CN110183322B - Method for treating low-concentration acetic acid wastewater containing mineral acid salts - Google Patents
Method for treating low-concentration acetic acid wastewater containing mineral acid salts Download PDFInfo
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Abstract
The invention discloses a method for treating low-concentration acetic acid wastewater containing mineral acid salts. The method comprises the steps of carrying out first MVR treatment on low-concentration acetic acid wastewater containing mineral acid salts, separating the mineral acid salts from the wastewater, carrying out calcification neutralization reaction on the separated acetic acid wastewater under the action of calcium carbonate to form a solution containing calcium acetate, carrying out concentration treatment in a second MVR device, drying the concentrated calcium acetate solution, and carrying out acidolysis reaction to obtain acetic acid, thereby realizing resource utilization of organic matters. Carrying out thermal desorption on the obtained mineral acid salt and the solid generated by filtering, and enabling the generated gas to enter an oxygen-critical cracking device, wherein the obtained solid material forms a mineral acid salt solid with the organic impurity content of less than 0.1%. The water vapor containing organic matters generated by MVR and the water vapor generated by calcium acetate drying enter the MVR device at the same time, and the tail gas and water treated by the oxygen cracking device reach the discharge standard. The method can realize the resource and purification treatment of the low-concentration acetic acid wastewater containing mineral acid salts.
Description
Technical Field
The invention relates to the field of treatment of industrial acetic acid wastewater, in particular to purification and resource treatment of low-concentration acetic acid wastewater containing mineral acid salts.
Background
Acetic acid is an important chemical raw material and has wide application. In the production processes of acetic acid, furfural, paper making, dyes, medicines and pesticides, vinyl acetate, acetic ester, polyethylene and the like, a large amount of acetic acid-containing wastewater is generated. Moreover, with the rapid development of the industry, a large amount of acetic acid wastewater is generated, so that the treatment thereof becomes a significant problem which is not negligible. The acetic acid wastewater contains acetic acid lost with water, intermediate products, byproducts, pollutants generated in the production process and the like. If the substances cannot be timely and effectively treated, the substances are directly thrown into the nature, and very serious environmental pollution is possibly caused. In addition, acetic acid has wide application in the aspects of dye, food, medicine, pesticide, plastic, chemical fiber, adhesive, organic solvent and the like, and has important function for many departments of national economy. Therefore, the method effectively purifies and treats the acetic acid wastewater, recycles and utilizes the acetic acid in the wastewater, and has important significance in the aspects of resource reutilization, environmental pollution control and the like. The acetic acid wastewater has high acidity and COD value up to tens of thousands to hundreds of thousands of mgO2and/L, a small amount of mineral acid salt often exists in the acetic acid wastewater, and the purification treatment difficulty is very high.
The acetic acid wastewater is generally purified and treated by a neutralization method in industry, and the obtained acetate is not generally recycled and is directly discharged. The treatment method has simple and convenient process operation and easy control. However, the treatment method only solves the acidity of the wastewater after neutralization, and the COD value is increased compared with that before neutralization. In addition, the problem of waste of acetic acid resource is also caused. Therefore, the recycling of acetic acid is the main direction of acetic acid wastewater treatment. The existing method for recycling acetic acid comprises the following steps: esterification: the acetate is produced by adding some compounds after concentrating the concentrated acetic acid waste water or dilute acetic acid waste water and reacting. However, the method has high cost of concentration and crystallization and is hindered from industrial popularization. The adsorption process is one effective method of treating low concentration acetic acid effluent and features that dilute acetic acid is first adsorbed and separated from effluent or other material with solid adsorbent and then desorbed and recovered with different methods. For example, in the technical scheme CN1354139A, activated carbon is adopted to adsorb and separate acetic acid from wastewater, and then a methanol water solution is used for washing an adsorption column to desorb the acetic acid, and an adsorbent is regenerated. The desorption solution containing methanol and acetic acid is continuously contacted with a cation exchange resin catalyst to generate a methyl acetate product which is recovered by rectification. However, the adsorption method has the defects of high adsorbent regeneration cost, easy pollution by heavy metal ions and the like. Extraction method for treating acetic acid wastewater by using extraction method, in the technical scheme CN101955274A, ethyl acetate is used for extracting organic matters and acetic acid, and according to the principle that ethyl acetate and water are azeotropic and do not azeotrope with acetic acid, ethyl acetate is separated out by a simple distillation method, and simultaneously, a large amount of water carried in the extraction liquid can be removed, thereby improving the concentration of recovered acetic acid. However, the method has the defects of large catalyst consumption, high extraction cost, increased energy consumption of a subsequent separation section and easy secondary pollution. Membrane separation method: the membrane separation method for treating acetic acid wastewater is very safe and environment-friendly, and in the technical scheme CN204369685U, the pH value of wastewater is adjusted through a medicine containing tank arranged in a pretreatment tank, and then concentrated acetic acid solution is obtained through a cartridge filter, a high-pressure pump and a membrane assembly in sequence. The wastewater membrane treatment device has the advantages of simple structure and small occupied area, and the treated wastewater can be reused in production process and circulating water, so that the wastewater membrane treatment device is energy-saving and environment-friendly. However, the preparation cost of the separation membrane used by the method is high, the separation membrane is easy to pollute, and the harmfulness of the industrial wastewater to membrane pollution needs to be deeply researched. The CN206799475U mentions that the rectification method is used for treating acetic acid wastewater, but the boiling points of acetic acid and water are similar, the boiling point of water is lower than that of acetic acid, and the relative volatilities of the two are also similar, so that the acetic acid can not be obtained by conventional rectification, and a special rectification method is required, thereby causing the defects of large equipment investment, high rectification cost and the like.
In summary, the existing treatment of acetic acid wastewater still has many disadvantages. Meanwhile, mineral acid salts and organic impurities in the acetic acid wastewater bring great troubles to the recycling and purification treatment of the acetic acid wastewater, and a new treatment method is greatly needed to be developed.
