CN107413173A - A kind of efficiently organic exhaust gas recovery and treatment method and complexes - Google Patents
A kind of efficiently organic exhaust gas recovery and treatment method and complexes Download PDFInfo
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- CN107413173A CN107413173A CN201610348973.3A CN201610348973A CN107413173A CN 107413173 A CN107413173 A CN 107413173A CN 201610348973 A CN201610348973 A CN 201610348973A CN 107413173 A CN107413173 A CN 107413173A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/229—Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/225—Multiple stage diffusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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Abstract
The present invention relates to a kind of organic exhaust gas recovery and treatment method and complexes.Including organic waste gas collection device, air accumulator, surge tank, one-level film unit, activated carbon adsorption unit, vavuum pump, knockout drum, compression condensation unit, second membrane module, low-temperature catalytic oxidation reactor and tubular heat exchanger.Use using secondary membrane as core technology, play membrane process efficiently, continuous, the rate of recovery height, high safety, suitable for high-concentration organic waste gas the advantages of, the recyclable component in recovery waste gas.And combine low-temperature catalytic oxidation technology, play the advantage of its advanced treating, the drawbacks of overcoming light hydrocarbon material to accumulate in systems, can either the valuable organic matter of high efficiente callback, and can is enough while petroleum chemical enterprise is met to the rigors of safety in production, advanced treating is carried out to organic exhaust gas, organic exhaust gas is met national discharge index.
Description
Technical field
The present invention relates to a kind of organic exhaust gas recovery and treatment method and complexes, it is mainly applied
Organic exhaust gas in petroleum chemical enterprise field recycles.It is specifically a kind of by embrane method organic waste
Gas recovery technology, compression condensation, absorbing process and low-temperature catalytic oxidation treatment technology carry out phase
After should optimizing, improve, coupling, the recovery for petroleum chemical enterprise's organic exhaust gas, the processing of formation
Method and complexes.
Background technology
With the horizontal raising of national economy and the transformation of production theory, to petrochemical industry such as oil-refining chemicals
The environmental protection index of enterprise is constantly lifted.Environmental protection has been listed in the side of giving priority to of 13 plans
To.Substantial amounts of organic exhaust gas discharges in usual petroleum chemical enterprise, wherein containing substantial amounts of volatile organic
Thing (VOCs), cause to also result in the waste of resource, Chinese Ministry of Environmental Protection while larger environmental pollution
The collection of drainage dues method for VOCs is put into effect in succession with each place Environmental Protection Agency so that petrochemical industry
The environmental protection pressure of enterprise improves.This requires high efficiente callback to utilize this part organic exhaust gas, so as to
Obtain good environmental benefit and economic benefit.Therefore, it is suitable for petrochemical industry demand, exploitation
With property is strong, disposal ability is big, safe organic exhaust gas recycling new technology has actively
Meaning.
Organic exhaust gas recycling technology mainly has recovery and destroys two classes.Recovery class method includes
Absorption process, absorption method, condensation method and embrane method.Destroying class method then has burning, low-temperature catalyzed oxygen
Change etc..All kinds of methods have intrinsic advantage and the optimal scope of application.
Absorption method (patent No. CN201210334393.0) can reclaim pollutant, adsorbent
More use activated carbon, advantage is that low cost, exhaust index are excellent, achievable advanced treating.Lack
Point is that active carbon adsorption amount is limited, and high-concentration waste gas can cause the rapid saturation of activated carbon, cause to locate
Manage effect to decline, change activated carbon operating process complexity, and equipment volume is big.In addition, absorption
Process is exothermic process, when adsorbing high-concentration organic waste gas, potential safety hazard be present.
Absorption process is that organic exhaust gas is absorbed with volatility less oil product, absorption process cost
It is relatively low, suitably high-concentration organic waste gas is pre-processed, but subject to conditions larger, device
Area does not have low volatility absorbent such as, then can not use absorption technique.
Condensation method is by reaching organic exhaust gas cooling below organic matter freezing point, making organic matter
Condense and the technology that is separated with gaseous state, when containing the low molecule amount that freezing point is relatively low in organic exhaust gas
During organic matter (such as propane, ethene lighter hydrocarbons), then removal, and cryogenic condensation can not be realized
Energy consumption it is higher.
Membrane separation process (patent No. 200820178507.6) is although processing organic exhaust gas has operation
Cost is low, component can modularization, the advantages that operating process is gentle, security is good.It is however, single
Solely using membrane technology there is also ooze residual air can not advanced treating, lighter hydrocarbons accumulate the problem of.
Low-temperature catalytic oxidation technology (patent No. CN103721510A) is the technique of core, is had
Have that energy consumption is low, can remove the advantage of lighter hydrocarbons.But it is difficult to the recovery to organic matter.
