CN1810743A - Method of utilizing cracked, C5 fraction - Google Patents
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Abstract
The method of utilizing cracked C5 fraction includes the first dimerizing cyclopentadiene in the cracked C5 fraction into dicyclopentadiene, separating dicyclopentadiene, selectively hydrogenating diene in the residual material into monoene and directly converting olefine to produce ethylene and propylene. The method may have etherification reaction before or after olefine conversion to produce methyl tert-amyl ether product and high purity isoamylene product further. The method may include a full hydrogenation process to produce pentane, which may be used as cracked material in a main cracking furnace or separated into n-pentane produce and isopentane product. The method is flexible and practical.
Description
Technical field
The present invention relates to a kind of method that fully utilizes cracked, C 5 fraction, specifically, the present invention relates to a kind of method that fully utilizes cracked, C 5 fraction system ethene, propylene.
Background technology
The C 5 fraction of by-product about 15～20% in the petroleum cracking process of producing ethylene.Along with the continuous expansion of ethylene unit, the improving constantly of throughput, the cracked, C 5 fraction of by-product also is on the increase, by nearly 800,000 tons/year of China's cracked, C 5 fraction in 2004.Therefore, how synthetically effectively utilizing this part fraction is current each petroleum and petrochemical industry enterprise question of common concern.And along with dwindling gradually of the benefit room for promotion of ethylene unit, also force each enterprise that sight is turned in the comprehensive utilization of this part fraction, rather than only rest on and do fuel and use.
The component that cracked, C 5 fraction is close by more than 20 kinds of boiling points, easily form azeotrope is to each other formed, its constituent classification is reduced: the content of isoprene, m-pentadiene and cyclopentadiene (dicyclopentadiene) is respectively about 20%, the content difference of side chain monoolefine and straight chain mono-olefins near 15～20%, also contains a spot of alkane, alkene and carbon four thereof, carbon six components greatly.But from cracked, C 5 fraction, isolate the higher C 5 diene of comprehensive utilization value, need take extraction rectifying method, its complex process, facility investment is many, is the approach that people avoid as far as possible.
On the other hand, the demand of propylene increases greatly in the market, the propylene breach occurred, needs to seek the whole bag of tricks and addresses this problem.Wherein at home and abroad a comparatively ardent method of research is the method that olefin metathesis transforms ethene, propylene, and many pieces of patent applications are at home and abroad all arranged at present.But conversion of olefines adopts c4 fraction mostly, seldom adopts cracked, C 5 fraction to do raw material.Analyze its reason and mainly contained two: one, contain a large amount of diolefins in the cracked, C 5 fraction, directly carry out conversion of olefines and can produce burnt matter, cause catalyst deactivation; The 2nd, contain the side chain monoolefine of 10-20% in the cracked, C 5 fraction, this part monoolefine can not be converted into ethene, propylene.
Therefore, need to seek a kind of suitable method cracked, C 5 fraction is converted into the raw material of conversion of olefines, could find an effective means for really fully utilizing cracked, C 5 fraction efficiently.
Summary of the invention
To the objective of the invention is the difficult problem that fully utilizes cracked, C 5 fraction rationally and effectively in order solving, and to find a rational growth point, propose a kind of method that fully utilizes cracked, C 5 fraction for the increasing propylene of present insufficiency of supply-demand.
Concrete, the method for utilizing cracked, C 5 fraction of the present invention may further comprise the steps:
(1) cracked, C 5 fraction raw material a is sent into dipolymer reactor, making cyclopentadiene dimerization wherein is dicyclopentadiene;
(2) material that contains dicyclopentadiene that dipolymer reactor is obtained is sent into and is taken off the dicyclopentadiene tower, and the tower still obtains comprising the material of dicyclopentadiene, and cat head obtains removing the cracked, C 5 fraction b of dicyclopentadiene;
(3) the cracked, C 5 fraction b that step (2) is obtained sends into hydrogenator, in the presence of hydrogenation catalyst and hydrogen, with the diolefin selective hydrogenation that comprises isoprene and m-pentadiene wherein is monoolefine, and the hydrogenation not substantially of monoolefine wherein obtains comprising the carbon five material c of uncle's amylene, 1-amylene, 2-amylene, 3-methyl-monoolefines such as 2-amylene;
(4) described carbon five material c are sent into olefin reactor, in the presence of the conversion of olefines catalyzer, wherein monoolefine is converted into ethene, propylene.
