Semi-coke wastewater treatment method without biochemical process

Abstract

The invention discloses a semi-coke wastewater treatment method without a biochemical process. The semi-coke wastewater treatment method comprises four stages of oil removal, ammonia distillation, adsorption and adsorbent regeneration, or three stages of ammonia distillation, adsorption and adsorbent regeneration; the ammonia nitrogen content of the semi-coke wastewater is lower than 1000mg / L, and the method only comprises two stages of adsorption and adsorbent regeneration; the semi-coke wastewater subjected to oil removal and ammonia distillation enters a plurality of adsorption towers which are connected in series or in parallel and is subjected to adsorption, oil removal, organic matter removal and ammonia removal through adsorbent slurry, and the water quality reaches the national coke quenching standard and the reclaimed water reuse standard; the adsorbent powder belongs to a high-entropy adsorbent and is of a carbon and oxide three-dimensional mesoporous structure, and the carbon content is 10-90%; the content of the multi-element oxide accounts for 10 to 90 weight percent; the diameter range of mesopores is 1-50 nanometers, and pores with the diameter of 2-10 nanometers account for 90% or above; according to the method, the high-entropy adsorbent is adopted, a biochemical process is omitted, phenol extraction and extraction agent regeneration processes are omitted, and the method is short in process, small in occupied area, low in investment, low in cost, small in VOC in sealed operation and large in treatment scale.

Description

Technical Field

[0001] The invention relates to a wastewater treatment method, in particular to a blue carbon wastewater treatment method without a biochemical process. Background Art

[0002] Semi-coke wastewater is wastewater generated in the process of coal-to-coke products and quenching coke. It mainly contains coal tar substances, such as methanol, ethanol, formic acid, acetic acid, benzene, toluene, xylene, trimethylbenzene, phenols, naphthalene, anthracene, quinones, etc. It also contains a large amount of cyclic organic compounds, azide inorganic compounds and ammonia nitrogen. Among them, the concentrations of COD, NH3-N, phenol and ammonia are relatively high, the organic components are complex, most of them exist in the form of polycyclic aromatic hydrocarbons, aromatic and heterocyclic compounds, and contain a considerable number of toxic and harmful substances with poor biodegradability. Some nitrogen-containing heterocyclic compounds are toxic, mutagenic and carcinogenic to humans and animals, so they are extremely harmful. In addition, since the distillation temperature in lignite production is relatively low, generally around 650°C, lignite wastewater contains a large amount of pollutants that have not been oxidized by high temperature. The concentration is about 10 times higher than that of coke wastewater. The concentrations of ammonia nitrogen and phenols are also much higher than those of coke wastewater. At the same time, there are certain contents of cyanide and thiocyanate, so the pollution is serious.

[0003] Due to the above characteristics of lignite wastewater, the main problems encountered when discharging lignite wastewater are: (1) High oil content: the oil content in lignite production wastewater is high, sometimes as high as 2500 mg / L, and a large amount of pollutants are dissolved in the oil; (2) High phenol content: the phenol content in the wastewater is as high as 2660 mg / L; (3) High ammonia nitrogen content: the ammonia content in lignite production wastewater is high, sometimes as high as 3000 mg / L; (4) The content of difficult-to-degrade organic matter is high; therefore, it cannot be discharged directly. Therefore, finding an effective wastewater treatment method suitable for industrial construction has become an urgent problem that needs to be solved.

[0004] The patent application with patent number 201510469604.5 discloses a method for treating semi-coke wastewater, which includes a pretreatment stage and a biochemical treatment stage. In the pretreatment stage, the production wastewater is separated from oil and water in an oil separation sedimentation tank and enters a regulating tank. The production wastewater in the regulating tank is then pumped to a coagulation flotation machine, and after flotation separation, the production wastewater enters a first intermediate water tank. The production wastewater in the first intermediate water tank is then pumped to a filtration system for filtration, and the filtered filtrate enters a phenol extraction system. The wastewater after extraction and dephenolization is pumped into an ammonia stripping tower to remove most of the free ammonia. In the biochemical treatment stage, the production wastewater after most of the ammonia nitrogen is removed by the ammonia stripping tower enters a hydrolysis acidification tank after passing through a comprehensive regulating tank, and the wastewater coming out of the hydrolysis acidification tank enters a HABR composite anaerobic baffle reactor, and then enters an A / O treatment system. Powdered activated carbon is added to the aerobic tank in the A / O treatment system. After the wastewater comes out of the A / O treatment system, it enters a sedimentation tank, and then passes through a third intermediate water tank and an aerated biological filter tank before being discharged in compliance with the standards. However, this traditional oil removal, ammonia evaporation, phenol extraction, phenol regeneration, and biochemical process cannot completely solve the pollution problem, and the cost is high, reaching about 100 yuan per ton. Summary of the invention

[0005] In view of the problems existing in the prior art, the purpose of the present invention is to provide a method for treating semi-coke wastewater without a biochemical process, which includes four stages: oil removal, ammonia evaporation, adsorption and adsorption regeneration; there is no phenol extraction and regeneration stage, no biochemical stage, and almost no VOC emissions. It has the characteristics of small footprint, low construction cost, and simple process flow, and after treatment, it can meet the reclaimed water discharge standard or the national coke quenching standard for coke quenching.

