The national ammonia wastewater treatment new technology site meeting was successfully concluded in Xuzhou, Jiangsu. At this meeting, representatives of Shandong Feida Chemical Technology Co., Ltd. and Henan Xinyang Asia New Energy Co., Ltd., which have applied new pollution control technologies, made speeches successively. With the remarkable results and considerable benefits of the new process, it was proved that the advanced technology is Realize the important guarantee of energy saving and emission reduction. Huang Huayao, director of the Xuzhou Institute of Water Treatment, one of the organizers, introduced 168 representatives of 86 synthetic ammonia enterprises in the conference to comprehensively introduce the ten major energy-saving and emission reduction technologies for the treatment of synthetic ammonia wastewater, which is the first to grasp the source and then treat the end. Answered the questions of various company representatives in sewage treatment.
The meeting also arranged for the delegate to go to another organizer, Shandong Hengtong (Lucheng) Chemical Co., Ltd., to visit the site. The company adopted a combination of pollution control at the source and pollution control at the end. The investment was 15 million yuan, which reduced the total wastewater from 250 cubic meters/hour. The advanced standard of 80 cubic meters per hour and the reduction of drainage to 3 to 4 cubic meters per ton of ammonia will save only annual sewage treatment costs and disposal fees of more than 10 million yuan, and the entire investment will be recovered in less than two years. Delegates looked at the external drainage at the site, the chemical oxygen demand of the effluent was less than 60 mg/l, the ammonia nitrogen was less than or equal to 15 mg/l, and the total nitrogen was less than or equal to 30 mg/l. All the indicators met and exceeded the drainage standards for large-scale nitrogen fertilizer companies. Thanks to the advanced technology, practicality, low investment, and good results, the visit representatives were deeply encouraged, and realized the original intention of the on-site meeting to provide practical technology services to enterprises, promote the energy saving and emission reduction of synthetic ammonia companies, and achieve zero emissions.
The ammonia industry is a large water user and is also a major sewage emitter. China's ammonia industry consumes an average of 58 tons of ammonia and consumes 2.7 billion tons of water per year. At the same time, it discharges 2.13 billion cubic meters of water per year, emits 0.990 million tons of pollutants per year, and there are more pollutants in the wastewater than the standard. Ammonia nitrogen, chemical oxygen demand, cyanide, sulphide, etc. must be treated several times before reaching the discharge standards.
Xuzhou Institute of Water Treatment Research, with years of follow-up services and research on synthetic ammonia industry water use, developed 10 advanced technologies for wastewater treatment. The 10 new energy-saving and emission reduction technologies are "something to be ruled, some to be cured, and eventually reaching a major point; The first source of pollution, followed by the end of treatment, and linkage treatment, resulting from the concept of pollution control, are targeted and practical. They complement each other to ensure the treatment effect. After the use of a full set of technologies, the external drainage of the enterprise can be reduced by more than 70%. More than 60% reduction in materials, reduce the end of the treatment investment and processing costs 40% to 60%, so that the ammonia industry is expected to remove the big sewage, big hat pollution.
- Reporter's notes
Synthetic Ammonia Wastewater Top Ten Energy-saving and Emission-reduction Control Technologies First, gasification wastewater micro-vortex treatment technology This technology proposes three principles of “deep purification, enhanced cooling, and water quality adjustment†for gasification and circulating water, and the application of water-in-water technology. With less investment and processing costs, the most polluting gas cooling water system achieves zero emissions. Such as Zhejiang Great Group adopts this technology, the gasification cooling water system has not discharged sewage for 4 years, and it truly achieves zero emission.
The technology has been adopted by more than 100 companies, and the treated water quality is good. The cost is only 0.03 yuan/cubic meter, saving about 5%. This technology has been evaluated by the China Nitrogenous Fertilizer Industry Association as a cyclical economic support technology for the nitrogen fertilizer industry from 2007 to 2010, which can reduce pollutants by 60% to 70%, and has made significant contributions to reducing end-of-end investment and disposal costs.
II. Technology for Reducing Concentration and Reducing Emissions from Circulating Cooling Water Circulating cooling water is the main water use link for chemical fertilizer companies. Its water consumption accounts for nearly 70% of the entire plant. How to reduce the amount of sewage discharged at this stage is of major importance. Circulating cooling water concentration and emission reduction technology can increase the concentration multiple from the current 2 times to 4 to 6 times, and the amount of sewage can be reduced by 70% to 80%. The key point of this technology is the selection of excellent agents and processes, and new types of rare earth filter media with high cutting force. After the enrichment, not only save water, but the water quality is clean. The cost of dosing treatment does not rise by 30%.
Third, desulfurization circulating water one yuan purifier technology Desulfurization cooling circulating water is second only to the second pollution source of circulating gas, not only high suspended solids content, sulfur and tar impurity content is also high. The sulphur foam is sticky, the precipitate is light, and it is not easy to precipitate. The viscous impurities cannot be removed by filtration. With the desulfurization circulating water one-way purifier technology, only one set of equipment is required to combine various functions such as impurity removal, desulfurization, and tar purification to solve the unresolved problems of desulfurization and circulating water treatment for many years. Jiangsu Hengsheng Chemical Group successively applied two sets of one-way purifiers to solve the problem of desulfurization and cooling circulating water pollution. The treated water quality is good, and the washing tower packing is not blocked, and the cooling and sulfur removal effects are significantly improved. The investment in the equipment is small and the cost of treated water is <0.1 yuan/cubic meter.
Fourth, urea analytical solution advanced treatment and reuse technology This technology can be used in the urea solution of urea in the role of catalyst under low pressure, low temperature to complete the deep processing and reuse. Its investment is more than 80% than that of deep hydrolysis technology, and it can turn wastewater into desalinated water and reuse it. This technology can be used to recover investment in one year, and pollution control and efficiency increase. The decomposed ammonia gas is removed by combustion in the jacket furnace and no secondary pollution occurs. The technology has been adopted by nearly one hundred urea plants, with a total of 150 units, which can save an investment of 400 million to 500 million yuan at a time. For example, 9 branches in Hubei Yihua have adopted this technology and saved a total investment of 30 million yuan.
