CN103055655B - A kind of processing method of cyclohexane oxidation system tail gas - Google Patents
A kind of processing method of cyclohexane oxidation system tail gas Download PDFInfo
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 52
- 230000003647 oxidation Effects 0.000 title claims abstract description 51
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000003672 processing method Methods 0.000 title claims abstract description 8
- 239000003463 adsorbent Substances 0.000 claims abstract description 201
- 238000003795 desorption Methods 0.000 claims abstract description 124
- 238000005406 washing Methods 0.000 claims abstract description 19
- 239000007789 gas Substances 0.000 claims description 185
- 238000001179 sorption measurement Methods 0.000 claims description 26
- 229920006395 saturated elastomer Polymers 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 7
- 238000011069 regeneration method Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 239000002250 absorbent Substances 0.000 claims description 5
- 230000002745 absorbent Effects 0.000 claims description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 16
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- 230000008901 benefit Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 26
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 230000008569 process Effects 0.000 description 15
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 10
- 239000002594 sorbent Substances 0.000 description 9
- 230000001590 oxidative effect Effects 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 5
- 235000011037 adipic acid Nutrition 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 239000002671 adjuvant Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
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- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- 229910000510 noble metal Inorganic materials 0.000 description 1
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- 238000005381 potential energy Methods 0.000 description 1
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- Separation Of Gases By Adsorption (AREA)
Abstract
The invention discloses a kind of cyclohexane oxidation system exhaust gas processing device and processing method, device comprises the tail gas heat exchanger, tail gas washing tower, the first adsorbent bed and with it and the second adsorbent bed connect that are connected successively, the arrival end of two adsorbent beds also connects two pipelines, wherein be connected to the first transfer valve and the second transfer valve in a pipeline, the 3rd transfer valve and the 4th transfer valve is connected in another article of pipeline, first transfer valve is connected with tail gas washing tower with the second transfer valve, is provided with desorption gas export pipeline between the 3rd transfer valve and the 4th transfer valve; The port of export two pipelines in parallel of two adsorbent beds, wherein one article of pipeline is connected to the 5th transfer valve and the 6th transfer valve, another article pipeline is connected to the 7th transfer valve and the 8th transfer valve, offgas outlet pipeline is provided with between the 5th transfer valve and the 6th transfer valve, be provided with the desorption gas inlet ductwork being connected to the 9th transfer valve between 7th transfer valve and the 8th transfer valve, there is the advantage that production cost is low, equipment investment is few, absorption efficiency is high.
Description
Technical field
The present invention relates to the device and method that cyclohexane oxidation prepares KA oil (mixture of cyclohexanol and cyclohexanone) or adipic acid, particularly a kind of processing method of cyclohexane oxidation system tail gas.
Background technology
The liquid phase oxidation of cyclohexane is the committed step manufacturing KA oil and adipic acid, all adopts oxygen-containing gas to be oxidant, under higher temperature and pressure (80 ~ 170 DEG C, 0.3 ~ 1.5MP), carries out oxidation reaction.Owing to containing the inert gas (being mainly nitrogen) not participating in a large number reacting in oxygen-containing gas, containing many organic principles in tail gas after oxidation, comprise raw material, solvent, byproduct of reaction etc., need the recovery and the gas cleaning that carry out organic component, could to environmental emission after reaching discharge standard.General cyclohexane liquid-phase oxidation vent gas treatment flow process comprises condensation liquefaction and spray washing two series winding unit, most organic in tail gas can be recycled, but, still be difficult to be removed by said method containing a small amount of low boiling organic principle in tail gas, make gas not reach discharge standard.Along with the raising day by day of environment protectment protection, how these low-concentration organic exhaust gas of purified treatment just become the problem of a generality.
Way current is at present that the cyclohexane liquid-phase oxidation tail gas feeding flare system these being contained low-concentration organic is burnt, and discharges, as Chinese patent Authorization Notice No. CN201593027U after making it change carbon dioxide into.This method Problems existing is: flare system generally need add combustion adjuvant and catalyst, and equipment investment is comparatively large, needs with noble metal as catalyst; Combustion adjuvant consumption is large, and in the tail gas of its amount ratio process, content of organics is high 4 ~ 8 times; Meanwhile, although this way has burnt poisonous and hazardous organic principle, add a lot of CO2 emission doubly, organic principle has not also been recycled utilization.