[0006] In order to achieve the above object, the technical solution of the present invention is:

[0007] A method for treating semi-coke wastewater without biochemical process comprises four stages of oil removal, ammonia evaporation, adsorption and adsorbent regeneration; or three stages of ammonia evaporation, adsorption and adsorbent regeneration; for semi-coke wastewater with ammonia nitrogen content lower than 1000 mg / L, only two stages of adsorption and adsorbent regeneration are included; the adsorbent powder is a high entropy adsorbent, and the carbon content accounts for 10wt%-90wt% of the total amount; the adsorbent powder contains different amounts of multi-element oxides, and the types of oxides include aluminum oxide, silicon oxide, calcium oxide, magnesium oxide or iron oxide, and the content of the oxides accounts for 10wt%-90wt% of the total amount of the adsorbent powder.

[0008] The oil removal stage is specifically as follows: the semi-coke wastewater is pumped into the oil-water separator for oil-water separation; the separated water enters the transfer water tank, which is pumped out by a pump and enters the deamination and deacidification system of the ammonia distillation stage; the separated hydrogen oil and heavy oil enter the transfer oil tank and are pumped out by a pump for deep use.

[0009] The effluent index of the oil removal stage is: petroleum ≤ 100 mg / L; the specific process parameters are:

[0010] The oil-water separators are connected in series, N or more than 1 according to the scale of the semi-coal wastewater treatment;

[0011] The capacity of each oil-water separator is equal to the scale of the semi-coal wastewater that needs to be treated per hour, and the capacity of a transfer water tank is equal to the amount of water that needs to be treated per hour; the capacity of the transfer oil tank is more than 5% of the semi-coal wastewater treatment volume per hour;

[0012] The flow rate of the water pump for pumping the semi-coke wastewater into the oil-water separator and the flow rate of the pump out of the transfer water tank are determined to be 5 tons-1000 tons according to the scale of semi-coke wastewater treated per hour; the head is above 100.

[0013] The ammonia evaporation stage is specifically as follows: the pH value of the deoiled semi-coke wastewater is adjusted to 10-12 by sodium hydroxide, a double-tower process is adopted, deacidification is carried out in the deacidification tower, and crude ammonia is produced at the top of the deammonification tower. High-purity ammonia is obtained by three-stage flash evaporation and sent to an ammonia water preparation device to finally obtain ammonia water. The semi-coke wastewater after ammonia evaporation in the deammonification tower enters the next adsorption stage.

[0014] The specific parameters of the effluent from the ammonia distillation stage are: the total content of free ammonia nitrogen in the effluent is less than 50 mg / L, and the content of hydrogen sulfide is less than 25 mg / L; the byproduct is ammonia water with a purity of more than 18%, wherein the content of hydrogen sulfide is less than 2%, and the content of phenol is less than 50 ppm;

[0015] The top temperature of the deacidification tower is 45-55 degrees, the temperature in the tower is 105-115 degrees, and the bottom temperature of the tower kettle is 140-145 degrees; the bottom pressure is 0.32±0.2MPA; the pressure in the tower is 0.3±0.2MPA; the top pressure is 0.3±0.2MPA;

[0016] The top temperature of the deamination tower is 140-145 degrees, the temperature in the tower is 145-150 degrees, and the bottom temperature of the kettle is 150-155 degrees; the bottom pressure is 0.42±0.2MPA; the pressure in the tower is 0.4±0.2MPA; and the top pressure is 0.4±0.2MPA.

[0017] The adsorption stage is specifically as follows: the semi-coke wastewater after ammonia evaporation enters multiple adsorption towers connected in series or in parallel for adsorption by adsorbent slurry to remove oil, organic matter and ammonia until the water quality reaches the national quenching standard and the reclaimed water reuse standard.

[0018] In the adsorption stage, the mass ratio of the adsorbent slurry to the semi-coke wastewater is 1:N, 2≤N≤100; the adsorbent slurry is prepared by mixing the adsorbent powder dry material and water in a mass ratio of 1:M, 1≤M≤100;

[0019] The adsorbent powder is a three-dimensional mesoporous skeleton with a mesopore diameter ranging from 1 to 50 nanometers, wherein pores with a diameter of 2 to 10 nanometers occupy more than 90%.

[0020] In the adsorption stage, the adsorbent powder can be directly added into the semi-coke wastewater for adsorption, and the mass ratio of the adsorbent powder to the semi-coke wastewater is 1:W, 3≤W≤100.

[0021] The particle size of the adsorbent powder is 1-1000 microns, or the adsorbent can be molded into granules of different shapes or sizes for use.

