CN102951984B - Separating carbon 5 fraction also produces the method for polymerization grade isoprene - Google Patents
Separating carbon 5 fraction also produces the method for polymerization grade isoprene Download PDFInfo
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Abstract
A kind of separating carbon 5 fraction also produces polymerization grade isoprene product, comprising: raw material C5 fraction removes light constituent impurity through rectifying; Material makes part cyclopentadiene be converted into dicyclopentadiene through preheating dimerization reaction; After preheating dimerization reaction, material is through rectifying separation Extraction parts isoprene, and tower top obtains enrichment isoprene material; Front kettle material makes residue ring pentadiene be converted into dicyclopentadiene through the hot dimerization reaction of second time; Material extracts remaining isoprene through rectifying separation, and tower top obtains enrichment isoprene material, and tower reactor obtains enrichment dicyclopentadiene and m-pentadiene material; Front kettle material is through rectifying separation dicyclopentadiene and m-pentadiene, and tower top obtains enrichment m-pentadiene material, and tower reactor obtains enrichment dicyclopentadiene material; Front enrichment isoprene material to be purified to obtain polymerization grade isoprene product through extracting rectifying.The invention has the advantages that sepn process isoprene and cyclopentadiene are total to hot dimerization reaction and are effectively suppressed, decrease isoprene and cyclopentadiene loss.
Description
Technical field
The present invention relates to the method for separating carbon 5 fraction, particularly obtained the method for thick dicyclopentadiene, coarse piperyene and polymerization grade isoprene product by the C5 fraction of petroleum cracking ethylene by-product by hot dimerization and the sepn process such as rectifying, extracting rectifying.
Background technology
Can go out a kind of C5 fraction by by-product in petroleum cracking process of producing ethylene, in all cracking of ethylene by-product materials, C5 fraction occupies higher proportion.Cyclopentadiene, isoprene and m-pentadiene that total amount is 40 ~ 60wt% is contained in 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, be separated produce cyclopentadiene, isoprene and m-pentadiene be C5 fraction main be also the Application way of most economic worth.C5 fraction complicated component, permitted multi-component boiling point close, or easily form azeotrope, and three kinds of easier autohemagglutinations of diolefin or mutually poly-and then generation dipolymer, therefore they respectively cannot be isolated highly purified product in C5 fraction by simple rectifying.In prior art, almost all carbon five separating technology is all first carry out preliminary separation (this process is called pre-separation or pre-treatment by industrial custom) to raw material, and then carry out the process such as rectifying or extracting rectifying respectively to obtain highly purified product to initial gross separation material.In three kinds of diolefins, the most easily there is hot dimerization reaction and generate the higher and good dicyclopentadiene of thermostability of boiling point in cyclopentadiene, isoprene then exists larger boiling-point difference with m-pentadiene and dicyclopentadiene.Therefore in the initial gross separation stage, usually cyclopentadiene is converted into dicyclopentadiene through dimerization reaction, then coordinates rectifying for several times to make three kinds of diolefins from C5 fraction, realize preliminary separation.
