CN212127860U - Coal chemical industry reverse osmosis concentrated water zero release and utilization's processing system - Google Patents
Coal chemical industry reverse osmosis concentrated water zero release and utilization's processing system Download PDFInfo
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Abstract
The utility model discloses a treatment system for zero discharge and resource utilization of reverse osmosis concentrated water in coal chemical industry, which comprises a hard-removing and silicon-removing unit, an advanced oxidation unit and a nanofiltration unit which are connected in sequence; the nanofiltration unit is respectively connected with the concentrated water membrane concentration unit and the produced water membrane concentration unit; the concentrated water film concentration unit is connected with the concentrated hydrothermal concentration unit, and the concentrated hydrothermal concentration unit is connected with the potassium sulfate preparation unit; the water producing film concentration unit is connected with the water producing hydrothermal concentration unit, and the water producing hydrothermal concentration unit is connected with the ionic membrane electrolysis unit; the ionic membrane electrolysis unit is respectively connected with the hydrochloric acid synthesis unit and the NaClO preparation unit; according to the system, the reverse osmosis concentrated water is pretreated to prepare the sodium chloride and sodium sulfate concentrated brine which are close to saturation, a crystallization process is not needed, the treatment cost is reduced, and finally the concentrated brine is prepared into acid base and potassium sulfate with industrial values, so that the resource utilization of the reverse osmosis concentrated water is realized.
Description
Technical Field
The invention belongs to the field of wastewater treatment, and particularly relates to a treatment system for zero discharge and resource utilization of reverse osmosis concentrated water in coal chemical industry.
Background
Energy distribution in China is characterized in that coal is rich in oil and less in oil, coal reserves are mainly distributed in the west, most coal chemical engineering projects are concentrated in the west with rich coal and water, at present, coal chemical enterprises generally adopt an ultrafiltration-reverse osmosis double-membrane process to realize wastewater recycling and reduce new water consumption, high-quality water recycling of about 75% is realized, meanwhile, 25% reverse osmosis concentrated water is generated, most pollutants in the wastewater are intercepted into the reverse osmosis concentrated water, if the pollutants are not treated, the pollutants are directly discharged into environmental water body to cause great pressure on water environment deterioration in the region where the enterprises are located, and sustainable development of the coal chemical industry is severely restricted.
Membrane concentration and evaporative crystallization are generally adopted to recover crystallized salt in the zero discharge process of coal chemical wastewater, the obtained salt product is difficult to meet the industrial use requirements, and the conventional treatment methods mainly comprise salt washing methods, high-temperature treatment methods, landfill methods and other methods. The salt washing method has the problems of low treatment efficiency, easy generation of secondary pollution and the like; the high-temperature treatment method has the problems of high treatment temperature, large energy consumption, easy melting, low treatment efficiency and the like; the landfill method has the problems of occupying a large amount of land, being easy to separate out and causing secondary pollution and the like. According to the handling cost of the ton hazardous waste of 2000 yuan, the handling cost is higher together with the costs of packaging, transportation and the like. Therefore, an effective and reasonable reverse osmosis concentrated water zero-discharge and resource treatment method is lacked.
SUMMERY OF THE UTILITY MODEL
In order to solve the problem, the utility model provides a coal chemical industry reverse osmosis dense water zero release and utilization's processing system, this system is through preparing out the sodium chloride and the sodium sulfate strong brine that are close the saturation with the dense water of reverse osmosis through the preliminary treatment, saves the crystallization process, has reduced treatment cost, prepares into the acid-base and the potassium sulfate that have industrial value with the strong brine at last, has realized the utilization of reverse osmosis dense water.
In order to achieve the purpose, the utility model adopts the following technical scheme:
a treatment system for zero discharge and resource utilization of reverse osmosis concentrated water in coal chemical industry comprises a hard-removing and silicon-removing unit, an advanced oxidation unit and a nanofiltration unit which are sequentially connected; the nanofiltration unit is respectively connected with the concentrated water membrane concentration unit and the produced water membrane concentration unit; the concentrated water film concentration unit is connected with a concentrated hydrothermal concentration unit, and the concentrated hydrothermal concentration unit is connected with a potassium sulfate preparation unit; the water producing membrane concentration unit is connected with the water producing hydrothermal concentration unit, and the water producing hydrothermal concentration unit is connected with the ionic membrane electrolysis unit; the ionic membrane electrolysis unit is respectively connected with the hydrochloric acid synthesis unit and the NaClO preparation unit.
The potassium sulfate preparation unit is also connected with the hydrothermal concentration unit, NaCl solution generated by potassium sulfate preparation enters the hydrothermal concentration unit, and the sodium chloride content of the membrane-concentrated produced water is more than 150 g/L.
The NaClO preparation unit is also connected with the advanced oxidation unit, and NaClO is reused in the advanced oxidation unit.
