CN103254932A - Process for extracting C4-C6 normal paraffins and co-producing isopentane and isomeric hexane from light naphtha - Google Patents
Process for extracting C4-C6 normal paraffins and co-producing isopentane and isomeric hexane from light naphtha Download PDFInfo
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- CN103254932A CN103254932A CN2013101971234A CN201310197123A CN103254932A CN 103254932 A CN103254932 A CN 103254932A CN 2013101971234 A CN2013101971234 A CN 2013101971234A CN 201310197123 A CN201310197123 A CN 201310197123A CN 103254932 A CN103254932 A CN 103254932A
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 title claims abstract description 58
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 30
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 230000008569 process Effects 0.000 title abstract description 17
- 238000001179 sorption measurement Methods 0.000 claims abstract description 87
- 238000011069 regeneration method Methods 0.000 claims abstract description 34
- 230000008929 regeneration Effects 0.000 claims abstract description 33
- 238000003795 desorption Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000012188 paraffin wax Substances 0.000 claims description 54
- 238000003860 storage Methods 0.000 claims description 28
- 238000010521 absorption reaction Methods 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 21
- 241000282326 Felis catus Species 0.000 claims description 19
- 238000005516 engineering process Methods 0.000 claims description 14
- 238000006073 displacement reaction Methods 0.000 claims description 13
- 239000003208 petroleum Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000002309 gasification Methods 0.000 claims description 8
- 239000004615 ingredient Substances 0.000 claims description 7
- 238000010926 purge Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 230000009183 running Effects 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 2
- 235000011089 carbon dioxide Nutrition 0.000 claims description 2
- 238000004523 catalytic cracking Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 239000003463 adsorbent Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 230000001172 regenerating effect Effects 0.000 abstract 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 18
- 230000009466 transformation Effects 0.000 description 14
- 239000012071 phase Substances 0.000 description 10
- 239000007791 liquid phase Substances 0.000 description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- 238000005194 fractionation Methods 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000003570 air Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- ZJKABZNFELLAQQ-UHFFFAOYSA-N octane Chemical compound CCCCCCCC.CCCCCCCC ZJKABZNFELLAQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a chemical separation process, in particular to a process for extracting C4-C6 normal paraffins and co-producing isopentane and isomeric hexane from light naphtha. The invention adopts a multi-tower pressure swing adsorption and rectification separation coupling process. Introducing a gas phase C4-C6 normal-iso hydrocarbon mixed raw material into an adsorption tower for adsorption separation, desorbing a bed layer by using gas phase C7-C9 normal-alkane as a desorbent after adsorption is finished, introducing the desorbed material into a rectifying tower to separate out products C4-C6 normal-alkane and desorbent C7-C9 normal-alkane, recycling the desorbent, regenerating the adsorption tower adsorbing the C7-C9 normal-alkane by using unadsorbed C4-C6 iso-alkane, and rectifying and separating the regenerated material twice to obtain high-purity desorbent C7-C9 normal-alkane, high-purity isopentane and iso-hexane. The invention can effectively separate the normal and isomeric alkanes, and the adsorbent has the advantages of easy regeneration, simple process flow, high economic benefit and greatly reduced energy consumption compared with other desorption processes.
Description
Technical field:
The present invention relates to a kind of chemical separating technology, relate in particular to C4 in a kind of extraction light naphthar～C6 normal paraffin coproduction iso-pentane and isomery hexane technology.
Background technology:
Light naphthar is one of product of hydrocracking in the Aromatic Hydrocarbon United Plant, because present most of device for producing hydrogen adopt natural gas hydrogen preparation, so light naphthar mainly is used as cracking ethylene preparation raw material and gasoline blending stock.Because isoparaffin in this petroleum naphtha is too high, not too suitable raw material as preparing ethylene by steam cracking; As gasoline blending stock, higher because of its normal paraffin content again, influence the oil product octane value.Therefore rationally separate in the light naphthar positive isoparaffin for the comprehensive utilization value that improves light naphthar, the light naphthar resource of integrated optimization increases the economic benefit of petroleum chemical enterprise, and is significant.
