CN109248564B - Recycling device and process for coarse ammonia water generated by acidic water treatment device of petrochemical refinery - Google Patents
Recycling device and process for coarse ammonia water generated by acidic water treatment device of petrochemical refinery Download PDFInfo
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- CN109248564B CN109248564B CN201811359123.9A CN201811359123A CN109248564B CN 109248564 B CN109248564 B CN 109248564B CN 201811359123 A CN201811359123 A CN 201811359123A CN 109248564 B CN109248564 B CN 109248564B
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Abstract
本发明提供了一种粗氨水的回收利用装置，包括：酸性水汽提装置；与所述酸性水汽提装置的粗氨水出口相连接的粗氨水沉降装置；与所述粗氨水沉降装置出口相连接的初级过滤器；与所述初级过滤器出口相连接的粗氨水精制罐；与所述粗氨水精制罐出口相连接的精制过滤器；与所述精制过滤器出口相连接的SNCR烟气脱硝系统。本发明将酸性水汽提装置蒸出的粗氨水用于锅炉系统SNCR烟气脱硝工艺中，既解决了上述粗氨水的处理难题，减少了环境污染和外委处理的成本，同时也降低了锅炉SNCR工艺脱硝剂氨水的原料成本，给原有SNCR烟气脱硝工艺中提供了所需要的大量氨水，达到了环保与效益共赢的可持续发展理念。
The invention provides a recovery and utilization device for crude ammonia water, comprising: an acid water stripping device; a crude ammonia water sedimentation device connected with the crude ammonia water outlet of the acid water stripping device; and a crude ammonia water sedimentation device connected with the outlet of the crude ammonia water sedimentation device A primary filter; a crude ammonia water purification tank connected to the outlet of the primary filter; a refined filter connected to the outlet of the crude ammonia water purification tank; an SNCR flue gas denitration system connected to the outlet of the refined filter. In the invention, the crude ammonia water distilled from the acid water stripping device is used in the SNCR flue gas denitration process of the boiler system, which not only solves the above-mentioned processing problem of the crude ammonia water, reduces the environmental pollution and the cost of outsourced treatment, but also reduces the boiler SNCR The raw material cost of ammonia water, the process denitrification agent, provides a large amount of ammonia water required in the original SNCR flue gas denitration process, achieving the sustainable development concept of environmental protection and win-win results.
Description
Technical Field
The invention belongs to the technical field of recycling of crude ammonia water generated by an acid water treatment device, relates to a device and a process for recycling crude ammonia water, and particularly relates to a device and a process for recycling crude ammonia water generated by an acid water treatment device of a petrochemical refinery.
Background
The acidic water of petrochemical refinery is one of the most common wastewater of petrochemical refinery enterprises, because sulfur-containing compounds and nitrogen-containing compounds exist in petroleum and its products, in the processing processes of atmospheric and vacuum distillation, catalytic cracking, thermal cracking, delayed coking, reforming pre-hydrogenation, hydrorefining, hydrocracking and the like, the compounds can generate sulfur-containing compounds and nitrogen-containing compounds through reactions such as high-temperature cracking, catalytic hydrogenation and the like, and enter product streams, and the product streams are subjected to condensation dehydration or water washing treatment to generate sulfur-containing and ammonia-containing wastewater, commonly called sulfur-containing wastewater or acidic water. The acidic water is generated in equipment such as an atmospheric and vacuum distillation tower top separator, a catalytic cracking fractionating tower top separator, a catalytic cracking compressed rich gas dehydration tank, a coking fractionating tower top separator, a high-pressure separator and a low-pressure separator for oil product hydrocracking and hydrofining, pollutants in the acidic water comprise oil, phenol, cyanogen and the like besides hydrogen sulfide and ammonia, and the concentration of sulfide and ammonia in the acidic water is changed along with the types of crude oil and different processing devices. Acidic waters produced by petrochemical refineries are generally divided into: non-phenolic acid water, phenolic acid water and desalter acid water.
Based on the development concept of green environmental protection, the acidic water contains a large amount of ammonia and hydrogen sulfide, and other impurities and organic matters. Is absolutely not allowed to be discharged, so it must be subsequently processed. Except for the acidic water in the desalting tank, the acidic water is subjected to acidic water stripping process flow mainly comprising a single-tower low-pressure stripping process, a double-tower pressurized stripping process and a single-tower pressurized extraction stripping process in the conventional treatment process at present. Among these, most of the stripping apparatuses distill off ammonia and hydrogen sulfide in sour water, and one of the materials is crude ammonia gas (crude ammonia water) with a low content of hydrogen sulfide. In order to avoid secondary pollution, part of factories adopt an ammonia burning process or a water absorption process to prepare crude ammonia water to process the crude gas ammonia, and part of factories adopt an ammonia refining process. The ammonia burning process is to burn a large amount of ammonia gas, which not only causes the waste of resources, but also generates a large amount of NOXWaste gas and environmental pollution. In the water absorption process, crude ammonia gas is absorbed by water, and about 20% of the produced crude ammonia water contains hydrogen sulfide, so that the utilization value is not high, and the crude ammonia water needs to be treated by outsourcing.