Traditional C5 fraction separation process scheme is all the hot dimerization reaction first carrying out cyclopentadiene usually in the initial gross separation stage, cyclopentadiene is converted into dicyclopentadiene, being separated of isoprene and m-pentadiene and dicyclopentadiene is realized again by rectifying, it is de-light that some then increases rectifying again before hot dimerization, to remove the light constituents such as carbon Four composition in raw material and alkynes.Industrially often this is called front hot dimerization method, the technical scheme that typical visible US Patent No. 3,510,405, Chinese patent ZL96116289.9 and ZL96102485.2 describe.Due to isoprene and cyclopentadiene altogether the activation energy of hot dimerization reaction and the activation energy of the hot dimerization reaction of cyclopentadiene comparatively close, while the hot dimerization of cyclopentadiene, very easily with the common hot dimerization reaction that isoprene and cyclopentadiene occur.Traditional front hot dimerization method flow process due to isoprene concentrations in hot dimerization reaction system higher, in addition require to complete the conversion of cyclopentadiene to dipolymer through once hot dimerization reaction, the reaction conditions adopted is comparatively violent, therefore has a considerable amount of isoprene and cyclopentadiene codimerization thing generates.This not only causes a large amount of losses of isoprene and cyclopentadiene, also can affect dicyclopentadiene product purity, because the boiling point of isoprene and cyclopentadiene dimer and dicyclopentadiene is very near, and both more difficult separation.Chinese patent ZL200710043976.7 proposes a kind of C5 fraction separation method of after heat dimerization, isoprene is first separated by rectifying by it before C5 fraction material carries out the hot dimerization reaction of cyclopentadiene from C5 fraction material, to avoid the generation of isoprene and cyclopentadiene dimer in hot dimerization reaction process.After heat dimerization processes overcomes the defect of front hot dimerization processes to a certain extent, but its shortcoming is that in material, cyclopentadiene is not yet converted into dicyclopentadiene when separation and Extraction isoprene, through a rectifying, isoprene is separated operation easier higher, rectifying tower overhead product easily carries cyclopentadiene secretly.But what is more important, the tower bottom of rectifying tower of separating isoprene and stripping section because of temperature residing for cyclopentadiene concentration and material all higher, very easily there is hot dimerization reaction altogether in the isoprene at these positions and cyclopentadiene, therefore still has a considerable amount of isoprene and cyclopentadiene dimer to generate in system.Chinese patent application 200910176552.7 proposes a kind of C5 fraction separation method of twice separation and Extraction isoprene for the defect of after heat dimerization processes, before the hot dipolymer reactor of its hot dimerization processes flow process before traditional, a rectifying tower is set again, the separation and Extraction isoprene at twice in the front and back of hot dimerization reaction.The method solves the problem that after heat dimerization processes isoprene rectifying separation column overhead overhead product easily carries cyclopentadiene secretly preferably.But the common hot dimerization reaction of isoprene and cyclopentadiene still inevitably occurs in the tower reactor of the first isoprene rectifying separation tower and stripping section, and it almost follows the after heat dimerization processes track of an overturned cart in this.
As can be seen here, existing C5 fraction separation method all cannot to solve in sepn process isoprene and cyclopentadiene well and generate this technical problem of dipolymer because of hot dimerization altogether.
Summary of the invention
The invention provides a kind of separating carbon 5 fraction and produce the method for polymerization grade isoprene, C5 fraction obtains thick dicyclopentadiene and coarse piperyene two kinds of initial gross separation materials and polymerization grade isoprene product after being separated.The present invention has done further improvement to separation process, the technical problem solved is that when not only overcoming after heat dimerization processes separating isoprene, rectifying tower ejects the defect that cyclopentadiene easily carried secretly by material, and substantially avoids the generation of isoprene and cyclopentadiene dimer in sepn process.
Below the technical scheme that the present invention solves the problems of the technologies described above:
Separating carbon 5 fraction also produces the method for polymerization grade isoprene, comprises the following steps:
1) raw material C5 fraction carries out rectifying with separation removal light constituent impurity through rectifying tower, and it is 60 ~ 90 DEG C that bottom temperature controls, and it is 40 ~ 50 DEG C that tower top temperature controls, and it is 0.10 ~ 0.40MPaG that working pressure controls, and control of reflux ratio is 20 ~ 40.Tower top discharges light constituent impurity, and tower reactor obtains C5 fraction material;
