waste liquid to 4.0, and obtaining the pretreated desulfurization waste liquid. And (3) introducing acidic gas generated in the process into a scrubber, washing by using a desulfurization solution, discharging the gas after washing, and returning the liquid to a desulfurization solution tank for recycling.
And secondly, introducing the pretreated desulfurization waste liquid into a filter for filtering, and selling the filtered solid in a sulfur paste form.
And thirdly, pressurizing the filtrate by adopting a pressurizing pump, wherein the pressure is 3 MPa.
And fourthly, introducing the desulfurization solution obtained in the step into a heat exchanger, and exchanging heat with the desulfurization solution after the catalytic oxidation reaction.
And fifthly, introducing the desulfurization solution obtained in the step into a heater for heating, wherein the heating temperature is 160 ℃, and the heating heat source is supplied by steam.
And sixthly, introducing the desulfurization solution obtained in the step into a catalytic oxidation reactor for catalytic oxidation treatment. In the oxidation process, the oxidant is air, and the catalyst is a heterogeneous wet oxidation catalyst taking copper as an active component. The reaction temperature in the catalytic oxidation process is 160 ℃, the pressure is 3 MPa, the reaction time is 5 min, the gas-liquid volume ratio is 1000, and the liquid space velocity is 30 h-1。
And step seven, returning the liquid obtained in the step above to the heat exchanger to exchange heat with the pressurized desulfurization liquid.
And step eight, introducing the liquid after heat exchange into an evaporator for evaporation and concentration. The main heat of evaporation is derived from the sensible heat of the desulfurized waste liquid after wet oxidation. CODcr =1200 mg · L in condensate generated during evaporation-1，NH3-N=20 ㎎·L-1Sulfide =5 mg · L-1The condensate is passed through A2And (4) performing treatment by using a biochemical process, and introducing 50 mL of generated concentrated solution into a catalytic conversion reactor for conversion treatment.
And step nine, introducing the concentrated solution generated in the step into a kettle type catalytic conversion reactor for conversion treatment. Adding 10 mL of 90 mass percent sulfuric acid in the conversion process, wherein the conversion reaction temperature is 95 ℃, the reaction time is 5 min, the used catalyst is a carbon-based catalyst, the catalyst takes wheat straws as a raw material, copper as an active component, performing precursor selective complexation, and carbonizing and activating to obtain the wheat straw carbon-based catalyst. The amount of the catalyst used was 100 g/L. And introducing the acidic gas generated in the conversion process into a scrubber, washing by using a desulfurization solution, discharging the gas after washing, and returning the washing solution to the desulfurization solution tank for recycling.
The tenth step, the liquid after conversion is filtered to obtain the ammonium sulfate with the concentration of 341.67 g.L-1The main component of the solid obtained after filtration is the carbon-based catalyst, 80 percent of the solid returns to the conversion reactor for recycling, and 20 percent of the solid is subjected to coal blending treatment.
And step ten, introducing the ammonium sulfate solution obtained in the step into an ammonium sulfate mother liquor tank, and recovering an ammonium sulfate product.
Example 2
The waste liquid used in the embodiment is desulfurization waste liquid generated by coking gas of a coking plant, 100 mL of the desulfurization waste liquid is taken, and the main component of the desulfurization waste liquid is 150 g.L of ammonium thiocyanate-1Ammonium thiosulfate 80 g.L-1Ammonium sulfate 50 g.L-1. The catalytic conversion reactor adopts a fixed bed type reactor.
