WO2016188326A1 - Semi coke wastewater treating and regenerative recycling method - Google Patents

Abstract

A semi coke wastewater treating and regenerative recycling method, comprising the following steps: (1) coarse filtration; (2) membrane filtration; (3) detarring; (4) dephenolizing; (5) ammonia-nitrogen removing; (6) desulfurizing; (7) anaerobic treatment; (8) aerobic treatment; (9) electrolysis; (10) secondary anaerobic treatment; (11) membrane treatment or biochemical treatment of a biological aerated filter; and (12) desalting.

Description

Blue carbon waste water treatment and recycling cycle utilization method Technical field

The invention belongs to the field of water pollution control of environmental engineering, and more specifically refers to a method for treating and recycling recycling of blue carbon waste water.

Background technique

Blue carbon, also known as semi-coke, coke powder, is an important raw material for iron alloy, coal gas, coal chemical production, and is obtained from low temperature dry distillation (about 650 °C). Blue carbon production and gas purification process will produce waste water, which is called blue carbon waste water. It is an industrial wastewater with complex composition, high concentration of pollutants, stable nature, poor biodegradability and great treatment. The inorganic pollutants in the blue carbon waste water mainly include sulfides, cyanide, ammonia nitrogen and thiocyanide. The organic pollutants are mainly coal tars, and the content of phenolic compounds is high. In addition, it contains polycyclic aromatics. a compound and a heterocyclic compound containing nitrogen, sulfur and oxygen. The blue carbon waste water is completely different from the coking wastewater. See Table 1 for comparison of the main pollutants of the blue carbon waste water and coking wastewater. From the comparison of Table 1 and Table 2, it can be seen that the main pollutant index of the blue carbon wastewater is ten times that of the coking wastewater. Therefore, although there are many treatment methods for coking wastewater, the treatment method is not suitable for blue carbon wastewater. At present, there is no mature method for the treatment of blue carbon waste water, and its treatment method and comprehensive utilization of its main components are very urgent. He Bin and Wang Yazhen reported on the treatment of blue carbon wastewater by ammonia-dephenol-SBR treatment in the 36th issue of Guangxi Chemical Industry; Yang Yipu et al. introduced the blue carbon in the 12th issue of Environmental Engineering Journal. The effect of extraction and recovery of phenolic substances in wastewater is only a solution to the problem of blue carbon wastewater. Although there are many reports on the treatment of blue carbon wastewater, there is no perfect and mature Lancan wastewater treatment method.

Table 1 Main pollutants indicators of blue carbon wastewater and coking wastewater

Serial number	Major pollutant	Blue carbon wastewater	Coking wastewater
1	COD (mg/L)	10000~75000	3500～5000
2	BOD (mg/L)	3000～5000	1170~2000
3	pH	8~10	8~9
4	Tar (mg/L)	5000～40000	100~200
5	Ammonia nitrogen (mg/L)	500～5000	200～400
6	Total phenol (mg/L)	1000～6000	600～800
7	Chromaticity (times)	10000～30000	1000～1500

The water quality characteristics of the blue carbon wastewater determine its complex hazard. For example, ammonia nitrogen, phenolic compounds and aromatic compounds contained in it pose a huge threat to the ecological environment. In addition, industrial by-products such as coal tar, ammonia, and phenol in blue carbon waste water have the value of recycling.

technical problem

The invention provides a blue carbon waste water treatment and regeneration recycling utilization method, and the main purpose thereof is to overcome the shortcomings of the prior art that the blue carbon waste water treatment depth is insufficient.

Technical solution

The invention adopts the following technical solutions:

A blue carbon waste water treatment and regeneration recycling device and method, comprising the following steps:

(1) Crude filtration: blue carbon wastewater with COD of 10000 to 75000 mg/L, ammonia nitrogen of 500 to 5000 mg/L, total phenol of 1000 to 6000 mg/L, color of 10,000 to 30,000 times, and pH of 8 to 10. Filtration through a grid or screen to remove large particles;

(2) Membrane filtration: the crude filtered carbon waste water for removing large particles is added to the acid to adjust the pH to 2-6, and then filtered through a membrane to obtain a coal tar-rich concentrate and a coal tar-removing dialysate, and the concentration is 3 to 10;

(3) Detarred oil: the step (2) is filtered through a membrane to obtain a concentrated solution rich in coal tar, which is subjected to gravity sedimentation separation or centrifugal separation to obtain de-tarred blue carbon waste water, and the COD removal rate thereof is 30 to 55%;

(4) Dephenolization: the dialysate obtained by the membrane filtration in step (2) and the blue carbon waste water after the step (3) decoking tar are uniformly mixed, and the dephenolated blue carbon waste water is extracted and extracted by extracting agent, and the COD removal rate is obtained. 35 to 70%;

(5) Deamination nitrogen: The blue carbon waste water obtained by removing the phenol from the step (4) is added to the alkali solution to adjust the pH to 9 to 11, and the ammonia gas is removed by heating and evaporation, and the ammonia gas is absorbed by the sulfuric acid solution to produce ammonium sulfate or cooled to obtain a liquid. Ammonia and deammonia wastewater;

(6) Desulfurization: adding desulfurization agent, such as ferrous sulfate, to the deaminated blue carbon wastewater after step (5) deamination of nitrogen to form iron sulfide precipitation and desulfurization blue carbon waste water, the COD removal rate is 10-20%, preventing Sulfide poisoning to biochemistry, improve its biochemical effects;

(7) Anaerobic treatment: the desulfurized blue carbon waste water obtained by desulfurization in step (6) is added to an alkali solution to adjust the pH to 6-9, and enters the anaerobic tank through the lift pump, and passes through the anaerobic and anaerobic bacteria in the anaerobic tank. The adsorption, fermentation and methanogenesis work together to decompose the organic acid into methane and carbon dioxide, improve the B/C value of the wastewater and remove most of the COD by anaerobic treatment, and improve the biodegradability of the wastewater;

(8) Aerobic treatment: after step (7) anaerobic treatment, the blue carbon waste water passes through the lift pump into the aerobic tank and the intermediate sedimentation tank, and part of the sludge in the intermediate sedimentation tank is returned to the aerobic tank through the reflux pump, and the good The oxygen treatment further oxidizes and decomposes the organic matter in the blue carbon waste water to deeply remove COD and BOD; the aerobic pool is uniformly filled with a large amount of biological suspended filler to provide a habitat for aerobic microorganisms to grow and reproduce, so that the microorganism forms a biofilm on the surface of the filler. An aeration and oxygenation agitation system is arranged at the bottom of the aerobic tank to oxygenate the sewage to maintain the dissolved oxygen in the water at 2 to 4 mg/L, and at the same time, the action of the gas rises to make the suspended matter and water in the pool more Full contact, and the agitation action of gas and water backwashing can effectively wash the aged biofilm grown on the surface of the filler, promote the replacement of the biofilm, and maintain the high activity of the biofilm;

(9) Electrolysis: After the aerobic treatment in step (8), the blue carbon waste water enters the electrolysis machine for electrolysis to remove the chromaticity and odor, and at the same time, the difficult biochemical macromolecular compound in the wastewater is opened and broken, and becomes biochemical. The small molecule further increases the B/C value and improves the conditions of the subsequent biochemical treatment; the voltage between the adjacent electrodes of the electrolysis machine is 2 to 12 V, and the current density is 10 to 320 mA/cm ² ;

(10) Secondary anaerobic treatment: the blue carbon waste water obtained by the electrolysis in step (9) is passed through a lift pump into a secondary anaerobic tank, and the anaerobic bacteria and facultative bacteria in the anaerobic tank are adsorbed, fermented, and methanogenic. The function is to decompose the organic acid into methane and carbon dioxide, improve the B/C value of the wastewater by anaerobic treatment and further remove most of the COD, thereby improving the biodegradability of the wastewater;

(11) MBR treatment or biological bioreactor biochemistry (BAF biochemistry)

Step (10) The second anaerobic treated blue carbon wastewater enters the MBR treatment device or the aerated biological filter, and the wastewater is purified by filtration separation or biological oxidative degradation of the membrane treatment device to further remove COD, SS and ammonia nitrogen. Obtaining purified wastewater;

(12) Desalting: Step (11) The wastewater after MBR treatment or biological bioreactor biochemistry (BAF biochemical) enters the desalination device, and the dialysis water and concentrated water are separated, the dialysis water enters the reclaimed water storage tank, and the concentrated water passes through the drainage channel. The effluent enters the evaporation crystallization tank for crystallization treatment; the desalination device may be one of a reverse osmosis system and a nanofiltration system.

The membrane filtration in the step (2) is one of ceramic membrane filtration or metal membrane filtration; the ceramic membrane element of the ceramic membrane filtration system has a pore diameter of 20 to 100 nm; the metal membrane element of the metal membrane filtration system has a pore diameter of 30 to 100 nm; and the working pressure It is 3 to 6 bar and the temperature is 15 to 55 °C. The membrane tar obtained by the step (2) is all concentrated in the concentrate, the COD of the dialysate is about 5,000 to 34,000 mg/L, and the COD removal rate is 30 to 55%.

Step (2) Membrane Filtration The membrane-filtered coal-rich tar-rich concentrate is pumped into a centrifuge and separated into coal tar and de-coke blue carbon wastewater by centrifugation; the centrifugal force of centrifugation is 2200-4000.

