CN107413173B - Efficient organic waste gas recovery treatment method and complete device - Google Patents
Efficient organic waste gas recovery treatment method and complete device Download PDFInfo
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Abstract
The invention relates to an organic waste gas recovery processing method and a complete set of device. The device comprises an organic waste gas collecting device, a gas storage tank, a buffer tank, a primary membrane unit, an activated carbon adsorption unit, a vacuum pump, a gas-liquid separation tank, a compression and condensation unit, a secondary membrane component, a low-temperature catalytic oxidation reactor and a tubular heat exchanger. The method adopts a secondary membrane as a core technology, exerts the advantages of high efficiency, continuity, high recovery rate, strong safety and suitability for high-concentration organic waste gas in the membrane process, and recovers recoverable components in the waste gas. The method combines the low-temperature catalytic oxidation technology, exerts the advantages of advanced treatment, overcomes the defect of accumulation of light hydrocarbon substances in the system, can efficiently recover valuable organic matters, and can meet the strict requirements of petrochemical enterprises on safety production and advanced treatment of organic waste gas to ensure that the organic waste gas meets the national emission index.
Description
Technical Field
The invention relates to an organic waste gas recovery processing method and a complete set of device, which are mainly applied to the organic waste gas recovery processing in the field of petrochemical enterprises. In particular to a method and a complete set of device for recovering and treating organic waste gas of petrochemical enterprises, which are formed by correspondingly optimizing, improving and coupling a membrane method organic waste gas recovery technology, a compression condensation and adsorption technology and a low-temperature catalytic oxidation treatment technology.
Background
With the improvement of the national economic level and the transformation of the production concept, the environmental protection indexes of petrochemical enterprises such as oil refining and chemical engineering are continuously improved. Environmental protection has been listed as the key development direction of thirteen-five plans. Generally, petrochemical enterprises discharge a large amount of organic waste gas containing a large amount of Volatile Organic Compounds (VOCs), which causes great environmental pollution and resource waste, and environmental protection departments and local environmental protection departments have successively made a method for collecting pollution discharge fees for the VOCs, so that the environmental protection pressure of the petrochemical enterprises is improved. This requires efficient recycling of this portion of the organic waste gas, thereby achieving good environmental and economic benefits. Therefore, aiming at the demand of the petrochemical industry, the development of a new organic waste gas recovery treatment process with strong applicability, high treatment capacity and high safety has positive significance.
The organic waste gas recovery treatment technology mainly comprises two types of recovery and destruction. The recovery method includes an absorption method, an adsorption method, a condensation method, and a membrane method. The destructive methods include combustion, low-temperature catalytic oxidation, and the like. Each method has advantages and optimal application range.
The adsorption method (patent No. CN201210334393.0) can recover pollutants, and the adsorbent mostly adopts activated carbon, and has the advantages of low cost, excellent exhaust index and realization of advanced treatment. The disadvantages are that the adsorption quantity of the activated carbon is limited, the activated carbon can be quickly saturated due to high-concentration waste gas, the treatment effect is reduced, the operation process of replacing the activated carbon is complicated, and the volume of the equipment is large. In addition, the adsorption process is a heat release process, and potential safety hazards exist when high-concentration organic waste gas is adsorbed.
The absorption method is used for absorbing the organic waste gas by using oil products with low volatility, is low in cost and suitable for pretreating high-concentration organic waste gas, but is greatly limited by conditions, and if no low-volatility absorbent exists in a device area, an absorption process cannot be adopted.
The condensation method is a technology for condensing organic matters and separating the organic matters from gas by cooling organic waste gas to a temperature below the freezing point of the organic matters, and when the organic waste gas contains low-molecular-weight organic matters with low freezing points (such as light hydrocarbons such as propane, ethylene and the like), the organic waste gas cannot be removed, and the energy consumption of low-temperature condensation is high.
The membrane separation method (patent No. 200820178507.6) for treating organic waste gas has the advantages of low operation cost, modularized components, mild operation process, good safety and the like. However, the adoption of the membrane technology alone also has the problems that the residual gas cannot be deeply treated and light hydrocarbon is accumulated.
The low-temperature catalytic oxidation technology (patent No. CN103721510A) is a core process, and has the advantages of low energy consumption and capability of removing light hydrocarbon. But it is difficult to achieve the recovery of organic matter.
In summary, there is no perfect method and complete equipment for recovering and treating organic waste gas of petrochemical enterprises, which can recover and treat complex organic waste gas.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a high-efficiency organic waste gas recovery treatment method and a complete set of equipment. The method can meet the emission index of the organic waste gas and the safety production requirement of petrochemical enterprises while recovering valuable pollutants in the organic waste gas. The problems of high construction cost, poor safety, substandard tail gas and the like of the conventional organic waste gas recovery and treatment device are solved.
