CN115970432A - Treatment process and method for volatile VOCs in coking and chemical production area - Google Patents
Treatment process and method for volatile VOCs in coking and chemical production area Download PDFInfo
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Abstract
The invention relates to a process and a method for treating volatile VOCs in a coking and chemical production area, which comprises the following steps: molecular sieve adsorption, nitrogen desorption and condensate recovery. The invention has the beneficial effects that: in the adsorption stage, VOCs with different concentrations and gas volumes are concentrated and enriched, so that the concentration of the VOCs is improved, and the cost of subsequent VOCs recovery treatment is reduced; in addition, the invention is matched with a condensation recovery method to enrich and recover the adsorbed VOCs, so that resource utilization can be carried out in the future, the discharged flue gas amount of the VOCs is greatly reduced, and the cooling agent is water and ethanol, so that the cost is low and easy to obtain, and the environmental pollution and the treatment cost are obviously reduced.
Description
Technical Field
The invention relates to the field of waste gas treatment, in particular to a process and a method for treating Volatile Organic Chemicals (VOCs) in a coking and chemical production area.
Background
Volatile Organic Compounds (VOCs) refer to Volatile hydrocarbons and their derivatives, including hydrocarbons, aromatic hydrocarbons, alcohols, aldehydes, ketones, esters, amines, organic acids, and the like. VOCs not only bring serious environmental pollution problems, but also harm human health, and generate great harm to environmental safety and human survival. In recent years, the national control and treatment of the discharge of VOCs pollutants in various industries is more and more strict, and a series of related VOCs discharge standards are provided in the country and various provinces and cities.
The coking industry is an important discharge source of VOCs, and with the stricter environmental protection policy and requirements of China, the collection, treatment and discharge of VOCs in each section of a coking plant are key points of future environmental protection work. The waste gas of the VOCs emission source in the coking industry has the characteristics of complex composition, various VOCs components, more VOCs production and discharge nodes, difference in production and discharge characteristics of each node and the like. Wherein, the chemical production area and the coking wastewater treatment link are the most main production and discharge sources of the coking VOCs waste gas. The chemical production area comprises a cold drum section, a desulfurization section, an ammonium sulfate section and a debenzolization section, and is the area with the most VOCs generated in the whole process. At present, VOCs dissipated gas in treatment and chemical production areas of the domestic and foreign coking industry generally adopts chemical washing, incineration, gas negative pressure pipeline absorption, adsorption, concentration, condensation and recovery, centralized collection and treatment, and enters a coke oven combustion system and the like. However, the coverage rate of the process industries is high, but the general treatment efficiency is low, the standard requirements are difficult to meet, or the requirements on the components of the waste gas are high, so that the high-efficiency and low-cost treatment of the volatile VOCs in the coking and chemical production area at present is difficult to realize.
At present, combustion methods are mostly adopted for purification of VOCs in coking and chemical production areas as final treatment modes, pollutants are subjected to destructive purification, waste of resources is formed for waste gas with recycling value, active carbon is mostly adopted as an adsorbent for adsorption of VOCs at present, and the adsorbed gas is single in type and limited in efficiency.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a process and a method for treating Volatile Organic Compounds (VOCs) in a coking and chemical production area.
In a first aspect, a system for treating VOCs by dissipation in coking and chemical production area is provided, comprising: the device comprises a filtering device, an adsorption system, a heating source, a nitrogen tank, a cooling system and a chimney;
the adsorption system comprises a first adsorption tank and a second adsorption tank, wherein the first adsorption tank and the second adsorption tank are arranged in parallel; the filtering device is sequentially connected with the adsorption system and the chimney; the nitrogen tank is connected with the adsorption system through the heating source; a circulation loop is formed between the adsorption system and the cooling system.
Preferably, the cooling system includes: the system comprises a primary cooler, a secondary cooler, a deep cooler and a cold tank; the primary cooler, the secondary cooler and the deep cooler are sequentially connected and are all connected with the cold tank.
Preferably, a first fan is arranged in front of the inlet end of the chimney, a second fan is arranged between the nitrogen tank and the heating source, and a third fan is arranged at one end, close to the deep cooler, of the cooling system.
Preferably, the adsorbent of the adsorption system comprises at least one of ZSM-5 and high-silicon USY molecular sieve.
Preferably, the adsorbent of the adsorption system is a hydrophobic molecular sieve.
Preferably, the heating temperature of the heating source is 150 to 180 ℃.
