CN114105181A - Method for treating waste containing organic phosphorus chlorohydrocarbon - Google Patents
Method for treating waste containing organic phosphorus chlorohydrocarbon Download PDFInfo
- Publication number
- CN114105181A CN114105181A CN202111114715.6A CN202111114715A CN114105181A CN 114105181 A CN114105181 A CN 114105181A CN 202111114715 A CN202111114715 A CN 202111114715A CN 114105181 A CN114105181 A CN 114105181A
- Authority
- CN
- China
- Prior art keywords
- reactor
- thermal cracking
- combustion
- gas
- organophosphorus
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/24—Chlorides
- C01F11/28—Chlorides by chlorination of alkaline-earth metal compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for treating organophosphorus-containing chlorohydrocarbon waste, which comprises the following steps: (1) continuously introducing the waste containing the organic phosphorus chlorohydrocarbon and the calcium-containing compound into a thermal cracking reactor for thermal cracking reaction to obtain a thermal cracking material and a first gas phase product; (2) continuously introducing the thermal cracking material obtained in the step (1) and oxygen-containing gas into a decarburization reactor for decarburization reaction to obtain chlorine-containing phosphorus slag and a second gas-phase product, continuously introducing the second gas-phase product, the first gas-phase product obtained in the step (1) and a combustion improver into a combustion reactor for combustion, and treating the tail gas obtained by combustion to reach the standard and discharging; (3) and (3) dissolving the chlorine-containing phosphorus slag obtained in the step (2) by using deionized water, adjusting the pH value of the solution, filtering, separating and drying to obtain a calcium chloride aqueous solution and calcium phosphate. The method has simple process, realizes the harmlessness and the resource of the treatment of the organophosphorus chlorohydrocarbon waste, does not generate secondary waste which is difficult to treat in the whole treatment process, and meets the requirements of green and environmental protection.
Description
Technical Field
The invention relates to the technical field of hazardous waste treatment, in particular to a method for treating organophosphorus-containing chlorohydrocarbon waste.
Background
In the production process of chemical industry, pesticide industry and the like, organic waste liquid containing phosphorus and chlorinated hydrocarbon is generated. The organic waste liquid contains high phosphorus element, which not only causes great harm to the environment, but also directly harms human health; the chlorinated hydrocarbons have the 'three cause' (carcinogenic, teratogenic and mutagenic) effect or suspicious 'three cause' effect, and are regarded as the pollutants which are preferably controlled by various countries, China lists the pollutants in the national records of dangerous wastes, and the chlorinated hydrocarbon dangerous wastes bring serious threats to the ecological environment and human life and severely restrict the economic development. With the increasing importance of the country on environmental protection and the pursuit of people on good living environment, how to safely, stably and reliably dispose the phosphorus-containing chlorinated hydrocarbon hazardous waste is a problem to be solved urgently at present.
Incineration is one of the most widely used methods of harmless treatment. However, the incineration disposal of hazardous waste of chlorinated hydrocarbons has the following problems:
organic chlorine has an inhibiting effect on combustion, and causes the conditions of unreasonable organization, poor combustion stability and incomplete combustion in the combustion process. The traditional single combustion chamber hearth is difficult to effectively treat the contradiction among coking, combustion temperature control and incineration efficiency when treating dangerous waste, and some furnace types also have the problems of uneven fuel mixing, low turbulence intensity of a combustion flow field, insufficient combustion and the like.
Secondly, the burning temperature control is difficult to meet the burning requirement of the hazardous waste. The incineration temperature of a common urban garbage incinerator (such as a grate or a fluidized bed boiler) is 800-900 ℃, but for the chlorohydrocarbon hazardous waste, the incineration temperature is required to be more than 1100 ℃, and the smoke retention time is more than 2 seconds, so that the traditional garbage incinerator cannot meet the incineration requirement of the chlorohydrocarbon hazardous waste. Although the combustion temperature of the industrial kiln can reach more than 1100 ℃, the problem of serious coking exists in a part of combustion areas due to overhigh temperature.
And thirdly, the smoke generated after combustion is easy to generate secondary pollution. The chlorohydrocarbon hazardous waste can generate secondary pollutants such as nitrogen oxides, dioxin and the like in the incineration process, and the traditional solid waste incineration equipment can hardly perform effective process control and subsequent emission control on the pollutants when treating the hazardous waste.