In order to achieve the above purposes, the technical scheme adopted by the invention is as follows:
a high-efficiency organic waste gas recovery and treatment complete device comprises an organic waste gas collecting device 1, a gas storage tank 2, a buffer tank 3, a primary membrane unit, an activated carbon adsorption unit, a vacuum pump 8, a gas-liquid separation tank 9, a compression and condensation unit, a secondary membrane unit, a low-temperature catalytic oxidation reactor 10 and a tubular heat exchanger 11;
the outlet of the organic waste gas collecting device 1 is connected with the inlet I of the gas storage tank 2, the outlet of the gas storage tank 2 is connected with the inlet of the buffer tank 3, the outlet of the buffer tank 3 is connected with the inlet of the primary membrane unit,
the permeation side of the primary membrane unit is connected with the inlet of the active carbon adsorption unit, the permeation side of the primary membrane unit is connected with the inlet of the vacuum pump 8,
the activated carbon adsorption unit is provided with an adsorption discharge port 7 for discharging standard gas; a return gas outlet of the active carbon adsorption unit is connected with a second inlet of the gas storage tank 2, a desorption gas outlet of the active carbon adsorption unit is connected with an inlet of the vacuum pump 8,
the outlet of the vacuum pump 8 is connected with the inlet of the gas-liquid separation tank 9, the condensable gas outlet of the gas-liquid separation tank 9 is connected with the inlet of the compression condensing unit, the outlet of the compression condensing unit is connected with the inlet of the secondary membrane unit,
the permeation side of the secondary membrane unit is connected with the inlet of the buffer tank 3, the permeation side of the secondary membrane unit is connected with the inlet of the vacuum pump 8,
the non-condensable gas outlet of the gas-liquid separation tank 9 is connected with the tube pass inlet of the tube heat exchanger 11, the tube pass outlet of the tube heat exchanger 11 is connected with the inlet of the low-temperature catalytic oxidation reactor 10, the outlet of the low-temperature catalytic oxidation reactor 10 is connected with the shell pass inlet of the tube heat exchanger 11, and the shell pass outlet of the tube heat exchanger 11 is communicated with the atmosphere.
On the basis of the scheme, a nitrogen-sealed gas pipeline and a pressure gauge 21 are arranged at the inlet of the organic waste gas collecting device 1.
On the basis of the scheme, a compressor 4a, a flow meter 16 and a valve are arranged between the outlet of the buffer tank 3 and the inlet of the primary membrane unit.
On the basis of the scheme, the primary membrane unit is formed by combining a plurality of primary membrane assemblies 5a in series or in parallel;
the secondary membrane unit is formed by combining a plurality of secondary membrane components 5b in series or in parallel;
the membrane module forms of the primary membrane unit and the secondary membrane unit are roll type, disc type or hollow fiber forms.
On the basis of the scheme, the activated carbon adsorption unit is formed by connecting two activated carbon adsorption tanks 6 in parallel through a four-way valve 15; while one activated carbon adsorption tank 6 is adsorbing, the other activated carbon adsorption tank 6 is performing vacuum desorption and regeneration processes.
On the basis of the above scheme, an electric control opening valve 22 is arranged between the standard gas outlet of the activated carbon adsorption unit and the adsorption discharge port 7; an electric control opening valve 22 is arranged between the return gas outlet of the active carbon adsorption unit and the gas storage tank 2.
On the basis of the scheme, a compressor 4b is arranged between the vacuum pump 8 and the gas-liquid separation tank 9.
On the basis of the scheme, the compression and condensation unit comprises a condensation heat exchanger 12, a refrigeration compressor 13, an air heat exchanger 14, a Freon storage tank 23 and two valves.
On the basis of the scheme, an electromagnetic valve 18 is arranged between the gas-liquid separation tank 9 and the condensing heat exchanger 12 in the compression and condensation unit.
On the basis of the scheme, a valve is arranged between the retentate side of the secondary membrane unit and the inlet of the buffer tank 3.
On the basis of the scheme, an electric control opening valve is arranged between the gas-liquid separation tank 9 and the tube heat exchanger 11.
On the basis of the scheme, a blower 20 is arranged between the tube side outlet of the tube nest heat exchanger 11 and the inlet of the low-temperature catalytic oxidation reactor 10.
On the basis of the scheme, a blower and a valve are arranged between the inlet of the low-temperature catalytic oxidation reactor 10 and the atmosphere.
On the basis of the scheme, a low-temperature catalytic oxidation discharge port 17 is arranged at the shell side outlet of the tubular heat exchanger 11.
On the basis of the scheme, a pressurized steam inlet and a steam outlet are arranged on the tube pass of the low-temperature catalytic oxidation reactor 10, and an electric control opening valve 22 is arranged on the pressurized steam inlet.
On the basis of the scheme, an oil phase outlet of the gas-liquid separation tank 9 is provided with a recovered oil product storage tank 19.