CN101148390A sets forth technique for extracting high-pure normal hexane product by pressure swing adsorption, adopts the four towers transformation adsorption process of heating, and realizes the desorption of sorbent material normal hexane under vacuum condition, obtains purity greater than 99% normal hexane after rectifying tower separates.
CN101134703A has invented transformation adsorbing and extracting normal heptane coproduction octane technology, adopt the multitower transformation adsorption process of heating, add rare gas element and purge in vacuum desorption, make bed obtain sufficient desorb, coproduction obtains purity all greater than 99% normal heptane and octane.
CN1634812A has proposed to separate the method for normal paraffin from C5～C6 alkane isomerization product, realized the separation under the liquid-phase condition, the employing rectification method removes the iso-pentane in the raw material, re-use the positive isoparaffin mixture of absorption method fractionation by adsorption,, as the liquid phase strippant bed is resolved with octane.
CN101148390A, CN101134703A are the invention achievement in this laboratory, owing to adopt the rare gas element desorption to require the subsequent condensation temperature to reach subzero, require condensing pressure higher, and energy consumption and facility investment are bigger.And adopt gas phase high-carbon C4～C6 normal paraffin as strippant, isoparaffin is that the associating separating process of regenerator does not appear in the newspapers, and technology co-producing high-purity iso-pentane and isomery hexane as required, and energy consumption reduces greatly, therefore on the basis of laboratory study, invent this technology.
Summary of the invention:
The objective of the invention is to provide in order to improve the deficiencies in the prior art and extract C4～C6 normal paraffin coproduction iso-pentane and isomery hexane technology in the light naphthar.The present invention adopts the absorption of multitower transformation and rectifying separation coupling technique.
Technical scheme of the present invention is: C4 in a kind of extraction light naphthar～C6 normal paraffin coproduction iso-pentane and isomery hexane technology, adsorb since the first adsorption tower T1, four towers continuous adsorption desorption simultaneously separate, concrete steps are as follows: (1) absorption, the positive isoparaffin mixing raw material of C4～C6 is exported from raw material storage tank V3, after gasification, enter first adsorption tower T1 absorption, normal paraffin in the raw material is adsorbed, absorbed component is not exported by the first adsorption tower T1 cat head, and the second adsorption tower T2 that finishes equal voltage rise is regenerated; (2) all pressure drops, the first adsorption tower T1 that finishes absorption all presses with the 3rd adsorption tower T3 that finishes desorb; (3) bed displacement uses inert gas replacement to go out the material of dead space in the first adsorption tower T1, and material obtains middle runnings through condensation; (4) desorb, C7～C9 normal paraffin single component or two or more blending ingredients enter the first adsorption tower T1 that finishes displacement after gasification, separate C4～C6 normal paraffin that sucking-off is adsorbed, and the desorb material is imported the second rectifying tower T6; (5) all voltage rises, the 3rd adsorption tower T3 that finishes absorption this moment all presses with the first adsorption tower T1 that finishes desorb; (6) bed regeneration, the isoparaffin that the 4th adsorption tower T4 cat head that is adsorbing is not adsorbed is as regenerator, desorption goes out the C7～C9 normal paraffin of the first adsorption tower T1 internal adsorption, realizes the regeneration of the first adsorption tower T1 internal adsorption agent, and the regeneration feed that obtains enters the first rectifying tower T5; (7) associating rectifying, the desorb material that the first adsorption tower T1 obtains is imported the second rectifying tower T6, and cat head obtains products C 4～C6 normal paraffin, and tower reactor obtains strippant C7～C9 normal paraffin, and C7～C9 normal paraffin recycles; The regeneration feed that the first adsorption tower T1 obtains enters the first rectifying tower T5, cat head obtains C4～C6 isoparaffin, tower reactor obtains strippant C7～C9 normal paraffin and recycles, cat head C4～C6 isoparaffin by the 3rd rectifying tower T7 again rectifying obtain iso-pentane and isomery hexane product respectively.