Disclosure of Invention
The invention aims to effectively realize the recycling and deep purification treatment of the low-concentration acetic acid wastewater containing mineral acid salts through a new process method, recover the acetic acid resource, realize the separation of non-acetic acid organic impurities and the recovered acetic acid in the wastewater, simultaneously convert the dangerous waste into harmless solid materials, greatly reduce the cost of treating the dangerous waste by enterprises, and convert the wastewater into purified water without further biochemical treatment.
The specific technical scheme of the invention is as follows:
a treatment method of low-concentration acetic acid wastewater containing mineral acid salts comprises acetic acid, sulfate and organic impurities, and comprises the following steps: the method comprises the following steps of firstly carrying out first MVR treatment on the low-concentration acetic acid wastewater containing mineral acid salts, separating the mineral acid salts from the low-concentration acetic acid wastewater containing the mineral acid salts, carrying out calcification neutralization on the low-concentration acetic acid wastewater after the mineral acid salts are separated under the action of calcium carbonate, converting acetic acid in the low-concentration acetic acid wastewater into calcium acetate, obtaining a calcium acetate aqueous solution, carrying out second MVR treatment on the calcium acetate aqueous solution, separating organic impurities from the calcium acetate in the aqueous solution, separating the organic impurities to obtain a calcium acetate suspension, drying to obtain a calcium acetate solid, and carrying out acidolysis treatment on the calcium acetate solid under the action of sulfuric acid to generate acetic acid and calcium sulfate; the first MVR obtains mineral acid salt and calcium sulfate generated by acidolysis is subjected to thermal desorption treatment, gas formed by thermal desorption treatment, water vapor containing organic impurities generated by the second MVR and water vapor generated by drying enter an adjacent oxygen cracking device, and deep purification treatment is performed under the air atmosphere.
Further, the method comprises the following specific steps:
(1) carrying out first MVR treatment on the waste water containing mineral acid salt and acetic acid, and separating the mineral acid salt from the waste water containing the mineral acid salt and acetic acid to respectively obtain a solid-liquid mixture containing the mineral acid salt and low-concentration acetic acid waste water; carrying out thermal desorption on the solid-liquid mixture containing mineral acid salt, separating to obtain solid materials and gas, wherein the solid materials generated by thermal desorption are the mineral acid salt and organic impurities, and the gas generated by thermal desorption enters an oxygen-critical cracking device for deep purification treatment;
(2) carrying out calcification neutralization treatment on the low-concentration acetic acid wastewater obtained in the step (1) in the presence of calcium carbonate to convert acetic acid in the low-concentration acetic acid wastewater into calcium acetate to form a calcium acetate aqueous solution containing organic impurities, wherein the calcification neutralization reaction is as follows: CaCO3+2CH3COOH＝(CH3COO)2Ca+H2O+CO2×, the addition amount of calcium carbonate is determined according to the stoichiometric ratio of acetic acid to calcium carbonate;
(3) carrying out secondary MVR treatment on the calcium acetate aqueous solution containing the organic impurities obtained in the step (2), and evaporating out water vapor containing the organic impurities to obtain a calcium acetate suspension; the steam containing organic impurities enters an oxygen cracking device to be subjected to deep purification treatment under the air condition, the water and steam discharged by the oxygen cracking device reach the standard and are discharged, and the COD (chemical oxygen demand) of the water discharged by the oxygen cracking device is less than 40mgO2L, gas VOC less than 50mg/m3Drying the calcium acetate suspension generated by the second MVR treatment;
(4) drying the calcium acetate suspension obtained in the step (3), wherein the water vapor generated in the drying process also enters an oxygen-critical cracking device, and drying to obtain a calcium acetate solid;
(5) and (3) carrying out acidolysis treatment on the calcium acetate solid obtained in the step (4) in the presence of sulfuric acid, wherein the acidolysis reaction is as follows: ca (CH)3COO)2+H2SO4＝CaSO4↓+2CH3COOH, the addition of sulfuric acid is determined according to the stoichiometric ratio of sulfuric acid and calcium acetate, the acid hydrolysis treatment generates acetic acid and calcium sulfate, the acetic acid can be recycled, the calcium sulfate solid is subjected to heat desorption, and the mineral acid salt generated by the heat desorption is treated as common solid waste.
Furthermore, the content of acetic acid in the low-concentration acetic acid wastewater containing mineral acid salts is 0.5-15 wt%, the content of organic impurities is 0.01-0.5 wt%, and the content of mineral acid salts is 1-5 wt%.
Furthermore, the organic impurities in the invention refer to organic matters except acetic acid in the low-concentration acetic acid wastewater containing mineral acid salts. The organic impurities are one or more of methyl acetate, ethyl acetate, propyl acetate, tert-butyl acetate, n-butyl acetate, methanol, ethanol, propanol, tert-butanol, and n-butanol.
Further, the mineral acid salt is one or a mixture of potassium sulfate, sodium sulfate, magnesium sulfate, ferric sulfate, lithium sulfate, chromium sulfate, nickel sulfate, zinc sulfate and manganese sulfate.
Further, the thermal desorption, namely the thermal desorption of the solid-liquid mixture containing the mineral acid salt in the step (1) and the thermal desorption of the calcium sulfate solid in the step (5), is carried out at the treatment temperature of 200-400 ℃, and gas generated after the thermal desorption enters an oxygen adjacent cracking device.
Further, the first MVR treatment time is 1-3 h, and the treatment temperature is 50-100 ℃.
Further, the calcium acetate aqueous solution is concentrated to a calcium acetate content of 30-40 wt% by the second MVR treatment, that is, the calcium acetate content in the calcium acetate suspension in the step (3) is 30-40 wt%, organic impurities in the calcium acetate aqueous solution enter the MVR gas phase, and the time for the second MVR treatment of the calcium acetate aqueous solution containing the organic impurities is 1-2 hours.