Preferably, the refrigerant of the secondary cooler and the chiller is ethylene glycol aqueous solution.
In a second aspect, there is provided a method for treating volatile VOCs in coking and chemical production area, which is performed by the system for treating volatile VOCs in coking and chemical production area of the first aspect, and comprises:
s1, collecting raw flue gas, wherein the raw flue gas enters a first adsorption box after impurities are filtered by a filtering device, and the flue gas adsorbed by a molecular sieve is introduced into a chimney;
s2, when the first adsorption tank is saturated, the original flue gas is switched to a second adsorption tank after passing through a filtering device;
s3, heating nitrogen to 150-180 ℃ through a heating source, then feeding the nitrogen into a first adsorption tank, and desorbing and taking out VOCs gas in the adsorption tank A;
and S4, enabling a part of the desorbed VOCs gas to enter a condensing system for condensation and recovery, and enabling the condensed non-condensable gas and the desorbed gas to enter the first adsorption tank again until all the VOCs gas is condensed, thus finishing a circulating system.
Preferably, in S1, the molecular sieve is modified, and the modification method includes an ion exchange method.
Preferably, in S4, the condensing recovery comprises: precooling, mechanical refrigeration and cryogenic cooling.
The invention has the beneficial effects that:
1. according to the invention, the discharge characteristics of the concentration of VOCs in the coking and chemical production area are fully considered, and the VOCs with different concentrations and gas amounts are concentrated and enriched in the adsorption stage aiming at the characteristic of difference of the concentration and gas amount of VOCs waste gas in the coking and chemical production area, so that the concentration of VOCs is improved, and the cost of subsequent VOCs recovery treatment is reduced.
2. The invention utilizes the advantage that the adsorption method can realize the simultaneous control of multiple pollutants, compared with the conventional active carbon VOCs adsorbent, the adopted molecular sieve adsorbent is aluminosilicate, can modulate the structure/surface property of the VOCs according to the types of the VOCs and the properties of waste gas, has good stability, can realize the synergistic adsorption of multi-component VOCs, and avoids the problems of easy reduction of the adsorption activity of the active carbon, easy high-temperature desorption and flammability and the like.
3. The invention is matched with a condensation recovery method to enrich and recover the adsorbed VOCs, so that resource utilization can be carried out in the future, the amount of discharged flue gas of the VOCs is greatly reduced, and the cooling agent is water and ethanol, so that the method is cheap and easy to obtain, and the environmental pollution and the treatment cost are obviously reduced.
Drawings
FIG. 1 is a schematic diagram of a system for treating VOCs escaping from a coking and chemical production area;
description of reference numerals: 1-filtering device, 2.1-first adsorption tank, 2.2-second adsorption tank, 3-heating source, 4-nitrogen tank, 5.1-first-stage cooler, 5.2-second-stage cooler, 5.3-deep cooler, 6-cooling tank and 7-chimney.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples are set forth merely to aid in the understanding of the invention. It should be noted that modifications can be made to the invention by a person skilled in the art without departing from the principle of the invention, and these modifications and modifications also fall within the scope of the claims of the invention.
Example 1:
aiming at the defects of the prior art, the invention provides a treatment process system for volatile VOCs in a coking and chemical production area, which is used for efficiently removing the volatile VOCs in the chemical production area, particularly a crude benzene area. The VOCs in the cold drum, the desulfurization and the deamination sections have low exhaust concentration, VOCs dissipated gas in the debenzolization sections, the benzene storage tanks, the loading and the like is easy to recycle, and the method has recycling value, and provides an efficient treatment process route combining molecular sieve adsorption, nitrogen desorption and condensate recycling aiming at the composition characteristics of high concentration and low flow of the dissipated VOCs in the crude benzene area.
Specifically, a coking and chemical production area volatile VOCs treatment process system, as shown in FIG. 1, comprises: the device comprises a filtering device 1, an adsorption system, a heating source 3, a nitrogen tank 4, a cooling system and a chimney 7;
the adsorption system comprises a first adsorption tank 2.1 and a second adsorption tank 2.2, wherein the first adsorption tank 2.1 and the second adsorption tank 2.2 are arranged in parallel; the filtering device is sequentially connected with the adsorption system and the chimney 7; the nitrogen tank 4 is connected with the adsorption system through a heating source 3; a circulation loop is formed between the adsorption system and the cooling system.
The cooling system includes: a primary cooler 5.1, a secondary cooler 5.2, a deep cooler 5.3 and a cold tank 6; the primary cooler 5.1, the secondary cooler 5.2 and the deep cooler 5.3 are connected in sequence and are all connected with the cold tank 6.
