CN117586055B - Automatic monitoring method and system for volatile organic sulfur in organic waste composting process - Google Patents
Automatic monitoring method and system for volatile organic sulfur in organic waste composting process Download PDFInfo
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- FCBUKWWQSZQDDI-UHFFFAOYSA-N rhamnolipid Chemical compound CCCCCCCC(CC(O)=O)OC(=O)CC(CCCCCCC)OC1OC(C)C(O)C(O)C1OC1C(O)C(O)C(O)C(C)O1 FCBUKWWQSZQDDI-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
- C05F17/90—Apparatus therefor
- C05F17/993—Arrangements for measuring process parameters, e.g. temperature, pressure or humidity
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
- C05F17/70—Controlling the treatment in response to process parameters
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
- C05F17/90—Apparatus therefor
- C05F17/964—Constructional parts, e.g. floors, covers or doors
- C05F17/971—Constructional parts, e.g. floors, covers or doors for feeding or discharging materials to be treated; for feeding or discharging other material
- C05F17/979—Constructional parts, e.g. floors, covers or doors for feeding or discharging materials to be treated; for feeding or discharging other material the other material being gaseous
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
-
- G—PHYSICS
- G05—CONTROLLING; REGULATING
- G05B—CONTROL OR REGULATING SYSTEMS IN GENERAL; FUNCTIONAL ELEMENTS OF SUCH SYSTEMS; MONITORING OR TESTING ARRANGEMENTS FOR SUCH SYSTEMS OR ELEMENTS
- G05B19/00—Programme-control systems
- G05B19/02—Programme-control systems electric
- G05B19/04—Programme control other than numerical control, i.e. in sequence controllers or logic controllers
- G05B19/05—Programmable logic controllers, e.g. simulating logic interconnections of signals according to ladder diagrams or function charts
- G05B19/054—Input/output
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
- G01N2030/8804—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 automated systems
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Molecular Biology (AREA)
- Biotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Automation & Control Theory (AREA)
- Processing Of Solid Wastes (AREA)
- Fertilizers (AREA)
Abstract
The invention belongs to the technical field of detection and environmental protection, and discloses an automatic monitoring method and system for volatile organic sulfur in an organic waste composting process, wherein the method comprises the following steps: s1, preparing each component part of an automatic monitoring system for volatile organic sulfur in the composting process of organic waste; s2, deploying an automatic monitoring system on site and setting working conditions; s3, the automatic monitoring system automatically operates to obtain a monitoring result; s4: the automatic monitoring system automatically regulates and controls, and achieves standard emission. According to the automatic monitoring method and system provided by the invention, according to the industrialization requirements of an organic fertilizer plant, the automatic monitoring system is driven to be linked with the composting PLC through the exhaust gas concentration detection data, the working conditions or exhaust paths of the air blower, the composting fermentation device and the composting gas filtering and discharging device are automatically adjusted, the generation amount of volatile organic sulfur is reduced or the filtering is enhanced, and finally, the atmospheric emission concentration or total amount of the volatile organic sulfur is lower than the set standard and reaches the standard for emission.
Description
Technical Field
The invention belongs to the technical field of detection and environmental protection, and particularly relates to an automatic monitoring method and system for volatile organic sulfur in the composting process of organic wastes such as livestock and poultry.
Background
Malodorous substances are nuisance gaseous pollutants which are unpleasant and harmful to human health caused by the action of air on human olfactory organs, wherein the malodorous substances are peculiar smell substances in the substances such as atmosphere, water, soil, wastes and the like. With the continuous development of town and industrialization, the influence of malodor pollution is more and more serious, and is considered as one of seven social effects of pollution. The main malodorous contaminants in air come from municipal solid waste treatment, wastewater treatment, livestock and poultry farming, and industrial manufacturing processes. The main odor contaminants are sulfur compounds, phenols, aldehydes, organic amines, organic acids, organic solvents, and the like. Among these compounds, sulfides have the lowest odor threshold concentration, are extremely toxic to humans, and can cause serious safety and environmental problems. The currently commonly adopted malodorous gas monitoring method is a three-point comparison type malodorous gas bag method, a sampling bag for the pollution source gas is generally adopted instead of a vacuum sampling bottle, because the concentration of the pollution source is high, the sampling bag can prevent secondary pollution caused by adsorption, the sampling operation of the sampling bag is complicated, the obtained gas sample is required to be brought back to a laboratory to obtain a detection result, and the real-time monitoring of the concentration and the total amount of the discharged malodorous gas on site cannot be realized.
In recent years, along with the rapid development of animal husbandry, the harmless and recycling treatment of livestock and poultry manure also needs to be correspondingly enhanced. For environmental and economic benefits, the adoption of composting equipment such as a fermentation tank for industrial composting is one of the best choices for treating livestock and poultry manure. In the prior art, the main working principle of the composting device technology is that organic waste is sent into a device (such as a fermentation tank) and is converted into organic fertilizer through a series of reactions and operations. The working principle mainly comprises a fermentation principle, an aerobic fermentation principle, an anaerobic fermentation principle and the like. The fermentation principle refers to a process of decomposing organic substances into organic acids, carbon dioxide, water and the like by utilizing the action of microorganisms. The main structure of the composting equipment process comprises a feeding system, a fermentation system, a ventilation system, a discharging system and the like. Wherein the feeding system consists of a feeding hopper, a feeding pump and the like; the fermentation system consists of a fermentation chamber, a turner and the like; the ventilation system consists of a ventilator, a ventilation channel and the like; the discharging system consists of a discharging hopper, a discharging pump and the like. In addition, the composting device is also provided with a dust removal system, a composting PLC controller and other auxiliary systems. However, in the composting process, along with the progress of reactions such as aerobic fermentation, anaerobic fermentation and the like, a large amount of malodorous gas is inevitably generated and released, and the health of people and livestock and the environmental quality are seriously affected. Such malodorous gases include ammonia, hydrogen sulfide, volatile organic sulfur, volatile fatty acids, alcohols, alkanes, ketones, esters, and the like. Although ammonia and hydrogen sulfide are the main gas components in the composting process, and the emission concentration of volatile organic sulfur gas is low, the odor threshold of the volatile organic sulfur gas is also low, and many researches indicate that the volatile organic sulfur gas is also a key odorizing substance. In order to protect the environment, ensure the health of residents and improve the environmental quality, the emission of volatile organic sulfur gas needs to be accurately monitored and controlled so as not to influence the health and the environmental quality of surrounding residents.
But the volatile organic sulfur gas has the characteristics of strong volatility, poor stability and easy conversion, which brings great technical difficulties to the collection and analysis of the volatile organic sulfur gas. It has been found that volatile organic sulfur remains stable in dry air for only 3 hours, with losses of up to 10-20% after 24 hours. In addition, because the concentration of volatile organic sulfur in the air is low, the concentration and enrichment pretreatment is usually needed after the collection, and the detection limit of the instrument can be reached. Conventional collection and pretreatment means include adsorption tube-thermal desorption, tank-preconcentration, and air bag-preconcentration. The adsorption tube is convenient to carry, and can be filled with a plurality of adsorbents to adapt to different target compounds. But for some of the highly volatile organic sulfur, such as methyl mercaptan, may escape the adsorbent tube. And the adsorption tube can also cause degradation of volatile organic sulfur, incomplete desorption of the adsorbent, and the like. Therefore, the collection of volatile organic sulfur by the adsorption tube often needs low-temperature condensation and enrichment under the liquid nitrogen environment. The inner wall of the tank is subjected to silane inerting treatment, so that the tank can stably store volatile organic sulfur for a longer time. However, the subsequent pre-concentration process is relatively complex, the analysis takes relatively long time, and the cost of the soda can-pre-concentration method is relatively high. When the sampling air bag collects the air sample, the air bag is portable and easy to carry, and can collect the all-air sample. The air bags made of materials such as Tedlar cube PVF, PTFE and the like commonly used at present have low adsorptivity to volatile organic sulfur and can be stably stored within 6-8 hours. In the analysis of volatile organic sulphur, the prior art generally uses gas chromatography or mass spectrometry for detection. Common detectors include Flame Photometric Detectors (FPDs), sulphur Chemiluminescence Detectors (SCDs) and Mass Spectrometric Detectors (MSDs).
For example, in the prior art, chinese invention document CN114324691a discloses a method for improving sulfide detection accuracy, which includes the following steps: (1) pre-processing components of a focus concentrator; (2) Connecting a focusing concentrator with a gas chromatograph with a sulfur chemiluminescence detector; (3) Collecting gas by the gas bag, sampling, focusing and concentrating, and detecting sulfide; according to the invention, through the silanization pretreatment of the SECA focusing concentrator component and the matching of the gas chromatograph with the sulfur chemiluminescence detector, the detection precision of 16 sulfides is greatly improved, and the concentration of large-volume sample injection can be realized. The invention solves the technical problem that trace sulfide in ambient air can be smelled but is not easy to detect, but the invention adopts a focusing concentrator to couple gas chromatography to enrich and concentrate volatile sulfide and then carry out sample injection detection, the equipment is large in volume and not suitable for on-site detection, and the collected sample is required to be retrieved into a laboratory to carry out detection, so that on one hand, the analysis time is longer, the loss of malodorous sulfide occurs due to the reactivity of the malodorous sulfide, and the real-time dynamic monitoring and the on-line monitoring cannot be realized and cannot be linked with a composting PLC controller; on the other hand, the gas chromatograph or the gas mass spectrum used in the invention has large volume and mass, liquid nitrogen is needed for refrigeration, the whole device has large volume, the device is needed to be arranged in a laboratory, the device cannot be applied to monitoring of a composting site, and the device is needed to collect a gas sample back to the laboratory for laboratory monitoring.
In addition, the online detection technology in the prior art cannot be applied to the real-time detection of volatile organic sulfur gas. For example, chinese patent application CN201710024318.7 discloses a gas detection device for composting organic fertilizer, which comprises a gas collecting device, a gas impurity water filtering device and a gas on-line detection device; the gas collecting device is a box body with a bottomless bottom, two small holes are formed in the upper surface of the box body, a pipeline is respectively inserted into the two small holes, and one pipeline is positioned above the box body and communicated with the outside air; one end of the other pipeline extends to the upper part of the organic fertilizer pile body, and the other end of the other pipeline is communicated with the gas impurity moisture filtering device and the gas on-line detection device; the gas impurity moisture filtering device filters volatile gas generated by the organic fertilizer compost, the gas on-line detecting device continuously detects the filtered volatile gas, and meanwhile, detection data are stored. The gas on-line detection device comprises a suction pump and a gas on-line detector, wherein the suction pump is used for collecting volatile gases of the organic fertilizer compost to the gas on-line detector, and the gas on-line detector is used for continuously detecting the concentration of various volatile gases and storing detection data. The invention generally needs to be provided with a gas impurity moisture filtering device (filtering moisture and impurities in gas), an air suction pump and a gas on-line detector (but no specific scheme is given, the technical personnel are hard to know what and what working principle the detector is), which records that the invention can be widely applied to the detection of volatile gases of organic fertilizer compost, but no specific volatile gases can be detected, and specific detection results and detection precision are not given, so that the invention is only a technical conception as a whole, but not a complete technical scheme; meanwhile, the device cannot be linked with composting fermentation equipment and a control system thereof, and the concentration of volatile gas which exceeds a set threshold value and is generated in the fermentation process is reduced and discharged after reaching the standard.