The common method of another kind of cleaning of off-gas is absorption, adopts the adsorbent organic principles such as active carbon, discharges after tail gas clean-up, reuse after adsorbent desorption and regeneration, the gas of desorption processes recovery organic component, further as China Patent Publication No. CN101306293A, CN102423601A.It is too high that the subject matter of this method is that desorption reclaims organic cost, after adopting steam or nitrogen desorption, desorption gas also needs to carry out the operation such as condensation liquefaction, rectifying separation removing organic principle, because organic matter content in desorption gas is extremely low, lot of energy is used for the process of desorption gas, when for large-scale industrial production, this part investment is just considerable with operating cost, governs the generally application of this method thus.
Summary of the invention
Instant invention overcomes the defect of prior art, provide the exhaust gas treating method of the cyclohexane oxidation system that a kind of production cost is low, equipment investment is few, absorption efficiency is high.
In order to solve the problems of the technologies described above, the present invention is achieved by the following technical solutions: a kind of processing method of cyclohexane oxidation system tail gas, a treating apparatus is set, comprises the tail gas heat exchanger, tail gas washing tower, the first adsorbent bed, the second adsorbent bed that is connected in parallel with the first adsorbent bed that are connected successively;
The first described adsorbent bed and the arrival end of the second adsorbent bed also connect two pipelines, wherein be connected to the first transfer valve and the second transfer valve in a pipeline, the 3rd transfer valve and the 4th transfer valve is connected in another article of pipeline, between the first transfer valve and the second transfer valve, there is pipeline to be connected with tail gas washing tower, between the 3rd transfer valve and the 4th transfer valve, be provided with desorption gas export pipeline;
The port of export two pipelines in parallel of the first described adsorbent bed and the second adsorbent bed, wherein be connected to the 5th transfer valve and the 6th transfer valve in one article of pipeline, the 7th transfer valve and the 8th transfer valve is connected in another article of pipeline, offgas outlet pipeline is provided with between the 5th transfer valve and the 6th transfer valve, desorption gas inlet ductwork is provided with between 7th transfer valve and the 8th transfer valve, the 9th transfer valve is connected in described desorption gas inlet ductwork, be connected to heater in described desorption gas inlet ductwork, processing method comprises the following steps:
A () closes the first transfer valve, the 4th transfer valve, the 5th transfer valve, the 8th transfer valve, open the second transfer valve, the 3rd transfer valve, the 6th transfer valve, the 7th transfer valve, the 9th transfer valve, cyclohexane oxidation system tail gas enters tail gas heat exchanger and tail gas washing tower cooling washing through inlet exhaust gas pipeline, most of organic principle in gas recovery, obtains containing a small amount of organic tail gas;
B () enters after the second adsorbent bed being filled with solid absorbent carries out adsorption cleaning by above-mentioned containing a small amount of organic tail gas, through offgas outlet pipeline qualified discharge or recycling after process further; Desorption gas enters organic first adsorbent bed in saturated adsorption tail gas through desorption gas inlet ductwork simultaneously, contact with saturated adsorption agent after carrying out desorption and discharge through desorption gas export pipeline, operating condition when first adsorbent bed carries out adsorption cleaning is: temperature 0 ~ 45 DEG C, pressure 300 ~ 900kPa, operating condition when second adsorbent bed carries out desorption is: temperature 120 ~ 200 DEG C, pressure 100 ~ 400kPa;
C the adsorbent of () second in adsorbent bed reaches capacity adsorbance, and after the adsorbent in the first adsorbent bed completes regeneration, close the second transfer valve, 3rd transfer valve, 6th transfer valve, 7th transfer valve, open the first transfer valve, 4th transfer valve, 5th transfer valve, 8th transfer valve, cyclohexane oxidation system tail gas is made to be switched to the first adsorbent bed from the second adsorbent bed, desorption gas is switched to the second adsorbent bed from the first adsorbent bed, two adsorbent bed exchange functions, first adsorbent bed carries out adsorption operations and the second adsorbent bed carries out desorption manipulation, so periodically operation, realize adsorption-desorption rotation.
