CN109704907A - It raffinates oil the method for preparing hexane - Google Patents
It raffinates oil the method for preparing hexane Download PDFInfo
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Abstract
The present invention relates to a kind of methods raffinated oil and prepare hexane, Aromatic raffinate F passes through first rectifying column, it obtains from first rectifying column top containing C5 and following components stream I, side line position is obtained containing isohexane, n-hexane, the stream I I of methyl cyclopentane and benzene, it feeds following position and obtains C7 and the above component streams III containing hexamethylene, C6 group lease making trans isomerism reactor in stream I II, it reacts obtained methyl cyclopentane and is recycled back to first rectifying column, the hydrogenated isomerization reactor of stream I I obtains stream I V, the isolated isohexane of stream I V, n-hexane, methyl cyclopentane, hexamethylene, wherein methyl cyclopentane is recycled to isomerization reactor.The present invention efficiently solves the problems, such as that existing Aromatic raffinate comprehensively utilizes that low, n-hexane yield is low, hexamethylene yield is low, hexane component is single, added value of product is low, can be applied in industrial continuous production.
Description
Technical field
The present invention relates to a kind of methods raffinated oil and prepare hexane, especially a kind of to prepare n-hexane, isohexane and hexamethylene
The method of alkane effectively improves the added value of Aromatic raffinate.
Background technique
Raffinating oil is by-product in aromatics production, based on saturated hydrocarbons, contains some olefin, and arene content is low, sulphur, nitrogen and
The magazines content such as heavy metal is extremely low, is suitble to the good solvent naphtha of production and hexane oil of high added value etc..It raffinates oil middle cycloalkane
Content it is very high, mainly have pentamethylene, methyl cyclopentane and hexamethylene etc., cycloalkane can be used as international sale of raffinating oil, chain
Alkane sends cracker outside and makees raw material, substantially increases the surcharge raffinated oil in this way.
Hexamethylene is important basic organic chemical industry raw material and organic solvent.Domestic existing hexamethylene and its derived product are all
It is the production of benzene hydrogenation method, at high cost, production capacity is small.High-purity hexamethylene is obtained with huge from oil field light hydrocarbon extracting rectifying
Potential and wide prospect.External hexamethylene is primarily used to manufacture nylon-6 and nylon -66.N-hexane is a kind of colourless
Prescribed liquid is industrial widely used one of hydrocarbon solvent, and most representative nonpolar solvent.N-hexane is organic
Solvent has good stickiness, is usually used in rubber food, pharmacy, perfume, shoemaking, adhesive tape, ball processed, grinding, leather, weaving, family
Tool, paint industry be to dilute or be cleaning solvent or be viscose.Isohexane have it is nontoxic, without sulfur-bearing, without aromatic hydrocarbons, dissolution
Property good, good security, to ozone layer without destroy, the spy strong, easily dry to metal, plastics, glass, the corrosion-free, penetration of ceramics
Point.Raising with country to environmental requirement is eliminated ODS cleaning agent primarily as low boiling point hydrocarbon solvent, is widely used in
Cleaning industry.
Alkane hydroisomerization is one of important reaction of petroleum refining process, be mainly used in production high-grade fuel oil and
Top-grade lubricating oil.Wherein, the hydroisomerization of light paraffins can produce high-octane gasoline blending component, and long chain alkane
Hydroisomerization is mainly used for improving the low temperature fluidity of intermediate oil (jet fuel and diesel oil) and lubricating oil.Catalysis
Agent plays the role of a nucleus in hygrogenating isomerization reaction, and hydroisomerisation catalysts are bifunctional catalysts, has both had plus hydrogen-is de-
Hydrogen activity has acid activity again.Such catalyst not only requires hydrogenation activity, and has isomerization activity.Acid carrier
There must be following several respects: increase the effective surface area of catalyst；Suitable pore structure is provided；It provides in acidity
The heart；Improve the mechanical strength of catalyst；Improve the thermal stability of catalyst；Increase the poison resistance of catalyst；Save metal group
The dosage divided, reduces cost.The application of molecular sieve has pushed the development of hydroisomerisation catalysts and mechanism study.According to classics
Difunctional mechanism, by adjust amorphous bifunctional catalyst metal and it is acid it is strong and weak match, it can be regulated and controled to adding hydrogen
The selectivity of isomerization reaction.