Step (3) De-tarding The gravity sedimentation separation is performed by placing the membrane-filtered concentrated coal-rich tar into a gravity sedimentation tank and separating it into coal tar and de-coke blue carbon wastewater by gravity sedimentation.

Step (3) De-tar treatment not only realizes the recovery and utilization of coal tar in the blue carbon wastewater, but also reduces the COD of the wastewater by 30-55%, greatly reduces the chroma and ensures the subsequent production process.

The detarred oil according to the step (3) is an acid added to adjust the pH to 2 to 5, and the acid used is one of sulfuric acid, hydrochloric acid or nitric acid; most preferably sulfuric acid, and the amount is 5 to 7 kg/m ³ .

Step (4) Phenol Removal of the extractant used is kerosene, N, N ^'- dimethylheptyl acetamide (N, ^N' one kind -503), or tributyl phosphate, or benzol mixture;

Step (4) Phenol Removal optimum extractant employed for the 20-30% of ^{N, N '- (-503 N} , N) dimethylheptyl ^acetamide' kerosene mixture.

Step (4) Dephenolization The preferred extractant used for the extraction is a mixture of 20-33% tributyl phosphate and kerosene.

The ratio of the extractant used in the step (4) dephenolization extraction to the blue carbon waste water is preferably 1:5, that is, 200 L of extractant per cubic meter of carbon waste water in Milan.

Step (9) Electrolytic electrolysis machine is provided with a power source and an electrolytic cell, and the electrode materials in the electrolysis cell are graphite, titanium, iron, aluminum, zinc, copper, lead, nickel, molybdenum, chromium, alloy and nano catalytic inert material. One of them.

The membrane module of the MBR device according to the step (11) is selected from the group consisting of a polyvinylidene fluoride hollow fiber membrane, a polypropylene hollow fiber membrane, a polysulfone hollow fiber membrane, a polyethersulfone, a polyacrylonitrile, and a polyvinyl chloride hollow fiber membrane. One of them has a membrane pore diameter of 0.10 to 0.2 μm, a working pressure of -1 to -50 kPa, and an operating temperature of 5 to 45 ° C;

Step (12) Desalting The reverse osmosis membrane module of the reverse osmosis system is a roll membrane module, and the membrane material is an acetate membrane or a composite membrane in an organic membrane. The molecular weight cutoff of the membrane material is 50-200 MWCO, and the inlet pressure can be 6.0. ~ 45.0 bar, the pressure can be 4.5 ~ 33.5bar.

Step (12) Desalting The nanofiltration membrane module in the nanofiltration system is a tubular membrane module, a membrane membrane module or a flat membrane module, and the working pressure is 6 to 45 bar, and the working temperature is 20 to 45 ° C. The optimum temperature is 35 to 40 °C.

Beneficial effect

As described above, the main pollutant removal effects of the various steps on the blue carbon waste water are shown in Table 2.

Table 2 Table 2 shows the removal effect of major pollution indicators

project	pH	Chroma	COD (mg/L)	Total phenol (mg/L)	Ammonia nitrogen (mg/L)	Contaminant removal rate (%)
Raw water	8-10	10000-30000	10000-75000	1000-6000	500-5000
Coarse filtration	8-10	1000-3000	10000-75000	1000-6000	500-5000
Demulsification	2-6	1000	10000-75000	1000-6000	500-5000
Detarred oil	2-6	500	5000-34000	1000-6000	500-5000	COD30～55%
Dephenolation	2-6	500	2000-19000	300-600	500-5000	COD35-70%
Deamination	9-11	500	1500-4500	300-400	30-80	More than 99% ammonia nitrogen
Desulfurization	7-8	300	1400-3800	80-200	30-80	COD10-20%
Oxidation	7-8	200	1400-3800	10-70	20-60
Anaerobic treatment	7-8	150	350-950	5-20	5-40	More than 75% COD
Aerobic	7-8	100	140-380	5-10	5-20	More than 60% COD
Electrolytic treatment	7-8	20	140-380	3-8	5-15
Secondary anaerobic treatment	7-7.5	10	70-190	----	5-10	More than 50% COD
MBR processing	6-7.5	15	35-90	----	5-10	More than 50% COD
RO	6-7.5	1	20	----	5

Compared with the prior art, the invention has the following advantages:

(1) After adjusting the pH of the blue carbon waste water to 2-6, the tar in the blue carbon waste water is concentrated into the concentrated liquid through membrane filtration, which can reduce the volume of the blue carbon waste water by more than three times, saving equipment investment and reducing energy consumption. , greatly reducing production costs.

(2) By gravity sedimentation separation or centrifugal separation, 5-40 kg of coal tar can be recovered from each cubic wastewater, which not only realizes the recovery and utilization of coal tar in the blue carbon wastewater, but also reduces the COD of the wastewater by 30-55%. Significantly reduce the chromaticity to ensure the subsequent production process.

(3) After mixing the dialysate obtained by membrane filtration and the detarred wastewater obtained from the recovery of coal tar, after extracting and separating, 1 to 6 kg of crude phenol can be recovered from each cubic wastewater to realize the recovery of phenol in the blue carbon wastewater. The use of phenol to the biochemical treatment of the back-end wastewater, and the COD of the blue carbon wastewater decreased by 35 to 75%.

(4) The dephenolized blue carbon waste water obtained by deamination can be removed by adjusting the pH and heating and evaporating, and 0.5 to 5 kg of ammonia can be recovered from each cubic wastewater to realize the recovery and utilization of ammonia.

(5) Through the combined treatment process of membrane filtration, coal tar recovery, dephenolization, deamination, anaerobic treatment, aerobic treatment, electrolytic reverse osmosis desalination, etc., advanced treatment of blue carbon wastewater, and finally recycling of wastewater reclaimed water To achieve pollution elimination and resource conservation.

(6) Through the recycling of coal tar, phenol, ammonia and other resources, not only the recycling of resources, but also the treatment cost of blue carbon wastewater is greatly reduced.

DRAWINGS

Figure 1 is a process flow diagram of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

A specific embodiment of the present invention will be described below with reference to Fig. 1 .

The invention is based on the composition, properties and existing treatment scheme of the blue carbon waste water, and designs a blue carbon waste water treatment and regeneration recycling method, which relates to membrane filtration, de-tarting, dephenolization, deamination, anaerobic treatment, aerobic treatment A combined treatment process of treatment, electrolysis, desalination, etc., thereby forming a method for effectively realizing the deep treatment and recycling of blue carbon waste water.

Embodiments of the invention

Example 1

A blue carbon waste water treatment and recycling cycle utilization method

(1) Crude filtration: The crude carbon waste water with COD of 10000 mg/L, ammonia nitrogen of 500 mg/L, total phenol of 1000 mg/L, color of 10000 times and pH of 8 is coarsely filtered through a grid or sieve. Remove large particles and debris;

(2) Membrane filtration: the coarsely filtered blue carbon waste water for removing large particles is added to sulfuric acid to adjust the pH to 6 demulsification, and the membrane concentrated to obtain the coal tar-rich concentrate and the coal tar-removed dialysate, the concentration factor is 8 ～10;

The membrane filtration is ceramic membrane filtration, and the ceramic membrane element of the ceramic membrane filtration system has a pore diameter of 30 nm; the working pressure is 3 to 6 bar, and the temperature is 15 to 55 °C.

(3) Detarred oil: The step (2) is filtered through a membrane to obtain a concentrated solution rich in coal tar, and after gravity sedimentation for 24 hours, the recovered coal tar and detarred oil wastewater are separated.

The gravity sedimentation is that the concentrated carbon waste water concentrated by the membrane filtration in the step (2) is placed in a gravity sedimentation tank, and separated into an upper layer of coal tar and a lower layer of decoking wastewater by gravity sedimentation, and the upper layer of coal tar is passed through The recovery pipe recovered 3 kg/m ³ of coal tar.

The degassed oil has a COD of 7213 mg/L, an ammonia nitrogen of 521 mg/L, a total phenol of 1103 mg/L, and a color of 500 times.

(4) Dephenolization: the dialysate obtained by filtering the ceramic membrane in step (2) and the blue carbon waste water recovered from the recovery of the coal tar in step (3) are added to an extractant to extract and obtain crude phenol 1kg/m ³ and dephenol blue waste water. .

The extractant used is extracted ^{N, N '- (-503 N} , N) dimethylheptyl ^acetamide' kerosene mixture.

The dephenolized wastewater has a COD of 2932 mg/L, an ammonia nitrogen of 532 mg/L, a total phenol of 103 mg/L, and a color of 500 times.

(5) Deamination nitrogen: The blue carbon waste water obtained by removing the phenol from the step (4) is added to the alkali solution to adjust the pH to 11, and the ammonia gas is removed by heating and evaporation, and the ammonia gas is absorbed by the sulfuric acid solution to produce ammonium sulfate or cooled to obtain liquid ammonia and Deammonia blue carbon wastewater.

The pollutant index of the decarbonized blue carbon waste water is: COD is 1913 mg / L, ammonia nitrogen is 65.1 mg / L, total phenol is 213.4 mg / L, and the color is 500 times.