2) by step 1) the C5 fraction material that obtains of tower reactor is converted into dicyclopentadiene through preheating dimerization reaction to make part cyclopentadiene, it is 40 ~ 60 DEG C that temperature of reaction controls, it is 0.40 ~ 0.80MPaG that reaction pressure controls, and the reaction time of material controls to be 240 ~ 600min;
3) through step 2) C5 fraction material after preheating dimerization reaction carries out rectifying with separation and Extraction part isoprene through rectifying tower, it is 60 ~ 80 DEG C that bottom temperature controls, it is 35 ~ 50 DEG C that tower top temperature controls, and it is 0.10 ~ 0.50MPaG that working pressure controls, and control of reflux ratio is 2 ~ 10.Tower top obtains the material of enrichment isoprene, and tower reactor obtains remaining C5 fraction material;
4) by step 3) the C5 fraction material that obtains of tower reactor is converted into dicyclopentadiene through the hot dimerization reaction of second time to make remaining cyclopentadiene, it is 100 ~ 150 DEG C that temperature of reaction controls, it is 0.80 ~ 1.20MPaG that reaction pressure controls, and the reaction time of material controls to be 60 ~ 120min;
5) through step 4) second time hot dimerization reaction after C5 fraction material carry out rectifying with the remaining isoprene of separation and Extraction through rectifying tower, it is 70 ~ 100 DEG C that bottom temperature controls, it is 50 ~ 80 DEG C that tower top temperature controls, it is 0.20 ~ 0.40MPaG that working pressure controls, and control of reflux ratio is 10 ~ 20.Tower top obtains the material of enrichment isoprene, and tower reactor obtains the material of enrichment dicyclopentadiene and m-pentadiene;
6) by step 5) material that obtains of tower reactor carries out rectifying to be separated dicyclopentadiene and m-pentadiene through rectifying tower, it is 100 ~ 120 DEG C that bottom temperature controls, it is 35 ~ 50 DEG C that tower top temperature controls, and it is 0.010 ~ 0.040MPaG that working pressure controls, and control of reflux ratio is 2 ~ 10.Tower top obtains coarse piperyene, and tower reactor obtains thick dicyclopentadiene;
7) by step 3) and step 5) the enrichment isoprene material that obtains carries out extracting rectifying with refining isoprene through extractive distillation column after merging, extraction agent is dimethyl formamide.Enrichment isoprene material and extractant feed weight ratio control to be 1: (4 ~ 10), and it is 50 ~ 90 DEG C that extractant feed temperature controls.It is 100 ~ 130 DEG C that bottom temperature controls, and it is 40 ~ 70 DEG C that tower top temperature controls, and it is 0.04 ~ 0.20MPaG that working pressure controls, and control of reflux ratio is 2 ~ 10.Tower top discharges raffinate carbon-5 cut material, and tower reactor obtains isoprene and extraction agent material, and this material to carry out after being separated of isoprene and extraction agent obtaining chemical grade isoprene product and extraction agent again, extraction agent recycled;
8) step 7) chemical grade isoprene that obtains carries out extracting rectifying to remove heavy constituent impurity through the second extractive distillation column, and extraction agent is dimethyl formamide.Chemical grade isoprene and extractant feed weight ratio control to be 1: (4 ~ 9), and it is 50 ~ 70 DEG C that extractant feed temperature controls, and it is 70 ~ 100 DEG C that extractive distillation column bottom temperature controls.It is 40 ~ 60 DEG C that tower top temperature controls, and it is 0.05 ~ 0.20MPaG that working pressure controls, and control of reflux ratio is 5 ~ 18.Tower top obtains isoprene material, and tower reactor must containing the extraction agent material of heavy constituent impurity, and the purification that this material carries out extraction agent through rectifying is again reclaimed, the extraction agent recycled of recovery;
9) by step 8) the isoprene material that obtains of the second extracting rectifying column overhead carries out rectifying to remove light constituent impurity through rectifying tower.It is 50 ~ 70 DEG C that bottom temperature controls, and it is 30 ~ 50 DEG C that tower top temperature controls, and it is 0.02 ~ 0.20MPaG that working pressure controls, and control of reflux ratio is 150 ~ 190.Tower top discharges light constituent impurity, and tower reactor side line obtains polymerization grade isoprene product, and tower reactor regularly discharges heavy constituent impurity.
Above-mentioned steps 2) described in temperature of reaction preferably control to be 45 ~ 55 DEG C, reaction pressure preferably controls to be 0.50 ~ 0.70MPaG, and the reaction time of material preferably controls to be 400 ~ 500min.
Above-mentioned steps 3) described in bottom temperature preferably control to be 65 ~ 75 DEG C, tower top temperature preferably controls to be 40 ~ 47 DEG C, and working pressure preferably controls to be 0.25 ~ 0.35MPaG, and reflux ratio preferably controls to be 3 ~ 8.
Above-mentioned steps 4) described in temperature of reaction preferably control to be 120 ~ 140 DEG C, reaction pressure preferably controls to be 0.90 ~ 1.10MPaG, and the reaction time of material preferably controls to be 70 ~ 90min.