Therefore, how to find a suitable method for treating the crude ammonia water after the acidic water is stripped so as to enable the crude ammonia water to be better recycled becomes one of the problems to be solved by many related enterprises in the industry.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a device and a process for recycling a crude ammonia water, in particular, a device and a process for recycling a crude ammonia water generated by an acid water treatment device of a petrochemical refinery. According to the recycling device and the process, the coarse ammonia water stripped by the acidic water is used for the SNCR flue gas denitration process of the boiler system after being treated, so that the problem of treatment of the coarse ammonia water is solved, the raw material cost of the boiler flue gas denitration process is greatly reduced, and meanwhile, the process route is simple and is suitable for industrial mass production.
The invention provides a device for recycling crude ammonia water, which comprises: an acid water stripping unit;
the crude ammonia water sedimentation device is connected with a crude ammonia water outlet of the acid water stripping device;
the primary filter is connected with the outlet of the coarse ammonia water settling device;
the coarse ammonia water refining tank is connected with the outlet of the primary filter;
the refining filter is connected with the outlet of the coarse ammonia water refining tank;
and the SNCR flue gas denitration system is connected with the outlet of the refining filter.
Preferably, the sour water stripping apparatus comprises a sour water stripper;
the crude ammonia water settling device comprises a crude ammonia water settling tank;
an overflow plate is arranged in the coarse ammonia water settling device;
the coarse ammonia water settling device is provided with a water inlet;
the crude ammonia water settling device comprises a first crude ammonia water settling device and a second crude ammonia water settling device which are arranged in parallel.
Preferably, the overflow plate is arranged along the height direction of the crude ammonia water settling device;
the crude ammonia water settling device is provided with an inlet and an outlet which are arranged from bottom to top;
the primary filter comprises one or more of a basket filter, a cartridge filter, and a self-cleaning filter;
the precision of the primary filter is 150-300 mu m.
Preferably, the recycling device further comprises a reflux mixing device;
the crude ammonia water outlet of the acidic water stripping device is connected with the first inlet of the reflux mixing device;
the outlet of the coarse ammonia water settling device is connected with the second inlet of the reflux mixing device;
the outlet of the reflux mixing device is connected with the inlet of the coarse ammonia water settling device;
and an overflow plate is arranged in the coarse ammonia water refining tank.
Preferably, the backflow mixing device comprises one or more of a pipeline mixer, a vortex mixer, a gas-liquid mixer and a static mixer;
the overflow plate is arranged along the height direction of the coarse ammonia water refining tank;
the coarse ammonia water refining tank is provided with an inlet and an outlet which are arranged from bottom to top;
the SNCR flue gas denitration system connected with the outlet of the refining filter is specifically as follows: and an ammonia water inlet of the SNCR flue gas denitration system is connected with an outlet of the refined filter.
Preferably, the polishing filter comprises one or more of a precision filter, a sintered mesh filter, and a metal-wound wire filter;
the precision of the refined filter is 50-100 mu m;
the SNCR flue gas denitration system comprises an SNCR flue gas denitration system of a coal-water slurry boiler;
and an ammonia water inlet of the SNCR flue gas denitration system is connected with an ammonia water aerial fog spray head of the SNCR flue gas denitration system.
The invention also provides a process for recycling the coarse ammonia water, which comprises the following steps:
1) settling the crude ammonia water evaporated by the acidic water stripping process to obtain settled crude ammonia water;
2) primarily filtering the settled crude ammonia water obtained in the step to obtain a secondary product;
3) refining and settling the two-step product obtained in the above step to obtain a three-step product;
4) and refining and filtering the three-step product obtained in the step to obtain refined ammonia water, and feeding the refined ammonia water into an SNCR flue gas denitration process for recycling.
Preferably, the sour water comprises sour water produced by a petrochemical refinery;
the crude ammonia water comprises, by mass, 15% -25% of ammonia gas, 0.5% -2% of hydrogen sulfide, 1% -10% of suspended matters, 0.01% -0.1% of volatile phenol and 65% -85% of water;
the COD content in the crude ammonia water is 18000-35000 mg/L;
the settling further comprises the step of diluting with water;
the settling time is 20-60 h;
the temperature of the sedimentation is 30-40 ℃.
Preferably, the step 1) is specifically:
11) mixing the crude ammonia water evaporated by the acidic water stripping process and a part of the precipitated crude ammonia water to obtain a mixture;
12) settling the mixture obtained in the step to obtain settled crude ammonia water;
13) and refluxing a part of the settled crude ammonia water to the mixing step, and allowing the other part of the settled crude ammonia water to enter the subsequent step.
Preferably, the reflux ratio of the reflux is (2-4): 1;
the refining and settling time is 20-60 h;
the temperature of the refining sedimentation is 22-30 ℃;
the SNCR flue gas denitration process is specifically an SNCR flue gas denitration gas-spray ammonia spraying process.
The invention provides a device for recycling crude ammonia water, which comprises: an acid water stripping unit; the crude ammonia water sedimentation device is connected with a crude ammonia water outlet of the acid water stripping device; the primary filter is connected with the outlet of the coarse ammonia water settling device; the coarse ammonia water refining tank is connected with the outlet of the primary filter; the refining filter is connected with the outlet of the coarse ammonia water refining tank; and the SNCR flue gas denitration system is connected with the outlet of the refining filter. Compared with the prior art, the method provided by the invention can be used for treating the part of crude gas ammonia by adopting an ammonia burning process or a water absorption process to prepare crude ammonia water aiming at acidic water containing a large amount of ammonia and hydrogen sulfide evaporated by a stripping device commonly used in petroleum refining. The ammonia burning process not only causes the waste of resources, but also generates a large amount of NOXWaste gas and environmental pollution; the crude ammonia water with the concentration of about 20 percent generated by the water absorption process has a plurality of defects of low utilization value, need of outsourcing treatment and the like because the crude ammonia water contains hydrogen sulfide.
