CN113698017B - Resource utilization and treatment method of alkynol wastewater - Google Patents
Resource utilization and treatment method of alkynol wastewater Download PDFInfo
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
Abstract
The invention discloses a resource utilization and treatment method of alkynol wastewater, which comprises the following steps: air stripping, namely, utilizing large air flow to strip free ammonia molecules in the alkynol wastewater; water absorption, namely absorbing ammonia blown off by air in the wastewater by adopting multi-stage water absorption to obtain ammonia water; evaporating and crystallizing, namely evaporating partial water and organic matters in the de-ammoniated brine to ensure that potassium carbonate and potassium bicarbonate in the wastewater are supersaturated and partial crystals are obtained; filtering, cooling, crystallizing and filtering the supersaturated potassium carbonate and potassium bicarbonate solution to obtain crude potassium carbonate and potassium bicarbonate salt containing organic matters, and combining the mother liquor and the deamination wastewater to be subjected to evaporative crystallization; alcohol washing, namely performing alcohol washing on the crude salt; thermal decomposition, the wet salt obtained by alcohol washing is thermally decomposed to obtain a dry potassium carbonate by-product. The invention can not only prepare ammonia water from ammonia nitrogen in the alkynol wastewater, but also prepare potassium carbonate and potassium bicarbonate into potassium carbonate byproducts, so that the reclaimed water recycling of the purified water is realized, the purified gas is discharged after reaching the standard, and the reclamation and zero discharge of the wastewater are realized.
Description
Technical Field
The invention belongs to the field of treatment of alkynol wastewater, relates to a resource utilization and treatment method of alkynol wastewater, and particularly relates to a resource utilization and purification method of alkynol wastewater containing free ammonia, organic impurities and high-concentration potassium carbonate.
Background
In the production process of alkynol (2-methyl-3-butyn-2-ol), under the catalytic action of an alkaline catalyst, acetone and acetylene react to generate alkynol, reaction liquid enters a rectification system, hydrous alkynol is recovered from the top of a finished product tower, and liquid alkali is added into tower bottoms to decompose and recover useful components, so that the alkynol wastewater is obtained. The wastewater has the characteristics of high COD, high ammonia nitrogen and high salt, the COD value of the wastewater is 10000-100000 mg/L, the ammonia nitrogen is 10000-40000 mg/L, and meanwhile, the wastewater contains high-concentration potassium carbonate, the content of the potassium carbonate is 15-35 wt.%, the content of the potassium bicarbonate is 0.1-1.0 wt.%, and the content of organic matters is 0.03-3.0 wt.%. This type of waste water belongs to hazardous waste, produces tens of thousands of tons every year, and the purification treatment degree of difficulty is very big, and it has not seen at present that suitable technique can properly handle this type of waste water
For high-concentration organic wastewater with high salt and high ammonia nitrogen, evaporative crystallization, membrane filtration and other modes are commonly adopted for desalting, air stripping, chemical precipitation, nitrification and denitrification modes are adopted for reducing the ammonia nitrogen value in the wastewater, and biochemical, catalytic wet oxidation, extraction, oxidation and other modes are adopted for reducing COD in the wastewater. However, the evaporation method mainly realizes the concentration and separation of pollutants in the wastewater by means of reducing saturated vapor pressure, heating and the like, often causes the problem of scaling in engineering application, and finally cannot convert the pollutants into harmless substances such as carbon dioxide, water and the like; the reverse osmosis filtration method overcomes osmotic pressure by increasing pressure at one end of an organic membrane, realizes the separation of water and organic matters and salts, and often causes the problems of membrane pollution and scrapping in engineering; in the extraction, the separation and enrichment of pollutants are carried out by utilizing the solubility difference of solutes in different solvents, but an extractant is expensive; the catalytic wet oxidation method is to oxidize organic matters in wastewater by an oxidant under the action of a catalyst under the conditions of high temperature and high pressure so as to reduce COD of the wastewater, but the method has high equipment investment cost and low removal rate of COD, and other technologies are usually adopted for further treatment of high-concentration organic wastewater.
For high-salt and high-ammonia nitrogen wastewater basically free of organic matters, the resource utilization of ammonia nitrogen and inorganic salt in the wastewater can be realized through air stripping and evaporative crystallization. However, the resource treatment of the high-concentration organic wastewater with high salt and high ammonia nitrogen generated in the production process of alkynol is still a difficult problem in the industry.
For high-concentration organic wastewater with high salt and high ammonia nitrogen generated in the production process of alkynol, most production enterprises adopt a biochemical method after dilution to treat the wastewater, however, because the salt concentration in the wastewater reaches about 20 percent, fresh water which is dozens of times of the volume of the wastewater is usually consumed when the wastewater is treated by the biochemical method, so that a large amount of fresh water resources are wasted, the discharge amount of the wastewater is greatly increased, and great burden is caused to a biochemical system. And some enterprises firstly carry out multi-effect evaporation desalination pretreatment on the high-salinity wastewater and then treat the distillate of the multi-effect evaporation by a biochemical method. The method of multi-effect evaporation desalination is adopted, the biggest obstacle is that the crystallized salt contains a large amount of organic matters and cannot be used as common industrial salt, and in most cases, the salt can only be regarded as dangerous solid waste, and a qualified unit must be entrusted to harmless disposal, so that the disposal cost is quite high.