5. Residues of methanol residue and dimethyl ether residue treatment Recycling technology Evaporation residue produced in the production of methanol and dimethyl ether, in which alcohols, ethers and other volatile organics are large, chemical oxygen demand concentration of 20,000 to 50,000 mg / l, great harm to the environment. Such high-concentration contaminants are treated with biochemical methods. The general project investment has exceeded 10 million yuan, and the annual treatment cost is several million yuan. Methanol residual liquid and dimethyl ether residue treatment and reuse technology and special equipment completely solve the problem of organic acid corrosion produced when the residual liquid waste water is directly recycled, and the backwater can reach the effect of desalinated water, which is extracted for methanol and dimethyl ether enterprises. A new approach to waste water treatment was used to treat pollution. It does not only cost money, but also yields several hundred thousand yuan a year.
Six, oily sewage purification technology Ammonia synthesis enterprise lubrication equipment will produce a lot of oily sewage, water is not large, but directly into any one water system, will cause harm. The oily sewage purification technology adopts a special oil purifier, the purified water is used for circulating water, replaces the primary water, and the investment province has low processing cost, far more than the oily sewage is discharged into the sewage system of the plant without treatment, and then all the water is removed. The method of remediation after the expansion of pollution by oil treatment saves money and has better results.
Seven, from the pay-off sewage treatment pH standard technology ion exchange method (departure method) to deal with desalinated water investment province, the water is good, easy to operate, recognized by the user, especially for the low water quality of the influent water, more reverse osmosis method Unmatched advantages. The pH of the sewage discharged from the traditional process exceeds the standard, corrodes the sewer, and pollutes the environment. The off-line wastewater pH standard technology can recover nearly 100% of the excess acid and alkali discharged during regeneration, and the wastewater can reach the standard without neutralizing the pH. Some plants have excess chemical oxygen demand in the effluent. This is not a problem of the separation process, but it is caused by the failure of the regenerant used. Only the replacement of qualified products can solve the problem. From the intersection of sewage and pH standard technology can reduce renewable acid, alkali 20% to 30%, is a pollution enhancement process. This technology not only adapts to the transformation of old equipment, but also to new water treatment projects.
Eight, ammonium nitrate wastewater A / B bed treatment reuse technology Many ammonia companies also produce ammonium nitrate, sodium nitrate, sodium and other products, resulting in a certain amount of nitrate wastewater, pollute the environment. Although the biochemical method can remove ammonium nitrate salt, the investment and processing costs are large. The A/B bed treatment and reuse process can recycle 100% of the ammonium nitrate wastewater, which solves the difficult problem of the trapped enterprise.
The special A/B bed equipment used in this technology can increase the concentration of nitrate in the drainage water by 10 to 30 times, reaching 6% to 10%, which is convenient for recycling. The treated water quality is also in line with the shallow salt water, and the conductivity is <30μs. /cm, can be directly used for boiler replenishment. The cost of using this technology to treat ammonium nitrate salt is only 0.1-0.2 yuan/cubic meter, and the investment is only 1/4 of electrodialysis technology.
Ninth, the end of the treatment of A / SBR short-cut nitrification new process After the source of water treatment drastically reduced, but also the need for small end-processing equipment, in order to ensure that the external drainage standards, and accident drainage. Because the ammonia nitrogen in the sewage is difficult to handle, and the need for adding alkali and methanol nitrification - denitrification need to adjust the water quality, so the processing costs are high. If the conventional ammonia-nitrogen removal process is used, the pharmaceutical agent costs 12-20 yuan/kg of ammonia nitrogen, and the investment is much greater. The A/O method and the improved technology are currently used to treat ammonia-containing nitrogen wastewater. The advantages are that the process is simple and easy to control. The disadvantages are poor impact resistance, large investment, and low total nitrogen removal rate.
The new short-cut nitrification A/SBR process at the end of the process solved the shortcomings of the A/O process and achieved three breakthroughs: First, the dominant bacteria were cultivated and acclimated to adapt to the new short-cut nitrification process, saving 40% of the carbon source and saving 25% of the oxygen. 35% of electricity, less production of sludge 60%, civil construction investment also reduced by 20% to 30%, and reduce the cost of ammonia nitrogen wastewater treatment by more than 30%. Second, the total nitrogen removal rate reached 95% to 98%, which solved the problem that the total nitrogen removal rate of the A/O process could not adapt to the new environmental protection standards. The third is to solve the load shock problem, the selection of dominant bacteria resistant to strong impact on the load, the process and the use of full-volume push-flow mixing, the water intake, water quality dozens of times buffer adjustment, to ensure the stability of the effluent water quality. Due to its low investment, low treatment costs, and good and stable effluent quality, this technology has become one of the latest processes for ammonia nitrogen removal, and was rated as a national key environmental protection technology in 2008 by the China Environmental Protection Industry Association.
X. Wastewater Recycling Treatment Technology Up-to-standard Wastewater Emissions Although environmental protection standards are met, desalination equipment should be considered for reuse. Which technology should be used for reuse should be determined according to the salt content. Only targeted selection can be used after verification. The technology can achieve the desired results. The salt content of wastewater is less than 1000 mg/L. It is recommended to use shallow salt removal technology, reuse investment <20,000 yuan/cubic meter, and effluent discharge rate from 5% to 10%. Because of low water content, it is easily digested by coal ash humidification. Used up, easy to achieve zero emissions. The wastewater containing 1000-1500 mg/L of salt is better than the double-membrane method (ultrafiltration-reverse osmosis). Its disadvantage is that the investment for reuse water is up to 40,000 yuan/cubic meter, the membrane cleaning times are many, and the concentration of concentrated water is high. 30%, there will be a small amount of water outside the row. Salt> 1500 mg / l of wastewater is easy to fouling, dosing and anti-scaling effect is not very good, so the choice of electric adsorption method is better, but the investment up to 70,000 ~ 80,000 yuan / cubic meter backwater, the concentration of the outer row of water Also reaching 30%, it is equally difficult to achieve zero emissions.