To sum up, it there is no now and perfect be directed to petroleum chemical enterprise's organic exhaust gas recovery and treatment method
With complexes, complicated organic exhaust gas can be recycled.
The content of the invention
For defect present in prior art, it is an object of the invention to provide one kind efficiently to have
Machine waste gas recovery processing method and complexes.Can be in the valuable dirt in reclaiming organic exhaust gas
While contaminating thing, meet that organic exhaust gas discharge index and petroleum chemical enterprise's safety in production require.Gram
Take existing organic exhaust gas recycling and processing device construction cost is high, and security is poor, and tail gas is not up to standard etc.
Problem.
To achieve the above objectives, the present invention adopts the technical scheme that：
A kind of efficiently organic exhaust gas recycling complexes, including organic waste gas collection device 1,
Air accumulator 2, surge tank 3, one-level film unit, activated carbon adsorption unit, vavuum pump 8, gas
Liquid knockout drum 9, compression condensation unit, two level film unit, low-temperature catalytic oxidation reactor 10
With tubular heat exchanger 11；
The outlet of organic exhaust gas collection device 1 is connected with the entrance one of air accumulator 2, air accumulator 2
Outlet be connected with the entrance of surge tank 3, the outlet of surge tank 3 and the entrance of one-level film unit
It is connected,
The retentate side of one-level film unit is connected with the entrance of activated carbon adsorption unit, one-level film unit
Per-meate side be connected with the entrance of vavuum pump 8,
Activated carbon adsorption unit is provided with absorption floss hole 7, for emission compliance gas；Activated carbon is inhaled
The backflow gas outlet of coupon member is connected with the entrance two of air accumulator 2, the solution of activated carbon adsorption unit
Suction outlet is connected with the entrance of vavuum pump 8,
The outlet of vavuum pump 8 is connected with the entrance of knockout drum 9, knockout drum 9 can
Solidifying gas outlet is connected with the entrance of compression condensation unit, the outlet of compression condensation unit and secondary membrane
The entrance of unit is connected,
The retentate side of two level film unit is connected with the entrance of surge tank 3, the infiltration of two level film unit
Side is connected with the entrance of vavuum pump 8,
The not condensated gas outlet of knockout drum 9 is connected with the tube-side inlet of tubular heat exchanger 11,
The tube side outlet of tubular heat exchanger 11 is connected with the entrance of low-temperature catalytic oxidation reactor 10, low
The outlet of warm catalyst oxidation reactor 10 is connected with the shell side inlet of tubular heat exchanger 11, tubulation
The shell-side outlet and atmosphere of heat exchanger 11.
On the basis of such scheme, the entrance of the organic exhaust gas collection device 1 seals provided with nitrogen
Gas piping and pressure gauge 21.
On the basis of such scheme, the outlet of the surge tank 3 and the entrance of one-level film unit
Between be provided with compressor 4a, flowmeter 16 and valve.
On the basis of such scheme, the one-level film unit by some one-level membrane module 5a with
Serial or parallel connection form combines；
The two level film unit combined by some second membrane module 5b in the form of serial or parallel connection and
Into；
The membrane module form of the one-level film unit and two level film unit be rolling, disc-type or in
Hollow fiber form.
On the basis of such scheme, the activated carbon adsorption unit is by two absorbent charcoal adsorption tanks
6 are formed by the parallel combination of four-way valve 15；It is another when one absorbent charcoal adsorption tank 6 adsorbs
Individual absorbent charcoal adsorption tank 6 carries out vacuum desorption and regenerative process.
On the basis of above-mentioned case, gas up to standard outlet and the absorption of the activated carbon adsorption unit are arranged
Put and be provided with automatically controlled aperture valve 22 between mouth 7；The backflow gas outlet of the activated carbon adsorption unit
Automatically controlled aperture valve 22 is provided between air accumulator 2.
On the basis of such scheme, pressure is provided between the vavuum pump 8 and knockout drum 9
Contracting machine 4b.
On the basis of such scheme, the compression condensation unit include condensing heat exchanger 12,
Refrigeration compressor 13, air heat exchanger 14, freon storage tank 23 and two valves.
On the basis of such scheme, the knockout drum 9 with it is cold in compression condensation unit
Magnetic valve 18 is provided between solidifying heat exchanger 12.
On the basis of such scheme, the retentate side of the two level film unit and entering for surge tank 3
Valve is provided between mouthful.
On the basis of such scheme, between the knockout drum 9 and tubular heat exchanger 11
Provided with automatically controlled aperture valve.
On the basis of such scheme, the tube side outlet of the tubular heat exchanger 11 is urged with low temperature
Air blower 20 is provided between the entrance of oxidation device 10.
On the basis of such scheme, the entrance of the low-temperature catalytic oxidation reactor 10 with it is big
Air blower and valve are provided between gas.