[0022] The effluent index of the adsorption stage is: pH value 6-9, suspended solids ≤70mg / L, COD ≤150mg / L, ammonia nitrogen ≤25mg / L, BOD ≤30mg / L, total nitrogen ≤50mg / L, total phosphorus ≤3.0mg / L, petroleum

[0023] ≤2.5mg / L, volatile phenol ≤0.3mg / L, sulfide ≤0.5mg / L, benzene ≤0.1mg / L, cyanide ≤0.2mg / L.

[0024] The regeneration stage is specifically as follows: the blue carbon water containing the adsorbent that has completed the adsorption treatment stage is filtered, and then dried and catalytically cracked by a heating device to restore the adsorption function and achieve regeneration.

[0025] The heating equipment used in the regeneration stage has a temperature of 50-500 degrees during heating and drying; the heating catalytic cracking temperature is between 400 degrees and 1000 degrees.

[0026] The heating device includes a rotary kiln, or other heating devices using external heating or internal heating.

[0027] The heating device adopts an internal heating mode when heating and drying; and adopts an external heating device when heating for catalytic cracking and regeneration.

[0028] During the heating process in the regeneration stage, the internal cavity of the heating device is purged and protected with an inert gas; the inert gas includes carbon dioxide or nitrogen.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] (1) After the oil removal process of the present invention, the content of heavy oil and light oil is reduced to below 100 mg / L.

[0031] (2) In the ammonia evaporation stage, ammonia can be removed to below 50 mg / L by adjusting pH, deacidification and deammoniation, and flash evaporation.

[0032] (3) The adsorbent completes the adsorption of heavy oil, emulsified oil, various organic matter, ammonia nitrogen, etc. through multiple adsorption towers connected in series or in parallel, so that it can be completed in one go and meet the standards; the indicators of the semi-coke wastewater in the adsorption process stage are COD 150mg / L or less; ammonia nitrogen 10mg / L; oil 5mg / L or less; impurities 5mg / L or less; the treated water is clear and transparent.

[0033] (4) The present invention omits the biochemical process and does not add any chemical agents, which will not cause secondary pollution to the lignite wastewater. The entire process is a closed cycle and VOC emissions are close to zero. Since there is no biochemical process and no bacterial culture cycle, the scale of lignite wastewater treatment is not limited, and the treatment is fast and efficient, and hundreds or even thousands of tons of lignite wastewater can be treated at one time. For large-scale treatment of lignite wastewater, adsorption towers of different sizes can be connected in parallel or in series indefinitely, and the treatment capacity can meet the requirements of lignite enterprises of various sizes.

[0034] (5) In the high entropy adsorbent of the present invention, the adsorbent particle size can be adjusted within the range of 1-1000 microns; the adsorbent can be directly added to the semi-coke wastewater for adsorption, or it can be made into a slurry and then adsorb the semi-coke wastewater; the adsorbent powder is a three-dimensional mesoporous skeleton: the mesopore diameter range is 1-50 nanometers, and the pores with a diameter of 2-10 nanometers account for more than 90%. The adsorbent powder contains different amounts of multi-element oxides, which are evenly distributed. The types of oxides are: aluminum oxide, silicon oxide, calcium oxide, magnesium oxide, iron oxide, etc., and their maximum content can be adjusted to 10-90%; the high entropy adsorbent has an extremely strong adsorption capacity for all oil substances, all organic matter, and all ammonia nitrogen substances.

[0035] (6) In the regeneration stage of the present invention, the adsorbent can be operated and moved forward by heating, drying and anaerobic cracking regeneration, thereby achieving continuous and cyclic use; the heating method can be external heating or internal heating; the cracking and regeneration equipment can be protected by inert gases such as carbon dioxide or nitrogen; the heating equipment can be, but is not limited to, rotary kiln equipment.

[0036] In summary, the present invention has no phenol extraction and regeneration stage, no biochemical stage, simple process flow, low construction cost, small footprint, almost no VOC emissions, advanced process technology, reliable standard operation, reasonable project investment, low operating cost, and the wastewater treated with high entropy adsorbent can eventually meet the discharge standards, thereby improving the economic, environmental and social benefits of the enterprise. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is a schematic diagram of the ammonia distillation process structure.

[0038] Figure 2 This is the adsorption process flow chart.

[0039] Figure 3 Schematic diagram of the regeneration process structure.

[0040] Figure 4 This is the pore distribution diagram of the adsorption material. DETAILED DESCRIPTION

[0041] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments.

[0042] Example 1

[0043] The wastewater treated by the present invention is semi-coke wastewater, which is the wastewater generated in the process of coal-to-coke production; emission standard: Semi-coke production wastewater shall comply with the "Coking Chemical Industry Pollutant Emission Standard"

[0044] (GB16171-2012), the main controlled water quality indicators and discharge concentration limits of the discharged wastewater should meet the requirements of Table 1; fill in the quenching standard table.

