CN104230626A - Method for desulfurizing isoprene separated from ethylene cracking carbon penta - Google Patents
Method for desulfurizing isoprene separated from ethylene cracking carbon penta Download PDFInfo
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- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 238000005336 cracking Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 27
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title abstract description 8
- 239000005977 Ethylene Substances 0.000 title abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title abstract description 7
- 229910052799 carbon Inorganic materials 0.000 title abstract description 7
- 230000003009 desulfurizing effect Effects 0.000 title abstract description 3
- 239000000463 material Substances 0.000 claims abstract description 67
- 238000000605 extraction Methods 0.000 claims abstract description 41
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 28
- 230000023556 desulfurization Effects 0.000 claims abstract description 27
- 238000000926 separation method Methods 0.000 claims abstract description 23
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 14
- 238000001179 sorption measurement Methods 0.000 claims abstract description 13
- 238000003860 storage Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 238000009835 boiling Methods 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 27
- OHBTULDTCSOWOY-UHFFFAOYSA-N [C].C=C Chemical compound [C].C=C OHBTULDTCSOWOY-UHFFFAOYSA-N 0.000 claims description 20
- 238000010992 reflux Methods 0.000 claims description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000003463 adsorbent Substances 0.000 claims description 3
- 230000002950 deficient Effects 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 239000012628 flowing agent Substances 0.000 claims description 3
- 235000003599 food sweetener Nutrition 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 239000003765 sweetening agent Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 abstract description 13
- 239000011593 sulfur Substances 0.000 abstract description 13
- 238000005406 washing Methods 0.000 abstract description 4
- 238000012719 thermal polymerization Methods 0.000 abstract 2
- 239000012141 concentrate Substances 0.000 abstract 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N 2-butyne Chemical compound CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 14
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 7
- 150000001941 cyclopentenes Chemical class 0.000 description 7
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 7
- BFAKENXZKHGIGE-UHFFFAOYSA-N bis(2,3,5,6-tetrafluoro-4-iodophenyl)diazene Chemical compound FC1=C(C(=C(C(=C1F)I)F)F)N=NC1=C(C(=C(C(=C1F)F)I)F)F BFAKENXZKHGIGE-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- -1 complex metal oxides Chemical class 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 229920001195 polyisoprene Polymers 0.000 description 3
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- BOFLDKIFLIFLJA-UHFFFAOYSA-N 2-methylbut-1-en-3-yne Chemical group CC(=C)C#C BOFLDKIFLIFLJA-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000010092 rubber production Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 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
- 238000000638 solvent extraction Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a method for desulfurizing isoprene separated from ethylene cracking carbon penta; feeding ethylene cracking carbon pentaraw materials into a thermal polymerization kettle for thermal polymerization, wherein cyclopentadiene in the raw materials is thermally polymerized into dicyclopentadiene; the hot polymeric material enters a pre-separation tower, dicyclopentadiene components in the material are removed, further purified isoprene is obtained at the tower top, the pre-separated material enters an extraction tower for extraction and separation, components with a boiling point close to that of the isoprene in the material are removed, the extracted material enters an analytical tower for analytical rectification, a concentrate mainly containing isoprene is obtained at the tower top, an extracting agent mainly containing acetonitrile and water is obtained at the tower bottom, the analyzed material enters a washing tower, pure isoprene is obtained at the tower top, the pure isoprene separated by washing enters an isoprene storage tank, and the pure isoprene is pumped into a fixed bed reactor through a pump for catalyst adsorption desulfurization; the method can reduce the sulfur content in the isoprene to less than 5 mu g/g, and has simple process conditions and easy control.
Description
Technical field
The present invention relates to the method for desulfurization in a kind of cracking of ethylene carbon five separating isoprene, particularly adopt acetonitrile extraction separating technology to obtain high purity isoprene, and adopt one or more fixed-bed reactor series connection use to carry out adsorption desulfurize.
Background technology
At present, desulfurization technology can be divided into two classes substantially: hydrogenating desulfurization and non-hydrogenating desulfurization.Hydrogenating desulfurization technology mainly comprises catalytic cracking feeds weighted BMO spaces technology, selective hydrodesulfurization technology, non-selective hydrogenating desulfurization technology and catalytic distillation hydrogenation desulfurization technology, it is sulfur method conventional in industrial production, but there is obvious shortcoming in it, such as product composition changes, facility investment is large, process cost is high, and operational condition is harsh, causes the problems such as cost significantly rises; Non-hydrogen addition technology mainly comprises adsorption desulfurize technology, oxidative desulfurization techniques, abstraction desulfurization technology, complexing desulfurization technology and biological desulfurizing technology etc., and these technology just progressively develop and draw attention.