Be equipped with first fan before the entry end of chimney 7, be equipped with the second fan between nitrogen gas jar 4 and the heating source 3, be close to among the cooling system the one end of deep cooler 5.3 is equipped with the third fan.
The adsorbent of the adsorption system comprises at least one of molecular sieves such as ZSM-5, high-silicon USY and the like. For example, the adsorbent is a combination of two or more molecular sieves.
In order to improve the selective adsorption effect of the molecular sieve adsorbent on the VOCs, the adsorbent of the adsorption system can be a hydrophobic molecular sieve, and can be adjusted in a targeted manner according to the types of the VOCs.
The heating source 3 may be an electric heater, or may be another heating method, and maintains the temperature of the desorbed gas within the range of 150-180 ℃, and may be adjusted as required.
The condensing system can adopt multi-stage condensation, and utilizes the condensing device to generate low temperature to reduce the temperature of the benzene and the benzene series-air mixed gas. When the mixed gas enters the condensing device, the components with different dew point temperatures in the VOCs are condensed into liquid state in turn and separated out. The refrigerants of the secondary cooler 5.2 and the chiller 5.3 are glycol aqueous solutions, and the proportion can be adjusted, for example, 50 percent glycol aqueous solution refrigerant is adopted.
The adsorption system can adopt an adsorption box or an adsorption tank, can be used for single-tank adsorption or multi-stage tank adsorption, and can be adjusted and manufactured according to the flue gas volume condition of actual working conditions in size.
Example 2:
a method for treating Volatile Organic Compounds (VOCs) in a coking and chemical production area is characterized in that the technical core is 'molecular sieve adsorption, nitrogen desorption and condensate recovery', and comprises the following steps:
s1, collecting VOCs (raw flue gas) in a crude benzene region, filtering impurities in the raw flue gas by a filter device 1, then feeding the raw flue gas into a first adsorption tank 2.1, and introducing the flue gas subjected to molecular sieve adsorption into a chimney 7;
s2, when the first adsorption tank 2.1 is saturated, the raw flue gas is switched to a second adsorption tank 2.2 after passing through the filtering device 1;
s3, heating nitrogen to 150-180 ℃ by a heating source 3, then feeding the nitrogen into a first adsorption tank 2.1, and desorbing and taking out VOCs gas in the adsorption tank A;
and S4, enabling a part of the desorbed VOCs gas to enter a condensing system for condensation and recovery, and enabling the condensed non-condensable gas and the desorbed gas to enter the first adsorption tank 2.1 again until all the VOCs gas is condensed, thus finishing a circulating system.
In S1, the molecular sieve is modified, and the modification method comprises an ion exchange method.
In S4, the condensation recovery comprises the following steps: precooling, mechanical refrigeration, deep cooling and the like. Specifically, the first stage of the condensing system is precooling, the primary cooler exchanges heat with the raw flue gas, the operating temperature of the precooler is above the freezing point of each component of the mixed gas, the temperature of a heat exchange outlet can be set to be about 3 ℃, and most of water vapor is condensed into water to be removed. The second stage of the condensing system is a shallow cooling stage, the temperature is set to be-15 ℃, the mixed gas enters a refrigerator, and the secondary cooler can recover high-carbon hydrocarbon substances such as C12 in oil gas. The third stage of the condensing system is a deep cooling stage, the oil gas enters a deep cooler, the temperature can be reduced to-35 ℃, and C6 (namely benzene and benzene series) can be condensed.
The cooler of the condensing system is arranged according to the actual working condition and can process 100m 3 Gas amount over h, concentration higher than 1000mg/m 3 The VOCs of (1).
Example 3:
the invention provides a treatment process system for VOCs in a crude benzene region, which has the characteristics of small gas quantity and high concentration of waste gas emission. Filtering VOCs (raw flue gas) in a crude benzene region by a filter, then entering a first adsorption tank 2.1, and directly discharging the flue gas after adsorption by a molecular sieve; when the adsorption tank is saturated, the original flue gas is switched to a second adsorption tank 2.2, at the moment, nitrogen is heated to 150-180 ℃ by a heating source and then enters a first adsorption tank 2.1, and VOCs gas in the first adsorption tank 2.1 is desorbed and carried out; and (3) enabling part of the desorbed high-concentration VOCs gas to enter a condensation system for condensation and recovery, and enabling the condensed non-condensable gas and the desorbed gas to enter the first adsorption tank 2.1 again until all the VOCs gas is condensed, thus finishing a circulation system.