(6) Desulfurization: adding desulfurization agent, such as ferrous sulfate, to the deaminated carbon waste water after step (5) deamination of nitrogen to form iron sulfide precipitation and desulfurization of blue carbon waste water, preventing the poisoning of the sulfide by biochemistry and improving its biochemical effect. The removal rate of COD was 18.7%;

The pollutant index of the desulfurized blue carbon waste water is: COD is 1554.92 mg/L, ammonia nitrogen is 49 mg/L, total phenol is 210 mg/L, and chroma is 200 times.

(7) Anaerobic treatment: the desulfurized blue carbon waste water obtained by desulfurization in step (6) is added to an alkali solution to adjust the pH to 6-9, and enters the anaerobic tank through the lift pump, and passes through the anaerobic and anaerobic bacteria in the anaerobic tank. The adsorption, fermentation and methanogenesis work together to decompose the organic acid into methane and carbon dioxide, improve the B/C value of the wastewater and remove most of the COD by anaerobic treatment, and improve the biodegradability of the wastewater.

The pollutant index of the anaerobic treated blue carbon waste water is: COD is 403 mg/L, ammonia nitrogen is 51 mg/L, total phenol is 11 mg/L, and chroma is 150 times.

(8 aerobic treatment: the step (7) after the anaerobic treatment, the blue carbon waste water passes through the lift pump into the aerobic tank and the intermediate sedimentation tank, and part of the sludge in the intermediate sedimentation tank is returned to the aerobic tank through the reflux pump, and is treated by aerobic treatment. Further oxidize and decompose organic matter in the blue carbon waste water to deeply remove COD and BOD; the aerobic pool is uniformly filled with a large amount of biological suspended filler to provide a habitat for aerobic microorganisms to grow and reproduce, so that microorganisms form a biofilm on the surface of the filler. The aerobic tank is equipped with an aeration and oxygenation agitation system to oxygenate the sewage to maintain the dissolved oxygen in the water at 2 to 4 mg/L. At the same time, the gas is used to make the suspended solids in the pool more fully contact with the water. In addition, through the agitation action of gas and water backwashing, the aged biofilm grown on the surface of the filler can be effectively washed, and the biofilm is replaced, so that the biofilm maintains high activity.

The pollutant index of the aerobic treated blue carbon waste water is: COD is 320 mg/L, ammonia nitrogen is 11 mg/L, total phenol is 1 mg/L, and chromaticity is 100 times.

(9 Electrolysis: Step (8) After the aerobic treatment, the blue carbon waste water enters the electrolysis machine for electrolysis to remove the color and smell, and at the same time, the difficult biochemical macromolecular compound in the wastewater is opened and broken, and becomes biochemically small. The molecule further increases the B/C value and improves the conditions of the subsequent biochemical treatment; the voltage between the adjacent electrodes of the electrolysis machine is 2 to 12 V, and the current density is 10 to 320 mA/cm ² ;

The electrolyzer is provided with a power source and an electrolytic cell, and the electrode material in the electrolytic cell is one of graphite, titanium, iron, aluminum, zinc, copper, lead, nickel, molybdenum, chromium, alloy and nano catalytic inert material. .

(10 times of anaerobic treatment: the step (9 blue carbon waste water obtained by electrolysis enters the secondary anaerobic tank through the lift pump, and the anaerobic bacteria, anaerobic bacteria adsorption, fermentation, and methanogenesis in the anaerobic tank will work together. The organic acid is decomposed into methane and carbon dioxide, and the B/C value of the wastewater is increased by anaerobic treatment and further COD is further removed to improve the biodegradability of the wastewater.

The pollutant index of the secondary anaerobic treatment of blue carbon waste water is: COD is 80.2 mg/L, ammonia nitrogen is 16 mg/L, total phenol is 1 mg/L, and color is 150 times.

(11 aerated biofilter biochemical (BAF biochemical)

Step (10 times of anaerobic treatment of blue carbon waste water into the biological aerated filter, the wastewater is purified by biooxidation degradation, further removing COD, SS and ammonia nitrogen to obtain purified wastewater, the COD is 50mg/L, SS is 15 mg / L, ammonia nitrogen 5 mg / L, color 8 times.

(12 desalination: step (11 aerated biological filter biochemical (BAF biochemical) wastewater into the desalination device, separated dialysis water (reclaimed water) and concentrated water, dialysis water into the reclaimed water storage tank for use, concentrated water through the drain Discharge into the evaporation crystallization tank for crystallization treatment;

The desalination device is a nanofiltration system.

The nanofiltration membrane module in the nanofiltration system is a tubular membrane module, a coil membrane module or a flat membrane module, and the working pressure is 6 to 45 bar, the working temperature is 20 to 45 ° C, and the optimal temperature is 35. ~40 ° C.

Example 2

A blue carbon waste water treatment and recycling cycle utilization method

(1) Crude filtration: The crude carbon waste water with a COD of 34967 mg/L, an ammonia nitrogen of 1911 mg/L, a total phenol of 6231 mg/L, a chromaticity of 2000 times, and a pH of 8.1 was coarsely filtered through a grid or a sieve. Remove large particles and debris;

(2) Membrane filtration: The coarsely filtered blue carbon waste water for removing large particles is added to sulfuric acid to adjust the pH to 3-4, and the membrane concentrated to obtain the coal tar-rich concentrate and the coal tar-removing dialysate, the concentration ratio is 5 Times

The membrane filtration is ceramic membrane filtration, and the ceramic membrane element of the ceramic membrane filtration system has a pore diameter of 20 to 100 nm, a working pressure of 3 to 6 bar, and a temperature of 15 to 55 °C.

The dialysate obtained by the membrane filtration has a COD of 9800 to 11500 mg/L.

(3) Detarred oil: The step (2) is filtered through a membrane to obtain a concentrated coal-rich tar, which is subjected to centrifugal separation, the lower layer of coal tar and the upper layer of decoking wastewater, and the lower layer of coal tar is recovered to obtain coal tar of 17.6 kg/m. ³ . The centrifugal force for centrifugation was 3219.

(4) Dephenolization: the dedialysis liquid obtained by the membrane filtration of the step (2) and the de-tarred wastewater obtained by the recovery of the coal tar of the step (3) are added to an extractant to extract and extract the crude phenol and the dephenol blue waste water.

The extractant used is extracted ^{N, N '- (-503 N} , N) dimethylheptyl ^acetamide' kerosene mixture.

The pollutant index of the dephenolized blue carbon waste water is: COD is 4905 mg/L, ammonia nitrogen is 2211 mg/L, total phenol is 339 mg/L, and chroma is 500 times.

(5) Deamination: The blue carbon waste water after the dephenolization in step (4) is added to the potassium hydroxide solution to adjust the pH to 10, and the ammonia gas is removed by heating and evaporation, and the ammonia gas is absorbed by the sulfuric acid solution to produce ammonium sulfate.

The pollutant index of the decarbonized blue carbon waste water is: COD is 1745.36 mg / L, ammonia nitrogen is 46.4 mg / L, total phenol is 207 mg / L, and the chromaticity is 500 times.

(6) Desulfurization: adding desulfurizing agent, such as ferrous sulfate, to the deaminated carbon waste water after step (5) deamination of nitrogen to form iron sulfide precipitated and desulfurized blue carbon waste water, preventing sulfide poisoning to biochemistry and improving its biochemical effect.

The pollutant index of the blue carbon waste water after desulfurization is: COD is 1455.36mg/L, ammonia nitrogen is 47.4mg/L, total phenol is 192mg/L, and chroma is 200 times.

(7) Anaerobic treatment: the desulfurized carbon waste water obtained by the step (6) desulfurization is added to the alkali solution to adjust the pH to 6-9, and the anaerobic tank enters the anaerobic tank through the lift pump, and passes through the anaerobic and anaerobic bacteria in the anaerobic tank. Adsorption, fermentation, and methanogenesis work together to decompose organic acids into methane and carbon dioxide, improve the B/C value of wastewater and remove most of the COD by anaerobic treatment, and improve the biodegradability of wastewater.

The pollutant index of the blue carbon waste water after the anaerobic treatment is: COD is 436.34 mg / L, ammonia nitrogen is 13.4 mg / L, total phenol is 207 mg / L, and the chromaticity is 500 times.

(8) Aerobic treatment: after step (7) anaerobic treatment, the blue carbon waste water passes through the lift pump into the aerobic tank and the intermediate sedimentation tank, and part of the sludge in the intermediate sedimentation tank is returned to the aerobic tank through the reflux pump, and the good The oxygen treatment further oxidizes and decomposes the organic matter in the blue carbon waste water to deeply remove COD and BOD; the aerobic pool is uniformly filled with a large amount of biological suspended filler to provide a habitat for aerobic microorganisms to grow and reproduce, so that the microorganism forms a biofilm on the surface of the filler. . An aerated oxygenation and agitation system is arranged at the bottom of the aerobic tank to oxygenate the sewage to maintain the dissolved oxygen in the water at 2 to 4 mg/L, and at the same time, the gas is used to increase the suspended matter and water in the pool. Contact, in addition to the agitation of gas and water backwashing, can effectively scouring the aged biofilm grown on the surface of the filler, promoting the replacement of the biofilm, so that the biofilm maintains high activity.