The invention creatively uses the coarse ammonia water evaporated by the acidic water stripping device in the SNCR flue gas denitration process of the boiler system, thereby not only solving the difficult problem of the treatment of the coarse ammonia water, reducing the environmental pollution and the outsourcing treatment cost, but also reducing the raw material cost of the denitration agent ammonia water of the SNCR process of the boiler, providing a large amount of ammonia water required in the original SNCR flue gas denitration process, and achieving the sustainable development concept of win-win environment and benefits.
The invention more creatively carries out a series of specific treatments on the coarse ammonia water evaporated by the acid water stripping device, so that the coarse ammonia water can be used in the SNCR flue gas denitration process of the coal water slurry boiler system, and a large amount of treated coarse ammonia water is injected into the boiler and is used together with NOXReacting to generate nitrogen, thereby reducing NO in the boiler flue gasXThe cost of purchasing ammonia water with the concentration of more than 20 percent in the prior SNCR flue gas denitration process is saved. The invention obtains the coarse ammonia water with the concentration of 20 percent after diluting the purified water generated by acidic water stripping, and simultaneously filters impurities by selecting a filter after carrying out double-tank replacement and sedimentation treatment on the coarse ammonia water, further improves the quality of the coarse ammonia water, and then carries out the purification treatment on the coarse ammonia waterAnd recovering the ammonia water into a crude ammonia water refining tank, refining and filtering again to obtain the ammonia water for boiler denitration.
Experimental results show that the device and the process for recycling the coarse ammonia water provided by the invention replace purchased ammonia water, so that the treatment problem of acidic water for extracting the coarse ammonia water is solved, the purchasing cost of the ammonia water for denitration is reduced, the environment-friendly emission is achieved, and the energy consumption cost can be saved.
Drawings
Fig. 1 is a schematic diagram of a main process flow of a device for recycling crude ammonia water generated by a petrochemical refinery acidic water treatment device provided by the invention.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention and are not intended to limit the invention to the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the invention are not particularly limited in purity, and the invention preferably adopts industrial pure or conventional purity required by raw materials of SNCR flue gas denitration process of a water-coal slurry boiler system.
All the noun expressions and acronyms of the invention belong to the conventional noun expressions and acronyms in the field, each noun expression and acronym is clearly and definitely clear in the relevant application field, and a person skilled in the art can clearly, exactly and uniquely understand the noun expressions and acronyms.
The invention provides a device for recycling crude ammonia water, which comprises: an acid water stripping unit;
the crude ammonia water sedimentation device is connected with a crude ammonia water outlet of the acid water stripping device;
the primary filter is connected with the outlet of the coarse ammonia water settling device;
the coarse ammonia water refining tank is connected with the outlet of the primary filter;
the refining filter is connected with the outlet of the coarse ammonia water refining tank;
and the SNCR flue gas denitration system is connected with the outlet of the refining filter.
The connection mode is not particularly limited by the present invention, and may be a conventional connection mode in the art, which is well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to the actual production situation, the raw material situation and the product requirement, and the connection mode is preferably connected by a pipeline, or connected by a pipeline and a pump. The invention is not particularly limited to the relevant control and monitoring equipment on the pipeline, and those skilled in the art can select and adjust the equipment according to the actual production conditions, raw material conditions and product requirements.
The acidic water stripping device and the specific structure thereof are not particularly limited, and the acidic water stripping device and the specific structure thereof are conventional acidic water stripping devices and structures in the process known by the skilled in the art, and the skilled in the art can select and adjust the acidic water stripping device according to the actual production situation, the raw material situation and the product requirement.
The crude ammonia water settling device is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, raw material conditions and product requirements.
The invention has no particular limitation on the internal structure of the coarse ammonia water settling device in principle, and a person skilled in the art can select and adjust the settling device according to the actual production condition, the raw material condition and the product requirement. The crude ammonia water settling device preferably has an inlet and an outlet which are arranged from bottom to top.
In order to better realize impurity removal of coarse ammonia water with complex components, simultaneously realize removal of upper-layer suspended matters and lower-layer precipitates and simultaneously facilitate subsequent application, the coarse ammonia water settling device is preferably provided with a water inlet, and more preferably provided with a water inlet at the upper part of the coarse ammonia water settling device. The effect of the device is that the dilution effect is realized in the sedimentation process, and meanwhile, the upper part of the device is provided with the water inlet, so that the device is more beneficial to the effective separation of various light and heavy impurities in the sedimentation process of the crude ammonia water.
In order to better integrate and refine the whole equipment flow and be more beneficial to continuous large-scale production in actual industry, the crude ammonia water settling device preferably comprises a first crude ammonia water settling device and a second crude ammonia water settling device which are arranged in parallel, namely a first crude ammonia water settling tank and a second crude ammonia water settling tank which are preferably arranged in parallel, so that a continuous production mode of double-tank replacement and sedimentation is realized.