On the basis of such scheme, the shell-side outlet of the tubular heat exchanger 11 is provided with low temperature
Catalysis oxidation floss hole 17.
On the basis of such scheme, set on the tube side of the low-temperature catalytic oxidation reactor 10
There are pressurized vapor entrance and steam (vapor) outlet, pressurized vapor entrance is provided with automatically controlled aperture valve 22.
On the basis of such scheme, the oil phase outlet of the knockout drum 9 is provided with oil recovery
Product storage tank 19.
On the basis of such scheme, film used by the one-level film unit and two level film unit
Can be organosilicon membrane, block copolymer film or inoranic membrane.
On the basis of such scheme, the adsorbent used in the activated carbon adsorption unit is
Activated carbon or molecular sieve, desorption method are vacuum desorption.
On the basis of such scheme, low-temperature catalytic oxidation reactor 10 and the tubulation heat exchange
The low-temperature catalytic oxidation unit that device 11 forms can pass through all kinds of routines such as absorption tower and absorber
Adsorbent equipment, which substitutes, to be realized, used absorbent is that the volatility such as diesel oil are smaller, boiling point is higher
Organic matter.
On the basis of such scheme, the complexes can be fixed design, or
Skid-mounted design, and transported by automobile.
A kind of efficiently organic exhaust gas recovery and treatment method, comprises the following steps：
1) pending organic exhaust gas first by organic exhaust gas collection device 1 through air accumulator 2, slow
Rush tank 3 and enter one-level film unit progress UF membrane；
2) the retentate side gas of one-level film unit enters activated carbon adsorption unit, after absorption
Gas it is up to standard after discharged by adsorbing floss hole 7, as below standard, pass through according to a certain percentage
The entrance two that return wire returns to air accumulator 2 continues with, and forms processing cycle, until row up to standard
Put；
3) the dense gas of the per-meate side of one-level film unit and the stripping gas of activated carbon adsorption unit pass through true
Empty pump 8 enters compressor 4b superchargings, subsequently into knockout drum 9；It is organic after separation
Thing is preserved by recovery oil product storage tank 19 and periodically reclaimed；It is cold that condensated gas after separation enter compression
Solidifying unit is compressed condensation, and two level UF membrane is carried out then into two level film unit；
4) the retentate side gas of two level film unit enters surge tank 3, then is entered by surge tank 3
One-level film unit and activated carbon adsorption unit carry out circular treatment；
5) the dense gas of per-meate side of the dense gas of the per-meate side of two level film unit and one-level film unit and circulate
Vavuum pump 8 is crossed after compressor 4b superchargings, into knockout drum 9；
6) after the not condensated gas in knockout drum 9 are by automatically controlled aperture valve regulating flow, enter
Enter and heated in tubular heat exchanger 11, after the air being passed through with air blower 20 mixes, into low temperature
Catalyst oxidation reactor 10；In the presence of catalyst, low-temperature catalytic oxidation reaction occurs,
Then cool in tubular heat exchanger 11, discharged eventually through low-temperature catalytic oxidation floss hole 17.
On the basis of such scheme, the retentate side pressure of the one-level film unit and two level film unit
Power scope is 0.1Mpa~1Mpa, and temperature is less than 50 DEG C；Osmotic lateral pressure is absolute pressure
0Mpa~0.02Mpa.
On the basis of such scheme, the pressure limit of the compression condensation unit is
0.2Mpa~1Mpa, refrigeration temperature levels are -10 DEG C~10 DEG C.
On the basis of such scheme, the low-temperature catalytic oxidation reactor 10 passes through mesolow
Steam is preheated or preheated by electric-heating heat-conductive oil；Stop after reaching catalysis oxidation initial temperature
Only heat, catalytic process starts, and the gas after catalysis oxidation passes through heat caused by oxidizing process
Maintenance reaction temperature.
The invention provides one kind by efficient UF membrane, adsorption technology, condensation recovery technology and
The group technology that is combined by the low-temperature catalytic oxidation technology of Curve guide impeller and into suit
Put, high efficiente callback processing is carried out to organic exhaust gas.
Device of the present invention in use, can both reclaim is worth higher organic in organic exhaust gas
Thing, can meet organic exhaust gas discharge index again, and the explosive-proof grade of device improves.The technique and
Complexes service condition is gentle, and core technology UF membrane and low-temperature catalytic oxidation all have height
The characteristics of effect, safe, durable, low energy consumption, Oil Recovery rate is high, and tail gas index is superior.