In recent years, the effective recycling treatment of salts in high-salt and high-ammonia nitrogen organic matter wastewater is not realized in the field of wastewater treatment of the high-salt and high-ammonia nitrogen organic matter. Chinese patent application CN 107304090A discloses a method for recycling high-salt wastewater containing sodium chloride and sodium sulfate, wherein the high-salt wastewater containing sodium chloride and sodium sulfate enters a primary nanofiltration device; the trapped liquid of the primary nanofiltration enters a diluting chamber of a monovalent ion selective electrodialyzer, and the permeate of the primary nanofiltration enters a concentrating chamber of the monovalent ion selective electrodialyzer after being concentrated by a first reverse osmosis device; fresh water at an outlet of the monovalent ion selective electrodialyzer enters a second reverse osmosis device, and a concentrated solution of the second reverse osmosis passes through a sodium sulfate crystallization system to obtain a sodium sulfate product; concentrated water at the outlet of the monovalent ion selective electrodialyzer enters a secondary nanofiltration device, trapped liquid of the secondary nanofiltration returns to the primary nanofiltration device for treatment, and permeate of the secondary nanofiltration passes through a sodium chloride evaporation crystallization system to obtain a sodium chloride product; the crystallization mother liquor is returned to the inlet of the diluting chamber of the monovalent ion selective electrodialyzer. Because the primary nanofiltration membrane can not separate potassium carbonate and potassium bicarbonate, and the organic matter content in the wastewater is too high, the membrane is easy to block, so the method is not suitable for high-salt, high-ammonia nitrogen and high-concentration organic wastewater generated in the production process of alkynol.
Chinese patent CN102849857A discloses a method for treating high-salt and high-ammonia nitrogen wastewater, which adopts an intermittent activated sludge method, carries out enrichment on nitrified sludge by a method of alternately increasing the salinity or ammonia nitrogen concentration of a culture solution, obtains high-salt-resistant and high-ammonia nitrogen-resistant nitrifying bacteria by domestication, and the domesticated high-efficiency nitrifying bacteria can treat high-salinity wastewater with the ammonia nitrogen concentration of 500mg/L and the salt content of less than 35g/L, so that the ammonia nitrogen concentration of effluent can reach less than 10mg/L and reach the national first-level discharge standard. The method has strict limits on the ammonia nitrogen concentration and the salt content in the wastewater, and can not treat alkynol wastewater with a COD value of 10000-100000 mg/L, ammonia nitrogen of 10000-40000 mg/L and potassium carbonate content of 15-35 wt.%.
The Chinese patent application CN 110697959A provides a resource recycling method of high-salt high-ammonia nitrogen wastewater, which preheats the high-salt high-ammonia nitrogen wastewater, and then evaporates and concentrates the high-salt high-ammonia nitrogen wastewater to obtain a concentrated solution; cooling and crystallizing the concentrated solution, and centrifuging to obtain ammonium salt and waste liquid; then, condensing the non-liquefied steam in the evaporation concentration process, adding magnesium salt and phosphate, and filtering to obtain composite magnesium ammonium salt and filtrate; and finally, the pH of the filtrate is adjusted after the filtrate is subjected to ozone treatment, and the clear water up to the standard is obtained to be discharged or recycled, so that the resource recycling of the high-salt high-ammonia nitrogen wastewater is realized. The method only aims at ammonia nitrogen and salinity pollutants, does not mention the treatment method of organic matters in the wastewater, and is not applicable to the alkynol wastewater.
Chinese patent application CN 106746110 a discloses a device and processing method for treating high ammonia nitrogen high salt waste water, the main equipment includes the pre-heater, the deamination tower, the evaporation crystallizer, vapor compressor and centrifuge, the pre-heater is equipped with the cold side entry that connects high ammonia nitrogen high salt waste water, the cold side export of pre-heater and the waste water entry linkage of deamination tower, the waste water export of deamination tower and the waste water entry linkage of evaporation crystallizer, the carrier gas entry and the vapor compressor entry of deamination tower are connected respectively to the secondary steam export of evaporation crystallizer, the magma export of evaporation crystallizer and the magma entry linkage of centrifuge, centrifuge is equipped with the crystallized salt export. The method can realize the deamination and denitrification desalination treatment of the high ammonia nitrogen and high salt wastewater with energy conservation and high efficiency, and can realize zero discharge and resource utilization of the high ammonia nitrogen and high salt wastewater, but inevitably, the ammonium salt obtained by the method contains other metal salt impurities, and the method cannot treat organic matter impurities in the wastewater.
Therefore, aiming at the high-concentration organic wastewater of high-salt and high-ammonia nitrogen generated in the production process of alkynol, a method which is flexible in operation, low in energy consumption and stable in quality of recovered ammonia water and potassium carbonate is urgently needed to be developed.
Disclosure of Invention
The invention aims to provide a resource utilization and treatment method of high-concentration organic wastewater with high salt content and high ammonia nitrogen content, which adopts a process combining air stripping, water absorption, evaporative crystallization, filtration, alcohol washing, rectification, thermal decomposition and temporary oxygen cracking purification, realizes resource utilization and zero emission of the wastewater and has important significance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a resource utilization and treatment method of alkynol wastewater comprises the following steps: air stripping, namely utilizing large-air-volume air to strip free ammonia molecules in the alkynol wastewater; water absorption, namely absorbing ammonia blown off by air in the wastewater by adopting multi-stage water absorption to obtain ammonia water; evaporating and crystallizing, namely evaporating partial water and organic matters in the de-ammoniated brine to ensure that potassium carbonate and potassium bicarbonate in the wastewater are supersaturated and partial crystals are obtained; filtering, cooling, crystallizing and filtering the supersaturated potassium carbonate and potassium bicarbonate solution to obtain crude potassium carbonate and potassium bicarbonate salt containing organic matters, and combining the mother liquor and the deamination wastewater to be subjected to evaporative crystallization for evaporative crystallization again; alcohol washing, namely washing the crude salt with alcohol, and washing high-boiling-point organic matters in the crude salt; thermal decomposition, the wet salt obtained by alcohol washing is thermally decomposed to obtain a dry potassium carbonate by-product.