As shown in fig. 2, the process flow is: and introducing the desulfurization waste liquid into a preprocessor 1 for preprocessing, discharging the generated gas from the upper part of a scrubber 10 after washing after the generated gas enters the bottom of the scrubber 10, introducing the desulfurization liquid from the upper part of the scrubber 10, washing the gas, and returning the desulfurization liquid from the bottom of the scrubber 10 to a desulfurization liquid tank 11 for recycling after washing. The pretreated solution is passed through a filter 2 for filtration, and the resulting solids are removed from the bottom of the filter 2 for export 3 in the form of sulfur paste or molten sulfur C. The liquid enters the heat exchanger 4 from the upper part of the filter 2 to exchange heat with the desulfurization liquid after catalytic oxidation reaction. And introducing the desulfurization solution subjected to heat exchange into a heater 5 for heating treatment. And introducing the heated desulfurization solution into a catalytic oxidation reactor 6 for catalytic oxidation treatment, introducing a catalyst D from a feed inlet in the middle of the catalytic oxidation reactor 6, introducing oxygen or air E from a feed inlet in the bottom of the catalytic oxidation reactor 6, and introducing the solution after the oxidation reaction into a heat exchanger 4 from the bottom of the catalytic oxidation reactor 6 for heat exchange with the pressurized desulfurization solution. Introducing the liquid after heat exchange into an evaporator 7 for evaporation and concentration, performing biochemical treatment 8 on condensate F generated in the evaporator 7, introducing the concentrated solution into a fixed bed type catalytic converter reactor 15 for conversion treatment, introducing dilute sulfuric acid B from a feed inlet above the fixed bed type catalytic converter reactor 15, and introducing a carbon-based catalyst I from a feed inlet in the middle of the fixed bed type catalytic converter reactor 15. Acid gas generated in the conversion process enters the bottom of the scrubber 10 from the upper part of the fixed bed type catalytic conversion reactor 15, is discharged from the upper part of the scrubber 10 after being washed, desulfurization liquid enters from the upper part of the scrubber 10 to wash the gas, and the desulfurization liquid returns to the desulfurization liquid tank 11 from the bottom of the scrubber 10 for recycling after being washed. And (3) introducing the liquid converted by the fixed bed catalytic converter 15 into a filter 12 for filtering, introducing the liquid into an ammonium sulfate mother liquor tank 13 from the upper part of the filter 12, and taking out the solid from the lower part of the filter 12 for recycling or coal blending treatment 14.
Firstly, introducing the desulfurization waste liquid into a stirring kettle for stirring, adding dilute sulfuric acid to adjust the pH value of the desulfurization waste liquid to 5.5, and obtaining the pretreated desulfurization waste liquid. And (3) introducing acidic gas generated in the process into a scrubber, washing by using a desulfurization solution, discharging the gas after washing, and returning the liquid to a desulfurization solution tank for recycling.
And secondly, filtering the pretreated desulfurization waste liquid, and selling the filtered solid in a sulfur paste form.
And thirdly, pressurizing the filtrate by adopting a pressurizing pump, wherein the pressure is 1 MPa.
And fourthly, introducing the desulfurization solution obtained in the step into a heat exchanger, and exchanging heat with the desulfurization solution after the catalytic oxidation reaction.
And fifthly, introducing the desulfurization solution obtained in the step into a heater for heating treatment, wherein the heating temperature is 80 ℃, and a heating source is supplied by steam.
And sixthly, introducing the desulfurization solution obtained in the step into a catalytic oxidation reactor for catalytic oxidation treatment. In the oxidation process, the oxidant is oxygen, and the catalyst is a heterogeneous wet oxidation catalyst taking copper as an active component. Catalytic oxygenThe reaction temperature in the chemical reaction process is 80 ℃, the pressure is 1 MPa, the reaction time is 30min, the gas-liquid volume ratio is 100, and the liquid airspeed is 2 h-1。
And step seven, returning the liquid obtained in the step above to the heat exchanger to exchange heat with the pressurized desulfurization liquid.
And step eight, introducing the liquid after heat exchange into an evaporator for evaporation and concentration. The main heat of evaporation is derived from the sensible heat of the desulfurized waste liquid after wet oxidation. CODcr =1200 mg · L in condensate generated during evaporation-1，NH3-N=20 ㎎·L-1Sulfide =5 mg · L-1The condensate is passed through A2And (4) performing treatment by using a biochemical process, and introducing 50 mL of generated concentrated solution into a catalytic conversion reactor for conversion treatment.
