CN102951989A - Separation method of C5 fraction - Google Patents
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- CN102951989A CN102951989A CN2011102355283A CN201110235528A CN102951989A CN 102951989 A CN102951989 A CN 102951989A CN 2011102355283 A CN2011102355283 A CN 2011102355283A CN 201110235528 A CN201110235528 A CN 201110235528A CN 102951989 A CN102951989 A CN 102951989A
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Abstract
The invention relates to a separation method of C5 fraction. The method includes: rectifying raw material C5 fraction to remove light component impurities; subjecting the material obtained in the last step to a pre-thermal dimerization reaction to make part of cyclopentadiene converted into dicyclopentadiene; rectifying the material that undergoes the pre-thermal dimerization reaction to separate and extract part of isoprene, thus obtaining an isoprene-concentrated material at the tower top; subjecting the tower bottom material obtained in the last step to a second thermal dimerization reaction so as to make the remaining cyclopentadiene converted into dicyclopentadiene; rectifying the material that undergoes the second thermal dimerization reaction to separate and extract the remaining isoprene, thus obtaining an isoprene-concentrated material at the tower top and a dicyclopentadiene and m-pentadiene concentrated material at the tower bottom; rectifying the tower bottom material obtained in the last step to separate the dicyclopentadiene and the m-pentadiene, thus obtaining an m-pentadiene concentrated material at the tower top and a dicyclopentadiene concentrated material at the tower bottom; and refining and purifying the isoprene-concentrated, m-pentadiene concentrated and dicyclopentadiene concentrated materials so as to obtain corresponding products. The invention has the advantage that in the separation process, the co-thermal dimerization reaction of isoprene and cyclopentadiene can be effectively inhibited, so that the loss of isoprene and cyclopentadiene is reduced.
Description
Technical field
The present invention relates to the method for separating carbon 5 fraction, the C5 fraction that is particularly related to by petroleum cracking ethylene by-product processed obtains dicyclopentadiene, isoprene and m-pentadiene initial gross separation material by processes such as hot dimerization and rectifying separation, and further obtains the method for dicyclopentadiene, isoprene and m-pentadiene purified product by processes such as rectifying and extracting rectifyings.
Background technology
Can go out a kind of C5 fraction by by-product in the petroleum cracking process of producing ethylene, C5 fraction occupies higher proportion in all cracking of ethylene by-product materials.Contain cyclopentadiene, isoprene and m-pentadiene that total amount is 40～60wt% in the C5 fraction, these three kinds of diolefin chemical property are active, can react with gas chromatography, all have been widely used at resin, rubber, medicine or agricultural chemicals and other field of fine chemical.At present, separate produce cyclopentadiene, isoprene and m-pentadiene be C5 fraction main also be the method for utilizing of tool economic worth.The C5 fraction complicated component, permitted multi-component boiling point close, or easily form azeotrope, and therefore three kinds of easier autohemagglutinations of diolefin or poly-and then generate dipolymer mutually can't each isolate highly purified product with them by simple rectifying in C5 fraction.In the prior art, almost all carbon five separating technologies all are first raw material to be carried out preliminary separation (industrial custom is called pre-separation or pre-treatment with this process), and then the initial gross separation material is carried out respectively the processes such as rectifying or extracting rectifying to obtain highly purified product.In three kinds of diolefins, hot dimerization reaction the most easily occurs and generates the higher and good dicyclopentadiene of thermostability of boiling point in cyclopentadiene, and then there is larger boiling-point difference in isoprene with m-pentadiene and dicyclopentadiene.Therefore in the initial gross separation stage, usually cyclopentadiene is converted into dicyclopentadiene through dimerization reaction, cooperating for several times, rectifying makes three kinds of diolefins realize preliminary separation from C5 fraction again.