Above-mentioned steps 5) described in bottom temperature preferably control to be 80 ~ 90 DEG C, tower top temperature preferably controls to be 55 ~ 70 DEG C, and working pressure preferably controls to be 0.25 ~ 0.30MPaG, and reflux ratio preferably controls to be 12 ~ 18.
Above-mentioned steps 6) described in bottom temperature preferably control to be 105 ~ 115 DEG C, tower top temperature preferably controls to be 40 ~ 50 DEG C, and working pressure preferably controls to be 0.025 ~ 0.035MPaG, and reflux ratio preferably controls to be 5 ~ 8.
Above-mentioned steps 7) described in enrichment isoprene material and extractant feed weight ratio preferably control to be 1: (5 ~ 8), extractant feed temperature preferably controls to be 55 ~ 75 DEG C, extractive distillation column bottom temperature preferably controls to be 110 ~ 120 DEG C, tower top temperature preferably controls to be 45 ~ 65 DEG C, working pressure preferably controls to be 0.08 ~ 0.15MPaG, and reflux ratio preferably controls to be 4 ~ 8.
Step 7) described in isoprene usually carry out in rectifying tower with being separated of extraction agent, obtain chemical grade isoprene product by tower top, tower reactor obtains extraction agent.Bottom temperature general control is 140 ~ 170 DEG C, and tower top temperature general control is 30 ~ 50 DEG C, and working pressure general control is 0.010 ~ 0.020MPaG, and reflux ratio general control is 4 ~ 15.
Above-mentioned steps 8) described in chemical grade isoprene and extractant feed weight ratio preferably control to be 1: (5 ~ 7), extractant feed temperature preferably controls to be 55 ~ 65 DEG C, extractive distillation column bottom temperature preferably controls to be 80 ~ 90 DEG C, tower top temperature preferably controls to be 48 ~ 55 DEG C, working pressure preferably controls to be 0.10 ~ 0.15MPaG, and reflux ratio preferably controls to be 8 ~ 15.
Step 8) described in extraction agent purification reclaim usually carry out in rectifying tower, tower top discharge described in heavy constituent impurity, tower reactor obtains extraction agent.Bottom temperature general control is 130 ~ 160 DEG C, and tower top temperature general control is 40 ~ 60 DEG C, and working pressure general control is 0.01 ~ 0.20MPaG, and reflux ratio general control is 5 ~ 25.
Above-mentioned steps 9) described in bottom temperature preferably control to be 52 ~ 64 DEG C, tower top temperature preferably controls to be 34 ~ 46 DEG C, and working pressure preferably controls to be 0.05 ~ 0.15MPaG, and reflux ratio preferably controls to be 170 ~ 185.
Essence of the present invention the hot dimerization reaction of cyclopentadiene is divided two sections to carry out on the basis of twice separation and Extraction isoprene technique.First and second sections of hot dimerization reactions are in the front and back of first time separation and Extraction isoprene respectively.Contriver found that by experiment, and the separation energy of carrying out C5 fraction by this flow process overcomes the defect that prior art exists well.
By Kinetic analysis, isoprene and cyclopentadiene concentration are the important factors affecting its hot dimerization reaction speed, the speed of reaction that isoprene and cyclopentadiene are total to hot dimerization reaction is directly proportional to isoprene, cyclopentadiene concentration product, and the concentration no matter reducing 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 are all attempt to come by reducing isoprene concentrations the generation of inhibition of isoprenyl and the common hot dimerization reaction of cyclopentadiene, but they ignore the separation and Extraction of carrying out isoprene when not reducing cyclopentadiene concentration jointly, at the temperature of tower reactor or stripping section isoprene and cyclopentadiene altogether hot dimerization reaction be easy to occur, in addition material residence time in rectifying tower is often difficult to uniformity, part isoprene more increases the chance with cyclopentadiene generation dimerization because of overstand.The strategy that the present invention takes allows the C5 fraction raw material after removing light constituent impurity first carry out a preheating dimerization, make the cyclopentadiene of quite a few complete dimerization, but process regulation hot dimerization reaction is altogether occurred cannot meet isoprene and cyclopentadiene.Because isoprene and cyclopentadiene altogether hot dimerization reaction have relatively high activation energy, as long as temperature and the residence time control suitably, in addition hot dimerization reaction adopts tubular reactor usually, and material can be guaranteed in the homogeneity of the reaction zone residence time, and above-mentioned target easily realizes.After preheating dimerization, cyclopentadiene concentration obviously reduces, and when this makes first time separation and Extraction isoprene, the common hot dimerization reaction of isoprene and cyclopentadiene is effectively inhibited.The hot dimerization reaction of second time carries out at a relatively high temperature, and certain reaction conditions is still controlled in suitable scope, to ensure dicyclopentadiene selectivity high as far as possible.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%.Cyclopentadiene amount remaining in system during second time separation and Extraction isoprene is considerably less, and isoprene and cyclopentadiene altogether hot dimerization reaction can not occur substantially.