The invention also comprises a primary filter connected with the outlet of the coarse ammonia water settling device. The invention is not limited in principle to the type and precision of the primary filter, and can be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, and the invention is to better remove various components by removing the coarse ammonia water with complicated components, and the primary filter preferably comprises one or more of a basket filter, a cylinder filter and a self-cleaning filter, and more preferably, the basket filter, the cylinder filter or the self-cleaning filter. The precision of the primary filter is preferably 150-300 μm, more preferably 180-280 μm, and more preferably 200-250 μm.
In order to better realize the impurity removal of the coarse ammonia water with complex components, improve the treatment effect, better integrate and refine the whole equipment flow and be more beneficial to continuous large-scale production in the actual industry, the recycling device preferably further comprises a reflux mixing device. Wherein, a crude ammonia water outlet of the acidic water stripping device is connected with a first inlet of the reflux mixing device; the outlet of the coarse ammonia water settling device is connected with the second inlet of the reflux mixing device; and the outlet of the reflux mixing device is connected with the inlet of the coarse ammonia water settling device.
The invention is not particularly limited in principle to the type of the reflux mixing device, and a person skilled in the art can select and adjust the reflux mixing device according to the actual production situation, the raw material situation and the product requirement, in order to better realize the impurity removal of coarse ammonia water with complex components and realize the effect of reflux treatment, the reflux mixing device preferably comprises one or more of a pipeline mixer, a vortex mixer, a gas-liquid mixer and a static mixer, and more preferably comprises the pipeline mixer, the vortex mixer, the gas-liquid mixer or the static mixer.
The invention has no particular limitation on the internal structure of the coarse ammonia water refining tank in principle, and a person skilled in the art can select and adjust the internal structure according to the actual production condition, the raw material condition and the product requirement. The coarse ammonia water refining tank preferably has an inlet and an outlet which are arranged from bottom to top.
The invention also comprises a refining filter connected with the outlet of the coarse ammonia water refining tank. The present invention is not particularly limited in its type and precision in principle, and can be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, and in order to achieve precise removal of the remaining components by removing the coarse ammonia water with complicated components, the refined filter preferably includes one or more of a precision filter, a sintered mesh filter and a metal-wound wire filter, and more preferably a precision filter, a sintered mesh filter or a metal-wound wire filter. The precision of the refined filter is preferably 50 to 100 μm, more preferably 60 to 90 μm, and still more preferably 70 to 80 μm.
The invention also comprises an SNCR flue gas denitration system connected with the outlet of the refining filter. The specific procedures of the SNCR flue gas denitration system are not particularly limited, and the conventional procedures of the SNCR flue gas denitration system known by the technical personnel in the field can be adopted, and the technical personnel in the field can select and adjust the SNCR flue gas denitration system according to the actual production condition, the raw material condition and the product requirement. And the ammonia water inlet of the SNCR flue gas denitration system is preferably connected with an ammonia water aerial fog spray head of the SNCR flue gas denitration system, namely is connected with the ammonia water aerial fog spray head in the boiler. In the invention, the ammonia water aerial fog nozzle is also connected with a pipeline for charging air.
The invention also provides a process for recycling the coarse ammonia water, which comprises the following steps:
1) settling the crude ammonia water evaporated by the acidic water stripping process to obtain settled crude ammonia water;
2) primarily filtering the settled crude ammonia water obtained in the step to obtain a secondary product;
3) refining and settling the two-step product obtained in the above step to obtain a three-step product;
4) and refining and filtering the three-step product obtained in the step to obtain refined ammonia water, and feeding the refined ammonia water into an SNCR flue gas denitration process for recycling.
The selection and composition of the equipment required in the process for recycling the crude ammonia water, and the corresponding preferred principle of the invention can correspond to the selection and composition of the equipment corresponding to the crude ammonia water recycling device, and the corresponding preferred principle, and are not described in detail herein.
The method comprises the steps of firstly settling the crude ammonia water evaporated by the acidic water stripping process to obtain the settled crude ammonia water.
The specific parameters of the crude ammonia water are not particularly limited in principle, and the conventional proportion of the crude ammonia water evaporated by the acidic water stripping process known to those skilled in the art can be selected and adjusted by those skilled in the art according to the actual production condition, the raw material condition and the product requirement.
The crude ammonia water specifically comprises, by mass, 15% -25% of ammonia gas, 0.5% -2% of hydrogen sulfide, 1% -10% of suspended matters, 0.01% -0.1% of volatile phenol and 65% -85% of water. Wherein the content of ammonia gas is more specifically 17-23%, more specifically 19-21%. The content of hydrogen sulfide is more specifically 0.8% to 1.8%, more specifically 1.0% to 1.5%. The content of suspended matter is more particularly between 3% and 8%, more particularly between 5% and 6%. The content of volatile phenol is more specifically 0.03% -0.08%, more specifically 0.05% -0.06%. The water content is more specifically 67% to 83%, more specifically 70% to 80%, more specifically 72% to 78%. The COD content in the crude ammonia water is specifically 18000-35000 mg/L, more specifically 20000-33000 mg/L, more specifically 23000-30000 mg/L, more specifically 25000-28000 mg/L.
The settling conditions are not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, raw material conditions and product requirements, the settling time is preferably 20-60 hours, more preferably 25-55 hours, more preferably 30-50 hours, and more preferably 35-45 hours, so that the settling effect is better improved, the content of various impurities in the crude ammonia water is reduced, and the settling time is better used in the subsequent SNCR flue gas denitration process of a boiler. The settling temperature is preferably 30-40 ℃, more preferably 32-38 ℃, and more preferably 34-36 ℃.