Adsorption desulfurize is reaction conditions gentleness, Be very effective, economically feasible compared with traditional sulfur removal technology, this adds increased it and applies to industrial possibility.Zhou Wei, Xu Wanzhen etc. describe the method for adsorption desulfurize, mechanism, sorbent material and adsorbent reactivation.Introduce the present Research of a series of sorbent material such as molecular sieve, gac, metal oxide and complex metal oxides, clay etc. and absorption property thereof according to adsorption mechanism, and the further research of adsorption desulfurize is looked forward to.
At present, domestic and international cracking of ethylene carbon five tripping device mainly adopts solvent extraction distillation method to carry out separating-purifying and obtains polymerization grade isoprene, carbon Wuyuan used material is the by product formed in cracking of ethylene process, account for 10% ~ 15% of ethylene yield, the isoprene that wherein content is more, cyclopentadiene/dicyclopentadiene and m-pentadiene account for 40% ~ 55% of C 5 fraction, these diolefins are owing to having special molecular structure, chemical property is active, many important high value added products can be synthesized, it is the precious resources that cracking of ethylene utilizes, with them for raw material can produce polyisoprene rubber, specialty elastomer, petroleum resin, SIS thermoplastic elastomer, agricultural chemicals, spices, solidifying agent, fire retardant, energy-saving and smoke-removing agent, quick-acting disinfectant, multiple oil cracking of ethylene and the meticulous cracking of ethylene products such as medicine.
Simultaneously, also containing a small amount of sulfocompound (see table 1) in the material of carbon Wuyuan, such as carbonylsulfide, mercaptan, thioether, disulphide and thiophene etc., this result also in polymerization grade isoprene also containing a small amount of sulphur, and sulphur has impact to polymerization process such as synthesis polyisoprene rubber, styrene isoprene styrene block copolymer (SIS) (SIS) etc., catalyst activity can be caused to reduce, affect usefulness and the quality product of catalyzer, simultaneously also etching apparatus, directly affects throughput and the product quality of device.
Sulfur distribution situation in the material of table 1. carbon Wuyuan
| Component | Molecular weight | wt% |
| Methyl mercaptan | 48.1 | 0.0004 |
| Propane thiol | 76.2 | 0.0114 |
| N-butyl mercaptan | 90.2 | 0.0001 |
| N-amylmercaptane | 104.2 | 0.0006 |
| Positive hexylmercaptan | 118.2 | 0.0005 |
| Methyl disulfide | 94.2 | 0.0019 |
| Dithiocarbonic anhydride | 76.1 | 0.0020 |
| Hydrogen sulfide | 34.1 | 0.0002 |
| Sulfur alcohol | 62.1 | 0.0004 |
| Dimethyl sulphide | 62.1 | 0.0006 |
| Thiophene | 84.1 | 0.0001 |
After the cracking of ethylene carbon Five Classics crosses the unit such as hot polymerization, pre-separation, extraction and parsing, major part sulfide removes with feed separation, in isoprene product, sulphur content is lower, and the sulfide finally entered in the middle of product just only has dithiocarbonic anhydride and disulfide sulfides.
The existence of this part sulfide makes the isolated isoprene of cracking of ethylene carbon five tripping device be difficult to meet the demand of polyisoprene rubber production, and traditional hydrodesulfurization can affect product composition, this brings certain difficulty with regard to giving the application of hydrogenating desulfurization technology.
Summary of the invention
The object of this invention is to provide a kind of reasonably isoprene desulfurization program, with cracking of ethylene carbon five for raw material, through hot polymerization, pre-separation, extraction, parsing and washing, then adopt fixed-bed reactor to carry out adsorption desulfurize, make the sulphur content in the middle of isoprene be reduced to 5 below μ g/g.