Further:
Return returning in cyclohexane oxidation system or other system through the gas of desorption gas export pipeline discharge in step (b)
Receive and utilize.
When the first adsorbent bed in step (b) desorption time compared with the second adsorbent bed the adsorption cleaning time in short-term, after desorption terminates, close the 9th transfer valve.
The second adsorbent bed is entered after being heated by the gas of desorption described in step (b) heater via.
Described desorption gas is the one in oxygen-containing gas, nitrogen, superheated steam or the saturated vapor used in cyclohexane oxidation system.
Adsorbent described in step (b) is the one in activated carbon granule, NACF or silica-rich zeolite.
The present invention adopts on the basis of condensation liquefaction and spray washing in conventional tail gas disposal, adds the low-concentration organic in two adsorbent bed alternating sorbent and desorption tail gas being filled with adsorbent, when organic component in an adsorbent bed adsorption and oxidation system tail gas, another adsorbent bed carries out desorption manipulation simultaneously and reclaims organic matter, and adsorbent is regenerated, desorption gas is oxygen-containing gas, nitrogen, one in superheated steam or saturated vapor, the oxidant used in preferred use cyclohexane oxidation system, if oxygen-containing gas or nitrogen or superheated steam or saturated vapor are as desorption gas, by the organic substance desorption after absorption, and return oxidative system or the recycling of follow-up stripping system with desorption gas, therefore no longer desorption Flash Gas Compression Skid System is increased, can directly to utilize in production system original exhaust gas processing device as condenser, spray column, strippers etc. reclaim organic matter, this just greatly reduces the cost of method for adsorbing and purifying, be convenient to its commercial Application.
The present invention does not have special requirement to adsorbent, all can be applicable to the present invention by the solid absorbent of organic component in absorption tail gas, such as, in the conventional favourable absorption tail gas material of organic component, the one in preferred activated carbon granule, activated carbon fiber, silica-rich zeolite.
Main feature of the present invention is oxidant oxygen-containing gas, protection gas nitrogen, superheated steam in cyclohexane oxidation production system or the saturated vapor that can select to use in the cyclohexane oxidation system organic matter as the attached absorption of desorption qi exhaustion of adsorbent bed; make adsorbent reactivation, the organic matter of desorption returns cyclohexane oxidation system with gas and recycles.Why select source of the gas in cyclohexane oxidation system as sweep gas, it is the device wishing to utilize original these gases of process in system, as compressor, condenser, scrubbing tower etc., for reclaiming the organic substance of desorption, thus do not need to increase extra equipment and expense, which saves equipment and the operating cost of desorption gas disposal.When the temperature of the gas entering oxidation reactor in cyclohexane oxidation system is higher, be more suitable for adopting the oxidant oxygen-containing gas used in cyclohexane oxidation system as desorption gas; When being protection gas N that handling safety need be supplemented in cyclohexane oxidation system
2measure N in comparatively large or system
2time superfluous, be more suitable for adopting nitrogen as desorption gas; When being protection gas N that handling safety need be supplemented in system
2measure N in less or system
2when measuring inadequate, adopt intrasystem part superheated steam or saturated vapor as desorption gas, the mist of oxygen-containing gas and nitrogen also can be adopted as desorption gas.
The desorption mode of adsorbent bed depends on selection and the condition of desorption gas can adopt desorption by heating or step-down desorption.Such as, if select the oxidant oxygen-containing gas of cyclohexane oxidation as desorption gas, then pressure is higher, oxygen-containing gas can be carried out desorption after heater heating, now when the first adsorbent bed carries out desorption manipulation, when the second adsorbent bed carries out adsorption operations, because the oxygen-containing gas temperature after heating is higher, first adsorbent bed temperature is higher than the second adsorbent bed, and desorption mode is exactly desorption by heating; If select normal pressure oxygen-containing gas as desorption gas, enter oxidation reactor again after the exit gas supercharging of the first adsorbent bed, the pressure of the first adsorbent bed is lower than the pressure of the second adsorbent bed in this case, and desorption mode is exactly step-down desorption.When adopting the nitrogen or superheated steam or saturated vapor that use in cyclohexane oxidation production system as desorption gas, be also according to the temperature of gas and and pressure condition adopt alternating temperature desorption and transformation desorption mode respectively.
