CN103450401A - C5 hydrogenated petroleum resin raw material, and preparation method and application thereof - Google Patents
C5 hydrogenated petroleum resin raw material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a C5 hydrogenated petroleum resin raw material, and a preparation method thereof. The method comprises the following steps: removing below C4 light hydrocarbon fractions in an ethylene cracking C5 product; dimerizing a below C4 light hydrocarbon fraction removed material; carrying out weight removal of a dimerized material to obtain an above C6 hydrocarbon fraction and a weight removed material; sending the weight removed material to a first rectifying tower for separation in order to obtain concentrated isoprene at the top of the tower and concentrated m-pentadiene at the bottom of the tower; sending the concentrated isoprene to a second rectifying tower for separation in order to obtain crude isoprene at the top of the tower and obtain a second rectification residue at the bottom of the tower; carrying out extracting separation of the most crude isoprene to obtain an extraction residue C5; and mixing the less crude isoprene, the concentrated m-pentadiene, the second rectification residue, the above C6 fraction and the extraction residue C5 mixture to obtain the C5 hydrogenated petroleum resin raw material. An apparatus realizes the optimization of the raw material based on the prior art, and the operation is stationary and controllable, so the product quality stability and controllability are guaranteed.
Description
Technical field
The present invention relates to a kind of method and a kind of C5 hydrogenated petroleum resin raw material prepared by the method for the C5 of preparation hydrogenated petroleum resin raw material of the present invention and the application in synthetic C5 hydrogenated petroleum resin thereof of the C5 of preparation hydrogenated petroleum resin raw material.
Background technology
Cracking of ethylene C5(is called for short C 5 fraction usually) be the by product of preparing ethylene by steam cracking device, generally be about 10～20 % by weight of ethylene yield, usually contain tens kinds of components such as alkane, alkene, diolefin, alkynes of 4～6 carbon atoms.What wherein content was more is isoprene, cyclopentadiene and m-pentadiene, and its content is respectively in 15～25 % by weight, 12～15 % by weight, 14～20 % by weight left and right, and the three accounts for 40～60 % by weight of cracking of ethylene C5.These diolefins due to have special molecular structure, chemical property active, can synthesize many important high value added products, be the precious resources of chemical utilization, take that they can produce multiple petrochemical complex and the fine chemical products such as 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, medicine as raw material.
Along with the fast-developing of ethylene industry with to the demand of synthetic rubber and synthetic resins, increase, the cracking of ethylene C 5 fraction is as a kind of important industrial chemicals, and its extraction and application has been subject to the generally attention of countries in the world day by day.At present, industrialized cracking of ethylene C5 separating technology mainly contains following several:
Acetonitrile (ACN) extraction process: the acetonitrile extraction process is external one of the most widely used C 5 fraction separation method, uses the U.S. ESSO company that mainly contains, U.S. Atlantic Richfield company, the Japan SYnthetic Rubber Co. Ltd of this technology.It is three steps that its know-why is divided into, the first step, C 5 fraction generates dicyclopentadiene by hot dimerization reaction by the cyclopentadiene polymerization in raw material, by rectifying, cyclopentadiene and m-pentadiene are separated and obtained thick isoprene, second step, the mixed solvent that adopts the acetonitrile of moisture 5 about % by weight or acetonitrile-vinyl cyanide-acetone and water is removed the hydrocarbon impurities such as monoolefine in thick isoprene, alkane, alkynes through two-stage solvent extraction rectifying separation, then obtains half refining isoprene through washing except the solvent acetonitrile of deentrainment; The 3rd step, half refining isoprene is by the de-polymerization grade isoprene product that obtains purity 99.5% after light, de-heavy of two-stage conventional distillation.The 90-95% that the total recovery of isoprene is isoprene in the extracting rectifying charging.