The pollutant index of the blue carbon waste water after the aerobic treatment is: COD is 174.54 mg/L, ammonia nitrogen is 9.4 mg/L, total phenol is 7 mg/L, and chromaticity is 80 times.

(9) Electrolysis: After the step (8), the blue carbon waste water enters the electrolysis machine for electrolysis to remove the chromaticity and odor, and at the same time, the difficult biochemical macromolecular compound in the waste water is opened and broken, and becomes biochemically small. The molecule further increases the B/C value and improves the conditions of the subsequent biochemical treatment; the voltage between the adjacent electrodes of the electrolysis machine is 2 to 12 V, and the current density is 10 to 320 mA/cm ² ;

The electrolyzer is provided with a power source and an electrolytic cell, and the electrode material in the electrolytic cell is one of graphite, titanium, iron, aluminum, zinc, copper, lead, nickel, molybdenum, chromium, alloy and nano catalytic inert material. .

(10) Anaerobic treatment: the blue carbon waste water obtained by the electrolysis in step (9) is passed through a lift pump into a secondary anaerobic tank, and the anaerobic bacteria, anaerobic bacteria adsorption, fermentation, and methanogenesis are combined in the anaerobic tank. The organic acid is decomposed into methane and carbon dioxide, and the B/C value of the wastewater is increased by anaerobic treatment and further COD is further removed to improve the biodegradability of the wastewater.

The pollutant index of the blue carbon waste water after the anaerobic treatment is: COD is 58.34 mg / L, ammonia nitrogen is 7.7 mg / L, total phenol is 1 mg / L, and the chromaticity is 20 times.

(11) MBR processing

Step (10) The second anaerobic treated blue carbon wastewater enters the MBR treatment device, and the wastewater is purified by filtration separation of the MBR treatment device to further remove COD, SS and ammonia nitrogen to obtain purified wastewater;

(12) Desalting: Step (11) The wastewater after membrane treatment enters the desalting device, and the dialysis water and concentrated water are separated, and the dialysis water enters the reclaimed water storage tank, and the concentrated water is discharged into the evaporation crystallization tank through the drainage channel for crystallization treatment;

The desalination device may be a reverse osmosis system, and the yield of reclaimed water is 75%.

The reverse osmosis membrane module of the reverse osmosis system is a roll membrane module, and the membrane material is an acetate membrane or a composite membrane in an organic membrane. The molecular weight cutoff of the membrane material is 50-200 MWCO, and the inlet pressure can be 6.0-45.0 bar. The pressure can be 4.5 to 33.5 bar.

Example 3

A blue carbon waste water treatment and recycling cycle utilization method

(1) Crude filtration: The crude carbon waste water with COD of 29335 mg/L, ammonia nitrogen of 1500 mg/L, total phenol of 4100 mg/L, color of 19,000 times and pH of 8.1 is coarsely filtered through a grid or sieve. Remove large particles and debris;

(2) Membrane filtration: the coarsely filtered blue carbon waste water for removing large particles is added to nitric acid to adjust the pH to 2 to 4, and the membrane-filtered to obtain a coal tar-rich concentrate and a coal tar-removing dialysate, and the concentration is 10 ;

The membrane filtration is ceramic membrane filtration, and the ceramic membrane element of the ceramic membrane filtration system has a pore diameter of 20 to 100 nm, a working pressure of 3 to 6 bar, and a temperature of 15 to 55 °C.

(3) recovery of coal tar: the step (2) is subjected to membrane filtration to obtain a concentrated solution rich in coal tar, and the recovered coal tar and detarred oil wastewater are obtained;

The centrifugal separation is to pump the concentrated carbon waste water separated and concentrated by the membrane into a centrifuge, and then centrifuge to separate the lower coal tar and the upper decoking wastewater, and the lower coal tar is recovered through the recovery pipe; centrifugal force of centrifugal separation It is 3400.

The coal tar was recovered to obtain coal tar of 15.2 kg/m ³ .

The pollutant index of the blue carbon waste water after the recovery of the coal tar is: COD is 11494 mg/L, ammonia nitrogen is 1617 mg/L, total phenol is 4239 mg/L, and the chromaticity is 500 times.

(4) Dephenolization: the dedialysis liquid obtained by the membrane filtration of the step (2) and the de-tarred wastewater obtained by the recovery of the coal tar of the step (3) are added to an extractant to extract and extract the crude phenol and the dephenol blue waste water.

The extractant used in the extraction is kerosene.

The pollutant index of the dephenolized blue carbon waste water is: COD is 5280.9 mg/L, ammonia nitrogen is 1701 mg/L, total phenol is 309 mg/L, and chroma is 500 times.

(5) Deamination: The blue carbon waste water after the dephenolization in step (4) is added to the potassium hydroxide solution to adjust the pH to 10, and the ammonia gas is removed by heating and evaporation, and the ammonia gas is absorbed by the sulfuric acid solution to produce ammonium sulfate.

The pollutant index of the blue carbon waste water after deamination is: 2488.4 mg/L COD, 43.9 mg/L ammonia nitrogen, 201 mg/L total phenol, and 500 times chromaticity.

(6) Desulfurization: adding desulfurization agent, such as ferrous sulfate, to the deaminated carbon waste water after step (5) deamination of nitrogen to form iron sulfide precipitation and desulfurization of blue carbon waste water, preventing the poisoning of the sulfide by biochemistry and improving its biochemical effect.

The pollutant index of the blue carbon waste water after desulfurization is: COD is 1959.00 mg/L, ammonia nitrogen is 39.8 mg/L, total phenol is 170 mg/L, and chroma is 200 times.

(7) Anaerobic treatment: the desulfurized blue carbon waste water obtained by desulfurization in step (6) is added to an alkali solution to adjust the pH to 6-9, and enters the anaerobic tank through the lift pump, and passes through the anaerobic and anaerobic bacteria in the anaerobic tank. The adsorption, fermentation and methanogenesis work together to decompose the organic acid into methane and carbon dioxide, improve the B/C value of the wastewater and remove most of the COD by anaerobic treatment, and improve the biodegradability of the wastewater.

The pollutant index of the anaerobic blue carbon waste water is: COD is 622.1 mg/L, ammonia nitrogen is 39.1 mg/L, total phenol is 9 mg/L, and chromaticity is 500 times.

(8) Aerobic treatment: after step (7) anaerobic treatment, the blue carbon waste water passes through the lift pump into the aerobic tank and the intermediate sedimentation tank, and part of the sludge in the intermediate sedimentation tank is returned to the aerobic tank through the reflux pump, and the good The oxygen treatment further oxidizes and decomposes the organic matter in the blue carbon waste water to deeply remove COD and BOD; the aerobic pool is uniformly filled with a large amount of biological suspended filler to provide a habitat for aerobic microorganisms to grow and reproduce, so that the microorganism forms a biofilm on the surface of the filler. . An aerated oxygenation and agitation system is arranged at the bottom of the aerobic tank to oxygenate the sewage to maintain the dissolved oxygen in the water at 2 to 4 mg/L, and at the same time, the gas is used to increase the suspended matter and water in the pool. Contact, in addition to the agitation of gas and water backwashing, can effectively scouring the aged biofilm grown on the surface of the filler, promoting the replacement of the biofilm, so that the biofilm maintains high activity.

The pollutant index of the aerobic blue carbon waste water is: COD is 241.6 mg/L, ammonia nitrogen is 9.1 mg/L, total phenol is 1 mg/L, and chroma is 70 times.

(9) Electrolysis: After the aerobic treatment in step (8), the blue carbon waste water enters the electrolysis machine for electrolysis to remove the chromaticity and odor, and at the same time, the difficult biochemical macromolecular compound in the wastewater is opened and broken, and becomes biochemical. The small molecule further increases the B/C value and improves the conditions of the subsequent biochemical treatment; the voltage between the adjacent electrodes of the electrolysis machine is 2 to 12 V, and the current density is 10 to 320 mA/cm ² ;

The electrolyzer is provided with a power source and an electrolytic cell, and the electrode material in the electrolytic cell is one of graphite, titanium, iron, aluminum, zinc, copper, lead, nickel, molybdenum, chromium, alloy and nano catalytic inert material. .

(10) Secondary anaerobic treatment: the blue carbon waste water obtained by the electrolysis in step (9) is passed through a lift pump into a secondary anaerobic tank, and the anaerobic bacteria and facultative bacteria in the anaerobic tank are adsorbed, fermented, and methanogenic. The function is to decompose the organic acid into methane and carbon dioxide, improve the B/C value of the wastewater by anaerobic treatment and further remove most of the COD, thereby improving the biodegradability of the wastewater;

(11) Biological aerated biofilter (BAF biochemical)

Step (10) After the secondary anaerobic treatment, the blue carbon waste water enters the biological aerated filter, and the wastewater is purified by biooxidation degradation to further remove COD, SS and ammonia nitrogen to obtain purified wastewater.

(12) Desalting: Step (11) The wastewater after biological biochemistry (BAF biochemical) of aerated biological filter enters the desalting device, and the dialysis water and concentrated water are separated, and the dialysis water enters the reclaimed water storage tank, and the concentrated water is discharged into the evaporation through the drainage channel. The crystallization tank is subjected to crystallization treatment;

The desalination device is a nanofiltration system.