[0045] A method for treating blue carbon wastewater comprises the following steps:

[0046] Step 1: Remove oil. Specifically, the semi-coke wastewater is pumped into the oil-water separator for oil-water separation; the separated water enters the transfer water tank, which is pumped out by a pump and enters the deamination and deacidification system in the ammonia distillation stage; the separated hydrogen oil and heavy oil enter the transfer oil tank and are pumped out by a pump for deep use.

[0047] The effluent index of the oil removal stage is: petroleum ≤ 100 mg / L; the specific process parameters are:

[0048] The oil-water separators are connected in series, N or more than 1 according to the scale of the semi-coal wastewater treatment;

[0049] The capacity of each oil-water separator is equal to the scale of the semi-coal wastewater that needs to be treated per hour, and the capacity of a transfer water tank is equal to the amount of water that needs to be treated per hour; the capacity of the transfer oil tank is more than 5% of the semi-coal wastewater treatment volume per hour;

[0050] The flow rate of the water pump for pumping the semi-coke wastewater into the oil-water separator and the flow rate of the pump out of the transfer water tank are determined to be 5 tons-1000 tons according to the scale of semi-coke wastewater treated per hour; the head is above 100.

[0051] Step 2: Follow Figure 1Process diagram, for ammonia evaporation, the deacidification and deammonification tower adopts a double-tower process, namely, deacidification tower, deammonification tower + ammonia water preparation device. The raw wastewater enters the tower from the upper part of the deacidification tower, and acid gases such as hydrogen sulfide and carbon dioxide are extracted at the top of the deacidification tower, and the acid gases are sent to the tail gas treatment system; deacidification wastewater is extracted in the kettle of the deacidification tower, and the deacidification wastewater is pumped to the upper part of the deamination water deacidification tower. Crude ammonia is extracted at the top of the deacidification tower, and the crude ammonia is flashed three times to obtain ammonia with higher purity. The ammonia is sent to the ammonia water preparation device, and finally 18% or more ammonia water is obtained; deammonification wastewater is extracted in the kettle of the deammonification tower, and the deammonification wastewater is cooled to 45°C and sent out of the device. The double-tower process has the advantages of stable operation and better indicators, and is suitable for high-purity wastewater treatment.

[0052] Steam temperature for deamination and deacidification: 180 degrees; pressure 0.8MPA;

[0053] The top temperature of the deacidification tower is 50 degrees, the temperature in the tower is 110 degrees, and the bottom temperature of the tower kettle is 142 degrees; the bottom pressure is 0.32MPA; the pressure in the tower is 0.3MPA; and the top pressure is 0.3MPA;

[0054] The top temperature of the deamination tower is 145 degrees, the temperature in the tower is 150 degrees, and the bottom temperature of the kettle is 153 degrees; the pressure at the bottom of the tower is 0.42 MPA; the pressure in the tower is 0.4 MPA; and the pressure at the top of the tower is 0.4 MPA.

[0055] After ammonia evaporation, the specific parameters are as follows: (2.1) the total content of free ammonia nitrogen in the effluent is less than 50 mg / L, and hydrogen sulfide is less than 25 mg / L; (2.2) the byproduct is ammonia water with a purity of more than 18%, of which the hydrogen sulfide content is less than 2% and the phenol content is less than 50 ppm; (2.3) the designed processing capacity is 35 m' / h, and the minimum processing capacity is 21 m 3 / h, maximum processing capacity 1000m 3 / h; (2.4) The design value of the operating cost per ton of wastewater is ≤ 25.5 yuan. The operating costs are: steam 90 yuan / ton, electricity 0.5 yuan / kWh, circulating water 0.15 yuan / ton, 32% liquid alkali 1000 yuan / ton; (2.5) Stable operation period of the device: After the device reaches stable operating conditions (more than 80% of the design load), the full-load continuous operation performance assessment and calibration for 72 hours is carried out.

[0056] The ammonia water preparation device is equipped with three condensation towers and three flash towers; each flash tower is equipped with a condensation tower; the first condensation tower is a first-stage condenser: outlet temperature: 115 degrees, pressure: 0.3MPA; the second condensation tower is a second-stage condenser: outlet temperature: 80 degrees, pressure: 0.2MPA; the third condensation tower is a third-stage condenser: outlet temperature: 60 degrees, pressure: 0.05MPA; ammonia absorption tower: top temperature 60 degrees, top pressure 0.02MPA, bottom pressure 0.03MPA;

[0057] Step 3: Prepare the adsorbent used in the adsorption stage. The semi-coke wastewater after ammonia evaporation enters multiple adsorption towers connected in series or in parallel for adsorption by adsorbent slurry, such as Figure 2 As shown, oil, organic matter and ammonia are removed, and the water quality meets the national coke quenching standard and the reclaimed water reuse standard; the ratio of the adsorbent slurry to the semi-coke wastewater is 1:N (2≤N≤100); the adsorbent slurry is a mixture of adsorbent dry material and water in a mass ratio of 1:M (1≤M≤100);