Further, the process conditions of the temporary oxygen cracking are as follows: the purification reaction temperature is 250-450 ℃, the reaction pressure is normal pressure, and the retention time is 0.1-10 kg.h/m3The volume ratio of the air introduction amount to the water vapor entering the temporary oxygen cracking device is 1-5: 1.
Further, the gas entering the temporary oxygen cracking device comprises steam generated by secondary MVR, gas generated by thermal analysis and water vapor generated by drying of a calcium acetate solution; the gas phase outlet of the MVR device is connected with the inlet of the temporary oxygen cracking device, and the outlet of the temporary oxygen cracking deviceThe high-temperature gas is connected with an inlet of a hot fluid pipe of the MVR device, heat released by the temporary oxygen cracking reaction is used for gasifying liquid in the MVR device, the temporary oxygen cracking device and the MVR device realize self-heating balance, and no external energy is needed for gasifying the liquid in the MVR device; the COD value in the water discharged by the temporary oxygen cracking device is 0-40 mgO2The total amount of VOC in the discharged waste gas is 5-50 mg/m3。
Further, sulfuric acid adopted in the acidolysis treatment is concentrated sulfuric acid with the mass fraction of not less than 98%, and the calcium sulfate formed after acidolysis is subjected to a heat removal and analysis process.
Furthermore, the content of organic impurities in the solid materials generated in the thermal desorption process is lower than 0.1 percent, and the solid materials do not belong to hazardous wastes.
The invention has the beneficial effects that:
according to the invention, the low-concentration acetic acid wastewater containing mineral acid salts is subjected to a new process route of first MVR, thermal analysis → calcification → second MVR, drying → temporary oxygen cracking → acidolysis, so that the recycling and deep purification treatment of the low-concentration acetic acid wastewater containing mineral acid salts is realized. The treatment method of the invention converts hazardous wastes (namely mineral acid salts and organic impurities) in the wastewater into harmless solid materials with the total content of the organic impurities lower than 0.1 through the first MVR treatment and thermal desorption, and separates the harmless solid materials from the wastewater. The separation of remaining organic impurity and calcification reaction intermediate product calcium acetate has been realized in the waste water through the MVR processing of the second time to retrieve the acetic acid resource in handling from intermediate product calcium acetate through the acidolysis, and separate out calcium acetate, simultaneously, steam, the gas that the thermal analysis produced, the steam of calcium acetate solution drying production that MVR produced all handle through the clinical oxygen cracker, discharge up to standard. The treatment method of the invention realizes the separation of sulfate and non-acetic acid organic impurities from the recovered acetic acid in the low-concentration acetic acid wastewater containing mineral acid salts. Simultaneously, the gaseous phase export of MVR device links to each other with facing the oxygen cracker import, faces that oxygen cracker export high temperature gas links to each other with MVR device hot-fluid pipe entry, faces the gasification that the heat that the oxygen cracking reaction discharged is arranged in MVR to handle liquid, faces oxygen cracker and MVR device and realizes self-heating balance, and the gasification of liquid need not plus energy in the MVR device, has effectively improved the utilization of energy. The technical scheme of the invention greatly reduces the cost of treating the hazardous waste by enterprises, and converts the waste water into purified water without further biochemical treatment.
Drawings
FIG. 1 is a process diagram of the treatment method of low-concentration acetic acid wastewater containing mineral acid salts.
Detailed Description
Example 1
The low-concentration acetic acid wastewater containing mineral acid salts comprises the following components: 5.8 percent of acetic acid, 0.02 percent of propanol, 0.012 percent of n-butyl alcohol, 0.013 percent of tertiary butyl alcohol, 0.011 percent of propyl acetate, 0.022 percent of tertiary butyl acetate, 0.02 percent of n-butyl acetate, 3.3 percent of potassium sulfate, 0.05 percent of magnesium sulfate, 1.4 percent of lithium sulfate, 0.21 percent of manganese sulfate and the balance of water.
The low concentration acetic acid wastewater containing mineral acid salt was fed into the MVR unit at a rate of 2000kg/h over 2h, and the first MVR treatment was carried out at 95 ℃. The discharge rate of mineral acid salt in the MVR device is 109.2kg/h, the material discharged out of the MVR system along with the mineral acid salt contains water of 72.8kg/h, the total amount of organic matters in the material discharged out of the MVR system along with the mineral acid salt is 0.098kg/h (wherein the flow rate of acetic acid is 0.0049kg/h), the solid-liquid mixture, namely the solid-liquid mixture containing the mineral acid salt obtained by the first MVR treatment enters a thermal desorption process, and the thermal desorption temperature is 380 ℃: the water vapor and organic matter vapor generated by thermal desorption enter an oxygen cracking device for deep purification treatment, and the process conditions of the oxygen cracking are as follows: the reaction temperature is 400 ℃, the reaction pressure is normal pressure, and the retention time is 4 kg.h/m3The volume ratio of the air introduction amount to the water vapor entering the temporary oxygen cracking device is 1.5. The solid materials obtained by thermal desorption are mineral acid salt and organic impurities, the contents of potassium sulfate, magnesium sulfate, lithium sulfate and manganese sulfate obtained by thermal desorption separation are respectively 66kg, 1kg, 28kg and 0.42kg, and the contents of organic impurities such as propanol, n-butyl alcohol, tert-butyl alcohol, propyl acetate, n-butyl acetate, tert-butyl acetate and the like are respectively 0.11kg, 0.02kg, 0.05kg, 0.006kg, 0.002kg,0.002kg, this solid material was disposed of as general solid waste.
The gas phase outlet of the MVR device is connected with the inlet of the temporary oxygen cracking device, high-temperature gas at the outlet of the temporary oxygen cracking device is connected with the steam inlet of the MVR device, and the heat released by the temporary oxygen cracking reaction is used for gasifying liquid in the MVR device.
The flow rate at the liquid phase outlet of the MVR device is 1817.9kg/h (wherein the flow rate of acetic acid is 115.9kg/h, organic impurities enter the temporary oxygen cracking device to be purified), and the distillate liquid phase, namely acetic acid wastewater, is 3635.8kg in total and enters an intermediate tank to be stored.