On the basis of the scheme, the membranes adopted by the primary membrane unit and the secondary membrane unit can be organic silicon membranes, block copolymer membranes or inorganic membranes.
On the basis of the scheme, the adsorbent used in the activated carbon adsorption unit is activated carbon or a molecular sieve, and the desorption method is vacuum desorption.
On the basis of the scheme, the low-temperature catalytic oxidation unit consisting of the low-temperature catalytic oxidation reactor 10 and the tubular heat exchanger 11 can be replaced by various conventional adsorption devices such as an absorption tower and an absorber, and the used absorbent is organic matters such as diesel oil with low volatility and high boiling point.
On the basis of the scheme, the complete device can be designed in a fixed mode or a skid-mounted mode and can be transported by an automobile.
A high-efficiency organic waste gas recovery treatment method comprises the following steps:
1) organic waste gas to be treated firstly enters a primary membrane unit from an organic waste gas collecting device 1 through a gas storage tank 2 and a buffer tank 3 for membrane separation;
2) the gas on the retentate side of the first-stage membrane unit enters an activated carbon adsorption unit, the adsorbed gas reaches the standard and is discharged through an adsorption discharge port 7, if the gas does not reach the standard, the gas returns to an inlet II of the gas storage tank 2 through a return line according to a certain proportion and is continuously treated, and a treatment cycle is formed until the gas reaches the standard and is discharged;
3) concentrated gas at the permeation side of the primary membrane unit and desorbed gas of the activated carbon adsorption unit enter a compressor 4b through a vacuum pump 8 for pressurization and then enter a gas-liquid separation tank 9; the separated organic matters are stored in a recovered oil storage tank 19 and are periodically recovered; the separated condensable gas enters a compression condensing unit for compression and condensation, and then enters a secondary membrane unit for secondary membrane separation;
4) the gas on the retentate side of the secondary membrane unit enters a buffer tank 3, and then enters the primary membrane unit and an active carbon adsorption unit from the buffer tank 3 for cyclic treatment;
5) the permeation side concentrated gas of the second-stage membrane unit and the permeation side concentrated gas of the first-stage membrane unit flow in parallel, pass through a vacuum pump 8, are pressurized by a compressor 4b, and then enter a gas-liquid separation tank 9;
6) the non-condensable gas in the gas-liquid separation tank 9 enters a tubular heat exchanger 11 for heating after the flow of the non-condensable gas is regulated by an electrically-controlled opening valve, is mixed with air introduced by an air blower 20, and then enters a low-temperature catalytic oxidation reactor 10; under the action of the catalyst, low-temperature catalytic oxidation reaction occurs, then the temperature is reduced in the tube heat exchanger 11, and finally the reaction product is discharged through a low-temperature catalytic oxidation discharge port 17.
On the basis of the scheme, the pressure range of the redundant side of the first-stage membrane unit and the second-stage membrane unit is 0.1 MPa-1 MPa, and the temperature is lower than 50 ℃; the pressure of the infiltration side is 0 MPa-0.02 MPa.
On the basis of the scheme, the pressure range of the compression condensing unit is 0.2 Mpa-1 Mpa, and the refrigeration temperature range is-10 ℃ to 10 ℃.
On the basis of the scheme, the low-temperature catalytic oxidation reactor 10 is preheated by medium and low pressure steam or by electrically heating heat conduction oil; and stopping heating after the initial temperature of the catalytic oxidation is reached, starting the catalytic process, and maintaining the reaction temperature of the gas after the catalytic oxidation through heat generated in the oxidation process.
The invention provides a combined process and a complete set of equipment for carrying out efficient recovery treatment on organic waste gas by combining an efficient membrane separation technology, an adsorption technology, a condensation recovery technology and an improved and designed low-temperature catalytic oxidation technology.
When the device is used, organic matters with higher value in the organic waste gas can be recovered, the emission index of the organic waste gas can be met, and the explosion-proof grade of the device is improved. The process and the complete equipment have mild operation conditions, and the core technology, namely membrane separation and low-temperature catalytic oxidation, have the characteristics of high efficiency, safety, durability, low energy consumption, high oil recovery rate and superior tail gas index.
The process flow creatively applies a secondary membrane process to further separate the concentrated gas of the primary membrane, reduce the concentration of the gas returned to the buffer tank, exert the advantages of high efficiency, continuity, high recovery rate, strong safety and suitability for high-concentration organic waste gas in the membrane process, recover the recoverable component in the waste gas and be beneficial to improving the standard reaching rate of the tail gas. Meanwhile, the concentration of organic matters in the compression condensing unit is improved, the total amount of compressed condensing gas is reduced, and the organic matter recovery efficiency is increased. The low-temperature catalytic oxidation reactor can regularly remove light hydrocarbon substances which are difficult to condense, the advantage of advanced treatment of the low-temperature catalytic oxidation reactor is exerted, and the defect that the light hydrocarbon substances are accumulated in a system is overcome. The method can not only efficiently recover valuable organic matters through a membrane technology, but also meet the strict requirement of petrochemical enterprises on safety production, and simultaneously, deeply treat the organic waste gas by using a low-temperature catalysis technology so that the organic waste gas meets the strictest national emission index. The process design has strong applicability, safety and economy and has better application prospect.