The innovative application two level membrane process of this technological process, enters one by the concentrated gas of one-level film
Step separation, reduces and returns to the gas concentration of surge tank, play membrane process efficiently, it is continuous, return
High income, high safety, suitable for high-concentration organic waste gas the advantages of, reclaim waste gas in can
Component is reclaimed, is advantageous to improve the compliance rate of tail gas.Meanwhile improve in compression condensation unit
Organic concentration, compression condensation gas gross is reduced, be advantageous to increase organic matter organic efficiency.
Low-temperature catalytic oxidation reactor then can periodically remove the light hydrocarbon material for being difficult to condense, and play it
The advantage of advanced treating, overcome the drawbacks of light hydrocarbon material is accumulated in systems.It can either lead to
The valuable organic matter of membrane technology high efficiente callback is crossed, and can is enough to meet petroleum chemical enterprise to safety in production
Rigors while, using low-temperature catalyzed technology to organic exhaust gas carry out advanced treating, make
Organic exhaust gas meets most stringent of national discharge index.The technological design applicability, security and
Economy is strong, has preferable application prospect.
The structure of the present invention is simple, skid-mounted design, convenient for installation and maintenance, Automatic-control water can be achieved
Flat height.All there is stronger applicability to different types of organic exhaust gas.It can realize that petrochemical industry is looked forward to
Industry organic exhaust gas reclaims and efficient process, solves the problem of VOCs treatment, has necessarily
Prospects for commercial application.
Brief description of the drawings
The present invention has drawings described below：
The structure chart of Fig. 1 present invention.
The clearance curve map of Fig. 2 membrane process and complexes.
In figure, 1- organic exhaust gas collection devices, 2- air accumulators, 3- surge tanks, 4a- compressors,
4b- compressors, 5a- one-level membrane modules, 5b- second membrane modules, 6- absorbent charcoal adsorption tanks, 7- inhale
Attached floss hole, 8- vavuum pumps, 9- knockout drums, 10- low-temperature catalytic oxidation reactors, 11-
Tubular heat exchanger, 12- condensing heat exchangers, 13- refrigeration compressors, 14- air heat exchangers, 15-
Four-way valve, 16- flowmeters, 17- low-temperature catalytic oxidation floss holes, 18- magnetic valves, 19- recovery
Oil product storage tank, 20- air blowers, 21- pressure gauges, the automatically controlled aperture valves of 22-, 23- freon storage tanks；
Note：Solid line is gas flow before catalysis burning, and dotted line is gas flow after catalysis burning
Embodiment
The present invention is described in further detail below in conjunction with accompanying drawing.
As shown in figure 1, the present invention is directed to petroleum chemical enterprise in accumulating, handling and production process institute
Caused organic exhaust gas, use using secondary membrane as core technology, urged with reference to absorbing process and low temperature
Change oxidation technology, develop organic exhaust gas recovery and treatment method and complexes.
A kind of efficiently organic exhaust gas recycling complexes, including organic waste gas collection device 1,
Air accumulator 2, surge tank 3, one-level film unit, activated carbon adsorption unit, vavuum pump 8, gas
Liquid knockout drum 9, compression condensation unit, two level film unit, low-temperature catalytic oxidation reactor 10
With tubular heat exchanger 11；
The outlet of organic exhaust gas collection device 1 is connected with the entrance one of air accumulator 2, air accumulator 2
Outlet be connected with the entrance of surge tank 3, the outlet of surge tank 3 and the entrance of one-level film unit
It is connected,
The retentate side of one-level film unit is connected with the entrance of activated carbon adsorption unit, one-level film unit
Per-meate side be connected with the entrance of vavuum pump 8,
Activated carbon adsorption unit is provided with absorption floss hole 7, for emission compliance gas；Activated carbon is inhaled
The backflow gas outlet of coupon member is connected with the entrance two of air accumulator 2, the solution of activated carbon adsorption unit
Suction outlet is connected with the entrance of vavuum pump 8,
The outlet of vavuum pump 8 is connected with the entrance of knockout drum 9, knockout drum 9 can
Solidifying gas outlet is connected with the entrance of compression condensation unit, the outlet of compression condensation unit and secondary membrane
The entrance of unit is connected,
The retentate side of two level film unit is connected with the entrance of surge tank 3, the infiltration of two level film unit
Side is connected with the entrance of vavuum pump 8,
The not condensated gas outlet of knockout drum 9 is connected with the tube-side inlet of tubular heat exchanger 11,
The tube side outlet of tubular heat exchanger 11 is connected with the entrance of low-temperature catalytic oxidation reactor 10, low
The outlet of warm catalyst oxidation reactor 10 is connected with the shell side inlet of tubular heat exchanger 11, tubulation
The shell-side outlet and atmosphere of heat exchanger 11.
On the basis of such scheme, the entrance of the organic exhaust gas collection device 1 seals provided with nitrogen
Gas piping and pressure gauge 21.