Add and remove light constituent impurity interior, raw material C5 fraction obtains three kinds of initial gross separation materials of enrichment isoprene, m-pentadiene and dicyclopentadiene after the process of the first six step.The initial gross separation material of enrichment m-pentadiene and dicyclopentadiene is directly as thick product, and these two kinds of thick products have the larger market requirement, known method certainly also can be adopted respectively again to carry out follow-up refinement treatment and obtain more highly purified product.The material of enrichment isoprene adopts extraction fractional distillation conventional in prior art to carry out refining purification and obtains polymerization grade isoprene, and extraction agent adopts conventional dimethyl formamide (DMF).
Compared with prior art, the present invention's progress is significantly no matter to be all effectively suppressed at hot dimerization or the separation and Extraction process isoprene of isoprene and the common hot dimerization reaction of cyclopentadiene, thus the yield of isoprene and dicyclopentadiene is all improved significantly.Its another advantage is that the separation of three kinds of diolefins is more thorough, the amount of carrying other diolefin in the isoprene initial gross separation material before coarse piperyene, thick dicyclopentadiene and extracting rectifying secretly is controlled in very low degree, this alleviates the burden of subsequent disposal on the one hand, also more easily obtains highly purified product simultaneously.
Attached Fig. 1 and 2 is process flow diagram of the present invention, and wherein accompanying drawing 1 is the schema in raw material C5 fraction initial gross separation stage, and accompanying drawing 2 is that isoprene initial gross separation material carries out refining schema of purifying.
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 tower top discharges light constituent impurity W3, and tower reactor obtains C5 fraction material W2; W2 enters a tubular reactor 2 to carry out preheating dimerization reaction and is converted into dicyclopentadiene to make part cyclopentadiene; W4 carries out rectifying with separation and Extraction part isoprene through rectifying tower 3 (theoretical plate number is 54), and tower top obtains the material W6 of enrichment isoprene, and tower reactor obtains remaining C5 fraction material W5; W5 enters a tubular reactor 4 to carry out the hot dimerization reaction of second time and is converted into dicyclopentadiene to make remaining cyclopentadiene.C5 fraction material W7 after the hot dimerization reaction of second time carries out rectifying with the remaining isoprene of separation and Extraction through rectifying tower 5 (theoretical plate number is 80), tower top obtains the material W8 of enrichment isoprene, W8 and W6 send follow-up isoprene to refine purification process after merging, and tower reactor obtains the material W9 of enrichment dicyclopentadiene and m-pentadiene.W9 carries out rectifying to be separated dicyclopentadiene and m-pentadiene through rectifying tower 6 (theoretical plate number is 50), and tower top obtains coarse piperyene product W11, and tower reactor obtains thick dicyclopentadiene product W10.
In fig 2, W6 and W8 merging material enters extractive distillation column 7 (theoretical plate number is 145) and carries out extracting rectifying, material is from the 83rd piece, the middle part column plate charging of tower, and the DMFW15 of recycled and the DMFW15-2 of fresh supplemented is the 11st piece of column plate charging from tower top.Tower top discharges raffinate carbon-5 cut material W13, obtains isoprene and extraction agent material W12 at the bottom of tower.W12 enters subsequently and reclaims the rectifying tower 8 (theoretical plate number is 75) of DMF and carry out being separated of isoprene and DMF, and obtain chemical grade isoprene product W14 by tower top, tower reactor obtains DMFW15, and DMFW15 returns extractive distillation column 7 recycled.