Aforesaid method is the solution of the present invention A.
In a preferred version B of the present invention, after above-mentioned four steps, also comprise: the conversion of olefines product that step (4) is obtained carries out gas-liquid separation, and five components of the carbon in the liquid phase material that obtains are separated, full hydrogenation obtains C 5 alkane in the presence of hydrogenation catalyst.
More preferably, in the solution of the present invention C, described C 5 alkane is separated into Skellysolve A product and iso-pentane product.
In another preferred version D of the present invention, the carbon five material c that described step (3) is obtained send into the etherificate unit earlier, described etherificate unit comprises methyltertiarvbutyl ether reactor and rectifying tower, in the presence of catalyst for etherification and methyl alcohol carry out etherification reaction, rectifying carbon five materials of uncle's amylene that are removed after the etherificate; Again it is sent into the described olefin reactor of step (4).
On the basis of scheme D, more preferably, after above-mentioned step (4) was carried out conversion of olefines, carbon five components in the liquid phase material that separation is obtained were separated, and full hydrogenation obtains the Skellysolve A product in the presence of hydrogenation catalyst.
Also scheme E of the present invention is: the conversion of olefines product that step (4) is obtained carries out gas-liquid separation, isolate ethene, propylene, the liquid phase material of remaining carbon containing five components is sent into the etherificate unit, described etherificate unit comprises methyltertiarvbutyl ether reactor and rectifying tower, in the presence of catalyst for etherification, carry out etherification reaction with methyl alcohol, enter rectifying tower rectifying after the etherificate, cat head obtains tert amyl methyl ether(TAME), and the tower still obtains containing the liquid phase material of C 5 monoolefin.
The liquid phase material that described etherificate unit rectifying Tata still is obtained carries out rectifying, and carbon five components are wherein separated, and is hydrogenated to C 5 alkane in the presence of hydrogenation catalyst entirely.
Above-mentioned etherificate unit comprises methyltertiarvbutyl ether reactor and rectifying tower, wherein,
In the described methyltertiarvbutyl ether reactor, used catalyst for etherification is preferably acidic ion exchange resin, and reaction bed is a fixed bed, and etherification temperature is 40-90 ℃, and etherificate pressure is 0.5-3.0MPa, and the liquid phase volume air speed of carbon five materials in methyltertiarvbutyl ether reactor is 0.4-8h
-1, the uncle's amylene in carbon five materials and the mol ratio of methyl alcohol are 1: 1-1.3;
Preferred described Rectification Column's Theoretical Plate Number is the 20-40 piece, and tower top temperature is 20-80 ℃, and tower top pressure is 0.06-0.5MPa, and tower still temperature is 50-110 ℃, and feed entrance point is at the middle part of tower.
It is preferred in above-mentioned each scheme,
In the step (1), described dimerization reaction temperature is 50-120 ℃, and reaction pressure is 0.3-2.5MPa, and the residence time is 30-120 minute.
In the step (2), the described number of theoretical plate that takes off the dicyclopentadiene tower is the 15-60 piece, and reflux ratio is 0.5-5, tower top pressure is 0.06-0.5MPa, and tower still pressure is 0.08-0.6MPa, and tower top temperature is 20-80 ℃, tower still temperature is 80-130 ℃, and feed entrance point is at the middle part of tower.
The used catalyzer of hydrogenation reaction described in the step (3) is the catalyzer of inorganic carrier nickel-loaded, cobalt and/or palladium, and temperature of reaction is 30-120 ℃, and reaction pressure is 0.1-3.0MPa, and the mol ratio of hydrogen and diolefin is 1-4: 1, and the liquid phase volume air speed is 1-8h
-1
In the step (4), described olefin reaction temperature is 400-600 ℃, and reaction pressure is 0.1-0.4MPa, and the volume ratio of inlet amount and catalyzer is 1-6h
-1, the conversion of olefines catalyzer is a zeolite containing catalyst.
Conversion of olefines catalyzer described in the preferred steps (4) comprises following components in weight percentage: Al
2O
3Or SiO
2For 20-45%, supersiliceous zeolite are 40-70%, modified component is 8-20%.
More preferably, described supersiliceous zeolite is ZRP series or ZSM-5 class zeolite, and described modified component is the oxide compound, alkaline earth metal oxide, rare-earth oxide of molybdenum oxide, Tungsten oxide 99.999, phosphorus or in them two or more.