The invention provides the method for desulfurization in a kind of cracking of ethylene carbon five separating isoprene.Specifically comprise the following steps:
(1) cracking of ethylene carbon Wuyuan expects that entering hot polymerization still carries out hot polymerization, and feeding temperature is 70 ~ 120 DEG C, polymerization temperature 60 ~ 150 DEG C, and polymerization time is 1 ~ 12 hour, and the cyclopentadiene hot polymerization in raw material is dicyclopentadiene;
(2) hot polymerization still material out enters pre-separation tower, remove dicyclopentadiene component in material, tower top obtains the isoprene of purifying further, pre-separation tower operational condition: tower top temperature is 20 ~ 100 DEG C, bottom temperature is 70 ~ 120 DEG C, working pressure is 0.1 ~ 1MPa, and reflux ratio is 1 ~ 15;
(3) pre-separation tower material out enters extraction tower and carries out extracting and separating, remove component close with isoprene boiling point in material, tower reactor obtains the material based on isoprene and extraction agent, wherein extraction agent is the acetonitrile solution of acetonitrile or moisture 2 ~ 20wt%, extraction agent and material feeding mass ratio are 0.1 ~ 15, extractant feed temperature is 20 ~ 80 DEG C, extraction tower operational condition: tower top temperature is 30 ~ 100 DEG C, bottom temperature is 150 ~ 220 DEG C, working pressure is 0.1 ~ 1MPa, and reflux ratio is 1 ~ 20;
(4) extraction tower material out enters Analytic Tower and carries out parsing rectifying, tower top obtains the enriched material based on isoprene, tower reactor obtains the extraction agent based on acetonitrile and water, extraction tower can be returned recycle, Analytic Tower operational condition: tower top temperature is 20 ~ 90 DEG C, bottom temperature is 140 ~ 200 DEG C, and working pressure is 0.1 ~ 1MPa, and reflux ratio is 1 ~ 20;
(5) Analytic Tower material out enters water wash column, and tower top obtains high purity isoprene, and the charge-mass ratio of water and material is 1 ~ 15, water wash column operational condition: tower top temperature is 20 ~ 60 DEG C, and bottom temperature is 40 ~ 90 DEG C, and working pressure is 0.1 ~ 1MPa;
(6) wash the isolated isoprene of tower top and enter isoprene storage tank, squeeze in fixed-bed reactor through pump and carry out Catalyst Adsorption desulfurization, the operational condition of fixed-bed reactor: air speed (isoprene flow and sweetening agent loadings ratio) 0.25 ~ 3, temperature of reaction 0 ~ 40 DEG C, working pressure 0.1 ~ 3.0MPa;
(7) after desulfurization, material enters products pot, regularly samples detection, and as defective, material is returned in raw material storage tank, until Product checking is qualified.
Described fixed-bed reactor are one or more fixed-bed reactor series connection use.
The desulfuration adsorbent of described fixed-bed reactor filling consists of by weight percentage: the nano aluminium oxide 15% ~ 85% that particle diameter is 100 ~ 300 μm, zinc oxide 5% ~ 25% and silicon oxide 5% ~ 75%.
The present invention is through isolated isoprene of unit such as hot polymerization, pre-separation, extraction, parsing and washings, fixed-bed reactor adsorption desulfurize technology is adopted to carry out desulfurization to isoprene, reduce the sulphur content in the middle of isoprene, and processing condition are simple, easy control, has high industrial application value.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of sulfur method in cracking of ethylene carbon five separating isoprene of the present invention.
Wherein, 1-hot polymerization still, 2-pre-separation tower, 3-extraction tower, 4-Analytic Tower, 5-water wash column, 6-isoprene storage tank, 7-feedstock transportation pump, 8-first fixed-bed reactor, 9-N fixed-bed reactor (N >=2), 10-products pot, 11-sampling spot.
Embodiment
Be further detailed below in conjunction with a kind of embodiment of accompanying drawing to treatment process provided by the present invention, all the other are various, and can to realize method of the present invention all similar, and the present invention repeats no more.As shown in Figure 1, method provided by the invention comprises the following steps:
1. cracking of ethylene carbon Wuyuan expects that entering hot polymerization still (1) carries out hot polymerization;
2. hot polymerization still (1) material out enters pre-separation tower (2), and tower top obtains the isoprene of purifying further;
3. pre-separation tower (2) material out enters extraction tower (3) and carries out extracting and separating, and tower reactor obtains the material based on isoprene and extraction agent;
4. extraction tower (3) material out enters Analytic Tower (4) and carries out parsing rectifying, and tower top obtains the enriched material based on isoprene;
5. Analytic Tower (4) material out enters water wash column (5), and tower top obtains high purity isoprene;
6. water wash column (5) pushes up isolated high purity isoprene and enters isoprene storage tank (6), squeezes in fixed-bed reactor (8,9) carry out Catalyst Adsorption desulfurization through pump (7);
7. after desulfurization, material enters products pot (10), and regularly sample detection at sampling spot (11), as defective, material is returned in raw material storage tank, until Product checking is qualified.