First adsorbent bed and the second adsorbent bed need exchange-column shift, switching time with the adsorbent beds of carrying out adsorption operations to or be good close to the saturated adsorption state under tail gas condition, depend on the item conditions such as the stable operation time of the adsorption capacity of adsorbent, admission space, gas treatment amount, discharge standard, system requirements.
In order to the stable operation of oxidative system in retaining ring hexane oxidation process units, the ratio of the desorption gas of drawing from system is the least possible, so that when desorption manipulation, the switching of gas can not cause the obvious fluctuation of system condition.In addition, an adsorbent bed can also be set up outside the first adsorbent bed and the second adsorbent bed, shunt tail gas or desorption gas when switching for gas gradually, make handover operation smooth transition.
Compared with prior art, advantage of the present invention is:
1, absorption efficiency is high, on the basis that conventional tail gas disposal adopts condensation liquefaction and spray washing, add the low-concentration organic in two adsorbent bed alternating sorbent and desorption tail gas being filled with adsorbent, organic matter more than 90% is recycled utilization, reach discharge standard after vent gas treatment, after process, in tail gas, content of organics is no more than 0.01%;
2, production cost is low, equipment investment is few, original exhaust gas processing device in cyclohexane oxidation production system directly can be utilized to reclaim organic matter as condenser, spray column, stripper etc., greatly reduce the cost of method for adsorbing and purifying, be convenient to its commercial Application;
3, cyclohexane oxidation production system internal oxidation agent oxygen-containing gas or nitrogen or superheated steam or saturated vapor can be used as desorption gas, by the organic substance desorption after absorption, and return oxidative system or the recycling of follow-up stripping system with desorption gas, no longer increase desorption Flash Gas Compression Skid System, reduce equipment investment further.
Accompanying drawing explanation
Fig. 1 is process chart of the present invention;
Fig. 2 is the adsorbent bed schematic diagram that the gas being filled with solid absorbent of the present invention flows vertically;
Fig. 3 is the adsorbent bed schematic diagram that the gas being filled with solid absorbent of the present invention radially flows.
As shown in Figure 1: 1 is tail gas heat exchanger, 2 is tail gas washing tower, and 3 be the first adsorbent bed, 4 is the second adsorbent bed, 5 is the first transfer valve, 6 is the second transfer valve, and 7 is the 3rd transfer valve, and 8 is the 4th transfer valve, 9 is the 5th transfer valve, 10 is the 6th transfer valve, and 11 is the 7th transfer valve, and 12 is the 8th transfer valve, 13 is heater, 14 is the 9th transfer valve, and 15 is air inlet pipe, and 16 is adsorbent packed beds, 17 is escape pipe, manage centered by 18,19 is adsorbent packed beds, 20 annular space passages, 21 bodies, 22 is escape pipe.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in further detail, but the present invention is not limited to described embodiment.
The adsorbent bed that the present invention adopts has two kinds, and one is axial packed bed, and as shown in Figure 2, gas enters from one end of bed, exports from the other end; Another kind is radial packed bed, and as shown in Figure 3, gas enters from bed center, exports after peripheral gauge.
Three parts are divided into: air inlet pipe 15, adsorbent packed beds 16 and escape pipe 17 in axial packed bed.Gas enters adsorbent packed beds 16 by air inlet pipe 15, and adsorbent packed beds 16 bed is filled with solid sorbent particles or fiber, and the gas entered, along the axial flow of bed, exports finally by escape pipe 17.
Five parts are divided into: central tube 18, adsorbent packed beds 19, annular space passage 20, bed body 21 and escape pipe 22 in radial packed bed.Gas centrally pipe 18 enters bed; on the wall of central tube, dense distribution many apertures; represented by dashed line; periphery is filled with solid sorbent particles or fiber; the gas entered, by the Radial Flow of the aperture on tube wall along bed, contacts with adsorbent packed beds 19, then enters annular space passage 20; along the flowing of bed body 21 wall, export finally by escape pipe 22.
The advantage of axial packed bed is that structure is simple, cost is low, subject matter is that the axial length of bed and diameter ratio are larger, cause bed pressure drop larger, the potential energy of the tail gas after losing absorption when adsorption operations, the pressure of the desorption gas entering desorption bed can be increased when desorption manipulation, thus increase the energy consumption of the gas dynamic facility (GDF) such as compressor, decompressor.