Below to technical scheme of the present invention explanation in further detail again.
Dimerization reaction described in the step (1) is at prior art comparative maturity, have no particular limits in the present invention, can control and adjust the reaction conditions and the residence time according to the cyclopentadiene content of reactor outlet, make cyclopentadiene content wherein be lower than 3%.
The distillation technology that takes off the dicyclopentadiene tower described in the step (2) is also comparative maturity in the prior art, can reasonably design the number of theoretical plate of tower according to the composition of carbon five materials, adjust operational condition according to the variation of material simultaneously, the cyclopentadiene content that contains in the material that makes cat head steam is lower than 2%, the material that the tower still is extracted out is based on dicyclopentadiene, and this can accomplish for those skilled in the art.Simultaneously at the as much as possible materials that steam of cat head, increasing the raw material of back conversion of olefines, the m-pentadiene content that the tower still is extracted out is low as much as possible or do not contain m-pentadiene substantially more.
Selective hydrogenation described in the step (3) has no particular limits, as long as make that the diolefin selective hydrogenation in the material is a monoolefine, simultaneously to be that the transformation efficiency of alkane is low just can satisfy requirement of the present invention to monoolefin hydrogenation.Isoprene is hydrogenated to 2-methyl-2-butene, 2-methyl-1-butene alkene and 3-methyl-1-butene, and m-pentadiene is hydrogenated to amylene-1 and amylene-2, and alkynes is hydrogenated to alkene.Therefore, employed catalyzer can be the catalyzer of inorganic carrier load base metal or precious metal.Disclosed catalyzer among the Chinese patent CN1178744C (ZL02104202.0) of China Petrochemical Industry Beijing Chemical Research Institute for example.Inorganic carrier can be selected aluminum oxide, silicon oxide, gac, titanium oxide and composite inorganic carrier etc. for use, and base metal can be nickel, cobalt etc., and precious metal can be palladium, rhodium, platinum etc.Catalyzer also can contain base metal and noble metal component simultaneously.Reaction conditions can be adjusted according to the diolefin content of catalyzer, reaction raw materials and reactor outlet.Reaction process can adopt two-stage hydrogenation reaction, single hop hydrogenation reaction, also can adopt circulation technology, and the material behind the hydrogenation is partly turned back to the diolefin content in the diluted material in the material before the hydrogenation, can reduce the temperature rise of reaction bed like this.
The conversion of olefines technology can adopt disclosed technology and catalyzer thereof among the Chinese patent application CN1490287 in the step (4).
In each scheme of the present invention, no matter be not contain the etherificate unit, still contain the etherificate unit after before conversion of olefines, containing etherificate unit or conversion of olefines, last employed catalyzer of full hydrogenation and processing condition are prior art, those skilled in the art just can realize, for example full hydrogenation catalyst can be non-precious metal catalysts such as nickel, cobalt, also can be noble metal catalysts such as palladium, platinum, and processing condition can be selected and adjust according to the industry spot situation.Related rectifying separation condition, those skilled in the art can freely select.
Described etherificate unit can adopt the catalyst etherifying rectifying tower, rectifying in uncle's amylene and methyl alcohol catalyst etherifying, isolate methyl alcohol and tert amyl methyl ether(TAME) at the tower still, steam carbon five materials that remove uncle's amylene, in this material, contain straight chain mono-olefins, 3-methyl-1-butene, alkane at cat head.
Described etherificate unit can comprise methyltertiarvbutyl ether reactor and rectifying tower.Uncle's amylene in methyltertiarvbutyl ether reactor (2-methyl-2-butene and 2-methyl-1-butene alkene) and methyl alcohol reaction generate tert amyl methyl ether(TAME), mixture enters rectifying tower rectifying then, tell the tert amyl methyl ether(TAME) of unreacted methanol and generation at the tower still, steam carbon five materials at cat head.
Employed catalyst for etherification is an acidic ion exchange resin, can oneself prepare, and macroporous ion exchange resin is carried out ion-exchange with sulfuric acid or hydrochloric acid, can use then; Also can on market, buy, for example the disclosed catalyzer of Chinese patent CN1051478C.
The tert amyl methyl ether(TAME) that obtains further cracking prepares highly purified isopentene product.The isopentene product is an important chemical material, can be widely used for industries such as agricultural chemicals, spices, makeup.