[0058] The adsorbent used is a high entropy adsorbent that meets the following physical characteristic parameters: (1) The adsorbent is a mesoporous material with a mesopore diameter range of 1-50 nanometers, and pores with a diameter of 2-10 nanometers account for more than 90%; (2) High carbon material: the carbon content of the material is more than 15%, and can be adjusted according to needs; (3) The adsorbent is a carbon-multi-oxide complex, and the types of oxides are: aluminum oxide, silicon oxide, calcium oxide, magnesium oxide, iron oxide, etc., and their maximum content can be adjusted to 10% to 90%; so that the adsorbent has the following adsorption functions: (1) It can adsorb all emulsified oils and heavy oils and hydrogen oils that have not been thoroughly treated in the early stage; (2) It can adsorb all organic matter, including phenol, ether, methanol, ethanol, formic acid, acetic acid, benzene, toluene, xylene, trimethylbenzene, phenolic substances, naphthalene, anthracene, quinone, and also contains a large number of cyclic organic compounds; (3) It can adsorb all ammonia nitrogen that has not been cleaned up in the early stage;

[0059] Step 4: In multiple adsorption towers connected in series, add semi-coke wastewater to the first adsorption tower, add adsorption materials, and add semi-coke wastewater and adsorption materials in a ratio of 3:1 or above: through the first adsorption device, remove 80% of oil, 80% of organic matter, about 20% of ammonia nitrogen, and reduce COD by 80%; the residual amount is: series oil 20%; series organic matter about 20%; series ammonia nitrogen 80%; residual COD 20%;

[0060] Step 6: Add blue carbon wastewater to the second adsorption tower, add adsorbent powder, blue carbon wastewater and adsorbent powder are added in a mass ratio of 3:1 or above, and through the second adsorption device, the series oil 20%; series organic matter about 20%; series ammonia nitrogen 80%; residual COD 20% are continued to be adsorbed after the first adsorption. The residual amount of various indicators of water after adsorption is: oil: about 4%; the remaining series organic matter is about 4%, the remaining ammonia nitrogen is about 64%, and the remaining COD is about 4%;

[0061] Step 7: Add blue carbon wastewater to the third adsorption tower, add adsorbent powder, blue carbon wastewater and adsorbent powder are added in a mass ratio of 3:1 or above: through the third adsorption device, the remaining series oil 4%; series organic matter about 4%; series ammonia nitrogen 64%; residual COD4% after the second adsorption is continued to be adsorbed, and the residual amount of various indicators of water after adsorption is: oil: about 0.8%; the remaining series organic matter is about 0.8%, the remaining ammonia nitrogen is about 52%, and the remaining COD is about 0.8%;

[0062] Step 8: Add blue carbon wastewater to the fourth adsorption tower, add adsorbent powder, blue carbon wastewater and adsorbent powder are added in a mass ratio of 3:1 or above: through the fourth adsorption device, the series oil 0.8%; series organic matter about 0.8%; series ammonia nitrogen 52%; residual COD0.8% after the third adsorption is continued to be adsorbed, and the residual amounts of various indicators of water after adsorption are: oil: about 0.16%; the remaining series organic matter is about 0.16%, the remaining ammonia nitrogen is about 40%, and the remaining COD is about 0.16%;

[0063] Step 9: Add blue carbon wastewater to the fifth adsorption tower, add adsorbent powder, blue carbon wastewater and adsorbent powder are added in a mass ratio of 3:1 or above, and through the fifth adsorption device, the remaining series oil 0.16% after the fourth adsorption; series organic matter about 0.16%; series ammonia nitrogen 40%; residual COD0.16% continue to be adsorbed, and the residual amounts of various indicators of water after adsorption are: oil: about 0.032%; the remaining series organic matter is about 0.032%, the remaining ammonia nitrogen is about 32%, and the remaining COD is about 0.032%;

[0064] Step 10: Add blue carbon wastewater and adsorbent powder to the sixth set of adsorption towers, and add blue carbon wastewater and adsorbent powder in a mass ratio of 3:1 or above: through the sixth adsorption device, continue to adsorb the remaining series oil 0.032% after the fifth adsorption; series organic matter about 0.032%; series ammonia nitrogen 32%; residual COD0.032%, and the residual amount of various indicators of water after adsorption is: oil: about 0.0064%; the remaining series organic matter is about 0.0064%, the remaining ammonia nitrogen is about 25%, and the remaining COD is about 0.0064%;

[0065] Step 11: Adding semi-coke wastewater to the seventh set of adsorption tower, adding adsorbent powder, semi-coke wastewater and adsorbent powder are added in a mass ratio of 3:1 or above: through the seventh adsorption device, the remaining series oil after the sixth adsorption is about 0.0064%; the remaining series organic matter is about 0.0064%, the remaining ammonia nitrogen is about 25%, and the remaining COD is about 0.0064%; continue to adsorb, the oil after adsorption is about 0.00128%; the remaining series organic matter is about 0.00128%, the remaining ammonia nitrogen is about 20%, and the remaining COD is about 0.00128%;