For example, CN111112290A discloses a method for dechlorinating chlorinated hydrocarbon waste, in which chlorinated hydrocarbon waste and lime are continuously fed into a reaction furnace to be dechlorinated at high temperature to generate dechlorinated slag containing calcium chloride and activated carbon. However, if the chlorinated hydrocarbon contains impurities such as organic phosphorus, the difficulty of controlling the treatment temperature increases, which affects the treatment efficiency. And chlorinated hydrocarbon with a combustion inhibiting effect and organic phosphorus with a high heat value cause uneven temperature and coking of materials in the combustion furnace, so that the problems of out-of-control temperature, blockage and sudden stop of a treatment device and the like are caused, and the treatment effect is influenced.
As described above, the conventional method for treating the waste containing organic phosphorus chlorohydrocarbons has problems of difficulty in controlling the operation, low and unstable treatment efficiency, and the occurrence of secondary pollution, and thus it is necessary to develop a method for treating the waste containing organic phosphorus chlorohydrocarbons more safely and economically to achieve the harmless and recycling of the waste containing organic phosphorus chlorohydrocarbons.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide a method for treating the waste containing the chlorinated hydrocarbons containing the organic phosphorus, which has the advantages of simple process, high efficiency, economy and environmental protection, and realizes the harmless and recycling treatment of the waste containing the chlorinated hydrocarbons containing the organic phosphorus.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for treating waste containing organophosphorus chlorohydrocarbon comprises the following steps:
(1) continuously introducing the waste containing the organic phosphorus chlorohydrocarbon and the calcium-containing compound into a thermal cracking reactor for thermal cracking reaction to obtain a thermal cracking material and a first gas phase product;
(2) continuously introducing the thermal cracking material obtained in the step (1) and oxygen-containing gas into a decarburization reactor for decarburization reaction to obtain chlorine-containing phosphorus slag and a second gas-phase product, continuously introducing the second gas-phase product, the first gas-phase product obtained in the step (1) and a combustion improver into a combustion reactor for combustion, and treating the tail gas obtained by combustion to reach the standard and discharging;
(3) and (3) dissolving the chlorine-containing phosphorus slag obtained in the step (2) by using deionized water, adjusting the pH value of the solution, filtering, separating and drying to obtain a calcium chloride aqueous solution and calcium phosphate.
As a preferred embodiment of the invention, the temperature of the thermal cracking reaction is 600-700 ℃, and the retention time is 3-6 h.
As a preferred embodiment of the invention, the temperature of the decarburization reaction is 700-750 ℃, and the residence time is 20-60 min.
As a preferred embodiment of the invention, the temperature of the combustion is 900-1100 ℃, and the residence time is 5-20 s.
In a preferred embodiment of the present invention, the calcium-containing compound is at least one of lime, slaked lime and calcium carbonate.
In a preferred embodiment of the invention, the calcium-containing compound is used in an amount of 1 to 1.5 times the theoretical amount of total chlorine and total phosphorus contained in the organophosphorus-containing chlorohydrocarbon waste, calculated as the amount of calcium.
As a preferred embodiment of the present invention, the oxygen-containing gas is air or oxygen; the combustion improver is natural gas.
As a preferred embodiment of the invention, the air intake quantity of the oxygen-containing gas is 2 to 5 times of the mass of the phosphorus-containing chlorohydrocarbon waste; the ratio of the combustion improver to the total volume of the first gas phase product and the second gas phase product is 5-10: 1.
as a preferred embodiment of the present invention, said adjusting the pH of the solution means neutralizing the solution to pH 5-8 with hydrochloric acid.
As a preferred embodiment of the present invention, the thermal cracking reactor is a scraper type reactor; the decarbonization reactor is a rotary kiln, a vertical incinerator, a horizontal incinerator, a grate incinerator and a fluidized bed incinerator; the combustion reactor is a combustion furnace for combustion of organic gas.
The invention continuously adds the waste containing the organic phosphorus chlorohydrocarbon and the calcium-containing compound into a thermal cracking reactor for reaction; adding the material obtained by thermal cracking into a decarbonization reactor, further purifying by high-temperature decarbonization, introducing the gas generated by decarbonization and the gas generated by thermal cracking into a combustion reactor for full combustion, and treating the tail gas obtained by combustion to reach the standard and discharging; and dissolving the chlorine-containing phosphorus slag purified by the decarbonization reactor, neutralizing with hydrochloric acid, filtering, separating and drying to obtain a calcium chloride aqueous solution and calcium phosphate. The method has simple process, realizes the harmless and resource treatment of the organophosphorus chlorohydrocarbon waste by treating the organophosphorus chlorohydrocarbon waste through the calcium-containing compound synergistic thermal cracking-decarburization-dissolving neutralization-filtering separation process, does not generate secondary waste which is difficult to treat in the whole treatment process, and meets the requirements of environmental protection and environmental protection.