The method of comprehensive utilization cracked, C 5 fraction of the present invention has the following advantages:
(1) method of the present invention can obtain the dicyclopentadiene product.The dicyclopentadiene product has good market at home and abroad, is important fine chemicals raw material, and can be used as the raw material of high quality resin.
(2) method of the present invention needs less amounts of hydrogen.The diolefin that the present invention adopts the selective hydrogenation technology will remove in carbon five materials of dicyclopentadiene is hydrogenated to monoolefine, straight chain mono-olefins so wherein can be converted into ethene, propylene in olefin process, compare as cracking stock with full hydrogenation, a large amount of hydrogen have been saved, even and the full hydrogenation of side chain monoolefine, can not be cracked into ethene, propylene.For example propose to remove dicyclopentadiene, selective hydrogenation, etherificate in Chinese patent CN1163457C, complete again hydrogenation is as cracking stock.Utilize the carbon five material cracking of full hydrogenation to prepare ethene, propylene, unlike direct conversion of olefines of the present invention prepare ethene, propylene has more advantage, yet the present invention does not need the step of a lot of hydrogen of these needs, does not carry out full hydrogenation, but directly as the raw material that transforms ethene, propylene.The hydrogen that selective hydrogenation needs in CN1163457C is identical with the hydrogen that the present invention needs, but full hydrogenation also needs the amounts of hydrogen of the selective hydrogenation of about twice, and needing so many hydrogen in fact is worthless in industry.
(3) method of the present invention can be supplied raw materials for conversion of olefines system ethene, propylene.
(4) propylene produced of method of the present invention can relax or solve the insufficiency of supply-demand of propylene in the market, is the project that Petroleum and Petrochemical Industry is badly in need of.
(5) method of the present invention with conversion of olefines after or conversion of olefines again carbon five materials after the etherificate carry out full hydrogenation, generate Skellysolve A and iso-pentane, can be used as cracking stock and send main pyrolyzer cracking ethylene preparation, propylene, also can be separated into Skellysolve A and iso-pentane is sold as product.Skellysolve A and iso-pentane are good solvents, also are important chemical material simultaneously.
(6) the present invention can big freedom in minor affairs select the etherificate unit according to the capital of the market requirement and investment, has very high handiness.
(7) method of the present invention can obtain tert amyl methyl ether(TAME).Tert amyl methyl ether(TAME) can be used as the gasoline blend component, improves the octane value of gasoline.Tert amyl methyl ether(TAME) is the isopentene product of cracking preparing high-purity further.
(8) method of the present invention can provide a rational and effective approach for the economic benefit and the social benefit of comprehensive utilization cracked, C 5 fraction, raising ethylene unit, can make the enterprise that wants to fully utilize cracked, C 5 fraction avoid the complicated approach of extracting and separating C 5 fraction, be fit to large-lot producer, the personal investment that also is fit to simultaneously small business even has risk capital is founded the factory, and instant effect, invest little, product category and composition thereof can freely be selected, the technology of each step is comparative maturity all, method of the present invention industrial be feasible.
Description of drawings
Fig. 1 is the schematic flow sheet of comprehensive utilization cracked, C 5 fraction option A of the present invention.
Fig. 2 is the schematic flow sheet of comprehensive utilization cracked, C 5 fraction option b of the present invention.
Fig. 3 is the schematic flow sheet of comprehensive utilization cracked, C 5 fraction scheme C of the present invention.
Fig. 4 is the schematic flow sheet of comprehensive utilization cracked, C 5 fraction scheme D of the present invention.
Fig. 5 is the schematic flow sheet of comprehensive utilization cracked, C 5 fraction scheme E of the present invention.
Embodiment
Further explain the present invention in conjunction with Figure of description.
In the solution of the present invention A, as shown in Figure 1, mixed pyrolysis C 5 fraction raw material a enters dipolymer reactor 1 and carries out dimerization reaction, and cyclopentadiene dimerization wherein becomes dicyclopentadiene; The material that comes out from dipolymer reactor enters and takes off dicyclopentadiene tower 2 and carry out rectifying, and the tower still is isolated the material based on dicyclopentadiene, and cat head obtains taking off the cracked, C 5 fraction b of dicyclopentadiene; Material b and hydrogen that cat head comes out enter hydrogenator 3, are monoolefine with wherein isoprene and m-pentadiene selective hydrogenation; The carbon five material c based on monoolefine that obtain behind the hydrogenation enter olefin reactor 4 and carry out conversion of olefines, and wherein normal olefine is converted into ethene, propylene.