Chemical grade isoprene W14 enters the second extractive distillation column 9 (theoretical plate number is 158) and carries out extracting rectifying, W14 is from the 93rd piece, the middle part column plate charging of tower, and the DMFW19 of recycled and the DMFW19-2 of fresh supplemented is the 10th piece of column plate charging from tower top.Tower top obtains isoprene material W17, and tower reactor must containing the extraction agent material W16 of heavy constituent impurity.W16 enters the purification recovery that rectifying tower 10 (theoretical plate number is 78) carries out DMF subsequently, and tower top discharges heavy constituent impurity W18, and tower reactor obtains DMFW19, and DMFW19 returns extractive distillation column 9 recycled.
Isoprene material W17 finally enters rectifying tower 11 (theoretical plate number is 86) and removes light constituent impurity.Tower top discharges light constituent impurity W20, obtains polymerization grade isoprene product W21 by tower reactor the 78th piece of column plate side line.Tower reactor periodic exhaustion heavy constituent impurity W22, W22 are mainly the polymer of rectifying accumulation.
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), polymerization grade isoprene product yield is respectively:
Wherein:
Flow × cyclopentadiene the molecular fraction of unit time cyclopentadiene mole of feed amount=W2;
Flow × isoprene the molecular fraction of unit time isoprene mole of feed amount=W2
Flow × dicyclopentadiene the molecular fraction of unit time dicyclopentadiene mole load=W10;
Flow × the isoprene of unit time isoprene and cyclopentadiene dimer mole load=W10 and cyclopentadiene dimer molecular fraction;
Flow × isoprene the molecular fraction of unit time isoprene molar product load=W21.
Embodiment
[embodiment 1 ~ 10]
Accompanying drawing is shown in the technical process of embodiment 1 ~ 10, and raw material C5 fraction W1 is that petroleum cracking ethylene by-product obtains, and it mainly forms in table 1.
Each embodiment rectifying tower 1,3,5 and 6, preheating dipolymer reactor and dipolymer reactor 2,4, the rectifying tower 8 of the first extractive distillation column 7 and recovery extraction agent, the rectifying tower 10 of the second extractive distillation column 9 and recovery extraction agent, remove the rectifying tower 11 of light constituent, the process conditions of these equipment is respectively in table 2 ~ 9.Adopt vapor-phase chromatography to analyze the composition of material W6, W8, W10, W11 and W14 respectively, in each material, the content of enriched composition is in table 10.Again in conjunction with the yield of the flow rate calculation cyclopentadiene transformation efficiency of each material, dicyclopentadiene selectivity (selectivity I), isoprene and cyclopentadiene dimer selectivity (selectivity II), polymerization grade isoprene product, the results are shown in Table 11.
Table 1.
Table 2.
Table 3.
Table 4.
Table 5.
Table 6.
Table 7.
Table 8.
Table 9.
Table 10.
Table 11.
