CN109250884B - Biogas slurry efficient deamination process combining digested sludge with thermal hydrolysis - Google Patents
Biogas slurry efficient deamination process combining digested sludge with thermal hydrolysis Download PDFInfo
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- C02F11/00—Treatment of sludge; Devices therefor
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Abstract
The invention discloses a biogas slurry high-efficiency deamination process combining digested sludge with thermal hydrolysis, wherein dehydrated sludge is pulped and anaerobically digested to obtain biogas and digested sludge, the thermal hydrolysis of the digested sludge and the deamination of the biogas slurry are combined, the deamination of the biogas slurry is realized by utilizing thermal hydrolysis pressure-release steam while the high-dry dehydration without adding chemicals is realized, the energy consumption of a system is reduced, the high-alkalinity characteristic of the biogas slurry is utilized to realize two-stage deamination without adding alkali, and CO in the biogas is fully utilized2And recovering ammonium bicarbonate, thereby realizing the high-efficiency removal and full recovery of ammonia nitrogen in the digested sludge.
Description
Technical Field
The invention belongs to the technical field of sewage and sludge treatment, and particularly relates to a biogas slurry high-efficiency deamination process for combined digestion and sludge pyrohydrolysis.
Background
With the improvement of the living standard of residents in China, a high-protein diet structure (the soybean import amount in China accounts for 60 percent of the global mass yield) becomes a main characteristic of the urbanization development process in China, and high protein consumption inevitably leads to the high ammonia nitrogen enrichment of municipal sewage sludge and domestic garbage landfill leachate. Meanwhile, rural agriculture needs to use a large amount of industrial nitrogen fertilizers, so that the problems of inconsistent and unblocked nitrogen circulation in the development process of cities and rural areas are caused, and the efficient recovery of nitrogen resources in sewage sludge and leachate is an important development direction for solving the problem of high ammonia nitrogen in cities in China.
According to statistics, the sludge yield in China reaches 4300 ten thousand tons per year (calculated by the water content of 80%), and anaerobic digestion can realize stabilization and reduction of sludge and recovery of biomass energy (biogas), so that the anaerobic digestion is a mainstream technology for sludge treatment in the world. 60% of COD and 40% of N in the sewage are accumulated in the sludge, carbon is converted into methane for recycling in the anaerobic digestion process, nitrogen exists in the biogas slurry in the form of ammonia nitrogen, and if the ammonia nitrogen in the biogas slurry is not effectively removed or recycled, the sewage treatment emission reduction target is greatly reduced. In addition, biogas slurry mainly comes from the sludge digestion dehydration process, and a large amount of dehydration agents are required to be added in the traditional anaerobic sludge digestion dehydration process. The thermal hydrolysis technology is developed to realize sludge high-dry dehydration at the earliest time, and recently, thermal hydrolysis is also used for digesting sludge, so that chemical-free high-dry dehydration is realized, and the anaerobic digestion performance is improved. Considering the whole chain of anaerobic sludge digestion, if thermal hydrolysis and biogas slurry deamination can be combined, the energy consumption and material consumption of the system can be effectively reduced.
At present, the ammonia nitrogen removal method of the biogas slurry mainly comprises air stripping, chemical precipitation, membrane deamination, anaerobic ammonia oxidation, stripping deamination and the like. Among them, air stripping has the disadvantages of low stripping efficiency, large consumption of alkali or lime for pH adjustment, and easy air pollution, and is prohibited by the environmental protection department. Chemical precipitation usually adopts the form of adding alkali and magnesium salt to generate struvite sediment, but ammonia nitrogen removal is limited, and the cost of adding medicaments is high. The membrane deamination technology also has the disadvantages of adding alkali and using dangerous chemicals such as sulfuric acid. Although ammonia nitrogen in the biogas slurry can be effectively removed by anaerobic ammonia oxidation, the anaerobic ammonia oxidation has high requirements on operation and water quality, long-term stable operation is difficult to realize, and ammonia nitrogen recovery cannot be realized. The stripping deamination needs to consume a large amount of steam, and if fresh steam of a methane boiler is adopted, the operation cost is also higher.