The invention has simple structure, can realize skid-mounted design, is convenient to install and maintain and has high automatic control level. Has stronger applicability to different kinds of organic waste gases. Can realize the organic waste gas recovery and high-efficient processing of petrochemical enterprises, solve the difficult problem of organic waste gas treatment, have certain industrial application prospect.
Drawings
The invention has the following drawings:
FIG. 1 is a block diagram of the present invention.
FIG. 2 is a graph of removal rate for a membrane process and kit.
In the figure, 1-organic waste gas collecting device, 2-gas storage tank, 3-buffer tank, 4 a-compressor, 4 b-compressor, 5 a-first stage membrane component, 5 b-second stage membrane component, 6-activated carbon adsorption tank, 7-adsorption discharge outlet, 8-vacuum pump, 9-gas-liquid separation tank, 10-low temperature catalytic oxidation reactor, 11-tube heat exchanger, 12-condensation heat exchanger, 13-refrigeration compressor, 14-air heat exchanger, 15-four-way valve, 16-flowmeter, 17-low temperature catalytic oxidation discharge outlet, 18-solenoid valve, 19-recovered oil storage tank, 20-blower, 21-pressure gauge, 22-electric control opening valve, 23-freon storage tank;
note: the solid line is the gas flow passage before catalytic combustion, and the dotted line is the gas flow passage after catalytic combustion
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
As shown in fig. 1, the invention develops an organic waste gas recovery processing method and a complete set of equipment by using a two-stage membrane as a core technology and combining an adsorption process and a low-temperature catalytic oxidation technology aiming at organic waste gas generated in the processes of storage, transportation, loading and unloading and production of petrochemical enterprises.
A high-efficiency organic waste gas recovery and treatment complete device comprises an organic waste gas collecting device 1, a gas storage tank 2, a buffer tank 3, a primary membrane unit, an activated carbon adsorption unit, a vacuum pump 8, a gas-liquid separation tank 9, a compression and condensation unit, a secondary membrane unit, a low-temperature catalytic oxidation reactor 10 and a tubular heat exchanger 11;
the outlet of the organic waste gas collecting device 1 is connected with the inlet I of the gas storage tank 2, the outlet of the gas storage tank 2 is connected with the inlet of the buffer tank 3, the outlet of the buffer tank 3 is connected with the inlet of the primary membrane unit,
the permeation side of the primary membrane unit is connected with the inlet of the active carbon adsorption unit, the permeation side of the primary membrane unit is connected with the inlet of the vacuum pump 8,
the activated carbon adsorption unit is provided with an adsorption discharge port 7 for discharging standard gas; a return gas outlet of the active carbon adsorption unit is connected with a second inlet of the gas storage tank 2, a desorption gas outlet of the active carbon adsorption unit is connected with an inlet of the vacuum pump 8,
the outlet of the vacuum pump 8 is connected with the inlet of the gas-liquid separation tank 9, the condensable gas outlet of the gas-liquid separation tank 9 is connected with the inlet of the compression condensing unit, the outlet of the compression condensing unit is connected with the inlet of the secondary membrane unit,
the permeation side of the secondary membrane unit is connected with the inlet of the buffer tank 3, the permeation side of the secondary membrane unit is connected with the inlet of the vacuum pump 8,
the non-condensable gas outlet of the gas-liquid separation tank 9 is connected with the tube pass inlet of the tube heat exchanger 11, the tube pass outlet of the tube heat exchanger 11 is connected with the inlet of the low-temperature catalytic oxidation reactor 10, the outlet of the low-temperature catalytic oxidation reactor 10 is connected with the shell pass inlet of the tube heat exchanger 11, and the shell pass outlet of the tube heat exchanger 11 is communicated with the atmosphere.
On the basis of the scheme, a nitrogen-sealed gas pipeline and a pressure gauge 21 are arranged at the inlet of the organic waste gas collecting device 1.
On the basis of the scheme, a compressor 4a, a flow meter 16 and a valve are arranged between the outlet of the buffer tank 3 and the inlet of the primary membrane unit.
On the basis of the scheme, the primary membrane unit is formed by combining a plurality of primary membrane assemblies 5a in series or in parallel;
the secondary membrane unit is formed by combining a plurality of secondary membrane components 5b in series or in parallel;
the membrane module forms of the primary membrane unit and the secondary membrane unit are roll type, disc type or hollow fiber forms.
On the basis of the scheme, the activated carbon adsorption unit is formed by connecting two activated carbon adsorption tanks 6 in parallel through a four-way valve 15; while one activated carbon adsorption tank 6 is adsorbing, the other activated carbon adsorption tank 6 is performing vacuum desorption and regeneration processes.