And the stream of radial packed bed gas is shorter, bed pressure drop is little, favourable energy-conservation, but complex structure, manufacturing cost is high.In embodiment of the present invention 1 ~ 5, be all the fixed bed that structure is identical owing to being used as the second adsorbent bed of adsorption operations with the first adsorbent bed of desorption manipulation, both can have been made two parallel autonomous devices during manufacture, and also can join end to end, integrator, segmentation uses.
Embodiment 1
As shown in Figure 1, cyclohexane oxidation system exhaust gas processing device, comprises the tail gas heat exchanger 1, tail gas washing tower 2, first adsorbent bed 3, the second adsorbent bed 4 that is connected in parallel with the first adsorbent bed 3 that are connected successively.
The first described adsorbent bed 3 and the arrival end of the second adsorbent bed 4 also connect two pipelines, wherein be connected to the first transfer valve 5 and the second transfer valve 6 in a pipeline, the 3rd transfer valve 7 and the 4th transfer valve 8 is connected in another article of pipeline, between the first transfer valve 5 and the second transfer valve 6, there is pipeline to be connected with tail gas washing tower 2, between the 3rd transfer valve 7 and the 4th transfer valve 8, be provided with desorption gas export pipeline;
The port of export two pipelines in parallel of the first described adsorbent bed 3 and the second adsorbent bed 4, wherein be connected to the 5th transfer valve 9 and the 6th transfer valve 10 in one article of pipeline, the 7th transfer valve 11 and the 8th transfer valve 12 is connected in another article of pipeline, between the 5th transfer valve and the 6th transfer valve, be provided with offgas outlet pipeline, between the 7th transfer valve and the 8th transfer valve, be provided with desorption gas inlet ductwork; The 9th transfer valve 14 is connected in described desorption gas inlet ductwork.
During operation, in Fig. 1, the first transfer valve 5, the 4th transfer valve 8, the 5th transfer valve 9, the 8th transfer valve 12 are closed condition, and the second transfer valve 6, the 3rd transfer valve 7, the 6th transfer valve 10, the 7th transfer valve 11, the 9th transfer valve 14 are opening.Cyclohexane oxidation system tail gas enters tail gas heat exchanger 1 and tail gas washing tower 2 cooling washing through inlet exhaust gas pipeline, most of organic principle in gas recovery, and condensate liquid and washing raffinate send into the recovery of other unit of system; Enter the second adsorbent bed 4 containing a small amount of organic tail gas and carry out adsorption cleaning, be filled with in second adsorbent bed 4 through regeneration, absorption organic component activated carbon granule adsorbent, after tail gas and adsorbent contact, at lower temperature and higher pressure, organic component is by adsorbent, gas is purified, purified gas can directly discharge, and also can send into follow-up treatment process and further recycle.Meanwhile, the first adsorbent bed 3 carries out desorption manipulation.It is organic adsorbent in saturated adsorption tail gas in first adsorbent bed 3, need to carry out desorption and regeneration, regeneration adopts a part to enter the compressed air of cyclohexane oxidation system internal oxidition reactor, enter the first adsorbent bed 3 by desorption gas inlet ductwork to contact with saturated adsorption agent, organic matter enters oxidation reactor with compressed air after desorption on the sorbent and recycles.After certain operating time, adsorbent in second adsorbent bed 4 reaches capacity adsorbance, adsorbent simultaneously in the first adsorbent bed 3 completes regeneration, now the second transfer valve 6, 3rd transfer valve 7, 6th transfer valve 10, 7th transfer valve 11 cuts out, and the first transfer valve 5, 4th transfer valve 8, 5th transfer valve 9, 8th transfer valve 12 is opened, tail gas is made to be switched to the first adsorbent bed 3 from the second adsorbent bed 4, oxygen-containing gas is switched to the second adsorbent bed 4 from the first adsorbent bed 3, two adsorbent bed exchange functions, first adsorbent bed 3 carries out adsorption operations and the second adsorbent bed 4 carries out desorption manipulation, so periodically operation, realize adsorption-desorption rotation.When desorption time comparatively adsorption time in short-term, after desorption terminates, close transfer valve 14.When desorption gas used again by needs, open transfer valve 14.