The waste containing the organophosphorus and the chlorohydrocarbon can be a fine chemical intermediate, a pesticide intermediate or liquid waste containing the organophosphorus and the chlorohydrocarbon or/and solid waste containing the organophosphorus and the chlorohydrocarbon generated in the production process of fine chemical engineering and pesticides, or the liquid waste containing the organophosphorus and the chlorohydrocarbon or/and solid waste containing the organophosphorus and the chlorohydrocarbon after treatment. The solid organophosphorus-containing chlorohydrocarbon waste material comprises organophosphorus-containing chlorohydrocarbon waste residues or/and organophosphorus-containing chlorohydrocarbon byproducts. The treatment of the liquid-state organophosphorus-containing chlorohydrocarbon waste or/and the solid-state organophosphorus-containing chlorohydrocarbon waste comprises concentration treatment, dehydration treatment, pH regulation treatment, extraction treatment, rectification treatment, treatment for removing phosphorus-free raw materials, byproducts and solvents, and the like.
In the invention, the feeding mode of the waste containing the organic phosphorus chlorohydrocarbon and the calcium-containing compound can be selected according to the actual production situation, and the solid waste containing the organic phosphorus chlorohydrocarbon and the calcium-containing compound can be uniformly mixed in a solid feeding hopper in advance according to a certain proportion, then enter a material kneading machine to be fully and uniformly mixed again, and then are added into a thermal cracking reactor; the liquid organic phosphorus-containing chlorohydrocarbon waste can be pumped from a liquid feed inlet of a material kneader by a liquid feed pump, the calcium-containing compound is added into a thermal cracking reactor from a solid feed hopper through the material kneader, and the proportion relation between the organic phosphorus-containing chlorohydrocarbon waste and the calcium-containing compound during continuous feeding is controlled by the material feed speed.
Aiming at the problems of the prior art that the waste containing the chlorinated hydrocarbons containing the organic phosphorus contains impurities such as the organic phosphorus and the like, the components are complex, and abnormal sound, blockage, unstable temperature, coking, poor treatment effect and the like of a thermal cracking reactor are generated in the actual thermal cracking process, the waste containing the chlorinated hydrocarbons containing the organic phosphorus is cooperatively treated by adopting a calcium-containing compound, so that the thermal cracking temperature can be effectively reduced; meanwhile, the generated coking waste can be timely removed and crushed through the thermal cracking reactors in the forms of a scraper type reaction furnace and the like, so that the influence of blocky coking materials generated in the material thermal cracking process on the thermal cracking treatment effect is prevented, and the whole thermal cracking reaction is stable and controllable.
The gas-phase product of the thermal cracking reaction and the gas-phase product of the decarburization reaction mainly comprise hydrogen chloride, carbon dioxide, a small amount of low-carbon alkane and the like, the hydrogen chloride, the carbon dioxide, the low-carbon alkane and the like enter a combustion reactor to be combusted with a combustion improver such as natural gas, tail gas obtained by combustion is subjected to conventional post-treatment operation in the field such as washing deacidification and the like to recover a byproduct hydrochloric acid, and then non-condensable gas can reach the standard emission.
The method for treating the waste containing the organophosphorus and the chlorohydrocarbon is different from the reaction process of the waste containing the organophosphorus and the chlorohydrocarbon with different components and contents. When Cl/H in the waste containing the organophosphorus chlorohydrocarbon is less than or equal to 1, the main reaction process is simpler, the waste is dechlorinated and decarbonized to generate active carbon, hydrogen chloride and part of combustible gas, the generated hydrogen chloride reacts with a calcium-containing compound such as lime to generate calcium chloride, and decomposed organophosphorus reacts to generate calcium phosphate; when Cl/H >1 in the waste containing organophosphorus chlorohydrocarbon is more complex, such as 1,1,1,3, 3-pentachloropropane (HCC-240fa) waste liquid and lime are cooperated with high-temperature dechlorination and decarbonization to involve the generation of chlorine and carbon monoxide, and the high-boiling point and nondegradable triethyl phosphate contained in the waste liquid is gradually decomposed by the reaction to finally generate calcium phosphate, which mainly involves the following reactions:
2C3H3Cl5＝6C+2Cl2+6HCl
Cl2+H2O＝HCl+HClO
2CaO+2HCl+2HClO＝CaCl2+Ca(ClO)2+2H2O
Ca(ClO)2＝CaCl2+O2
2C+O2＝2CO
2CO+O2＝2CO2
(C2H5O)3PO+H2O＝(C2H5O)2POOH+C2H5OH
(C2H5O)2POOH+H2O＝(C2H5O)PO3H2+C2H5OH
(C2H5O)PO3H2+H2O＝H3PO4+C2H5OH
2H3PO4+3CaO＝Ca3(PO4)2+3H2O
due to the adoption of the technical scheme, the invention has the following beneficial effects:
1. the method has the advantages of high efficiency, wide application range, good treatment effect, high organic phosphorus and organic chlorine removal efficiency, organic chlorine removal rate of over 99.88 percent and organic phosphorus removal rate of over 99.99 percent, and capability of treating high-concentration phosphorus-containing and chlorine-containing organic wastes with high concentration, complex chemical composition, toxicity, harm and poor biodegradability.