Representative Li Nawei (Director of Shandong Sinochem Plain Chemical Group Co., Ltd.):
Plain Chemical Co., formerly known as the Plains Deqilong Chemical Group, produces 1.2 million tons of ammonia and methanol per year. It is a well-known large-scale chemical enterprise at home and abroad.
Our company adopted the source control technology of the Xuzhou Institute of Water Treatment and the tons of ammonia drainage has dropped to the advanced level of 3 to 4 cubic meters. However, due to the large scale of production, the total amount of external drainage still reaches 400 to 500 cubic meters per hour. If conventional treatment processes are used, it is generally necessary to invest hundreds of millions of dollars in treating such large amounts of waste water. Afterwards, our company cooperated with Xuzhou Institute of Water Treatment and divided the whole plant drainage into three major categories according to quality.
For the cooling water with a large amount of water (cooling capacity of 100,000 cubic meters/hour), the water quality has reached the environmental protection standard, and after collection, it is sent to the wastewater treatment plant by pipelines, and only physical treatment is required. Water containing large amounts of pollutants such as ammonia nitrogen and chemical oxygen demand (such as gas recycling, desulfurization, carbonization, etc.) is separately collected and sent to the wastewater treatment plant for in-depth chemical-biological treatment. The biochemical process uses A/SBR. New Technology. For another kind of oily wastewater with less water, a collection-purification treatment process is adopted. The purified wastewater is incorporated into the over-standard sewage for biochemical treatment, and the separated oil can also be exported. Due to the adoption of new processing concepts and technologies, our company's large-scale enterprises have invested only 17 million yuan (2,200 yuan/m3 of water investment per ton), which has achieved the goal of wastewater treatment and wastewater treatment for the whole plant, at least compared with similar enterprises. Save 20 million to 30 million yuan.
The sewage works of our company completed the civil construction in February 2007, and began to be commissioned in May of the same year. The operation was completed on June 10 and it has been running for more than a year. Even if the water temperature is low in winter, there is no phenomenon of excessive drainage. Steady production has played an escort role.
In respect of wastewater treatment indicators, our company's influent chemical oxygen demand is 800-1000 mg/L, ammonia nitrogen 350-500 mg/L, effluent chemical oxygen demand <70 mg/L, ammonia nitrogen ≤ 15 mg/L, total nitrogen ≤ 30 mg/L, which is better than the design standard, reached the first-grade drainage standard for the new environmental protection standards to be implemented in the near future. Especially for the treatment of total nitrogen, we have designed ahead of time. We have accepted the recommendations of the Xuzhou Institute of Water Treatment. We must not only meet the ammonia nitrogen standard, but also make the total nitrogen reach the standard in order to avoid the need to reform the treatment facilities after the implementation of the new standard. In a single step, the results did not increase the amount of investment to make ammonia nitrogen, chemical oxygen demand, total nitrogen removal rate reached 90% to 98%, which is the effect of the old process can not be achieved.
In addition, due to the small amount of groundwater storage in the plant area and the inability to meet production needs, the next step is to prepare the company's wastewater reuse treatment equipment so that the external drainage can be reduced by 70% to 80%, and the reused water resources can be fully utilized.
Yin Yin Xue (Deputy Director of Shandong Feida Chemical Technology Co.):
FeiDa Chemical Group is a large-scale chemical enterprise that produces synthetic ammonia, chemicals, and rubber additives. The plant site is in the key control area of ​​the South-to-North Water Diversion of the East Line. The external water quality requirements are higher than the national standard, and the original sewage treatment equipment is not qualified. Make a change. In order to select partners, our company invited various pollution control units to the factory for technical exchanges on March 28, 2007. After being evaluated by provincial and municipal environmental protection experts, we finally selected the short-cut nitrification of strong bacteria of A/SBR from Xuzhou Institute of Water Treatment. new technology.
The water output of our design is 1,920 cubic meters per day (80 cubic meters per hour); the designed influent water quality is 1,000 milligrams per liter chemical oxygen demand, 600 milligrams ammonia nitrogen, and sulfur ≤ 30 milligrams per liter; the design water quality is chemical Oxygen demand ≤ 60 mg/l, ammonia nitrogen ≤ 15 mg/l, total nitrogen ≤ 30 mg/l, and sulfur <1 mg/l.
Due to poor water quality and high investment, the total investment is 6 million yuan, the investment in tons of water is 6 million ÷ 1920 = 3125 yuan/cubic meter, the sewage treatment cost is actually 1.13 yuan/cubic meter, and the measured water quality is chemical demand. Oxygen content ≤ 50 mg/l, ammonia nitrogen ≤ 5 mg/l, and total nitrogen content <20 mg/l, which is superior to the strictest requirements of the provincial standard and has passed environmental protection acceptance. It is worth mentioning that the process has good load impact resistance, and the water quality and water volume in our factory will fluctuate. For example, the ammonia nitrogen in the influent water will fluctuate between 300 and 1000 mg/l, while the actual treatment of water ammonia and nitrogen will be 10 mg/L, ammonia nitrogen removal rate and total nitrogen removal rate are all > 95%, far superior to other old processes. From the three hard indicators of investment, processing fee, and water quality, it can be seen that the new A/SBR process is a reliable process for ammonia synthesis companies.
He Xinxin (Director of Anhui Sanxing Chemical Company):
Samsung Chemical Co., formerly known as Guoyang Chemical Fertilizer Plant, has developed into a production scale of 230,000 tons of synthetic ammonia per year, 80,000 tons of methanol per year, and 1,300 tons of melamine per year. Our factory is in the upper reaches of the Huaihe River, and its water quality for drainage is very strict. To this end, our factory has adopted the advanced concepts and techniques of pollution control at the Xuzhou Institute of Water Treatment. The drainage and chemical oxygen demand, ammonia and other pollutants have all dropped significantly, and 2 million tons of waste water has been discharged. In 2010, a 100-kilowatt/hour water pump was stopped, and only one power-saving was achieved at 700,000 kWh/year, which resulted in energy savings and emissions reductions. This was the result of adopting advanced technology.