Traditional C5 fraction separation process scheme all is the hot dimerization reaction that carries out first cyclopentadiene usually in the initial gross separation stage, cyclopentadiene is converted into dicyclopentadiene, realize separating of isoprene and m-pentadiene and dicyclopentadiene by rectifying again, some then increases rectifying again before hot dimerization takes off gently, to remove the light constituents such as carbon four components in the raw material and alkynes.Industrial front hot dimerization method, the technical scheme that typical visible US Patent No. 3,510,405, Chinese patent ZL96116289.9 and ZL96102485.2 describe of often this being called.Because the activation energy of the common hot dimerization reaction of isoprene and cyclopentadiene and the activation energy of the hot dimerization reaction of cyclopentadiene are comparatively approaching, in the time of the hot dimerization of cyclopentadiene, very easily follow the common hot dimerization reaction that isoprene and cyclopentadiene occur.Traditional front hot dimerization method flow process since in the hot dimerization reaction system isoprene concentration higher, require to finish cyclopentadiene to the conversion of dipolymer through hot dimerization reaction once in addition, the reaction conditions that adopts is comparatively violent, therefore has a considerable amount of isoprene and cyclopentadiene codimerization thing and generates.A large amount of losses that this not only causes isoprene and cyclopentadiene also can affect the dicyclopentadiene product purity, and very near because of the boiling point of isoprene and cyclopentadiene codimerization thing and dicyclopentadiene, both are difficult the separation.Chinese patent ZL200710043976.7 has proposed a kind of C5 fraction separation method of after heat dimerization, it is separated isoprene by rectifying first before the C5 fraction material carries out the hot dimerization reaction of cyclopentadiene from the C5 fraction material, to avoid the generation of isoprene and cyclopentadiene dipolymer in the hot dimerization reaction process.The defective of hot dimerization processes before the after heat dimerization processes has overcome to a certain extent, but its shortcoming be when the separation and Extraction isoprene in the material cyclopentadiene not yet be converted into dicyclopentadiene, through a rectifying isoprene is separated operation easier higher, rectifying tower cat head overhead product is easily carried cyclopentadiene secretly.Yet what is more important, the tower bottom of rectifying tower of separating isoprene and stripping section are all higher because of cyclopentadiene concentration and material temperature of living in, altogether hot dimerization reaction very easily occurs in the isoprene at these positions and cyclopentadiene, so still has a considerable amount of isoprene and cyclopentadiene dipolymer to generate in the system.Chinese patent application 200910176552.7 has proposed a kind of C5 fraction separation method of twice separation and Extraction isoprene for the defective of after heat dimerization processes, it arranges a rectifying tower again before the hot dipolymer reactor of traditional front hot dimerization processes flow process, the separation and Extraction isoprene at twice in the front and back of hot dimerization reaction.The method has solved the problem that after heat dimerization processes isoprene rectifying separation column overhead overhead product is easily carried cyclopentadiene secretly preferably.But at the common hot dimerization reaction that isoprene and cyclopentadiene still occur inevitably for tower reactor and the stripping section of the first isoprene rectifying separation tower, it almost follows the after heat dimerization processes track of an overturned cart in this.
This shows, existing C5 fraction separation method all can't solve well in the sepn process isoprene and cyclopentadiene and generate this technical problem of dipolymer because of hot dimerization altogether.
Summary of the invention
The invention provides a kind of separation method of C5 fraction, the present invention is by having done further improvement to the flow process in initial gross separation stage, the technical problem that solves is that rectifying tower ejects the defective that material is easily carried cyclopentadiene secretly when not only overcoming after heat dimerization processes separating isoprene, and substantially avoids the generation of isoprene and cyclopentadiene dipolymer in the sepn process.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of separation method of C5 fraction may further comprise the steps:
1) the raw material C5 fraction is carried out rectifying with separation removal light constituent impurity through rectifying tower.The tower reactor temperature is controlled to be 60～90 ℃, and tower top temperature is controlled to be 40～50 ℃, and working pressure is controlled to be 0.10～0.40MPaG, and control of reflux ratio is 20～40.Cat head is discharged light constituent impurity, and tower reactor gets the C5 fraction material;
2) by step 1) the C5 fraction material that obtains of tower reactor through the preheating dimerization reaction so that the part cyclopentadiene is converted into dicyclopentadiene.Temperature of reaction is controlled to be 40～60 ℃, and reaction pressure is controlled to be 0.40～0.80MPaG, and the reaction time of material is controlled to be 240～600min;