On the basis of the above scheme, an electric control opening valve 22 is arranged between the standard gas outlet of the activated carbon adsorption unit and the adsorption discharge port 7; an electric control opening valve 22 is arranged between the return gas outlet of the active carbon adsorption unit and the gas storage tank 2.
On the basis of the scheme, a compressor 4b is arranged between the vacuum pump 8 and the gas-liquid separation tank 9.
On the basis of the scheme, the compression and condensation unit comprises a condensation heat exchanger 12, a refrigeration compressor 13, an air heat exchanger 14, a Freon storage tank 23 and two valves.
On the basis of the scheme, an electromagnetic valve 18 is arranged between the gas-liquid separation tank 9 and the condensing heat exchanger 12 in the compression and condensation unit.
On the basis of the scheme, a valve is arranged between the retentate side of the secondary membrane unit and the inlet of the buffer tank 3.
On the basis of the scheme, an electric control opening valve is arranged between the gas-liquid separation tank 9 and the tube heat exchanger 11.
On the basis of the scheme, a blower 20 is arranged between the tube side outlet of the tube nest heat exchanger 11 and the inlet of the low-temperature catalytic oxidation reactor 10.
On the basis of the scheme, a blower and a valve are arranged between the inlet of the low-temperature catalytic oxidation reactor 10 and the atmosphere.
On the basis of the scheme, a low-temperature catalytic oxidation discharge port 17 is arranged at the shell side outlet of the tubular heat exchanger 11.
On the basis of the scheme, a pressurized steam inlet and a steam outlet are arranged on the tube pass of the low-temperature catalytic oxidation reactor 10, and an electric control opening valve 22 is arranged on the pressurized steam inlet.
On the basis of the scheme, an oil phase outlet of the gas-liquid separation tank 9 is provided with a recovered oil product storage tank 19.
On the basis of the scheme, the membranes adopted by the primary membrane unit and the secondary membrane unit can be organic silicon membranes, block copolymer membranes or inorganic membranes.
On the basis of the scheme, the adsorbent used in the activated carbon adsorption unit is activated carbon or a molecular sieve, and the desorption method is vacuum desorption.
On the basis of the scheme, the low-temperature catalytic oxidation unit consisting of the low-temperature catalytic oxidation reactor 10 and the tubular heat exchanger 11 can be replaced by various conventional adsorption devices such as an absorption tower and an absorber, and the used absorbent is organic matters such as diesel oil with low volatility and high boiling point.
On the basis of the scheme, the complete device can be designed in a fixed mode or a skid-mounted mode and can be transported by an automobile.
A high-efficiency organic waste gas recovery treatment method comprises the following steps:
1) organic waste gas to be treated firstly enters a primary membrane unit from an organic waste gas collecting device 1 through a gas storage tank 2 and a buffer tank 3 for membrane separation;
2) the gas on the retentate side of the first-stage membrane unit enters an activated carbon adsorption unit, the adsorbed gas reaches the standard and is discharged through an adsorption discharge port 7, if the gas does not reach the standard, the gas returns to an inlet II of the gas storage tank 2 through a return line according to a certain proportion and is continuously treated, and a treatment cycle is formed until the gas reaches the standard and is discharged;
3) concentrated gas at the permeation side of the primary membrane unit and desorbed gas of the activated carbon adsorption unit enter a compressor 4b through a vacuum pump 8 for pressurization and then enter a gas-liquid separation tank 9; the separated organic matters are stored in a recovered oil storage tank 19 and are periodically recovered; the separated condensable gas enters a compression condensing unit for compression and condensation, and then enters a secondary membrane unit for secondary membrane separation;
4) the gas on the retentate side of the secondary membrane unit enters a buffer tank 3, and then enters the primary membrane unit and an active carbon adsorption unit from the buffer tank 3 for cyclic treatment;
5) the permeation side concentrated gas of the second-stage membrane unit and the permeation side concentrated gas of the first-stage membrane unit flow in parallel, pass through a vacuum pump 8, are pressurized by a compressor 4b, and then enter a gas-liquid separation tank 9;
6) the non-condensable gas in the gas-liquid separation tank 9 enters a tubular heat exchanger 11 for heating after the flow of the non-condensable gas is regulated by an electrically-controlled opening valve, is mixed with air introduced by an air blower 20, and then enters a low-temperature catalytic oxidation reactor 10; under the action of the catalyst, low-temperature catalytic oxidation reaction occurs, then the temperature is reduced in the tube heat exchanger 11, and finally the reaction product is discharged through a low-temperature catalytic oxidation discharge port 17.
On the basis of the scheme, the pressure range of the redundant side of the first-stage membrane unit and the second-stage membrane unit is 0.1 MPa-1 MPa, and the temperature is lower than 50 ℃; the pressure of the infiltration side is 0 MPa-0.02 MPa.