More detailed step is as follows: (1) absorption, C4 among the raw material storage tank V3～C6 paraffinic feedstock enters first adsorption tower T1 absorption by first pipeline 1 by the second constant-flux pump P3 after the 3rd interchanger E3 gasification (the second adsorption tower T2 successively carries out equal pressure drop and regeneration in the T1 adsorption process, the 3rd adsorption tower is carrying out desorb, the 4th adsorption tower successively carries out equal pressure drop and displacement), C4～C6 normal paraffin is adsorbed, and C4～C6 isoparaffin enters the second adsorption tower T2 and regenerates; (2) all pressure drops, the first adsorption tower T1 that finishes absorption passes through the 5 equal pressure drops of the 5th pipeline with the 3rd adsorption tower T3 that finishes desorb; (3) bed displacement, the rare gas element among the displacement gas nitrogen storage tank V2 displaces the material of dead space in the first adsorption tower T1 by the 4th pipeline 4, and this material enters intermediates storage tank V5 by the 3rd pipeline 3, the 8th pipeline 8 and the 11 pipeline pipeline 11; (4) desorb, C7～C9 normal paraffin strippant (single component or two or more blending ingredients) among strippant C7～C9 normal paraffin storage tank V1 enters the first adsorption tower T1 that just finish displacement by the 6th pipeline 6 by the first constant-flux pump P1 after first interchanger E1 gasification heat exchange, separate C4～C6 normal paraffin that sucking-off is adsorbed, the desorb material that obtains enters the second rectifying tower T6 by second pipeline 2 and the 9th pipeline 9; (5) all voltage rises, the 3rd adsorption tower T3 that finishes absorption this moment passes through the 5 equal voltage rises of the 5th pipeline to the first adsorption tower T1 that finishes desorb; (6) bed regeneration, this moment, the 4th adsorption tower T4 adsorbed, C4～C6 the isoparaffin of not absorption is mixed together the input first adsorption tower T1 by the 5th pipeline 5 and regenerator in the regenerator isoparaffin storage tank V4 of gasification, mixed gaseous C4～C6 isoparaffin is regenerated to the first adsorption tower T1 that just finishes equal voltage rise as regenerator, purge C7～C9 normal paraffin of separating the sucking-off first adsorption tower T1 internal adsorption, realize the regeneration of the first adsorption tower T1 internal adsorption agent, the regeneration feed that obtains is by the 3rd pipeline 3, the 8th pipeline 8 and the 12 pipeline 12 enter the first rectifying tower T5; (7) associating rectifying, obtain the desorb material during the first adsorption tower T1 desorb and enter the second rectifying tower T6, it is that C4～C6 normal paraffin of 99.0%～99.5% enters C4～C6 normal paraffin product storage tank V6 that the second rectifying tower T6 cat head obtains product purity, it is C7～C9 normal paraffin strippant of 99.0%～99.5% that the second rectifying tower T6 tower reactor obtains purity, C7～C9 normal paraffin by the 7th pipeline 7 input strippant C7～C9 normal paraffin storage tank V1 for recycling; The regeneration feed that obtains during the regeneration of the first adsorption tower bed is imported the first rectifying tower T5, the T5 cat head obtains the C4～C6 isoparaffin of purity 99.0%～99.5%, portion C 4～C6 isoparaffin is diverted to C4～C6 isoparaffin product storage tank V7, C4～C6 isoparaffin of C4～C6 isoparaffin product storage tank V7 is imported in the V4 storage tank again, as regenerator, the T5 tower reactor obtains the C7～C9 normal paraffin of purity 99.0%～99.5%, C7～C9 normal paraffin supplies to recycle by the 7th pipeline 7 input V1, C4～C6 the isoparaffin that is not diverted to C4～C6 isoparaffin product storage tank V7 enters the 3rd rectifying tower T7, the T7 cat head obtains purity 99.0%～99.8% iso-pentane product, input iso-pentane storage tank V9, the T7 tower reactor obtains purity 99.5%～99.8% isomery hexane product, and the isomery hexane produces input isomery hexane storage tank V8.So far, finish a transformation sorption cycle, four adsorption towers continuously carry out simultaneously.