The exhaust flow and the composition (representing with mass percentage, lower same) thereof that enter the second adsorbent bed 4 list in table 1.
Table 1: the flow of cyclohexane oxidation KA oil tail gas and composition
Second adsorbent bed adopts the axial packed bed of activated carbon granule, and as shown in Figure 2, relevant adsorbent and the operating parameter of the second adsorbent bed 4 list in table 2.
Table 2: adsorbent and the second adsorbent bed 4 operating parameter
Compressed air is adopted for the desorption gas in the first adsorbent bed 3 of desorption, make the organic matter of absorption at elevated temperatures from desorption adsorbent, kind, the average grain diameter of adsorbent are identical with the second adsorbent bed 4 with the amount of the adsorbent of filling in the first desorption bed 3.Other operating parameter and the operating result of the first adsorbent bed 3 list in table 3.
Table 3: the first adsorbent bed 3 operating parameter and operating result
In the above-described embodiments, by two adsorbent bed alternate operations, in tail gas, organic matter more than 93% is recycled utilization, reaches discharge standard after tail gas clean-up.
Embodiment 2
Device and operating process, the cyclohexane oxidation off-gas flow entering the second adsorbent bed 4 and composition are with embodiment 1.As different from Example 1, desorption gas adopts a part to enter the protection gas N of cyclohexane oxidation system internal oxidition reactor
2, but need by heater 14 be heated to be close to or higher than oxidation reactor reaction temperature after enter the first adsorbent bed 3 by desorption gas inlet ductwork and contact with the saturated adsorption agent in bed, organic matter on the sorbent after desorption with the protection gas N of oxidation reactor
2enter oxidation reactor after being mixed together to recycle.
After the operating parameter of the second adsorbent bed 4 and process, in offgas outlet gas, organic matter maximum level is identical with embodiment 1, identical with the second adsorbent bed 4 with average grain diameter as the amount of adsorbent of filling in the first adsorbent bed 3 of desorption, the kind of adsorbent.Other operating parameter and the operating result of the first adsorbent bed 3 list in table 4.
Table 4: the first adsorbent bed 3 operating parameter
In the above-described embodiments, by two adsorbent bed alternate operations, in tail gas, organic matter more than 90% is recycled utilization, reaches discharge standard after tail gas clean-up.
Embodiment 3
Device and operating process are with embodiment 1.As different from Example 1, the exhaust flow and the organic matter composition thereof that enter the second adsorbent bed 4 are different, desorption gas in first adsorbent bed 3 adopts saturated vapor, and the thick adipic acid refining system that organic matter enters cyclohexane oxidation adipic acid follow-up with the saturated vapor of desorption after desorption on the sorbent recycles.
The exhaust flow and the composition (representing with mass percentage, lower same) thereof that enter the second adsorbent bed 4 list in table 5.
Table 5: the flow of cyclohexane oxidation adipic acid tail gas and composition
Adsorbent bed adopts the axial packed bed of activated carbon granule, and as shown in Figure 2, relevant adsorbent and the parameter of the second adsorbent bed 4 list in table 6.
Table 6: adsorbent and the second adsorbent bed 4 operating parameter
Desorption gas for the first adsorbent bed 3 of desorption adopts saturated vapor, make the organic matter of absorption at a higher temperature from desorption adsorbent, kind, the average grain diameter of adsorbent are identical with the second adsorbent bed 4 with the amount of the adsorbent of filling in the first adsorbent bed 3.Other operating parameter and the operating result of the first adsorbent bed 3 list in table 7.
Table 7: the first adsorbent bed 3 operating parameter and operating result
In the above-described embodiments, by two adsorbent bed alternate operations, in tail gas, organic matter more than 90% is recycled utilization, reaches discharge standard after tail gas clean-up.In addition, the operating time of adsorbent bed 3 is less than the operating time of the second adsorbent bed 4.After desorption terminates, close the 9th transfer valve 14.When desorbing agent used again by needs, open the 9th transfer valve 14.