3) through step 2) C5 fraction material behind the preheating dimerization reaction carries out rectifying with separation and Extraction part isoprene through rectifying tower.The tower reactor temperature is controlled to be 60～80 ℃, and tower top temperature is controlled to be 35～50 ℃, and working pressure is controlled to be 0.10～0.50MPaG, and control of reflux ratio is 2～10.Cat head gets the material of enrichment isoprene, and tower reactor gets remaining C5 fraction material;
4) by step 3) the C5 fraction material that obtains of tower reactor through hot dimerization reaction for the second time so that remaining cyclopentadiene is converted into dicyclopentadiene.Temperature of reaction is controlled to be 100～150 ℃, and reaction pressure is controlled to be 0.80～1.20MPaG, and the reaction time of material is controlled to be 60～120min;
5) through step 4) for the second time the C5 fraction material behind the hot dimerization reaction carry out rectifying with the remaining isoprene of separation and Extraction through rectifying tower.The tower reactor temperature is controlled to be 70～100 ℃, and tower top temperature is controlled to be 50～80 ℃, and working pressure is controlled to be 0.20～0.40MPaG, and control of reflux ratio is 10～20.Cat head gets the material of enrichment isoprene, and tower reactor gets the material of enrichment dicyclopentadiene and m-pentadiene;
6) by step 5) material that obtains of tower reactor carries out rectifying to separate dicyclopentadiene and m-pentadiene through rectifying tower.The tower reactor temperature is controlled to be 100～120 ℃, and tower top temperature is controlled to be 35～50 ℃, and working pressure is controlled to be 0.010～0.040MPaG, and control of reflux ratio is 2～10.Cat head gets the material of enrichment m-pentadiene, and tower reactor gets the material of enrichment dicyclopentadiene;
7) by step 6) material that obtains of tower reactor carries out the refining of dicyclopentadiene through rectifying tower.The tower reactor temperature is controlled to be 100～130 ℃, and tower top temperature is controlled to be 70～90 ℃, and working pressure is controlled to be-0.030～-0.005MPaG, control of reflux ratio is 10～30.The tower reactor side line must be made with extra care the dicyclopentadiene product, and cat head is discharged light constituent impurity, and tower reactor is discharged restructuring minute impurity;
8) by step 6) material that obtains of cat head is through carrying out extracting rectifying with refining m-pentadiene through extractive distillation column, and extraction agent is dimethyl formamide.Enrichment m-pentadiene material and extractant feed weight ratio are controlled to be 1: (7～15), extractant feed temperature are controlled to be 40～60 ℃.The tower reactor temperature is controlled to be 90～110 ℃, and tower top temperature is controlled to be 35～50 ℃, and working pressure is controlled to be 0.05～0.15MPaG, and control of reflux ratio is 5～15.Cat head is discharged raffinate carbon-5 cut material, and tower reactor gets m-pentadiene and extraction agent material, and this material carries out must making with extra care m-pentadiene product and extraction agent, the extraction agent recycled after separating of m-pentadiene and extraction agent again;
9) by step 3) and step 5) the enrichment isoprene material that obtains merges by extractive distillation column and carry out extracting rectifying with refining isoprene, extraction agent is dimethyl formamide.Enrichment isoprene material and extractant feed weight ratio are controlled to be 1: (4～10), extractant feed temperature are controlled to be 50～90 ℃.The tower reactor temperature is controlled to be 100～130 ℃, and tower top temperature is controlled to be 40～70 ℃, and working pressure is controlled to be 0.04～0.20MPaG, and control of reflux ratio is 2～10.Cat head is discharged raffinate carbon-5 cut material, and tower reactor gets isoprene and extraction agent material, and this material carries out after separating of isoprene and extraction agent getting chemical grade isoprene product and extraction agent, extraction agent recycled again;
10) by step 9) chemical grade isoprene that obtains carries out extracting rectifying to remove restructuring minute impurity through extractive distillation column, and extraction agent is dimethyl formamide.Chemical grade isoprene and extractant feed weight ratio are controlled to be 1: (4～9), extractant feed temperature are controlled to be 50～70 ℃, and extractive distillation column tower reactor temperature is controlled to be 70～100 ℃.Tower top temperature is controlled to be 40～60 ℃, and working pressure is controlled to be 0.05～0.20MPaG, and control of reflux ratio is 5～18.Cat head gets the isoprene material, and tower reactor must contain the extraction agent material of restructuring minute impurity, and this material carries out the purification recovery of extraction agent, the extraction agent recycled of recovery again through rectifying;
11) by step 10) the isoprene material that obtains of extracting rectifying column overhead carries out rectifying to remove light constituent impurity through rectifying tower.The tower reactor temperature is controlled to be 50～70 ℃, and tower top temperature is controlled to be 30～50 ℃, and working pressure is controlled to be 0.02～0.20MPaG, and control of reflux ratio is 150～190.Cat head is discharged light constituent impurity, and the tower reactor side line gets the polymerization grade isoprene product, and tower reactor is regularly discharged restructuring minute impurity.