[0066] Step 12: Adding semi-coke wastewater to the eighth set of adsorption tower, adding adsorbent powder, semi-coke wastewater and adsorbent powder are added in a mass ratio of 3:1 or above: through the eighth adsorption device, the remaining series oil after the seventh adsorption is about 0.00128%; the remaining series organic matter is about 0.00128%, the remaining ammonia nitrogen is about 20%, and the remaining COD is about 0.00128%; continue to adsorb, the oil after adsorption is about 0.000256%; the remaining series organic matter is about 0.000256, the remaining ammonia nitrogen is about 16%, and the remaining COD is about 0.000256%;

[0067] Step 13: Adding semi-coke wastewater to the ninth set of adsorption tower, adding adsorbent powder, semi-coke wastewater and adsorbent powder are added in a mass ratio of 3:1 or above: through the ninth adsorption device, the remaining series oil after the eighth adsorption is about 0.000256%; the remaining series organic matter is about 0.000256, the remaining ammonia nitrogen is about 16%, and the remaining COD is about 0.000256%; continue to adsorb, the oil after adsorption is about 0.0000512%; the remaining series organic matter is about 0.0000512%, the remaining ammonia nitrogen is about 16%, and the remaining COD is about 0.0000512%;

[0068] Step 14: add semi-coke wastewater to the tenth adsorption tower, add adsorbent powder, and add semi-coke wastewater and adsorbent powder in a mass ratio of 3:1 or above: through the tenth adsorption device, the remaining series oil after the ninth adsorption is about 0.0000512%; the remaining series organic matter is about 0.0000512%, the remaining ammonia nitrogen is about 16%, and the remaining COD is about 0.0000512%; continue to adsorb, the oil after adsorption is about 0.00001024%; the remaining series organic matter is about 0.00001024%, the remaining ammonia nitrogen is about 12.8%, and the remaining COD is about 0.00001024%;

[0069] Step 15: Use a high-power pump to pump the qualified water + adsorbent slurry into the filter press for filtration. The adsorbent filtered out enters the rotary kiln for drying and catalytic regeneration; the qualified water is transported to the coke quenching condition or the reclaimed water reuse condition for reuse;

[0070] Step 16: Reference Figure 3 The drying rotary kiln adopts internal heating at a temperature of 50-500 degrees; the catalytic cracking furnace regeneration rotary can be heated by an external heating device at a temperature of 400-1000 degrees to achieve catalytic regeneration, and the regeneration time is adjustable from 0.5 hours to 3 hours; after qualified regeneration, it enters the stirring tank, is stirred with water, forms an adsorbent slurry, and is reused.

[0071] The heating equipment adopts a rotary kiln, and adopts internal heating during heating and drying to improve energy utilization; external heating equipment is used during heating for catalytic cracking regeneration to reduce the oxygen content and its oxidation of the adsorbent. At the same time, for safety reasons, during the heating process in the regeneration stage, the internal cavity of the heating equipment is purged and protected with an inert gas to prevent oxygen from entering the oxidized adsorbent and causing an explosion; the inert gas includes carbon dioxide or nitrogen.

[0072] Effects of Example 1:

[0073] When the raw water indicators are: COD 33185 mg / L; ammonia nitrogen 50 mg / L; volatile phenol 4429 mg / L; oil content 239.3 mg / L; the ratio of blue carbon wastewater to adsorbent is 4:1, after 10 adsorptions in Example 1, various indicators are as shown in the following table; it can be seen from the table that after the fifth adsorption, COD, volatile phenol, ammonia nitrogen and oil indicators all meet the national quenching standards; after 10 adsorptions, the water indicators have reached the national standards for reclaimed water reuse.

[0074]

[0075]

[0076] When the raw water has the following indicators: COD 50100 mg / L; ammonia nitrogen 47 mg / L; volatile phenol 6072 mg / L; oil content 258.2 mg / L; the ratio of blue carbon wastewater to adsorbent is 3:1. After 10 adsorptions in Example 1, various indicators are as shown in the following table. It can be seen from the table that after the sixth adsorption, COD, volatile phenol, ammonia nitrogen and oil indicators all meet the national quenching standards. After 10 adsorptions, the water indicators have reached the national standards for reclaimed water reuse.