The preferred C4 of the present invention～C6 paraffinic feedstock is for being hydrocracking petroleum naphtha, reformation tops or catalytic cracking petroleum naphtha, 60 ℃～165 ℃ petroleum fractions.
Adsorption temp is preferably 150～450 ℃ in the adsorption process of the present invention, gas phase air speed 40～2000h
-1, adsorptive pressure is 0～3Mpa(gauge pressure).
Bed displacement rare gas element of the present invention is preferably nitrogen, helium, carbonic acid gas or hydrogen, and air speed is at 15～500h
-1
Desorption temperature is preferably 120～450 ℃ in the desorption process of the present invention, pressure 0～1Mpa(gauge pressure), gas phase air speed 40～2000h
-1, the desorption method that adopts is for purging desorb, and the strippant that adopts is C7～C9 single component normal paraffin or two or more blending ingredients.
The regenerator of bed regeneration of the present invention is preferably rare gas element N
2, H
2, He, CO
2Or the isoparaffin of C4～C6, the isoparaffin of C4～C6 more preferably, regeneration is for purging regeneration, and regeneration temperature is preferably 120～450 ℃, pressure is preferably 0～2Mpa(gauge pressure), the gas phase air speed is preferably 40～2000h
-1
The present invention uses rectifying tower T6 rectifying separation to go out C4～C6 normal paraffin and C7～C9 normal paraffin, the tower reactor temperature is preferably 80～200 ℃, tower top temperature is preferably 50～200 ℃, theoretical plate number is preferably 40～120, cat head obtain product purity 99.0%～99.5% C4～C6 normal paraffin, tower reactor obtains purity at C7～C9 normal paraffin of 99.0%～99.5%, and C7～C9 normal paraffin is by the 7th pipeline 7 input V1 use to be recycled.
The present invention uses rectifying tower T5 rectifying separation to go out C4～C6 isoparaffin and C7～C9 normal paraffin strippant, 80～200 ℃ of tower reactor temperature, 60～200 ℃ of tower top temperatures, 35～120 of theoretical plate numbers, cat head obtains the C4～C6 isoparaffin of purity 99.0%～99.5%, tower reactor obtains the C7～C9 normal paraffin of purity 99.0%～99.5%, and C7～C9 normal paraffin is by pipeline 7 input V1 use to be recycled.
The present invention uses rectifying tower T7 rectifying sub-argument to go out iso-pentane and isomery hexane, 50～200 ℃ of tower reactor temperature, 40～200 ℃ of tower top temperatures, 40～150 of theoretical plate numbers, cat head obtains purity 99.0%～99.8% iso-pentane product, and tower reactor obtains purity 99.5%～99.8% isomery hexane product.
The positive isoparaffin technology of above-mentioned transformation fractionation by adsorption C4～C6 combines with the rectifying separation process for the absorption of multitower transformation.Preferred two towers to ten of multitower pressure swing adsorption technique four tower transformation adsorption process, the best is four tower pressure swing adsorption process.
Beneficial effect:
The present invention is for adopting gas phase high-carbon normal paraffin as strippant, and isoparaffin is the associating separating process of regenerator, and co-producing high-purity iso-pentane and isomery hexane.With respect to traditional rectifying separation, the fractionation by adsorption energy consumption reduces greatly, and the resolution height of positive isoparaffin; With respect to vacuum desorption, the security of this technology is remarkable; With respect to the inert gas purge desorb, desorption rate of the present invention is obviously accelerated, and energy consumption significantly reduces.Therefore, this technology has great industrial advantages.