Above-mentioned steps 2) described temperature of reaction preferably is controlled to be 45～55 ℃, and reaction pressure preferably is controlled to be 0.50～0.70MPaG, and the reaction time of material preferably is controlled to be 400～500min.
Above-mentioned steps 3) described tower reactor temperature preferably is controlled to be 65～75 ℃, and tower top temperature preferably is controlled to be 40～47 ℃, and working pressure preferably is controlled to be 0.25～0.35MPaG, and reflux ratio preferably is controlled to be 3～8.
Above-mentioned steps 4) described temperature of reaction preferably is controlled to be 120～140 ℃, and reaction pressure preferably is controlled to be 0.90～1.10MPaG, and the reaction time of material preferably is controlled to be 70～90min.
Above-mentioned steps 5) described tower reactor temperature preferably is controlled to be 80～90 ℃, and tower top temperature preferably is controlled to be 55～70 ℃, and working pressure preferably is controlled to be 0.25～0.30MPaG, and reflux ratio preferably is controlled to be 12～18.
Above-mentioned steps 6) described tower reactor temperature preferably is controlled to be 105～115 ℃, and tower top temperature preferably is controlled to be 40～50 ℃, and working pressure preferably is controlled to be 0.025～0.035MPaG, and reflux ratio preferably is controlled to be 5～8.
Above-mentioned steps 8) described m-pentadiene carried out in rectifying tower with separating usually of extraction agent, must make with extra care the m-pentadiene product by cat head, and tower reactor gets extraction agent.Tower reactor temperature general control is 130～152 ℃, and the tower top temperature general control is 30～50 ℃, and the working pressure general control is 0.06～0.02MPaG, and the reflux ratio general control is 0.5～8.
Above-mentioned steps 9) described isoprene carried out in rectifying tower with separating usually of extraction agent, got the chemical grade isoprene product by cat head, and tower reactor gets extraction agent.Tower reactor temperature general control is 140～170 ℃, and the tower top temperature general control is 30～50 ℃, and the working pressure general control is 0.010～0.020MPaG, and the reflux ratio general control is 4～15.
Above-mentioned steps 10) purification of described extraction agent is reclaimed and is usually carried out in rectifying tower, and cat head is discharged described restructuring and divided impurity, and tower reactor gets extraction agent.Tower reactor temperature general control is 130～160 ℃, and the tower top temperature general control is 40～60 ℃, and the working pressure general control is 0.01～0.20MPaG, and the reflux ratio general control is 5～25.
Essence of the present invention is to divide two sections to carry out the hot dimerization reaction of cyclopentadiene on the basis of twice separation and Extraction isoprene technique.First and second sections hot dimerization reactions are in respectively for the first time front and back of separation and Extraction isoprene.The contriver found that by experiment, and the separation energy of carrying out C5 fraction by this flow process overcomes the defective that prior art exists well.
Press Kinetic analysis, isoprene and cyclopentadiene concentration are the important factors that affects its hot dimerization reaction speed, isoprene is directly proportional with isoprene, cyclopentadiene concentration product with the speed of reaction that cyclopentadiene is total to hot dimerization reaction, and the concentration that no matter reduces isoprene or cyclopentadiene all can suppress the speed of reaction of their hot dimerization.Prior art after heat dimerization processes or twice separation and Extraction isoprene technique all are to attempt to come the altogether generation of hot dimerization reaction of inhibition of isoprenyl and cyclopentadiene by reducing isoprene concentration, yet having ignored jointly, they do not reduce the separation and Extraction that cyclopentadiene concentration is carried out isoprene, isoprene and cyclopentadiene are total to hot dimerization reaction and are easy to generation under the temperature of tower reactor or stripping section, material residence time in rectifying tower often is difficult to uniformity in addition, and the part isoprene more increases chance with cyclopentadiene generation dimerization because of overstand.The strategy that the present invention takes is to allow the C5 fraction raw material that removes behind the light constituent impurity at first carry out the preheating dimerization one time, make the cyclopentadiene of quite a few finish dimerization, but process regulation can't satisfied altogether hot dimerization reaction of isoprene and cyclopentadiene generation.Because isoprene and cyclopentadiene altogether hot dimerization reaction have relatively high activation energy, as long as temperature and residence time control are suitably, hot dimerization reaction adopts tubular reactor usually in addition, and material can be guaranteed in the homogeneity of the reaction zone residence time, and above-mentioned target is easily to realize.Cyclopentadiene concentration obviously reduces after the preheating dimerization, this so that for the first time during the separation and Extraction isoprene isoprene effectively be inhibited with the common hot dimerization reaction of cyclopentadiene.Hot dimerization reaction carries out under relatively high temperature for the second time, and reaction conditions still is controlled in suitable scope certainly, to guarantee high as far as possible dicyclopentadiene selectivity.Experimental result shows, material is after these three steps, and the transformation efficiency of cyclopentadiene and the selectivity of dicyclopentadiene generally all can reach more than 95%.For the second time during the separation and Extraction isoprene in the system remaining cyclopentadiene amount considerably less, the common hot dimerization reaction of isoprene and cyclopentadiene can not occur basically.