In the prior art, gas chromatography-ion mobility spectrometry (Gas Chromatography-Ion Mobility Spectrometry, GC-IMS) was one separation detection technique that emerged in the 70 s of the 20 th century. The principle is that after a sample to be detected is separated by gas chromatography, the sample reacts with hydrated molecules in carrier gas under the irradiation of beta rays emitted by a tritium source to form hydrated protons, the hydrated protons and the sample to be detected form molecular ions, and then the separation detection of the sample is realized according to the difference of migration rates of the molecular ions to be detected in an electric field. The GC-IMS has simple structure and can be used under normal pressure. In addition, the GC-IMS has sensitive response to substances containing halogen atoms, can be directly analyzed under the condition of no pretreatment, has small volume and mass, can carry out analysis and test without a vacuum environment, and can be used for on-site monitoring of pollutants. The GC-IMS in the prior art can be used for detecting volatile organic compounds in air, soil and water, including organic solvents, volatile organic compounds, gaseous nitrides, formaldehyde, benzene and other compounds. However, since the malodorous gas generated by organic waste composting such as feces generated in livestock and poultry breeding contains high-concentration ammonia besides volatile organic sulfur, the existence of ammonia can interfere qualitative and quantitative determination of the volatile organic sulfur, the existing GC-IMS can not directly detect the mixed gas generated by organic waste composting, and especially the GC-IMS parameter system in the prior art is complex and can not automatically operate on line for a long time, and the detection result is linked with the control system of composting equipment, measures are automatically taken to regulate and control the working condition of a fermentation device, reduce the total amount and concentration of malodorous gas generated and discharged beyond standard, so that the influence on the health and environmental quality of residents around a factory area is avoided.
In addition, the industrial composting fermentation equipment (taking a fermentation tank as a main body) of enterprises such as an organic fertilizer plant and the like in the prior art has low intelligent, automatic, high-efficiency, environment-friendly and other degrees, is difficult to integrate high-precision volatile gas detection equipment, and is applied to automatic control of the composting equipment; in a large-scale composting factory, a plurality of sets or even tens of sets of composting fermentation equipment are often arranged, and when one set of detection equipment in the prior art is used for detecting one set of composting equipment, a large number of detection equipment is required to be arranged, so that the cost is high, and the operation and maintenance difficulties are high.
In summary, a new method for online automatic detection and regulation of generation and emission of volatile organic sulfur in livestock and poultry organic waste compost containing ammonia across multiple fields is researched aiming at the production process of large-scale and industrialized composting fermentation treatment equipment of an organic fertilizer plant and the like, the total equipment amount is simplified, the automation degree is improved, the method is applied to large-scale continuous monitoring of the generation, emission concentration and total amount of the volatile organic sulfur in the livestock and poultry organic waste composting process, the total generation amount and emission concentration of malodorous gas in the organic waste composting process are managed, the generation and emission amount of the malodorous gas is reduced by optimizing the composting fermentation process of the composting fermentation equipment, the working condition of the equipment and the like, and an effective technical support is provided for improving the intelligent and automatic degree of the composting fermentation equipment and the control process.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the automatic monitoring method and the system for the volatile organic sulfur in the organic waste compost of livestock, poultry and the like, which are suitable for an organic fertilizer factory, overcomes the technical difficulty of crossing multiple fields, constructs the one-to-many automatic detection and regulation method and the system for the monitoring device through the integrated collaborative improvement of software and hardware, simplifies the total equipment, improves the automation degree, supports the continuous monitoring of the generation, the emission concentration and the total quantity of the volatile organic sulfur in the large-scale and industrialized organic waste composting process, manages the emission concentration and the total quantity of malodorous gas in the organic waste composting process, reduces the generation and the emission quantity of the malodorous gas through optimizing the fermentation process, the equipment and the like, improves the intelligent and automatic degree of the industrialized composting fermentation equipment and the control process, and provides effective technical support.
The technical scheme provided by the invention for solving the problems is as follows:
an automatic monitoring method for volatile organic sulfur in organic waste composting process comprises the following steps:
s1, preparing each component part of an automatic monitoring system for volatile organic sulfur in organic waste composting process
Respectively preparing at least one compost PLC controller, a blower, a compost fermentation device, a compost gas filtering and discharging device and a compost discharging gas automatic detecting device;
Wherein, compost exhaust gas automated inspection device includes: a gas flowmeter, a gas sampling treatment device and a gas chromatograph-ion mobility spectrometer (GC-IMS); the gas sampling treatment device adsorbs ammonia in the treated gas sample;
s2, deploying an automatic monitoring system on site and setting working conditions
S21, connecting an on-site air blower, a composting fermentation device and a composting gas filtering and discharging device with a gas flowmeter, a gas sampling and processing device and a GC-IMS in an automatic composting gas discharging detection device through gas connecting pipelines respectively, and connecting a composting PLC (programmable logic controller), the air blower and the GC-IMS through a network;
A composting PLC controller, a blower, a composting fermentation device and a composting gas filtering and discharging device form a set of composting fermentation operation unit, and the composting fermentation operation unit is abutted against a composting gas automatic detecting device;
S22, setting the operation condition of the automatic monitoring system
Setting the working conditions of GC-IMS automatic monitoring:
setting gas chromatography conditions: setting the type and working condition of chromatographic column;
Ion mobility spectrometry conditions are set: setting gas chromatography-ion mobility spectrometry test conditions;
Setting the temperatures of the filling column, the IMS migration tube and the transmission line to be consistent;
setting carrier gas flow;
Initializing a composting PLC controller, feeding materials, organic wastes and composting fermentation bacteria into a composting fermentation device, and performing composting fermentation;
S3, automatically operating an automatic monitoring system to obtain a monitoring result
The method comprises the steps that a composting PLC controller controls a blower to blow air into a composting fermentation device, volatile organic sulfur exhaust gas discharged in the composting process inside the composting fermentation device is sent into a composting gas filtering and discharging device and a composting exhaust gas automatic detection device, part of the filtered gas sequentially flows through the composting gas filtering and discharging device and is discharged into the atmosphere, the other part of the filtered gas flows through a gas flowmeter, a gas sampling and processing device and a GC-IMS, ammonia components in a gas sample are adsorbed and processed by the gas sampling and processing device, then the gas sample is automatically detected by the machine according to set GC-IMS automatic monitoring working conditions, and monitoring data of the volatile organic sulfur exhaust gas discharged in the composting process are obtained after analysis and calculation;
S4: automatic regulation and control of automatic monitoring system to realize standard emission
The automatic monitoring system feeds back the monitoring data to the composting PLC controller according to the comparison result of the monitoring data and a preset monitoring threshold value (preset emission standard data), and is linked with the composting PLC controller, the composting PLC controller automatically adjusts working conditions or exhaust paths of the air blower, the composting fermentation device and the composting gas filtering and discharging device, reduces the generation amount of the volatile organic sulfur or strengthens the filtering, and finally realizes that the atmospheric emission concentration or total amount of the volatile organic sulfur is lower than the set standard and reaches the emission standard;
s5: automatic monitoring system dynamic, continuous and automatic monitoring
The automatic monitoring system repeats steps S3-S4, the automatic detection device for the composting exhaust gas circularly monitors, records and calculates the concentration and total amount of volatile organic sulfur in the gas components exhausted by the composting fermentation device according to a set time interval (for example, 30-120 minutes), and is linked with the composting PLC controller according to the comparison result of the monitoring data and a preset monitoring threshold value, so that the working condition or the gas exhaust path of each part is automatically regulated and controlled, the standard emission is realized, and the long-time continuous and automatic dynamic monitoring is realized.
An automatic monitoring system for volatile organic sulfur in the composting process of organic waste is characterized by comprising a set of composting fermentation operation unit and a composting exhaust gas automatic detection device, wherein the set of composting fermentation operation unit is formed by at least one composting PLC (programmable logic controller), a blower, a composting fermentation device and a composting gas filtering and exhausting device which are sequentially communicated by gas connecting pipelines; the composting fermentation operation unit is in butt joint with the composting exhaust gas automatic detection device through a gas connection pipeline;
The automatic detection device for the compost discharge gas comprises: a gas flowmeter, a gas sampling processing device and a GC-IMS;
The air blower, the compost fermentation device, the compost gas filtering and discharging device and a gas flowmeter, a gas sampling and processing device and a GC-IMS in the compost discharged gas automatic detection device are respectively connected by gas connecting pipelines, and the compost PLC, the air blower, the GC-IMS and the gas sampling and processing device are connected by a network;
The composting gas filtering and discharging device comprises a first-stage composting gas filtering and discharging mechanism and a second-stage composting gas filtering and discharging mechanism which are sequentially connected in series; the first-stage compost gas filtering and discharging mechanism is internally provided with a biological drip filtration and deodorization structure, and the second-stage compost gas filtering and discharging mechanism is internally provided with a physical adsorption filtration and deodorization structure;
The air outlet end of the first-stage compost gas filtering and discharging mechanism is divided into two paths: one path of the device is connected with the automatic detection device of the compost discharge gas, the other path of the device is connected with the first electromagnetic valve and then is divided into two paths from the first electromagnetic valve, one path of the device is connected with the second-stage compost gas filtering and discharging mechanism, and the other path of the device is connected with the first-stage outer discharge pipe; a gas flowmeter is integrated in the first electromagnetic valve;
the air outlet end of the secondary compost gas filtering and discharging mechanism is one path, and is directly connected with a secondary outer discharging pipe which is divided into two paths: one path of the air is connected with the external atmosphere, and the other path of the air is connected with an automatic compost discharge gas detection device;
Volatile organic sulfur gas generated by the composting fermentation device in the organic waste composting process is filtered together with air introduced by the air blower through the composting gas filtering and discharging device, and then enters the composting gas automatic detecting device for concentration detection; if the concentration of the gas filtered by the first-stage compost gas filtering and discharging mechanism is detected to exceed the standard, the gas is automatically led into the second-stage compost gas filtering and discharging mechanism for filtering and detecting again, and the gas with qualified concentration is discharged into the atmosphere.
Compared with the prior art, the automatic monitoring method and system for the volatile organic sulfur in the organic waste composting process have the beneficial effects that at least the following points are included:
1. According to the automatic monitoring method and system for the volatile organic sulfur in the organic waste composting process, which are provided by the invention, aiming at industrial requirements of an organic fertilizer plant and the like, the technical difficulties across multiple fields are overcome, the on-site continuous and automatic detection and monitoring method for the volatile organic sulfur-methyl sulfide, ethyl sulfide, dimethyl disulfide and carbon disulfide in the organic waste composting process of livestock and poultry is established by adopting the gas collecting bag, the gas chromatography-ion mobility spectrometry technology through synchronous improvement of instrument equipment, a detection method, an analysis model and a monitoring method, the collection of the composting malodorous gas can be completed only by adopting the gas bag without pretreatment steps such as concentration and enrichment, the detection sensitivity and the response are rapid, the automatic monitoring and the regulation can be performed in a time-sharing manner, and the technical support can be provided for the automatic management of the emission concentration and the total emission amount of the malodorous gas in the organic waste composting process of the organic fertilizer plant.
2. According to the automatic monitoring method and system provided by the invention, according to the industrial production requirements of the organic fertilizer plant, the automatic monitoring system is driven to be linked with the composting PLC controller through the exhaust gas concentration detection data, so that a series of problems of pretreatment of ammonia gas samples, miniaturization, automation, simplified monitoring flow and the like of detection instrument equipment in the organic fertilizer plant are solved, and the continuous, automatic detection and regulation and control in the field and outdoors can be supported. The invention does not adopt the traditional gas collecting bag and the like as a sample collecting container, but replaces the traditional gas collecting and processing device which automatically works on line, and uses the GC-IMS which meets the conditions of automatic operation (parameter set) as an automatic detection means of the volatile organic sulfur under the condition of pretreatment such as sample enrichment free and the like, so that the invention can detect and control a plurality of composting fermentation operation units at multiple points and multiple time periods on site, thereby providing efficient technical support for the production, emission concentration and emission total amount management of each composting fermentation operation unit of the organic waste composting malodorous gas. The invention samples a one-to-many mode and dynamically and continuously detects and regulates the generation and emission of volatile organic sulfur in the organic waste composting equipment; the system can automatically adjust (automatically change the filtering exhaust channel, increase or decrease the ventilation quantity, etc.) according to the set exhaust concentration threshold value, manage the generation and exhaust concentration and total quantity, reduce the generation and the exhaust quantity of the volatile organic sulfur by a method of cooperation of software and hardware, and reduce the adverse effect on the environment.