On the basis of the scheme, the pressure range of the compression condensing unit is 0.2 Mpa-1 Mpa, and the refrigeration temperature range is-10 ℃ to 10 ℃.
On the basis of the scheme, the low-temperature catalytic oxidation reactor 10 is preheated by medium and low pressure steam or by electrically heating heat conduction oil; and stopping heating after the initial temperature of the catalytic oxidation is reached, starting the catalytic process, and maintaining the reaction temperature of the gas after the catalytic oxidation through heat generated in the oxidation process.
Example 1
The recovery treatment process application result of organic waste gas discharged from catalytic gasoline tank at vault of oil storage tank area is that the main body of organic waste gas composition (volume fraction) is nitrogen, and the concentration of Volatile Organic Compounds (VOCs) is about 150000-300000 mg/m3In the meantime. Device design throughput was 40m3Per hour, rated intake maximum concentration of 200000mg/m3The pressure of the first-stage membrane retentate side is 0.2MPa, the pressure of the second-stage membrane retentate side is 0.38MPa, the pressure of the compression condensation process in the device is 0.4MPa, the temperature is 2 ℃, the vacuum degree of the permeation side is not lower than-0.09 MPa, and the initial temperature of the low-temperature catalysis process is 260-340 ℃. The device comprises an inlet gas flow, an inlet gas non-methane total hydrocarbon concentration, an adsorption discharge port 7 and low-temperature catalytic oxygen during the operation processThe exhaust gas concentration at the discharge port 17 and the recovery rate of organic substances by the apparatus are shown in table 1:
TABLE 1 treatment Effect of Membrane modules and devices on VOCs
Example 2
The method and the device have the effect of recycling and treating the organic waste gas discharged by the breather valve of the floating-roof slop oil tank in the intermediate tank area in an oil refinery. The organic waste gas composition (volume fraction) is mainly composed of 80-88% of nitrogen by volume fraction and 12-20% of Volatile Organic Compounds (VOCs) by volume fraction. The main hydrocarbon substances in the VOCs are light hydrocarbons including methane, ethane, ethylene, propane, propylene, isobutane, n-butane, n-butene, isobutene, butylene and carbon 5. In addition, the exhaust gas also contains a small amount of hydrogen sulfide and oxygen. Device design throughput was 40m3Per hour, rated intake maximum concentration 300000mg/m3Or the volume fraction is 20 percent (v/v), the pressure of the first-stage membrane retentate side is 0.2Mpa, the pressure of the second-stage membrane retentate side is 0.38Mpa, the pressure in the compression condensation process is 0.4Mpa, the temperature is 2 ℃, the vacuum degree of the permeation side is not lower than-0.09 Mpa, and the initial temperature in the low-temperature catalysis process is 260 ℃ to 340 ℃. The concentrations of various organic waste gases at the inlet and the outlet of the device are shown in a table 2:
TABLE 2 concentration of exhaust gas from the device inlet and adsorption vents 7
As can be seen from the data in Table 2, the method disclosed by the invention has a total removal rate of VOCs (volatile organic compounds) of more than 99.5%, and has a good treatment effect on various light hydrocarbons, such as methane, ethane, ethylene, propane, propylene, isobutane, n-butane, n-butene, isobutene and butene.
Example 3
The method comprises the steps of firstly, theoretically estimating the concentration of VOCs in the discharged gas in the treatment of the waste gas of a catalyst production workshop, wherein the VOCs in the waste gas mainly come from hexane and toluene which are used as raw materials in the production process,due to process conditions during the production process, some of the toluene and hexane may be vented to the atmosphere along with nitrogen during the production process as the equipment operates. The concentration fluctuation of hexane and non-methane total hydrocarbon in the system inlet gas is large, and most concentration value is 20000mg/m3To 140000mg/m3In between, the hydrocarbons in the VOCs mainly contain n-hexane and toluene. Device design throughput is 50m3H, the maximum concentration of inlet gas does not exceed 350000mg/m3The pressure of the first-stage membrane retentate side is 0.2MPa, the pressure of the second-stage membrane retentate side is 0.38MPa, the pressure of the compression condensation process is 0.4MPa, the temperature is 2 ℃, the vacuum degree of the permeation side is not lower than-0.09 MPa, and the initial temperature of the low-temperature catalysis process is 260-340 ℃. The concentration of organic waste gas at the inlet and outlet of the device, the flow rate of inlet air, the membrane process and the removal rate of the whole device are shown in figure 2.
The data show that the kit of the present invention can stably remove over 99.75% of organic contaminants. Due to the combination of compression condensation and low-temperature catalytic oxidation technology, the advanced treatment and oil recovery of the waste gas after membrane process treatment can be ensured, the standard reaching rate of the tail gas is 100 percent, and the average tail gas concentration is 45mg/m3The average removal rate is higher than 99.85%, and the recovery rate and the removal rate are far higher than those of the existing organic waste gas recovery treatment technology.