The invention aims to better realize the impurity removal of coarse ammonia water with complex components, simultaneously realize the removal of upper suspended matters and lower precipitates and is beneficial to subsequent application, and the precipitation also comprises a step of diluting with water, more particularly preferably diluting with purified water generated by acidic water stripping. The method not only can realize the dilution effect in the sedimentation process, but also is more beneficial to the effective separation of various light and heavy impurities in the sedimentation process of the crude ammonia water.
In order to better realize the impurity removal of coarse ammonia water with complex components, improve the treatment effect, better integrate and refine the whole equipment flow and be more beneficial to continuous large-scale production in actual industry, the step 1) of the invention is specifically as follows:
11) mixing the crude ammonia water evaporated by the acidic water stripping process and a part of the precipitated crude ammonia water to obtain a mixture;
12) settling the mixture obtained in the step to obtain settled crude ammonia water;
13) and refluxing a part of the settled crude ammonia water to the mixing step, and allowing the other part of the settled crude ammonia water to enter the subsequent step.
The invention preferably provides a reflux mixing process, wherein one part of the settled crude ammonia water is refluxed to the mixing step, namely 11), and the other part of the settled crude ammonia water enters the subsequent step, namely 2), so that the settling effect is better improved, and the industrial continuous production is more facilitated. The mixing mode of the invention preferably comprises one or more of pipeline mixing, vortex mixing, gas-liquid mixing and static mixing, and more preferably pipeline mixing, vortex mixing, gas-liquid mixing or static mixing.
The reflux ratio of the reflux is not particularly limited in principle, and a person skilled in the art can select and adjust the reflux ratio according to actual production conditions, raw material conditions and product requirements, so that the reflux mixing effect is better improved, the sedimentation effect is further improved, the industrial continuous production is more facilitated, and the reflux ratio of the reflux is preferably (2-4): 1, more preferably (2.2 to 3.8): 1, more preferably (2.5 to 3.5): 1, more preferably (2.7 to 3.3): 1.
the invention then primarily filters the settled crude ammonia water obtained in the above steps to obtain a two-step product.
The mode and precision of the primary filtration are not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, and the primary filtration mode preferably comprises one or more of basket filtration, cylinder filtration and self-cleaning filtration, and more preferably comprises basket filtration, cylinder filtration or self-cleaning filtration, so as to remove various components in order to better remove impurity of coarse ammonia water with complicated components. The precision of the primary filtration is preferably 150-300 μm, more preferably 180-280 μm, and more preferably 200-250 μm.
The two-step product obtained in the above-mentioned step is refined and settled to obtain three-step product.
The refining and settling conditions are not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, raw material conditions and product requirements, the secondary refining and settling effect is better improved, the content of various trace impurities in crude ammonia water is reduced, the secondary refining and settling time is preferably 20-60 hours, more preferably 25-55 hours, more preferably 30-50 hours, and more preferably 35-45 hours, and the secondary refining and settling time is preferably used in a subsequent boiler SNCR flue gas denitration process. The temperature of the refining sedimentation is preferably 22-30 ℃, more preferably 24-28 ℃, and more preferably 25-27 ℃.
Finally, refining and filtering the three-step product obtained in the step to obtain refined ammonia water, and feeding the refined ammonia water into an SNCR flue gas denitration process for recycling.
The mode and precision of the refined filtration are not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, raw material conditions and product requirements, and in order to better realize precise impurity removal of coarse ammonia water with complex components and precise removal of the rest components, the mode of the refined filtration preferably comprises one or more of precise filtration, sintered mesh filtration and metal wound wire filtration, and more preferably, the mode of the refined filtration, the sintered mesh filtration or the metal wound wire filtration. The precision of the refined filter is preferably 50 to 100 μm, more preferably 60 to 90 μm, and still more preferably 70 to 80 μm.
In order to better realize the application of the coarse ammonia water, the SNCR flue gas denitration process preferably refers to an SNCR flue gas denitration process of a coal-water slurry boiler. The SNCR flue gas denitration process is particularly preferably an SNCR flue gas denitration aerosol ammonia spraying process.
Referring to fig. 1, fig. 1 is a schematic diagram of a main process flow of a device for recycling crude ammonia water generated by a petrochemical refinery acidic water treatment device provided by the present invention. Wherein A is acid water, B is ammonia gas, C is purified water, and D is purified air; 1. acid water stripper, 2, mixer, 3, crude ammonia water tank (1), 4, crude ammonia water tank (2), 5, crude ammonia water pump (1), 6, crude ammonia water pump (2), 7, filter (1), 8, arginine water tank (1), 9, arginine water pump, 10, filter (2), 11, spray gun, 12, boiler.
The invention provides a device and a process for recycling coarse ammonia water generated by an acid water treatment device of a petrochemical refinery, wherein the coarse ammonia water evaporated by an acid water stripping device is used in an SNCR (selective non-catalytic reduction) flue gas denitration process of a boiler system, so that the treatment problem of the coarse ammonia water is solved, the environmental pollution and the outsourcing treatment cost are reduced, the raw material cost of a denitration agent ammonia water of the SNCR process of the boiler is reduced, a large amount of ammonia water required in the original SNCR flue gas denitration process is provided, and the sustainable development concept of win-win environment protection and benefits is achieved.