2. The method is economic and environment-friendly, can efficiently remove the organic phosphorus and the organic chlorine in the waste containing the organic phosphorus chlorohydrocarbon, realizes the harmless and recycling of the treatment of the organic phosphorus chlorohydrocarbon waste, obtains high-purity phosphate fertilizer and calcium chloride mother liquor, changes waste into valuable, and has good economy.
3. The treatment process is safe and controllable, and the problems that the chlorinated hydrocarbon contains organic phosphorus and other impurities, the components are complex, the thermal cracking device produces abnormal sound, the material is coked, the temperature is unstable, the treatment effect is poor and the like in the actual thermal cracking process are solved; meanwhile, the generated coking waste can be timely removed and crushed through the thermal cracking reactors in the forms of a scraper type reaction furnace and the like, so that the influence of blocky coking materials generated in the material thermal cracking process on the thermal cracking treatment effect is prevented, and the whole thermal cracking reaction is stable and controllable.
4. Simple process, strong operability, easy realization of industrialization, short treatment period and large treatment capacity compared with the treatment by adopting a biological method and a chemical method.
Drawings
FIG. 1 is a process flow diagram of the present invention.
In the figure, a solid feed hopper 1, a waste liquid pump 2, a waste liquid tank 3, a material kneading machine 4, a thermal cracking reactor 5, a combustion reactor 6 and a decarbonization reactor 7.
Detailed Description
As shown in figure 1, the method for treating the waste containing the organophosphorus chlorinated hydrocarbon comprises the following operation flows:
(1) continuously introducing the waste containing the organic phosphorus chlorohydrocarbon and the calcium-containing compound into a thermal cracking reactor 5 for thermal cracking reaction to obtain a thermally cracked material and a first gas-phase product; the feeding mode of the waste containing the organic phosphorus chlorohydrocarbon and the calcium-containing compound can be selected according to the actual production situation, the solid or the waste containing the organic phosphorus chlorohydrocarbon with the solid content of more than 30 percent can be uniformly mixed with the calcium-containing compound in a solid feeding hopper 1 in advance according to a certain proportion, and then the mixture enters a material kneader 4 to be fully and uniformly mixed again and then is added into a thermal cracking reactor 5. The liquid waste containing the organic phosphorus chlorohydrocarbon can be pumped into a thermal cracking reactor 5 from a waste liquid tank 3 through a waste liquid pump 2 and a material kneading machine 4, the calcium-containing compound is added into the thermal cracking reactor 5 from a solid feeding hopper 1 through the material kneading machine 4, and the proportion relation between the waste containing the organic phosphorus chlorohydrocarbon and the calcium-containing compound is controlled by changing the material feeding speed during continuous feeding. Controlling the solid feeding speed by changing the frequency of the material kneading machine 4, and determining the solid feeding amount by calculating the solid addition amount required for maintaining the material level of the solid feeding hopper 1 in a certain time; the liquid feeding speed is controlled by changing the rotating speed of the waste liquid pump 2, and the feeding amount of the waste liquid containing the organophosphorus chlorohydrocarbon is determined by calculating the weight reduction of the waste liquid tank 3 in a certain time;
(2) continuously introducing the thermally cracked material obtained in the step (1) and oxygen-containing gas into a decarbonization reactor 7 for decarbonization reaction to obtain chlorine-containing phosphorus slag and a second gas-phase product, continuously introducing the second gas-phase product, the first gas-phase product obtained in the step (1) and a combustion improver into a combustion reactor 6 for combustion, and performing additional treatment on tail gas obtained by combustion through a tail gas treatment system to achieve the emission standard;
(3) and (3) dissolving the chlorine-containing phosphorus slag obtained in the step (2) by using deionized water, adjusting the pH value of the solution by using hydrochloric acid, filtering, separating and drying to obtain a calcium chloride aqueous solution and calcium phosphate.