The absorption/desorption system adopts single-tank absorption/desorption, and the adsorption tank is 10000m 3 The/h gas quantity and the concentration of VOCs are 50mg/m 3 And the penetrating adsorption quantity of the adsorbent is 50 mg/g. Desorption of N 2 By a heat sourceThe temperature of the desorption gas can be adjusted within the range of 200-350 ℃. The condensing system adopts multi-stage condensation, the first-stage cooler adopts heat exchange with raw flue gas, the temperature of a heat exchange outlet is set to be about 3 ℃, the second-stage cooler and the third-stage cooler adopt 50% glycol aqueous solution refrigerant, the temperature of the second-stage cooler is set to be-15 ℃, and the temperature of the third-stage cooler (namely a deep cooler) is set to be-32 DEG C o C, a cooler is 100m 3 Per hour of gas, concentration of VOCs 1000mg/m 3 And (5) designing. 90.5% of VOCs removal efficiency can be realized to VOCs waste gas in the adsorption stage, and 99% of VOCs recovery efficiency can be realized by a recovery system.
Claims (10)
1. A coking and chemical production area volatile VOCs treatment process system is characterized by comprising: the device comprises a filtering device (1), an adsorption system, a heating source (3), a nitrogen tank (4), a cooling system and a chimney (7);
the adsorption system comprises a first adsorption tank (2.1) and a second adsorption tank (2.2), wherein the first adsorption tank (2.1) and the second adsorption tank (2.2) are arranged in parallel; the filtering device is sequentially connected with the adsorption system and the chimney (7); the nitrogen tank (4) is connected with the adsorption system through the heating source (3); a circulation loop is formed between the adsorption system and the cooling system.
2. The coking, chemical and area airborne VOCs treatment process system of claim 1, wherein the cooling system comprises: a primary cooler (5.1), a secondary cooler (5.2), a deep cooler (5.3) and a cold tank (6); the primary cooler (5.1), the secondary cooler (5.2) and the deep cooler (5.3) are sequentially connected and are all connected with the cold tank (6).
3. The coking and chemical production area dissipated VOCs treatment process system according to claim 2, characterized in that a first fan is arranged in front of the inlet end of the chimney (7), a second fan is arranged between the nitrogen tank (4) and the heating source (3), and a third fan is arranged at one end of the cooling system close to the deep cooler (5.3).
4. The coker chemical production zone escaped VOCs process system of claim 1 wherein the adsorbent of the adsorption system comprises at least one of ZSM-5, high silica USY molecular sieves.
5. The coking and chemical production area volatile VOCs treatment process system of claim 1, wherein the adsorbent of the adsorption system is a hydrophobic molecular sieve.
6. The coking and chemical production area dissipated VOCs processing system of claim 1, wherein the heating temperature of the heating source (3) is 150-180 ℃.
7. The coker chemical production area escaped VOCs process system of claim 2 wherein the refrigerant of the secondary cooler (5.2) and chiller (5.3) is an aqueous glycol solution.
8. A coking and chemical production area escaped VOCs treatment method, performed by the coking and chemical production area escaped VOCs treatment process system of claim 1, comprising:
s1, collecting raw flue gas, wherein the raw flue gas enters a first adsorption box (2.1) after impurities are filtered by a filtering device (1), and the flue gas adsorbed by a molecular sieve is introduced into a chimney (7);
s2, when the first adsorption tank (2.1) is saturated, the raw flue gas is switched to a second adsorption tank (2.2) after passing through the filtering device (1);
s3, heating nitrogen to 150-180 ℃ by a heating source (3), then feeding the nitrogen into a first adsorption tank (2.1), and desorbing and taking out VOCs gas in the adsorption tank A;
and S4, enabling a part of the desorbed VOCs gas to enter a condensing system for condensation and recovery, and enabling the condensed non-condensable gas and the desorbed gas to enter the first adsorption tank (2.1) again until all the VOCs gas is condensed, thus finishing a circulating system.
9. The method of claim 8, wherein the molecular sieve is modified in S1 by ion exchange.
10. The method of claim 8, wherein the condensing and recovering step S4 comprises: precooling, mechanical refrigeration and deep cooling.
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| CN202211585956.3A CN115970432A (en) | 2022-12-07 | 2022-12-07 | Treatment process and method for volatile VOCs in coking and chemical production area |
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