The nanofiltration membrane module in the nanofiltration system is a tubular membrane module, a coil membrane module or a flat membrane module, and the working pressure is 6 to 45 bar, the working temperature is 20 to 45 ° C, and the optimal temperature is 35. ~40 ° C.

Example 4

A blue carbon waste water treatment and recycling cycle utilization method

(1) Crude filtration: The crude carbon waste water with a COD of 34967 mg/L, an ammonia nitrogen of 1911 mg/L, a total phenol of 6231 mg/L, a chromaticity of 2000 times, and a pH of 8.1 was coarsely filtered through a grid or a sieve. Remove large particles and debris;

(2) Membrane filtration: the coarsely filtered large-particle-removed blue carbon waste water is subjected to membrane filtration to obtain a coal tar-rich concentrate and a coal tar-removed dialysate, and the concentration is 5;

The membrane is filtered into a ceramic membrane, and the ceramic membrane element of the ceramic membrane filtration system has a pore diameter of 20 to 100 nm, a working pressure of 3 to 6 bar, and a temperature of 15 to 55 °C.

(3) Detarred oil: The step (2) is filtered through a membrane to obtain a concentrated solution rich in coal tar, and sulfuric acid is added to adjust the pH to 4, and after centrifugation, the lower layer of coal tar and the upper layer of decoking waste water are recovered, and the lower layer of coal tar is recovered. The coal tar was 17.8 kg/m ³ . The centrifugal force for centrifugation was 3219.

(4) Dephenolization: the dedialysis liquid obtained by the membrane filtration of step (2) and the de-tarred wastewater obtained by the recovery of the coal tar of step (3) are added to a sulfuric acid solution to adjust the pH to 3.5, and the crude phenol is removed by extraction with an extractant. Phenol blue carbon wastewater.

The extractant used for the extraction is a mixture of tributyl phosphate and kerosene as an extractant.

The pollutant index of the dephenolized blue carbon waste water is: COD is 4116 mg/L, ammonia nitrogen is 2200 mg/L, total phenol is 357 mg/L, and chromaticity is 500 times.

(5) Deamination: The blue carbon waste water after the dephenolization in step (4) is added to a sodium hydroxide solution to adjust the pH to 10, and the ammonia gas is removed by heating and evaporation, and the ammonia gas is absorbed by the sulfuric acid solution to produce ammonium sulfate.

The pollutant index of the blue carbon waste water after deamination is: COD is 1642.31 mg/L, ammonia nitrogen is 36.5 mg/L, total phenol is 226 mg/L, and color is 500 times.

(6) Desulfurization: adding desulfurizing agent, such as ferrous sulfate, to the deaminated carbon waste water after step (5) deamination of nitrogen to form iron sulfide precipitated and desulfurized blue carbon waste water, preventing sulfide poisoning to biochemistry and improving its biochemical effect.

(7) Anaerobic treatment: the desulfurized blue carbon waste water obtained by desulfurization in step (6) is added to an alkali solution to adjust the pH to 6-9, and enters the anaerobic tank through the lift pump, and passes through the anaerobic and anaerobic bacteria in the anaerobic tank. The adsorption, fermentation and methanogenesis work together to decompose the organic acid into methane and carbon dioxide, improve the B/C value of the wastewater and remove most of the COD by anaerobic treatment, and improve the biodegradability of the wastewater.

The pollutant index of the blue carbon waste water after the anaerobic treatment is: COD is 314.31 mg/L, ammonia nitrogen is 11.5 mg/L, total phenol is 197 mg/L, and chromaticity is 500 times.

(8) Aerobic treatment: after step (7) anaerobic treatment, the blue carbon waste water passes through the lift pump into the aerobic tank and the intermediate sedimentation tank, and part of the sludge in the intermediate sedimentation tank is returned to the aerobic tank through the reflux pump, and the good The oxygen treatment further oxidizes and decomposes the organic matter in the blue carbon waste water to deeply remove COD and BOD; the aerobic pool is uniformly filled with a large amount of biological suspended filler to provide a habitat for aerobic microorganisms to grow and reproduce, so that the microorganism forms a biofilm on the surface of the filler. . An aerated oxygenation and agitation system is arranged at the bottom of the aerobic tank to oxygenate the sewage to maintain the dissolved oxygen in the water at 2 to 4 mg/L, and at the same time, the gas is used to increase the suspended matter and water in the pool. Contact, in addition to the agitation of gas and water backwashing, can effectively scouring the aged biofilm grown on the surface of the filler, promoting the replacement of the biofilm, so that the biofilm maintains high activity.

The pollutant index of the blue carbon waste water after the aerobic treatment is: COD is 97.80 mg/L, ammonia nitrogen is 10.7 mg/L, total phenol is 1 mg/L, and chromaticity is 80 times.

(9) Electrolysis: After the aerobic treatment in step (8), the blue carbon waste water enters the electrolysis machine for electrolysis to remove the chromaticity and odor, and at the same time, the difficult biochemical macromolecular compound in the wastewater is opened and broken, and becomes biochemical. The small molecule further increases the B/C value and improves the conditions of the subsequent biochemical treatment; the voltage between the adjacent electrodes of the electrolysis machine is 2 to 12 V, and the current density is 10 to 320 mA/cm ² ;

The electrolyzer is provided with a power source and an electrolytic cell, and the electrode material in the electrolytic cell is one of graphite, titanium, iron, aluminum, zinc, copper, lead, nickel, molybdenum, chromium, alloy and nano catalytic inert material. .

(10) Secondary anaerobic treatment: the blue carbon waste water obtained by the electrolysis in step (9) is passed through a lift pump into a secondary anaerobic tank, and the anaerobic bacteria and facultative bacteria in the anaerobic tank are adsorbed, fermented, and methanogenic. The function is to decompose the organic acid into methane and carbon dioxide, improve the B/C value of the wastewater by anaerobic treatment and further remove most of the COD, thereby improving the biodegradability of the wastewater.

The pollutant index of the blue carbon waste water after the anaerobic treatment is: COD is 48.34 mg/L, ammonia nitrogen is 7.5 mg/L, and the chromaticity is 10 times.

(11) MBR processing

Step (10) The second anaerobic treated blue carbon waste water enters the MBR treatment device, and the wastewater is purified by filtration separation of the membrane treatment device to further remove COD and ammonia nitrogen to obtain purified wastewater;

(12) Desalting: Step (11) The wastewater after MBR treatment enters the desalination device, and the dialysis water and concentrated water are separated, and the dialysis water enters the reclaimed water storage tank, and the concentrated water is discharged into the evaporation crystallization tank through the drainage channel for crystallization treatment;

The desalination device may be a reverse osmosis system, and the yield of reclaimed water is 75%.

The reverse osmosis membrane module of the reverse osmosis system is a roll membrane module, and the membrane material is an acetate membrane or a composite membrane in an organic membrane. The molecular weight cutoff of the membrane material is 50-200 MWCO, and the inlet pressure can be 6.0-45.0 bar. The pressure can be 4.5 to 33.5 bar.

Example 5

A blue carbon waste water treatment and recycling cycle utilization method

(1) Crude filtration: The crude carbon waste water with a COD of 14393 mg/L, an ammonia nitrogen of 1772 mg/L, a total phenol of 1900 mg/L, a color of 19,000 times, and a pH of 8.3 is coarsely filtered through a grid or a sieve. Remove large particles and debris;

(2) Membrane filtration: the coarsely filtered blue carbon waste water for removing large particles is added to nitric acid to adjust the pH to 2 to 4, and the membrane-filtered to obtain a coal tar-rich concentrate and a coal tar-removing dialysate, and the concentration is 10 ;

The membrane filtration is ceramic membrane filtration, and the ceramic membrane element of the ceramic membrane filtration system has a pore diameter of 20 to 100 nm, a working pressure of 3 to 6 bar, and a temperature of 15 to 55 °C.

(3) Detarred oil: the step (2) is subjected to membrane filtration to obtain a concentrated solution rich in coal tar, and the recovered coal tar and detarred oil wastewater are obtained;

The centrifugal separation is to pump the concentrated carbon waste water separated and concentrated by the membrane into a centrifuge, and then centrifuge to separate the lower coal tar and the upper decoking wastewater, and the lower coal tar is recovered through the recovery pipe; centrifugal force of centrifugal separation It is 3400.

The coal tar was recovered to obtain coal tar of 3.2 kg/m ³ .

The pollutant index of the blue carbon waste water after the recovery of the coal tar is: COD is 11196 mg / L, ammonia nitrogen is 1817 mg / L, total phenol is 5039 mg / L, and the chromaticity is 500 times.

(4) Dephenolization: adding the dialysate obtained by the membrane filtration of step (2) and the de-tarred wastewater obtained by the recovery of the coal tar of step (3) to a sulfuric acid solution to adjust the pH value to 6, and extracting and extracting the crude phenol and extracting the extractant. Dephenol blue carbon waste water.

The extracting agent used for the extraction is crude benzene.

The pollutant indicators of the dephenolized blue carbon waste water are: COD is 2447.9 mg/L, ammonia nitrogen is 1701 mg/L, total phenol is 309 mg/L, and color is 500 times.