The present invention will be described in further detail with reference to examples, but the present invention is not limited to the following examples.
The thermal cracking reactors used in the examples all used a scraper type reactor with an effective volume of 5L.
The combustion promoters used in the examples were all natural gas.
Example 1
(1) Starting a thermal cracking reactor 5 (a scraper type reaction furnace, adopting electric heating for temperature control), and heating the thermal cracking reactor 5 to 650 ℃; starting a stirrer of the solid feeding hopper 1 and the material kneading machine 4, and feeding lime (the content of calcium oxide is 92.1%) into the thermal cracking reactor 5 from the solid feeding hopper 1 through the material kneading machine 4 at the speed of 420 g/h; starting a waste liquid pump 2 to ensure that 1,1,1,3, 3-pentachloropropane (HCC-240fa) waste liquid (the total chlorine content is 62.41 percent and the total phosphorus content is 2.60 percent) enters a thermal cracking reactor 5 through a material kneading machine 4 at the speed of 660 g/h; continuously feeding the waste liquid and lime into a thermal cracking reactor 5, reacting in the thermal cracking reactor 5, wherein the retention time of the materials is 4.8 hours, separating the materials obtained by the reaction at an outlet of the thermal cracking reactor 5, discharging a gas-phase product from the upper part of the thermal cracking reactor 5, feeding the gas-phase product into a combustion reactor 6, and feeding other products into a decarbonization reactor 7 (a horizontal incinerator) through a bin of the thermal cracking reactor 5;
(2) introducing oxygen into a decarburization reactor 7 at a speed of 15.4L/min, controlling the temperature of the decarburization reactor 7 at 750 ℃, keeping the material residence time at 20min, separating the materials generated by the reaction at an outlet of the decarburization reactor 7, introducing chlorine-containing phosphorus slag into a bin of the decarburization reactor 7, and discharging a gas-phase product of the decarburization reaction from the upper part of the decarburization reactor 7 to enter a combustion reactor 6; the temperature of the combustion reactor 6 is controlled at 1000 ℃, the retention time is 20s, and the ratio of the natural gas air input to the total volume of the gas-phase product of the thermal cracking reaction and the gas-phase product of the decarburization reaction is 8: 1;
(3) after the parameters such as the reaction temperature, the material feeding amount and the like of the thermal cracking reactor 5, the combustion reactor 6 and the decarbonization reactor 7 are stable for 6 hours, 730g of the discharged material of the chlorine-containing phosphorus slag obtained within 1 hour is collected, and the contents of inorganic chlorine and organic chlorine are 56.38 percent and 0.036 percent respectively;
(4) weighing 100g of the chlorine-containing phosphorus slag obtained in the step (3), adding 300g of deionized water, stirring at room temperature for 30min, neutralizing with hydrochloric acid until the pH value is 7.20, filtering to obtain a filtrate containing 29.43% of calcium chloride, and drying a filter cake to obtain 11.71g of calcium phosphate.
Example 2
(1) Starting the thermal cracking reactor 5, and heating the thermal cracking reactor 5 to 680 ℃; uniformly mixing lime (the content of calcium oxide is 90.0%) and waste containing organophosphorus chlorohydrocarbon (the content of total chlorine is 46.63%, the content of total phosphorus is 6.48%) in a solid feeding hopper 1 in advance according to the mass ratio of 1.85: 3, starting a material kneading machine 4, feeding the mixture of the lime and the waste containing organophosphorus chlorohydrocarbon into a thermal cracking reactor 5 from the solid feeding hopper 1 through the material kneading machine 4 at the speed of 1730g/h, mixing and reacting in the thermal cracking reactor 5, wherein the retention time of the material is 3.03 hours, separating the material obtained by the reaction at an outlet of the thermal cracking reactor 5, discharging a gas-phase product from the upper part of the thermal cracking reactor 5 into a combustion reactor 6, and feeding other products into a decarbonization reactor 7 (a horizontal incinerator) through a bin of the thermal cracking reactor 5;
(2) introducing oxygen into the decarburization reactor 7 at a speed of 37.45L/min, controlling the temperature of the decarburization reactor 7 at 710 ℃, keeping the material for 60min, separating the material generated by the reaction at the outlet of the decarburization reactor 7, introducing chlorine-containing phosphorus slag into a bin of the decarburization reactor 7, and discharging the gas-phase product of the decarburization reaction from the upper part of the decarburization reactor 7 to enter the combustion reactor 6; the temperature of the combustion reactor 6 is controlled at 1100 ℃, the retention time is 10s, and the ratio of the natural gas air input to the total volume of the gas-phase product of the thermal cracking reaction and the gas-phase product of the decarburization reaction is 7: 1;
(3) after the parameters such as the reaction temperature of the thermal cracking reactor 5, the combustion reactor 6 and the decarbonization reactor 7, the feeding amount of each material and the like are stable for 6 hours, 1127.1g of the discharged material of the chlorine-containing phosphorus slag obtained within 1 hour is collected, and the contents of inorganic chlorine and organic chlorine are 44.22 percent and 0.038 percent respectively;
(4) weighing 100g of the chlorine-containing phosphorus slag obtained in the step (3), adding 300g of deionized water, stirring at room temperature for 30min, neutralizing with hydrochloric acid until the pH value is 7.80, filtering to obtain filtrate containing 23.09% of calcium chloride, and drying a filter cake to obtain 30.72g of calcium phosphate.