In order to solve the problem of biogas slurry deamination, patent document 201310642769.9 discloses a method for biogas slurry deamination and ammonia recovery, which mainly removes ammonia nitrogen in biogas slurry by adding lime to adjust the pH and by vacuum, but has the disadvantages of large consumption of chemical agents and low removal efficiency due to no external heating. Patent document 201510452491.8 discloses a high-concentration ammonia nitrogen wastewater ammonia stripping and recycling treatment system and treatment method, ammonia nitrogen is removed by adjusting alkali and blowing at high temperature, the problem of alkali addition is also existed, and the process system is complex. Patent document 201720402927.7 discloses a comprehensive treatment device for biogas slurry wastewater and biogas tail gas, which utilizes alkalinity of biogas slurryThe characteristics of realizing negative pressure deamination without adding alkali liquor and simultaneously utilizing CO in the waste gas of the biogas thermoelectric generator set2Ammonium bicarbonate is generated, the deamination steam is used for introducing into the desorption tower to heat the biogas slurry in the process, the effective utilization of the steam is realized, but CO in the desorption section can be influenced2Effect of removal, in addition to removal of ammonia and CO2Complete mixing may also affect the subsequent ammonia absorption and carbonization effect. Patent document 201610892778.7 discloses a biogas slurry decarburization combined deamination system, which realizes two-stage deamination without external alkali addition, and simultaneously adopts negative pressure ammonia distillation to reduce steam energy consumption, but the decarbonization process of the system utilizes air to blow off and remove CO2And in addition, the system only forms ammonia water, and the formation of products with higher added values is not considered.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a high-efficiency biogas slurry deamination process combining digested sludge with thermal hydrolysis, wherein the digested sludge thermal hydrolysis and the biogas slurry deamination are combined, the thermal hydrolysis pressure-relief steam is used for realizing the biogas slurry deamination while the high-dry dehydration without adding chemicals is realized, the energy consumption of a system is reduced, the high-alkalinity characteristic of the biogas slurry is used for realizing the two-stage deamination without adding alkali, and CO in the biogas is fully utilized2Realizing the recovery of ammonium bicarbonate.
In order to achieve the purpose, the high-efficiency deamination process of biogas slurry by combining digested sludge and thermal hydrolysis, which is provided by the invention, comprises the steps of slurrying and anaerobic digestion of dehydrated sludge to obtain biogas and digested sludge, purifying the biogas to obtain natural gas, and releasing pressurized CO2(ii) a Wherein the digested sludge is subjected to efficient deamination of biogas slurry by the following steps:
pre-dewatering the digested sludge to obtain pre-dewatered biogas residue and biogas slurry;
(ii) pyrohydrolysis of the pre-dewatered biogas residue to produce a pyrohydrolyzed sludge and a CO-containing product2And ammonia nitrogen pressure-released steam; the thermal hydrolysis sludge is subjected to high-dry dehydration and solar drying treatment to be used as biological carbon soil;
(iii) subjecting the biogas slurry to CO removal in sequence2Deamination, ammonia absorption and carbonization.
In the step (i), the ammonia nitrogen concentration of the biogas slurry is 2000-3500 mg/L, and the total alkalinity is 8000-15000 mgCaCO3L, and a dehydration medicament without ferric trichloride is added in the pre-dehydration process.
In step (i), the dewatering agent is an organic polymeric flocculant.
In the step (i), the organic polymeric flocculant is polyacrylamide.
In the step (ii), the temperature of the pre-dehydrated biogas residue is 160-170 ℃, the time is 20-40 min, and the alkalinity of the bicarbonate in the biogas residue is decomposed to release a large amount of CO2And ammonia nitrogen is released along with the pressure-released steam, and the pH value is increased to be more than 9.
In the step (ii), the thermal hydrolysis sludge is directly subjected to high-dry dehydration treatment without adding drugs, and a mud cake with the solid content not lower than 40% and high-temperature high-COD thermal hydrolysis liquid are generated; the mud cake is used as biological carbon soil after being dried by solar energy, and the high-temperature high-COD pyrohydrolysis liquid is refluxed for producing methane.