Claims (11)
1. separating carbon 5 fraction produce the method for polymerization grade isoprene, comprises the following steps:
1) raw material C5 fraction carries out rectifying with separation removal light constituent impurity through rectifying tower, it is 60 ~ 90 DEG C that bottom temperature controls, it is 40 ~ 50 DEG C that tower top temperature controls, it is 0.10 ~ 0.40MPaG that working pressure controls, control of reflux ratio is 20 ~ 40, tower top discharges light constituent impurity, and tower reactor obtains C5 fraction material;
2) by step 1) the C5 fraction material that obtains of tower reactor is converted into dicyclopentadiene through preheating dimerization reaction to make part cyclopentadiene, it is 40 ~ 60 DEG C that temperature of reaction controls, it is 0.40 ~ 0.80MPaG that reaction pressure controls, and the reaction time of material controls to be 240 ~ 600min;
3) through step 2) C5 fraction material after preheating dimerization reaction carries out rectifying with separation and Extraction part isoprene through rectifying tower, it is 60 ~ 80 DEG C that bottom temperature controls, it is 35 ~ 50 DEG C that tower top temperature controls, it is 0.10 ~ 0.50MPaG that working pressure controls, control of reflux ratio is 2 ~ 10, tower top obtains the material of enrichment isoprene, and tower reactor obtains remaining C5 fraction material;
4) by step 3) the C5 fraction material that obtains of tower reactor is converted into dicyclopentadiene through the hot dimerization reaction of second time to make remaining cyclopentadiene, it is 100 ~ 150 DEG C that temperature of reaction controls, it is 0.80 ~ 1.20MPaG that reaction pressure controls, and the reaction time of material controls to be 60 ~ 120min;
5) through step 4) second time hot dimerization reaction after C5 fraction material carry out rectifying with the remaining isoprene of separation and Extraction through rectifying tower, it is 70 ~ 100 DEG C that bottom temperature controls, it is 50 ~ 80 DEG C that tower top temperature controls, it is 0.20 ~ 0.40MPaG that working pressure controls, control of reflux ratio is 10 ~ 20, tower top obtains the material of enrichment isoprene, and tower reactor obtains the material of enrichment dicyclopentadiene and m-pentadiene;
6) by step 5) material that obtains of tower reactor carries out rectifying to be separated dicyclopentadiene and m-pentadiene through rectifying tower, it is 100 ~ 120 DEG C that bottom temperature controls, it is 35 ~ 50 DEG C that tower top temperature controls, it is 0.010 ~ 0.040MPaG that working pressure controls, control of reflux ratio is 2 ~ 10, tower top obtains coarse piperyene, and tower reactor obtains thick dicyclopentadiene;
7) by step 3) and step 5) the enrichment isoprene material that obtains carries out extracting rectifying with refining isoprene through extractive distillation column after merging, extraction agent is dimethyl formamide, enrichment isoprene material and extractant feed weight ratio control to be 1: (4 ~ 10), it is 50 ~ 90 DEG C that extractant feed temperature controls, it is 100 ~ 130 DEG C that bottom temperature controls, it is 40 ~ 70 DEG C that tower top temperature controls, it is 0.04 ~ 0.20MPaG that working pressure controls, control of reflux ratio is 2 ~ 10, tower top discharges raffinate carbon-5 cut material, tower reactor obtains isoprene and extraction agent material, this material to carry out after being separated of isoprene and extraction agent obtaining chemical grade isoprene product and extraction agent again, extraction agent recycled,
8) step 7) chemical grade isoprene that obtains carries out extracting rectifying to remove heavy constituent impurity through the second extractive distillation column, extraction agent is dimethyl formamide, chemical grade isoprene and extractant feed weight ratio control to be 1: (4 ~ 9), it is 50 ~ 70 DEG C that extractant feed temperature controls, it is 70 ~ 100 DEG C that extractive distillation column bottom temperature controls, it is 40 ~ 60 DEG C that tower top temperature controls, it is 0.05 ~ 0.20MPaG that working pressure controls, control of reflux ratio is 5 ~ 18, tower top obtains isoprene material, tower reactor must containing the extraction agent material of heavy constituent impurity, the purification that this material carries out extraction agent through rectifying is again reclaimed, the extraction agent recycled reclaimed,
9) by step 8) the isoprene material that obtains of the second extracting rectifying column overhead carries out rectifying to remove light constituent impurity through rectifying tower, it is 50 ~ 70 DEG C that bottom temperature controls, it is 30 ~ 50 DEG C that tower top temperature controls, it is 0.02 ~ 0.20MPaG that working pressure controls, control of reflux ratio is 150 ~ 190, tower top discharges light constituent impurity, and tower reactor side line obtains polymerization grade isoprene product, and tower reactor regularly discharges heavy constituent impurity.
2. separating carbon 5 fraction according to claim 1 produce the method for polymerization grade isoprene, it is characterized in that step 2) described in temperature of reaction control be 45 ~ 55 DEG C, it is 0.50 ~ 0.70MPaG that reaction pressure controls, and the reaction time of material controls to be 400 ~ 500min.