Example 3
(1) Starting the thermal cracking reactor 5, and heating the thermal cracking reactor 5 to 600 ℃; starting the stirrer of the solid feeding hopper 1 and the material kneading machine 4, and feeding calcium hydroxide (calcium hydroxide content 76.60%) from the solid feeding hopper 1 into the thermal cracking reactor 5 through the material kneading machine 4 at a speed of 580 g/h; starting a waste liquid pump 2 to ensure that the HCC-240fa waste liquid (the total chlorine content is 62.41 percent and the total phosphorus content is 2.60 percent) enters a thermal cracking reactor 5 through a material kneader 4 at the speed of 560 g/h; the HCC-240fa waste liquid and the calcium hydroxide continuously enter a thermal cracking reactor 5 to react in the thermal cracking reactor 5, the retention time of the materials is 4.33 hours, the materials obtained by the reaction are separated at the outlet of the thermal cracking reactor 5, a gas phase product is discharged from the upper part of the thermal cracking reactor 5 to enter a combustion reactor 6, and other products enter a decarbonization reactor 7 (a horizontal incinerator) through a bin of the thermal cracking reactor 5;
(2) introducing oxygen into the decarburization reactor 7 at a speed of 19.6L/min, controlling the temperature of the decarburization reactor 7 at 720 ℃, keeping the materials for 30min, separating the materials generated by the reaction at an outlet of the decarburization reactor 7, introducing chlorine-containing phosphorus slag into a bin of the decarburization reactor 7, and discharging a gas-phase product of the decarburization reaction from the upper part of the decarburization reactor 7 to enter the combustion reactor 6; the temperature of the combustion reactor 6 is controlled to be 900 ℃, the material retention time is 15s, and the ratio of the natural gas air input to the total volume of the gas-phase product of the thermal cracking reaction and the gas-phase product of the decarburization reaction is 10: 1;
(3) after the parameters such as the reaction temperature, the material feeding amount and the like of the thermal cracking reactor 5, the combustion reactor 6 and the decarbonization reactor 7 are stable for 6 hours, 619.6g of the discharged chlorine-containing phosphorus slag obtained in 1 hour is collected, and the contents of inorganic chlorine and organic chlorine are 56.36 percent and 0.039 percent respectively;
(4) weighing 100g of the chlorine-containing phosphorus slag obtained in the step (3), adding 300g of deionized water, stirring at room temperature for 30min, neutralizing with hydrochloric acid until the pH value is 7.60, filtering to obtain a filtrate containing 29.43% of calcium chloride, and drying a filter cake to obtain 11.72g of calcium phosphate.