The water producing membrane concentration unit is preferably one or both of reverse osmosis or electrodialysis.
Compared with the prior art, the utility model discloses following beneficial effect has:
1. the reverse osmosis concentrated water is pretreated to prepare the sodium chloride and sodium sulfate concentrated brine which are nearly saturated, so that the crystallization process is omitted, the treatment cost is reduced, and finally the concentrated brine is prepared into acid, alkali and potassium sulfate with industrial value, so that the resource utilization of the reverse osmosis concentrated water is realized;
2. the pretreatment advanced oxidation adopts self-produced sodium hypochlorite to realize the removal of organic matters, and no external agent or other equipment is required to be added;
3. the nanofiltration concentrated water organic matter is oxidized by heating and activating sodium persulfate, the organic matter removal efficiency is high, sodium persulfate is converted into sodium sulfate, other miscellaneous salts are not introduced, and the combination of organic matter oxidation and thermal concentration is realized.
Drawings
FIG. 1 is a process flow diagram of the treatment system of the present invention.
In the figure: 1-hard removing and silicon removing unit; 2-advanced oxidation unit; 3-a nanofiltration unit; 4-concentrated water membrane concentration unit; 5-water producing membrane concentration unit; 6-concentrated hydrothermal concentration unit; 7-potassium sulfate preparation unit 8-produced hydrothermal concentration unit; 9-an ionic membrane electrolysis unit; a 10-hydrochloric acid synthesis unit; 11-NaClO preparation Unit.
Detailed Description
In order to better explain the present invention and facilitate understanding of the technical solutions of the present invention, the present invention is further explained in detail below. The following embodiments are merely exemplary of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
As shown in fig. 1, a treatment system for zero discharge and resource utilization of reverse osmosis concentrated water in coal chemical industry comprises a hard-removing and silicon-removing unit 1, an advanced oxidation unit 2 and a nanofiltration unit 3 which are connected in sequence; the nanofiltration unit 3 is respectively connected with a concentrated water membrane concentration unit 4 and a water production membrane concentration unit 5; the concentrated water film concentration unit 4 is connected with a concentrated hydrothermal concentration unit 6, and the concentrated hydrothermal concentration unit 6 is connected with a potassium sulfate preparation unit 7; the water production membrane concentration unit 5 is connected with the water production hydrothermal concentration unit 8, and the water production hydrothermal concentration unit 8 is connected with the ionic membrane electrolysis unit 9; the ionic membrane electrolysis unit 9 is respectively connected with a hydrochloric acid synthesis unit 10 and a NaClO preparation unit 11.
The potassium sulfate preparation unit 7 is also connected with the produced hydrothermal concentration unit 8, NaCl solution produced by potassium sulfate preparation enters the produced hydrothermal concentration unit 8, and the content of sodium chloride in the produced water by membrane concentration is more than 150 g/L.
The NaClO preparation unit 11 is also connected to the advanced oxidation unit 2, and NaClO is reused in the advanced oxidation unit 2.
The water producing membrane concentration unit 5 is preferably one or both of reverse osmosis or electrodialysis.
In practical application, reverse osmosis concentrated water firstly enters the hard removing and silicon removing unit 1, and a softening agent and a silicon removing agent are added, wherein the softening agent is sodium hydroxide or calcium hydroxide, sodium carbonate and magnesium oxide.
The effluent of the hard silicon removal unit 1 enters an advanced oxidation unit 2 to remove organic matters, NaClO of a later NaClO preparation unit 11 is adopted to oxidize and remove the organic matters in the wastewater, and the content of the organic matters in the wastewater is determined according to the following formula (m) (NaClO): m (COD) =1-4 adding NaClO.
The effluent of the advanced oxidation unit 3 enters a nanofiltration unit 4 for salt separation to obtain concentrated water rich in sodium sulfate and produced water rich in sodium chloride.
Concentrated water enters a concentrated water membrane concentration unit 5, the membrane concentration unit 5 is one or the combination of reverse osmosis and electrodialysis, and the content of sodium sulfate in membrane concentration brine is more than 150 g/L;
adding oxidant sodium persulfate into the effluent of the concentrated water membrane concentration unit 5, then feeding the effluent into a concentrated water thermal concentration unit 6, wherein the thermal concentration heating temperature is 70-100 ℃, and the sodium persulfate removes organic matters in the brine through heating, activating and oxidizing according to the m (Na)2S2O8): m (TOC) =2-6, sodium persulfate is added, and the content of sodium sulfate in hot concentrated brine is more than 300 g/L.
The effluent of the concentrated hydrothermal concentration unit 6 enters a potassium sulfate preparation unit 7 to obtain a potassium sulfate product and a sodium chloride solution.