As a preferable technical scheme of the resource utilization and treatment method of the alkynol wastewater, the method also comprises the following steps: the waste gas containing ammonia molecules after being absorbed by multi-stage water, the water vapor containing organic matters generated by evaporation and crystallization, the waste gas generated in the alcohol rectification recovery process, the kettle residue and the organic vapor generated by wet salt thermal decomposition all enter an oxygen cracking device, deep purification treatment is carried out under the air condition by adopting a metal oxide loaded molecular sieve catalyst, the purified water is recycled as reclaimed water, and the purified gas is discharged after reaching the standard.
Specifically, the resource utilization and treatment method of alkynol wastewater comprises the following steps:
step (1), air stripping and water absorption: blowing air into the alkynol wastewater to blow off free ammonia in the wastewater; adopting multi-stage water absorption, taking water as absorption liquid to absorb ammonia blown off by air to prepare ammonia water, and enabling waste gas containing a small amount of ammonia molecules after water absorption to enter an oxygen cracking device for deep purification treatment;
step (2), evaporation and crystallization: carrying out evaporative crystallization on the deamination wastewater obtained in the step (1) by adopting MVR treatment to obtain a supersaturated solution of potassium carbonate and potassium bicarbonate, cooling, crystallizing and filtering the supersaturated solution of potassium carbonate and potassium bicarbonate to obtain crude salt and a mother solution, combining the mother solution and the deamination wastewater to be subjected to evaporative crystallization, and allowing organic matter-containing water vapor generated by evaporative crystallization to enter an oxygen-critical cracking device;
Step (3), alcohol washing and rectification: carrying out alcohol washing on the crude salt, dissolving high-boiling-point organic matters in the crude salt in an alcohol washing liquid, and recovering alcohol in the alcohol washing liquid through rectification;
step (4), thermal decomposition: carrying out thermal decomposition on wet salt obtained by alcohol washing to obtain potassium carbonate, and allowing waste gas containing organic steam generated in the thermal decomposition process to enter an oxygen cracking device for deep purification treatment.
The alkynol wastewater is alkaline. The COD value of the alkynol wastewater is 10000 mg/L-100000 mg/L, the ammonia nitrogen value is 10000-40000 mg/L, the ammonia nitrogen value is totally contributed by free ammonia, the content of potassium carbonate is 15-35 wt.%, the content of potassium bicarbonate is 0.1-1.0 wt.%, and the content of organic matters is 0.03-3.0 wt.%.
The organic matter is 2-methyl-3-butine-2-alcohol, enol, acetone and high boiling point organic matter produced in the production process of alkynol, such as 2, 5-dimethyl-3-hexine-2, 5-diol, etc. The boiling point of the high-boiling-point organic matter is more than or equal to 120 ℃.
In the step (1), air stripping is carried out in a stripping tower. Specifically, in the stripping tower, the alkynol wastewater circularly flows from top to bottom, air is reversely blown from bottom to top, and the mass-volume ratio of the air to the alkynol wastewater is controlled to be 10: 1-15: 1kg/m 3 And the removal rate of free ammonia in the alkynol wastewater can be ensured.
The multistage water absorption is carried out in 2-5 ammonia absorption towers connected in series for 2-5 stages of water absorption, absorption liquid of each ammonia absorption tower circulates independently, and the flow rate of the absorption liquid of each absorption tower is the same. The ammonia blown off by air enters the ammonia absorption towers connected in series from bottom to top in sequence and is in countercurrent contact with the absorption liquid, and the gas discharged from the final ammonia absorption tower does not contain ammonia basically. When the ammonia concentration of the 1 st-stage absorption liquid reaches 15-20. wt.%, the absorption liquid is transferred to an ammonia water product tank, fresh water is added to serve as the final stage for absorption, the original 2 nd-stage absorption is changed into the 1 st-stage absorption, the original 3 rd-stage absorption is changed into the 2 nd-stage absorption, and the like.
The inventor finds out through examination that: after three-stage water absorption, the gas discharged from the final-stage ammonia gas absorption tower basically does not contain ammonia molecules, and when the stage number of the multi-stage water absorption is less than 3, the gas discharged from the final-stage ammonia gas absorption tower contains ammonia molecules, so that the energy consumption is increased if the multi-stage water absorption is more than 3. Therefore, preferably, the multistage water absorption is performed in 3 stages of water absorption in 3 ammonia absorption towers connected in series.
The concentration of the ammonia water is 15-20. wt.%, and the ammonia water is circulated to an alkynol production section.
In the step (2), the generation rate of the water vapor in the MVR treatment process is 500-5000 m 3 And h, allowing part of organic impurities in the deamination wastewater to enter an MVR gas phase to realize separation of part of organic impurities and salt in the aqueous solution.
The potassium carbonate and potassium bicarbonate supersaturated solution contains 60-80 wt% of potassium carbonate and 0.5-5.0 wt% of potassium bicarbonate.
The cooling crystallization temperature of the supersaturated potassium carbonate and potassium bicarbonate solution is 0-25 ℃.