Those not described in detail in this specification are within the skill of the art.
Claims (4)
1. A high-efficiency organic waste gas recovery and treatment complete device comprises an organic waste gas collecting device (1), a gas storage tank (2), a buffer tank (3), a primary membrane unit, an activated carbon adsorption unit, a vacuum pump (8), a gas-liquid separation tank (9), a compression and condensation unit, a secondary membrane unit, a low-temperature catalytic oxidation reactor (10) and a tube heat exchanger (11);
the outlet of the organic waste gas collecting device (1) is connected with the inlet I of the gas storage tank (2), the outlet of the gas storage tank (2) is connected with the inlet of the buffer tank (3), the outlet of the buffer tank (3) is connected with the inlet of the primary membrane unit,
the permeation side of the first-stage membrane unit is connected with the inlet of the active carbon adsorption unit, the permeation side of the first-stage membrane unit is connected with the inlet of a vacuum pump (8),
the activated carbon adsorption unit is provided with an adsorption discharge port (7) for discharging standard gas; a backflow gas outlet of the active carbon adsorption unit is connected with a second inlet of the gas storage tank (2), a desorption gas outlet of the active carbon adsorption unit is connected with an inlet of the vacuum pump (8),
the outlet of the vacuum pump (8) is connected with the inlet of the gas-liquid separation tank (9), the condensable gas outlet of the gas-liquid separation tank (9) is connected with the inlet of the compression condensation unit, the outlet of the compression condensation unit is connected with the inlet of the secondary membrane unit,
the seepage side of the secondary membrane unit is connected with the inlet of the buffer tank (3), the seepage side of the secondary membrane unit is connected with the inlet of the vacuum pump (8),
an incondensable gas outlet of the gas-liquid separation tank (9) is connected with a tube pass inlet of a tube heat exchanger (11), a tube pass outlet of the tube heat exchanger (11) is connected with an inlet of a low-temperature catalytic oxidation reactor (10), an outlet of the low-temperature catalytic oxidation reactor (10) is connected with a shell pass inlet of the tube heat exchanger (11), and a shell pass outlet of the tube heat exchanger (11) is communicated with the atmosphere;
the primary membrane unit is formed by combining a plurality of primary membrane components (5a) in series or in parallel;
the secondary membrane unit is formed by combining a plurality of secondary membrane components (5b) in series or in parallel;
the membrane module forms of the first-stage membrane unit and the second-stage membrane unit are roll type, disc type or hollow fiber forms;
the membranes adopted by the first-stage membrane unit and the second-stage membrane unit are organic silicon membranes, block copolymer membranes or inorganic membranes;
the compression and condensation unit comprises a condensation heat exchanger (12), a refrigeration compressor (13), an air heat exchanger (14), a Freon storage tank (23) and two valves;
an inlet of the organic waste gas collecting device (1) is provided with a nitrogen seal gas pipeline and a pressure gauge (21);
a compressor (4a), a flowmeter (16) and a valve are arranged between the outlet of the buffer tank (3) and the inlet of the primary membrane unit;
an electric control opening valve (22) is arranged between the standard gas outlet of the active carbon adsorption unit and the adsorption discharge port (7); an electric control opening valve (22) is arranged between a return gas outlet of the active carbon adsorption unit and the gas storage tank (2);
a compressor (4b) is arranged between the vacuum pump (8) and the gas-liquid separation tank (9); an electromagnetic valve (18) is arranged between the gas-liquid separation tank (9) and a condensing heat exchanger (12) in the compression and condensation unit;
a valve is arranged between the retentate side of the secondary membrane unit and the inlet of the buffer tank (3);
an oil phase outlet of the gas-liquid separation tank (9) is provided with a recovered oil product storage tank (19);
an electric control opening valve is arranged between the gas-liquid separation tank (9) and the tube heat exchanger (11);
a blower (20) is arranged between the tube pass outlet of the tube heat exchanger (11) and the inlet of the low-temperature catalytic oxidation reactor (10);
a low-temperature catalytic oxidation discharge port (17) is arranged at the shell pass outlet of the tube heat exchanger (11);
a blower and a valve are arranged between the inlet of the low-temperature catalytic oxidation reactor (10) and the atmosphere;
a pressurized steam inlet and a steam outlet are arranged on the tube side of the low-temperature catalytic oxidation reactor (10), and an electric control opening valve (22) is arranged on the pressurized steam inlet;
the low-temperature catalytic oxidation unit consisting of the low-temperature catalytic oxidation reactor (10) and the tube heat exchanger (11) is replaced by a conventional absorption tower and an absorber;
the adsorbent used in the active carbon adsorption unit is active carbon or a molecular sieve, and the desorption method is vacuum desorption.