On the basis of such scheme, the outlet of the surge tank 3 and the entrance of one-level film unit
Between be provided with compressor 4a, flowmeter 16 and valve.
On the basis of such scheme, the one-level film unit by some one-level membrane module 5a with
Serial or parallel connection form combines；
The two level film unit combined by some second membrane module 5b in the form of serial or parallel connection and
Into；
The membrane module form of the one-level film unit and two level film unit be rolling, disc-type or in
Hollow fiber form.
On the basis of such scheme, the activated carbon adsorption unit is by two absorbent charcoal adsorption tanks
6 are formed by the parallel combination of four-way valve 15；It is another when one absorbent charcoal adsorption tank 6 adsorbs
Individual absorbent charcoal adsorption tank 6 carries out vacuum desorption and regenerative process.
On the basis of above-mentioned case, gas up to standard outlet and the absorption of the activated carbon adsorption unit are arranged
Put and be provided with automatically controlled aperture valve 22 between mouth 7；The backflow gas outlet of the activated carbon adsorption unit
Automatically controlled aperture valve 22 is provided between air accumulator 2.
On the basis of such scheme, pressure is provided between the vavuum pump 8 and knockout drum 9
Contracting machine 4b.
On the basis of such scheme, the compression condensation unit include condensing heat exchanger 12,
Refrigeration compressor 13, air heat exchanger 14, freon storage tank 23 and two valves.
On the basis of such scheme, the knockout drum 9 with it is cold in compression condensation unit
Magnetic valve 18 is provided between solidifying heat exchanger 12.
On the basis of such scheme, the retentate side of the two level film unit and entering for surge tank 3
Valve is provided between mouthful.
On the basis of such scheme, between the knockout drum 9 and tubular heat exchanger 11
Provided with automatically controlled aperture valve.
On the basis of such scheme, the tube side outlet of the tubular heat exchanger 11 is urged with low temperature
Air blower 20 is provided between the entrance of oxidation device 10.
On the basis of such scheme, the entrance of the low-temperature catalytic oxidation reactor 10 with it is big
Air blower and valve are provided between gas.
On the basis of such scheme, the shell-side outlet of the tubular heat exchanger 11 is provided with low temperature
Catalysis oxidation floss hole 17.
On the basis of such scheme, set on the tube side of the low-temperature catalytic oxidation reactor 10
There are pressurized vapor entrance and steam (vapor) outlet, pressurized vapor entrance is provided with automatically controlled aperture valve 22.
On the basis of such scheme, the oil phase outlet of the knockout drum 9 is provided with oil recovery
Product storage tank 19.
On the basis of such scheme, film used by the one-level film unit and two level film unit
Can be organosilicon membrane, block copolymer film or inoranic membrane.
On the basis of such scheme, the adsorbent used in the activated carbon adsorption unit is
Activated carbon or molecular sieve, desorption method are vacuum desorption.
On the basis of such scheme, low-temperature catalytic oxidation reactor 10 and the tubulation heat exchange
The low-temperature catalytic oxidation unit that device 11 forms can pass through all kinds of routines such as absorption tower and absorber
Adsorbent equipment, which substitutes, to be realized, used absorbent is that the volatility such as diesel oil are smaller, boiling point is higher
Organic matter.
On the basis of such scheme, the complexes can be fixed design, or
Skid-mounted design, and transported by automobile.
A kind of efficiently organic exhaust gas recovery and treatment method, comprises the following steps：
1) pending organic exhaust gas first by organic exhaust gas collection device 1 through air accumulator 2, slow
Rush tank 3 and enter one-level film unit progress UF membrane；
2) the retentate side gas of one-level film unit enters activated carbon adsorption unit, after absorption
Gas it is up to standard after discharged by adsorbing floss hole 7, as below standard, pass through according to a certain percentage
The entrance two that return wire returns to air accumulator 2 continues with, and forms processing cycle, until row up to standard
Put；
3) the dense gas of the per-meate side of one-level film unit and the stripping gas of activated carbon adsorption unit pass through true
Empty pump 8 enters compressor 4b superchargings, subsequently into knockout drum 9；It is organic after separation
Thing is preserved by recovery oil product storage tank 19 and periodically reclaimed；It is cold that condensated gas after separation enter compression
Solidifying unit is compressed condensation, and two level UF membrane is carried out then into two level film unit；
4) the retentate side gas of two level film unit enters surge tank 3, then is entered by surge tank 3
One-level film unit and activated carbon adsorption unit carry out circular treatment；
5) the dense gas of per-meate side of the dense gas of the per-meate side of two level film unit and one-level film unit and circulate
Vavuum pump 8 is crossed after compressor 4b superchargings, into knockout drum 9；
6) after the not condensated gas in knockout drum 9 are by automatically controlled aperture valve regulating flow, enter
Enter and heated in tubular heat exchanger 11, after the air being passed through with air blower 20 mixes, into low temperature
Catalyst oxidation reactor 10；In the presence of catalyst, low-temperature catalytic oxidation reaction occurs,
Then cool in tubular heat exchanger 11, discharged eventually through low-temperature catalytic oxidation floss hole 17.