Description of drawings:
Fig. 1 separates the process flow sheet of positive isoparaffin for the present invention; Wherein T1 is first adsorption tower, and T2 is second adsorption tower, and T3 is the 3rd adsorption tower, and T4 is the 4th adsorption tower; T5 is first rectifying tower, and T6 is second rectifying tower, and T7 is the 3rd rectifying tower; P1 is first constant-flux pump, and P3 second constant-flux pump, P4 are the 3rd constant-flux pump, and P2 is first mass flowmeter; E1 first interchanger, E2 are second interchanger, and E3 is the 3rd interchanger, and E4 is the 4th interchanger; V1 is strippant C7～C9 normal paraffin storage tank, V2 is the displacement gas nitrogen storage tank, V3 is raw material storage tank, V4 is regenerator isoparaffin storage tank, V5 is the intermediates storage tank, and V6 is C4～C6 normal paraffin product storage tank, and V7 is C4～C6 isoparaffin product storage tank, V8 is isomery hexane storage tank, and V9 is the iso-pentane storage tank; 1 is first pipeline, and 2 is second pipeline, and 3 is the 3rd pipeline, and 4 is the 4th pipeline, and 5 is the 5th pipeline, and 6 is the 6th pipeline, and 7 is the 7th pipeline, and 8 is the 8th pipeline, and 9 is the 9th pipeline, and 10 is the tenth pipeline, and 11 is the 11 pipeline, and 12 is the 12 pipeline.
The change curve of two constituent mass marks in desorb material when Fig. 2 is normal heptane desorb Skellysolve A.
When Fig. 3 regenerates to bed for isoparaffin, the concentration curve of normal heptane in the regeneration feed.
C4～C6 normal paraffin massfraction change curve in stripping liquid when Fig. 4 is liquid phase normal heptane desorb C4～C6 normal paraffin and gas phase normal heptane desorb C4～C6 normal paraffin.
Embodiment:
Case study on implementation 1: certain petroleum chemical enterprise's hydrocracking light naphthar is raw material, and light naphthar is mainly formed as shown in table 1:
Table 1 light naphthar is formed
Four tower transformation sorption cycle times distributed as shown in table 2: a transformation sorption cycle cycle is 24min, and the concrete time in each stage distributes as table 2.
Table 2 four tower transformation sorption cycle timetables
[notes]: A-absorption, the equal pressure drop of ED-, R-displacement, V-desorb, the equal voltage rise of ER-, H-regeneration
According to transformation fractionation by adsorption n-alkane in Light Naphtha technical process Fig. 1, absorption: V3 storage tank light naphthar raw material, through constant-flux pump P3 input vaporizing chamber E3,150 ℃ and 0.4MPa(gauge pressure) gasify under the condition, the light naphthar of gasification 1 enters T1 by the road; All pressure drops after absorption is finished, all are put into T2 by pipeline 5 with the T1 internal pressure, and the T1 pressure tower drops to 0.18MPa, and the T2 pressure tower is raised to 0.2MPa; Bed displacement, this moment nitrogen storage tank V2 nitrogen after under meter P2 metering with air speed 30h
-1Enter preheater E2,150 ℃ and 0.4Mpa(gauge pressure) preheating under the condition, the material in pipeline 4 displaces the T1 dead space is collected and is obtained middle runnings by pipeline 3,8 and 11 input storage tanks 5; Desorb, after displacement was finished, the normal heptane of storage tank V1 was through constant-flux pump P1 input vaporizer E1,150 ℃ and 0Mpa(gauge pressure) condition under gasify, through pipeline 6 with 40h