3. separating carbon 5 fraction according to claim 1 produce the method for polymerization grade isoprene, it is characterized in that step 3) described in bottom temperature control be 65 ~ 75 DEG C, it is 40 ~ 47 DEG C that tower top temperature controls, and it is 0.25 ~ 0.35MPaG that working pressure controls, and control of reflux ratio is 3 ~ 8.
4. separating carbon 5 fraction according to claim 1 produce the method for polymerization grade isoprene, it is characterized in that step 4) described in temperature of reaction control be 120 ~ 140 DEG C, it is 0.90 ~ 1.10MPaG that reaction pressure controls, and the reaction time of material controls to be 70 ~ 90min.
5. separating carbon 5 fraction according to claim 1 produce the method for polymerization grade isoprene, it is characterized in that step 5) described in bottom temperature control be 80 ~ 90 DEG C, it is 55 ~ 70 DEG C that tower top temperature controls, it is 0.25 ~ 0.30MPaG that working pressure controls, and control of reflux ratio is 12 ~ 18.
6. separating carbon 5 fraction according to claim 1 produce the method for polymerization grade isoprene, it is characterized in that step 6) described in bottom temperature control be 105 ~ 115 DEG C, it is 40 ~ 50 DEG C that tower top temperature controls, it is 0.025 ~ 0.035MPaG that working pressure controls, and control of reflux ratio is 5 ~ 8.
7. separating carbon 5 fraction according to claim 1 produce the method for polymerization grade isoprene, it is characterized in that step 7) described in enrichment isoprene material and extractant feed weight ratio control to be 1: (5 ~ 8), it is 55 ~ 75 DEG C that extractant feed temperature controls, it is 110 ~ 120 DEG C that extractive distillation column bottom temperature controls, it is 45 ~ 65 DEG C that tower top temperature controls, it is 0.08 ~ 0.15MPaG that working pressure controls, and control of reflux ratio is 4 ~ 8.
8. the separating carbon 5 fraction according to claim 1 or 7 also produces the method for polymerization grade isoprene, it is characterized in that step 7) described in isoprene and being separated in rectifying tower of extraction agent carry out, chemical grade isoprene product is obtained by tower top, tower reactor obtains extraction agent, it is 140 ~ 170 DEG C that bottom temperature controls, it is 30 ~ 50 DEG C that tower top temperature controls, and it is 0.010 ~ 0.020MPaG that working pressure controls, and control of reflux ratio is 4 ~ 15.
9. separating carbon 5 fraction according to claim 1 produce the method for polymerization grade isoprene, it is characterized in that step 8) described in chemical grade isoprene and extractant feed weight ratio control to be 1: (5 ~ 7), it is 55 ~ 65 DEG C that extractant feed temperature controls, it is 80 ~ 90 DEG C that extractive distillation column bottom temperature controls, it is 48 ~ 55 DEG C that tower top temperature controls, it is 0.10 ~ 0.15MPaG that working pressure controls, and control of reflux ratio is 8 ~ 15.
10. the separating carbon 5 fraction according to claim 1 or 9 also produces the method for polymerization grade isoprene, it is characterized in that step 8) described in the purification of extraction agent be recovered in rectifying tower and carry out, heavy constituent impurity described in tower top discharge, tower reactor obtains extraction agent, it is 130 ~ 160 DEG C that bottom temperature controls, it is 40 ~ 60 DEG C that tower top temperature controls, and it is 0.01 ~ 0.20MPaG that working pressure controls, and control of reflux ratio is 5 ~ 25.
11. separating carbon 5 fractions according to claim 1 also produce the method for polymerization grade isoprene, it is characterized in that step 9) described in bottom temperature control be 52 ~ 64 DEG C, it is 34 ~ 46 DEG C that tower top temperature controls, it is 0.05 ~ 0.15MPaG that working pressure controls, and control of reflux ratio is 170 ~ 185.
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| CN107879879A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | The method for preparing polymerization grade isoprene |
| CN107879881A (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 polymerization grade isoprene |
| 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 |
| CN109665934B (en) * | 2017-10-16 | 2021-10-19 | 中国石油化工股份有限公司 | Method for preparing dicyclopentadiene |
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