The sodium chloride produced water enters a water production membrane concentration unit 5, the membrane concentration unit is one or the combination of reverse osmosis and electrodialysis, and the sodium chloride content of the membrane concentration produced water is more than 150 g/L;
and the sodium chloride solution prepared from the effluent of the water producing membrane concentration unit 5 and the potassium sulfate enters a water producing hydrothermal concentration unit 8, and the content of the sodium chloride in the hot concentrated effluent is more than 300 g/L.
The produced water of the hydrothermal concentration unit 8 enters an ionic membrane electrolysis unit 9, and the product is H2、Cl2And about 30% NaOH solution.
H2Part of Cl2Enters a hydrochloric acid synthesis unit 10 to prepare about 30 percent HCl solution and part of Cl2And the NaOH solution enters a NaClO preparation unit 11 to prepare NaClO.
The NaClO prepared by the NaClO preparation unit 11 is reused for removing organic matters in brine by advanced oxidation, and a 30% HCl solution and a 30% NaOH solution are reused in a water treatment system or sold for sale.
Example 1
The reverse osmosis concentrated water of a certain coal chemical industry water treatment unit is shown in table 1 and is treated by the following steps:
TABLE 1 coal chemical reverse osmosis concentrated water index
| Item | Ca | Mg | SiO2 | COD | TOC | TDS | Cl- | SO4 2- |
| Numerical value, mg/L | 120 | 40 | 80 | 195 | 65 | 22000 | 7100 | 13200 |
(1) The reverse osmosis concentrated water firstly enters a hardness removing and silicon removing unit, and a softening agent and a silicon removing agent are added, wherein the softening agent is calcium hydroxide, sodium carbonate and magnesium oxide, and the water outlet Ca of the hardness removing and silicon removing unit is as follows: 5Mg/L, Mg: 5mg/L, SiO2：10mg/L。
(2) And (2) enabling the effluent in the step (1) to enter a high-grade oxidation unit to remove organic matters, and oxidizing and removing the organic matters in the wastewater by adopting NaClO of a later NaClO preparation unit according to the ratio of m (NaClO): m (COD) =2 adding NaClO, and the COD of the effluent is reduced to 92 mg/L.
(3) And (3) allowing the water discharged from the step (2) to enter a nanofiltration unit for salt separation to obtain concentrated water rich in sodium sulfate and produced water rich in sodium chloride. The content of concentrated water sodium sulfate is 51200mg/L, and the content of fresh water sodium chloride is 7100 mg/L.
(4) And (4) enabling the concentrated water obtained in the step (3) to enter a concentrated water membrane concentration unit, wherein the membrane concentration adopts high-pressure reverse osmosis concentration, and the sodium sulfate content of the membrane concentrated brine is 152 g/L.
(5) Step 4, adding an oxidant sodium persulfate into the produced water, then feeding the water into a concentrated hydrothermal concentration unit, wherein the heating temperature of the thermal concentration is 80 ℃, and removing organic matters in the brine by heating, activating and oxidizing the sodium persulfate according to the formula of m (Na)2S2O8): m (TOC) =3, sodium persulfate is added, the content of sodium sulfate is concentrated by heat is 310g/L, and TOC is 8 mg/L.
(6) And 5, enabling the effluent obtained in the step 5 to enter a potassium sulfate preparation unit to obtain a potassium sulfate product and a sodium chloride solution.
(7) And (3) enabling the produced water obtained in the step (3) to enter a water production membrane concentration unit, wherein the membrane concentration unit is a combination of reverse osmosis and electrodialysis, and the content of sodium chloride in membrane concentrated brine is 155 g/L.
(8) And (4) feeding the water produced in the step (7) and the sodium chloride solution obtained in the step (6) into a water-producing heat concentration unit, wherein the content of sodium chloride in the heat-concentrated brine is 310 g/L.
(9) Step 8, the produced water enters an ion membrane electrolysis unit, and the product is H2、Cl2And about 30% NaOH solution.
（10）H2Part of Cl2The solution enters a hydrochloric acid synthesis unit to prepare about 30 percent HCl solution, and part of Cl2And the NaOH solution enters a NaClO preparation unit to prepare NaClO.
(11) The NaClO prepared by the NaClO preparation unit is reused for removing organic matters in brine by advanced oxidation, and the 30% HCl solution and the 30% NaOH solution are reused in a water treatment system or sold for sale.