-1Air speed enters adsorption column T1, separate C4～C6 normal paraffin that sucking-off has been adsorbed, the desorb material is through pipeline 2 and 9 input rectifying tower T6,40 of rectifying tower T6 number of effective plates, obtain C4～C6 normal paraffin and purity 99.4% normal heptane of purity 99.5%, normal heptane is transported to V1 through pipeline 7 and recycles; All voltage rises all drop to the T1 that finishes desorb with the pressure of finishing the T3 of absorption through pipeline 5, realize the equal voltage rise of T1; Bed regeneration, the isoparaffin that does not adsorb among the T4 that is adsorbing this moment enters T1 through pipeline 5, is used for the normal heptane of desorb absorption, realizes the regeneration of bed, and the isoparaffin air speed is 40h
-1, replenish by V4 when the isoparaffin among the T4 is in shortage, obtain fresh molecular sieve; Associating rectifying, regenerated liquid enters rectifying tower T5 through pipeline 3,8 and 12, the T5 number of effective plate is 35, isoparaffin and tower reactor that cat head obtains purity 99.3% obtain purity 99.3% normal heptane, normal heptane recycles through pipeline 7, and the T5 cat head obtains isoparaffin and imports rectifying tower T7 again, and the T7 number of effective plate is 40, it is 99.3% iso-pentane that cat head obtains purity, and it is 99.7% isomery hexane that tower reactor obtains purity.So far, finish a transformation sorption cycle.According to this order, four adsorption towers carry out simultaneously continuously.
The concentration curve of normal heptane desorb Skellysolve A as shown in Figure 2, normal heptane can be separated the sucking-off Skellysolve A in preceding 25 minutes, and normal heptane self does not reach breakthrough point.
When isoparaffin is regenerated to bed, in the regeneration feed massfraction change curve of normal heptane as shown in Figure 3, as can be seen from Figure 3, isoparaffin is fast to the normal heptane regeneration rate, and the bed regeneration rate reaches more than 90%, satisfies the requirement of next circulation.
Table 3 each product purity for obtaining after the rectifying.
Each component purity after table 3 rectifying
Case study on implementation 2: certain petroleum chemical enterprise's catalytic pyrolysis petroleum naphtha is separated.Technical process and example 1 are similar.
Adsorption temp is 450 ℃, adsorptive pressure 3MPa(gauge pressure), 450 ℃ of desorption temperatures, desorption pressures 1MPa(gauge pressure), desorb air speed 2000h
-1, 450 ℃ of regeneration temperatures, regeneration pressure 2MPa(gauge pressure), regeneration air speed 2000h-1, strippant is quality blending ingredients such as normal heptane and normal hexane, uses C4～C6 isoparaffin to carry out the regeneration of bed after desorb is finished.It is 120,120 and 150 that rectifying tower T5, T6 and T7 number of effective plate are respectively, and it is as shown in table 4 finally to obtain product purity.
Each component purity after table 4 rectifying
Case study on implementation 3: adopting certain factory's reformation tops is raw material, and raw material is formed as shown in table 5.
Table 5 reformation tops is formed
Still adopt four tower transformation adsorptive separation technologies, absorbing process is similar, adopts the stronger octane of adsorption as desorbing agent during desorption, has contrasted gas phase and liquid phase desorption rate and desorption effect.Bed regeneration uses iso-pentane as regenerator.
When equivalent liquid phase flow rate strippant carries out desorb, the desorb of laggard promoting the circulation of qi phase contrasts as shown in Figure 4 with direct liquid phase desorption rate through gasifying, as can be seen from Figure 4, the gas phase desorption rate is obviously greater than the liquid phase desorption rate, in 5min, just reach maximum desorption rate, and the liquid phase desorption rate is little, does not also reach maximum desorption rate behind 25min.