Embodiment 1
(1) cracking of ethylene carbon Wuyuan expects that (material composition is in table 2) enters hot polymerization still and carry out hot polymerization, and feeding temperature is 80 DEG C, polymerization temperature 120 DEG C, and polymerization time is 4 hours;
(2) hot polymerization still material out enters pre-separation tower, pre-separation tower operational condition: tower top temperature is 40 DEG C, and bottom temperature is 90 DEG C, and working pressure is 0.2MPa, and reflux ratio is 10;
(3) pre-separation tower material out enters extraction tower and carries out extracting and separating, wherein extraction agent is the acetonitrile solution of acetonitrile or moisture 5wt%, extraction agent and material feeding mass ratio are 5, extractant feed temperature is 60 DEG C, extraction tower operational condition: tower top temperature is 40 DEG C, bottom temperature is 180 DEG C, and working pressure is 0.25MPa, and reflux ratio is 5;
(4) extraction tower material out enters Analytic Tower and carries out parsing rectifying, Analytic Tower operational condition: tower top temperature is 45 DEG C, and bottom temperature is 170 DEG C, and working pressure is 0.15MPa, and reflux ratio is 1;
(5) Analytic Tower material out enters water wash column, and the charge-mass ratio of water and material is 3, water wash column operational condition: tower top temperature is 30 DEG C, and bottom temperature is 50 DEG C, and working pressure is 0.3MPa.
(6) wash the isolated high purity isoprene of tower top and enter isoprene storage tank, squeeze in fixed-bed reactor through pump and carry out Catalyst Adsorption desulfurization, the operational condition of fixed-bed reactor: air speed (isoprene flow and sweetening agent loadings ratio) 0.25, temperature of reaction 20 DEG C, working pressure 0.1MPa.
(7) after desulfurization, material enters products pot, detects in sampling spot sampling, detects data in table 3.
Table 2. carbon Wuyuan material composition table
| Component | Content, wt% | Component | Content, wt% |
| 2-butylene | 4.45 | Along amylene-2 | 0.99 |
| 1,3-divinyl | 3.94 | 2-methyl-2-butene | 1.97 |
| Normal butane | 0.66 | Sow distrust among one's enemies pentadiene | 7.96 |
| 3-methyl-1-butene | 0.48 | Valylene | 0.48 |
| Iso-pentane | 6.02 | Cyclopentadiene | 10.13 |
| Isosorbide-5-Nitrae-pentadiene | 1.91 | Along m-pentadiene | 4.73 |
| 2-butyne | 1.09 | Cyclopentenes | 3.17 |
| 1-amylene | 2.23 | Pentamethylene | 1.32 |
| 2-methyl-1-butene alkene | 3.44 | Benzene | 0.28 |
| Skellysolve A | 9.97 | Dicyclopentadiene | 9.1 |
| Isoprene | 18.67 | Other | 5.48 |
| Anti-amylene-2 | 1.53 | Total sulfur, μ g/g | 80.4 |
Table 3. embodiment 1 detected result material composition table
| Component | Content, wt% | Component | Content, wt% |
| 2-butyne | 1.96 | Cyclopentadiene | 0.76 |
| Cyclopentenes | 0.02 | Isoprene | 95.44 |
| Cis-2 amylenes | 0.15 | Iso-pentane | 0.02 |
| Along m-pentadiene | 0.02 | Dicyclopentadiene | 0.45 |
| Sow distrust among one's enemies pentadiene | 0.15 | Total sulfur, μ g/g | 2.52 |
Embodiment 2
According to the isolated isoprene materials of disposal methods cracking of ethylene carbon five tripping device of embodiment 1, unlike: in step (1), feeding temperature is 90 DEG C; Step (2) pre-separation tower reflux ratio is 9; Step (3) extraction agent and material feeding mass ratio are 6, and extraction tower reflux ratio is 4; Step (6) fixed-bed reactor adopt 2 fixed-bed reactor series connection to use, and detected result is in table 4.