The invention more creatively carries out a series of specific treatments on the coarse ammonia water evaporated by the acid water stripping device, so that the coarse ammonia water can be used in the SNCR flue gas denitration process of the coal water slurry boiler system, and a large amount of treated coarse ammonia water is injected into the boiler and is used together with NOXReacting to generate nitrogen, thereby reducing NO in the boiler flue gasXThe cost of purchasing ammonia water with the concentration of more than 20 percent in the prior SNCR flue gas denitration process is saved. The method comprises the steps of diluting purified water generated by acidic water stripping to obtain coarse ammonia water with the concentration of 20%, carrying out double-tank replacement, sedimentation and dilution treatment on the coarse ammonia water at a specific structure and an inlet and outlet position, preferably further improving the sedimentation effect by adopting a backflow mixing device, selecting a filter to filter impurities, recovering the coarse ammonia water into a coarse ammonia water refining tank at the specific structure and the inlet and outlet position after further improving the quality of the coarse ammonia water, refining and filtering again to obtain the ammonia water for boiler denitration. The experimental result shows that the device and the process for recycling the crude ammonia water provided by the invention replace the purchased ammonia water,the treatment problem of acid water stripping coarse ammonia water is solved, the purchase cost of ammonia water for denitration is reduced, environment-friendly emission is achieved, and energy consumption cost can be saved.
In order to further illustrate the present invention, the following will describe in detail a device and a process for recycling crude ammonia water provided by the present invention with reference to the following examples, but it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and specific operation procedures are given, which are only for further illustrating the features and advantages of the present invention, but not for limiting the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
Referring to fig. 1, fig. 1 is a schematic diagram of a main process flow of a device for recycling crude ammonia water generated by a petrochemical refinery acidic water treatment device provided by the present invention.
The device for recycling the coarse ammonia water comprises an acid water stripping tower, a reflux mixing device, a first coarse ammonia water settling tank, a second coarse ammonia water settling tank, a primary filter, a coarse ammonia water refining tank, a refining filter and a water-coal-slurry boiler.
Wherein, the coarse ammonia water export of acid water stripping tower is connected with the import of backflow mixing device, and backflow mixing device's coarse ammonia export is connected with first coarse ammonia water settling cask and second coarse ammonia water settling cask respectively, and parallelly connected setting between first coarse ammonia water settling cask and the second coarse ammonia water settling cask.
Be provided with the water inlet in first coarse ammonia water settling cask and the coarse ammonia water settling cask of second respectively to be provided with the overflow plate in the middle of the jar body on the direction of height, simultaneously, first coarse ammonia water settling cask and the coarse ammonia water settling cask bottom of second are provided with the exit of coarse ammonia water, and both subtend sets up, and the lower business turn over of realization coarse ammonia water is gone out down.
The crude ammonia water outlets of the first crude ammonia water settling tank and the second crude ammonia water settling tank are respectively connected with a first feed inlet and a second feed inlet of the reflux mixing device and also connected with a feed inlet of a primary filter (with the precision of 300 mu m). The discharge hole of the primary filter is connected with the feed inlet of a coarse ammonia water refining tank, the discharge hole of the coarse ammonia water refining tank is connected with the feed inlet of a refining filter (the precision is 100 mu m), and the discharge hole of the refining filter is directly connected with a spray head of an ammonia water spraying system of an SNCR flue gas denitration system in a coal water slurry boiler.
Acidic water produced by petrochemical refinery is subjected to acidic water stripping process to evaporate crude ammonia water (flow: 14000 m)3H, temperature: feeding into reflux mixing device at 100 deg.C and 0.2Mpa, settling in first and/or second coarse ammonia water settling tanks, and stripping with acidic water to obtain purified water (purified water flow of 30 m)3H, temperature: 35 ℃ and 0.45Mpa) and the crude ammonia water is mixed and diluted with steam and water, the temperature is controlled at 40 ℃, and the crude ammonia water after sedimentation is obtained after 30 hours.
Wherein, the crude ammonia water comprises 25 percent of ammonia gas, 2 percent of hydrogen sulfide, 7.9 percent of suspended matters, 0.1 percent of volatile phenol and 65 percent of water according to the mass percentage; the COD content was 35000 mg/L.
After sedimentation, the suspended matter in the crude ammonia water is reduced to about 3%.
The crude ammonia water that the reflux mixing device came out can subside through first crude ammonia water settling cask, also can subside through second crude ammonia water settling cask, also can simultaneously through first crude ammonia water settling cask and second crude ammonia water settling cask. The two are arranged in parallel and can be switched, the treatment capacity can be improved, the continuous sedimentation process is realized, and meanwhile, the process control and maintenance are facilitated.
And (3) allowing one part of the coarse ammonia water subjected to sedimentation in the first coarse ammonia water sedimentation tank and the second coarse ammonia water sedimentation tank to enter a primary filter with the precision of 300 mu m, and allowing the other part of the coarse ammonia water to flow back to a backflow mixing device, wherein the backflow ratio is (2-4): 1, enhancing the treatment effect. And refining and settling the two-step product (suspended matters are reduced to about 1%) subjected to primary filtration at 35 ℃ for 24 hours to obtain a three-step product. Then after the crude ammonia water is refined and filtered with the precision of 100 mu m, the content of suspended substances in the crude ammonia water is reduced to about 0.05 percent, the COD content is 8000-10000 mg/L, and the temperature is as follows: the denitration agent is directly injected into a boiler spray gun at the temperature of 30 ℃ and the pressure of 0.4Mpa to achieve the aim of removing the nitrogen oxides in the boiler flue gas.