[0077]

[0078]

[0079] The adsorbent used in Example 1 is as shown in Table 1, and the pore diameter distribution of adsorbent No. 1 is as follows: Figure 4 As shown;

[0080] Table 1 Composition of adsorbent No. 1

[0081] element C O Si Al Ca other content% 29.95％ 38.63％ 19.69％ 4.29％ 6.20％ 1.24％

[0082] Example 2

[0083] The other conditions are the same as those in Example 1. When the adsorbent uses the adsorbent composition shown in Table 2, and the pore diameter distribution of adsorbent No. 2 is as follows: Figure 4 As shown;

[0084] Table 2 Composition of adsorbent No. 2

[0085] element C O Si Al Ca other content% 40.13％ 22.46％ 15.35％ 6.24％ 7.20％ 8.62％

[0086] Example 3

[0087] The remaining conditions are the same as those in Example 1. When the adsorbent uses the adsorbent composition shown in Table 3, and the pore diameter distribution of adsorbent No. 3 is as follows: Figure 4 As shown;

[0088] Table 3 Composition of adsorbent No. 3

[0089] element C O Si Ca other content% 84.56％ 11.68％ 3.10％ 0.58％ 0.08％

[0090] According to the three adsorbent composition tables given in the above three embodiments, according to the process of Example 1, the treated blue carbon water meets the national standards, see Table 4 and Table 5.

[0091] Table 4 "Emission Standards of Pollutants for Coking Chemical Industry" (GB 16171-2012) and the effects achieved by the present invention (unit: mg / L)

[0092]

[0093] Table 5 Water quality requirements for recycled water (unit: mg / L) and the effects achieved by the present invention

[0094] Serial number project unit index Embodiment 1 Embodiment 2 Embodiment 3 1 Turbidity NTU ≤5 3 2 4 2 Suspended matter mg / L ≤10 8 7 9 3 pH / 7.0～8.5 8 7.5 8 4 BOD5 mg / L ≤5 Trace Trace Trace 5 CODcr mg / L ≤30 0.04 0.35 0.21 6 NH3-N mg / L ≤5 Trace Trace Trace 7 Total Phosphorus mg / L ≤1.0 Trace Trace Trace 8 Total dissolved solids mg / L ≤1000 Trace Trace Trace 9 Calcium hardness (CaC03) mg / L ≤250 Trace Trace Trace 10 Methyl orange alkalinity (CaCO3) mg / L ≤200 Trace Trace Trace 11 C|- mg / L ≤250 Trace Trace Trace 12 iron mg / L ≤0.5 Trace Trace Trace 13 manganese mg / L ≤0.2 Trace Trace Trace 14 Petroleum mg / L ≤5 Trace Trace Trace 15 Fecal coliform bacteria pcs / L <1000 Trace Trace Trace

[0095] In summary, in the adsorption treatment stage of the present invention, the functional characteristics of the adsorbent are as follows: (1) it can adsorb emulsified oil and heavy oil and hydrogen oil that have not been thoroughly treated in the early stage; (2) it can adsorb all organic matter, including phenol, ether, methanol, ethanol, formic acid, acetic acid, benzene, toluene, xylene, trimethylbenzene, phenolic substances, naphthalene, anthracene, quinone, and also contains a large number of cyclic organic compounds and ammonia nitrogen; (3) it can adsorb ammonia nitrogen that has not been treated cleanly in the early stage; (4) The adsorption process of the present invention realizes the integrated removal of oil, organic matter and ammonia in one go.

Claims

1. A method for treating blue carbon wastewater without biochemical process, characterized in that: It includes four stages: oil removal, ammonia evaporation, adsorption, and adsorbent regeneration; or three stages: ammonia evaporation, adsorption, and adsorbent regeneration; for semi-coke wastewater with an ammonia nitrogen content lower than 1000 mg / L, it only includes two stages: adsorption and adsorbent regeneration; the adsorbent used in the adsorption stage is a high entropy adsorbent, and the carbon content accounts for 10wt%-90wt% of the total; the adsorbent powder contains different amounts of multi-element oxides, and the types of oxides include aluminum oxide, silicon oxide, calcium oxide, magnesium oxide or iron oxide, and their content accounts for 10wt%-90wt% of the total adsorbent powder.

2. The method for treating blue carbon wastewater without biochemical process according to claim 1, characterized in that: The deoiling stage is specifically as follows: the semi-coke wastewater is pumped into the oil-water separator for oil-water separation; the separated water enters the transfer water tank, which is pumped out by a pump and enters the deamination and deacidification system of the ammonia distillation stage; the separated hydrogen oil and heavy oil enter the transfer oil tank and are pumped out by a pump for deep use; The ammonia evaporation stage is specifically as follows: the pH value of the deoiled semi-coke wastewater is adjusted to 10-12 by sodium hydroxide, a double-tower process is adopted, deacidification is carried out in the deacidification tower, crude ammonia is extracted at the top of the deammonification tower, and high-purity ammonia is obtained by three-stage flash evaporation and sent to the ammonia water preparation device to finally obtain ammonia water. The semi-coke wastewater after ammonia evaporation in the deammonification tower enters the next adsorption stage; The adsorption stage is specifically as follows: the semi-coke wastewater after ammonia evaporation enters multiple adsorption towers connected in series or in parallel for adsorption by adsorbent slurry to remove oil, organic matter and ammonia until the water quality reaches the national coke quenching standard and the reclaimed water reuse standard; The regeneration stage is specifically as follows: the blue carbon water containing the adsorbent that has completed the adsorption treatment stage is filtered, and then dried and catalytically cracked by a heating device to restore the adsorption function and achieve regeneration.