Case study on implementation 4: be raw material with certain petroleum chemical enterprise's shortening petroleum naphtha.With example 1 similarly, the employing octane is strippant, 300 ℃ of desorption temperatures, pressure 0.2MPa(gauge pressure), gas phase air speed 40h
-1Carry out desorb under the condition, it is that 102,98 and 114 the finished product purity are as shown in table 6 that rectifying tower T5, T6 and T7 number of effective plate are respectively.
Each component purity after table 6 rectifying
Claims (7)
1. one kind is extracted C4～C6 normal paraffin coproduction iso-pentane and isomery hexane technology in the light naphthar, adsorb since the first adsorption tower T1, four towers continuous adsorption desorption simultaneously separate, concrete steps are as follows: (1) absorption, the positive isoparaffin mixing raw material of C4～C6 enters first adsorption tower T1 absorption from raw material storage tank V3 output after gasification, the normal paraffin in the raw material is adsorbed, absorbed component is not exported by the first adsorption tower T1 cat head, and the second adsorption tower T2 that finishes equal voltage rise is regenerated; (2) all pressure drops, the first adsorption tower T1 that finishes absorption all presses with the 3rd adsorption tower T3 that finishes desorb; (3) bed displacement uses inert gas replacement to go out the material of dead space in the first adsorption tower T1, and material obtains middle runnings through condensation; (4) desorb, C7～C9 normal paraffin single component or two or more blending ingredients enter the first adsorption tower T1 that finishes displacement after gasification, separate C4～C6 normal paraffin that sucking-off is adsorbed, and the desorb material is imported the second rectifying tower T6; (5) all voltage rises, the 3rd adsorption tower T3 that finishes absorption this moment all presses with the first adsorption tower T1 that finishes desorb; (6) bed regeneration, the isoparaffin that the 4th adsorption tower T4 cat head that is adsorbing is not adsorbed is as regenerator, desorption goes out the C7～C9 normal paraffin of the first adsorption tower T1 internal adsorption, realizes the regeneration of the first adsorption tower T1 internal adsorption agent, and the regeneration feed that obtains enters the first rectifying tower T5; (7) associating rectifying, the desorb material that the first adsorption tower T1 obtains is imported the second rectifying tower T6, and cat head obtains products C 4～C6 normal paraffin, and tower reactor obtains strippant C7～C9 normal paraffin, and C7～C9 normal paraffin recycles; The regeneration feed that the first adsorption tower T1 obtains enters the first rectifying tower T5, cat head obtains C4～C6 isoparaffin, tower reactor obtains strippant C7～C9 normal paraffin and recycles, cat head C4～C6 isoparaffin by the 3rd rectifying tower T7 again rectifying obtain iso-pentane and isomery hexane product respectively.
2. according to right 1 described method, it is characterized in that the positive isoparaffin blending ingredients of C4～C6 is hydrocracking petroleum naphtha, reformation tops or catalytic cracking petroleum naphtha, 60 ℃～165 ℃ petroleum fractions.
3. according to right 1 described method, it is characterized in that 150～450 ℃ of adsorption temps; Gas phase air speed 40～2000h
-1Pressure 0～3MPa(gauge pressure).
4. according to right 1 described method, the rare gas element that it is characterized in that replacing usefulness is nitrogen, helium, carbonic acid gas or hydrogen; Air speed is at 15～500h
-1
5. according to right 1 described method, it is characterized in that 120～450 ℃ of desorption temperatures; Pressure 0～1Mpa; Gas phase air speed 40～2000h
-1The desorption method that adopts is for purging desorb, and the strippant that adopts is C7～C9 single component normal paraffin or two or more blending ingredients.
6. according to right 1 described method, it is characterized in that regenerator is rare gas element N
2, H
2, He, CO
2Or the isoparaffin of C4～C6.
7. according to right 6 described methods, it is characterized in that regeneration is to purge regeneration; 120～450 ℃ of regeneration temperatures; Pressure 0～2Mpa(gauge pressure); The gas phase air speed is 40～2000h
-1
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