In the step (iii), the specific process is as follows:
pumping the biogas slurry with the temperature of 40-50 ℃ into a horizontal rotary disc to remove CO2Introducing a small amount of pressure-release steam obtained after thermal hydrolysis in the step (ii) after the tank, and removing CO in the biogas slurry under the conditions of negative pressure and stirring by a rotary disc2And part of HCO3 -The pH naturally rises;
pumping the decarbonized biogas slurry into a deamination tower, introducing pressure release steam obtained after thermal hydrolysis in the step (ii), and performing high-temperature negative-pressure steam stripping nitrogen evaporation deamination treatment under the conditions that the temperature of the biogas slurry is 70-80 ℃ and the vacuum pressure is- (0.07-0.08) MPa to obtain deamination biogas slurry and ammonia-containing steam;
then absorbing and cooling the ammonia-containing steam into concentrated ammonia water by the ammonia, wherein the concentrated ammonia water and the pressurized CO released in the biogas purification process2And carrying out carbonization reaction in a carbonization tower to obtain an ammonium bicarbonate product.
In the step (iii), the deamination biogas slurry is absorbed by biogas, the pH of the biogas slurry after biogas absorption is adjusted, and the subsequent water treatment process is carried out.
In the step (iii), the nitrogen removal rate of the marsh liquid in the deamination tower is not less than 80%.
Compared with the prior art, the invention has the beneficial effects that:
1. fully utilizes the high alkalinity characteristic of the biogas slurry and the large amount of CO contained in the thermal hydrolysis steam2And NH3The alkalinity of the biogas slurry is improved during the steam heating process, and the mode of dissolving CO in the biogas slurry by adopting a horizontal rotary disc is innovatively adopted2The rapid removal enables the pH value of the biogas slurry to naturally rise to more than 9 under the condition of no alkali addition, and creates favorable conditions for the subsequent ammonia nitrogen removal.
2. The thermal hydrolysis of the digested sludge can realize high-dry dehydration without adding drugs, the produced high-COD low-ammonia nitrogen thermal hydrolysis liquid can obviously improve the yield of system methane, the pre-dehydration of the digested sludge greatly reduces the volume and energy consumption of the thermal hydrolysis, and the thermal hydrolysis pressure-releasing steam is adopted for denitrification, so that on one hand, the effective utilization of the thermal hydrolysis steam is realized, on the other hand, the ammonia nitrogen in the thermal hydrolysis steam can be simultaneously recovered, and further, the high-efficiency removal and full recovery of the ammonia nitrogen in the digested sludge are realized.
3. The carbonization process fully utilizes CO in the existing methane2Resource, without outsourcing CO2In addition, the ammonium bicarbonate product produced in the process does not contain any industrial raw material, and is an ecological ammonium fertilizer synthesized by utilizing natural products.
4. The pH value of the deaminated biogas slurry is alkaline, and the deaminated biogas slurry can be used for absorbing CO in biogas2On one hand, the biogas is purified, the percentage content of methane in the biogas is improved, and meanwhile, the pH value of the biogas slurry is adjusted, the alkalinity of the biogas slurry is supplemented, and the subsequent biochemical treatment is facilitated.
5. The biogas slurry decarburization and deamination process adopts a negative pressure full-sealing device, no outside air is introduced, and a tail gas absorption device is arranged, so that the pollution problem to the surrounding environment is reduced to the maximum extent.
Drawings
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is a schematic diagram of the process flow of the efficient biogas slurry deamination by combining digested sludge with thermal hydrolysis.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples, but the present invention is not limited thereto.