On the basis of such scheme, the retentate side pressure of the one-level film unit and two level film unit
Power scope is 0.1Mpa~1Mpa, and temperature is less than 50 DEG C；Osmotic lateral pressure is absolute pressure
0Mpa~0.02Mpa.
On the basis of such scheme, the pressure limit of the compression condensation unit is
0.2Mpa~1Mpa, refrigeration temperature levels are -10 DEG C~10 DEG C.
On the basis of such scheme, the low-temperature catalytic oxidation reactor 10 passes through mesolow
Steam is preheated or preheated by electric-heating heat-conductive oil；Stop after reaching catalysis oxidation initial temperature
Only heat, catalytic process starts, and the gas after catalysis oxidation passes through heat caused by oxidizing process
Maintenance reaction temperature.
Embodiment 1
Organic gas withdrawal processing technique application result is arranged outside the vault catalytic gasoline tank of Oil Tank Area,
Its organic exhaust gas composition (volume integral number scale) main body is nitrogen, volatile organism (VOCs)
Concentration is about 150000 to 300000mg/m3Between.Device design treatment amount is 40m3/ h,
Specified air inlet maximum concentration 200000mg/m3, one-level film retentate side pressure 0.2Mpa, two level
Film retentate side pressure 0.38Mpa, compression condensation pressure process 0.4MPa, 2 DEG C of temperature in device,
It is not less than -0.09Mpa through side vacuum, 260 DEG C of low temperature catalytic processes initial temperature is extremely
340℃.Plant running process charge flow rate, air inlet NMHC concentration, absorption floss hole
7 and low-temperature catalytic oxidation floss hole 17 exhaust concentration and device to the rate of recovery of organic matter,
It is shown in Table 1：
The treatment effect of the membrane module of table 1 and device to VOCs
Embodiment 2
This method and device are directed to outside intermediate tank farm inner floating roof slop tank breather valve in oil plant to be arranged
The effect of organic exhaust gas recycling application.Its organic exhaust gas forms (volume integral number scale) main body
Account for volume fraction for nitrogen 80% to 88%, volatile organism (VOCs) account for volume
Between the 12% to 20% of fraction.In VOCs in hydrocarbons be mainly lighter hydrocarbons include methane,
Ethane, ethene, propane, propylene, iso-butane, normal butane, n-butene, isobutene, anti-fourth
Alkene, carbon 5.Also contain a small amount of hydrogen sulfide and oxygen in other waste gas.Device design treatment amount is
40m3/ h, specified air inlet maximum concentration 300000mg/m3Or volume fraction 20% (v/v), one
Level film retentate side pressure 0.2Mpa, secondary membrane retentate side pressure 0.38Mpa, compression condensation mistake
2 DEG C of stroke pressure 0.4MPa, temperature, it is not less than -0.09Mpa through side vacuum, low temperature is urged
260 DEG C to 340 DEG C of change process initial temperature.The various organic exhaust gas concentration of device inlet and outlet are shown in
Table 2：
The concentration of gas is discharged in the device air inlet of table 2. with absorption floss hole 7
From the data in table 2, it can be seen that this patent method VOCs total removal rate is up to 99.5% with
On, and to all kinds of lighter hydrocarbons, as methane, ethane, ethene, propane, propylene, iso-butane,
Normal butane, n-butene, isobutene, anti-butylene are respectively provided with good treatment effect.
Embodiment 3
Processing to Catalyst Production house exhaust, to discharge capacity, its VOCs concentration is carried out first
Theoretical calculation, VOCs mostlys come from raw materials used hexane and first in production process in waste gas
Benzene, because the process conditions of production process limit, have part toluene and hexane and produced
As equipment operation is drained into air together with nitrogen in journey.Hexane and non-methane in system air inlet
Total hydrocarbon concentration fluctuation is larger, and most of concentration value is in 20000mg/m3To 140000mg/m3It
Between, mainly include n-hexane and toluene in hydrocarbons in VOCs.Device design treatment amount is
50m3/ h, air inlet maximum concentration are no more than 350000mg/m3, one-level film retentate side pressure
0.2Mpa, secondary membrane retentate side pressure 0.38Mpa, compression condensation pressure process 0.4MPa,
2 DEG C of temperature, it is not less than -0.09Mpa, low temperature catalytic processes initial temperature through side vacuum
260 DEG C to 340 DEG C.Device imports and exports organic exhaust gas concentration, charge flow rate, membrane process and whole
The clearance of covering device is shown in Fig. 2.