Example 4
(1) Starting the thermal cracking reactor 5, and heating the thermal cracking reactor 5 to 700 ℃; starting a stirrer of the solid feeding hopper 1 and the material kneading machine 4, and feeding limestone (calcium carbonate content is 98.0%) into the thermal cracking reactor 5 from the solid feeding hopper 1 through the material kneading machine 4 at a speed of 626 g/h; starting a waste liquid pump 2 to ensure that the HCC-240fa waste liquid (the total chlorine content is 62.72 percent and the total phosphorus content is 2.95 percent) enters a thermal cracking reactor 5 through a material kneader 4 at the speed of 560 g/h; the HCC-240fa waste liquid and limestone continuously enter a thermal cracking reactor 5 to react in the thermal cracking reactor 5, the retention time of the materials is 4.12 hours, the materials obtained by the reaction are separated at the outlet of the thermal cracking reactor 5, a gas phase product is discharged from the upper part of the thermal cracking reactor 5 and enters a combustion reactor 6, and other products enter a decarbonization reactor 7 (a horizontal incinerator) through a bin of the thermal cracking reactor 5;
(2) introducing oxygen into the decarburization reactor 7 at a speed of 26.13L/min, controlling the temperature of the decarburization reactor 7 at 740 ℃, keeping the materials for 50min, separating the materials generated by the reaction at an outlet of the decarburization reactor 7, introducing chlorine-containing phosphorus slag into a bin of the decarburization reactor 7, and discharging a gas-phase product of the decarburization reaction from the upper part of the decarburization reactor 7 to enter the combustion reactor 6; the temperature of the combustion reactor 6 is controlled to be 1000 ℃, the material retention time is 20s, and the ratio of the natural gas air input to the total volume of the gas-phase product of the thermal cracking reaction and the gas-phase product of the decarburization reaction is 6: 1;
(3) after the parameters such as the reaction temperature of the thermal cracking reactor 5, the combustion reactor 6 and the decarbonization reactor 7, the feeding amount of each material and the like are stable for 6 hours, 632g of chlorine-containing phosphorus slag discharge obtained within 1 hour is collected, and the contents of inorganic chlorine and organic chlorine are 55.53 percent and 0.039 percent respectively;
(4) weighing 100g of the chlorine-containing phosphorus slag obtained in the step (3), adding 300g of deionized water, stirring at room temperature for 30min, neutralizing with hydrochloric acid until the pH value is 7.70, filtering to obtain a filtrate containing 28.99% of calcium chloride, and drying a filter cake to obtain 13.03g of calcium phosphate.
Example 5
(1) Starting the thermal cracking reactor 5, and heating the thermal cracking reactor 5 to 620 ℃; limestone (calcium carbonate content 98.0%) and waste containing organophosphorus chlorohydrocarbon (total chlorine content 46.63% and total phosphorus content 6.48%) are uniformly mixed in a solid charging hopper 1 in advance according to a mass ratio of 1.09: 1, a material kneading machine 4 is started, the mixture of the limestone and the waste containing organophosphorus chlorohydrocarbon enters a thermal cracking reactor 5 from the solid charging hopper 1 through the material kneading machine 4 at a speed of 816g/h, the mixture is mixed and reacted in the thermal cracking reactor 5, the retention time of the materials is 6 hours, the materials obtained by the reaction are separated at an outlet of the thermal cracking reactor 5, a gas-phase product is discharged from the upper part of the thermal cracking reactor 5 and enters a combustion reactor 6, and other products enter a decarbonization reactor 7 (horizontal incinerator) through a bin of the thermal cracking reactor 5;
(2) introducing oxygen into the decarburization reactor 7 at a speed of 22.75L/min, controlling the temperature of the decarburization reactor 7 at 700 ℃, keeping the material for 40min, separating the material generated by the reaction at the outlet of the decarburization reactor 7, introducing chlorine-containing phosphorus slag into a bin of the decarburization reactor 7, and discharging the gas-phase product of the decarburization reaction from the upper part of the decarburization reactor 7 to enter the combustion reactor 6; the temperature of the combustion reactor 6 is controlled at 1100 ℃, the retention time is 5s, and the ratio of the natural gas air input to the total volume of the gas-phase product of the thermal cracking reaction and the gas-phase product of the decarburization reaction is 5: 1;
(3) after the parameters such as the reaction temperature of the thermal cracking reactor 5, the combustion reactor 6 and the decarbonization reactor 7, the feeding amount of each material and the like are stable for 6 hours, 411.6g of the discharged material of the chlorine-containing phosphorus slag obtained within 1 hour is collected, and the contents of inorganic chlorine and organic chlorine are 44.24 percent and 0.038 percent respectively;