Dimethyl formamide (DMF) extraction process: the dimethyl formamide extraction process claims again the GPI method, is succeeded in developing and built up full scale plant in 1971 by Nippon Zeon Co., Ltd..Domestic built C5 separation industries device all adopts this technology at present.Its know-why is that at first C 5 fraction generates dicyclopentadiene by dipolymer reactor by the cyclopentadiene polymerization in raw material, by de-heavy and rectifying separation, goes out cyclopentadiene and m-pentadiene obtains thick isoprene; Then to adopt dimethyl formamide be solvent removes the hydrocarbon impurities such as monoolefine in thick isoprene, alkane, alkynes and obtains half refining isoprene through two-stage solvent extraction rectifying separation, then by the two-stage conventional distillation, half refining isoprene is purified to 99.5% polymerization grade isoprene product.The total recovery of isoprene be in the extracting rectifying charging isoprene 90～95%.
N-methyl pyrrolidone (NMP) method: N-methyl pyrrolidone method is developed the earliest by German BASF AG, after improve again, be characterized in adopting the mode of the solvent extraction of N-methyl pyrrolidone and hydrogenation to remove cyclopentadiene, m-pentadiene and alkynes, rather than adopting hot dimerization to remove dicyclopentadiene, the isoprene yield is than Gao Keda more than 97%.Its know-why is that at first C 5 fraction enters extraction tower, and the side line extraction diolefine in C 5 fraction extracted by tower with the nmp solvent of moisture 3-10% enters rectifying tower, and rectifying tower top obtains purity and is about 97% isoprene; At the bottom of tower, the mixture of dicyclopentadiene, m-pentadiene, alkynes and saturated solvent returns to the extraction tower bottom again, and extracts out and enter hydrogenator from bottom, by the m-pentadiene hydrocracking, is amylene and pentane, and dicyclopentadiene is converted into to cyclopentenes and pentamethylene; Monoolefine after hydrogenation and alkane turn back to ，You top, extraction tower top again and deviate from.Although the yield of the comparatively simple isoprene of this technique is also higher, the purity of isoprene does not reach the requirement of polymerization-grade far away, and this technique is larger to chemical resource destruction potential in C5, and therefore domestic do not have enterprise to adopt the method.
Hence one can see that, adopt at present C 5 fraction to separate the method for preparing polymerization grade isoprene and mainly contain acetonitrile extraction process and dimethyl formamide extraction process, and acetonitrile extraction process and dimethyl formamide extraction process separation of C 5 cuts all mainly comprise pre-treatment and the thick large step of isoprene extracting rectifying two of C 5 fraction, wherein, the pre-treatment of C 5 fraction mainly comprises: the removing of the following cut of C4, the hot dimerization of cyclopentadiene and de-heavy, isoprene and m-pentadiene separate several steps; The main purpose of extracting rectifying is thick isoprene process solvent extraction rectifying and the conventional distillation that pre-treatment is obtained, and removes monoolefine, alkane and alkynes wherein, and then de-light, de-recuperation is greater than 99.5% polymerization grade isoprene to purity.In order to guarantee that extracting rectifying can finally obtain the polymerization grade isoprene that m-pentadiene content is less than 50ppm, in the thick isoprene that pre-separation obtains, m-pentadiene concentration must be less than 10ppm.With the separating technology of current C 5 fraction, isoprene monomer is with respect to the yield of isoprene in the C5 total raw material lower (being only generally 60% left and right).The rate of recovery that improves isoprene monomer has two approach, one is the rate of recovery that further improves extracting rectifying workshop section isoprene, and one is to improve by improving pre-separation technique the rate of recovery that improves isoprene into the isoprene total amount of extracting rectifying workshop section.The technical study of extracting rectifying is comparatively ripe at present, extracting rectifying workshop section isoprene total recovery generally can reach more than 92%, can reach 85 left and right (can produce a small amount of chemical industry grade isoprene) through de-frivolous heavy post polymerization grade isoprene with respect to the isoprene yield in the thick isoprene of extracting rectifying charging, the space of isoprene yield of further improving extracting rectifying and rear centrifugal station is very limited; It is a new bright spot that thereby the improvement by pre-separating system improves the rate of recovery that improves isoprene monomer in whole C 5 fraction separating technology into the isoprene amount of extracting rectifying.
The raw material of C5 hydrogenated petroleum resin is material after the de-C4 of cracking of ethylene C5 at present, due to the production of upstream ethylene unit and the fluctuation processed raw material, the fluctuation that causes cracking of ethylene C5 to form, make C5 hydrogenated petroleum resin device can't realize that component comprises that the adjusting of the ratio of the ratio of three kinds of diolefins and active single diene controls, make thus the physico-chemical property of its production process and product be difficult to obtain further and optimize.