We have adopted the clean and recycling process of separation from the sources, that is, the recovery of spent acid and waste alkali, and the pH value has reached the standard. In addition, the micro-vortex purification process was adopted in the gas recycling water process, and the existing old gas cabinet was reconstructed, thus realizing zero-emission of closed-circuit gas generation and increasing the amount of air-injection.
The content of chemical oxygen demand, ammonia nitrogen, and urea in the raffinate residue and urea analysis residual solution are high. The deep hydrolysis technology requires investment of 4 million to 5 million yuan. After the plant, the deep processing and reuse jacket of Xuzhou Institute of Water Treatment was selected. Process, using desalinated water instead of desalinated water, water saving 170,000 yuan / year, and residual liquid treatment effect is good. The circulating water link adopts the concentration and emission reduction technology of the Xuzhou Institute of Water Treatment. The concentration factor is increased from 2 to 4 and the water saving is obvious. The ammonia drainage is reduced to 2 cubic meters. On the basis of source control, our company has also launched an end-of-sewage treatment project using a new A/SBR process. Influent water quality chemical oxygen demand is 1000 ~ 2000 mg / l, ammonia nitrogen is 200 ~ 400 mg / l, water quality concentration fluctuations. When the designed water output is 80 cubic meters/hour, the effluent quality is COD ≤ 70 mg/L, ammonia nitrogen ≤ 20 mg/L, and total nitrogen ≤ 30 mg/L, which is superior to the first-class external drainage standard and meets the external requirements of the Huaihe River region. Drainage water quality requirements. In addition, since both nitrification and denitrification do not add alkali and methanol, the annual cost of alkali and alkali is RMB 700,000, the cost of wastewater treatment is <1 yuan/cubic meter, the total investment is 5.1 million yuan, and the investment per ton of water is 2600 yuan/cubic meter, only saving. Drainage fees and electricity charges do not require two years to recover the investment.
In short, our company achieved good results in wastewater discharge compliance, pollution control and efficiency enhancement. This is the result of the company's active use of advanced technology from the Xuzhou Institute of Water Treatment, and it is also a result of close cooperation between production companies and environmental research institutes.
Cao Xuebin (Deputy director of Shandong Hengtong Chemical Co., Ltd.):
Hengtong Chemical is a large-scale chemical group that integrates ammonia, co-alcohol, electrolysis chemical industry and power generation. Chemical fertilizer wastewater is the focus of the Group's governance, and the chemical oxygen demand and ammonia nitrogen content of wastewater are high, so governance is imminent.
The current pollution control processes are different. Choosing the right process has a major bearing on the treatment effect, investment costs, and disposal costs. For this reason, our group specially organized a group of inspections and researches to decide which process to use. We investigated a total of four representative processes (see chart).
Through research and sampling and analysis of the water quality back to the factory, it can be clearly seen that the effluent quality of the three companies is basically qualified, and the investment costs vary widely, reaching 5 to 7 times! Processing costs also vary widely. The new A/SBR process of the Xuzhou Institute of Water Treatment not only fully complies with the effluent standards, but also meets the emission requirements of the new environmental protection standards that will be implemented in the near future. More importantly, this technology saves investment and processing costs and is attractive to companies. With the approval of the leaders, we finally chose the new A/SBR process.
The designed water output of the plant is designed at 2,160 cubic meters per day (90 cubic meters per hour), leaving room for future development. Designed to have a chemical oxygen demand of 500 mg/L and ammonia nitrogen of 200 mg/L; designed water quality to be COD ≤ 100 mg/L, ammonia nitrogen ≤ 15 mg/L, total nitrogen ≤ 30 mg/L, granules Suspended material ≤ 50 mg/l.
The treatment plant completed the civil construction at the end of March this year, and it began trial operation on May 28 and was officially put into operation in early July. The actual water intake is 75 m3/h, the influent chemical oxygen demand is 400-600 mg/l, the ammonia nitrogen is 150-220 mg/l, the measured chemical oxygen demand is ≤60 mg/l, and the ammonia nitrogen is 0, Total nitrogen <25. According to actual calculations, the investment was 6.426 million yuan, and the investment per ton of water was 6.426 million ÷ 2160 = 2975 yuan/cubic meter. The cost of treated water is 1.3 to 1.5 yuan/cubic meter. Practice has proved that we have chosen the process to be correct. We have only saved more than RMB 10 million in investment, and discharged 1.2 million cubic meters of wastewater per year. We have discharged less chemical oxygen demand and 600-700 tons of ammonia nitrogen per year. We tasted the rule first. "The source, after treatment of the end" of the sweetness.
Chang Zhengzheng (Director of Henan Xinyang New Energy Company):
Asia New Energy Corporation is a wholly foreign-owned company that produces 150,000 tons of synthetic ammonia per year, 260,000 tons of urea per year, 200,000 tons of methanol per year, and 200,000 tons of dimethyl ether per year. The local environmental protection standards are chemical oxygen demand <50 mg/l and ammonia nitrogen <40 mg/l. To meet environmental protection requirements, we have selected A/SBR short-cut nitrification of Xuzhou Institute of Water Treatment which has many application cases. Process.
The water output of our plant is 1,920 cubic meters per day (80 cubic meters per hour); the designed influent water quality is 150 milligrams per liter chemical oxygen demand, 200 milligrams ammonia nitrogen, and 150 milligrams per liter of suspended particulate matter; the design water quality is Chemical oxygen demand ≤ 50 mg/l, ammonia nitrogen ≤ 20 mg/l, particulate suspended matter ≤ 50 mg/l. The project civil construction was completed on December 15, 2007, and it was commissioned on January 1, 2008 and reached the standard on January 21. Due to the selection of dominant bacteria, the commissioning took only 20 days to achieve water compliance. From January 21 to January 30, 2008, the chemical oxygen demand of the effluent was between 41 and 47 mg/L for a continuous measurement for 10 days. The fluctuation was small; the ammonia nitrogen was between 18 and 22 mg/L, and the water quality was good. Very stable. The total investment for the project is 4.82 million yuan, and the investment for tons of water is 4.82 million yuan for 1920=2510 yuan/cubic meter, and the treatment water cost is 1.2 to 1.5 yuan/cubic meter, all reaching the design value.