3. The invention adopts a mode of two-stage filtration deodorization and automatic monitoring system for multiple (one set of detection device is simultaneously connected with a plurality of composting fermentation devices in a butt joint mode, and one set of automatic control system controls a plurality of monitoring systems), and the method is used for automatic sampling, monitoring and feedback, time-sharing and cyclic detection, thereby greatly simplifying the quantity and flow of monitoring equipment, designing a gas sampling treatment device, solving the technical problem of quantitative analysis of volatile organic sulfur in composting gas with complex components and meeting the requirements of organic fertilizer factories. The invention specifically overcomes the complex flow of pretreatment such as pretreatment of the existing main flow detection method of the volatile organic sulfur, gas chromatography or gas mass spectrum, pretreatment such as adsorption tube-thermal desorption, a gamma tank-preconcentration, an air bag-preconcentration and the like, and solves the technical problem that the collection of the volatile organic sulfur can not be almost completed by sampling the adsorption tube under the condition of no liquid nitrogen. The inner wall of the Suma tank is subjected to silane inerting treatment, so that the volatile organic sulfur can be stably stored for a longer time, the subsequent pre-concentration treatment operation is complicated, the analysis time is long, and the cost of the Suma tank-pre-concentration method is high. The existing gas chromatography or gas mass spectrometry equipment is large in size and heavy in mass, and is only suitable for laboratory detection but not suitable for field detection. If an adsorption tube-thermal desorption method is adopted, an external heating desorption instrument is needed; adopts a soda tank-preconcentration method, and requires an additional preconcentrator. Therefore, the traditional methods have higher cost, can not realize on-line, rapid and automatic sampling, processing and analysis of an outdoor sampling site, and can not support the linkage control with composting fermentation equipment because the samples are required to be brought back to a laboratory for detection and analysis. The invention can realize one-to-many automatic sampling, processing and detection without sampling the adsorption tube under the condition of liquid nitrogen, and can support the linkage control with the composting fermentation equipment.
4. According to the automatic monitoring method and system for the volatile organic sulfur in the organic waste composting process, provided by the invention, the problems that the concentration of the volatile organic sulfur in the livestock and poultry organic waste composting environment gas is low, the volatile organic sulfur is usually concentrated and enriched and can be detected, the volatile organic sulfur is easy to escape when collected by an adsorption tube, the volatile organic sulfur is poor in stability and easy to convert, and is required to be analyzed as soon as possible after collection so as to avoid the problems that the degradation of the volatile organic sulfur cannot be detected and the like are solved.
5. According to the invention, the specific treatment and the reasonable setting of GC-IMS detection parameter sets and working conditions are carried out on various monitored gas components in the fertilizer gas, besides the prior removal of ammonia gas, the multi-aspect adjustment is carried out according to the requirements of accurate detection, automatic detection and long-time detection of various organic sulfur contents (generally 10 -3~102 mg/m3) in a sample, so that the situation that the ion mobility spectrometry possibly supersaturates the high-concentration organic sulfur in the gas, the low-concentration organic sulfur possibly has insufficient sensitivity, and the continuous operation and the service life of the GC-IMS are influenced by unreasonable parameter setting is avoided. Therefore, through adjusting the multi-aspect operation parameter settings of the GC-IMS, such as sensor block, sensor object, voltage and the like, a specific parameter set is formed, the stability of the automatic operation of the equipment and the longer service life can be considered on the basis of ensuring the detection accuracy of various organic sulfur gases, the concentration of various organic sulfur components can be synchronously and accurately detected, the total discharge amount can be conveniently calculated by combining a flowmeter, and the total production amount, the production period and the production rate of each gas component in the fermentation process can be calculated by filtering the rate.
6. According to the automatic monitoring method and system for the volatile organic sulfur in the organic waste composting process, the problems that in the prior art, instruments and equipment are numerous, large in size and heavy in weight, the pretreatment process is complicated and complicated, the cost is high, the detection instruments and equipment cannot automatically and continuously run for a long time and the like are effectively solved by integrally improving the sampling, equipment, working conditions, detection methods and regulation methods according to the demands of enterprises such as an organic fertilizer plant, so that the method can be effectively applied to outdoor field detection, rapid detection, low-cost detection and continuous detection of the volatile organic sulfur in a large-scale livestock and poultry organic waste composting plant, and is combined with an automatic control technology, so that the dynamic and automatic monitoring is realized, the preset environment-friendly aim is intelligently realized, and the efficient technical support is provided.
7. The automatic monitoring method and system for the volatile organic sulfur in the organic waste composting process provided by the invention comprehensively adopt the technologies such as a gas sampling treatment device and a gas chromatography-ion mobility spectrometry, overcome the technical difficulties in multiple fields, establish the on-site continuous and automatic detection and regulation method for the volatile organic sulfur-methyl sulfide, ethyl sulfide, dimethyl disulfide, carbon disulfide and other gas components in the organic waste composting under a pair of modes suitable for multi-equipment workshop production, can complete the collection of composting malodorous gas only by adopting the gas sampling treatment device without pretreatment steps such as concentration enrichment, has sensitive detection and quick response, can timely obtain detection data and feed back the detection data to a composting fermentation control system, can be widely applied to the on-site monitoring of workshops for the generation and emission concentration of the volatile organic sulfur in the industrial composting gas, and the monitoring of the generation and emission total amount of the monitored gases such as the volatile organic sulfur, and is beneficial to the improvement of the automation and the intellectualization of composting equipment and composting processes of units such as an organic fertilizer factory, a farm and the like.
Drawings
FIG. 1 is a schematic diagram of the overall structure of an automatic monitoring system according to embodiment 1 of the present invention;
FIG. 2 is a schematic diagram of the overall network structure and flow of the automatic monitoring system according to embodiment 2 of the present invention;
FIG. 3 is a schematic representation of the response of four volatile organic sulfur compounds on a MXT-1 and MXT-5 packed column in accordance with an embodiment of the invention;
FIG. 4 is an ion mobility spectrum of four volatile organic sulfur compounds on an MXT-1 packed column according to an embodiment of the invention, wherein the left graph is a positive mode schematic, and the right graph is a negative mode schematic;
FIG. 5 is a graph showing the response of four volatile organic sulfur compounds according to an embodiment of the present invention, wherein (a) is different temperatures and (b) is different flow rates;
FIG. 6 is a schematic diagram of four volatile organic sulfur standard curves according to an embodiment of the present invention;
FIG. 7 is a graph showing the effect of composting materials of different water content on the concentration of dimethyl sulfide emissions in accordance with an embodiment of the present invention.
In the figure:
1. a composting fermentation device; 2. a blower; 3. a gas connection line; 31. a first-stage outer discharge pipe; 32. a second-stage outer discharge tube; 4. a first-stage composting gas filtering and discharging mechanism; 5. a secondary compost gas filtering and discharging mechanism; 6. a gas flow meter; 7. a gas sampling processing device; 71. a gas sampling processing vessel; 72. sampling an air inlet pipe; 73. sampling an air outlet pipe; 74. a chemical; 75. an ammonia concentration sensor; 8. GC-IMS; 9. a remote control server; 10. a first electromagnetic valve; 11. and a second electromagnetic valve.
The present invention will be described in detail with reference to the accompanying drawings and examples.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Example 1
Referring to fig. 1, the embodiment of the invention provides an economical and efficient automatic monitoring method for volatile organic sulfur in an organic waste composting process, which is designed according to the actual requirements of an industrial composting fermentation factory (short for an organic fertilizer factory), and comprises the following steps:
s1, preparing each component part of an automatic monitoring system for volatile organic sulfur in organic waste composting process
In a composting fermentation workshop of an organic fertilizer plant, a composting PLC controller (specifically, siemens S7-200Smart series PLC controllers, which can be adopted), a blower 2, a composting fermentation device 1, a composting gas filtering and discharging device and a composting gas automatic detecting device are respectively prepared;
wherein, compost exhaust gas automated inspection device includes: a gas flowmeter 6, a gas sampling processing device 7 and a GC-IMS 8; the gas sampling processing device 7 adsorbs ammonia in the processed gas sample;
The gas sampling treatment device 7 comprises a gas sampling treatment container, a sampling air inlet pipe, a sampling air outlet pipe, an ammonia concentration sensor and a chemical agent, wherein the ammonia concentration sensor and the chemical agent are arranged in the gas sampling treatment container, the gas sampling treatment container is internally sealed, and the chemical agent (such as calcium chloride granules or powder) for absorbing ammonia components in composting gas is arranged at the lower part; the gas inlet of the sampling gas inlet pipe is connected with the gas outlet of the gas flowmeter, and the gas outlet is inserted into the bottom of the gas sampling treatment container and the chemical agent; the gas inlet of the sampling gas outlet pipe is higher than the upper surface of the chemical agent, and the gas outlet of the sampling gas outlet pipe is connected with the gas inlet of the GC-IMS (gas chromatography-ion mobility spectrometry combined instrument); in actual operation, a support device or equipment such as a nitrogen source configured to continuously supply gas for GC-IMS is also required;
s2, deploying an automatic monitoring system on site and setting working conditions
S21, connecting an on-site air blower 2 (specifically a cold and hot air blower, the ventilation temperature, ventilation quantity, ventilation flow rate, ventilation gap and other working parameters of the air blower are regulated by a composting PLC controller), a composting fermentation device 1 (a main structure is a fermentation tank), a composting gas filtering and discharging device (at least comprising a primary composting gas filtering and discharging mechanism) and a gas flowmeter 6, a gas sampling and processing device 7 and a GC-IMS 8 in an automatic composting gas discharging detection device respectively by using gas connecting pipelines, and connecting the composting PLC controller, the air blower 2 and the GC-IMS 8 by using a network;
Wherein, at least one composting PLC controller, a blower 2, a composting fermentation device 1 (mainly comprising a fermentation tank, a motion mechanism, a heating mechanism, a spraying mechanism, a ventilation mechanism and other operation auxiliary mechanisms, wherein the motion mechanism comprises stirring, vibration, tank posture adjustment and the like), and a composting gas filtering and discharging device form a set of composting fermentation operation unit, and the composting fermentation operation unit is abutted against a composting discharge gas automatic detection device;
S22, setting the operation condition of the automatic monitoring system
According to the automatic operation requirement, setting the working conditions (parameter combination) of GC-IMS automatic monitoring:
setting gas chromatography conditions: setting the type and working condition of chromatographic column;
Ion mobility spectrometry conditions are set: setting gas chromatography-ion mobility spectrometry test conditions;
Setting the temperatures of the filling column, the IMS migration tube and the transmission line to be consistent;
setting carrier gas flow;
in this embodiment, among the set operation conditions of the automatic monitoring system, the working conditions of GC-IMS automatic monitoring are:
An MXT-1 chromatographic column is adopted, the working temperature is 80 ℃ under the positive mode, the carrier gas flow is 5 mL/min, the working temperature is 45 ℃ under the negative mode, the carrier gas flow is 3 mL/min, and the positive mode and the negative mode are set to be automatically switched;
Initializing a composting PLC controller, feeding materials, organic wastes, composting fermentation bactericides and the like into a composting fermentation device, starting the composting fermentation device 1 to perform composting fermentation operation, wherein the fermentation operation time of each round under an aerobic fermentation process is usually 7-15 days;
S3, automatically operating an automatic monitoring system to obtain a monitoring result
The composting PLC controller controls a blower to introduce air into the composting fermentation device 1, volatile organic sulfur exhaust gas (including other volatile organic compounds TVOC) exhausted in the composting process in the composting fermentation device 1 is sequentially fed into a composting gas filtering and exhausting device and a composting exhaust gas automatic detection device, the gas sequentially flows through the composting gas filtering and exhausting device (most of gas phase ammonia and volatile organic compounds in the filtered gas are converted into water phase components), part of the filtered gas is exhausted into the atmosphere, the other part of the filtered gas flows through a gas flowmeter, a gas sampling and processing device and a GC-IMS, ammonia components in a gas sample are adsorbed and processed by the gas sampling and processing device 7, then the adsorbed and processed gas sample is automatically detected by a machine according to set GC-IMS automatic monitoring working conditions, and monitoring data of the volatile organic sulfur exhaust gas exhausted in the composting process are obtained after analysis and calculation;
S4: automatic regulation and control of automatic monitoring system to realize standard emission
According to the result of comparing the monitoring data with a preset monitoring threshold (preset emission standard data, specifically, referring to table 1, the actual set threshold is lower than table 1), or feeding the monitoring data back to the composting PLC controller, linking with the composting PLC controller, automatically adjusting working condition parameters or exhaust paths (independently through a primary composting gas filtering and discharging mechanism or sequentially through the primary composting gas filtering and discharging mechanism and a secondary composting gas filtering and discharging mechanism) of a blower, a (motion mechanism, a spraying mechanism, a heating mechanism and the like) composting fermentation device and a composting gas filtering and discharging device by the composting PLC controller, reducing the generation amount of volatile organic sulfur or enhancing the filtering, and finally realizing that the atmospheric emission concentration or total amount of the volatile organic sulfur is lower than the set standard and reaches the standard (lower than the set monitoring threshold) emission;
s5: automatic monitoring system dynamic, continuous and automatic monitoring
The automatic monitoring system repeats the steps S3-S4, controls the automatic detection device of the composting exhaust gas to carry out the cyclic monitoring, recording and operation on the concentration and the total exhaust amount of the volatile organic sulfur in the gas component exhausted by the composting fermentation device according to the set time interval (for example, each interval is 30-120 minutes, sampling detection is carried out on a fermentation tank in one work), and directly sends detection data to a composting PLC (programmable logic controller) according to the comparison result of the monitoring data and the preset monitoring threshold value, and is linked with the composting PLC, the composting PLC automatically regulates and controls the working conditions (comprising ventilation volume, ventilation speed, ventilation temperature, ventilation intermittence, stirring, water content, filtering duration and the like) or the gas exhaust path of each part of the composting fermentation device, a blower and the like, realizes the emission, and realizes the long-time continuous and automatic dynamic monitoring; only when the chemical agent in the gas sampling treatment device is completely saturated and ammonia gas can not be adsorbed, the manual intervention and the replacement of new chemical agent are needed, besides, all the components of the automatic monitoring system can automatically operate, so that the automation and the intelligent degree of the equipment are greatly improved. The total discharged amount and the total amount actually generated in the composting fermentation device (calculated according to the filtering rate) can be calculated according to the concentration and the flow of the detected volatile organic sulfur in the gas component, and the optimal working condition (the working condition with the lowest total gas production, total gas discharge and concentration) of the composting fermentation process of each batch can be obtained by continuous iteration.