Summary of the invention
The invention provides and a kind ofly can optimize the application in synthetic C5 hydrogenated petroleum resin of C5 hydrogenated petroleum resin raw material, preparation method and C5 hydrogenated petroleum resin raw material.
To achieve these goals, the invention provides a kind of method of the C5 of preparation hydrogenated petroleum resin raw material, the method comprises:
(1) after cracking of ethylene C5 raw material being sent into to de-C4 tower and being removed the following light ends fractionation of C4, carry out the dimerization of cyclopentadiene, then take off heavyly, obtain the above hydrocarbon-fraction of C6 and take off the material after weighing;
(2) material that will take off after heavy is sent into the first rectifying tower, from the tower top of the first rectifying tower, obtains concentrated isoprene, and tower reactor obtains concentrated m-pentadiene, and in concentrated m-pentadiene, isoprene content is lower than 0.6 % by weight;
(3) will concentrate isoprene and send in Second distillation column and carry out the second rectifying separation, and from the tower top of Second distillation column, obtain thick isoprene, in thick isoprene, the weight content of m-pentadiene is lower than 10ppm; Tower reactor obtains the second rectifying residuum;
(4) major part is sent in the first extractive distillation column and carried out extracting and separating with extraction solvent for the production of the thick isoprene of polymerization grade isoprene, obtain from tower top the mixture that raffinate C5(is C5 monoolefine and C5 alkane), tower reactor obtains the mixture that contains extraction solvent and isoprene, and this mixture is through the second extracting rectifying and de-frivolously heavyly can obtain the polymerization grade isoprene product;
(5) mixture of the above hydrocarbon-fraction of described C6, the thick isoprene of small part, concentrated m-pentadiene, the second rectifying residuum and raffinate C5 is mixed, as the mixing raw material of hydrogenated petroleum resin.
The invention provides the C5 hydrogenated petroleum resin raw material that a kind of the method according to this invention prepares.
The application of the C5 hydrogenated petroleum resin raw material that the present invention also provides a kind of the method according to this invention to prepare in synthetic C5 hydrogenated petroleum resin.
For various components in the C5 hydrogenated petroleum resin raw material that further optimization method of the present invention obtains, so that it has better physico-chemical property as the synthetic C5 hydrogenated petroleum resin obtained of C5 hydrogenated petroleum resin raw material is (as good as color, the molecular distribution amount is narrow etc.) and higher product yield, for the present invention, under preferable case, thick isoprene in described C5 hydrogenated petroleum resin raw material, concentrated m-pentadiene, the above hydrocarbon-fraction of C6, the weight ratio of raffinate C5 and the second rectifying residuum is 1～3:0.5～2.5:1～3:0～0.7:1, be preferably 1.8～2.2:0.9～1.3:12～1.6:0～0.4:1.In the C5 resin raw material obtained according to preceding method, the ratio of isoprene, m-pentadiene, three kinds of diolefins of cyclopentadiene is preferably isoprene: m-pentadiene: cyclopentadiene is 0.9～1.1:0.9～1.1:0.9～1.1, the above hydrocarbon-fraction of C6, thick isoprene, concentrated m-pentadiene and the second rectifying residuum are in the C5 diolefin, the mixture of raffinate C5(C5 monoolefine and C5 alkane), in the C5 monoolefine, the best ratio of C5 monoolefine and C5 diolefin is 0.25～0.35:1.Adopt the C5 resin raw material that method of the present invention obtains will there is good physico-chemical property.Can further realize effective control of three kinds of diolefin content in the feed composition of the hydrogenated petroleum resin that adopts method of the present invention to obtain, the ratio of single diolefin also can be regulated and controled, the technology controlling and process that implement device is produced better, make the apparent mass of product comprise that the indexs such as colourity, molecular weight distribution, softening temperature all can be controlled effectively.
The method according to this invention, in order well to control the ratio of the mono-diolefin of C5 in the C5 resin raw material, under preferable case, in the mixture that contains extraction solvent and isoprene that the first extractive distillation column tower reactor obtains, the content of C5 monoolefine and C5 alkane is less than 0.1 % by weight.