As shown by data, complexes of the present invention can with steady removal having more than 99.75%
Organic pollutants.Due to combining compression condensation and low-temperature catalytic oxidation technology, it is ensured that to film mistake
Waste gas after journey processing carries out advanced treating and Oil Recovery, and tail gas compliance rate is 100%, is put down
Equal tail gas concentration 45mg/m3, average removal rate is higher than 99.85%, its rate of recovery and clearance
It is significantly larger than existing organic exhaust gas recycling technology.
The content not being described in detail in this specification belongs to known in professional and technical personnel in the field
Prior art.
Claims (11)
1. a kind of efficiently organic exhaust gas recycling complexes, including organic gas sampling dress
Put (1), air accumulator (2), surge tank (3), one-level film unit, activated carbon adsorption unit,
Vavuum pump (8), knockout drum (9), compression condensation unit, two level film unit, low temperature are urged
Oxidation device (10) and tubular heat exchanger (11)；
The outlet of organic exhaust gas collection device (1) is connected with the entrance one of air accumulator (2), storage
The outlet of gas tank (2) is connected with the entrance of surge tank (3), the outlet of surge tank (3) with
The entrance of one-level film unit is connected,
The retentate side of one-level film unit is connected with the entrance of activated carbon adsorption unit, one-level film unit
Per-meate side be connected with the entrance of vavuum pump (8),
Activated carbon adsorption unit is provided with absorption floss hole (7), for emission compliance gas；Activated carbon
The backflow gas outlet of absorbing unit is connected with the entrance two of air accumulator (2), charcoal absorption list
The stripping gas outlet of member is connected with the entrance of vavuum pump (8),
The outlet of vavuum pump (8) is connected with the entrance of knockout drum (9), knockout drum
(9) condensated gas outlet is connected with the entrance of compression condensation unit, and compression condensation unit goes out
Mouth is connected with the entrance of two level film unit,
The retentate side of two level film unit is connected with the entrance of surge tank (3), two level film unit
Per-meate side is connected with the entrance of vavuum pump (8),
The not condensated gas outlet of knockout drum (9) and the tube side of tubular heat exchanger (11) enter
Mouth is connected, tube side outlet and the low-temperature catalytic oxidation reactor (10) of tubular heat exchanger (11)
Entrance be connected, the outlet of low-temperature catalytic oxidation reactor (10) and tubular heat exchanger (11)
Shell side inlet be connected, the shell-side outlet and atmosphere of tubular heat exchanger (11).
2. efficiently organic exhaust gas recycling complexes as claimed in claim 1, it is special
Sign is：The compression condensation unit include condensing heat exchanger (12), refrigeration compressor (13),
Air heat exchanger (14), freon storage tank (23) and two valves.
3. efficiently organic exhaust gas recycling complexes as claimed in claim 2, it is special
Sign is：The entrance of the organic exhaust gas collection device (1) is provided with nitrogen envelope gas piping and pressure
Power table (21)；
Compressor is provided between the outlet of the surge tank (3) and the entrance of one-level film unit
(4a), flowmeter (16) and valve；
It is provided between the gas up to standard outlet of the activated carbon adsorption unit and absorption floss hole (7)
Automatically controlled aperture valve (22)；The backflow gas outlet of the activated carbon adsorption unit and air accumulator (2)
Between be provided with automatically controlled aperture valve (22)；
Compressor (4b) is provided between the vavuum pump (8) and knockout drum (9)；Institute
State and be provided between the condensing heat exchanger (12) in knockout drum (9) and compression condensation unit
Magnetic valve (18)；
Valve is provided between the retentate side of the two level film unit and the entrance of surge tank (3)；
The oil phase outlet of the knockout drum (9) is provided with recovery oil product storage tank (19)；
Automatically controlled aperture valve is provided between the knockout drum (9) and tubular heat exchanger (11)；
Tube side outlet and the low-temperature catalytic oxidation reactor (10) of the tubular heat exchanger (11)
Entrance between be provided with air blower (20)；
The shell-side outlet of the tubular heat exchanger (11) is provided with low-temperature catalytic oxidation floss hole (17)；
Between the entrance and air of the low-temperature catalytic oxidation reactor (10) be provided with air blower and
Valve；
The tube side of the low-temperature catalytic oxidation reactor (10) is provided with pressurized vapor entrance and steaming
Vapor outlet, pressurized vapor entrance are provided with automatically controlled aperture valve (22).
4. efficiently organic exhaust gas recycling complexes as claimed in claim 1, it is special
Sign is：The one-level film unit is by some one-level membrane modules (5a) in the form of serial or parallel connection
Combine；
The two level film unit is combined by some second membrane modules (5b) in the form of serial or parallel connection
Form；
The membrane module form of the one-level film unit and two level film unit be rolling, disc-type or in
Hollow fiber form.