In this embodiment, the compost gas filtering and discharging device in step S1 includes a first-stage compost gas filtering and discharging mechanism and a second-stage compost gas filtering and discharging mechanism connected in sequence;
The first-stage compost gas filtering and discharging mechanism comprises a gas connecting pipeline, a biological drip filtration deodorization structure, a first electromagnetic valve and a first-stage external discharging pipe; the air inlet end of the biological drip filtration deodorization structure is connected with the composting fermentation device through an air connecting pipeline, the air outlet end is divided into two paths, one path is connected with the air inlet end of the first electromagnetic valve through the air connecting pipeline, and the other path is connected with one path of air inlet end of the second electromagnetic valve; the biological trickling filtration deodorization structure can specifically adopt Sub>A rhamnolipid reinforced biological trickling filtration washing device (BTF) comprising two types of BTF-A (filled volcanic rock) and BTF-B (filled haydite), and can optimize Sub>A microbial community in the washing device structure and deeply treat malodorous gas generated in the aerobic composting process of livestock and poultry manure by combining the two types of biological trickling filtration washing devices so as to obtain Sub>A better biological trickling filtration deodorization effect.
The secondary compost gas filtering and discharging mechanism 5 comprises a gas connecting pipeline 3, a physical adsorption filtering and deodorizing structure and a secondary discharging pipe 32; the physical adsorption filtration deodorization structure is connected with one air outlet end of the first electromagnetic valve 10 through an air connecting pipeline 3, the air inlet end of the secondary outer discharge pipe 32 is connected with the air outlet end of the physical adsorption filtration deodorization structure, and the air outlet end of the secondary outer discharge pipe is connected with the other air inlet end of the second electromagnetic valve 11; the physical adsorption filtration deodorization structure comprises an adsorption filtration unit with a multi-layer structure, which is a core part of the deodorization structure and comprises a multi-layer filter bed filled with activated carbon or other adsorption materials; the activated carbon has strong adsorption capacity and can adsorb harmful substances and peculiar smell in the air; the filter bed ensures that the gas is in sufficient contact with the adsorbent material to achieve optimal adsorption.
In the steps S3-S5, the composting PLC controller controls the air blower to introduce air (three types of normal temperature gas, high temperature gas and low temperature gas can be introduced according to the requirement) into the composting fermentation device, and the air and the gas generated by the internal fermentation of the composting fermentation device are mixed to form mixed gas, and the mixed gas is discharged into the first-stage composting gas filtering and discharging mechanism 4 through the gas connecting pipeline 3: the mixed gas firstly passes through a biological drip deodorizing mechanism, ammonia gas, volatile organic sulfur gas and the like in the mixed gas are removed under the synergistic effect of microorganism flora and water in the drip deodorizing mechanism, part of the treated gas is firstly introduced into a composting exhaust gas automatic detection device to synchronously monitor the concentration of various gas components, and if the concentration of each monitored gas can reach a set threshold value, the rest part of the gas is discharged into the atmosphere through a first-stage discharge pipe 31; if any gas concentration can not reach the set threshold value, the first electromagnetic valve 10 leads the gas into the secondary compost gas filtering and discharging mechanism 5 for secondary deep filtration;
After the mixed gas led into the secondary compost gas filtering and discharging mechanism 5 is subjected to secondary filtering treatment, one part of the mixed gas is firstly led into a compost discharged gas automatic detecting device to synchronously monitor the concentration of various gases, and if the concentration of various monitored gases can reach a set threshold value, the rest part of the mixed gas is discharged into the atmosphere through a secondary discharging tube 32; if any concentration can not reach the set threshold value, the second electromagnetic valve 11 simultaneously closes the second-stage discharging pipe 32 and the gas connecting pipeline of the automatic detection device for guiding the compost discharge gas, increases the filtering time of the first-stage and second-stage filtering discharge mechanisms to the set length (the prolonged time length is 45-60 minutes, for example), opens the gas connecting pipeline of the automatic detection device for guiding the compost discharge gas, detects again, and opens the second-stage discharging pipe 32 to discharge the volatile organic sulfur which does not reach the standard in the gas after the volatile organic sulfur is further filtered and can reach the set threshold value;
In the continuous automatic monitoring process of each composting fermentation device, the following two working condition selection and adjustment control processes exist: A. when the filtration capacity is adjusted to decrease in sequence: when the primary filtering and discharging mechanism and the secondary filtering and discharging mechanism are both operated (such as the middle stage of the composting fermentation process), after the secondary filtering and discharging mechanism is operated at a set time interval (such as 30 minutes), determining whether to close the secondary composting gas filtering and discharging mechanism according to the latest gas concentration detection data of the secondary discharging pipe: if the concentration of the gas discharged at the moment (all the monitored gases) can reach the standard stably for a plurality of times continuously, closing the secondary compost gas filtering and discharging mechanism, and only keeping the primary compost gas filtering and discharging mechanism to work until the whole compost fermentation operation is finished (particularly at the initial stage and the final stage of the compost fermentation); B. the filtration capacity was adjusted to rise in sequence: after the primary compost gas filtration discharge mechanism is operated to a predetermined time interval (e.g., 30 minutes), determining whether to open the secondary compost gas filtration discharge mechanism based on the latest gas concentration detection data of the primary discharge pipe: if the concentration of the gas discharged by the first-stage composting gas filtering and discharging mechanism 4 is at any time or any one of the gas cannot reach the standard at the moment, the second-stage composting gas filtering and discharging mechanism 5 is directly started to work, at the moment, the first-stage composting gas filtering and discharging mechanism 4 and the second-stage composting gas filtering and discharging mechanism 5 are cascaded and work simultaneously until the condition is reached (the discharge concentration of all the monitored gas reaches the standard), and the control process of reducing the filtering capability of A is repeated.
And the composting PLC controller and the automatic monitoring system respectively or simultaneously control the composting fermentation devices, and alternately operate the process A or the process B according to the fermentation operation progress until the composting fermentation operation of a single round is finished.
An automatic monitoring system for volatile organic sulfur in the composting process of organic waste comprises a composting PLC (programmable logic controller) (not shown in figure 1), a blower 2, a composting fermentation device 1 and a composting gas filtering and discharging device which are sequentially communicated by gas connecting pipelines, and a composting gas automatic detecting device; the composting fermentation operation unit is in butt joint with the composting exhaust gas automatic detection device through a gas connection pipeline;
the automatic detection device for the compost discharge gas comprises: a gas flowmeter 6, a gas sampling processing device 7 and a GC-IMS 8;
The air blower 2, the composting fermentation device 1, the composting gas filtering and discharging device and a gas flowmeter, a gas sampling and processing device and a GC-IMS in the composting gas automatic detecting device are respectively connected by gas connecting pipelines, and the composting PLC, the air blower, the GC-IMS and the composting gas automatic detecting device are connected by a network;
the composting gas filtering and discharging device comprises a first-stage composting gas filtering and discharging mechanism 4 and a second-stage composting gas filtering and discharging mechanism 5 which are sequentially connected in series; the first-stage compost gas filtering and discharging mechanism 4 is internally provided with a biological drip filtration and deodorization structure, and the second-stage compost gas filtering and discharging mechanism 5 is internally provided with a physical adsorption filtration and deodorization structure;
The air outlet end of the first-stage compost gas filtering and discharging mechanism is divided into two paths: one path of the device is connected with an automatic detection device of the compost discharge gas, the other path of the device is connected with a first electromagnetic valve 10 and then is divided into two paths from the first electromagnetic valve, one path of the device is connected with a secondary compost gas filtering and discharging mechanism, and the other path of the device is connected with a primary discharging pipe 31; a gas flowmeter is integrated in the first electromagnetic valve 10;
The air outlet end of the secondary compost gas filtering and discharging mechanism 5 is one path and is directly connected with the secondary outer discharging pipe 32, and the air outlet end of the secondary outer discharging pipe 32 is divided into two paths: one path of the air is connected with the external atmosphere, and the other path of the air is connected with an automatic compost discharge gas detection device;
Volatile organic sulfur gas generated by the composting fermentation device 1 in the organic waste composting process is filtered by a composting gas filtering and discharging device together with air introduced by the air blower 2, and then enters a composting discharging gas automatic detecting device for concentration detection; if the concentration of the gas filtered by the first-stage compost gas filtering and discharging mechanism is detected to exceed the standard, the gas is automatically led into the second-stage compost gas filtering and discharging mechanism for filtering and detecting again, and the gas with qualified concentration is discharged into the atmosphere.
The gas sampling treatment device 7 comprises a gas sampling treatment container 71 (glass bottle), a sampling air inlet pipe 72, a sampling air outlet pipe 73, an ammonia concentration sensor 75 and a chemical agent 74 (specifically, a granular adsorbent such as calcium chloride capable of adsorbing ammonia) which are arranged in the gas sampling treatment container 71, wherein the gas sampling treatment container 71 is internally sealed, and the chemical agent 74 for absorbing ammonia components in composting gas is arranged at the lower part; the gas inlet of the sampling gas inlet pipe 72 is connected with the gas outlet of the gas flowmeter 6, the gas outlet is inserted into the bottom of the gas sampling treatment container 71 and the chemical agent 74, and when the gas passes through the gap of the chemical agent, the chemical agent reacts or absorbs the ammonia gas in the gas, and the ammonia gas does not react or absorb other components in the gas; the air inlet of the sampling air outlet pipe 73 is higher than the upper surface of the chemical agent 74, and the air outlet of the sampling air outlet pipe is connected with the air inlet of the GC-IMS 8;
the air blower 2, the composting fermentation device 1, the composting gas filtering and discharging device and a gas flowmeter 6, a gas sampling and processing device 7 and a GC-IMS 8 in the composting gas automatic detecting device are respectively connected by gas connecting pipelines, and the composting PLC (PLC controller), the air blower 2, an ammonia concentration sensor 75 and the GC-IMS 8 are mutually connected through a network;
a first electromagnetic valve 10 is arranged on a gas connecting pipe line between the air outlet end of the first-stage compost gas filtering and discharging mechanism and the air inlet end of the second-stage compost gas filtering and discharging mechanism; a second electromagnetic valve 11 is arranged on a gas connecting pipeline between a second-stage external discharge pipe of the first-stage compost gas filtering and discharging mechanism and the compost discharged gas automatic detecting device; the first electromagnetic valve 10 and the second electromagnetic valve 11 are all electric control three-way electromagnetic valves, and are internally integrated with gas flow meters, and the two electromagnetic valves are controlled by an automatic monitoring system and/or a composting PLC controller to select specific gas paths to open and close and control working parameters such as the flow direction, the flow velocity and the flow quantity of gas in the gas paths.