In the step (3), the mass-to-volume ratio of the crude salt to the alcohol is 1-1: 5 kg/L.
The alcohol is lower alcohol (boiling point less than 120 deg.C), and is selected from one or two of methanol, ethanol, n-propanol, isopropanol, and n-butanol; specifically, when the alcohol is a mixed alcohol of two alcohols, the two alcohols are mixed in equal volume.
The alcohol obtained by rectification and recovery is circularly used in the alcohol washing working section.
In the step (4), the wet salt is subjected to thermal decomposition treatment in a thermal decomposition reactor.
The thermal decomposition treatment conditions are nitrogen atmosphere and 160-200 ℃.
During the thermal decomposition, potassium bicarbonate is decomposed into potassium carbonate and carbon dioxide, and the residual alcohol in the wet salt is evaporated into organic vapor.
The waste gas to be treated entering the oxygen cracking device comprises waste gas containing ammonia molecules from an ammonia gas absorption tower, water vapor containing organic matters generated by evaporation and crystallization, waste gas generated in the alcohol rectification recovery process, kettle residue and wet salt thermal decomposition The organic vapor produced. The deep purification treatment conditions are as follows: the volume ratio of fresh air to waste gas to be treated entering the temporary oxygen cracking device is 1-5: 1, a metal oxide loaded molecular sieve catalyst is used as a catalyst, and the space velocity is 2000-20000 h -1 The reaction temperature is 250-450 ℃, and the reaction pressure is normal pressure. The carrier of the metal oxide loaded molecular sieve catalyst is one of a ZSM-5 molecular sieve, an MCM molecular sieve and a Y molecular sieve, the active component is 1-2 of ferric oxide, zinc oxide, manganese dioxide, zirconium dioxide and cobalt dioxide, and the load capacity of the metal oxide is 1.0-20 wt.%.
The MCM molecular sieve is selected from an MCM-41 molecular sieve and an MCM-22 molecular sieve.
The heat released by the deep purification treatment is used for vaporizing the liquid of the MVR device; the temporary oxygen cracking device realizes self-heating balance without external energy; COD value in water at the outlet of the oxygen cracking device is 0-40 mg/L, and the total amount of VOC in the discharged tail gas is 5-50 mg/m 3 The method meets the requirement of the emission standard DB 32/3151-.
The invention has the beneficial effects that:
aiming at high-concentration organic wastewater containing high salt and high ammonia nitrogen generated in the production process of alkynol, the novel process route of wastewater air stripping, water absorption, evaporative crystallization, filtration, alcohol washing, rectification, thermal decomposition and temporary oxygen cracking is adopted, so that not only can clean treatment of the wastewater be realized, but also ammonia nitrogen in the wastewater can be prepared into ammonia water, potassium carbonate and potassium bicarbonate are prepared into potassium carbonate byproducts, the wastewater is purified after desalination, the water is recycled after purification, the purified gas reaches the standard and is discharged, and the resource utilization and zero discharge of the wastewater are realized.
Drawings
FIG. 1 is a process flow diagram of the resource utilization and treatment method of alkynol wastewater.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples, but the present invention is not limited to the examples.
Example 1
The alkynol wastewater comprises the following components: the COD value is 45960mg/L, the ammonia nitrogen value is 18051mg/L, the content of potassium carbonate is 25.2 wt.%, the content of potassium bicarbonate is 0.5 wt.%, the content of organic substances is 1.53 wt.%, and the balance is water.
Referring to fig. 1, a resource utilization and treatment method of alkynol wastewater comprises the following steps:
Pumping the alkynol wastewater into a stripping tower, wherein the wastewater circularly flows from top to bottom at a flow rate of 1500kg/h, and stripping air flows at an air flow rate of 120m 3 H, back flushing from bottom to top; the ammonia gas blown off by air is discharged from the blow-off tower, enters three ammonia absorption towers which are sequentially connected in series, water is taken as absorption liquid to carry out three-stage water absorption, the absorption liquid in each stage of absorption tower is independently and circularly absorbed, and the circulation flow of the absorption liquid is 2.4m 3 And h, 105.0kg/h of ammonia water recovered by the first-stage absorption tower, wherein the concentration of the ammonia water is 21.2%.
Pumping the deamination wastewater obtained in the step (2) and the step (1) into an MVR device at the flow rate of 1455kg/h for evaporation crystallization, wherein the generation rate of water vapor in the MVR treatment process is 873.4kg/h, the content of potassium carbonate in the generated supersaturated solution of potassium carbonate and potassium bicarbonate is 65.2 wt.%, and the content of potassium bicarbonate is 1.29 wt.%, cooling and crystallizing the supersaturated solution at 12 ℃, filtering to obtain crude potassium carbonate and potassium bicarbonate (340.2kg/h) containing organic matters and mother liquor, and combining the mother liquor with the deamination wastewater to be subjected to MVR treatment for the next evaporation crystallization.
And (3) transferring the crude salt (340.2kg/h) into an alcohol washing kettle, washing with methanol, wherein the alcohol consumption is 1020L/h, rectifying the alcohol washing liquor to recover alcohol, recovering to obtain 918.5L/h alcohol, and discharging 18.4kg/h kettle residue.