The method according to this invention, the present invention to described the first extracting rectifying condition without particular requirement, method according to the extraction of the one-level in the extracting rectifying unit in this area (being the solvent extracting rectifying) can realize purpose of the present invention, for the present invention, under preferable case, the operational condition of described the first extractive distillation column is: described extraction solvent is acetonitrile and/or dimethyl formamide, theoretical plate number is 60～150, be preferably 80～120, reflux ratio is 1～10, is preferably 2～5.Concrete example obtains the mixture (raffinate C5) of C5 monoolefine and C5 alkane and contains extraction solvent and the mixture of isoprene as dimethyl formamide extraction process, the acetonitrile extraction process that can adopt prior art carries out the one-level extracting rectifying, for example can carry out the one-level extracting rectifying to realize purpose of the present invention to thick isoprene according to the method for the disclosed extracting rectifying of step in CN101244976B (2) more specifically.
All can realize purpose of the present invention according to preceding method, for the condition that makes the second rectifying is easily controlled, for the present invention, preferably in the concentrated m-pentadiene of described the first tower bottom of rectifying tower gained, the content of m-pentadiene is more than 65 % by weight.
In thick isoprene, the amount of m-pentadiene can meet under the prerequisite of requirement of extracting rectifying, and in order further to improve the yield of thick isoprene, in Second distillation column tower reactor gained the second rectifying residuum, isoprene content is lower than 20 % by weight.
The method according to this invention, optional a wider range of described the first rectifying tower operational condition, for the present invention, preferred described the first rectifying tower operational condition: total stage number or theoretical plate number are 60～120, are preferably 70～100; The tower reactor temperature is 65～110 ℃, is preferably 80～100 ℃; Tower top temperature is 35～70 ℃, is preferably 40～65 ℃; Reflux ratio is 4～10, is preferably 5～8.
The method according to this invention, the optional a wider range of described Second distillation column operational condition, for the present invention, preferred described Second distillation column operational condition: total stage number or theoretical plate number are 60～120, are preferably 70～100; The tower reactor temperature is 60～105 ℃, is preferably 70～100 ℃; Tower top temperature is 30～65 ℃, is preferably 40～60 ℃; Reflux ratio is 12～18, is preferably 13～16.
The method according to this invention, the method in step (1), the following light ends fractionation of C4 in described cracking of ethylene C5 removed can be carried out with reference to prior art, and the content that preferably removes the following light ends fractionation of C4 in the material after the following light ends fractionation of C4 is 0.01～0.03 % by weight.
The method according to this invention, preferably the operational condition of de-C4 tower is: total stage number or the theoretical plate number of de-C4 tower are 20～50, and the temperature of de-C4 tower tower reactor is 80～120 ℃, and tower top temperature is 30～60 ℃, and reflux ratio is 8～15.
The method according to this invention, it is heavy that the material after dimerization takes off, and in the material after preferably de-heavy, the content of the above hydrocarbon-fraction of C6 is lower than 0.01～0.03 % by weight.
The method according to this invention, preferably take off the material after described dimerization and weigh, and de-heavy condition is: total stage number or theoretical plate number are 20～50, and the temperature of tower reactor is 100～140 ℃, and tower top temperature is 30～60 ℃, and reflux ratio is 1～5.
The method according to this invention, the method that removes material after the following light ends fractionation of C4 and carry out the dimerization of cyclopentadiene can be carried out with reference to prior art, be converted more than preferably after dimerization, making cyclopentadiene 90 % by weight in the material of the following light ends fractionation of the described C4 of removing.
The method according to this invention, the by product that preferred described cracking of ethylene C5 is the preparing ethylene by steam cracking device, more preferably described cracking of ethylene C5 contains isoprene 15～28 % by weight, m-pentadiene 12～24 % by weight, cyclopentadiene 10～28 % by weight, following light ends fractionation 5～18 % by weight of C4, above hydrocarbon-fraction 8～20 % by weight of C6.