By counting the technical scheme provided by the invention, the ammonia water amount can be saved by 15-20% and can be saved by 200kg/h, and the smoke gas amount of a 35t/h coal water slurry boiler is 100000m3The concentration of nitrogen oxides in the boiler flue gas is 600mg/m3Reduced to 100mg/m3And the purchase cost of the ammonia water is saved by 350 ten thousand yuan per year through calculation. Meanwhile, the corresponding treatment cost of the crude ammonia water is also reduced.
Example 2
Referring to fig. 1, fig. 1 is a schematic diagram of a main process flow of a device for recycling crude ammonia water generated by a petrochemical refinery acidic water treatment device provided by the present invention.
The device for recycling the coarse ammonia water comprises an acid water stripping tower, a reflux mixing device, a first coarse ammonia water settling tank, a second coarse ammonia water settling tank, a primary filter, a coarse ammonia water refining tank, a refining filter and a water-coal-slurry boiler.
Wherein, the coarse ammonia water export of acid water stripping tower is connected with the import of backflow mixing device, and backflow mixing device's coarse ammonia export is connected with first coarse ammonia water settling cask and second coarse ammonia water settling cask respectively, and parallelly connected setting between first coarse ammonia water settling cask and the second coarse ammonia water settling cask.
Be provided with the water inlet in first coarse ammonia water settling cask and the coarse ammonia water settling cask of second respectively to be provided with the overflow plate in the middle of the jar body on the direction of height, simultaneously, first coarse ammonia water settling cask and the coarse ammonia water settling cask bottom of second are provided with the exit of coarse ammonia water, and both subtend sets up, and the lower business turn over of realization coarse ammonia water is gone out down.
The crude ammonia water outlets of the first crude ammonia water settling tank and the second crude ammonia water settling tank are respectively connected with a first feed inlet and a second feed inlet of the reflux mixing device and also connected with a feed inlet of a primary filter (with the precision of 200 mu m). The discharge hole of the primary filter is connected with the feed inlet of a coarse ammonia water refining tank, the discharge hole of the coarse ammonia water refining tank is connected with the feed inlet of a refining filter (with the precision of 80 microns), and the discharge hole of the refining filter is directly connected with a spray head of an ammonia water spraying system of an SNCR flue gas denitration system in a coal water slurry boiler.
Acidic water produced by petrochemical refinery is treated byAfter the acidic water stripping process, crude ammonia water is distilled out (flow: 14000 m)3H, temperature: feeding into reflux mixing device at 100 deg.C and 0.2Mpa, settling in first and/or second coarse ammonia water settling tanks, and stripping with acidic water to obtain purified water (purified water flow rate of 35 m)3H, temperature: 33 ℃ and the pressure of 0.45Mpa) and the crude ammonia water is mixed and diluted, the temperature is controlled at 35 ℃ and the crude ammonia water after sedimentation is obtained after 36 hours.
Wherein, the crude ammonia water comprises 25 percent of ammonia gas, 2 percent of hydrogen sulfide, 7.9 percent of suspended matters, 0.1 percent of volatile phenol and 65 percent of water according to the mass percentage; the COD content was 35000 mg/L.
After sedimentation, the suspended matter in the crude ammonia water is reduced to about 2.8%.
The crude ammonia water that the reflux mixing device came out can subside through first crude ammonia water settling cask, also can subside through second crude ammonia water settling cask, also can simultaneously through first crude ammonia water settling cask and second crude ammonia water settling cask. The two are arranged in parallel and can be switched, the treatment capacity can be improved, the continuous sedimentation process is realized, and meanwhile, the process control and maintenance are facilitated.
And (3) allowing one part of the coarse ammonia water subjected to sedimentation in the first coarse ammonia water sedimentation tank and the second coarse ammonia water sedimentation tank to enter a primary filter with the precision of 150-300 mu m, and allowing the other part of the coarse ammonia water to flow back to a backflow mixing device, wherein the backflow ratio is (2-4): 1, enhancing the treatment effect. And (3) refining and settling the two-step product (suspended matters are reduced to about 1%) subjected to primary filtration at 33 ℃ for 24 hours to obtain a three-step product. And then refining and filtering the ammonia water with the precision of 80 mu m, reducing the content of crude ammonia water suspended matters to about 0.04 percent, the COD content is 6000-8000 mg/L, and the temperature is as follows: the denitration agent is directly injected into a boiler spray gun at the temperature of 28 ℃ and the pressure of 0.4Mpa to achieve the aim of removing the nitrogen oxides in the boiler flue gas.
By counting the technical scheme provided by the invention, the ammonia water amount can be saved by 15-20% and can be saved by 200kg/h, and the smoke gas amount of a 35t/h coal water slurry boiler is 100000m3The concentration of nitrogen oxides in the boiler flue gas is 600mg/m3Reduced to 100mg/m3And the purchase cost of the ammonia water is saved by 350 ten thousand yuan per year through calculation. While also reducingThe corresponding treatment cost of the crude ammonia water is saved.
Example 3
Referring to fig. 1, fig. 1 is a schematic diagram of a main process flow of a device for recycling crude ammonia water generated by a petrochemical refinery acidic water treatment device provided by the present invention.