The meeting also arranged for the delegate to go to another organizer, Shandong Hengtong (Lucheng) Chemical Co., Ltd., to visit the site. The company adopted a combination of pollution control at the source and pollution control at the end. The investment was 15 million yuan, which reduced the total wastewater from 250 cubic meters/hour. The advanced standard of 80 cubic meters per hour and the reduction of drainage to 3 to 4 cubic meters per ton of ammonia will save only annual sewage treatment costs and disposal fees of more than 10 million yuan, and the entire investment will be recovered in less than two years. Delegates looked at the external drainage at the site, the chemical oxygen demand of the effluent was less than 60 mg/l, the ammonia nitrogen was less than or equal to 15 mg/l, and the total nitrogen was less than or equal to 30 mg/l. All the indicators met and exceeded the drainage standards for large-scale nitrogen fertilizer companies. Thanks to the advanced technology, practicality, low investment, and good results, the visit representatives were deeply encouraged, and realized the original intention of the on-site meeting to provide practical technology services to enterprises, promote the energy saving and emission reduction of synthetic ammonia companies, and achieve zero emissions.
The ammonia industry is a large water user and is also a major sewage emitter. China's ammonia industry consumes an average of 58 tons of ammonia and consumes 2.7 billion tons of water per year. At the same time, it discharges 2.13 billion cubic meters of water per year, emits 0.990 million tons of pollutants per year, and there are more pollutants in the wastewater than the standard. Ammonia nitrogen, chemical oxygen demand, cyanide, sulphide, etc. must be treated several times before reaching the discharge standards.
Xuzhou Institute of Water Treatment Research, with years of follow-up services and research on synthetic ammonia industry water use, developed 10 advanced technologies for wastewater treatment. The 10 new energy-saving and emission reduction technologies are "something to be ruled, some to be cured, and eventually reaching a major point; The first source of pollution, followed by the end of treatment, and linkage treatment, resulting from the concept of pollution control, are targeted and practical. They complement each other to ensure the treatment effect. After the use of a full set of technologies, the external drainage of the enterprise can be reduced by more than 70%. More than 60% reduction in materials, reduce the end of the treatment investment and processing costs 40% to 60%, so that the ammonia industry is expected to remove the big sewage, big hat pollution.
- Reporter's notes
Synthetic Ammonia Wastewater Top Ten Energy-saving and Emission-reduction Control Technologies First, gasification wastewater micro-vortex treatment technology This technology proposes three principles of “deep purification, enhanced cooling, and water quality adjustment†for gasification and circulating water, and the application of water-in-water technology. With less investment and processing costs, the most polluting gas cooling water system achieves zero emissions. Such as Zhejiang Great Group adopts this technology, the gasification cooling water system has not discharged sewage for 4 years, and it truly achieves zero emission.
The technology has been adopted by more than 100 companies, and the treated water quality is good. The cost is only 0.03 yuan/cubic meter, saving about 5%. This technology has been evaluated by the China Nitrogenous Fertilizer Industry Association as a cyclical economic support technology for the nitrogen fertilizer industry from 2007 to 2010, which can reduce pollutants by 60% to 70%, and has made significant contributions to reducing end-of-end investment and disposal costs.
II. Technology for Reducing Concentration and Reducing Emissions from Circulating Cooling Water Circulating cooling water is the main water use link for chemical fertilizer companies. Its water consumption accounts for nearly 70% of the entire plant. How to reduce the amount of sewage discharged at this stage is of major importance. Circulating cooling water concentration and emission reduction technology can increase the concentration multiple from the current 2 times to 4 to 6 times, and the amount of sewage can be reduced by 70% to 80%. The key point of this technology is the selection of excellent agents and processes, and new types of rare earth filter media with high cutting force. After the enrichment, not only save water, but the water quality is clean. The cost of dosing treatment does not rise by 30%.
Third, desulfurization circulating water one yuan purifier technology Desulfurization cooling circulating water is second only to the second pollution source of circulating gas, not only high suspended solids content, sulfur and tar impurity content is also high. The sulphur foam is sticky, the precipitate is light, and it is not easy to precipitate. The viscous impurities cannot be removed by filtration. With the desulfurization circulating water one-way purifier technology, only one set of equipment is required to combine various functions such as impurity removal, desulfurization, and tar purification to solve the unresolved problems of desulfurization and circulating water treatment for many years. Jiangsu Hengsheng Chemical Group successively applied two sets of one-way purifiers to solve the problem of desulfurization and cooling circulating water pollution. The treated water quality is good, and the washing tower packing is not blocked, and the cooling and sulfur removal effects are significantly improved. The investment in the equipment is small and the cost of treated water is <0.1 yuan/cubic meter.
Fourth, urea analytical solution advanced treatment and reuse technology This technology can be used in the urea solution of urea in the role of catalyst under low pressure, low temperature to complete the deep processing and reuse. Its investment is more than 80% than that of deep hydrolysis technology, and it can turn wastewater into desalinated water and reuse it. This technology can be used to recover investment in one year, and pollution control and efficiency increase. The decomposed ammonia gas is removed by combustion in the jacket furnace and no secondary pollution occurs. The technology has been adopted by nearly one hundred urea plants, with a total of 150 units, which can save an investment of 400 million to 500 million yuan at a time. For example, 9 branches in Hubei Yihua have adopted this technology and saved a total investment of 30 million yuan.