Adding 2000kg of acetic acid wastewater in the intermediate tank into a calcification neutralization reaction kettle, slowly adding 130kg of calcium carbonate in batches under a stirring state to convert acetic acid in distillate into calcium acetate, stirring at room temperature for 1 hour, raising the pH value of the wastewater to 6-7, filtering the reaction liquid to remove excessive calcium carbonate, then entering the calcification neutralization filter liquid intermediate tank to obtain a calcium acetate aqueous solution containing organic impurities, and waiting for secondary MVR treatment.
Inputting an aqueous solution of calcium acetate containing organic impurities into the MVR device at a rate of 2000kg/h within 1h, and carrying out secondary MVR treatment at 95 ℃:
the gas phase outlet of the MVR device is connected with the inlet of the temporary oxygen cracking device, the vapor containing organic impurities and evaporated in the second MVR treatment enters the temporary oxygen cracking device in the form of gas phase, the high-temperature gas at the outlet of the temporary oxygen cracking device is connected with the gas phase inlet of the MVR device, and the heat released in the temporary oxygen cracking reaction is used for the gasification of the liquid in the MVR device.
The discharge rate of calcium acetate in the MVR device is 150.8kg/h, the material discharged out of the MVR system along with the calcium acetate contains 237.1kg/h of water, and the solid-liquid mixture is the calcium acetate suspension with the calcium acetate content of 38.9% obtained by the second MVR treatment. And (3) drying the calcium acetate suspension: and (3) introducing water vapor generated by drying into an oxygen-critical cracking device, and drying the calcium acetate suspension to obtain 152.7kg of calcium acetate solid.
The gas entering the temporary oxygen cracking device comprises the steam generated by the MVR, the gas generated by the thermal analysis and the gas generated by the drying of the calcium acetate solutionThe water vapor is subjected to the oxygen cracking reaction, and the COD value of the water finally discharged out of the oxygen cracking system is 8mgO2Per L, VOC concentration in the gas phase of 12mg/m3。
100kg of calcium acetate solid obtained after drying treatment of the calcium acetate suspension is added into an acidolysis reaction kettle at normal temperature, 49.1kg of 98% concentrated sulfuric acid is slowly added, stirring reaction is carried out for half an hour, then filtration is carried out, 84.4kg of calcium sulfate solid (containing 0.65kg of acetic acid) and 57.1kg of acetic acid are obtained, the obtained calcium sulfate solid is removed from a thermal desorption reactor, sulfate generated by thermal desorption is treated as common solid waste, and the acetic acid is recycled.
Example 2
The experiment was carried out by the same process as in example 1.
The low-concentration acetic acid wastewater containing mineral acid salts comprises the following components: 1.5 percent of acetic acid, 0.02 percent of methanol, 0.012 percent of ethanol, 0.013 percent of tertiary butanol, 0.011 percent of methyl acetate, 0.022 percent of ethyl acetate, 0.02 percent of tertiary butyl acetate, 2.3 percent of potassium sulfate, 0.05 percent of magnesium sulfate, 1.4 percent of chromium sulfate, 0.21 percent of nickel sulfate and the balance of water.
The mineral acid salt-containing low-concentration acetic acid wastewater was fed into the MVR device at a rate of 1500kg/h over 2 hours, and subjected to a first MVR treatment at 95 ℃. The discharge rate of mineral acid salt in the MVR device is 69.4kg/h, the material discharged out of the MVR system along with the mineral acid salt contains 50.0kg/h of water, the total amount of organic matters in the material discharged out of the MVR system along with the mineral acid salt is 0.026kg/h (wherein the flow rate of acetic acid is 0.0013kg/h), the solid-liquid mixture, namely the solid-liquid mixture containing the mineral acid salt obtained by the first MVR treatment enters a thermal desorption process, and the thermal desorption temperature is 380 ℃: the water vapor and organic matter vapor generated by thermal desorption enter an oxygen cracking device for deep purification treatment, and the process conditions of the oxygen cracking are as follows: the reaction temperature is 400 ℃, the reaction pressure is normal pressure, and the retention time is 5 kg.h/m3The volume ratio of the air introduction amount to the water vapor entering the temporary oxygen cracking device is 2. The solid material obtained by thermal desorption is mineral acid salt and organic impurities, and thermal desorption is carried outThe contents of mineral acid salts such as potassium sulfate, magnesium sulfate, chromium sulfate, nickel sulfate and the like obtained by separation are 69kg, 1.5kg, 42kg and 6.3kg respectively, and the contents of organic impurities such as methanol, ethanol, tertiary butanol, methyl acetate, ethyl acetate, tertiary butyl acetate and the like are 0.01kg, 0.012kg, 0.005kg, 0.003kg, 0.001kg and 0.001kg respectively.
The gas phase outlet of the MVR device is connected with the inlet of the temporary oxygen cracking device, high-temperature gas at the outlet of the temporary oxygen cracking device is connected with the steam inlet of the MVR device, and the heat released by the temporary oxygen cracking reaction is used for gasifying liquid in the MVR device.
The flow rate at the liquid phase outlet of the MVR device is 1384.3kg/h (the flow rate of acetic acid is 22.5kg/h, organic impurities enter the temporary oxygen cracking device to be purified), and the distillate liquid phase, namely acetic acid wastewater, is 2768.6kg in total and enters an intermediate tank to be stored.
Adding 2000kg of acetic acid wastewater in the intermediate tank into a calcification neutralization reaction kettle, slowly adding 30kg of calcium carbonate in batches under a stirring state to convert acetic acid in distillate into calcium acetate, stirring at room temperature for 1 hour, raising the pH value of the wastewater to 6-7, filtering the reaction liquid to remove excessive calcium carbonate, then feeding the reaction liquid into a calcification neutralization filter liquid intermediate tank to obtain a calcium acetate aqueous solution containing organic impurities, and waiting for secondary MVR treatment.