3. A method for treating blue carbon wastewater without biochemical process according to claim 2, characterized in that: The effluent index of the oil removal stage is: petroleum ≤ 100 mg / L; the specific process parameters are: The oil-water separators are connected in series, N or more than 1 according to the scale of the semi-coal wastewater treatment; The capacity of each oil-water separator is equal to the scale of the semi-coal wastewater that needs to be treated per hour, and the capacity of a transfer water tank is equal to the amount of water that needs to be treated per hour; the capacity of the transfer oil tank is more than 5% of the semi-coal wastewater treatment volume per hour; The flow rate of the water pump for pumping the semi-coke wastewater into the oil-water separator and the flow rate of the pump out of the transfer water tank are determined according to the scale of semi-coke wastewater treated per hour, which is 5 tons to 1000 tons; the head is above 100.

4. The method for treating blue carbon wastewater without biochemical process according to claim 2, characterized in that: The specific parameters of the effluent from the ammonia distillation stage are: the total content of free ammonia nitrogen in the effluent is less than 50 mg / L, and the content of hydrogen sulfide is less than 25 mg / L; the byproduct is ammonia water with a purity of more than 18%, wherein the content of hydrogen sulfide is less than 2%, and the content of phenol is less than 50 ppm; The top temperature of the deacidification tower is 45-55 degrees, the temperature in the tower is 105-115 degrees, and the bottom temperature of the tower kettle is 140-145 degrees; the bottom pressure is 0.32±0.2MPA; the pressure in the tower is 0.3±0.2MPA; the top pressure is 0.3±0.2MPA; The top temperature of the deamination tower is 140-145 degrees, the temperature in the tower is 145-150 degrees, and the bottom temperature of the tower kettle is 150-155 degrees; the pressure at the bottom of the tower is 0.42±0.2MPA; the pressure in the tower is 0.4± 0.2MPA; the top pressure is 0.4±0.2MPA.

5. The method for treating blue carbon wastewater without biochemical process according to claim 2, characterized in that: In the adsorption stage, the mass ratio of the adsorbent slurry to the semi-coke wastewater is 1:N, 2≤N≤100; the adsorbent slurry is prepared by mixing the adsorbent powder dry material and water in a mass ratio of 1:M, 1≤M≤100; The adsorbent powder is a three-dimensional mesoporous skeleton with a mesopore diameter ranging from 1 to 50 nanometers, wherein pores with a diameter of 2 to 10 nanometers occupy more than 90%.

6. The method for treating blue carbon wastewater without biochemical process according to claim 5, characterized in that: In the adsorption stage, the adsorbent powder can be directly added to the semi-coke wastewater for adsorption, and the mass ratio of the adsorbent powder to the semi-coke wastewater is 1:W, 3≤W≤100; The particle size of the adsorbent powder is 1-1000 microns, or the adsorbent can be molded into granules of different shapes or sizes for use.

7. The method for treating blue carbon wastewater without biochemical process according to claim 5, characterized in that: The effluent index of the adsorption stage is: pH value 6-9, suspended matter ≤70mg / L, COD≤150mg / L, ammonia nitrogen≤25mg / L, BOD≤30mg / L, total nitrogen≤50mg / L, total phosphorus≤3.0mg / L, petroleum≤2.5mg / L, volatile phenol≤0.3mg / L, sulfide≤0.5mg / L, benzene≤0.1mg / L, cyanide≤0.2mg / L.

8. The method for treating blue carbon wastewater without biochemical process according to claim 2, characterized in that: The heating equipment used in the adsorbent regeneration stage has a temperature of 50-500 degrees during heating and drying; the heating catalytic cracking temperature is between 400 degrees and 1000 degrees.

9. The method for treating blue carbon wastewater without biochemical process according to claim 2, characterized in that: The heating device includes a rotary kiln, or other heating devices using external heating or internal heating; The heating device adopts internal heating when heating and drying, and adopts external heating when heating for catalytic cracking and regeneration; During the heating process in the regeneration stage, the inner cavity of the heating device is purged and protected with an inert gas; the inert gas includes carbon dioxide or nitrogen.

10. The method for treating blue carbon wastewater without biochemical process according to claim 2, characterized in that: The top temperature of the deacidification tower is 50 degrees, the temperature in the tower is 110 degrees, and the bottom temperature of the tower kettle is 142 degrees; the bottom pressure is 0.32MPA; the pressure in the tower is 0.3MPA; and the top pressure is 0.3MPA; The top temperature of the deamination tower is 145 degrees, the temperature in the tower is 150 degrees, and the bottom temperature of the tower kettle is 153 degrees; the bottom pressure of the tower is 0.42MPA; the pressure in the tower is 0.4MPA; and the top pressure is 0.4MPA; The lignite wastewater after ammonia evaporation enters ten adsorption towers connected in series for adsorption by adsorbent powder. The mass ratio of lignite wastewater to adsorbent powder is 3:1.

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