5. efficiently organic exhaust gas recycling complexes as claimed in claim 1, it is special
Sign is：Film is organosilicon membrane, block used by the one-level film unit and two level film unit
Co-polymer membrane or inoranic membrane.
6. efficiently organic exhaust gas recycling complexes as claimed in claim 1, it is special
Sign is：The activated carbon adsorption unit passes through four-way valve by two absorbent charcoal adsorption tanks (6)
(15) parallel combination forms；During one absorbent charcoal adsorption tank (6) absorption, another activity
Charcoal adsorption tanks (6) carry out vacuum desorption and regenerative process；
Adsorbent used in the activated carbon adsorption unit is activated carbon or molecular sieve, is desorbed
Method is vacuum desorption.
7. efficiently organic exhaust gas recycling complexes as claimed in claim 1, it is special
Sign is：What the low-temperature catalytic oxidation reactor (10) and tubular heat exchanger (11) formed
Low-temperature catalytic oxidation unit is substituted by conventional absorption tower and absorber and realized.
8. efficiently organic exhaust gas recycling complexes as claimed in claim 1, it is special
Sign is：The complexes are fixed design or skid-mounted design.
A kind of 9. efficiently organic exhaust gas recovery and treatment method, using any rights of claim 1-8
It is required that described efficient organic exhaust gas recycling complexes, it is characterised in that including following
Step：
1) pending organic exhaust gas first by organic exhaust gas collection device (1) through air accumulator (2),
Surge tank (3) enters one-level film unit and carries out UF membrane；
2) the retentate side gas of one-level film unit enters activated carbon adsorption unit, after absorption
Gas it is up to standard after by adsorb floss hole (7) discharge, if below standard according to a certain percentage
The entrance two that air accumulator (2) is returned by return wire continues with, and forms processing cycle, directly
To qualified discharge；
3) the dense gas of the per-meate side of one-level film unit and the stripping gas of activated carbon adsorption unit pass through true
Empty pump (8) is pressurized into compressor (4b), subsequently into knockout drum (9)；Separation
Organic matter afterwards is preserved by recovery oil product storage tank (19) and periodically reclaimed；Condensated gas after separation
Condensation is compressed into compression condensation unit, secondary membrane is carried out then into two level film unit
Separation；
4) the retentate side gas of two level film unit enters surge tank (3), then by surge tank (3)
Circular treatment is carried out into one-level film unit and activated carbon adsorption unit；
5) the dense gas of per-meate side of the dense gas of the per-meate side of two level film unit and one-level film unit and circulate
Vavuum pump (8) is crossed after compressor (4b) supercharging, into knockout drum (9)；
6) after the not condensated gas in knockout drum (9) are by automatically controlled aperture valve regulating flow,
Heated into tubular heat exchanger (11), after the air being passed through with air blower (20) mixes,
Into low-temperature catalytic oxidation reactor (10)；In the presence of catalyst, occur low-temperature catalyzed
Oxidation reaction, then cool in tubular heat exchanger (11), eventually through low-temperature catalytic oxidation
Floss hole (17) discharges.
10. efficiently organic exhaust gas recovery and treatment method, its feature as claimed in claim 9 exist
In：The retentate side pressure limit of the one-level film unit and two level film unit is
0.1Mpa~1Mpa, temperature are less than 50 DEG C；Osmotic lateral pressure is absolute pressure 0Mpa~0.02Mpa；
The pressure limit of the compression condensation unit is 0.2Mpa~1Mpa, refrigeration temperature levels
For -10 DEG C~10 DEG C.
11. efficiently organic exhaust gas recovery and treatment method, its feature as claimed in claim 9 exist
In：The low-temperature catalytic oxidation reactor (10) is preheated or passed through by low pressure steam
Electric-heating heat-conductive oil preheats；Stop heating after reaching catalysis oxidation initial temperature, catalytic process opens
Dynamic, the gas after catalysis oxidation passes through heat maintenance reaction temperature caused by oxidizing process.
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| CN111482060A (en) * | 2020-06-02 | 2020-08-04 | 连云港市拓普科技发展有限公司 | Oil gas recovery device and method by organic membrane separation method |
| CN111617613A (en) * | 2019-02-28 | 2020-09-04 | 中国石油化工股份有限公司 | Method and system for treating waste gas of refining and chemical enterprises |
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| CN113856392A (en) * | 2021-09-23 | 2021-12-31 | 大连理工大学 | Full-concentration VOCs collecting system and method based on compression condensation, membrane separation and adsorption coupling |
| 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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| CN113883826B (en) * | 2021-09-30 | 2024-05-28 | 西安交通大学 | System for low temperature condensation retrieves volatile gas |
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