Inputting an aqueous solution of calcium acetate containing organic impurities into the MVR device at a rate of 2000kg/h within 1h, and carrying out secondary MVR treatment at 95 ℃:
the gas phase outlet of the MVR device is connected with the inlet of the temporary oxygen cracking device, the vapor containing organic impurities and evaporated in the second MVR treatment enters the temporary oxygen cracking device in the form of gas phase, the high-temperature gas at the outlet of the temporary oxygen cracking device is connected with the gas phase inlet of the MVR device, and the heat released in the temporary oxygen cracking reaction is used for the gasification of the liquid in the MVR device.
The discharge rate of calcium acetate in the MVR device is 30.8kg/h, the material discharged out of the MVR system along with the calcium acetate contains 49.2kg/h of water, and the solid-liquid mixture is the calcium acetate suspension with the calcium acetate content of 38.5% obtained by the second MVR treatment. And (3) drying the calcium acetate suspension: and (3) introducing water vapor generated by drying into an oxygen cracking device, and drying the calcium acetate suspension to obtain 229.1kg of calcium acetate solid.
The gas entering the temporary oxygen cracking device comprises the steam generated by MVR, the gas generated by thermal analysis and the water vapor generated by drying the calcium acetate solution, and the COD value in the water finally discharged from the temporary oxygen cracking system is 2.1mgO through the temporary oxygen cracking reaction2Per L, VOC concentration in the gas phase of 3mg/m3。
Taking 200kg of calcium acetate solid after drying treatment of a calcium acetate suspension, adding the calcium acetate solid into an acidolysis reaction kettle at normal temperature, slowly adding 98kg of 98% concentrated sulfuric acid, stirring for reacting for half an hour, filtering to obtain 162.8kg of calcium sulfate solid (the calcium sulfate solid contains 1.3kg of acetic acid) and 115.4kg of acetic acid, removing the obtained calcium sulfate solid from a thermal desorption reactor, treating sulfate generated by thermal desorption as common solid waste, and recycling the acetic acid.
Example 3
The experiment was carried out by the same process as in example 1.
The low-concentration acetic acid wastewater containing mineral acid salts comprises the following components: 7.8 percent of acetic acid, 0.02 percent of propanol, 0.012 percent of normal butanol, 0.013 percent of tertiary butanol, 0.011 percent of propyl acetate, 0.022 percent of tertiary butyl acetate, 0.02 percent of normal butyl acetate, 3.6 percent of ferric sulfate, 0.05 percent of potassium sulfate, 0.4 percent of magnesium sulfate, 0.21 percent of lithium sulfate and the balance of water.
The low concentration acetic acid wastewater containing mineral acid salt was fed into the MVR unit at a rate of 2000kg/h over 2h, and the first MVR treatment was carried out at 95 ℃. The discharge rate of mineral acid salt in the MVR device is 135.2kg/h, the material discharged out of the MVR system along with the mineral acid salt contains 90.1kg/h of water, the total amount of organic matters in the material discharged out of the MVR system along with the mineral acid salt is 0.013kg/h (wherein the acetic acid flow rate is 0.0066kg/h), the solid-liquid mixture, namely the solid-liquid mixture containing the mineral acid salt obtained by the first MVR treatment enters a thermal analysis process, the thermal analysis temperature is 380 ℃, water vapor and organic matter vapor generated by thermal analysis enter an oxygen cracking device for deep purification treatment, and the process conditions of the oxygen cracking are as follows: the reaction temperature is 400 ℃, the reaction pressure is normal pressure, the residence time is 4 kg.h/m 3, and the volume ratio of the air introduction amount to the water vapor entering the temporary oxygen cracking device is 2. The solid materials obtained by thermal analysis are mineral acid salts and organic impurities, the contents of the mineral acid salts such as ferric sulfate, potassium sulfate, magnesium sulfate, lithium sulfate and the like obtained by thermal analysis separation are respectively 144kg, 2kg, 16kg and 8.4kg, and the contents of the organic impurities such as propanol, n-butyl alcohol, tert-butyl alcohol, propyl acetate, n-butyl acetate, tert-butyl acetate and the like are respectively 0.01kg, 0.0012kg, 0.0015kg, 0.003kg, 0.002kg and 0.003 kg.
The gas phase outlet of the MVR device is connected with the inlet of the temporary oxygen cracking device, high-temperature gas at the outlet of the temporary oxygen cracking device is connected with the steam inlet of the MVR device, and the heat released by the temporary oxygen cracking reaction is used for gasifying liquid in the MVR device.
The flow rate at the liquid phase outlet of the MVR device is 1774.5kg/h (the flow rate of acetic acid is 156.0kg/h, organic impurities enter the temporary oxygen cracking device to be purified), and the distillate liquid phase, namely acetic acid wastewater, is 3549kg in total and enters an intermediate tank to be stored.
Adding 2000kg of acetic acid wastewater in the intermediate tank into a calcification neutralization reaction kettle, slowly adding 175kg of calcium carbonate in batches under a stirring state to convert acetic acid in distillate into calcium acetate, stirring at room temperature for 1 hour, raising the pH value of the wastewater to 6-7, filtering the reaction liquid to remove excessive calcium carbonate, then feeding the reaction liquid into a calcification neutralization filter liquid intermediate tank to obtain a calcium acetate aqueous solution containing organic impurities, and waiting for secondary MVR treatment.
Inputting an aqueous solution of calcium acetate containing organic impurities into the MVR device at a rate of 2000kg/h within 1h, and carrying out secondary MVR treatment at 95 ℃:
the gas phase outlet of the MVR device is connected with the inlet of the temporary oxygen cracking device, the vapor containing organic impurities and evaporated in the second MVR treatment enters the temporary oxygen cracking device in the form of gas phase, the high-temperature gas at the outlet of the temporary oxygen cracking device is connected with the gas phase inlet of the MVR device, and the heat released in the temporary oxygen cracking reaction is used for the gasification of the liquid in the MVR device.