5. Residues of methanol residue and dimethyl ether residue treatment Recycling technology Evaporation residue produced in the production of methanol and dimethyl ether, in which alcohols, ethers and other volatile organics are large, chemical oxygen demand concentration of 20,000 to 50,000 mg / l, great harm to the environment. Such high-concentration contaminants are treated with biochemical methods. The general project investment has exceeded 10 million yuan, and the annual treatment cost is several million yuan. Methanol residual liquid and dimethyl ether residue treatment and reuse technology and special equipment completely solve the problem of organic acid corrosion produced when the residual liquid waste water is directly recycled, and the backwater can reach the effect of desalinated water, which is extracted for methanol and dimethyl ether enterprises. A new approach to waste water treatment was used to treat pollution. It does not only cost money, but also yields several hundred thousand yuan a year.
Six, oily sewage purification technology Ammonia synthesis enterprise lubrication equipment will produce a lot of oily sewage, water is not large, but directly into any one water system, will cause harm. The oily sewage purification technology adopts a special oil purifier, the purified water is used for circulating water, replaces the primary water, and the investment province has low processing cost, far more than the oily sewage is discharged into the sewage system of the plant without treatment, and then all the water is removed. The method of remediation after the expansion of pollution by oil treatment saves money and has better results.
Seven, from the pay-off sewage treatment pH standard technology ion exchange method (departure method) to deal with desalinated water investment province, the water is good, easy to operate, recognized by the user, especially for the low water quality of the influent water, more reverse osmosis method Unmatched advantages. The pH of the sewage discharged from the traditional process exceeds the standard, corrodes the sewer, and pollutes the environment. The off-line wastewater pH standard technology can recover nearly 100% of the excess acid and alkali discharged during regeneration, and the wastewater can reach the standard without neutralizing the pH. Some plants have excess chemical oxygen demand in the effluent. This is not a problem of the separation process, but it is caused by the failure of the regenerant used. Only the replacement of qualified products can solve the problem. From the intersection of sewage and pH standard technology can reduce renewable acid, alkali 20% to 30%, is a pollution enhancement process. This technology not only adapts to the transformation of old equipment, but also to new water treatment projects.
Eight, ammonium nitrate wastewater A / B bed treatment reuse technology Many ammonia companies also produce ammonium nitrate, sodium nitrate, sodium and other products, resulting in a certain amount of nitrate wastewater, pollute the environment. Although the biochemical method can remove ammonium nitrate salt, the investment and processing costs are large. The A/B bed treatment and reuse process can recycle 100% of the ammonium nitrate wastewater, which solves the difficult problem of the trapped enterprise.
The special A/B bed equipment used in this technology can increase the concentration of nitrate in the drainage water by 10 to 30 times, reaching 6% to 10%, which is convenient for recycling. The treated water quality is also in line with the shallow salt water, and the conductivity is <30μs. /cm, can be directly used for boiler replenishment. The cost of using this technology to treat ammonium nitrate salt is only 0.1-0.2 yuan/cubic meter, and the investment is only 1/4 of electrodialysis technology.
Ninth, the end of the treatment of A / SBR short-cut nitrification new process After the source of water treatment drastically reduced, but also the need for small end-processing equipment, in order to ensure that the external drainage standards, and accident drainage. Because the ammonia nitrogen in the sewage is difficult to handle, and the need for adding alkali and methanol nitrification - denitrification need to adjust the water quality, so the processing costs are high. If the conventional ammonia-nitrogen removal process is used, the pharmaceutical agent costs 12-20 yuan/kg of ammonia nitrogen, and the investment is much greater. The A/O method and the improved technology are currently used to treat ammonia-containing nitrogen wastewater. The advantages are that the process is simple and easy to control. The disadvantages are poor impact resistance, large investment, and low total nitrogen removal rate.
The new short-cut nitrification A/SBR process at the end of the process solved the shortcomings of the A/O process and achieved three breakthroughs: First, the dominant bacteria were cultivated and acclimated to adapt to the new short-cut nitrification process, saving 40% of the carbon source and saving 25% of the oxygen. 35% of electricity, less production of sludge 60%, civil construction investment also reduced by 20% to 30%, and reduce the cost of ammonia nitrogen wastewater treatment by more than 30%. Second, the total nitrogen removal rate reached 95% to 98%, which solved the problem that the total nitrogen removal rate of the A/O process could not adapt to the new environmental protection standards. The third is to solve the load shock problem, the selection of dominant bacteria resistant to strong impact on the load, the process and the use of full-volume push-flow mixing, the water intake, water quality dozens of times buffer adjustment, to ensure the stability of the effluent water quality. Due to its low investment, low treatment costs, and good and stable effluent quality, this technology has become one of the latest processes for ammonia nitrogen removal, and was rated as a national key environmental protection technology in 2008 by the China Environmental Protection Industry Association.
X. Wastewater Recycling Treatment Technology Up-to-standard Wastewater Emissions Although environmental protection standards are met, desalination equipment should be considered for reuse. Which technology should be used for reuse should be determined according to the salt content. Only targeted selection can be used after verification. The technology can achieve the desired results. The salt content of wastewater is less than 1000 mg/L. It is recommended to use shallow salt removal technology, reuse investment <20,000 yuan/cubic meter, and effluent discharge rate from 5% to 10%. Because of low water content, it is easily digested by coal ash humidification. Used up, easy to achieve zero emissions. The wastewater containing 1000-1500 mg/L of salt is better than the double-membrane method (ultrafiltration-reverse osmosis). Its disadvantage is that the investment for reuse water is up to 40,000 yuan/cubic meter, the membrane cleaning times are many, and the concentration of concentrated water is high. 30%, there will be a small amount of water outside the row. Salt> 1500 mg / l of wastewater is easy to fouling, dosing and anti-scaling effect is not very good, so the choice of electric adsorption method is better, but the investment up to 70,000 ~ 80,000 yuan / cubic meter backwater, the concentration of the outer row of water Also reaching 30%, it is equally difficult to achieve zero emissions.
Representative Li Nawei (Director of Shandong Sinochem Plain Chemical Group Co., Ltd.):
Plain Chemical Co., formerly known as the Plains Deqilong Chemical Group, produces 1.2 million tons of ammonia and methanol per year. It is a well-known large-scale chemical enterprise at home and abroad.