In preliminary separation stage, add to remove light constituent impurity interior, the raw material C5 fraction obtains two kinds of initial gross separation materials and the dicyclopentadiene purified product of enrichment isoprene and m-pentadiene altogether after the processing of seven steps.The initial gross separation material of enrichment isoprene and m-pentadiene obtains polymerization grade isoprene and highly purified m-pentadiene product after then further adopting the processing of the processes such as conventional extracting rectifying and rectifying.
Compared with prior art, no matter the present invention is significant progressive is common hot dimerization reaction at the separation and Extraction process isoprene of hot dimerization or isoprene and cyclopentadiene all by establishment, thereby the yield of isoprene and dicyclopentadiene all is improved significantly.The separation that its another advantage is three kinds of diolefins is more thorough, the amount of carrying other diolefin in the material before the initial gross separation material of enrichment isoprene or m-pentadiene and dicyclopentadiene are refining secretly is controlled in very low degree, this has alleviated the burden of follow-up refinement treatment on the one hand, also more easily obtains highly purified product simultaneously.
Accompanying drawing has been showed specific embodiments of the present invention, and wherein accompanying drawing 1 is the schematic flow sheet of raw material C5 fraction pre-separation part; Accompanying drawing 2 is schematic flow sheets of the refining part of purifying of m-pentadiene; Accompanying drawing 3 is schematic flow sheets of the refining part of purifying of isoprene.
In accompanying drawing 1, raw material C5 fraction W1 carries out rectifying with separation removal light constituent impurity through rectifying tower 1 (theoretical plate number is 85), and cat head is discharged light constituent impurity W3, and tower reactor gets C5 fraction material W2; W2 enters a tubular reactor 2 and carries out the preheating dimerization reaction so that the part cyclopentadiene is converted into dicyclopentadiene; W4 carries out rectifying with separation and Extraction part isoprene through rectifying tower 3 (theoretical plate number is 54), and cat head gets the material W6 of enrichment isoprene, and tower reactor gets remaining C5 fraction material W5; W5 enters a tubular reactor 4 and carries out the second time hot dimerization reaction so that remaining cyclopentadiene is converted into dicyclopentadiene.C5 fraction material W7 behind the hot dimerization reaction carries out rectifying with the remaining isoprene of separation and Extraction through rectifying tower 5 (theoretical plate number is 80) for the second time, cat head gets the material W8 of enrichment isoprene, W8 and W6 can send follow-up isoprene refining step after merging, and tower reactor gets the material W9 of enrichment dicyclopentadiene and m-pentadiene.
W9 carries out rectifying to separate dicyclopentadiene and m-pentadiene through rectifying tower 6 (theoretical plate number is 50), and cat head gets the material W11 of enrichment m-pentadiene, and W11 send follow-up m-pentadiene refining step, also can be directly as the coarse piperyene product.Tower reactor gets the material W10 of enrichment dicyclopentadiene.W10 can W10-1 enters rectifying tower 7 (theoretical plate number is 75), and to carry out dicyclopentadiene refining, also can W10-2 directly as thick cyclopentadiene product.The tower reactor of rectifying tower 7 from lower to upper the 2nd column plate place side line must make with extra care dicyclopentadiene product W12, cat head is discharged light constituent impurity W13, tower reactor is regularly discharged a restructuring minute impurity W14.
In accompanying drawing 2, material W11 enters extractive distillation column 8 (theoretical plate number is 48) and carries out extracting rectifying, and material is from the 28th column plate charging in middle part of tower, and the DMF W18 of recycled and the DMF W18-2 of fresh supplemented be the 2nd column plate charging from tower top.Cat head is discharged raffinate carbon-5 cut material W16, gets m-pentadiene and extraction agent material W15 at the bottom of the tower.W15 enters the rectifying tower 9 (theoretical plate number is 30) that reclaims DMF subsequently to carry out separating of m-pentadiene and DMF, must make with extra care m-pentadiene product W17 by cat head, and tower reactor gets DMF W18, and DMF W18 returns extractive distillation column 7 recycleds.