And (4) transferring the potassium carbonate and the potassium bicarbonate wet salt subjected to alcohol washing into a thermal decomposition reactor, and performing thermal decomposition at 180 ℃ in a nitrogen atmosphere to obtain 321.3kg of potassium carbonate solid, wherein the content of the potassium carbonate is 99.2%, the content of the potassium bicarbonate is 0.1%, and the ignition loss is 0.7%, and the indexes of superior products in GB/T1587-2000 Industrial Potassium carbonate are achieved.
From ammonia gasAir containing a small amount of ammonia from the absorption tower, water vapor containing organic matters such as acetone and alkynol evaporated by an MVR device, waste gas generated by rectification, kettle residue and gas containing organic matters such as carbon dioxide, nitrogen and alcohol generated by thermal decomposition enter a temporary oxygen cracking device (the used catalyst is a molecular sieve catalyst loaded by metal oxide, the carrier is an MCM-41 molecular sieve, the active ingredients are ferric oxide and zirconium dioxide, the loading amounts of the ferric oxide and the zirconium dioxide are respectively 7.0 wt.% and 8.2 wt.%, and the using amount of the catalyst is 0.7m 3 ) Simultaneously introducing fresh air, wherein the volume ratio of the air introduction amount to the waste gas to be treated entering the temporary oxygen cracking device is 3:1, and the airspeed is 5565h -1 Deep purification treatment is carried out in the air atmosphere, the reaction temperature is 300 ℃, and the reaction pressure is normal pressure; the COD value of the water from the temporary oxygen cracking device is 22mgO 2 Per L, VOC concentration in the gas phase of 9.5mg/m 3 。
Example 2
The alkynol wastewater comprises the following components: the COD value is 62198mg/L, the ammonia nitrogen value is 25043mg/L, the content of potassium carbonate is 31.6 wt.%, the content of potassium bicarbonate is 0.3 wt.%, the content of organic matters is 2.07 wt.%, and the balance is water.
A resource utilization and treatment method of alkynol wastewater comprises the following steps:
pumping the alkynol wastewater into a stripping tower, wherein the wastewater circularly flows from top to bottom at a flow rate of 1800kg/h, and stripping air flows at a flow rate of 144m 3 H, back flushing from bottom to top; the ammonia gas blown off by air is discharged from the blow-off tower, enters three ammonia absorption towers which are sequentially connected in series, water is taken as absorption liquid to carry out three-stage water absorption, the absorption liquid in each stage of absorption tower is independently and circularly absorbed, and the circulation flow of the absorption liquid is 2.9m 3 And h, recycling 170.2kg/h of ammonia water from the first-stage absorption tower, wherein the concentration of the ammonia water is 21.0%.
Pumping the deamination wastewater obtained in the step (2) and the step (1) into an MVR device at a flow rate of 1746kg/h, wherein the generation rate of water vapor in the MVR treatment process is 940.3kg/h, the content of potassium carbonate in the generated supersaturated potassium bicarbonate solution is 70.6 wt.%, and the content of potassium bicarbonate is 0.67 wt.%, cooling and crystallizing the supersaturated solution at 10 ℃, filtering to obtain crude potassium carbonate and potassium bicarbonate (511.9kg) containing organic matters and a mother solution, and combining the mother solution with the deamination wastewater to be subjected to MVR treatment for next evaporation and crystallization.
Step (3), transferring the potassium carbonate and potassium bicarbonate crude salt (511.9kg/h) containing the organic matters into an alcohol washing kettle, and carrying out alcohol washing by adopting ethanol, wherein the using amount of the alcohol is 1535L/h; the alcohol washing liquid is rectified to recover alcohol, 1382L/h of alcohol is obtained after recovery, and 29.9kg/h of kettle residue is discharged.
And (4) transferring the potassium carbonate and the potassium bicarbonate wet salt subjected to alcohol washing into a thermal decomposition reactor, and performing thermal decomposition at 180 ℃ in a nitrogen atmosphere to obtain 483.5kg of potassium carbonate solid, wherein the content of the potassium carbonate is 99.1%, the content of the potassium bicarbonate is 0.1%, the ignition loss is 0.8%, and the indexes of superior products in GB/T1587-2000 Industrial Potassium carbonate are achieved.
Air containing a small amount of ammonia from an ammonia gas absorption tower, water vapor containing organic matters such as acetone and alkynol evaporated by an MVR device, waste gas generated by rectification, kettle residue and gas containing organic matters such as carbon dioxide, nitrogen and alcohol generated by thermal decomposition enter a temporary oxygen cracking device (the used catalyst is a molecular sieve catalyst loaded by metal oxide, a carrier is a ZSM-5 molecular sieve, active ingredients are ferric oxide and manganese dioxide, the loading amounts of the ferric oxide and the manganese dioxide are respectively 7.0 wt.% and 8.9 wt.%, and the using amount of the catalyst is 0.8m 3 ) Simultaneously introducing fresh air, wherein the volume ratio of the air introduction amount to the waste gas to be treated entering the temporary oxygen cracking device is 3:1, and the space velocity is 6050h -1 Deep purification treatment is carried out in the air atmosphere, the reaction temperature is 300 ℃, and the reaction pressure is normal pressure; the COD value of the water from the temporary oxygen cracking device is 29mgO 2 Per L, VOC concentration in the gas phase of 8.3mg/m 3 。
Example 3
The alkynol wastewater comprises the following components: the COD value is 52080mg/L, the ammonia nitrogen value is 20619mg/L, the potassium carbonate content is 28.1 wt.%, the potassium bicarbonate content is 0.4 wt.%, the organic matter content is 1.74 wt.%, and the balance is water.