In the solution of the present invention B, as shown in Figure 2, carbon five components that can be provided with after olefin reactor 4 in the liquid phase material after a rectifying separation tower 5 will transform are separated, and enter full hydrogenator 6 again and carry out full hydrogenation production pentane.
In the solution of the present invention C, as shown in Figure 3, on the basis of option b and then can increase a pentane knockout tower 7 and produce Skellysolve A product and iso-pentane products.
In the solution of the present invention D, as shown in Figure 4, can before olefin reactor 4, increase an etherificate unit, comprise methyltertiarvbutyl ether reactor 8 and rectifying tower 9, in the presence of catalyst for etherification, be tert amyl methyl ether(TAME) with the uncle's amylene etherificate in the material, by rectifying it is separated.Can also carry out full hydrogenation behind the conversion of olefines as option b simultaneously, can direct production Skellysolve A product.
In the solution of the present invention E, as shown in Figure 5, can increase an etherificate unit in olefin reactor 4 backs, comprise methyltertiarvbutyl ether reactor 8 and rectifying tower 9, in the presence of catalyst for etherification, be that tert amyl methyl ether(TAME) is separated with the uncle's amylene etherificate in the material.Simultaneously can also after etherificate, increase a full hydrogenator and carry out full hydrogenation, can direct production Skellysolve A product.
Mode with embodiment further specifies the present invention below.
(1) cracked, C 5 fraction with Yanshan Petrochemical is a raw material, its table 1 composed as follows, the content in the table 1 content that is weight percentage.Above-mentioned material is sent into dipolymer reactor carry out dimerization reaction, the dimerization reaction temperature is 80 ℃, and reaction pressure is 0.5MPa, and the residence time is 60 minutes.
(2) material that dipolymer reactor is come out is sent into and is taken off the dicyclopentadiene tower, and extracting dicyclopentadiene out at the tower still is main material, and cat head steams the cracked, C 5 fraction b that removes dicyclopentadiene; The number of theoretical plate that takes off the dicyclopentadiene tower is 20, and reflux ratio is 1, and tower top pressure is 0.08MPa, and tower still pressure is 0.10MPa, and tower top temperature is 30 ℃, and tower still temperature is 95 ℃, and feed entrance point is on the 10th block of plate of tower.
(3) above-mentioned cracked, C 5 fraction b and hydrogen are sent into hydrogenator together, diolefin selective hydrogenation that will be wherein in the presence of hydrogenation catalyst is a monoolefine, and the hydrogenation not substantially of monoolefine wherein, obtaining monoolefine is main carbon five material c; The catalyzer of embodiment 1 among the Chinese patent ZL02104202.0 of catalyzer use Beijing Chemical Research Institute, temperature of reaction is 80 ℃, and reaction pressure is 1.0MPa, and the mol ratio of hydrogen and diolefin is 2: 1, and the liquid phase volume air speed is 1.5h
-1
(4) carbon five material c are sent into the etherificate unit, in the presence of catalyst for etherification and methyl alcohol carry out etherification reaction, the rectifying carbon five material d of uncle's amylene that are removed after the etherificate;
Used catalyst for etherification is an acidic ion exchange resin, use the disclosed catalyzer of Chinese patent ZL96109509.1, reaction bed is a fixed bed, and etherification temperature is 80 ℃, etherificate pressure is 1.0MPa, and the liquid phase volume air speed of carbon five material c in methyltertiarvbutyl ether reactor is 4h
-1, the uncle's amylene among the carbon five material c and the mol ratio of methyl alcohol are 1: 1.1.
Described Rectification Column's Theoretical Plate Number is 30, and tower top temperature is 40 ℃, and tower top pressure is 0.2MPa, and tower still temperature is 100 ℃, and feed entrance point is at the middle part of tower.
(5) carbon five material d are sent into olefin reactor, in the presence of the conversion of olefines catalyzer, monoolefine wherein is converted into ethene, propylene.
The olefin reaction temperature is 500 ℃, and reaction pressure is 0.2MPa, and the volume ratio of inlet amount and catalyzer is 3h
-1, the conversion of olefines catalyzer is the catalyzer of embodiment 1 among the Chinese patent application CN1490287A of Beijing Chemical Research Institute.With the cracked, C 5 fraction is benchmark, and the yield that is converted into ethene is 11%, and the yield that is converted into propylene is 22%.