In accompanying drawing 3, W6 and W8 merging material enter extractive distillation column 10 (theoretical plate number is 145) and carry out extracting rectifying, material is from the 83rd column plate charging in middle part of tower, and the DMF W22 of recycled and the DMF W22-2 of fresh supplemented be the 11st column plate charging from tower top.Cat head is discharged raffinate carbon-5 cut material W20, gets isoprene and extraction agent material W19 at the bottom of the tower.W19 enters the rectifying tower 11 (theoretical plate number is 75) that reclaims DMF subsequently to carry out separating of isoprene and DMF, gets chemical grade isoprene product W21 by cat head, and tower reactor gets DMF W22, and DMF W22 returns extractive distillation column 9 recycleds.
Chemical grade isoprene W21 enters the second extractive distillation column 12 (theoretical plate number is 158) and carries out extracting rectifying, W21 is from the 93rd column plate charging in middle part of tower, and the DMF W26 of recycled and the DMF W26-2 of fresh supplemented be the 10th column plate charging from tower top.Cat head gets isoprene material W24, and tower reactor must contain the extraction agent material W23 of restructuring minute impurity.W23 enters the purification recovery that rectifying tower 13 (theoretical plate number is 78) carries out DMF subsequently, and cat head is discharged a restructuring minute impurity W25, and tower reactor gets DMF W26, and DMF W26 returns extractive distillation column 11 recycleds.
Isoprene material W24 enters at last rectifying tower 14 (theoretical plate number is 86) and removes light constituent impurity.Cat head is discharged light constituent impurity W27, gets polymerization grade isoprene product W28 by the 78th column plate place side line of tower reactor.Tower reactor is regularly discharged restructuring minute impurity W29, and W29 is mainly the polymer of rectifying accumulation.
The below will the invention will be further described by specific embodiment, in an embodiment, the definition of cyclopentadiene transformation efficiency, dicyclopentadiene selectivity (selectivity I), isoprene and dicyclopentadiene dipolymer selectivity (selectivity II), dicyclopentadiene purified product yield is respectively:
Wherein:
The flow of unit time cyclopentadiene mole of feed amount=W2 * cyclopentadiene molecular fraction;
The flow of unit time m-pentadiene mole of feed amount=W2 * m-pentadiene molecular fraction;
The flow of unit time isoprene mole of feed amount=W2 * isoprene molecular fraction;
The flow of unit time dicyclopentadiene mole load=W10 * dicyclopentadiene molecular fraction;
Flow * isoprene of unit time isoprene and cyclopentadiene dipolymer mole load=W10 and cyclopentadiene dipolymer molecular fraction;
The flow of unit time dicyclopentadiene molar product load=W12 * dicyclopentadiene molecular fraction;
The flow of unit time m-pentadiene molar product load=W17 * m-pentadiene molecular fraction;
The flow of unit time isoprene molar product load=W28 * isoprene molecular fraction.
Embodiment
Accompanying drawing is seen in the technical process of [embodiment 1～10] embodiment 1～10, and raw material C5 fraction W1 is that petroleum cracking ethylene by-product processed obtains, and its chief component sees Table 1.
The rectifying tower 1,3,5,6 and 7 of pre-separation part, preheating dipolymer reactor and dipolymer reactor 2,4 process conditions see Table respectively 2～5.The extractive distillation column 8 of the refining purification part of m-pentadiene and the process conditions of rectifying tower 9 see Table respectively 6 and 7.The process conditions of the extractive distillation column 10 of isoprene FF, rectifying tower 11, extractive distillation column 12, rectifying tower 13 and rectifying tower 14 sees Table respectively 8～12.
Adopt vapor-phase chromatography to analyze respectively the composition of material W6, W8, W10, W11, W12, W17 and W28, the content of enriched composition or product purity see Table 13 and 15 in each material.In conjunction with flow rate calculation cyclopentadiene transformation efficiency, dicyclopentadiene selectivity (selectivity I), isoprene and cyclopentadiene dipolymer selectivity (selectivity II), dicyclopentadiene purified product, m-pentadiene purified product and the polymerization grade isoprene product yield of each material, the results are shown in Table 14 and 15 again.