The working principle of the invention is as follows: the removal of ammonia nitrogen in biogas slurry mainly depends on dissociation equilibrium (ionization equilibrium) of ammonia nitrogen in liquid and free ammonia liquid equilibrium (henry law), and the ammonia nitrogen in biogas slurry mainly exists in the form of ammonium ions, so that the pH and temperature of biogas slurry need to be increased to increase the proportion of free ammonia. The invention utilizes the characteristic of high alkalinity of biogas slurry and CO2And NH3The Henry constant is obviously different, and the thermal hydrolysis steam is used for heating the biogas slurry to decompose the bicarbonate and release CO2The thermal hydrolysis steam can also supplement the alkalinity of the biogas slurry, thereby obviously improving the pH of the biogas slurry, realizing the high-efficiency deamination without adding alkali, simultaneously recovering ammonia nitrogen in the thermal hydrolysis, and finally purifying residual pressurized CO by utilizing the biogas2Carbonizing to generate ammonium bicarbonate product, and using the alkaline deamination biogas slurry to further absorb CO in the biogas2Has the double functions of improving the methane percentage content of the biogas and supplementing the alkalinity of the biogas slurry.
Referring to the attached figure 1, the biogas slurry high-efficiency deamination process combining digested sludge and thermal hydrolysis comprises the steps of slurrying and anaerobic digestion of dehydrated sludge to obtain biogas and digested sludge, purifying the biogas to obtain natural gas and releasing pressurized CO2(ii) a The method comprises the following steps of efficiently deaminating digested sludge by using biogas slurry:
adding a dehydrating agent without ferric trichloride into the digested sludge for pre-dehydration to obtain pre-dehydrated biogas residues and CaCO with the ammonia nitrogen concentration of 2000-3500 mg/L and the total alkalinity of 8000-15000 mgCaCO3L of biogas slurry.
(ii) performing thermal hydrolysis on the pre-dehydrated biogas residue at 160-170 ℃ for 20-40 min to obtain thermal hydrolysis sludge and CO2And ammonia nitrogen pressure release steam, and the pH value is increased to be more than 9; directly carrying out high-dry dehydration on the thermal hydrolysis sludge without adding chemicals to obtain the solid contentNot less than 40 percent of mud cakes and high-temperature high-COD thermal hydrolysis liquid, the mud cakes are subjected to solar drying treatment to obtain biological carbon soil, and the high-temperature high-COD thermal hydrolysis liquid flows back to be used for producing methane.
(iii) biogas slurry is sequentially subjected to CO removal2Deamination, ammonia absorption and carbonization treatment, the specific process is as follows:
pumping biogas slurry with the temperature of 40-50 ℃ into a horizontal rotary disc to remove CO2Introducing a small amount of pressure-release steam obtained after thermal hydrolysis in the step (ii) after the tank, and removing CO in the biogas slurry under the conditions of negative pressure and rotary disc stirring2And part of HCO3 -The pH naturally rises.
And (3) pumping the decarbonized biogas slurry into a deamination tower, introducing pressure release steam obtained after thermal hydrolysis in the step (ii), and performing high-temperature negative-pressure steam stripping nitrogen evaporation deamination treatment under the conditions that the temperature of the biogas slurry is 70-80 ℃ and the vacuum pressure is- (0.07-0.08) MPa to obtain deamination biogas slurry and ammonia-containing steam, wherein the nitrogen removal rate of the biogas slurry in the deamination tower is not lower than 80%.
Then absorbing ammonia in ammonia to cool the ammonia-containing steam into concentrated ammonia water, and purifying the concentrated ammonia water and pressurized CO released in the process of methane purification2And carrying out carbonization reaction in a carbonization tower to obtain an ammonium bicarbonate product. The deamination biogas slurry is absorbed by biogas, and the pH of the biogas slurry after biogas absorption is adjusted to enter the subsequent water treatment process.