Our company adopted the source control technology of the Xuzhou Institute of Water Treatment and the tons of ammonia drainage has dropped to the advanced level of 3 to 4 cubic meters. However, due to the large scale of production, the total amount of external drainage still reaches 400 to 500 cubic meters per hour. If conventional treatment processes are used, it is generally necessary to invest hundreds of millions of dollars in treating such large amounts of waste water. Afterwards, our company cooperated with Xuzhou Institute of Water Treatment and divided the whole plant drainage into three major categories according to quality.
For the cooling water with a large amount of water (cooling capacity of 100,000 cubic meters/hour), the water quality has reached the environmental protection standard, and after collection, it is sent to the wastewater treatment plant by pipelines, and only physical treatment is required. Water containing large amounts of pollutants such as ammonia nitrogen and chemical oxygen demand (such as gas recycling, desulfurization, carbonization, etc.) is separately collected and sent to the wastewater treatment plant for in-depth chemical-biological treatment. The biochemical process uses A/SBR. New Technology. For another kind of oily wastewater with less water, a collection-purification treatment process is adopted. The purified wastewater is incorporated into the over-standard sewage for biochemical treatment, and the separated oil can also be exported. Due to the adoption of new processing concepts and technologies, our company's large-scale enterprises have invested only 17 million yuan (2,200 yuan/m3 of water investment per ton), which has achieved the goal of wastewater treatment and wastewater treatment for the whole plant, at least compared with similar enterprises. Save 20 million to 30 million yuan.
The sewage works of our company completed the civil construction in February 2007, and began to be commissioned in May of the same year. The operation was completed on June 10 and it has been running for more than a year. Even if the water temperature is low in winter, there is no phenomenon of excessive drainage. Steady production has played an escort role.
In respect of wastewater treatment indicators, our company's influent chemical oxygen demand is 800-1000 mg/L, ammonia nitrogen 350-500 mg/L, effluent chemical oxygen demand <70 mg/L, ammonia nitrogen ≤ 15 mg/L, total nitrogen ≤ 30 mg/L, which is better than the design standard, reached the first-grade drainage standard for the new environmental protection standards to be implemented in the near future. Especially for the treatment of total nitrogen, we have designed ahead of time. We have accepted the recommendations of the Xuzhou Institute of Water Treatment. We must not only meet the ammonia nitrogen standard, but also make the total nitrogen reach the standard in order to avoid the need to reform the treatment facilities after the implementation of the new standard. In a single step, the results did not increase the amount of investment to make ammonia nitrogen, chemical oxygen demand, total nitrogen removal rate reached 90% to 98%, which is the effect of the old process can not be achieved.
In addition, due to the small amount of groundwater storage in the plant area and the inability to meet production needs, the next step is to prepare the company's wastewater reuse treatment equipment so that the external drainage can be reduced by 70% to 80%, and the reused water resources can be fully utilized.
Yin Yin Xue (Deputy Director of Shandong Feida Chemical Technology Co.):
FeiDa Chemical Group is a large-scale chemical enterprise that produces synthetic ammonia, chemicals, and rubber additives. The plant site is in the key control area of ​​the South-to-North Water Diversion of the East Line. The external water quality requirements are higher than the national standard, and the original sewage treatment equipment is not qualified. Make a change. In order to select partners, our company invited various pollution control units to the factory for technical exchanges on March 28, 2007. After being evaluated by provincial and municipal environmental protection experts, we finally selected the short-cut nitrification of strong bacteria of A/SBR from Xuzhou Institute of Water Treatment. new technology.
The water output of our design is 1,920 cubic meters per day (80 cubic meters per hour); the designed influent water quality is 1,000 milligrams per liter chemical oxygen demand, 600 milligrams ammonia nitrogen, and sulfur ≤ 30 milligrams per liter; the design water quality is chemical Oxygen demand ≤ 60 mg/l, ammonia nitrogen ≤ 15 mg/l, total nitrogen ≤ 30 mg/l, and sulfur <1 mg/l.
Due to poor water quality and high investment, the total investment is 6 million yuan, the investment in tons of water is 6 million ÷ 1920 = 3125 yuan/cubic meter, the sewage treatment cost is actually 1.13 yuan/cubic meter, and the measured water quality is chemical demand. Oxygen content ≤ 50 mg/l, ammonia nitrogen ≤ 5 mg/l, and total nitrogen content <20 mg/l, which is superior to the strictest requirements of the provincial standard and has passed environmental protection acceptance. It is worth mentioning that the process has good load impact resistance, and the water quality and water volume in our factory will fluctuate. For example, the ammonia nitrogen in the influent water will fluctuate between 300 and 1000 mg/l, while the actual treatment of water ammonia and nitrogen will be 10 mg/L, ammonia nitrogen removal rate and total nitrogen removal rate are all > 95%, far superior to other old processes. From the three hard indicators of investment, processing fee, and water quality, it can be seen that the new A/SBR process is a reliable process for ammonia synthesis companies.
He Xinxin (Director of Anhui Sanxing Chemical Company):
Samsung Chemical Co., formerly known as Guoyang Chemical Fertilizer Plant, has developed into a production scale of 230,000 tons of synthetic ammonia per year, 80,000 tons of methanol per year, and 1,300 tons of melamine per year. Our factory is in the upper reaches of the Huaihe River, and its water quality for drainage is very strict. To this end, our factory has adopted the advanced concepts and techniques of pollution control at the Xuzhou Institute of Water Treatment. The drainage and chemical oxygen demand, ammonia and other pollutants have all dropped significantly, and 2 million tons of waste water has been discharged. In 2010, a 100-kilowatt/hour water pump was stopped, and only one power-saving was achieved at 700,000 kWh/year, which resulted in energy savings and emissions reductions. This was the result of adopting advanced technology.
We have adopted the clean and recycling process of separation from the sources, that is, the recovery of spent acid and waste alkali, and the pH value has reached the standard. In addition, the micro-vortex purification process was adopted in the gas recycling water process, and the existing old gas cabinet was reconstructed, thus realizing zero-emission of closed-circuit gas generation and increasing the amount of air-injection.