A resource utilization and treatment method of alkynol wastewater comprises the following steps:
step (1), pumping the alkynol wastewater and waste into a stripping towerThe water circularly flows from top to bottom at a flow rate of 2000kg/h, and the air flow rate of the air blown off is 160m 3 H, back flushing from bottom to top; the ammonia gas blown off by air is discharged from the blow-off tower, enters three ammonia absorption towers which are sequentially connected in series, water is taken as absorption liquid to carry out three-stage water absorption, the absorption liquid in each stage of absorption tower is independently and circularly absorbed, and the circulation flow of the absorption liquid is 3.2m 3 And h, 161.9kg of ammonia water is recovered by the first-stage absorption tower, and the concentration of the ammonia water is 20.6%.
Pumping the deamination wastewater obtained in the step (2) and the step (1) into an MVR device at a flow rate of 1940kg/h, wherein the generation rate of water vapor in the MVR treatment process is 1134.8kg/h, the contents of generated potassium carbonate and potassium bicarbonate in a supersaturated solution are 69.8 wt.%, and 1.0 wt.%, cooling and crystallizing the supersaturated solution at 9 ℃, filtering to obtain potassium carbonate and potassium bicarbonate crude salt (505.8kg) containing organic matters and a mother solution, and combining the mother solution with the deamination wastewater to be subjected to MVR treatment for the next evaporation and crystallization.
Step (3), transferring the potassium carbonate and potassium bicarbonate crude salt (505.8kg/h) containing the organic matters into an alcohol washing kettle, and carrying out alcohol washing by adopting mixed alcohol with the volume ratio of methanol to ethanol being 1:1, wherein the using amount of the alcohol is 1517L/h; rectifying alcohol washing liquor to recover alcohol, wherein 1366L/h of recovered alcohol is obtained, and discharging 27.8kg/h of kettle residue.
And (4) transferring the potassium carbonate and the potassium bicarbonate wet salt subjected to alcohol washing into a thermal decomposition reactor, and performing thermal decomposition under the conditions of nitrogen atmosphere and reaction temperature of 180 ℃ to obtain 477.7kg of potassium carbonate solid, wherein the content of the potassium carbonate is 99.3%, the content of the potassium bicarbonate is 0.1%, and the ignition loss is 0.6%, so that the indexes of superior products in GB/T1587-2000 Industrial Potassium carbonate are achieved.
Air containing a small amount of ammonia from an ammonia absorption tower, water vapor containing acetone, alkynol and other organic matters evaporated by an MVR device, waste gas generated by rectification, kettle residue and gas containing carbon dioxide, nitrogen, alcohol and other organic matter vapor generated by thermal decomposition enter a temporary oxygen cracking device (the used catalyst is a molecular sieve catalyst loaded by metal oxide, a carrier is an MCM-22 molecular sieve, active ingredients are ferric oxide and zirconium dioxide, the loading amounts of the ferric oxide and the zirconium dioxide are respectively 7.5 wt.% and 8.1 wt.%, and the dosage of the catalyst is 0.8m 3 ) Simultaneously introducing fresh air, wherein the volume ratio of the air introduction amount to the waste gas to be treated entering the temporary oxygen cracking device is 3:1, and the space velocity is 7082h -1 Deep purification treatment is carried out in the air atmosphere, the reaction temperature is 300 ℃, and the reaction pressure is normal pressure; the COD value of the water from the temporary oxygen cracking device is 19mgO 2 Per L, VOC concentration in the gas phase of 10.2mg/m 3 。
Example 4
The alkynol wastewater comprises the following components: the COD value is 62491mg/L, the ammonia nitrogen value is 29543mg/L, the potassium carbonate content is 26.9 wt.%, the potassium bicarbonate content is 0.5 wt.%, the organic matter content is 2.08 wt.%, and the balance is water.
A resource utilization and treatment method of alkynol wastewater comprises the following steps:
pumping the alkynol wastewater into a stripping tower, wherein the wastewater circularly flows from top to bottom at a flow rate of 2200kg/h, and stripping air flows at an air flow rate of 176m 3 H, back flushing from bottom to top; the ammonia gas blown off by air is discharged from the blow-off tower, enters three ammonia absorption towers which are sequentially connected in series, water is taken as absorption liquid to carry out three-stage water absorption, the absorption liquid in each stage of absorption tower is independently and circularly absorbed, and the circulation flow of the absorption liquid is 3.5m 3 And h, recovering 246.1kg/h of ammonia water from the first-stage absorption tower, wherein the concentration of the ammonia water is 21.5%.
Pumping the deamination wastewater obtained in the step (2) and the step (1) into an MVR device at a flow rate of 2134kg/h, wherein the generation rate of water vapor in the MVR treatment process is 1324.4kg/h, the content of potassium carbonate in the generated supersaturated potassium bicarbonate solution is 73.1 wt.%, and the content of potassium bicarbonate is 1.36 wt.%, cooling and crystallizing the supersaturated solution at 12 ℃, filtering to obtain crude potassium carbonate and potassium bicarbonate (532.6kg) containing organic matters and a mother solution, and combining the mother solution with the deamination wastewater to be subjected to MVR treatment for next evaporation and crystallization.
Step (3), transferring the potassium carbonate and potassium bicarbonate crude salt (532.6kg/h) containing organic matters into an alcohol washing kettle, and carrying out alcohol washing by adopting mixed alcohol with the volume ratio of methanol to n-propanol being 1:1, wherein the use amount of the alcohol is 1600L/h; the alcohol washing liquid is rectified to recover alcohol, 1438L/h of alcohol is obtained after recovery, and 36.7kg/h of kettle residue is discharged.