(4) weighing 100g of the chlorine-containing phosphorus slag obtained in the step (3), adding 300g of deionized water, stirring at room temperature for 30min, neutralizing with hydrochloric acid until the pH value is 6.80, filtering to obtain filtrate containing 23.10% of calcium chloride, and drying a filter cake to obtain 30.71g of calcium phosphate.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111114715.6A CN114105181A (en) | 2021-09-23 | 2021-09-23 | Method for treating waste containing organic phosphorus chlorohydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111114715.6A CN114105181A (en) | 2021-09-23 | 2021-09-23 | Method for treating waste containing organic phosphorus chlorohydrocarbon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114105181A true CN114105181A (en) | 2022-03-01 |
Family
ID=80441172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111114715.6A Pending CN114105181A (en) | 2021-09-23 | 2021-09-23 | Method for treating waste containing organic phosphorus chlorohydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114105181A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115722521A (en) * | 2022-11-23 | 2023-03-03 | 北京科技大学 | Treatment method and system for chlorine-containing disinfectant solid waste |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1126235A (en) * | 1994-06-16 | 1996-07-10 | 英国石油化学品有限公司 | waste disposal |
| CN102874786A (en) * | 2012-10-12 | 2013-01-16 | 山东潍坊润丰化工有限公司 | Processing method of glyphosate mother liquor |
| CN103710036A (en) * | 2014-01-09 | 2014-04-09 | 山东潍坊润丰化工股份有限公司 | Treatment method for phosphorus-containing waste materials in pesticide production |
| CN103708572A (en) * | 2014-01-09 | 2014-04-09 | 山东潍坊润丰化工股份有限公司 | Resourceful treatment method for inorganic salts in industrial waste water |
| CN111112286A (en) * | 2019-12-17 | 2020-05-08 | 宁波巨化化工科技有限公司 | Organic waste treatment method |
| CN111112290A (en) * | 2019-12-20 | 2020-05-08 | 浙江巨化技术中心有限公司 | Dechlorination method for chlorinated hydrocarbon waste |
-
2021
- 2021-09-23 CN CN202111114715.6A patent/CN114105181A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1126235A (en) * | 1994-06-16 | 1996-07-10 | 英国石油化学品有限公司 | waste disposal |
| CN102874786A (en) * | 2012-10-12 | 2013-01-16 | 山东潍坊润丰化工有限公司 | Processing method of glyphosate mother liquor |
| CN103710036A (en) * | 2014-01-09 | 2014-04-09 | 山东潍坊润丰化工股份有限公司 | Treatment method for phosphorus-containing waste materials in pesticide production |
| CN103708572A (en) * | 2014-01-09 | 2014-04-09 | 山东潍坊润丰化工股份有限公司 | Resourceful treatment method for inorganic salts in industrial waste water |
| CN111112286A (en) * | 2019-12-17 | 2020-05-08 | 宁波巨化化工科技有限公司 | Organic waste treatment method |
| CN111112290A (en) * | 2019-12-20 | 2020-05-08 | 浙江巨化技术中心有限公司 | Dechlorination method for chlorinated hydrocarbon waste |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115722521A (en) * | 2022-11-23 | 2023-03-03 | 北京科技大学 | Treatment method and system for chlorine-containing disinfectant solid waste |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108559857B (en) | Waste mercury catalyst mercury recovery and slag harmless treatment process | |
| CN109539272A (en) | The high-temperature plasma recycling recovery process of waste containing chlorine and system | |
| CN111234880A (en) | Clean resource treatment method for solid waste and hazardous waste | |
| CN111112290B (en) | Dechlorination method for chlorinated hydrocarbon waste | |
| CN112320822B (en) | Waste salt recycling treatment method | |
| CN110624938A (en) | Treatment system for hazardous waste salt production by-products | |
| CN105000775A (en) | Deep dewatering system and method for sludge | |
| US4384923A (en) | Process for the hygienization of carbonation sludges | |
| JP2007196153A (en) | Ash treatment method and apparatus | |
| CN114105181A (en) | Method for treating waste containing organic phosphorus chlorohydrocarbon | |
| JP4087657B2 (en) | Waste treatment method and cement raw material manufacturing method | |
| CN111288466A (en) | High-salt waste liquid incineration treatment method | |
| CN105945028A (en) | Domestic garbage incineration, regeneration and utilization process | |
| CN109099437B (en) | Comprehensive waste treatment system and treatment method thereof | |
| JP2003247710A (en) | Integrated treatment method for waste and its device | |
| JP3952702B2 (en) | Pyrolysis treatment facility using gas engine power generation facility using digestion gas | |
| CN111102584A (en) | Polychlorinated hydrocarbon waste treatment device and method | |
| CN211191372U (en) | Treatment system for hazardous waste salt production by-products | |
| CN114812156A (en) | Waste salt pyrolysis treatment system and method based on multi-hearth furnace | |
| CN209309994U (en) | Chlorine Waste High Temperature Plasma Recycling System | |
| JP6606132B2 (en) | Radiocesium removal method and treatment facility | |
| CN112723430A (en) | Method for treating and recycling waste liquid generated in production of polyolefin catalyst | |
| CN218811433U (en) | A device for firing ceramsite by incineration fly ash flotation coupled with rotary kiln | |
| RU2831578C1 (en) | System for thermal treatment of biological waste water treatment sludge | |
| JP4097573B2 (en) | Waste gas treatment furnace waste gas treatment method and treatment system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220301 |
|
| RJ01 | Rejection of invention patent application after publication |