(5) Deamination: The blue carbon waste water after the dephenolization in step (4) is added to the potassium hydroxide solution to adjust the pH to 10, and the ammonia gas is removed by heating and evaporation, and the ammonia gas is absorbed by the sulfuric acid solution to produce ammonium sulfate.

The pollutant index of the blue carbon waste water after deamination is: COD is 1527.4 mg/L, ammonia nitrogen is 65.3 mg/L, total phenol is 201 mg/L, and color is 500 times.

(6) Desulfurization: adding desulfurizing agent, such as ferrous sulfate, to the deaminated carbon waste water after step (5) deamination of nitrogen to form iron sulfide precipitated and desulfurized blue carbon waste water, preventing sulfide poisoning to biochemistry and improving its biochemical effect.

(7) Anaerobic treatment: the desulfurized blue carbon waste water obtained by desulfurization in step (6) is added to an alkali solution to adjust the pH to 6-9, and enters the anaerobic tank through the lift pump, and passes through the anaerobic and anaerobic bacteria in the anaerobic tank. The adsorption, fermentation and methanogenesis work together to decompose the organic acid into methane and carbon dioxide, improve the B/C value of the wastewater and remove most of the COD by anaerobic treatment, and improve the biodegradability of the wastewater.

The pollutant index of the anaerobic blue carbon waste water is: COD is 332.6 mg/L, ammonia nitrogen is 39.1 mg/L, total phenol is 9 mg/L, and chromaticity is 500 times.

(8) Aerobic treatment: after step (7) anaerobic treatment, the blue carbon waste water passes through the lift pump into the aerobic tank and the intermediate sedimentation tank, and part of the sludge in the intermediate sedimentation tank is returned to the aerobic tank through the reflux pump, and the good The oxygen treatment further oxidizes and decomposes the organic matter in the blue carbon waste water to deeply remove COD and BOD; the aerobic pool is uniformly filled with a large amount of biological suspended filler to provide a habitat for aerobic microorganisms to grow and reproduce, so that the microorganism forms a biofilm on the surface of the filler. . An aerated oxygenation and agitation system is arranged at the bottom of the aerobic tank to oxygenate the sewage to maintain the dissolved oxygen in the water at 2 to 4 mg/L, and at the same time, the gas is used to increase the suspended matter and water in the pool. Contact, in addition to the agitation of gas and water backwashing, can effectively scouring the aged biofilm grown on the surface of the filler, promoting the replacement of the biofilm, so that the biofilm maintains high activity.

The pollutant index of the aerobic blue carbon waste water is: COD is 152.6 mg/L, ammonia nitrogen is 9.1 mg/L, total phenol is 1 mg/L, and chromaticity is 70 times.

(9) Electrolysis: After the aerobic treatment in step (8), the blue carbon waste water enters the electrolysis machine for electrolysis to remove the chromaticity and odor, and at the same time, the difficult biochemical macromolecular compound in the wastewater is opened and broken, and becomes biochemical. The small molecule further increases the B/C value and improves the conditions of the subsequent biochemical treatment; the voltage between the adjacent electrodes of the electrolysis machine is 2 to 12 V, and the current density is 10 to 320 mA/cm ² ;

The electrolyzer is provided with a power source and an electrolytic cell, and the electrode material in the electrolytic cell is one of graphite, titanium, iron, aluminum, zinc, copper, lead, nickel, molybdenum, chromium, alloy and nano catalytic inert material. .

(10) Secondary anaerobic treatment: the blue carbon waste water obtained by the electrolysis in step (9) is passed through a lift pump into a secondary anaerobic tank, and the anaerobic bacteria and facultative bacteria in the anaerobic tank are adsorbed, fermented, and methanogenic. The function is to decompose the organic acid into methane and carbon dioxide, improve the B/C value of the wastewater by anaerobic treatment and further remove most of the COD, thereby improving the biodegradability of the wastewater;

(11) Biological aerated biofilter (BAF biochemical)

Step (10) After the secondary anaerobic treatment, the blue carbon waste water enters the biological aerated filter, and the wastewater is purified by biooxidation degradation to further remove COD, SS and ammonia nitrogen to obtain purified wastewater.

(12) Desalting: Step (11) The wastewater after biological biochemistry (BAF biochemical) of aerated biological filter enters the desalting device, and the dialysis water and concentrated water are separated, and the dialysis water enters the reclaimed water storage tank, and the concentrated water is discharged into the evaporation through the drainage channel. The crystallization tank is subjected to crystallization treatment;

The desalination device may be a reverse osmosis system, and the yield of reclaimed water is 75%.

The reverse osmosis membrane module of the reverse osmosis system is a roll membrane module, and the membrane material is an acetate membrane or a composite membrane in an organic membrane. The molecular weight cutoff of the membrane material is 50-200 MWCO, and the inlet pressure can be 6.0-45.0 bar. The pressure can be 4.5 to 33.5 bar.

Example 6

Method for treating and recycling recycling of a blue carbon waste water (cold circulating water)

(1) Crude filtration: The crude carbon waste water with a COD of 14679 mg/L, an ammonia nitrogen of 1740 mg/L, a total phenol of 4900 mg/L, a color of 18,000 times, and a pH of 8.3 is coarsely filtered through a grid or a sieve. Remove large particles and debris;

(2) Membrane filtration: the coarsely filtered blue carbon waste water for removing large particles is added to nitric acid to adjust the pH to 2 to 4, and the membrane-filtered to obtain a coal tar-rich concentrate and a coal tar-removing dialysate, and the concentration is 10 ;

The membrane filtration is ceramic membrane filtration, and the ceramic membrane element of the ceramic membrane filtration system has a pore diameter of 20 to 100 nm, a working pressure of 3 to 6 bar, and a temperature of 15 to 55 °C.

The COD of the dialysate obtained by the filtration of the ceramic membrane was 9679 mg/L, and the removal rate of COD by membrane filtration was 34%.

(3) Detarred oil: the step (2) is subjected to membrane filtration to obtain a concentrated solution rich in coal tar, and the recovered coal tar and detarred oil wastewater are obtained;

The centrifugal separation is to pump the concentrated carbon waste water separated and concentrated by the membrane into a centrifuge, and then centrifuge to separate the lower coal tar and the upper decoking wastewater, and the lower coal tar is recovered through the recovery pipe; centrifugal force of centrifugal separation It is 3400.

The coal tar was recovered to obtain coal tar of 5.2 kg/m ³ .

The pollutant index of the blue carbon waste water after the de-tarring oil is: COD is 9991 mg/L, ammonia nitrogen is 1817 mg/L, total phenol is 5039 mg/L, and the chromaticity is 500 times.

(4) Dephenolization: the dedialysis liquid obtained by the membrane filtration of the step (2) and the de-tarred wastewater obtained by the recovery of the coal tar of the step (3) are added to an extractant to extract and extract the crude phenol and the dephenol blue waste water.

The extracting agent used for the extraction is crude benzene.

The extracted organic phase is separated by distillation to obtain 4.753 kg/m ^{3 of} crude phenol, and the organic phase is recycled as crude benzene.

The pollutant index of the dephenolized blue carbon waste water is: COD is 3580.9 mg/L, ammonia nitrogen is 1771 mg/L, total phenol is 309 mg/L, and chroma is 500 times.

(5) Deamination: The blue carbon waste water after the dephenolization in step (4) is added to the potassium hydroxide solution to adjust the pH to 11, and the ammonia gas is removed by heating and evaporation, and the ammonia gas is absorbed by the sulfuric acid solution to produce ammonium sulfate.

The pollutant index of the blue carbon waste water after deamination is: COD is 2088.4 mg/L, ammonia nitrogen is 43.9 mg/L, total phenol is 201 mg/L, and chromaticity is 500 times.

(6) Desulfurization: adding desulfurizing agent, such as ferrous sulfate, to the deaminated carbon waste water after step (5) deamination of nitrogen to form iron sulfide precipitated and desulfurized blue carbon waste water, preventing sulfide poisoning to biochemistry and improving its biochemical effect.

The pollutant index of the blue carbon waste water after desulfurization is: COD is 1655.9 mg/L, ammonia nitrogen is 46.9 mg/L, total phenol is 160 mg/L, and chroma is 200 times.

(7) Anaerobic treatment: the desulfurized blue carbon waste water obtained by desulfurization in step (6) is added to an alkali solution to adjust the pH to 6-9, and enters the anaerobic tank through the lift pump, and passes through the anaerobic and anaerobic bacteria in the anaerobic tank. The adsorption, fermentation and methanogenesis work together to decompose the organic acid into methane and carbon dioxide, improve the B/C value of the wastewater and remove most of the COD by anaerobic treatment, and improve the biodegradability of the wastewater.

The pollutant index of the anaerobic blue carbon waste water is: COD is 411.6 mg/L, ammonia nitrogen is 39.1 mg/L, total phenol is 9 mg/L, and chromaticity is 500 times.