When the automatic monitoring system is automatically operated, the ammonia concentration sensor 75 automatically sends the sensed data to the composting PLC controller, if the concentration data is not zero (the chemical agent adsorption capacity is saturated at the moment), the second electromagnetic valve 11 is closed, the automatic composting exhaust gas detection device is stopped to work, after the new chemical agent 74 is manually replaced, the second electromagnetic valve 11 is opened again, and the automatic composting exhaust gas detection device is restored to work;
the exhaust port of the automatic compost exhaust gas detection device is connected with the air inlet of the gas flowmeter 6, and the air outlet of the gas flowmeter 6 is connected with the air inlet of the gas sampling treatment device 7 by a pipeline; the sampling air outlet pipe of the gas sampling processing device 7 is connected with the gas sample inlet of the gas chromatograph in the GC-IMS 8, and the gas chromatograph is connected with the mass spectrometer through an interface; the mass spectrum analyzer is connected with a remote control server 9 through a network to form an on-site on-line automatic monitoring system;
When the automatic monitoring system operates automatically, air (with different temperatures and flow rates) is introduced into the composting fermentation device 1 by the air blower 2, mixed gas discharged from the composting fermentation device 1 is introduced into a biological drip filtration deodorization structure of a first-stage composting gas filtration discharge mechanism for biological filtration and deodorization, and part of the filtered gas is firstly sent into a composting discharge gas automatic detection device through a second electromagnetic valve for detection, and if the concentration reaches the standard, the first electromagnetic valve 10 is opened, and the rest of the gas is led into a first-stage discharge pipe and discharged into the atmosphere; if the concentration does not reach the standard, the first electromagnetic valve 10 closes the passage leading to the first-stage outer discharge pipe, opens the passage leading to the second-stage compost gas filtering and discharging mechanism, so that the gas is discharged into the atmosphere through the second-stage outer discharge pipe after passing through the physical adsorption filtering and deodorizing structure (such as an active carbon filtering layer) and being filtered again, and meanwhile, the second electromagnetic valve 11 conducts the second discharge pipe with a gas passage directly of the compost discharge gas automatic detecting device, the compost discharge gas automatic detecting device carries out partial sampling detection, and detected data are sent to a compost PLC controller; if the detected gas concentration does not reach the standard, the fermentation condition of the composting fermentation device is changed through the composting PLC controller, or the filtration duration or the filtration strength of the first-stage composting gas filtration and discharge mechanism is enhanced, so that the concentration or the total amount of the monitored gas finally discharged into the atmosphere reaches the standard.
Example 2
Referring to fig. 2, the method and system for automatically monitoring volatile organic sulfur in an organic waste composting process provided in this embodiment are basically the same as that in embodiment 1, and are different in that six air inlet ends of each GC-IMS are fully utilized, when a plurality of sets (more than six sets) of composting fermentation operation units are provided in a workshop of an organic fertilizer factory, i.e. a monitoring site, each set of composting fermentation devices is abutted with one set of composting exhaust gas automatic detection device, wherein each set of abutted exhaust end of the composting fermentation devices is abutted with one air inlet end of the GC-IMS in the composting exhaust gas automatic detection device, and detection and monitoring of exhaust gas of each set of composting fermentation devices is completed in a time-sharing manner, in this embodiment, twelve sets of composting fermentation devices are provided, and the steps of each monitoring method in embodiment 1 further include the following steps:
s11, preparing two sets of automatic monitoring systems for volatile organic sulfur in organic waste composting process
According to the embodiment, a set of automatic detection device for compost discharge gas is configured according to every six sets of compost fermentation devices, and a set of automatic control system is used to form a monitoring system; according to the embodiment, two sets of automatic control systems which independently operate are configured according to two different types and numbers of fermentation tanks; one set of automatic control system manages the composting fermentation device consisting of six sets of fermentation tanks with the capacity of 20m 3, and the other set of automatic control system manages the composting fermentation device consisting of six sets of fermentation tanks with the capacity of 30m 3;
In other embodiments, the same set of automatic control system can be shared by all the composting fermentation devices and the automatic detection devices of the composting exhaust gas configured in the whole factory, and the control programs of all the subsystems are set in the automatic control system and correspond to all the monitoring systems.
S21, deploying two sets of automatic monitoring systems on site, and respectively setting working conditions
According to different capacities of the fermentation tanks, the six composting fermentation operation units with the same capacity and fixed quantity are combined into a group, and are respectively and simultaneously connected with a set of automatic compost discharge gas detection device through gas connection pipelines provided with three-way electromagnetic valves, and then connected with an automatic control system to form a monitoring system; the three-way electromagnetic valve comprises a first electromagnetic valve 10 and a second electromagnetic valve 11; setting the working conditions of each set of automatic compost discharge gas detection device to be the same; twelve sets of composting fermentation devices, and a composting exhaust gas automatic detection device and an automatic control system which are configured by the twelve sets of composting fermentation devices respectively form two monitoring systems;
S31, each set of automatic monitoring system automatically operates to obtain a monitoring result
Each set of automatic monitoring system controls the automatic compost discharge gas detection device in the system to monitor the gas discharged by each set of composting fermentation operation unit in a time-sharing and circulating way according to a preset time interval, and obtains monitoring results and sends the monitoring results to the corresponding composting PLC controller;
S41: each set of automatic monitoring system is automatically connected with the butted composting PLC controller, and the composting PLC controller correspondingly regulates and controls each set of composting fermentation device and composting gas filtering and discharging device, so that the generation amount of volatile organic sulfur gas is reduced, or the discharging of the volatile organic sulfur reaches the set concentration threshold value through filtering, and the standard-reaching discharging of the composting gas is realized.
In the embodiment, n in fig. 2 is a natural number greater than 2, in the embodiment, n=6, and every 6 composting fermentation operation units are grouped into a group, and the same automatic monitoring system is used for controlling the fermentation tanks with the same capacity; in other embodiments, medium-or large-sized fermenters having a capacity of 80-100m 3 may also be grouped and controlled as desired.
Example 3
Referring to fig. 2, the method and system for automatically monitoring volatile organic sulfur in organic waste composting process provided in this embodiment are basically the same as those in embodiment 2, and a remote server is introduced to provide a hardware carrier for operation of the automatic monitoring system, and facilitate remote centralized control, where the difference between the method and system for automatically monitoring is that:
the automatic monitoring system also comprises a remote server which is used as an operation carrier of the automatic monitoring system, wherein a time-sharing monitoring program, a GC-IMS data processing analysis calculation program and an automatic monitoring linkage program are arranged in the remote server, and the remote server is used for carrying out cooperation and control on a plurality of sets of automatic monitoring systems;
the remote server is connected with the air blower, the composting PLC controller, the electromagnetic valve and the GC-IMS of each composting fermentation operation unit through a network and controls the time-sharing operation of the remote server;
The remote control server analyzes and calculates GC-IMS detection data obtained by the plurality of sets of automatic monitoring systems, an external standard method is adopted, the on-machine detection data is compared with a standard curve, qualitative and quantitative detection results of the concentration of various volatile organic sulfur in a gas sample collected on site are obtained after analysis and calculation, the results are compared with a preset emission standard, and instructions whether to switch a gas emission path and whether to adjust ventilation flow are sent to each composting PLC controller so as to reduce the total amount of the generated volatile organic sulfur and reduce emission concentration.
The ammonia concentration sensor is arranged near an air inlet of the sampling air outlet pipe, is connected with the remote server or the composting PLC controller through a network, and automatically transmits the collected ammonia concentration data to the remote server or the composting PLC controller, stops detection when the chemical preparation adsorption capacity is saturated, and informs production management staff to change a new chemical preparation to recover the adsorption and removal capacity of ammonia.
Correspondingly, the automatic monitoring system for volatile organic sulfur in the composting process of organic waste provided by the embodiment further comprises a remote server, wherein a time-sharing monitoring program, a GC-IMS data processing analysis calculation program and an automatic monitoring linkage program are arranged in the remote server, and the remote server cooperates and controls the plurality of sets of automatic monitoring systems when a plurality of sets of composting fermentation operation units exist on site;
The remote server is connected with the air blower, the composting PLC controller, the electromagnetic valve and the GC-IMS of each composting fermentation operation unit through a network, and controls the time-sharing and circulating operation of the remote server;
The GC-IMS is provided with a plurality of input ends, the composting fermentation operation units are simultaneously connected with a plurality of sample injection ends of a set of composting exhaust gas automatic detection device (specific pipelines are respectively connected one by one, and the gas outlet end of one operation unit pipeline is connected with one sample injection end of the GC-IMS) to form a one-to-many detection device-operation unit system;
the detection devices and the composting fermentation operation unit systems are respectively connected with a remote server network to form a one-to-many remote control and detection device and composting fermentation operation unit system;
the remote control server calculates time-sharing GC-IMS detection data obtained by the plurality of sets of automatic monitoring systems to obtain qualitative and quantitative detection results of the concentration of various volatile organic sulfur in the gas sample collected by each detection device-composting fermentation operation unit system in real time, and then sends instructions whether to switch a gas discharge path and whether to adjust ventilation flow to each composting PLC controller according to a built-in program so as to reduce the total amount of volatile organic sulfur and reduce the discharge concentration, and the automatic operation of the plurality of sets of automatic monitoring systems is controlled in a time-sharing and circulating manner.
According to the embodiment of the invention, the composting fermentation device and the fermentation process can be automatically regulated and controlled according to the qualitative and quantitative detection results of the concentration of one or more volatile organic sulfur in the gas sample. The effect of different water content of the compost raw material on the emission concentration of the dimethyl sulfide is shown in figure 7. The invention can respectively set sampling points at a plurality of places of farms and organic fertilizer factory workshops (livestock and poultry organic waste composting sites), respectively groups according to the number of set equipment, places and time intervals, respectively or simultaneously carries out site online detection, and a manager can remotely obtain the concentration (comprising one or more) of the volatile organic sulfur gas discharged by each place, each time point and each composting working unit, and after analysis and calculation, obtain the discharge concentration and the discharge total amount of the volatile organic sulfur gas continuously discharged in each time period, thereby realizing the remote, dynamic and continuous monitoring and control of the site discharge of the volatile organic sulfur in the livestock and poultry organic waste composting. The standard reference values (emission concentration control thresholds) for malodorous contaminant factory marks set in the examples of the present invention are shown in table 1.
TABLE 1
Referring to fig. 3-7, the following detailed description of the present invention will be provided with a plurality of specific examples.
Example 4
The embodiment of the invention provides an automatic monitoring method and system for volatile organic sulfur in the organic waste composting process, which are further refined on the basis of the embodiment 1-3, and provide a specific technical scheme for combining all parts.
In the embodiment, the GC-IMS is made in China, a gas source adopted when a standard curve is established is a high-purity nitrogen continuous pipeline or a high-purity nitrogen generator, and a dynamic diluter is ENTECH and 4630;
The types and working conditions of the chromatographic column are set as follows: filling a column with a nonpolar bonding stationary phase MXT-1, wherein the column is 30m, 0.53mm and 4um;
The set gas chromatography-ion mobility spectrometry test conditions are as follows: ionization source: a tritium source (3H); sample inlet temperature: 80 ℃; column temperature: 80 ℃; transmission line temperature: 80 ℃; IMS transfer tube temperature: 80 ℃; quantitative ring volume: 1 mL; carrier gas pressure: 0.3Mpa; the carrier gas and the drift gas are high-purity nitrogen, and the flow rates are 5 mL/min and 75 mL/min respectively; migration tube voltage: 2131 V, V;
Setting the temperatures of the filling column, the IMS migration tube and the transmission line to be consistent;
The carrier gas flow rate is set as follows: the flow rate in the positive mode was 5 mL/min, and the flow rate in the negative mode was 3 mL/min.