Example 1
The digested sludge is pre-dehydrated to the solid content of 16 percent, the addition amount of a dehydrating agent PAM is about 3 per mill (dry basis), the ammonia nitrogen concentration of the biogas slurry is 2000mg/L, the total alkalinity is 8000mg/L, and the pH value is 7.8. The pyrohydrolysis temperature of the mud cake is 160 deg.C, the time is 30min, and CO in the pressure-releasing steam is released280 percent, contains a small amount of ammonia gas, and the solid content of the thermally hydrolyzed sludge dewatered mud cake reaches 45 percent. Introducing small amount of steam into horizontal rotary disc decarbonization reactor to increase biogas slurry temperature to 45 deg.C, total alkalinity of biogas slurry to 15000mg/L, simultaneously starting rotary disc stirring and vacuum pumping system at rotation speed of 50rpm under vacuum pressure of-0.08 MPa for 30min, enlarging gas-liquid interface of rotary disc to dissolve CO in biogas slurry2Releasing, promoting the decomposition of the bicarbonate alkalinity, and increasing the pH of the biogas slurry to 9.5. CO removal2Pumping biogas slurry from the top of the deamination tower and injecting the biogas slurry from the bottomAnd (3) performing thermal hydrolysis steam convection, wherein the temperature of the biogas slurry in the deamination tower is 80 ℃, the pressure is-0.07 MPa, free ammonia in the biogas slurry is taken out by steam under the conditions of high temperature and negative pressure, the nitrogen removal rate of the biogas slurry can reach more than 90%, and the ammonia nitrogen concentration of the deamination biogas slurry is lower than 200 mg/L. Cooling ammonia-containing steam to form 17% concentrated ammonia water, and pressurizing CO with marsh gas2The reaction produces ammonium bicarbonate crystal, and the ammonium bicarbonate product is formed through low speed centrifugation. The pH value of the deamination biogas slurry is 8.5, the deamination biogas slurry is used for filtering biogas, the percentage content of methane in the biogas is increased from 60% to more than 70%, and the pH value of the biogas slurry is reduced to 7.5, and then the subsequent biological treatment is carried out.
The process can realize the recovery of ammonia nitrogen with over 70 percent of thermal hydrolysis steam, and can recover over 15kgNH at most when treating each ton of biogas slurry4HCO3And (5) producing the product.
Example 2
The digested sludge is pre-dehydrated to the solid content of 15%, the addition amount of a dehydrating agent PAM is about 2.5 per mill (dry basis), the ammonia nitrogen concentration of the biogas slurry is 3000mg/L, the total alkalinity is 12000mg/L, and the pH is 8.0. The pyrohydrolysis temperature of the mud cake is 170 deg.C, the time is 30min, and CO in the pressure-releasing steam is released2About 85 percent, contains a small amount of ammonia gas, and the solid content of the thermally hydrolyzed sludge dewatered mud cake reaches 40 percent. Introducing small amount of steam into horizontal rotary disc decarbonization reactor to increase the temperature of biogas slurry to 50 deg.C, increasing the total alkalinity of biogas slurry to 18000mg/L, starting rotary disc stirring and vacuum pumping system at 60rpm under-0.08 MPa for 30min, enlarging gas-liquid interface of rotary disc to dissolve CO in biogas slurry2Releasing, promoting the decomposition of the bicarbonate alkalinity, and increasing the pH of the biogas slurry to 10. CO removal2The biogas slurry is pumped from the top of the deamination tower and flows counter-currently with hot hydrolysis steam injected from the bottom, the temperature of the biogas slurry in the deamination tower is 70 ℃, the pressure is-0.08 MPa, free ammonia in the biogas slurry is carried out by the steam under the conditions of high temperature and negative pressure, the nitrogen removal rate of the biogas slurry can reach more than 90 percent, and the ammonia nitrogen concentration of the deamination biogas slurry is lower than 300 mg/L. Cooling ammonia-containing steam to form 17% concentrated ammonia water, and pressurizing CO with marsh gas2The reaction produces ammonium bicarbonate crystal, and the ammonium bicarbonate product is formed through low speed centrifugation. The pH of the deamination biogas slurry is about 8.7, and the deamination biogas slurry is used for filtering biogas to increase the percentage content of methane in the biogas from 65% to 75% toMeanwhile, the pH value of the biogas slurry is reduced to about 7.6, the alkalinity is recovered to a normal level, and then the subsequent biological treatment is carried out.