Dimerization in the present embodiment, to take off dicyclopentadiene, selective hydrogenation and conversion of olefines identical with embodiment 1, and different is not contain etherification step.In the conversion of olefines step, be benchmark with the cracked, C 5 fraction, the yield that is converted into ethene is 11%, the yield that is converted into propylene is 22%.
Present embodiment is identical with embodiment 1 basically, different be conversion of olefines after, adopt the conventional distillation method full hydrogenation that will carbon five feed separation wherein comes out to carry out again, the catalyzer of embodiment 1 among the Chinese patent ZL02104202.0 of catalyzer use Beijing Chemical Research Institute, temperature of reaction is 60 ℃, reaction pressure is 1.0MPa, and the mol ratio of hydrogen and alkene is 1.5: 1, and the liquid phase volume air speed is 1.0h
-1The Skellysolve A that contains 95 weight % in the material behind the full hydrogenation.
Table 1
| Component | Raw material | The dipolymer reactor outlet | Take off dicyclopentadiene cat head material | Take off dicyclopentadiene tower still material | Material behind the hydrogenation | Etherificate rectifying tower top material |
| Carbon four | 2.1 | 2.1 | 2.8 | 3.2 | 5 | |
| Iso-pentane | 2.1 | 2.1 | 2.8 | 2.8 | 4.4 | |
| 3-methyl butene-1 | 1.24 | 1.24 | 1.6 | 5.1 | 7.9 | |
| Skellysolve A | 1.43 | 1.43 | 1.9 | 1.9 | 3 | |
| Amylene-1 | 7.14 | 7.14 | 9.4 | 19.5 | 30.4 | |
| 2-methyl butene-1 | 6.67 | 6.67 | 8.8 | 18.8 | 0.8 | |
| Anti-amylene-2 | 5.71 | 5.71 | 7.5 | 12.6 | 19.6 | |
| Along amylene-2 | 2.67 | 2.67 | 3.5 | 10.1 | 15.7 | |
| Pentadiene-1,4 | 1.43 | 1.43 | 1.9 | 1.9 | 3 | |
| 2-methyl butene-2 | 2.86 | 2.86 | 3.8 | 16.7 | 0.8 | |
| Pentamethylene | 0.76 | 0.76 | 1 | 1 | 1.6 | |
| Isoprene | 20.48 | 20.48 | 27 | 0.5 | ||
| Cyclopentenes | 3.81 | 3.81 | 5 | 5.1 | 7.9 | |
| Crotonylene | 0.32 | 0.32 | 0.4 | 0 | ||
| Anti-pentadiene-1,3 | 10 | 10 | 13.2 | 0.5 | ||
| Along pentadiene-1,3 | 6.35 | 6.35 | 8.4 | 0.1 | ||
| Cyclopentadiene | 12.13 | 0.13 | 0.2 | 0.1 | ||
| Dicyclopentadiene | 6.7 | 18.7 | 0 | 77.3 | 0 | |
| Pentyne-1 | 0.1 | 0.1 | 0.1 | 0 | ||
| Pentyne-2 | 0.1 | 0.1 | 0.1 | 0 | ||
| Valylene | 0.3 | 0.3 | 0.4 | 0 | ||
| Benzene | 5.6 | 5.6 | 0.1 | 22.7 | 0.1 |
Claims (11)
1. method of utilizing cracked, C 5 fraction, it may further comprise the steps:
(1) cracked, C 5 fraction raw material a is sent into dipolymer reactor, making cyclopentadiene dimerization wherein is dicyclopentadiene;
(2) material that contains dicyclopentadiene that dipolymer reactor is obtained is sent into and is taken off the dicyclopentadiene tower, and the tower still obtains comprising the material of dicyclopentadiene, and cat head obtains removing the cracked, C 5 fraction b of dicyclopentadiene;
(3) the cracked, C 5 fraction b that step (2) is obtained sends into hydrogenator, in the presence of hydrogenation catalyst and hydrogen, with the diolefin selective hydrogenation that comprises isoprene and m-pentadiene wherein is monoolefine, obtains comprising uncle's amylene, 1-amylene, 2-amylene, the 3-methyl-2-amylene carbon five material c at interior monoolefine;
(4) described carbon five material c are sent into olefin reactor, in the presence of the conversion of olefines catalyzer, wherein monoolefine is converted into ethene, propylene.