Method of the present invention, on the basis of existing technology, raw material technical requirements in conjunction with the C5 hydrogenated petroleum resin, by increasing isoprene in pre-separation operation knockout tower again, and make the tower reactor leftover materials as one of raw material of downstream C5 hydrogenated petroleum resin device, make method of the present invention not only improve the yield of thick isoprene than prior art, and guaranteed the precision as the thick isoprene of follow-up extracting rectifying raw material, and adopt method of the present invention isoprene can be separated fully with m-pentadiene in the preprocessing process of cracking of ethylene C5, and method of the present invention is separated to 4 kinds of materials (the concentrated isoprene obtained, concentrated m-pentadiene, the above hydrocarbon-fraction of C6, the second rectifying residuum) and 5 strands of materials of the mixture (raffinate C5) of the alkane of the monoolefine of the C5 of the first extracting rectifying tower top and C5 be in harmonious proportion the structure of the C5 hydrogenated petroleum resin raw material that obtains and obtained optimization, and then can make the physico-chemical property of rosin products be further improved.As can be seen here, method of the present invention only increases than prior art the maximization that a rectifying tower can realize the thick isoprene yield of cracking of ethylene C5 preprocessing process, and construction and cost of investment are little, and processing condition are simple, easily controls.Based on above-mentioned advantage, method of the present invention has high industrial application value.
Except separation obtains the isoprene of polymerization-grade, all the other each strand main material of cracking of ethylene C 5 fraction after separating: the thick isoprene of the small part that pre-treatment obtains, concentrated m-pentadiene, the second rectifying residuum, and the by products such as raffinate C5 that most of thick isoprene obtains after one-section abstraction rectifying all can be used for mediation preparation C5 hydrogenated petroleum resin raw material.The contriver finds, in the raw material of C5 hydrogenated petroleum resin, there are two indexs most important to the raising stable and product yield of quality product, an index is three kinds of diolefins: the ratio between isoprene, m-pentadiene and dicyclopentadiene, another index is the ratio between single, double alkene.Three kinds of diolefin materials applying that technology of the present invention can also be further passes through by mixing that the C5 pre-separation obtains and isoprene knockout tower (being Second distillation column) end leftover materials are again adjusted arbitrarily the ratio of three kinds of diolefins, again raffinate C5 monoolefine and the alkane of extracting rectifying the first extraction tower top are mixed to adjust the ratio of single diolefin with diolefin, make the effecting reaction component of resin raw material realize controlled design, thereby realize making more stablizing of production of resins controlled, realize the raising of the stable and yield of quality product.
The present invention is in conjunction with the technology of the full separation of produced isoprene monomer of cracking of ethylene C5 component, on the basis of existing technology, by the improvement to the C 5 fraction preprocessing part, increase Second distillation column (being isoprene knockout tower again) in improving preprocessing process in thick isoprene yield, the thick isoprene obtained can also be made to separate and the requirement (general requirement m-pentadiene content is lower than 10ppm) for preparing the raw material of polymerization grade isoprene as extracting rectifying can be met, and Second distillation column tower reactor leftover materials can be fully utilized as the raw material of C5 hydrogenated petroleum resin, the raffinate C5 monoolefine material obtained by the concentrated diolefin material of its excess-three kind that pre-separation is obtained and one-level extracting rectifying be in harmonious proportion the ratio of three kinds of diolefins of raw material of the C5 hydrogenated petroleum resin that obtains can realize producing go up desirable evenly controlled, and the ratio of single diolefin also can realize the control index of producing, make the physico-chemical property of rosin products further to optimize, the economic worth that realizes thus cracking of ethylene C 5 fraction isolation technique maximizes.
The accompanying drawing explanation
Fig. 1 is application a kind of process flow diagram for preparing the method for C5 hydrogenated petroleum resin raw material of the present invention.
Wherein, equipment and device: T1-takes off C4 tower, R1-dipolymer reactor, T2-weight-removing column, T3-the first rectifying tower, T4-Second distillation column, T5-one-level extractive distillation column, P1-C5 hydrogenated petroleum resin device.
Material: 1-cracking of ethylene C5 raw material, the following cut of 2-C4,3-removes the following cut material of C4, the 4-dimers, 5-removes the above component materials of C6, the above component of 6-C6,7-concentrates isoprene, 8-concentrates m-pentadiene, the thick isoprene of 9-, 10-the second rectifying residuum, 11-advances the thick isoprene of extracting rectifying, the 12-extraction agent, 13-raffinate C5,14-rich solvent.