And (4) transferring the potassium carbonate and the potassium bicarbonate wet salt subjected to alcohol washing into a thermal decomposition reactor, and performing thermal decomposition at the temperature of 180 ℃ in the nitrogen atmosphere to obtain 503kg of potassium carbonate solid, wherein the content of the potassium carbonate is 99.1%, the content of the potassium bicarbonate is 0.1%, the ignition loss is 0.8%, and the indexes of superior products in GB/T1587-2000 Industrial Potassium carbonate are achieved.
Air containing a small amount of ammonia from an ammonia gas absorption tower, water vapor containing organic matters such as acetone and alkynol evaporated by an MVR device, waste gas generated by rectification, kettle residue and gas containing organic matters such as carbon dioxide, nitrogen and alcohol generated by thermal decomposition enter a temporary oxygen cracking device (the used catalyst is a molecular sieve catalyst loaded by metal oxide, a carrier is a Y molecular sieve, active ingredients are ferric oxide and manganese dioxide, the loading amounts of the ferric oxide and the manganese dioxide are respectively 7.3 wt.% and 7.9 wt.%, and the dosage of the catalyst is 1.0m 3 ) Simultaneously introducing fresh air, wherein the volume ratio of the air introduction amount to the waste gas to be treated entering the temporary oxygen cracking device is 3:1, and the space velocity is 6600h -1 Deep purification treatment is carried out in the air atmosphere, the reaction temperature is 300 ℃, and the reaction pressure is normal pressure; the COD value of the water from the temporary oxygen cracking device is 36mgO 2 Per L, VOC concentration in the gas phase of 12.3mg/m 3 。
Example 5
The alkynol wastewater comprises the following components: the COD value is 40159mg/L, the ammonia nitrogen value is 16203mg/L, the potassium carbonate content is 23.8 wt.%, the potassium bicarbonate content is 0.5 wt.%, the organic matter content is 1.34 wt.%, and the balance is water.
A resource utilization and treatment method of alkynol wastewater comprises the following steps:
pumping the alkynol wastewater into a stripping tower, wherein the wastewater circularly flows from top to bottom at a flow rate of 2400kg/h, and stripping air flows at a flow rate of 190m 3 H, back flushing from bottom to top; the ammonia gas blown off by air is discharged from the blow-off tower, enters three ammonia absorption towers which are sequentially connected in series, water is taken as absorption liquid to carry out three-stage water absorption, the absorption liquid in each stage of absorption tower is independently and circularly absorbed, and the circulation flow of the absorption liquid is 3.8m 3 And h, 141.9kg/h of ammonia water recovered by the first-stage absorption tower, wherein the concentration of the ammonia water is 22.7%.
Pumping the deamination wastewater obtained in the step (2) and the step (1) into an MVR device at a flow rate of 2328kg/h, wherein the generation rate of water vapor in the MVR treatment process is 1529.1kg/h, the content of potassium carbonate in the generated potassium carbonate and potassium bicarbonate supersaturated solution is 71.5 wt.%, and the content of potassium bicarbonate is 1.50 wt.%, cooling and crystallizing the potassium carbonate and potassium bicarbonate supersaturated solution at 11 ℃, filtering to obtain crude potassium carbonate and potassium bicarbonate salt (514.1kg) containing organic matters and a mother liquor, and combining the mother liquor with the deamination wastewater to be subjected to MVR treatment for next evaporation and crystallization.
Transferring potassium carbonate and potassium bicarbonate crude salt (514.1kg/h) containing organic matters into an alcohol washing kettle, and carrying out alcohol washing by adopting mixed alcohol of ethanol and n-propanol in a volume ratio of 1:1, wherein the using amount of the alcohol is 1542L/h; the alcohol washing liquid is rectified to recover alcohol, 1388L/h of alcohol is obtained through recovery, and 25.7kg/h of residue is discharged.
And (4) transferring the potassium carbonate and the potassium bicarbonate wet salt subjected to alcohol washing into a thermal decomposition reactor, and carrying out thermal decomposition at 180 ℃ in a nitrogen atmosphere to obtain 485.5kg of solid potassium carbonate, wherein the content of the potassium carbonate is 99.2%, the content of the potassium bicarbonate is 0.1%, and the ignition loss is 0.7%, and the indexes of superior products in GB/T1587-2000 Industrial Potassium carbonate are achieved.