The content of chemical oxygen demand, ammonia nitrogen, and urea in the raffinate residue and urea analysis residual solution are high. The deep hydrolysis technology requires investment of 4 million to 5 million yuan. After the plant, the deep processing and reuse jacket of Xuzhou Institute of Water Treatment was selected. Process, using desalinated water instead of desalinated water, water saving 170,000 yuan / year, and residual liquid treatment effect is good. The circulating water link adopts the concentration and emission reduction technology of the Xuzhou Institute of Water Treatment. The concentration factor is increased from 2 to 4 and the water saving is obvious. The ammonia drainage is reduced to 2 cubic meters. On the basis of source control, our company has also launched an end-of-sewage treatment project using a new A/SBR process. Influent water quality chemical oxygen demand is 1000 ~ 2000 mg / l, ammonia nitrogen is 200 ~ 400 mg / l, water quality concentration fluctuations. When the designed water output is 80 cubic meters/hour, the effluent quality is COD ≤ 70 mg/L, ammonia nitrogen ≤ 20 mg/L, and total nitrogen ≤ 30 mg/L, which is superior to the first-class external drainage standard and meets the external requirements of the Huaihe River region. Drainage water quality requirements. In addition, since both nitrification and denitrification do not add alkali and methanol, the annual cost of alkali and alkali is RMB 700,000, the cost of wastewater treatment is <1 yuan/cubic meter, the total investment is 5.1 million yuan, and the investment per ton of water is 2600 yuan/cubic meter, only saving. Drainage fees and electricity charges do not require two years to recover the investment.
In short, our company achieved good results in wastewater discharge compliance, pollution control and efficiency enhancement. This is the result of the company's active use of advanced technology from the Xuzhou Institute of Water Treatment, and it is also a result of close cooperation between production companies and environmental research institutes.
Cao Xuebin (Deputy director of Shandong Hengtong Chemical Co., Ltd.):
Hengtong Chemical is a large-scale chemical group that integrates ammonia, co-alcohol, electrolysis chemical industry and power generation. Chemical fertilizer wastewater is the focus of the Group's governance, and the chemical oxygen demand and ammonia nitrogen content of wastewater are high, so governance is imminent.
The current pollution control processes are different. Choosing the right process has a major bearing on the treatment effect, investment costs, and disposal costs. For this reason, our group specially organized a group of inspections and researches to decide which process to use. We investigated a total of four representative processes (see chart).
Through research and sampling and analysis of the water quality back to the factory, it can be clearly seen that the effluent quality of the three companies is basically qualified, and the investment costs vary widely, reaching 5 to 7 times! Processing costs also vary widely. The new A/SBR process of the Xuzhou Institute of Water Treatment not only fully complies with the effluent standards, but also meets the emission requirements of the new environmental protection standards that will be implemented in the near future. More importantly, this technology saves investment and processing costs and is attractive to companies. With the approval of the leaders, we finally chose the new A/SBR process.
The designed water output of the plant is designed at 2,160 cubic meters per day (90 cubic meters per hour), leaving room for future development. Designed to have a chemical oxygen demand of 500 mg/L and ammonia nitrogen of 200 mg/L; designed water quality to be COD ≤ 100 mg/L, ammonia nitrogen ≤ 15 mg/L, total nitrogen ≤ 30 mg/L, granules Suspended material ≤ 50 mg/l.
The treatment plant completed the civil construction at the end of March this year, and it began trial operation on May 28 and was officially put into operation in early July. The actual water intake is 75 m3/h, the influent chemical oxygen demand is 400-600 mg/l, the ammonia nitrogen is 150-220 mg/l, the measured chemical oxygen demand is ≤60 mg/l, and the ammonia nitrogen is 0, Total nitrogen <25. According to actual calculations, the investment was 6.426 million yuan, and the investment per ton of water was 6.426 million ÷ 2160 = 2975 yuan/cubic meter. The cost of treated water is 1.3 to 1.5 yuan/cubic meter. Practice has proved that we have chosen the process to be correct. We have only saved more than RMB 10 million in investment, and discharged 1.2 million cubic meters of wastewater per year. We have discharged less chemical oxygen demand and 600-700 tons of ammonia nitrogen per year. We tasted the rule first. "The source, after treatment of the end" of the sweetness.
Chang Zhengzheng (Director of Henan Xinyang New Energy Company):
Asia New Energy Corporation is a wholly foreign-owned company that produces 150,000 tons of synthetic ammonia per year, 260,000 tons of urea per year, 200,000 tons of methanol per year, and 200,000 tons of dimethyl ether per year. The local environmental protection standards are chemical oxygen demand <50 mg/l and ammonia nitrogen <40 mg/l. To meet environmental protection requirements, we have selected A/SBR short-cut nitrification of Xuzhou Institute of Water Treatment which has many application cases. Process.
The water output of our plant is 1,920 cubic meters per day (80 cubic meters per hour); the designed influent water quality is 150 milligrams per liter chemical oxygen demand, 200 milligrams ammonia nitrogen, and 150 milligrams per liter of suspended particulate matter; the design water quality is Chemical oxygen demand ≤ 50 mg/l, ammonia nitrogen ≤ 20 mg/l, particulate suspended matter ≤ 50 mg/l. The project civil construction was completed on December 15, 2007, and it was commissioned on January 1, 2008 and reached the standard on January 21. Due to the selection of dominant bacteria, the commissioning took only 20 days to achieve water compliance. From January 21 to January 30, 2008, the chemical oxygen demand of the effluent was between 41 and 47 mg/L for a continuous measurement for 10 days. The fluctuation was small; the ammonia nitrogen was between 18 and 22 mg/L, and the water quality was good. Very stable. The total investment for the project is 4.82 million yuan, and the investment for tons of water is 4.82 million yuan for 1920=2510 yuan/cubic meter, and the treatment water cost is 1.2 to 1.5 yuan/cubic meter, all reaching the design value.
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