Embodiment
A kind of embodiment below in conjunction with accompanying drawing to method provided by the present invention is further detailed, and all the other are various can realize method of the present invention all similarly, and the present invention repeats no more.
Obtain C5 hydrogenated petroleum resin raw material by technique shown in Fig. 1:
(1) cracking of ethylene C5 is sent in de-C4 tower T101 to remove a small amount of following light ends fractionation of C4 in cracking of ethylene C5 raw material, tower top obtains the following light ends fractionation of C4, and tower reactor obtains removing the material of the following light ends fractionation of C4;
(2) material that removes the following light ends fractionation of C4 step (1) obtained is sent into the material after the dimerization of carrying out cyclopentadiene in dipolymer reactor R1 obtains dimerization;
(3) material after dimerization step (2) obtained is sent in weight-removing column T102 to remove the above cut of C6, and wherein the above cut of C6 distillates from tower reactor, and the material (also claiming de-material after heavy) that removes the above cut of C6 distillates from tower top;
(4) material after de-weight step (3) obtained is sent in rectifying tower T103 and is carried out rectifying separation, from the tower top of rectifying tower T103, obtains concentrated isoprene, and tower reactor obtains concentrated m-pentadiene;
(5) concentrated isoprene step (4) obtained is sent in rectifying tower T104 and is carried out rectifying separation, from the tower top of rectifying tower T104, obtains thick isoprene, and tower reactor obtains the second rectifying residuum.
(6) the thick isoprene of major part step (5) obtained and extraction solvent (being labeled as SOLVENT in figure) are sent in extractive distillation column T201 and are carried out extracting and separating, obtain the mixture (being called for short raffinate C5) of C5 monoolefine and C5 alkane from the tower top of T201, tower reactor obtains the mixture that contains extraction solvent and isoprene;
(7) the above cut of C6, the thick isoprene of small part, concentrated m-pentadiene, the second rectifying residuum, raffinate C5 mixture are mixed.
Raw material by 5 strands of materials of C5 pre-separation and extracting rectifying output as C5 hydrogenated petroleum resin device, wherein the second rectifying residuum material 10 is all to measure, and the above component materials 6 of the C6 that comprises dicyclopentadiene, the concentrated m-pentadiene material 8 that comprises m-pentadiene, the thick isoprene material 9 that comprises isoprene and the raffinate C5 material 13 that comprises the C5 monoolefine are the part amount.
Embodiment 1
Prepare C5 hydrogenated petroleum resin raw material according to the flow process shown in Fig. 1, concrete steps are as follows:
(1) Lanzhou Petrochemical cracking of ethylene C5(material is formed in Table 1) (flow is 400kg/hr) send in de-C4 tower T101 and carry out removing of the following light ends fractionation of C4, tower top obtains the following light ends fractionation T101-OUT(of C4 material and forms in Table 1), tower reactor obtains removing the material R1-IN(material composition of the following light ends fractionation of C4 in Table 1), wherein, the interior operating parameters of tower is in Table 2;
(2) the material R1-IN that removes the following light ends fractionation of C4 step (1) obtained sends in dipolymer reactor R1, and the material T102-IN(material after dimerization forms in Table 1), wherein, in tower, the dimerization condition is in Table 2;
(3) the material T102-IN after dimerization step (2) obtained sends in weight-removing column T102, the above cut T102-OUT(of C6 material forms in Table 1) from tower reactor, distillate, remove material T103-IN(after the above cut of C6 and also claim de-material after heavy) (material forms in Table 1) distillate from tower top, wherein, the interior operational condition of tower is in Table 2;
(4) the material T103-IN after de-weight step (3) obtained sends in rectifying tower T103, obtain concentrated isoprene T104-IN(material composition in Table 1 from the tower top of rectifying tower T103), tower reactor obtains concentrated m-pentadiene T103-OUT(material and forms in Table 1), wherein the interior operational condition of tower is in Table 2;
(5) concentrated isoprene T104-IN step (4) obtained sends in rectifying tower T104 and carries out rectifying separation, obtain thick isoprene T104-OUT(material composition in Table 1 from the tower top of rectifying tower T104), tower reactor obtains the second rectifying residuum T104-BTM(material and forms in Table 1), wherein the interior operational condition of tower is in Table 2.