The device for recycling the coarse ammonia water comprises an acid water stripping tower, a reflux mixing device, a first coarse ammonia water settling tank, a second coarse ammonia water settling tank, a primary filter, a coarse ammonia water refining tank, a refining filter and a water-coal-slurry boiler.
Wherein, the coarse ammonia water export of acid water stripping tower is connected with the import of backflow mixing device, and backflow mixing device's coarse ammonia export is connected with first coarse ammonia water settling cask and second coarse ammonia water settling cask respectively, and parallelly connected setting between first coarse ammonia water settling cask and the second coarse ammonia water settling cask.
Be provided with the water inlet in first coarse ammonia water settling cask and the coarse ammonia water settling cask of second respectively to be provided with the overflow plate in the middle of the jar body on the direction of height, simultaneously, first coarse ammonia water settling cask and the coarse ammonia water settling cask bottom of second are provided with the exit of coarse ammonia water, and both subtend sets up, and the lower business turn over of realization coarse ammonia water is gone out down.
The crude ammonia water outlets of the first crude ammonia water settling tank and the second crude ammonia water settling tank are respectively connected with a first feed inlet and a second feed inlet of the reflux mixing device and also connected with a feed inlet of a primary filter (with the precision of 150 mu m). The discharge hole of the primary filter is connected with the feed inlet of a coarse ammonia water refining tank, the discharge hole of the coarse ammonia water refining tank is connected with the feed inlet of a refining filter (with the precision of 50 microns), and the discharge hole of the refining filter is directly connected with a spray head of an ammonia water spraying system of an SNCR flue gas denitration system in a coal water slurry boiler.
Acidic water produced by petrochemical refinery is subjected to acidic water stripping process to evaporate crude ammonia water (flow: 14000 m)3H, temperature: feeding into reflux mixing device at 100 deg.C and 0.2Mpa, settling in first and/or second coarse ammonia water settling tanks, and stripping with acidic water to obtain purified water (purified water flow rate of 35 m)3H, temperature: 33 ℃ and the pressure of 0.45Mpa) and the crude ammonia water is mixed and diluted, the temperature is controlled at 35 ℃ and the crude ammonia water after sedimentation is obtained after 36 hours.
Wherein, the crude ammonia water comprises 25 percent of ammonia gas, 2 percent of hydrogen sulfide, 7.9 percent of suspended matters, 0.1 percent of volatile phenol and 65 percent of water according to the mass percentage; the COD content was 35000 mg/L.
After sedimentation, the suspended matter in the crude ammonia water is reduced to about 2.5%.
The crude ammonia water that the reflux mixing device came out can subside through first crude ammonia water settling cask, also can subside through second crude ammonia water settling cask, also can simultaneously through first crude ammonia water settling cask and second crude ammonia water settling cask. The two are arranged in parallel and can be switched, the treatment capacity can be improved, the continuous sedimentation process is realized, and meanwhile, the process control and maintenance are facilitated.
And (3) allowing one part of the coarse ammonia water subjected to sedimentation in the first coarse ammonia water sedimentation tank and the second coarse ammonia water sedimentation tank to enter a primary filter with the precision of 150-300 mu m, and allowing the other part of the coarse ammonia water to flow back to a backflow mixing device, wherein the backflow ratio is (2-4): 1, enhancing the treatment effect. And (3) refining and settling the two-step product (suspended matters are reduced to about 1%) subjected to primary filtration at 33 ℃ for 24 hours to obtain a three-step product. And then after refining and filtering with the precision of 50 mu m, reducing the suspended substance of the crude ammonia to about 0.035%, COD content is 5000-7000 mg/L, and the temperature is as follows: the denitration agent is directly injected into a boiler spray gun at the temperature of 28 ℃ and the pressure of 0.4Mpa to achieve the aim of removing the nitrogen oxides in the boiler flue gas.
By counting the technical scheme provided by the invention, the ammonia water amount can be saved by 15-20% and can be saved by 200kg/h, and the smoke gas amount of a 35t/h coal water slurry boiler is 100000m3The concentration of nitrogen oxides in the boiler flue gas is 600mg/m3Reduced to 100mg/m3And the purchase cost of the ammonia water is saved by 350 ten thousand yuan per year through calculation. Meanwhile, the corresponding treatment cost of the crude ammonia water is also reduced.
While the present invention has been described in detail with respect to the apparatus and process for recycling raw ammonia produced by a petrochemical refinery sour water treatment plant, the principles and embodiments of the present invention are described herein using specific examples, which are intended to facilitate an understanding of the methods and their core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
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| CN115178081A (en) * | 2022-08-15 | 2022-10-14 | 安徽东至广信农化有限公司 | Ammonia water recycling process suitable for SNCR (selective non-catalytic reduction) process |
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| DE19848499C1 (en) * | 1998-10-21 | 2000-02-24 | Metallgesellschaft Ag | Ammonia recovery from waste liquor containing acid and inert gases e.g. from petroleum refinery uses pre purification column with reboiler heating, total separating column and condenser |
| CN1248963C (en) * | 2004-08-16 | 2006-04-05 | 中国石油化工集团公司 | A combination process for refining ammonia |
| DE102008058143B4 (en) * | 2008-11-20 | 2012-04-12 | Lurgi Gmbh | Process and plant for recovering NH3 from a mixture containing NH3 and sour gases |
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