2. The efficient organic waste gas recovery processing plant as set forth in claim 1, wherein: the activated carbon adsorption unit is formed by combining two activated carbon adsorption tanks (6) in parallel through a four-way valve (15); when one activated carbon adsorption tank (6) adsorbs, the other activated carbon adsorption tank (6) carries out vacuum desorption and regeneration processes.
3. The efficient organic waste gas recovery processing plant as set forth in claim 1, wherein: the complete set of devices is designed in a fixed mode or a skid-mounted mode.
4. A high-efficiency organic waste gas recovery and treatment method, which applies the high-efficiency organic waste gas recovery and treatment complete equipment of any claim 1 to 3, is characterized by comprising the following steps:
1) organic waste gas to be treated firstly enters a primary membrane unit from an organic waste gas collecting device (1) through a gas storage tank (2) and a buffer tank (3) for membrane separation;
2) the gas on the retentate side of the primary membrane unit enters an activated carbon adsorption unit, the gas after adsorption reaches the standard and is discharged through an adsorption discharge port (7), if the gas does not reach the standard, the gas returns to an inlet II of the gas storage tank (2) through a return line according to a certain proportion and is continuously treated, and a treatment cycle is formed until the gas reaches the standard and is discharged;
3) concentrated gas on the permeation side of the primary membrane unit and desorbed gas of the activated carbon adsorption unit enter a compressor (4b) through a vacuum pump (8) for pressurization, and then enter a gas-liquid separation tank (9); the separated organic matters are stored in a recycled oil storage tank (19) and are recycled periodically; the separated condensable gas enters a compression condensing unit for compression and condensation, and then enters a secondary membrane unit for secondary membrane separation;
4) the gas on the retentate side of the secondary membrane unit enters a buffer tank (3), and then enters the primary membrane unit and the activated carbon adsorption unit from the buffer tank (3) for cyclic treatment;
5) the permeation side concentrated gas of the second-stage membrane unit and the permeation side concentrated gas of the first-stage membrane unit flow in parallel, pass through a vacuum pump (8), are pressurized by a compressor (4b), and then enter a gas-liquid separation tank (9);
6) after the flow of the non-condensable gas in the gas-liquid separation tank (9) is regulated by an electrically-controlled opening valve, the non-condensable gas enters a tubular heat exchanger (11) for heating, is mixed with air introduced by an air blower (20), and then enters a low-temperature catalytic oxidation reactor (10); under the action of a catalyst, low-temperature catalytic oxidation reaction is carried out, then the temperature is reduced in a tube heat exchanger (11), and finally the reaction product is discharged through a low-temperature catalytic oxidation discharge port (17);
the pressure range of the redundant side of the first-stage membrane unit and the second-stage membrane unit is 0.1 Mpa-1 Mpa, and the temperature is lower than 50 ℃; the osmotic side pressure is 0-0.02 MPa;
the pressure range of the compression condensing unit is 0.2 Mpa-1 Mpa, and the refrigeration temperature range is-10 ℃ to 10 ℃;
the low-temperature catalytic oxidation reactor (10) is preheated by medium-low pressure steam or by electrically heating heat conduction oil; and stopping heating after the initial temperature of the catalytic oxidation is reached, starting the catalytic process, and maintaining the reaction temperature of the gas after the catalytic oxidation through heat generated in the oxidation process.
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| CN111617613B (en) * | 2019-02-28 | 2022-07-12 | 中国石油化工股份有限公司 | Method and system for treating waste gas of refining and chemical enterprises |
| CN112657321A (en) * | 2020-11-19 | 2021-04-16 | 江苏国态环保集团有限公司 | VOCs exhaust treatment device |
| CN113788776B (en) * | 2021-09-03 | 2023-03-24 | 深圳市德尼环境技术有限公司 | Lithium ion battery coating procedure NMP purification method and system |
| CN113856392B (en) * | 2021-09-23 | 2023-09-19 | 大连理工大学 | Compression condensation, membrane separation and adsorption coupled full-concentration VOCs (volatile organic compounds) collecting system and method |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035625A (en) * | 1988-02-26 | 1989-09-20 | Gkss-研究中心盖斯特哈赫特有限公司 | The method of separation of organic substances from air/permanent gases mixture |
| CN102908799A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Treatment method for emissions of aromatic hydrocarbon storage tank |
| CN204294073U (en) * | 2014-11-02 | 2015-04-29 | 大连举扬科技有限公司 | A kind of VOCs Volatile Gas recycle device |
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-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035625A (en) * | 1988-02-26 | 1989-09-20 | Gkss-研究中心盖斯特哈赫特有限公司 | The method of separation of organic substances from air/permanent gases mixture |
| CN102908799A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Treatment method for emissions of aromatic hydrocarbon storage tank |
| CN204294073U (en) * | 2014-11-02 | 2015-04-29 | 大连举扬科技有限公司 | A kind of VOCs Volatile Gas recycle device |
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