Embodiment 4
Device and operating process, the cyclohexane oxidation off-gas flow entering the second adsorbent bed 4 and composition are with embodiment 1.As different from Example 1, the operating condition of the second adsorbent bed 4 is different from embodiment 1, desorption gas in first adsorbent bed 3 adopts superheated steam, and organic matter enters the follow-up peroxide caustic digestion systemic circulation of cyclohexane oxidation technique with the superheated steam of desorption after desorption on the sorbent and utilizes.
First adsorbent bed 3 and the second adsorbent bed 4 adopt axial packed bed, and as shown in Figure 2, filler is silica-rich zeolite.The operating parameter of the second adsorbent bed 4 lists in table 8.
Table 8: the second adsorbent bed 4 operating parameter
Desorption gas for the first adsorbent bed 3 of desorption adopts superheated steam, makes the organic matter of absorption at elevated temperatures from desorption adsorbent.First adsorbent bed 3 operates at higher temperature and lower pressure, is conducive to desorption manipulation.Operating parameter and the operating result of the first adsorbent bed 3 list in table 9.
Table 9: the first adsorbent bed 3 operating parameter and operating result
In the above-described embodiments, by two adsorbent bed alternate operations, in tail gas, organic matter more than 90% is recycled utilization, reaches discharge standard after tail gas clean-up.
Embodiment 5
Device, operating process, the cyclohexane oxidation system exhaust flow entering the second adsorbent bed 4 and composition are with embodiment 1.As different from Example 1, adopt superheated steam for the desorption gas in the first adsorbent bed 3 of desorption, the first adsorbent bed 3 and the second adsorbent bed 4 adopt the radial bed shown in Fig. 3 to reduce bed pressure drop, and meanwhile, adsorbent adopts NACF.The operating parameter of adsorbent and the second adsorbent bed 4 lists in table 10, and all the other operating parameters are identical with embodiment 1.
Table 10: the operating parameter of adsorbent and the second adsorbent bed 4
As can be seen from Table 10, NACF specific activity charcoal granular absorption capacity is high, and bed pressure drop is low, like this, only needs the purification object that less adsorbent just can reach same.In addition, adopt radial bed to decrease gas by adsorbent bed distance, bed overall presure drop is reduced greatly, be conducive to reducing energy consumption.
Adopt superheated steam for the desorption gas in the first adsorbent bed 3 of desorption, make the organic matter of absorption at elevated temperatures from desorption adsorbent.First adsorbent bed 3 operates at higher temperature and lower pressure, is conducive to desorption manipulation.Organic matter enters the follow-up peroxide caustic digestion systemic circulation of cyclohexane oxidation technique with the superheated steam of desorption after desorption on the sorbent and utilizes.Operating parameter and the operating result of the first adsorbent bed 3 list in table 11.
Table 11: the first adsorbent bed 3 operating parameter and operating result
In the present embodiment, by two adsorbent bed alternate operations, in tail gas, organic matter more than 90% is recycled utilization, reaches discharge standard after tail gas clean-up.
Claims (1)
1. the processing method of a cyclohexane oxidation system tail gas, a treating apparatus is set, this treating apparatus comprises the tail gas heat exchanger (1) be connected successively, tail gas washing tower (2), first adsorbent bed (3), the second adsorbent bed (4) be connected in parallel with the first adsorbent bed (3), described the first adsorbent bed (3) and the arrival end of the second adsorbent bed (4) also connect two pipelines, wherein be connected to the first transfer valve (5) and the second transfer valve (6) in a pipeline, the 3rd transfer valve (7) and the 4th transfer valve (8) is connected in another article of pipeline, between the first transfer valve (5) and the second transfer valve (6), there is pipeline to be connected with tail gas washing tower (2), desorption gas export pipeline is provided with between 3rd transfer valve (7) and the 4th transfer valve (8), the port of export two pipelines in parallel of described the first adsorbent bed (3) and the second adsorbent bed (4), wherein be connected to the 5th transfer valve (9) and the 6th transfer valve (10) in one article of pipeline, the 7th transfer valve (11) and the 8th transfer valve (12) is connected in another article of pipeline, offgas outlet pipeline is provided with between the 5th transfer valve (9) and the 6th transfer valve (10), desorption gas inlet ductwork is provided with between 7th transfer valve (11) and the 8th transfer valve (12), the 9th transfer valve (14) is connected in described desorption gas inlet ductwork, heater (13) is connected in described desorption gas inlet ductwork, it is characterized in that processing method comprises the following steps:
A () closes the first transfer valve (5), the 4th transfer valve (8), the 5th transfer valve (9), the 8th transfer valve (12), open the second transfer valve (6), the 3rd transfer valve (7), the 6th transfer valve (10), the 7th transfer valve (11), the 9th transfer valve (14), cyclohexane oxidation system tail gas enters tail gas heat exchanger (1) and tail gas washing tower (2) cooling washing through inlet exhaust gas pipeline, most of organic principle in gas recovery, obtains containing a small amount of organic tail gas;
B () enters the second adsorbent bed (4) being filled with solid absorbent by above-mentioned carry out adsorption cleaning containing a small amount of organic tail gas, the exhaust flow entering the second adsorbent bed (4) is 20140Nm
3/ hr, temperature is 41.5 DEG C, and pressure is 940kPa, comprises: cyclohexane 0.042%, oxygen 1.55%, cyclohexanone 0.036%, N with the composition that mass percentage represents
297.73%, be filled with in second adsorbent bed (4) through regeneration, average grain diameter is 600 microns, adsorption capacity is 0.4kg/kg activated carbon granule 1350kg, the bed pressure drop 22kPa/m of the second adsorbent bed (4), operating condition when second adsorbent bed (4) carries out adsorption cleaning is: temperature 5 DEG C, pressure 600kPa, recycles through offgas outlet pipeline qualified discharge or after processing further; Adopt compressed air to enter organic first adsorbent bed (3) in saturated adsorption tail gas as desorption gas through desorption gas inlet ductwork simultaneously, kind, the average grain diameter of the adsorbent of filling in the first adsorbent bed (3) are identical with the second adsorbent bed (4) with the amount of adsorbent, and the flow of desorption gas is 3600Nm
3/ hr, the bed pressure drop 22kPa/m of the first adsorbent bed (3), operating condition when the first adsorbent bed (3) carries out desorption is: temperature 160 DEG C, and pressure 100kPa, contacts with saturated adsorption agent after carrying out desorption and discharge through desorption gas export pipeline;
C the adsorbent of () second in adsorbent bed (4) reaches capacity adsorbance, and after the adsorbent in the first adsorbent bed (3) completes desorption, close the second transfer valve (6), 3rd transfer valve (7), 6th transfer valve (10), 7th transfer valve (11), open the first transfer valve (5), 4th transfer valve (8), 5th transfer valve (9), 8th transfer valve (12), cyclohexane oxidation system tail gas is made to be switched to the first adsorbent bed (3) from the second adsorbent bed (4), desorption gas is switched to the second adsorbent bed (4) from the first adsorbent bed (3), two adsorbent bed exchange functions, first adsorbent bed (3) carries out adsorption operations and the second adsorbent bed (4) carries out desorption manipulation, when desorption time, comparatively adsorption time is in short-term, after desorption terminates, close the 9th transfer valve (14), when desorption gas used again by needs, open the 9th transfer valve (14), so periodically operation is after 24 hours, realize adsorption-desorption rotation.
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| CN103585854B (en) * | 2013-10-29 | 2015-09-09 | 嘉园环保有限公司 | A kind of charcoal absorption, N 2the technique of desorption recycling organic exhaust gas |
| CN106565443A (en) * | 2015-10-12 | 2017-04-19 | 中国石油化工股份有限公司 | Method for continuous removal of impurities in cyclohexanone |
| CN107866135B (en) * | 2016-09-28 | 2021-06-01 | 中国石油化工股份有限公司 | CO capture2Apparatus and method of |
| CN107469615A (en) * | 2017-08-31 | 2017-12-15 | 成都普瑞得科技有限公司 | A kind of oxidizing cyclohexanone tail gas clean-up and method of comprehensive utilization and system |
| CN113477027B (en) * | 2021-08-04 | 2023-01-31 | 中冶赛迪技术研究中心有限公司 | Integrated device and method for desulfurization, adsorption, regeneration, cooling and recovery of blast furnace gas |
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| CN1973958A (en) * | 2006-11-10 | 2007-06-06 | 浙江大学 | Process and apparatus for purifying arene oxidizing tail gas |
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