Table 4. embodiment 2 detected result material composition table
| Component | Content, wt% | Component | Content, wt% |
| 2-butyne | 1.94 | Cyclopentadiene | 0.74 |
| Cyclopentenes | 0.02 | Isoprene | 95.39 |
| Cis-2 amylenes | 0.14 | Iso-pentane | 0.02 |
| Along m-pentadiene | 0.02 | Dicyclopentadiene | 0.42 |
| Sow distrust among one's enemies pentadiene | 0.12 | Total sulfur, μ g/g | 1.32 |
Embodiment 3
According to the isolated isoprene materials of disposal methods cracking of ethylene carbon five tripping device of embodiment 1, unlike: in step (1), feeding temperature is 90 DEG C; Step (2) pre-separation tower reflux ratio is 8; Step (3) extraction agent and material feeding mass ratio are 6, and extraction tower reflux ratio is 3; Step (6) fixed-bed reactor adopt 3 fixed-bed reactor series connection to use, and detected result is in table 5.
Table 5. embodiment 3 detected result material composition table
| Component | Content, wt% | Component | Content, wt% |
| 2-butyne | 1.94 | Cyclopentadiene | 0.72 |
| Cyclopentenes | 0.02 | Isoprene | 95.38 |
| Cis-2 amylenes | 0.15 | Iso-pentane | 0.02 |
| Along m-pentadiene | 0.02 | Dicyclopentadiene | 0.40 |
| Sow distrust among one's enemies pentadiene | 0.14 | Total sulfur, μ g/g | 1.05 |
Embodiment 4
According to the isolated isoprene materials of disposal methods cracking of ethylene carbon five tripping device of embodiment 1, unlike: in step (1), feeding temperature is 90 DEG C; Step (2) pre-separation tower reflux ratio is 9; Step (3) extraction agent and material feeding mass ratio are 7, and extraction tower reflux ratio is 4; The operational condition of step (6) fixed-bed reactor is air speeds 0.5, and detected result is in table 6.
Table 6. embodiment 4 detected result material composition table
| Component | Content, wt% | Component | Content, wt% |
| 2-butyne | 1.95 | Cyclopentadiene | 0.72 |
| Cyclopentenes | 0.02 | Isoprene | 95.40 |
| Cis-2 amylenes | 0.15 | Iso-pentane | 0.02 |
| Along m-pentadiene | 0.02 | Dicyclopentadiene | 0.44 |
| Sow distrust among one's enemies pentadiene | 0.14 | Total sulfur, μ g/g | 3.95 |
Embodiment 5
According to the isolated isoprene materials of disposal methods cracking of ethylene carbon five tripping device of embodiment 1, unlike: in step (1), feeding temperature is 90 DEG C; Step (2) pre-separation tower reflux ratio is 8; Step (3) extraction agent and material feeding mass ratio are 7, and extraction tower reflux ratio is 4; The operational condition of step (6) fixed-bed reactor is air speeds 3, and detected result is in table 7.
Table 7. embodiment 5 detected result material composition table
| Component | Content, wt% | Component | Content, wt% |
| 2-butyne | 1.96 | Cyclopentadiene | 0.75 |
| Cyclopentenes | 0.02 | Isoprene | 95.39 |
| Cis-2 amylenes | 0.13 | Iso-pentane | 0.02 |
| Along m-pentadiene | 0.02 | Dicyclopentadiene | 0.41 |
| Sow distrust among one's enemies pentadiene | 0.16 | Total sulfur, μ g/g | 4.14 |
Embodiment 6
According to the isolated isoprene materials of disposal methods cracking of ethylene carbon five tripping device of embodiment 1, unlike: in step (1), feeding temperature is 90 DEG C; Step (2) pre-separation tower reflux ratio is 8; Step (3) extraction agent and material feeding mass ratio are 6, and extraction tower reflux ratio is 3; The operational condition of step (6) fixed-bed reactor is temperature 30 DEG C, and detected result is in table 8.