And step nine, introducing the concentrated solution obtained in the step into a fixed bed type catalytic conversion reactor for conversion treatment. Adding 80 mL of 30 mass percent sulfuric acid in the conversion process, wherein the conversion reaction temperature is 70 ℃, the reaction time is 60 min, the used catalyst is a carbon-based catalyst, the catalyst takes wheat straws as a raw material, iron as an active component, performing precursor selective complexation, and carbonizing and activating to obtain the wheat straw carbon-based catalyst. The liquid space velocity is 5 h-1And introducing the acidic gas generated in the conversion process into a scrubber, washing by using a desulfurization solution, discharging the gas after washing, and returning the washing solution to the desulfurization solution tank for recycling.
The tenth step, the liquid after conversion is filtered to obtain the ammonium sulfate with the concentration of 146.43 g.L-1The main solid component obtained after filtration of the solution (2) is a carbon-based catalyst, and all the components are subjected to coal blending treatment.
And step ten, introducing the ammonium sulfate solution obtained in the step into an ammonium sulfate mother liquor tank, and recovering an ammonium sulfate product.
Claims (10)
1. A resource treatment process of coking desulfurization waste liquid is characterized by comprising the following steps:
(1) pretreating the desulfurization waste liquid;
(2) filtering the pretreated desulfurization waste liquid;
(3) pressurizing the filtrate;
(4) introducing the desulfurization solution obtained in the step (3) into a heat exchanger, and exchanging heat with the desulfurization solution after catalytic oxidation reaction;
(5) introducing the desulfurized liquid after heat exchange into a heater for heating treatment;
(6) introducing the desulfurization solution obtained in the step (5) into a catalytic oxidation reactor for catalytic oxidation treatment; returning the liquid after the catalytic oxidation reaction to the heat exchanger, and exchanging heat with the pressurized desulfurization liquid in the step (3);
(7) introducing the liquid subjected to heat exchange in the step (4) into an evaporator for evaporation and concentration;
(8) introducing the concentrated solution generated in the step (7) into a catalytic conversion reactor for conversion treatment; adding 30-90% of sulfuric acid in percentage by mass in the conversion process, wherein the volume ratio of the sulfuric acid to the desulfurization waste liquid is 1: 1-1: 10; the conversion reaction temperature is 70-95 ℃, the reaction time is 5-60 min, the used catalyst is a carbon-based catalyst, the catalyst takes wheat straws as raw materials, copper, iron and manganese as active components, precursor selective complexation is carried out, and the wheat straw carbon-based catalyst is obtained after carbonization and activation;
(9) filtering the liquid after the catalytic conversion reaction; introducing the filtered filtrate into an ammonium sulfate mother liquor tank to obtain ammonium sulfate; and (4) recycling the filtered solid or treating the filtered solid with coal.
2. The resource treatment process of the coking desulfurization waste liquid according to claim 1, characterized in that: in the step (1), stirring the desulfurization waste liquid by using a stirring kettle, and adjusting the pH of the desulfurization waste liquid to 4.0-5.5 by using dilute sulfuric acid; and introducing acid gas generated in the pretreatment process into a scrubber, washing by using a desulfurization solution, discharging the gas after washing, and returning the liquid to a desulfurization solution tank for recycling.
3. The resource treatment process of the coking desulfurization waste liquid according to claim 1, characterized in that: and (2) performing pressure treatment on the filtrate obtained by filtering, and directly selling the solid obtained by filtering in a sulfur paste form or selling the solid after melting treatment.
4. The resource treatment process of the coking desulfurization waste liquid according to claim 1, characterized in that: and (3) pressurizing the filtrate obtained in the step (2) by using a pressurizing pump, wherein the pressure is 0.3-3 MPa.
5. The resource treatment process of the coking desulfurization waste liquid according to claim 1, characterized in that: in the step (5), a heater is adopted to heat the desulfurization solution, the heating temperature is 80-160 ℃, and a heating source is supplied by burning steam, heat conduction oil or coal gas.