Table 1.
Table 2.
Table 3.
Table 4.
Table 5.
Table 6.
Table 7.
Table 8.
Table 9.
Table 10.
Table 11.
Table 12.
Table 13.
Table 14.
Table 15.
。
Claims (9)
1. the separation method of a C5 fraction may further comprise the steps:
1) the raw material C5 fraction is carried out rectifying with separation removal light constituent impurity through rectifying tower, the tower reactor temperature is controlled to be 60～90 ℃, tower top temperature is controlled to be 40～50 ℃, working pressure is controlled to be 0.10～0.40MPaG, control of reflux ratio is 20～40, cat head is discharged light constituent impurity, and tower reactor gets the C5 fraction material;
2) by step 1) the C5 fraction material that obtains of tower reactor through the preheating dimerization reaction so that the part cyclopentadiene is converted into dicyclopentadiene, temperature of reaction is controlled to be 40～60 ℃, reaction pressure is controlled to be 0.40～0.80MPaG, and the reaction time of material is controlled to be 240～600min;
3) through step 2) C5 fraction material behind the preheating dimerization reaction carries out rectifying with separation and Extraction part isoprene through rectifying tower, the tower reactor temperature is controlled to be 60～80 ℃, tower top temperature is controlled to be 35～50 ℃, working pressure is controlled to be 0.10～0.50MPaG, control of reflux ratio is 2～10, cat head gets the material of enrichment isoprene, and tower reactor gets remaining C5 fraction material;
4) by step 3) the C5 fraction material that obtains of tower reactor through hot dimerization reaction for the second time so that remaining cyclopentadiene is converted into dicyclopentadiene, temperature of reaction is controlled to be 100～150 ℃, reaction pressure is controlled to be 0.80～1.20MPaG, and the reaction time of material is controlled to be 60～120min;
5) through step 4) for the second time the C5 fraction material behind the hot dimerization reaction carry out rectifying with the remaining isoprene of separation and Extraction through rectifying tower, the tower reactor temperature is controlled to be 70～100 ℃, tower top temperature is controlled to be 50～80 ℃, working pressure is controlled to be 0.20～0.40MPaG, control of reflux ratio is 10～20, cat head gets the material of enrichment isoprene, and tower reactor gets the material of enrichment dicyclopentadiene and m-pentadiene;
6) by step 5) material that obtains of tower reactor carries out rectifying to separate dicyclopentadiene and m-pentadiene through rectifying tower, the tower reactor temperature is controlled to be 100～120 ℃, tower top temperature is controlled to be 35～50 ℃, working pressure is controlled to be 0.010～0.040MPaG, control of reflux ratio is 2～10, cat head gets the material of enrichment m-pentadiene, and tower reactor gets the material of enrichment dicyclopentadiene;
7) by step 6) material that obtains of tower reactor carries out the refining of dicyclopentadiene through rectifying tower, the tower reactor temperature is controlled to be 100～130 ℃, tower top temperature is controlled to be 70～90 ℃, working pressure is controlled to be-0.030～-0.005MPaG, control of reflux ratio is 10～30, the tower reactor side line must be made with extra care the dicyclopentadiene product, and cat head is discharged light constituent impurity, and tower reactor is discharged restructuring minute impurity;
8) by step 6) material that obtains of cat head is through carrying out extracting rectifying with refining m-pentadiene through extractive distillation column, extraction agent is dimethyl formamide, enrichment m-pentadiene material and extractant feed weight ratio are controlled to be 1: (7～15), the extractant feed temperature is controlled to be 40～60 ℃, the tower reactor temperature is controlled to be 90～110 ℃, tower top temperature is controlled to be 35～50 ℃, working pressure is controlled to be 0.05～0.15MPaG, control of reflux ratio is 5～15, cat head is discharged raffinate carbon-5 cut material, tower reactor gets m-pentadiene and extraction agent material, this material carries out must making with extra care m-pentadiene product and extraction agent, the extraction agent recycled after separating of m-pentadiene and extraction agent again;
9) by step 3) and step 5) the enrichment isoprene material that obtains merges by extractive distillation column and carry out extracting rectifying with refining isoprene, extraction agent is dimethyl formamide, enrichment isoprene material and extractant feed weight ratio are controlled to be 1: (4～10), the extractant feed temperature is controlled to be 50～90 ℃, the tower reactor temperature is controlled to be 100～130 ℃, tower top temperature is controlled to be 40～70 ℃, working pressure is controlled to be 0.04～0.20MPaG, control of reflux ratio is 2～10, cat head is discharged raffinate carbon-5 cut material, tower reactor gets isoprene and extraction agent material, this material carries out after separating of isoprene and extraction agent getting chemical grade isoprene product and extraction agent, extraction agent recycled again;