(8) Aerobic treatment: after step (7) anaerobic treatment, the blue carbon waste water passes through the lift pump into the aerobic tank and the intermediate sedimentation tank, and part of the sludge in the intermediate sedimentation tank is returned to the aerobic tank through the reflux pump, and the good The oxygen treatment further oxidizes and decomposes the organic matter in the blue carbon waste water to deeply remove COD and BOD; the aerobic pool is uniformly filled with a large amount of biological suspended filler to provide a habitat for aerobic microorganisms to grow and reproduce, so that the microorganism forms a biofilm on the surface of the filler. . An aerated oxygenation and agitation system is arranged at the bottom of the aerobic tank to oxygenate the sewage to maintain the dissolved oxygen in the water at 2 to 4 mg/L, and at the same time, the gas is used to increase the suspended matter and water in the pool. Contact, in addition to the agitation of gas and water backwashing, can effectively scouring the aged biofilm grown on the surface of the filler, promoting the replacement of the biofilm, so that the biofilm maintains high activity.

The pollutant index of the aerobic blue carbon waste water is: COD is 156.1 mg/L, ammonia nitrogen is 9.1 mg/L, total phenol is 1 mg/L, and chroma is 70 times.

(9) Electrolysis: After the aerobic treatment in step (8), the blue carbon waste water enters the electrolysis machine for electrolysis to remove the chromaticity and odor, and at the same time, the difficult biochemical macromolecular compound in the wastewater is opened and broken, and becomes biochemical. The small molecule further increases the B/C value and improves the conditions of the subsequent biochemical treatment; the voltage between the adjacent electrodes of the electrolysis machine is 2 to 12 V, and the current density is 10 to 320 mA/cm ² ;

The electrolyzer is provided with a power source and an electrolytic cell, and the electrode material in the electrolytic cell is one of graphite, titanium, iron, aluminum, zinc, copper, lead, nickel, molybdenum, chromium, alloy and nano catalytic inert material. .

(10) Secondary anaerobic treatment: the blue carbon waste water obtained by the electrolysis in step (9) is passed through a lift pump into a secondary anaerobic tank, and the anaerobic bacteria and facultative bacteria in the anaerobic tank are adsorbed, fermented, and methanogenic. The function is to decompose the organic acid into methane and carbon dioxide, improve the B/C value of the wastewater by anaerobic treatment and further remove most of the COD, thereby improving the biodegradability of the wastewater;

(11) Biological aerated biofilter (BAF biochemical)

Step (10) After the secondary anaerobic treatment, the blue carbon waste water enters the biological aerated filter, and the wastewater is purified by biooxidation degradation to further remove COD, SS and ammonia nitrogen to obtain purified wastewater.

(12) Desalting: Step (11) The wastewater after biological biochemistry (BAF biochemical) of aerated biological filter enters the desalting device, and the dialysis water and concentrated water are separated, and the dialysis water enters the reclaimed water storage tank, and the concentrated water is discharged into the evaporation through the drainage channel. The crystallization tank is subjected to crystallization treatment;

The desalination device is a nanofiltration system.

The nanofiltration membrane module in the nanofiltration system is a tubular membrane module, a coil membrane module or a flat membrane module, and the working pressure is 6 to 45 bar, the working temperature is 20 to 45 ° C, and the optimal temperature is 35. ~40 ° C.

Example 7

A blue carbon waste water treatment recycling cycle utilization and comprehensive utilization of resources.

(1) coarse filtration: crude carbon waste water with a COD of 75000 mg/L, an ammonia nitrogen of 5000 mg/L, a total phenol of 6000 mg/L, a chromaticity of 30,000 times, and a pH of 10 is coarsely filtered through a grid or a sieve. Remove large particles and debris;

(2) Membrane filtration: The coarsely filtered blue carbon waste water for removing large particles is added to the acid to adjust the pH to 3-4, and the membrane-filtered to obtain the coal tar-rich concentrate and the coal tar-removing dialysate, the concentration is 3 ;

The membrane filtration is metal membrane filtration; the metal membrane element of the metal membrane filtration system has a pore diameter of 30 to 100 nm; the working pressure is 3 to 6 bar, and the temperature is 15 to 55 °C.

(3) Detarred oil: The step (2) is filtered through a membrane to obtain a concentrated solution rich in coal tar, and centrifuged to obtain recovered coal tar and detarred oil wastewater.

The centrifugal separation is to pump the concentrated carbon waste water separated and concentrated by the membrane into a centrifuge, and then centrifuge to separate the lower coal tar and the upper decoking wastewater, and the lower coal tar is recovered to obtain tar 40 kg/m ³ .

The pollutant index of the blue carbon waste water after the de-tarring is: COD is 23841 mg/L, ammonia nitrogen is 6383 mg/L, total phenol is 6305.9 mg/L, and the chromaticity is 500 times.

(4) Dephenolization: the dialysate obtained by filtering the metal membrane of step (2) and the blue carbon waste water obtained by decoking the oil of step (3) are uniformly mixed, and then the hydrochloric acid solution is added to adjust the pH to 2, and the extracting agent is extracted and separated to obtain crude phenol and Dephenol blue carbon waste water.

The extracting agent used for the extraction is kerosene, the ratio of kerosene to wastewater is 1:5, extracted three times, the phenol is extracted into the kerosene organic phase, and the liquid-liquid separation is performed to obtain the phenol-containing kerosene organic phase and the blue carbon waste water phase. The crude phenol was separated by 5.9 kg/m ³ .

The pollutant index of the wastewater after the dephenolation treatment is: COD is 9928 mg / L, ammonia nitrogen is 6383 mg / L, total phenol is 305.3 mg / L, and the color is 500.

(4) Deamination: The dedialysis solution obtained by the membrane filtration of step (2) and the de-tarred wastewater obtained by the recovery of the coal tar of step (3) are added to an alkali solution to adjust the pH to 9, and the ammonia gas is removed by heating and evaporation, and the ammonia gas is cooled. Liquid ammonia and deaminated blue carbon waste water.

The pollutant index of the wastewater after the deamination treatment is: COD is 2587.5 mg/L, ammonia nitrogen is 81 mg/L, total phenol is 301.5 mg/L, and chroma is 500 times.

(6) Desulfurization: adding desulfurizing agent, such as ferrous sulfate, to the deaminated carbon waste water after step (5) deamination of nitrogen to form iron sulfide precipitated and desulfurized blue carbon waste water, preventing sulfide poisoning to biochemistry and improving its biochemical effect.

(7) Anaerobic treatment: the desulfurized blue carbon waste water obtained by desulfurization in step (6) is added to an alkali solution to adjust the pH to 6-9, and enters the anaerobic tank through the lift pump, and passes through the anaerobic and anaerobic bacteria in the anaerobic tank. The adsorption, fermentation and methanogenesis work together to decompose the organic acid into methane and carbon dioxide, improve the B/C value of the wastewater and remove most of the COD by anaerobic treatment, and improve the biodegradability of the wastewater.

The pollutant index of the wastewater after the anaerobic treatment is: COD is 595.2 mg/L, ammonia nitrogen is 51 mg/L, total phenol is 433 mg/L, and chromaticity is 500 times.

(8) Aerobic treatment: after step (7) anaerobic treatment, the blue carbon waste water passes through the lift pump into the aerobic tank and the intermediate sedimentation tank, and part of the sludge in the intermediate sedimentation tank is returned to the aerobic tank through the reflux pump, and the good The oxygen treatment further oxidizes and decomposes the organic matter in the blue carbon waste water to deeply remove COD and BOD; the aerobic pool is uniformly filled with a large amount of biological suspended filler to provide a habitat for aerobic microorganisms to grow and reproduce, so that the microorganism forms a biofilm on the surface of the filler. . An aerated oxygenation and agitation system is arranged at the bottom of the aerobic tank to oxygenate the sewage to maintain the dissolved oxygen in the water at 2 to 4 mg/L, and at the same time, the gas is used to increase the suspended matter and water in the pool. Contact, in addition to the agitation of gas and water backwashing, can effectively scouring the aged biofilm grown on the surface of the filler, promoting the replacement of the biofilm, so that the biofilm maintains high activity.

The pollutant index of the wastewater after the aerobic treatment is: COD is 232.1 mg/L, ammonia nitrogen is 11 mg/L, total phenol is 0.3 mg/L, and chroma is 200 times.

(9) Electrolysis: After the aerobic treatment in step (8), the blue carbon waste water enters the electrolysis machine for electrolysis to remove the chromaticity and odor, and at the same time, the difficult biochemical macromolecular compound in the wastewater is opened and broken, and becomes biochemical. The small molecule further increases the B/C value and improves the conditions of subsequent biochemical treatment; the voltage between adjacent electrodes of the electrolysis machine is 2 to 12 V, and the current density is 10 to 320 mA/cm ² .

The electrolyzer is provided with a power source and an electrolytic cell, and the electrode material in the electrolytic cell is one of graphite, titanium, iron, aluminum, zinc, copper, lead, nickel, molybdenum, chromium, alloy and nano catalytic inert material. .

(10) Secondary anaerobic treatment: the blue carbon waste water obtained by the electrolysis in step (9) is passed through a lift pump into a secondary anaerobic tank, and the anaerobic bacteria and facultative bacteria in the anaerobic tank are adsorbed, fermented, and methanogenic. The function is to decompose the organic acid into methane and carbon dioxide, improve the B/C value of the wastewater by anaerobic treatment and further remove most of the COD, thereby improving the biodegradability of the wastewater.

The pollutant index of the wastewater after the anaerobic treatment is: COD is 116.08 mg/L, ammonia nitrogen is 9 mg/L, and the chroma is 200 times.