The standard curve is established by the following steps:
Introducing high-purity nitrogen to prepare mixed standard gases of various volatile organic sulfur, vacuumizing a plurality of gas sampling treatment devices, respectively connecting to a dynamic diluter, diluting the original mixed standard gases with pure nitrogen according to a set proportion, and configuring a standard curve according to the following concentration gradient: 0.01,0.02,0.04,0.08,0.10,0.20,0.40,0.50,0.80 mu mol/mol, and establishing a standard curve for subsequent quantitative analysis;
Respectively preparing mixed standard gases of four volatile organic sulfur, namely dimethyl sulfide, ethylene sulfide, dimethyl disulfide and carbon disulfide, wherein the original concentration is 10 mu mol/mol, and the mixed standard gases are balanced by high-purity nitrogen;
Establishing a standard curve: after the plurality of gas sampling treatment devices are vacuumized, the gas sampling treatment devices are respectively connected to a dynamic diluter, original mixed standard gas is diluted by pure nitrogen according to a set proportion, and a standard curve is configured according to the following concentration gradient: 0.01,0.02,0.04,0.08,0.10,0.20,0.40,0.50,0.80. Mu. Mol/mol;
The mixed standard gas after being prepared is used within 2 hours.
The on-machine detection specifically comprises the following steps:
Performing on-machine detection under set parameters, adopting an MXT-1 chromatographic column, wherein the working temperature is 80 ℃ in a positive mode, the carrier gas flow is 5 mL/min, the working temperature is 45 ℃ in a negative mode, and the carrier gas flow is 3 mL/min, and performing on-machine detection on standard samples with different concentrations respectively;
And calculating to obtain a mixed standard gas detection result: by adopting external standard method analysis, the GC-IMS built-in program can output the concentration detection result of the mixed standard gas, and specifically, the nonlinear Boltzmann equation, namely formula 1, is fitted by the peak volume response value of the target component and the corresponding concentration level:
equation 1
Wherein: y i is the response value of the target component i, the peak volume (mV.s.ms), x i is the mass concentration of the target component i, and mg/m 3;A1、A2、X0 is a correlation constant, so that a plurality of volatile organic sulfur standard curves, fitting parameters and linear ranges are respectively obtained;
verification detection limit: analyzing the high-purity nitrogen as a sample, and detecting the baseline noise of each organic sulfur component; calculating the concentration of the component when the signal-to-noise ratio is equal to 3, thereby obtaining a detection limit;
and (3) verifying the precision and recovery rate of the detection result: diluting the mixed standard gas with high-purity nitrogen to prepare gas with a set concentration level; the sample was continuously fed 7 times, and the Relative Standard Deviation (RSD) and recovery rate of the 4 volatile organic sulfur detection values were calculated.
The preparation of the gas sample to be detected specifically comprises the following steps:
Each gas sampling apparatus 7 is inspected before use to replace the chemical;
The mixed gas discharged from each composting fermentation device is collected by using a gas sampling treatment container 71 according to a set working sequence and time intervals (such as sampling at intervals of 30 minutes), ammonia in the gas sample is removed by using a chemical agent (such as calcium chloride), and then the gas sample is stored;
The gas sample stored in the gas sampling container 71 is detected by a set detecting instrument and working conditions thereof, and compared with a standard curve, and the qualitative and quantitative detection results of the concentration of various volatile organic sulfur in the gas sample discharged from each composting fermentation device are obtained by on-site collection and analysis.
The method comprises the steps of respectively numbering and grouping a plurality of composting fermentation devices in an industrial livestock and poultry organic waste composting workshop such as an organic fertilizer factory, sequentially and respectively sampling, detecting, regulating and controlling, time-sharing and cycle sampling and detecting, adjusting composting fermentation conditions or gas filtering paths according to monitoring results, realizing that the whole process, the whole time period, the time-sharing and the cycle of the composting fermentation process are realized, continuously discharging the concentration and the total discharge amount of volatile organic sulfur gas of each composting fermentation device are monitored, recorded and monitored, and a manager can manage the operation of a plurality of sets of equipment in the factory through remote control, and research to obtain optimal working conditions and control parameter sets.
Example 5
The embodiment of the invention provides an automatic monitoring method and system for volatile organic sulfur in the organic waste composting process, which are further refined on the basis of the embodiments 1-4, and provide a specific technical scheme for combining all parts.
The industrialized large-scale compost fermentation devices provided by the embodiment have the capacity of 100m 3, and can monitor and control the emission of fermentation gas of chicken manure, cow manure and the like with high yield of ammonia gas and volatile organic sulfur gas in the composting fermentation process, wherein the composting fermentation tank mainly adopts aerobic composting, and the running period of single composting turn is generally 10-15 days. Because the front end is provided with the air inlet of the air blower 2, the whole gas connecting pipeline always has air flow, and the conditions of fermentation completion and no air in the gas path are avoided. Generally speaking, the fermentation of volatile sulfide during composting takes more time of about 7-8 days, and the time period should be closely monitored, and comprehensive measures such as adjusting ventilation rate, water content (spraying), raw material carbon nitrogen ratio, microbial inoculum addition ratio, stirring (turning) in a composting fermentation device, and adjusting a filtering and deodorizing line (primary filtering or two-stage filtering) after discharge are adopted, so that the aims of low generation, low emission and standard discharge of volatile organic sulfur gas are fulfilled.
(1) Experimental instrument and reagent
GC-IMS is produced by China sea energy instruments, inc., dynamic dilution instrument ENTECH, 4630, beijing pritaceae, inc.
Mixed standard gas of 4 components such as dimethyl sulfide, ethyl sulfide, dimethyl disulfide and carbon disulfide (Dalian big special gas Co., ltd.): the original concentration was 10. Mu. Mol/mol, balanced with high purity nitrogen. When the standard curve is established, a Tedlar PVF air collection bag (large Lian Delin), n-butanone-n-octanone calibration solution and high-purity nitrogen (> 99.999%) can be used.
The GC-IMS instrument used in this embodiment has the following features: the internal pump and the six-way valve can automatically or manually sample; carrying out portability; the detection result can be displayed on a touch screen or output in an analog signal through a network cable; the GC-IMS can realize the concentration control of the sniffing agent through the self-contained operation interface, the automatic sample injection and the data output, and can realize the concentration detection task through the three-dimensional data visualization and analysis through the self-contained LAV software without a special analysis technology. The instrument integrated six-way valve corresponds to six sampling air inlet ends, and each air inlet end can be in butt joint with the exhaust end of one composting fermentation device. However, since GC-IMS has a very large number of relevant measurement parameters, the operator must choose from a targeted set of parameters that can be adapted to the automated operation and to the object under test.
(2) Setting detection conditions of a gas chromatograph-ion mobility spectrometer GC-IMS
Type of column: MXT-1 (30 m,0.53mm,4 um) and MXT-5 (30 m,0.53mm,4 um) (Rui Si Tai kang technology Co., ltd., china).
Gas chromatography-ion mobility spectrometry test conditions: ionization source: a tritium source (3H); sample inlet temperature: 80 ℃; column temperature: 80 ℃; transmission line temperature: 80 ℃; IMS transfer tube temperature: 80 ℃; quantitative ring volume: 1 mL; carrier gas pressure: 0.3Mpa. The carrier gas and the drift gas are high-purity nitrogen, and the flow rates are 5 mL/min and 75 mL/min respectively; migration tube voltage: 2131 V is provided.
(3) Detection step and procedure
(3-1) Sample collection and preservation
The gas sampling apparatus is refreshed and cleaned prior to use. The method comprises the following specific steps: the gas sampling vessel was filled with high purity nitrogen and equilibrated at 50 ℃ for 2 hours. And then reversely multiplexing high-purity nitrogen to fill the gas sampling treatment containers, vacuumizing, taking one of the gas sampling treatment containers to fill the high-purity nitrogen, and detecting the background value of the gas generated in the gas sampling treatment container until no impurity peak is detected. As the malodorous gas generated by the organic waste compost contains ammonia gas with higher concentration, the ammonia gas and water belong to the same polar substance, and the peak time of the ammonia gas and the water on a nonpolar or low-polar chromatographic column is similar. And the proton affinity of ammonia (853.6 KJ/mol) is stronger than that of water (691.06 KJ/mol). Therefore, when ammonia exists in the sample, the generation of hydrated protons can be seriously influenced, so that the formation of molecular ions of the compound to be tested is further influenced, and the qualitative and quantitative determination of the volatile organic sulfur is interfered. Therefore, before collecting the sample, the ammonia gas in the gas sample needs to be removed by using a gas sampling treatment device (see fig. 1) and calcium chloride.
(3-2) Standard Curve configuration
After the gas sampling treatment container is vacuumized, the gas sampling treatment container is connected to a dynamic diluter and dilutes the original mixed standard gas according to a certain proportion, and a standard curve is configured according to the following concentration gradient: 0.01,0.02,0.04,0.08,0.10,0.20,0.40,0.50,0.80. Mu. Mol/mol. Can be used within 2 hours after being prepared.
The four volatile organic sulfur standard curve diagrams of the embodiment of the invention are shown in figure 6.
(3-3) Selection of instrument operating conditions
Selection of chromatographic columns: separation analysis of dimethyl sulfide, ethyl sulfide, dimethyl disulfide and carbon disulphide against a non-polar bound stationary phase (MXT-1) packed column and a weakly polar bound stationary phase (MXT-5) packed column. The four volatile organic sulfur compounds can be separated on the two packed columns, and the peak position is positioned at the front. However, the response (in peak volumes) of MXT-1 to each volatile organic sulfur was more than 25% higher than that of MXT-5 (FIG. 2). For example, the response of dimethyl disulfide and carbon disulfide on an MXT-1 packed column is more than 2 times that on an MXT-5 packed column. Thus, the MXT-1 packed column was finally selected for analysis of volatile organic sulfur. Fig. 3 is an ion mobility spectrum when four volatile organic sulfur species were analyzed using an MXT-1 packed column. Wherein, dimethyl sulfide, ethyl sulfide and dimethyl disulfide are detected under positive mode conditions, and carbon disulfide is detected under negative mode conditions. The responses of the four volatile organic sulfur compounds on the MXT-1 and MXT-5 packed columns are shown in FIG. 3. The ion mobility spectrum of the four volatile organic sulfur compounds on the MXT-1 packed column is shown in fig. 4, wherein the left graph is in positive mode; the right graph is negative mode.
(3-4) Optimization of the temperature of the detecting instrument
In this embodiment, the temperatures of the filling column, the IMS migration tube and the transmission line are set to be consistent. The response of each volatile organic sulfur was examined at-45, 60, and 80 ℃ for different detection systems. The response of dimethyl sulfide (1.39 mg/m 3), ethyl sulfide (2.01 mg/m 3), dimethyl disulfide (21.0 mg/m 3) and carbon disulfide (1.70 mg/m 3) at different temperatures is shown in FIG. 5 (a). It can be seen that both the dimethyl sulfide and the carbon disulfide gradually become lower in response as the temperature of the detection system increases. This is mainly because the boiling points of dimethyl sulphide and carbon disulphide are 38 ℃ and 46.2 ℃ respectively. Thus, when the detection system temperature is raised from 45 ℃ to 80 ℃, adsorption of dimethyl sulfide and carbon disulfide on the packed column is not favored. Whereas the response of ethylene sulfide and dimethyl disulfide is significantly higher at 60 ℃ and 80 ℃ than at 45 ℃. Finally, the response of dimethyl sulfide is highest considering the same concentration. And the higher the temperature, the faster the peak time of the dimethyl sulfide, ethyl sulfide and dimethyl disulfide. Thus, 80 ℃ was selected in the positive mode. While 45 c was selected as the detection temperature in the negative mode.