10) by step 9) chemical grade isoprene that obtains carries out extracting rectifying to remove restructuring minute impurity through extractive distillation column, extraction agent is dimethyl formamide, chemical grade isoprene and extractant feed weight ratio are controlled to be 1: (4～9), the extractant feed temperature is controlled to be 50～70 ℃, extractive distillation column tower reactor temperature is controlled to be 70～100 ℃, tower top temperature is controlled to be 40～60 ℃, working pressure is controlled to be 0.05～0.20MPaG, control of reflux ratio is 5～18, cat head gets the isoprene material, tower reactor must contain the extraction agent material of restructuring minute impurity, and this material carries out the purification recovery of extraction agent, the extraction agent recycled of recovery again through rectifying;
11) by step 10) the isoprene material that obtains of extracting rectifying column overhead carries out rectifying to remove light constituent impurity through rectifying tower, the tower reactor temperature is controlled to be 50～70 ℃, tower top temperature is controlled to be 30～50 ℃, working pressure is controlled to be 0.02～0.20MPaG, control of reflux ratio is 150～190, cat head is discharged light constituent impurity, and the tower reactor side line gets the polymerization grade isoprene product, and tower reactor is regularly discharged restructuring minute impurity.
2. the separation method of C5 fraction according to claim 1 is characterized in that step 2) described temperature of reaction is controlled to be 45～55 ℃, and reaction pressure is controlled to be 0.50～0.70MPaG, and the reaction time of material is controlled to be 400～500min.
3. the separation method of C5 fraction according to claim 1 is characterized in that step 3) described tower reactor temperature is controlled to be 65～75 ℃, and tower top temperature is controlled to be 40～47 ℃, and working pressure is controlled to be 0.25～0.35MPaG, and control of reflux ratio is 3～8.
4. the separation method of C5 fraction according to claim 1 is characterized in that step 4) described temperature of reaction is controlled to be 120～140 ℃, and reaction pressure is controlled to be 0.90～1.10MPaG, and the reaction time of material is controlled to be 70～90min.
5. the separation method of C5 fraction according to claim 1 is characterized in that step 5) described tower reactor temperature is controlled to be 80～90 ℃, and tower top temperature is controlled to be 55～70 ℃, and working pressure is controlled to be 0.25～0.30MPaG, and control of reflux ratio is 12～18.
6. the separation method of C5 fraction according to claim 1, it is characterized in that step 6) described tower reactor temperature is controlled to be 105～115 ℃, tower top temperature is controlled to be 40～50 ℃, and working pressure is controlled to be 0.025～0.035MPaG, and control of reflux ratio is 5～8.
7. the separation method of C5 fraction according to claim 1, it is characterized in that step 8) described m-pentadiene and being separated in the rectifying tower of extraction agent carry out, must make with extra care the m-pentadiene product by cat head, tower reactor gets extraction agent, the tower reactor temperature is controlled to be 130～152 ℃, tower top temperature is controlled to be 30～50 ℃, and working pressure is controlled to be 0.06～0.02MPaG, and control of reflux ratio is 0.5～8.
8. the separation method of C5 fraction according to claim 1, it is characterized in that step 9) described isoprene and being separated in the rectifying tower of extraction agent carry out, get the chemical grade isoprene product by cat head, tower reactor gets extraction agent, the tower reactor temperature is controlled to be 140～170 ℃, tower top temperature is controlled to be 30～50 ℃, and working pressure is controlled to be 0.010～0.020MPaG, and control of reflux ratio is 4～15.
9. the separation method of C5 fraction according to claim 1, it is characterized in that step 10) purification of described extraction agent is recovered in the rectifying tower and carries out, cat head is discharged described restructuring and is divided impurity, tower reactor gets extraction agent, the tower reactor temperature is controlled to be 130～160 ℃, tower top temperature is controlled to be 40～60 ℃, and working pressure is controlled to be 0.01～0.20MPaG, and control of reflux ratio is 5～25.
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| CN107879880A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of separation method of chemical grade isoprene |
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