Air containing a small amount of ammonia from an ammonia absorption tower, water vapor containing organic matters such as acetone and alkynol evaporated by an MVR device, waste gas generated by rectification, kettle residue and gas containing organic matters such as carbon dioxide, nitrogen and alcohol generated by thermal decomposition enter a temporary oxygen cracking device (the used catalyst is a molecular sieve catalyst loaded by metal oxide, a carrier is a ZSM-5 molecular sieve, active ingredients are ferric oxide and cobalt dioxide, the loading amounts of the ferric oxide and the cobalt dioxide are respectively 7.5 wt.% and 9.1 wt.%, and the using amount of the catalyst is 0.9m 3 ) Simultaneously introducing fresh air, wherein the volume ratio of the air introduction amount to the waste gas to be treated entering the temporary oxygen cracking device is 4:1, and the space velocity is 8550h -1 Deep purification treatment is carried out in the air atmosphere, the reaction temperature is 300 ℃, and the reaction pressure is normal pressure; the COD value of the water from the temporary oxygen cracking device is 24mgO 2 Per L, VOC concentration in the gas phase 9.9mg/m 3 。
Claims (8)
1. A resource utilization and treatment method of alkynol wastewater is characterized in that: the method comprises the following steps:
step (1), air stripping and water absorption: blowing air into the alkynol wastewater to blow off free ammonia in the wastewater; adopting multi-stage water absorption, taking water as absorption liquid to absorb ammonia blown out by air to prepare ammonia water, and enabling waste gas containing a small amount of ammonia molecules after water absorption to enter an oxygen cracking device for deep purification treatment; wherein the alkynol is 2-methyl-3-butyn-2-ol; the COD value of the alkynol wastewater is 10000 mg/L-100000 mg/L, the ammonia nitrogen value is 10000-40000 mg/L, the content of potassium carbonate is 15-35 wt.%, the content of potassium bicarbonate is 0.1-1.0 wt.%, and the content of organic matters is 0.03-3.0 wt.%;
step (2), evaporation and crystallization: carrying out evaporative crystallization on the deamination wastewater obtained in the step (1) by adopting MVR treatment to obtain a supersaturated solution of potassium carbonate and potassium bicarbonate, cooling, crystallizing and filtering the supersaturated solution of potassium carbonate and potassium bicarbonate to obtain crude salt and a mother solution, combining the mother solution and the deamination wastewater to be subjected to evaporative crystallization, and allowing organic matter-containing water vapor generated by evaporative crystallization to enter an oxygen-critical cracking device;
Step (3), alcohol washing and rectification: carrying out alcohol washing on the crude salt, dissolving high-boiling-point organic matters in the crude salt in an alcohol washing liquid, and recovering alcohol in the alcohol washing liquid through rectification;
step (4), thermal decomposition: carrying out thermal decomposition on wet salt obtained by alcohol washing to obtain potassium carbonate, and allowing waste gas containing organic steam generated in the thermal decomposition process to enter an oxygen cracking device for deep purification treatment; the deep purification treatment conditions are as follows: the volume ratio of fresh air to waste gas to be treated entering the temporary oxygen cracking device is 1-5: 1, a metal oxide loaded molecular sieve catalyst is used as a catalyst, and the space velocity is 2000-20000 h -1 The reaction temperature is 250-450 ℃, and the reaction pressure is normal pressure; the carrier of the metal oxide loaded molecular sieve catalyst is one of a ZSM-5 molecular sieve, an MCM molecular sieve and a Y molecular sieve, the active component is 1-2 of ferric oxide, zinc oxide, manganese dioxide, zirconium dioxide and cobalt dioxide, and the load capacity of the metal oxide is 1.0-20 wt.%.
2. The resource utilization and treatment method of alkynol wastewater according to claim 1, characterized in that: the organic matter is high boiling point organic matter with boiling point not less than 120 deg.c produced in the production process of 2-methyl-3-butine-2-ol, enol, acetone and alkynol.
3. The resource utilization and treatment method of alkynol wastewater according to claim 1, characterized in that: air stripping is carried out in a stripping tower, and the mass volume ratio of the air to the alkynol wastewater is 10: 1-15: 1 kg/m 3 ；
The multistage water absorption is carried out in 2-5 ammonia absorption towers which are connected in series for 2-5 stages of water absorption, when the ammonia concentration of the 1 st-stage absorption liquid reaches 15-20. wt.%, the absorption liquid is transferred to an ammonia water product tank, fresh water is added to be used as the last stage of absorption, the original 2 nd stage of absorption is changed into the 1 st stage of absorption, the original 3 rd stage of absorption is changed into the 2 nd stage of absorption, and the like.
4. The resource utilization and treatment method of alkynol wastewater according to claim 3, characterized in that: the multistage water absorption is carried out in 3 stages of water absorption in 3 ammonia absorption towers connected in series.
5. The resource utilization and treatment method of alkynol wastewater according to claim 1, characterized in that: the generation rate of the water vapor in the MVR treatment process is 500-5000 m 3 /h；
The potassium carbonate and potassium bicarbonate supersaturated solution contains 60-80 wt.% of potassium carbonate and 0.5-5.0 wt.% of potassium bicarbonate;
the cooling crystallization temperature of the supersaturated potassium carbonate and potassium bicarbonate solution is 0-20 ℃.
6. The resource utilization and treatment method of alkynol wastewater according to claim 1, characterized in that: the mass volume ratio of the crude salt to the alcohol is 1-1: 5 kg/L; the alcohol is a lower alcohol.
7. The resource utilization and treatment method of alkynol wastewater according to claim 1, characterized in that: the thermal decomposition condition is nitrogen atmosphere and the temperature is 160-200 ℃.
8. The resource utilization and treatment method of alkynol wastewater according to claim 1, characterized in that: the heat released by the deep purification treatment is used for the vaporization of the liquid of the MVR device.
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| CN103130361A (en) * | 2013-03-22 | 2013-06-05 | 天津大学 | Ammonia-removing method and device for high-concentration ammonia-containing wastewater |
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| CN103130361A (en) * | 2013-03-22 | 2013-06-05 | 天津大学 | Ammonia-removing method and device for high-concentration ammonia-containing wastewater |
| CN106430244A (en) * | 2016-11-08 | 2017-02-22 | 南京大学 | Method for recovering and purifying ammonia gas from ammonia nitrogen wastewater |
| CN106746110A (en) * | 2016-12-02 | 2017-05-31 | 广州市心德实业有限公司 | A kind of device and processing method for processing high ammonia nitrogen and high salt waste water |
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