(3-5) Optimization of Carrier gas flow
In this example, the response diagrams of the four volatile organic sulfur compounds at different temperatures and different flow rates are shown in fig. 5, where (a) in fig. 5 is a response diagram at different temperatures and (b) in fig. 5 is a response diagram at different flow rates.
According to the optimized temperature of the detection system, the concentrations of the four samples are respectively according to the concentrations in (3-4), and the influence of different gas chromatography carrier gas flows of-3 mL/min, 5 mL/min and 10 mL/min on the detection of the volatile organic sulfur is tested. As in FIG. 5 (b), the response at a flow rate of 10 mL/min was the lowest for all four volatile organosulfur. Whereas for dimethyl sulfide, ethyl sulfide and carbon disulphide, the response is highest at a flow rate of 3 mL/min. This is because the lower carrier gas flow rate enables the sample to flow more fully through the packed column stationary phase, and the probability of being effectively adsorbed is greater, so that the material separation time is longer and the separation effect is better. For dimethyl disulfide, the response was highest at a flow rate of 5 mL/min. This is probably because the boiling point (109 ℃) of dimethyl disulfide is the highest of the four volatile organosulfur, requiring higher flow rates to desorb from the packed column. In the positive mode, when the flow is 3 mL/min, the total peak time is 600 seconds; and at a flow rate of 5 mL/min, the total off-peak time was 400 seconds. Considering that the response of dimethyl disulfide is lower than that of dimethyl sulfide and ethyl sulfide, the flow rate in the positive mode was chosen to be 5 mL/min. While in negative mode the flow rate is chosen to be 3 mL/min.
(3-6) Linear Range and detection Limit
Standard samples of different concentrations were analyzed under optimized parameters (MXT-1 column, positive mode operating temperature 80 ℃, carrier gas flow 5 mL/min, negative mode operating temperature 45 ℃, carrier gas flow 3 mL/min). Equation 1 is fitted with the boltzmann equation that is nonlinear with the target component peak volume response values and corresponding concentration levels.
Equation 1
Wherein: y i is the response value of the target component i, the peak volume (mV.s.ms), x i is the mass concentration of the target component i, and mg/m 3;A1、A2、X0 is the correlation constant.
The fitting parameters and linear ranges of the four volatile organic sulfur standard curves in the embodiment are shown in table 2, and the four established volatile organic sulfur standard curves are shown in fig. 6.
TABLE 2
(3-7) Verification of detection limit
High purity nitrogen was analyzed as a sample to detect baseline noise for each organic sulfur component. The concentration of this component was calculated at a signal-to-noise ratio equal to 3, from which the detection limit was obtained (see Table 3). According to the environmental air quality standard of GB 3095-1996 and the malodorous pollutant emission standard of GB 14554-1993 in China, the detection limit of the dimethyl sulfide and the carbon disulfide is lower than the emission standard of a first class area, namely a natural protection area, and the detection limit of the dimethyl disulfide is lower than the emission standard of a second class area, namely a living area or a general industrial area. Therefore, the GC-IMS is adopted for on-site rapid detection, and a reference basis can be provided for the emission management of organic sulfur in the composting gas.
(3-8) Verification of precision and recovery rate
And diluting the mixed standard gas with high-purity nitrogen to prepare the gas with a certain concentration level. Sampling is continuously carried out for 7 times, and the Relative Standard Deviation (RSD) and recovery rate of the detection values of the 4 volatile organic sulfur are calculated; the detection limits, the precision and the recovery test results in this example are shown in Table 3.
TABLE 3 Table 3
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(4) Testing of gas samples at factory workshop site sampling points
The single-point discharged gas sample filtered by the first-stage compost gas filtration and discharge device was collected by a livestock manure composting fermentation device (fermenter) of an organic fertilizer plant workshop by using a gas sampling treatment device 7, and was measured according to the above-mentioned test method, and the test results (actual sample measurement results) are shown in table 4. The types of organic sulfur discharged during composting will vary somewhat with the composting time. However, the levels of ethyl sulfide and carbon disulfide in all samples after the first filtration were less than the detection limit. In other embodiments, if either the ethylene sulfide or carbon disulfide content in the sample after the primary filtration is greater than the detection limit, the secondary filtration is started to ensure that the concentration content of all the monitored gas components in the sample is less than the detection limit.
TABLE 4 Table 4
In summary, the embodiment of the invention establishes an automatic monitoring method for the generation and emission of volatile organic sulfur gas in livestock and poultry organic waste compost by adopting the blower, the compost PLC, the sampling treatment device and the gas chromatograph-ion mobility spectrometer. The invention comprehensively considers the actual requirements of the industrial production of the organic fertilizer plant, and optimizes the influences of the type of the gas chromatographic column, the working temperature and the carrier gas flow in the detection process. The detection method can realize quantitative analysis of the dimethyl sulfide, the ethyl sulfide, the dimethyl disulfide and the carbon disulfide in a positive mode and a negative mode, has wide linear range and high precision and recovery rate, and can meet the monitoring requirement of organic sulfur emission in the first-class area and the second-class area in GB 14554-1993. The invention has simple integral operation, avoids pretreatment such as concentration enrichment of samples, and can automatically operate monitoring systems and equipment. Therefore, the invention provides a convenient, feasible, economical and practical technical approach for the on-site detection and monitoring of the emission management of the volatile organic sulfur in the industrialized composting units such as the organic fertilizer plants.
According to the embodiment of the invention, the ion mobility spectrometry adopted in the detection method has higher sensitivity to malodorous sulfides, and can be used for directly detecting without sample pretreatment. And because the ion mobility spectrometry is small in size, the characteristics of no vacuum and the like are not needed, the sample inlet can be automatically started, shut down and replaced, the operation is convenient and rapid, the analysis time is short, and the real-time and on-line monitoring, time-sharing and cycle detection of malodorous sulfide discharged by a single composting fermentation operation unit can be realized. The ion mobility spectrometry is a technology for separating and detecting based on different movement rates of gas-phase ions in an external electric field under the atmospheric pressure state, has the advantages of high detection speed, high sensitivity, low price and the like, and is a real-time dynamic detection technology with great application prospect. After bad smell is collected through the air bag, the bad smell sulfide in the concentrated air bag is not needed to be enriched, the bad smell sulfide is directly connected with the ion mobility spectrometry, and one or more of the bad smell sulfide is detected on site and quantitatively through a standard working curve.
The embodiment of the invention adopts the mutual cooperation of the components of a blower, a composting PLC controller, a composting fermentation device, a gas sampling treatment device, a gas chromatography-ion mobility spectrometry, a remote server and the like, and establishes the automatic sampling, detecting, regulating and controlling methods and systems of the volatile organic sulfur-methyl sulfide, ethyl sulfide, dimethyl disulfide and carbon disulfide in the livestock and poultry organic waste compost. The gas discharged from each composting fermentation device is filtered and sampled, and then separated by an MXT-1 gas chromatographic filling column, and concentration detection is carried out under the optimized carrier gas flow and system temperature conditions by adopting a positive mode and a negative mode. The results show that the correlation coefficient of the four organic sulfur is more than 0.99 in each linear range; the detection limit is 0.008-0.097 mg/m 3, the recovery rate is 85% -116%, and the Relative Standard Deviation (RSD) is 1.13% -8.42%. The automatic monitoring method provided by the invention does not need to carry out pretreatment such as concentration and enrichment on the gas sample, can complete synchronous collection of various composting malodorous gases by adopting the gas sampling treatment device, has sensitive detection and quick response, and can be widely used for workshop site monitoring and equipment working condition control of various volatile organic sulfur in composting gases of units such as farms, organic fertilizer factories and the like. The type of composting fermentation device (apparatus) and the main parameters that can be used in other embodiments of the invention are shown in table 5 below.
TABLE 5
According to the automatic monitoring method and the system for the volatile organic sulfur in the organic waste composting process, provided by the embodiment of the invention, the monitoring flow is greatly simplified, the number of equipment is reduced, the detection device can be linked with composting equipment and a control system thereof, and an important technical means is provided for realizing the industrialization of the composting production flow and automation by the cooperative cooperation among the composting equipment, the process and the detection instrument, so that the method and the system have important significance for improving the industrialization composting production efficiency, reducing the environmental pollution and promoting the sustainable development of agriculture.
In other embodiments of the present invention, the technical effects described in the present invention may be achieved by performing specific selection of other different schemes within the ranges of the apparatus, the device, the steps, the components, the proportions, the process parameters and the control conditions described in the present invention, so that the present invention is not listed one by one.
The above description is only of the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention or modifications to equivalent embodiments using the methods and technical contents disclosed above, without departing from the scope of the technical solution of the present invention. All equivalent changes of the components, proportions and processes according to the invention are covered in the protection scope of the invention.