Table 8. embodiment 6 detected result material composition table
| Component | Content, wt% | Component | Content, wt% |
| 2-butyne | 1.93 | Cyclopentadiene | 0.72 |
| Cyclopentenes | 0.02 | Isoprene | 95.40 |
| Cis-2 amylenes | 0.12 | Iso-pentane | 0.02 |
| Along m-pentadiene | 0.02 | Dicyclopentadiene | 0.40 |
| Sow distrust among one's enemies pentadiene | 0.15 | Total sulfur, μ g/g | 4.50 |
Claims (3)
1. a method for desulfurization in cracking of ethylene carbon five tripping device separating isoprene, is characterized in that: the method comprises the following steps:
(1) cracking of ethylene carbon Wuyuan expects that entering hot polymerization still carries out hot polymerization, and feeding temperature is 70 ~ 120 DEG C, polymerization temperature 60 ~ 150 DEG C, and polymerization time is 1 ~ 12 hour, and the cyclopentadiene hot polymerization in raw material is dicyclopentadiene;
(2) hot polymerization still material out enters pre-separation tower, remove dicyclopentadiene component in material, tower top obtains the isoprene of purifying further, pre-separation tower operational condition: tower top temperature is 20 ~ 100 DEG C, bottom temperature is 70 ~ 120 DEG C, working pressure is 0.1 ~ 1MPa, and reflux ratio is 1 ~ 15;
(3) pre-separation tower material out enters extraction tower and carries out extracting and separating, remove component close with isoprene boiling point in material, tower reactor obtains the material based on isoprene and extraction agent, wherein extraction agent is the acetonitrile solution of acetonitrile or moisture 2 ~ 20wt%, extraction agent and material feeding mass ratio are 0.1 ~ 15, extractant feed temperature is 20 ~ 80 DEG C, extraction tower operational condition: tower top temperature is 30 ~ 100 DEG C, bottom temperature is 150 ~ 220 DEG C, working pressure is 0.1 ~ 1MPa, and reflux ratio is 1 ~ 20;
(4) extraction tower material out enters Analytic Tower and carries out parsing rectifying, tower top obtains the enriched material based on isoprene, tower reactor obtains the extraction agent based on acetonitrile and water, extraction tower can be returned recycle, Analytic Tower operational condition: tower top temperature is 20 ~ 90 DEG C, bottom temperature is 140 ~ 200 DEG C, and working pressure is 0.1 ~ 1MPa, and reflux ratio is 1 ~ 20;
(5) Analytic Tower material out enters water wash column, and tower top obtains high purity isoprene, and the charge-mass ratio of water and material is 1 ~ 15, water wash column operational condition: tower top temperature is 20 ~ 60 DEG C, and bottom temperature is 40 ~ 90 DEG C, and working pressure is 0.1 ~ 1MPa;
(6) wash the isolated high purity isoprene of tower top and enter isoprene storage tank, squeeze in fixed-bed reactor through pump and carry out Catalyst Adsorption desulfurization, the operational condition of fixed-bed reactor: air speed (isoprene flow and sweetening agent loadings ratio) 0.25 ~ 3, temperature of reaction 0 ~ 40 DEG C, working pressure 0.1 ~ 3.0MPa;
(7) after desulfurization, material enters products pot, regularly samples detection, and as defective, material is returned in raw material storage tank, until Product checking is qualified.
2. the method for desulfurization in cracking of ethylene carbon five tripping device separating isoprene according to claim 1, is characterized in that: in step (6), and described fixed-bed reactor are one or more fixed-bed reactor series connection use.
3. the method for desulfurization in cracking of ethylene carbon five tripping device separating isoprene according to claim 1, is characterized in that:
The desulfuration adsorbent of described fixed-bed reactor filling consists of by weight percentage: the nano aluminium oxide 15% ~ 85% that particle diameter is 100 ~ 300 μm, zinc oxide 5% ~ 25% and silicon oxide 5% ~ 75%.
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| CN100999434A (en) * | 2006-01-11 | 2007-07-18 | 北京化工大学 | 5C separating and comprehensive utilization by acetonitrile solvent method |
| WO2012133732A1 (en) * | 2011-03-31 | 2012-10-04 | 日本ゼオン株式会社 | Method for producing hydrocarbon material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111875469A (en) * | 2020-07-21 | 2020-11-03 | 辽宁石油化工大学 | Ultra-deep removal method for carbon disulfide in isoprene product |
| CN111875469B (en) * | 2020-07-21 | 2023-02-28 | 辽宁石油化工大学 | Ultra-deep removal method for carbon disulfide in isoprene product |
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