The discharge rate of calcium acetate in the MVR device is 215.6kg/h, the material discharged out of the MVR system along with the calcium acetate contains 332.0kg/h of water, and the solid-liquid mixture is the calcium acetate suspension with the calcium acetate content of 39.4% obtained by the second MVR treatment. And (3) drying the calcium acetate suspension: and (3) introducing water vapor generated by drying into an oxygen cracking device, and drying the calcium acetate suspension to obtain 410.8kg of calcium acetate solid.
The gas entering the temporary oxygen cracking device comprises the steam generated by MVR, the gas generated by thermal analysis and the water vapor generated by drying the calcium acetate solution, and the COD value in the water finally discharged from the temporary oxygen cracking system is 11mgO through the temporary oxygen cracking reaction2L, VOC concentration in gas phase 15mg/m3。
Taking 200kg of calcium acetate solid obtained after drying treatment of a calcium acetate suspension, adding the calcium acetate solid into an acidolysis reaction kettle at normal temperature, slowly adding 98kg of 98% concentrated sulfuric acid, stirring for reacting for half an hour, filtering to obtain 165.4kg of calcium sulfate solid (the calcium sulfate solid contains 1.3kg of acetic acid) and 112.3kg of acetic acid, removing heat from the obtained calcium sulfate to a thermal desorption reactor, treating sulfate generated by thermal desorption as common solid waste, and recycling the acetic acid.
Example 4
The experiment was carried out by the same process as in example 1.
The low-concentration acetic acid wastewater containing mineral acid salts comprises the following components: 15% of acetic acid, 0.02% of methanol, 0.012% of ethanol, 0.013% of tert-butanol, 0.011% of methyl acetate, 0.02% of ethyl acetate, 0.022% of tert-butyl acetate, 4.3% of magnesium sulfate, 0.05% of chromium sulfate, 0.4% of lithium sulfate, 0.21% of sodium sulfate and the balance of water.
The low-concentration acetic acid wastewater containing mineral acid salt is input into the MVR device at the rate of 2500kg/h within 1h, and the first MVR treatment is carried out at the temperature of 95 ℃. The discharge rate of the mineral acid salt in the MVR device was 159.0kg/h, the moisture content in the material discharged out of the MVR system together with the mineral acid salt was 106.0kg/h, and the total organic matter content in the material discharged out of the MVR system together with the mineral acid salt was 0.026kg/h (wherein the acetic acid flow rate was 0.013kg/h), which part of the solid-liquid mixture, i.e. the one obtained from the first MVR treatmentAnd (3) feeding the solid-liquid mixture containing the mineral acid salt into a thermal desorption process, wherein the thermal desorption temperature is 380 ℃: the water vapor and organic matter vapor generated by thermal desorption enter an oxygen cracking device for deep purification treatment, and the process conditions of the oxygen cracking are as follows: the reaction temperature is 450 ℃, the reaction pressure is normal pressure, the residence time is 6 kg.h/m 3, and the volume ratio of the air input to the water vapor entering the temporary oxygen cracking device is 2. The solid material obtained by thermal desorption is mineral acid salt and organic impurities, and magnesium sulfate, chromium sulfate and sulfuric acid are obtained by thermal desorption separationLithium ion sourceThe contents of mineral acid salts such as sodium sulfate are respectively 107.5kg, 1.25kg, 10kg and 5.25kg, and the contents of organic impurities such as methanol, ethanol, tert-butyl alcohol, methyl acetate, ethyl acetate and tert-butyl acetate are respectively 0.01kg, 0.0012kg, 0.0015kg, 0.001kg, 0.002kg and 0.002 kg.
The gas phase outlet of the MVR device is connected with the inlet of the temporary oxygen cracking device, high-temperature gas at the outlet of the temporary oxygen cracking device is connected with the steam inlet of the MVR device, and the heat released by the temporary oxygen cracking reaction is used for gasifying liquid in the MVR device.
The flow rate at the liquid phase outlet of the MVR device is 2234.7kg/h (wherein the flow rate of acetic acid is 374.9kg/h, organic impurities enter the temporary oxygen cracking device to be purified), and the distillate liquid phase, namely acetic acid wastewater, is 2234.7kg in total and enters an intermediate tank to be stored.
Adding 2000kg of acetic acid wastewater in the intermediate tank into a calcification neutralization reaction kettle, slowly adding 330kg of calcium carbonate in batches under a stirring state to convert acetic acid in distillate into calcium acetate, stirring at room temperature for 1 hour, raising the pH value of the wastewater to 6-7, filtering the reaction liquid to remove excessive calcium carbonate, then feeding the reaction liquid into a calcification neutralization filter liquid intermediate tank to obtain a calcium acetate aqueous solution containing organic impurities, and waiting for secondary MVR treatment.
Inputting an aqueous solution of calcium acetate containing organic impurities into the MVR device at a rate of 2000kg/h within 1h, and carrying out secondary MVR treatment at 95 ℃:
the gas phase outlet of the MVR device is connected with the inlet of the temporary oxygen cracking device, the vapor containing organic impurities and evaporated in the second MVR treatment enters the temporary oxygen cracking device in the form of gas phase, the high-temperature gas at the outlet of the temporary oxygen cracking device is connected with the gas phase inlet of the MVR device, and the heat released in the temporary oxygen cracking reaction is used for the gasification of the liquid in the MVR device.
The discharge rate of calcium acetate in the MVR device is 425.5kg/h, the materials discharged out of the MVR system along with the calcium acetate contain 648.0kg/h of moisture, and the solid-liquid mixture is the calcium acetate suspension with the calcium acetate content of 39.6 percent obtained by the second MVR treatment. And (3) drying the calcium acetate suspension: and (3) introducing the water vapor generated by drying into an oxygen cracking device, and drying the calcium acetate suspension to obtain 493.7kg of calcium acetate solid.