(6) according to the method for 1 step of embodiment in CN101244976B (2), thick isoprene T104-OUT is carried out to separation of extractive distillation: the thick isoprene of major part is sent into the first extractive distillation column T201 from the middle part of the first extractive distillation column T201, extraction solvent acetonitrile (being not limited to acetonitrile) is sent into the first extractive distillation column T201 from the top of T201, carry out extracting and separating, obtain the mixture (figure referred to as " raffinate C5 ") (material forms in Table 1) of C5 monoolefine and C5 alkane from the tower top of T201, tower reactor obtains the mixture T201-OUT that contains extraction solvent and isoprene, wherein the interior operational condition of tower is in Table 2,
(7) mixture of the thick isoprene of small part, concentrated m-pentadiene, the second rectifying residuum, the above cut of C6, C5 monoolefine and C5 alkane is mixed to get to the C5 hydrogenated petroleum resin, the ratio of mixing is in Table " isoprene: m-pentadiene: cyclopentadiene " and " O/D value " in 2.
Embodiment 2～3
Method according to embodiment 1 prepares C5 hydrogenated petroleum resin raw material, different, and in step (7), the blending ratio of 5 strands of materials has certain variation, and in Table 2, all the other conditions are all identical.
Comparative Examples 1
For the current mode of production, pass through above-mentioned steps (1), tower reactor obtains removing the material R1-IN(material composition of the following light ends fractionation of C4 in Table 1) the direct raw material synthetic as resin, due to the blending technology that there is no raw material, the ratio of three kinds of diolefins and the ratio of active single diene are all uncontrollable, the fluctuation of production upstream device will cause the fluctuation that the petroleum resin device is produced, and all the other conditions are in Table 2.
Table 1
Table 2
In table 2, thick isoprene: the concentrated above cut of m-pentadiene: C6: the ratio of the second rectifying residuum: raffinate C5 is weight ratio; The total concentration that Comparative Examples 1 cyclopentadiene is dicyclopentadiene and cyclopentadiene; The O/D value refers to the ratio of active monoolefine (3-methyl-1-butene+Isosorbide-5-Nitrae-pentadiene, 1-amylene+2-methyl-1-butene alkene+2-methyl-2-butene+cyclopentenes) and diolefin (isoprene+sow distrust among one's enemies pentadiene+along m-pentadiene+cyclopentadiene+dicyclopentadiene).
In table, data can be found out, the C5 hydrogenated petroleum resin raw material that adopts method of the present invention to prepare has three kinds of diolefins and is evenly distributed, single diolefin ratio is controlled, can also adjust composition of raw materials according to product demand, illustrate by C5 hydrogenated petroleum resin material allocation technology and can make on the basis of existing technology the device raw material further be optimized.In addition, use method of the present invention also to make operation more steady, controlled, thereby guarantee the stable, controlled of quality product.
Claims (18)
1. a method for preparing C5 hydrogenated petroleum resin raw material is characterized in that the method comprises:
(1) after cracking of ethylene C5 raw material being sent into to de-C4 tower and being removed the following light ends fractionation of C4, carry out the dimerization of cyclopentadiene, then take off heavyly, obtain the above hydrocarbon-fraction of C6 and take off the material after weighing;
(2) material that will take off after heavy is sent into the first rectifying tower, from the tower top of the first rectifying tower, obtains concentrated isoprene, and tower reactor obtains concentrated m-pentadiene, and in concentrated m-pentadiene, isoprene content is lower than 0.6 % by weight;
(3) will concentrate isoprene and send in Second distillation column and carry out the second rectifying separation, and from the tower top of Second distillation column, obtain thick isoprene, in thick isoprene, the weight content of m-pentadiene is lower than 10ppm; Tower reactor obtains the second rectifying residuum;
(4) major part is sent in the first extractive distillation column and carried out extracting and separating with extraction solvent for the production of the thick isoprene of polymerization grade isoprene, from tower top, obtain raffinate C5, tower reactor obtains the mixture that contains extraction solvent and isoprene;
(5) the above hydrocarbon-fraction of described C6, the thick isoprene of small part, concentrated m-pentadiene, the second rectifying residuum and raffinate C5 mixture are mixed.