6. The resource treatment process of the coking desulfurization waste liquid according to claim 1, characterized in that: in the step (6), the oxidant is air or oxygen in the oxidation process, and the catalyst is a heterogeneous wet oxidation catalyst taking copper-iron transition metal and platinum noble metal as active components; the reaction temperature in the catalytic oxidation process is 80-160 ℃, the pressure is 0.3-3 MPa, the reaction time is 5-30 min, the gas-liquid volume ratio is 100--1。
7. The resource treatment process of the coking desulfurization waste liquid according to claim 1, characterized in that: the main heat of evaporation in the evaporator in the step (7) comes from sensible heat of the desulfurization waste liquid after wet oxidation, or steam or heat conducting oil is fed in an auxiliary manner; and (4) carrying out biochemical treatment on the condensate generated in the evaporation process, and introducing the condensate into a catalytic conversion reactor for conversion treatment.
8. The resource treatment process of the coking desulfurization waste liquid according to claim 1, characterized in that: in the step (8), the conversion reactor is a kettle type or a fixed bed type, and when the kettle type reactor is used, the using amount of the catalyst is 50-100 g/L; when the reactor is a fixed bed, the liquid airspeed is 5-50 h-1Introducing acidic gas generated in the conversion process into a scrubber, washing with desulfurizing liquid, discharging the gas after washing, and returning the washing liquid to the desulfurizing liquid tank for circulationThe ring is used.
9. The resource treatment process of the coking desulfurization waste liquid according to claim 8, characterized in that: if the conversion reactor is in a kettle type, returning part of the filtered solids in the step (9) to the conversion reactor for recycling, and performing coal blending treatment on the other part of the filtered solids;
and (4) if the conversion reactor is in a fixed bed type, all the filtered solids in the step (9) are subjected to coal blending treatment.
10. A resource treatment device of coking desulfurization waste liquid, which is used for the resource treatment process of the coking desulfurization waste liquid as claimed in any one of claims 1 to 9, and is characterized in that: the device comprises a preprocessor, a filter, a heat exchanger, a heater, a catalytic oxidation reactor, an evaporator, a catalytic conversion reactor, a scrubber, a desulfurization liquid tank, a second filter and an ammonium sulfate mother liquid tank;
the desulfurization waste liquid is introduced into a preprocessor, a gas outlet of the preprocessor is connected with the bottom of a scrubber, a gas outlet and a desulfurization liquid inlet are arranged above the scrubber, and the bottom of the scrubber is connected with a desulfurization liquid tank; a liquid outlet of the preprocessor is connected with a filter, a solid outlet is arranged at the bottom of the filter, a liquid outlet above the filter is connected with a heat exchanger, and the heat exchanger is connected with the bottom of the catalytic oxidation reactor; a liquid outlet of the heat exchanger is connected with a heater, the other end of the heater is connected with a catalytic oxidation reactor, a catalyst inlet is formed in the middle of the catalytic oxidation reactor, an oxygen or air feeding hole is formed in the bottom of the catalytic oxidation reactor, and a solution outlet after oxidation reaction is formed in the solution after oxidation reaction from the bottom of the catalytic oxidation reactor; a liquid outlet of the heat exchanger is connected with an evaporator, a condensate outlet generated in the evaporator leads to a biochemical treatment process, a concentrated solution outlet of the evaporator is connected with a catalytic conversion reactor, and a dilute sulfuric acid and carbon-based catalyst feeding hole is formed above the catalytic conversion reactor; an acid gas outlet above the catalytic conversion reactor is connected with the bottom of the scrubber; and a liquid outlet of the catalytic conversion reactor is connected with a second filter, a liquid outlet above the second filter is connected with an ammonium sulfate mother liquor tank, and a solid outlet is arranged below the second filter.
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| CN112340913A (en) * | 2020-10-10 | 2021-02-09 | 青岛科技大学东营资源化研究院 | Efficient dangerous waste liquid reduction skid-mounted device and waste liquid treatment process |
| CN112844041B (en) * | 2021-01-27 | 2023-01-31 | 太原理工大学 | Process for desulfurization and denitrification of coking wastewater |
| CN114349090B (en) * | 2021-12-29 | 2023-08-15 | 太原理工大学 | Coking desulfurization waste liquid harmless treatment process |
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