2. method according to claim 1 is characterized in that, the conversion of olefines product that step (4) is obtained carries out gas-liquid separation, and five components of the carbon in the liquid phase material that obtains are separated, and hydrogenation in the presence of hydrogenation catalyst obtains C 5 alkane.
3. method according to claim 2 is characterized in that, described C 5 alkane is separated into Skellysolve A product and iso-pentane product.
4. method according to claim 1, it is characterized in that, the carbon five material c that described step (3) is obtained send into the etherificate unit earlier, described etherificate unit comprises methyltertiarvbutyl ether reactor and rectifying tower, carry out etherification reaction with methyl alcohol in the presence of catalyst for etherification, rectifying obtains removing carbon five materials of uncle's amylene after the etherificate; Again it is sent into the described olefin reactor of step (4).
5. method according to claim 4 is characterized in that, after described step (4) is carried out conversion of olefines, five components of the carbon in the liquid phase material that obtains is separated, and hydrogenation in the presence of hydrogenation catalyst obtains the Skellysolve A product.
6. method according to claim 1, it is characterized in that, the conversion of olefines product that step (4) is obtained carries out gas-liquid separation, the liquid phase material of carbon containing five components is sent into the etherificate unit, described etherificate unit comprises methyltertiarvbutyl ether reactor and rectifying tower, carries out etherification reaction with methyl alcohol in the presence of catalyst for etherification, enters rectifying tower rectifying after the etherificate, cat head obtains tert amyl methyl ether(TAME), and the tower still obtains containing the liquid phase material of C 5 monoolefin.
7. method according to claim 6 is characterized in that, carbon five components in the liquid phase material that described etherificate unit rectifying Tata still is obtained are separated, and hydrogenation in the presence of hydrogenation catalyst obtains C 5 alkane.
8. according to claim 4 or 6 described methods, it is characterized in that,
In the described methyltertiarvbutyl ether reactor, used catalyst for etherification is an acidic ion exchange resin, and reaction bed is a fixed bed, and etherification temperature is 40-90 ℃, and etherificate pressure is 0.5-3.0MPa, and the liquid phase volume air speed of material in methyltertiarvbutyl ether reactor is 0.4-8h
-1, the uncle's amylene in the material and the mol ratio of methyl alcohol are 1: 1-1.3;
The unitary Rectification Column's Theoretical Plate Number of described etherificate is the 20-40 piece, and tower top temperature is 20-80 ℃, and tower top pressure is 0.06-0.5MPa, and tower still temperature is 50-110 ℃, and feed entrance point is at the middle part of tower.
9. according to the described method of one of claim 1-7, it is characterized in that,
In the step (1), described dimerization reaction temperature is 50-120 ℃, and reaction pressure is 0.3-2.5MPa, and the residence time is 30-120 minute;
In the step (2), the described number of theoretical plate that takes off the dicyclopentadiene tower is the 15-60 piece, and reflux ratio is 0.5-5, tower top pressure is 0.06-0.5MPa, and tower still pressure is 0.08-0.6MPa, and tower top temperature is 20-80 ℃, tower still temperature is 80-130 ℃, and feed entrance point is at the middle part of tower;
In the step (3), the used catalyzer of described hydrogenation reaction is the catalyzer of inorganic carrier nickel-loaded, cobalt and/or palladium, and temperature of reaction is 30-120 ℃, and reaction pressure is 0.1-3.0MPa, the mol ratio of hydrogen and diolefin is 1-4: 1, and the liquid phase volume air speed is 1-8h
-1
In the step (4), described olefin reaction temperature is 400-600 ℃, and reaction pressure is 0.1-0.4MPa, and the volume ratio of inlet amount and catalyzer is 1-6h
-1, the conversion of olefines catalyzer is a zeolite containing catalyst.
10. method according to claim 9 is characterized in that, the conversion of olefines catalyzer described in the step (4) comprises following components in weight percentage: Al
2O
3Or SiO
2For 20-45%, supersiliceous zeolite are 40-70%, modified component is 8-20%.
11. method according to claim 10, it is characterized in that, described supersiliceous zeolite is ZRP series or ZSM-5 class zeolite, and described modified component is the oxide compound, alkaline earth metal oxide, rare-earth oxide of molybdenum oxide, Tungsten oxide 99.999, phosphorus or in them two or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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