2. method according to claim 1, is characterized in that in the mixture that contains extraction solvent and isoprene that the first extractive distillation column tower reactor obtains, the content of C5 monoolefine and C5 alkane is less than 0.1 % by weight.
3. method according to claim 1, it is characterized in that the first extracting rectifying condition: extraction solvent is acetonitrile and/or dimethyl formamide, and theoretical plate number is 60～150, and reflux ratio is 1～10.
4. method according to claim 1, is characterized in that the content of m-pentadiene in the concentrated m-pentadiene of tower top gained of the first rectifying tower is more than 65 % by weight.
5. method according to claim 1, is characterized in that in the tower reactor gained second rectifying residuum of the first rectifying tower that isoprene content is lower than 20 % by weight.
6. method according to claim 1, the first rectifying tower rectifying condition that it is characterized in that is: theoretical plate number is 60～120, and the tower reactor temperature is 65～110 ℃, and tower top temperature is 35～70 ℃, and reflux ratio is 4～10.
7. method according to claim 1, it is characterized in that Second distillation column rectifying condition is: theoretical plate number is 60～120, and the tower reactor temperature is 60～105 ℃, and tower top temperature is 30～65 ℃, and reflux ratio is 12～18.
8. method according to claim 1, is characterized in that the content of the following light ends fractionation of C4 in the material after step (1) removes the following light ends fractionation of C4 is 0.01～0.03 % by weight.
9. method according to claim 1, it is characterized in that de-C4 tower is operating as: theoretical plate number is 20～50, and the temperature of tower reactor is 80～120 ℃, and tower top temperature is 30～60 ℃, and reflux ratio is 8～15.
10. method according to claim 1, it is characterized in that material after dimerization take off heavy after, in the material after de-heavy, the content of the above hydrocarbon-fraction of C6 is lower than 0.01～0.03 % by weight.
11. method according to claim 1, is characterized in that the material after dimerization takes off while weighing, de-retry condition is that theoretical plate number is 20～50, and the temperature of tower bottom of rectifying tower is 100～140 ℃, and tower top temperature is 30～60 ℃, and reflux ratio is 1～5.
12. method according to claim 1, is characterized in that the by product that cracking of ethylene C5 raw material is the preparing ethylene by steam cracking device.
13. method according to claim 14, wherein, described cracking of ethylene C5 raw material contains isoprene 15～28 % by weight, m-pentadiene 12～24 % by weight, cyclopentadiene 10～28 % by weight, following light ends fractionation 5～18 % by weight of C4, above hydrocarbon-fraction 8～20 % by weight of C6.
14. the C5 hydrogenated petroleum resin raw material prepared by the described method of any one in claim 1～13.
15. C5 hydrogenated petroleum resin raw material according to claim 14, is characterized in that thick isoprene, concentrated m-pentadiene, the above hydrocarbon-fraction of C6, C5 monoolefine and the mixture of C5 alkane and the weight ratio of the second rectifying residuum are 1～3:0.5～2.5:1～3:0～0.7:1.
16. be C5 hydrogenated petroleum resin raw material according to claim 14, it is characterized in that thick isoprene, concentrated m-pentadiene, the above hydrocarbon-fraction of C6, C5 monoolefine and the mixture of C5 alkane and the weight ratio of the second rectifying residuum are 1.8～2.2:0.9～1.3:12～1.6:0～0.4:1.
17. C5 hydrogenated petroleum resin raw material according to claim 14, it is characterized in that the above hydrocarbon-fraction of C6, thick isoprene, concentrated m-pentadiene and the second rectifying residuum are in the C5 diolefin, raffinate C5 is in the C5 monoolefine, and the ratio of C5 monoolefine and C5 diolefin is 0.25～0.35:1.
18. the application of the described C5 hydrogenated petroleum resin of claim 14 raw material in synthetic C5 hydrogenated petroleum resin.
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| CN105585666B (en) * | 2014-10-22 | 2019-01-04 | 中国石油化工股份有限公司 | A kind of preparation method of dicyclopentadiene hydrogenated petroleum resin |
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