(11) MBR processing

Step (10) The secondary anaerobic treated blue carbon wastewater enters the MBR treatment device, and the wastewater is purified by filtration separation or biological oxidative degradation of the MBR treatment device to further remove COD and ammonia nitrogen to obtain purified wastewater.

The membrane module of the MBR device is selected from the group consisting of a polyvinylidene fluoride hollow fiber membrane, a polypropylene hollow fiber membrane, a polysulfone hollow fiber membrane, a polyethersulfone, a polyacrylonitrile, and a polyvinyl chloride hollow fiber membrane. It is 0.10 to 0.2 μm, the working pressure is -1 to -50 kPa, and the working temperature is 5 to 45 °C.

The pollutant index of the wastewater after the MBR treatment is 71.11 mg/L, the ammonia nitrogen is 8 mg/L, and the color is 12.

(12) Desalting: Step (11) The wastewater after membrane treatment enters the desalting device, and the dialysis water and concentrated water are separated, and the dialysis water enters the reclaimed water storage tank, and the concentrated water is discharged into the evaporation crystallization tank through the drainage channel for crystallization treatment;

The desalination device is a nanofiltration system.

The nanofiltration membrane module in the nanofiltration system is a tubular membrane module, a coil membrane module or a flat membrane module, and the working pressure is 6 to 45 bar, the working temperature is 20 to 45 ° C, and the optimal temperature is 35. ~40 ° C.

Industrial applicability

 The invention can be applied industrially and has good industrial applicability.

Claims (9)

1. A method for treating and recycling a blue carbon waste water, comprising the steps of:

   (1) Crude filtration: blue carbon wastewater with COD of 10000 to 75000 mg/L, ammonia nitrogen of 500 to 5000 mg/L, total phenol of 1000 to 6000 mg/L, color of 10,000 to 30,000 times, and pH of 8 to 10. Filtration through a grid or screen to remove large particles;

   (2) Membrane filtration: the crude filtered carbon waste water for removing large particles is added to the acid to adjust the pH to 2-6, and then filtered through a membrane to obtain a coal tar-rich concentrate and a coal tar-removing dialysate, and the concentration is 3 to 10;

   (3) Detarred oil: the step (2) is filtered through a membrane to obtain a concentrated solution rich in coal tar, which is subjected to gravity sedimentation separation or centrifugal separation to obtain de-tarred blue carbon waste water, and the COD removal rate thereof is 30 to 55%;

   (4) Dephenolization: the dialysate obtained by the membrane filtration in step (2) and the blue carbon waste water after the step (3) decoking tar are uniformly mixed, and the dephenolated blue carbon waste water is extracted and extracted by extracting agent, and the removal rate of COD is 35 to 70%;

   (5) Deamination nitrogen: The blue carbon waste water obtained by removing the phenol from the step (4) is added to the alkali solution to adjust the pH to 9 to 11, and the ammonia gas is removed by heating and evaporation, and the ammonia gas is absorbed by the sulfuric acid solution to produce ammonium sulfate or cooled to obtain a liquid. Ammonia and deammonia wastewater;

   (6) Desulfurization: adding desulfurization agent, such as ferrous sulfate, to the deaminated blue carbon wastewater after step (5) deamination of nitrogen to form iron sulfide precipitation and desulfurization of blue carbon waste water to prevent the chemical toxicity of sulfides and improve their biochemical effects. The removal rate of COD is 10-20%;

   (7) Anaerobic treatment: the desulfurized blue carbon waste water obtained by desulfurization in step (6) is added to an alkali solution to adjust the pH to 6-9, and enters the anaerobic tank through the lift pump, and passes through the anaerobic and anaerobic bacteria in the anaerobic tank. The adsorption, fermentation and methanogenesis work together to decompose the organic acid into methane and carbon dioxide, improve the B/C value of the wastewater and remove most of the COD by anaerobic treatment, and improve the biodegradability of the wastewater;

   (8) Aerobic treatment: after step (7) anaerobic treatment, the blue carbon waste water passes through the lift pump into the aerobic tank and the intermediate sedimentation tank, and part of the sludge in the intermediate sedimentation tank is returned to the aerobic tank through the reflux pump, and the good The oxygen treatment further oxidizes and decomposes the organic matter in the blue carbon waste water to deeply remove COD and BOD; the aerobic pool is uniformly filled with a large amount of biological suspended filler; and an aerated oxygenation stirring system is arranged at the bottom of the aerobic tank to oxygenate the sewage The dissolved oxygen in the water is maintained at 2 to 4 mg/L, and the suspended solids in the pool are more fully contacted with water by the action of gas rising, and the surface of the filler can be effectively grown by the agitation action of gas and water backwashing. The aging biofilm is washed to promote the replacement of the biofilm, so that the biofilm maintains a high activity;

   (9) Electrolysis: After the aerobic treatment in step (8), the blue carbon waste water enters the electrolysis machine for electrolysis to remove the chromaticity and odor, and at the same time, the difficult biochemical macromolecular compound in the wastewater is opened and broken, and becomes biochemical. The small molecule further increases the B/C value and improves the conditions of the subsequent biochemical treatment; the voltage between the adjacent electrodes of the electrolysis machine is 2 to 12 V, and the current density is 10 to 320 mA/cm ² ;

   (10) Secondary anaerobic treatment: the blue carbon waste water obtained by the electrolysis in step (9) is passed through a lift pump into a secondary anaerobic tank, and the anaerobic bacteria and facultative bacteria in the anaerobic tank are adsorbed, fermented, and methanogenic. The function is to decompose the organic acid into methane and carbon dioxide, improve the B/C value of the wastewater by anaerobic treatment and further remove most of the COD, thereby improving the biodegradability of the wastewater;

   (11) Biochemical treatment of MBR treatment or biological aerated filter: Step (10) After the secondary anaerobic treatment, the blue carbon waste water enters the MBR treatment device or the biological aerated filter, and is filtered or separated by bio-oxidation by the membrane treatment device. Purifying wastewater, further removing COD, SS and ammonia nitrogen to obtain purified wastewater;

   (12) Desalination: Step (11) The wastewater after biochemical treatment of MBR treatment or biological aerated filter enters the desalination device, and the dialysis water and concentrated water are separated. The dialysis water enters the reclaimed water storage tank, and the concentrated water is discharged into the evaporation crystallization through the drainage channel. The tank is subjected to crystallization treatment; the desalination device is one of a reverse osmosis system or a nanofiltration system.
2. The blue carbon waste water treatment and regeneration recycling method according to claim 1, wherein the membrane filtration in the step (2) is a ceramic membrane filtration or a metal membrane filtration; and the ceramic membrane element pore diameter of the ceramic membrane filtration system It is 20 to 100 nm; the metal membrane element of the metal membrane filtration system has a pore diameter of 30 to 100 nm; the working pressure is 3 to 6 bar, and the temperature is 15 to 55 °C.
3. The method for treating and recycling a blue carbon waste water according to claim 1, wherein the step (3) recovery of coal tar is carried out by gravity sedimentation, and the membrane-filtered concentrated coal-rich tar is placed. In the gravity sedimentation tank, it is separated into coal tar and de-coke blue carbon wastewater by gravity sedimentation.
4. The blue carbon waste water treatment and regeneration recycling method according to claim 1, wherein the membrane filtration of the membrane-filtered coal tar-rich concentrate is pumped into a centrifuge and centrifuged. It is coal tar and defocal blue carbon waste water; the centrifugal force of centrifugal separation is 2200-4000.
5. Blue carbon and recycling of wastewater treatment method as claimed in claim 1, wherein: step (4) of the extractant of phenol removal is used is kerosene, N, N ^'- dimethylheptyl acetamide (N,N ^' -503), one of tributyl phosphate or crude benzene or a mixture thereof.
6. The blue carbon waste water treatment and regeneration recycling method according to claim 1, wherein the electrolysis machine of the step (9) is provided with a power source and an electrolytic cell, and the electrode material in the electrolytic cell is graphite, titanium or iron. One of aluminum, zinc, copper, lead, nickel, molybdenum, chromium, alloys and nanocatalytic inert materials.
7. The method for treating and recycling a blue carbon waste water according to claim 1, wherein the membrane module of the MBR device according to the step (11) is selected from the group consisting of a polyvinylidene fluoride hollow fiber membrane and a polypropylene hollow fiber membrane. One of polysulfone hollow fiber membrane, polyethersulfone, polyacrylonitrile and polyvinyl chloride hollow fiber membrane, the membrane pore diameter is 0.10-0.2 μm, the working pressure is -1 to -50 kPa, and the working temperature is 5 to 45 °C. .
8. The method for treating and recycling a blue carbon waste water according to claim 1, wherein the reverse osmosis membrane module of the reverse osmosis system of the step (12) is a roll membrane module, and the membrane material is acetic acid in the organic membrane. The fiber membrane or the composite membrane has a molecular weight cut off of 50 to 200 MWCO, a pressure of 6.0 to 45.0 bar, and a pressure of 4.5 to 33.5 bar.
9. The blue carbon waste water treatment and regeneration recycling method according to claim 1, wherein the nanofiltration membrane module in the nanofiltration system in the step (12) is desalted is a tubular membrane module, a rolled membrane module or a flat plate. One type of membrane module, the working pressure is 6 to 45 bar, and the working temperature is 20 to 45 °C.