Claims (5)
1. An automatic monitoring method for volatile organic sulfur in organic waste composting process is characterized by comprising the following steps:
s1, preparing each component part of an automatic monitoring system for volatile organic sulfur in organic waste composting process
Respectively preparing at least one compost PLC controller, a blower, a compost fermentation device, a compost gas filtering and discharging device, a compost discharging gas automatic detecting device and a remote server;
The remote server is internally provided with a time-sharing monitoring program, a GC-IMS data processing analysis calculation program and an automatic monitoring linkage program, and is used for carrying out cooperation and control on a plurality of sets of automatic monitoring systems; the remote server is connected with a blower of a composting fermentation operation unit, a composting PLC controller, an electromagnetic valve and a GC-IMS through a network and controls the time-sharing operation of the remote server;
The automatic detection device for the compost discharge gas comprises: a gas flowmeter, a gas sampling treatment device and a gas chromatograph-ion mobility spectrometer (GC-IMS); the gas sampling treatment device adsorbs ammonia in the treated gas sample;
The composting gas filtering and discharging device comprises a first-stage composting gas filtering and discharging mechanism and a second-stage composting gas filtering and discharging mechanism which are sequentially connected;
the first-stage compost gas filtering and discharging mechanism comprises a gas connecting pipeline, a biological drip filtration deodorization structure, a first electromagnetic valve and a first-stage external discharging pipe; the air inlet end of the bio-drip deodorizing mechanism is connected with the composting fermentation device through an air connecting pipeline, the air outlet end is divided into two paths, one path is connected with the air inlet end of the first electromagnetic valve through the air connecting pipeline, and the other path is connected with one path of air inlet end of the second electromagnetic valve;
The secondary compost gas filtering and discharging mechanism comprises a gas connecting pipeline, a physical adsorption filtering and deodorizing structure and a secondary outer discharging pipe; the physical adsorption filtration deodorization structure is connected with one air outlet end of the second electromagnetic valve through an air connecting pipeline, the air inlet end of the secondary outer discharge pipe is connected with the air outlet end of the physical adsorption filtration deodorization structure, and the air outlet end of the secondary outer discharge pipe is connected with the other air inlet end of the second electromagnetic valve;
The gas sampling treatment device comprises a gas sampling treatment container, a sampling air inlet pipe, a sampling air outlet pipe, an ammonia concentration sensor and a chemical agent, wherein the ammonia concentration sensor and the chemical agent are arranged in the gas sampling treatment container, the gas sampling treatment container is internally sealed, and the chemical agent for absorbing ammonia components in composting gas is arranged at the lower part; the gas inlet of the sampling gas inlet pipe is connected with the gas outlet of the gas flowmeter, and the gas outlet is inserted into the bottom of the gas sampling treatment container and the chemical agent; the air inlet of the sampling air outlet pipe is higher than the upper surface of the chemical agent, and the air outlet of the sampling air outlet pipe is connected with the air inlet of the GC-IMS; the ammonia concentration sensor is arranged near an air inlet of the sampling air outlet pipe and is connected with the remote server or the composting PLC controller through a network;
s2, deploying an automatic monitoring system on site and setting working conditions
S21, connecting an on-site air blower, a composting fermentation device and a composting gas filtering and discharging device with a gas flowmeter, a gas sampling and processing device and a GC-IMS in an automatic composting gas discharging detection device through gas connecting pipelines respectively, and connecting a composting PLC (programmable logic controller), the air blower and the GC-IMS through a network;
A composting PLC controller, a blower, a composting fermentation device and a composting gas filtering and discharging device form a set of composting fermentation operation unit, and the composting fermentation operation unit is abutted against a composting gas automatic detecting device;
S22, setting the operation condition of the automatic monitoring system
Setting the working conditions of GC-IMS automatic monitoring as follows:
An MXT-1 chromatographic column is adopted, the working temperature is 80 ℃ under the positive mode, the carrier gas flow is 5 mL/min, the working temperature is 45 ℃ under the negative mode, the carrier gas flow is 3 mL/min, and the positive mode and the negative mode are set to be automatically switched;
setting gas chromatography conditions: setting the type and working condition of chromatographic column;
Ion mobility spectrometry conditions are set: setting gas chromatography-ion mobility spectrometry test conditions;
Setting the temperatures of the filling column, the IMS migration tube and the transmission line to be consistent;
setting carrier gas flow;
Initializing a composting PLC controller, feeding materials, organic wastes and composting fermentation bacteria into a composting fermentation device, and performing composting fermentation;
S3, automatically operating an automatic monitoring system to obtain a monitoring result
The method comprises the steps that a composting PLC controller controls a blower to blow air into a composting fermentation device, volatile organic sulfur exhaust gas discharged in the composting process inside the composting fermentation device is sent into a composting gas filtering and discharging device and a composting exhaust gas automatic detection device, part of the filtered gas sequentially flows through the composting gas filtering and discharging device and is discharged into the atmosphere, the other part of the filtered gas flows through a gas flowmeter, a gas sampling and processing device and a GC-IMS, ammonia components in a gas sample are adsorbed and processed by the gas sampling and processing device, then the gas sample is automatically detected by the machine according to set GC-IMS automatic monitoring working conditions, and monitoring data of the volatile organic sulfur exhaust gas discharged in the composting process are obtained after analysis and calculation;
S4: automatic regulation and control of automatic monitoring system to realize standard emission
The automatic monitoring system is used for automatically adjusting working conditions or exhaust paths of the air blower, the composting fermentation device and the composting gas filtering and discharging device by the composting PLC according to a comparison result of the monitoring data and a preset monitoring threshold value or feeding back the monitoring data to the composting PLC and linking the composting PLC, so that the generation amount of the volatile organic sulfur is reduced or the filtering is enhanced, and finally, the atmospheric emission concentration or total amount of the volatile organic sulfur is lower than a set standard and is discharged up to the standard;
The remote control server analyzes and calculates GC-IMS detection data obtained by the automatic monitoring system, compares the on-machine detection data with a standard curve by adopting an external standard method, obtains qualitative and quantitative detection results of the concentration of various volatile organic sulfur in a gas sample collected on site after analysis and calculation, compares the results with a preset emission standard, and sends instructions whether to switch a gas emission path and whether to adjust ventilation flow to a composting PLC controller so as to reduce the total amount of volatile organic sulfur and reduce emission concentration;
the plurality of volatile organic sulfur is concretely dimethyl sulfide, ethyl sulfide, dimethyl disulfide and carbon disulfide;
s5: automatic monitoring system dynamic, continuous and automatic monitoring
The automatic monitoring system repeats the steps S3-S4, the automatic detection device of the composting exhaust gas carries out cyclic monitoring, recording and operation on the concentration and the total amount of volatile organic sulfur in the gas components exhausted by the composting fermentation device according to the set time interval, and the automatic detection device is linked with the composting PLC controller according to the comparison result of the monitoring data and the preset monitoring threshold value, so that the working condition or the exhaust path of each part is automatically regulated and controlled, the up-to-standard emission is realized, and the long-time continuous and automatic dynamic monitoring is realized;
In the steps S3-S5, the composting PLC controller controls the air blower to introduce air into the composting fermentation device, and the air and the gas generated by the internal fermentation of the composting fermentation device are mixed to form mixed gas, and the mixed gas is discharged into the first-stage composting gas filtering and discharging mechanism through the gas connecting pipeline: the mixed gas firstly passes through a biological drip filtration deodorization structure, ammonia gas and volatile organic sulfur gas in the mixed gas are removed through the biological drip filtration deodorization structure, a part of the treated gas is firstly introduced into an automatic compost discharge gas detection device for concentration monitoring, and if the concentration of the treated gas reaches a set threshold value, the rest part of the treated gas is discharged into the atmosphere through a first-stage outer discharge pipe; if the set threshold value cannot be reached, the first electromagnetic valve guides all the gas into the secondary compost gas filtering and discharging mechanism for secondary filtration;
After the mixed gas led into the secondary compost gas filtering and discharging mechanism is filtered by the physical adsorption filtering and deodorizing structure, one part of the mixed gas is firstly led into the automatic compost discharging gas detecting device for concentration monitoring, and the other part is discharged into the atmosphere through a secondary outer discharging pipe if the concentration of the mixed gas reaches a set threshold value; if the set threshold value cannot be reached, the second electromagnetic valve simultaneously closes the secondary external discharge pipe and the gas connecting pipeline of the automatic compost discharge gas detection device, increases the filtering time to a set length, opens the gas connecting pipeline of the automatic compost discharge gas detection device, detects again, and opens the secondary external discharge pipe to discharge into the atmosphere after the volatile organic sulfur in the gas reaches the set threshold value.
2. The method for automatically monitoring volatile organic sulfur in an organic waste composting process according to claim 1, wherein when a plurality of composting fermentation operation units are provided on the monitoring site, each step further comprises the following steps:
s11, preparing one or more sets of automatic monitoring system for volatile organic sulfur in organic waste composting process
S21, deploying an automatic monitoring system on site and setting working conditions
Simultaneously butting a set of automatic compost discharge gas detection devices with a fixed number of composting fermentation operation units through gas connection pipelines provided with electromagnetic valves; setting the working conditions of each set of automatic compost discharge gas detection device to be the same;
S31, each set of automatic monitoring system automatically operates to obtain a monitoring result
Each set of automatic compost discharge gas detection device monitors the gas discharged by each set of composting fermentation operation unit in a time-sharing and circulating way according to a preset time interval, and obtains monitoring results and sends the monitoring results to a corresponding composting PLC controller;
s41: each set of automatic monitoring system is automatically connected with the butted composting PLC controller to perform corresponding regulation and control, reduce the generation amount of volatile organic sulfur, or filter the volatile organic sulfur to a set concentration threshold value, so as to realize the standard emission of composting gas.
3. An automatic monitoring device for volatile organic sulfur in organic waste composting process, which is characterized by comprising a set of composting fermentation operation unit and a composting exhaust gas automatic detection device, wherein the set of composting fermentation operation unit is formed by at least one composting PLC controller, a blower, a composting fermentation device and a composting gas filtering and exhausting device which are communicated with each other by gas connecting pipelines in sequence, and the automatic monitoring device is used for realizing the automatic monitoring method of any one of claims 1-2; the composting fermentation operation unit is in butt joint with the composting exhaust gas automatic detection device through a gas connection pipeline;
The automatic detection device for the compost discharge gas comprises: a gas flowmeter, a gas sampling processing device and a GC-IMS;
The air blower, the compost fermentation device, the compost gas filtering and discharging device and a gas flowmeter, a gas sampling and processing device and a GC-IMS in the compost discharged gas automatic detection device are respectively connected by gas connecting pipelines, and the compost PLC, the air blower, the GC-IMS and the gas sampling and processing device are connected by a network;
The composting gas filtering and discharging device comprises a first-stage composting gas filtering and discharging mechanism and a second-stage composting gas filtering and discharging mechanism which are sequentially connected in series; the first-stage compost gas filtering and discharging mechanism is internally provided with a biological drip filtration and deodorization structure, and the second-stage compost gas filtering and discharging mechanism is internally provided with a physical adsorption filtration and deodorization structure;
the air outlet end of the first-stage compost gas filtering and discharging mechanism is divided into three paths: one path of the device is connected with an automatic detection device for the compost discharge gas, and the other path of the device is connected with a secondary compost gas filtering and discharging mechanism and a primary outer discharging pipe;
the air outlet end of the secondary compost gas filtering and discharging mechanism is one path, and is directly connected with a secondary outer discharging pipe which is divided into two paths: one path of the air is connected with the external atmosphere, and the other path of the air is connected with an automatic compost discharge gas detection device;
Volatile organic sulfur gas generated by the composting fermentation device in the organic waste composting process is filtered together with air introduced by the air blower through the composting gas filtering and discharging device, and then enters the composting gas automatic detecting device for concentration detection; if the concentration of the gas filtered by the first-stage compost gas filtering and discharging mechanism is detected to exceed the standard, the gas is automatically led into the second-stage compost gas filtering and discharging mechanism for filtering and detecting again, and the gas with qualified concentration is discharged into the atmosphere.
4. An automatic monitoring device for volatile organic sulphur in organic waste composting as claimed in claim 3, characterized in that,
The gas sampling treatment device also comprises an ammonia concentration sensor; the air blower, the compost fermentation device, the compost gas filtering and discharging device and a gas flowmeter, a gas sampling and processing device and the GC-IMS in the compost discharged gas automatic detection device are respectively connected by gas connecting pipelines, and the compost PLC, the air blower, the ammonia concentration sensor and the GC-IMS are connected through a network;
a first electromagnetic valve is arranged on a gas connecting pipe line between the air outlet end of the first-stage compost gas filtering and discharging mechanism and the air inlet end of the second-stage compost gas filtering and discharging mechanism; a second electromagnetic valve is arranged on a gas connecting pipeline between a second-stage outer discharge pipe of the first-stage compost gas filtering and discharging mechanism and the compost discharged gas automatic detection device;
when the automatic monitoring system operates automatically, the data sensed by the ammonia concentration sensor is sent to the composting PLC controller, if the concentration data is not zero, the second electromagnetic valve is closed, the composting exhaust gas automatic detection device is stopped to work, the second electromagnetic valve is restarted again after the chemical agent is replaced, and the composting exhaust gas automatic detection device is restored to work;
when the automatic monitoring system operates automatically, the gas of the biological drip filtration deodorization structure of the first-stage composting gas filtration and discharge mechanism is sent to the composting gas automatic detection device through the second electromagnetic valve to be detected, and if the concentration reaches the standard, the first electromagnetic valve is started to be led into the first-stage outer discharge pipe and discharged into the atmosphere; if the concentration does not reach the standard, the first electromagnetic valve is closed to guide the first-stage outer discharge pipe, the guide second-stage compost gas filtering and discharging mechanism is opened, so that gas is discharged into the atmosphere through the second-stage outer discharge pipe after being filtered again through the physical adsorption filtering deodorizing structure, meanwhile, the second electromagnetic valve is used for conducting the second discharge pipe with a gas path directly of the compost discharge gas automatic detecting device, the compost discharge gas automatic detecting device is used for carrying out partial sampling detection, and detection data are sent to the compost PLC controller.
5. An automatic monitoring device for volatile organic sulfur in organic waste composting process according to claim 3, wherein when a monitoring site is provided with a plurality of sets of composting fermentation operation units, the automatic monitoring device further comprises a remote server, wherein a time-sharing monitoring program, a GC-IMS data processing analysis calculation program and an automatic monitoring linkage program are arranged in the remote server, and the plurality of sets of automatic monitoring systems are cooperated and controlled by the remote server;
the remote server is connected with the air blower, the composting PLC controller, the electromagnetic valve and the GC-IMS of each composting fermentation operation unit through a network and controls the time-sharing operation of the remote server;
The composting fermentation operation units are simultaneously connected with a set of automatic detection device for composting exhaust gas to form a one-to-many detection device-operation unit system;
The detection device-operation unit systems are respectively connected with a remote server network to form a one-to-many remote control-detection device-operation unit system;
the remote control server calculates time-sharing GC-IMS detection data obtained by the plurality of sets of automatic monitoring systems to obtain qualitative and quantitative detection results of the concentration of various volatile organic sulfur in the gas sample collected by each detection device-operation unit system in real time, and then sends instructions whether to switch a gas discharge path and whether to adjust ventilation flow to each composting PLC controller according to a built-in program so as to reduce the total amount of volatile organic sulfur and reduce the discharge concentration, and the automatic operation of the plurality of sets of automatic monitoring systems is controlled in a time-sharing manner.
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| CN117586055A (en) | 2024-02-23 |
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