The gas entering the temporary oxygen cracking device comprises the steam generated by MVR, the gas generated by thermal analysis and the water vapor generated by drying the calcium acetate solution, and the COD value in the water finally discharged from the temporary oxygen cracking system is 21mgO through the temporary oxygen cracking reaction2Per L, VOC concentration in the gas phase of 30mg/m3。
200kg of calcium acetate solid obtained after drying treatment is taken and added into an acidolysis reaction kettle at normal temperature, 98kg of 98% concentrated sulfuric acid is slowly added, stirring reaction is carried out for half an hour and then filtration is carried out, 167.8kg of calcium sulfate solid (the calcium sulfate solid contains 1.3kg of acetic acid) and 113.2kg of acetic acid are obtained, the obtained calcium sulfate is removed from a thermal desorption reactor, sulfate generated by thermal desorption is treated as common solid waste, and the acetic acid is recycled.
Example 5
The experiment was carried out by the same process as in example 1.
The low-concentration acetic acid wastewater containing mineral acid salts comprises the following components: 3.5 percent of acetic acid, 0.023 percent of propanol, 0.011 percent of normal butanol, 0.014 percent of tertiary butanol, 0.013 percent of propyl acetate, 0.022 percent of tertiary butyl acetate, 0.02 percent of normal butyl acetate, 4.3 percent of ferric sulfate, 0.05 percent of magnesium sulfate, 0.4 percent of lithium sulfate, 0.21 percent of chromium sulfate and the balance of water.
The low concentration acetic acid wastewater containing mineral acid salt was fed into the MVR unit at a rate of 1800kg/h over 2h, and the first MVR treatment was carried out at 95 ℃. The discharge rate of mineral acid salt in the MVR device is 117.3kg/h, the material discharged out of the MVR system along with the mineral acid salt contains water of 78.2kg/h, the total amount of organic matters in the material discharged out of the MVR system along with the mineral acid salt is 0.060kg/h (wherein the flow rate of acetic acid is 0.003kg/h), the solid-liquid mixture, namely the solid-liquid mixture containing the mineral acid salt obtained by the first MVR treatment enters a thermal analysis process, the thermal analysis temperature is 380 ℃, water vapor and organic matter vapor generated by thermal analysis enter an oxygen cracking device for deep purification treatment, and the process conditions of the oxygen cracking are as follows: the reaction temperature is 450 ℃, the reaction pressure is normal pressure, the residence time is 5.5 kg.h/m 3, and the volume ratio of the air input to the water vapor entering the temporary oxygen cracking device is 2. The solid materials obtained by thermal desorption are mineral acid salts and organic impurities, the contents of the mineral acid salts such as ferric sulfate, magnesium sulfate, lithium sulfate, chromium sulfate and the like obtained by thermal desorption separation are respectively 154.8kg, 1.8kg, 14.4kg and 7.56kg, and the contents of the organic impurities such as propanol, n-butyl alcohol, tert-butyl alcohol, propyl acetate, n-butyl acetate, tert-butyl acetate and the like are respectively 0.01kg, 0.012kg, 0.015kg, 0.03kg, 0.015kg and 0.012 kg.
The gas phase outlet of the MVR device is connected with the inlet of the temporary oxygen cracking device, high-temperature gas at the outlet of the temporary oxygen cracking device is connected with the steam inlet of the MVR device, and the heat released by the temporary oxygen cracking reaction is used for gasifying liquid in the MVR device.
The flow rate at the liquid phase outlet of the MVR device is 1604.5kg/h (the flow rate of acetic acid is 63.0kg/h, organic impurities enter the temporary oxygen cracking device to be purified), and the distillate liquid phase, namely acetic acid wastewater, accounts for 3209kg, and enters an intermediate tank for storage.
Adding 2000kg of acetic acid wastewater in the intermediate tank into a calcification neutralization reaction kettle, slowly adding 80kg of calcium carbonate in batches under the stirring state to convert acetic acid in distillate into calcium acetate, then stirring at room temperature for 1 hour, raising the pH value of the wastewater to 6-7, filtering the reaction liquid to remove excessive calcium carbonate, then entering the calcification neutralization filter liquid intermediate tank to obtain a calcium acetate aqueous solution containing organic impurities, and waiting for secondary MVR treatment.
Inputting an aqueous solution of calcium acetate containing organic impurities into the MVR device at a rate of 2000kg/h within 1h, and carrying out secondary MVR treatment at 95 ℃:
the gas phase outlet of the MVR device is connected with the inlet of the temporary oxygen cracking device, the vapor containing organic impurities and evaporated in the second MVR treatment enters the temporary oxygen cracking device in the form of gas phase, the high-temperature gas at the outlet of the temporary oxygen cracking device is connected with the gas phase inlet of the MVR device, and the heat released in the temporary oxygen cracking reaction is used for the gasification of the liquid in the MVR device.
The discharge rate of calcium acetate in the MVR device is 89.4kg/h, the material discharged out of the MVR system along with the calcium acetate contains 140.1kg/h of moisture, and the solid-liquid mixture is the calcium acetate suspension with the calcium acetate content of 38.9% obtained by the second MVR treatment. And (3) drying the calcium acetate suspension: and (3) introducing water vapor generated by drying into a temporary oxygen cracking device, and drying the calcium acetate suspension to obtain 165.9kg of calcium acetate solid.
The gas entering the temporary oxygen cracking device comprises the steam generated by MVR, the gas generated by thermal analysis and the water vapor generated by drying the calcium acetate solution, and the COD value in the water finally discharged from the temporary oxygen cracking system is 4.9mgO through the temporary oxygen cracking reaction2Per L, VOC concentration in the gas phase of 7mg/m3。
100kg of calcium acetate solid obtained after drying treatment is taken and added into an acidolysis reaction kettle at normal temperature, 49kg of 98% concentrated sulfuric acid is slowly added, stirring reaction is carried out for half an hour, then filtration is carried out, 84.9kg of calcium sulfate solid (the calcium sulfate solid contains 0.65kg of acetic acid) and 57.6kg of acetic acid are obtained, the obtained calcium sulfate is removed from a thermal desorption reactor, sulfate generated by thermal desorption is treated as common solid waste, and the acetic acid is recycled.