Example 2
The reverse osmosis concentrated water of a certain coal chemical industry water treatment unit is shown in table 2 and is treated by the following steps:
TABLE 2 coal chemical reverse osmosis concentrated water index
| Item | Ca | Mg | SiO2 | COD | TOC | TDS | Cl- | SO4 2- |
| Numerical value, mg/L | 110 | 60 | 90 | 240 | 80 | 25600 | 16100 | 8100 |
(1) The reverse osmosis concentrated water firstly enters a hardness removing and silicon removing unit, and a softening agent and a silicon removing agent are added, wherein the softening agent is calcium hydroxide, sodium carbonate and magnesium oxide, and the water outlet Ca of the hardness removing and silicon removing unit is as follows: 6Mg/L, Mg: 4mg/L, SiO2：12mg/L。
(2) And (2) enabling the effluent in the step (1) to enter a high-grade oxidation unit to remove organic matters, and oxidizing and removing the organic matters in the wastewater by adopting NaClO of a later NaClO preparation unit according to the ratio of m (NaClO): m (COD) =2 adding NaClO, and the COD of the effluent is reduced to 125 mg/L.
(3) And (3) allowing the water discharged from the step (2) to enter a nanofiltration unit for salt separation to obtain concentrated water rich in sodium sulfate and produced water rich in sodium chloride. The content of concentrated water sodium sulfate is 31200mg/L, and the content of fresh water sodium chloride is 17200 mg/L.
(4) And (3) enabling the concentrated water obtained in the step (3) to enter a concentrated water membrane concentration unit, and performing combined concentration on the membrane concentration by adopting high-pressure reverse osmosis and electrodialysis, wherein the sodium sulfate content of the membrane concentrated brine is 161 g/L.
(5) Step 4, adding an oxidant sodium persulfate into the produced water, then feeding the water into a concentrated hydrothermal concentration unit, wherein the heating temperature of the thermal concentration is 80 ℃, and removing organic matters in the brine by heating, activating and oxidizing the sodium persulfate according to the formula of m (Na)2S2O8): m (TOC) =4, sodium persulfate is added, the content of sodium sulfate is concentrated by heat and is 320g/L, and TOC is 8 mg/L.
(6) And 5, enabling the effluent obtained in the step 5 to enter a potassium sulfate preparation unit to obtain a potassium sulfate product and a sodium chloride solution.
(7) And (3) enabling the produced water obtained in the step (3) to enter a water production membrane concentration unit, wherein the membrane concentration unit is a combination of reverse osmosis and electrodialysis, and the content of sodium chloride in membrane concentrated brine is 161 g/L.
(8) And (4) feeding the water produced in the step (7) and the sodium chloride solution obtained in the step (6) into a water-producing heat concentration unit, wherein the content of sodium chloride in the heat-concentrated brine is 320 g/L.
(9) Step 8, the produced water enters an ion membrane electrolysis unit, and the product is H2、Cl2And about 30% NaOH solution.
（10）H2Part of Cl2The solution enters a hydrochloric acid synthesis unit to prepare about 30 percent HCl solution, and part of Cl2And the NaOH solution enters a NaClO preparation unit to prepare NaClO.
(11) The NaClO prepared by the NaClO preparation unit is reused for removing organic matters in brine by advanced oxidation, and the 30% HCl solution and the 30% NaOH solution are reused in a water treatment system or sold for sale.
The applicant states that the present invention is illustrated by the above embodiments, but the present invention is not limited to the above detailed process equipment and process flow, i.e. the present invention is not meant to be implemented by relying on the above detailed process equipment and process flow. It should be clear to those skilled in the art that any improvement of the present invention, to the equivalent replacement of each raw material of the present invention, the addition of auxiliary components, the selection of specific modes, etc., all fall within the protection scope and disclosure scope of the present invention.
Claims (4)
1. A treatment system for zero discharge and resource utilization of reverse osmosis concentrated water in coal chemical industry is characterized by comprising a hardness and silicon removal unit (1), an advanced oxidation unit (2) and a nanofiltration unit (3) which are sequentially connected; the nanofiltration unit (3) is respectively connected with a concentrated water membrane concentration unit (4) and a water production membrane concentration unit (5); the concentrated water film concentration unit (4) is connected with a concentrated hydrothermal concentration unit (6), and the concentrated hydrothermal concentration unit (6) is connected with a potassium sulfate preparation unit (7);
the water producing membrane concentration unit (5) is connected with the water producing hydrothermal concentration unit (8), and the water producing hydrothermal concentration unit (8) is connected with the ionic membrane electrolysis unit (9); the ionic membrane electrolysis unit (9) is respectively connected with a hydrochloric acid synthesis unit (10) and a NaClO preparation unit (11).
2. The treatment system according to claim 1, wherein the potassium sulfate preparation unit (7) is further connected with a hydrothermal concentration unit (8), the NaCl solution produced by the potassium sulfate preparation enters the hydrothermal concentration unit (8), and the sodium chloride content of the produced water by membrane concentration is more than 150 g/L.
3. The treatment system as claimed in claim 1 or 2, wherein the NaClO preparation unit (11) is also connected to the advanced oxidation unit (2), and NaClO is reused in the advanced oxidation unit (2).
4. A treatment system as claimed in claim 3, wherein the water producing membrane concentration unit (5) is one or both of reverse osmosis or electrodialysis.
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