The thermal hydrolysis pressure release steam in the process can completely meet the energy consumption required by deamination, and residual pressurized CO in methane purification2Can completely meet the carbonization requirement, simultaneously recovers more than 70 percent of ammonia nitrogen in the thermal hydrolysis steam, and can recover more than 22.5kgNH at most when treating each ton of biogas slurry4HCO3And (5) producing the product.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (6)
1. The high-efficiency biogas slurry deamination process combining digested sludge with thermal hydrolysis is characterized in that dehydrated sludge is pulped and anaerobically digested to obtain biogas and digested sludge, the biogas is purified to obtain natural gas, and pressurized CO is released2(ii) a The digested sludge is subjected to efficient deamination of biogas slurry by the following steps:
pre-dehydrating digested sludge, and adding a dehydration medicament without ferric trichloride in the pre-dehydration process to obtain pre-dehydrated biogas residue and biogas slurry; the ammonia nitrogen concentration of the biogas slurry is 2000-3500 mg/L, and the total alkalinity is 8000-15000 mgCaCO3/L；
(ii) performing thermal hydrolysis on the pre-dehydrated biogas residue at 160-170 ℃ for 20-40 min to generate thermal hydrolysis sludge and CO2And ammonia nitrogen pressure-release steam, wherein the thermal hydrolysis sludge is subjected to high-dry dehydration and solar drying treatment to be used as biological carbon soil; decomposing the bicarbonate alkalinity in the biogas residue to release a large amount of CO2Ammonia nitrogen is released along with the pressure-released steam, and the pH value is increased to be more than 9;
(iii) subjecting the biogas slurry to CO removal in sequence2Deamination, ammonia absorption and carbonization treatment, wherein the process comprises the following steps: pumping the biogas slurry with the temperature of 40-50 ℃ into a horizontal rotary disc to remove CO2A tank is filled with a small amount of pressure-release steam after the thermal hydrolysis in the step (ii), and CO in the biogas slurry is removed under the conditions of negative pressure and stirring by a rotary disc2And part of HCO3 -The pH naturally rises;
pumping the decarbonized biogas slurry into a deamination tower, introducing pressure release steam obtained after thermal hydrolysis in the step (ii), and performing high-temperature negative-pressure steam stripping nitrogen evaporation deamination treatment under the conditions that the temperature of the biogas slurry is 70-80 ℃ and the vacuum pressure is- (0.07-0.08) MPa to obtain deamination biogas slurry and ammonia-containing steam;
the ammonia-containing steam is absorbed and cooled into concentrated ammonia water by the ammonia, and the concentrated ammonia water and the pressurized CO released in the biogas purification process2And carrying out carbonization reaction in a carbonization tower to obtain an ammonium bicarbonate product.
2. The process for efficiently deaminating biogas slurry by combining digested sludge and thermal hydrolysis according to claim 1, wherein in the step (i), the dewatering agent is an organic polymeric flocculant.
3. The process for efficiently deaminating biogas slurry by combining digested sludge and thermal hydrolysis according to claim 2, wherein in the step (i), the organic polymeric flocculant is polyacrylamide.
4. The process for efficiently deaminating biogas slurry by combining digested sludge and thermal hydrolysis according to claim 1, wherein in the step (ii), the thermal hydrolyzed sludge is subjected to high-dry dehydration treatment directly without adding any chemicals, so that a mud cake with a solid content of not less than 40% and high-temperature high-COD thermal hydrolysate are generated; the mud cake is used as biological carbon soil after being dried by solar energy, and the high-temperature high-COD pyrohydrolysis liquid is refluxed for producing methane.
5. The process for efficiently deaminating biogas slurry according to claim 1, wherein in step (iii), the deaminating biogas slurry is prepared by absorbing CO in biogas2Improving the percentage content of methane, adjusting the pH value of the biogas slurry after methane absorption to be alkalescent, and performing subsequent water treatment.
6. The process for efficiently deaminating biogas slurry by combining digested sludge and thermal hydrolysis according to claim 1, wherein in the step (iii), the nitrogen removal rate of biogas slurry in the deamination tower is not less than 80%.
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