Claims (7)
1. A method for treating low-concentration acetic acid wastewater containing mineral acid salts is characterized by comprising the following specific steps:
(1) carrying out first MVR treatment on the waste water containing mineral acid salt and acetic acid, and separating the mineral acid salt from the waste water containing the mineral acid salt and acetic acid to respectively obtain a solid-liquid mixture containing the mineral acid salt and low-concentration acetic acid waste water; carrying out thermal desorption on the solid-liquid mixture containing mineral acid salt, separating to obtain solid materials and gas, wherein the solid materials are the mineral acid salt and organic impurities, the total content of the organic impurities in the solid materials is lower than 0.1 wt%, and the gas generated by thermal desorption enters an oxygen cracking device for deep purification treatment; the first MVR treatment time is 1-3 h, and the treatment temperature is 50-100 ℃; the organic impurities are one or more of methyl acetate, ethyl acetate, propyl acetate, tert-butyl acetate, n-butyl acetate, methanol, ethanol, propanol, tert-butanol and n-butanol;
(2) carrying out calcification neutralization treatment on the low-concentration acetic acid wastewater obtained in the step (1) in the presence of calcium carbonate, and converting acetic acid in the low-concentration acetic acid wastewater into calcium acetate to form a calcium acetate aqueous solution containing organic impurities;
(3) carrying out secondary MVR treatment on the calcium acetate aqueous solution containing the organic impurities obtained in the step (2), and evaporating out water vapor containing the organic impurities to obtain a calcium acetate suspension; the water vapor containing organic impurities enters an oxygen cracking device, deep purification treatment is carried out under the air condition, the water and the steam discharged by the oxygen cracking device reach the standard and are discharged, and the COD of the water discharged by the oxygen cracking device is less than 40mgO2The VOC gas is less than 50mg/m3, and the calcium acetate suspension generated by the second MVR treatment is subjected to drying treatment;
(4) drying the calcium acetate suspension obtained in the step (3), wherein the water vapor generated in the drying process also enters an oxygen-critical cracking device, and drying to obtain a calcium acetate solid;
(5) carrying out acidolysis treatment on the calcium acetate solid obtained in the step (4) in the presence of sulfuric acid to generate acetic acid and calcium sulfate, wherein the acetic acid can be recycled, the calcium sulfate solid is subjected to heat desorption, and mineral acid salt generated by the heat desorption is treated as common solid waste;
the mineral acid salt is sulfate;
the process conditions for carrying out deep purification treatment on the temporary oxygen cracking device are as follows: the purification reaction temperature is 250-450 ℃, the reaction pressure is normal pressure, and the retention time is 0.1-10 kg.h/m3The volume ratio of the air introduction amount to the water vapor entering the temporary oxygen cracking device is 1-5: 1.
2. The method for treating the low-concentration acetic acid wastewater containing mineral acid salts according to claim 1, wherein the content of acetic acid in the low-concentration acetic acid wastewater containing mineral acid salts is 0.5-15 wt%, the content of organic impurities is 0.01-0.5 wt%, and the content of mineral acid salts is 1-5 wt%.
3. The method for treating the low-concentration acetic acid wastewater containing the mineral acid salt according to claim 1, wherein the mineral acid salt is one or a mixture of more of potassium sulfate, sodium sulfate, magnesium sulfate, ferric sulfate, lithium sulfate, chromium sulfate, nickel sulfate, zinc sulfate and manganese sulfate.
4. The method for treating the low-concentration acetic acid wastewater containing mineral acid salts according to claim 1, wherein the thermal desorption temperature is 200-400 ℃.
5. The method for treating the low-concentration acetic acid wastewater containing the mineral acid salt according to claim 1, wherein the calcium acetate aqueous solution is concentrated to a calcium acetate content of 30-40 wt% by the second MVR treatment, and the time for treating the calcium acetate aqueous solution containing the organic impurities by the second MVR treatment is 1-2 hours.
6. The method for treating the mineral acid salt-containing low-concentration acetic acid wastewater according to claim 1, wherein the temporary oxygen cracking device realizes self-heating balance without external energy; the COD value in the water discharged by the temporary oxygen cracking device is 0-40 mgO2The total amount of VOC in the discharged waste gas is 5-50 mg/m3。
7. The method for treating low-concentration acetic acid wastewater containing mineral acid salts according to claim 1, wherein sulfuric acid used in the acidolysis treatment is concentrated sulfuric acid having a mass fraction of not less than 98%.
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| US1052446A (en) * | 1911-03-02 | 1913-02-04 | Carl Walter Volney | Manufacture of acetate of lime and wood-alcohol. |
| US1314765A (en) * | 1919-09-02 | Process of recovering acid | ||
| US4898644A (en) * | 1988-05-02 | 1990-02-06 | Qo Chemicals, Inc. | Removal of volatile acids from aqueous solutions |
| CN101481189A (en) * | 2009-01-20 | 2009-07-15 | 大连理工大学 | Integrated process of furfural production as well as wastewater, waste slag and waste gas treatment |
| CN107098415A (en) * | 2017-05-31 | 2017-08-29 | 南京工业大学 | The processing method and system of a kind of salt-containing organic wastewater |
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| US1314765A (en) * | 1919-09-02 | Process of recovering acid | ||
| US1052446A (en) * | 1911-03-02 | 1913-02-04 | Carl Walter Volney | Manufacture of acetate of lime and wood-alcohol. |
| US4898644A (en) * | 1988-05-02 | 1990-02-06 | Qo Chemicals, Inc. | Removal of volatile acids from aqueous solutions |
| CN101481189A (en) * | 2009-01-20 | 2009-07-15 | 大连理工大学 | Integrated process of furfural production as well as wastewater, waste slag and waste gas treatment |
| CN107098415A (en) * | 2017-05-31 | 2017-08-29 | 南京工业大学 | The processing method and system of a kind of salt-containing organic wastewater |
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