104718179 A of CN discloses methyl cyclopentane and benzene prepares the new method of hexamethylene, which is to utilize raw material
The hydrocarbon mixture of methyl cyclopentane (MCP) and benzene first pass around step of hydrogenation for benzene and are converted into hexamethylene, then acidity from
It is isomerizated into the presence of sub- liquid as hexamethylene, purpose product is hexamethylene.
201999872 U of CN discloses a kind of device of preparing hexane by refining raffinate oil.The utility model discloses one kind
The device of preparing hexane by refining raffinate oil, including lightness-removing column, hexane tower and hydrogenator are connected on the lightness-removing column de- light
Tower feed pump is connected with lightness-removing column preheater between the lightness-removing column feed pump and the lightness-removing column；The tower of the hexane tower
Kettle is connected by hexane tower reactor liquid pump with the lightness-removing column preheater.The utility model raffinates oil by using oil refining and carries out rectifying
Method carry out the preparation of hexane, now separated by lightness-removing column and hexane tower two-tower rectification, hexane tower bottoms is extracted in back end hydrogenation purification out
Device has reasonably been coupled using the discharging heat preheating material of hexane tower tower reactor as the heat transfer medium of lightness-removing column preheater
Energy, reduce the scale of device, reduce the energy consumption of device.
105143410 A of CN discloses a kind of hydroisomerisation catalysts based on the molecular sieve containing FE.By it is renewable Lai
The hydroisomerization for the paraffinic feedstock that source obtains by making charging by the inclusion of crystalline metallosilicate molecule in the presence of hydrogen
The hydroisomerisation catalysts of sieve effectively realize, a part packet of crystalline framework in the crystalline metallosilicate molecular sieve
Iron content.
1432550 A of CN discloses a kind of method of the hygrogenating isomerization reaction of linear paraffin, including by one kind containing straight
The raw material and hydrogen of alkane contact under hydroisomerizing reaction condition with a kind of hydroisomerization catalyst, and device is characterized in that described
Contain 5~10000ppm in raw material, preferably the compound of the element containing strong electronegativity of 10~4000ppm is as reaction promoter.It adopts
When carrying out hygrogenating isomerization reaction with the inventive method, available higher reaction equilibrium conversion and preferable isoparaffin
Selectivity.
103588603 A of CN discloses a kind of process using reforming raffinate oil production n-hexane；It raffinates oil de-
Low-boiling light five component of mixing carbon is distillated by five column overhead of decarburization after pretreatment in light dydrocarbon tower, six carbon seven of mixing carbon of tower bottom
Component enters seven tower of decarburization；Mixing seven component of carbon is discharged by tower bottom after seven groups of seven tower of the lease making decarburization processing of mixing six carbon of carbon, is not divided
From mixed component six knockout tower of carbon is entered by tower top；Overhead is mixing six component of carbon after the processing of six knockout tower of carbon,
Tower bottom mixture enters extractive distillation column；Extraction and separation overhead fraction is the n-hexane of high-purity, and the mixture of tower bottom enters molten
Agent recovery tower；Solvent recovery tower overhead is methyl cyclopentane, and tower bottom is extractant, is recycled；Present method solves
The problem of complex utilization of the reforming raffinate oil of oil plant, the deep processing for improving oil product is horizontal, the concentration of normal hexane product,
Reach 95% or more, while having recycled mixing light dydrocarbon, mixing carbon six and mixing seven component of carbon.
The present invention is to utilize raw material of raffinating oil, through first rectifying column, hydroisomerization unit and product separative unit, finally
Product isohexane, n-hexane and hexamethylene are obtained, and by first rectifying column kettle liquid trans isomerism, again by the hexamethylene in raw material
It is converted into methyl cyclopentane circulating involuting system, effectively prevents the loss of raw material Aromatic raffinate cyclohexane, aromatic hydrocarbons is improved and takes out
The comprehensive utilization ratio of excess oil.
Summary of the invention
Problem to be solved by this invention be it is existing raffinate oil comprehensively utilize low, n-hexane yield is low, hexamethylene yield is low,
The problem that hexane component is single, added value of product is low proposes a kind of new method for preparing hexane of raffinating oil, and this method is for taking out
Excess oil produces hexane, especially production n-hexane, isohexane and when hexamethylene, have Aromatic raffinate comprehensive utilization it is high, just oneself
The advantages that alkane high income, hexamethylene high income, hexane component are various, added value of product is high.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows, a method of it raffinates oil and prepares hexane,
The following steps are included:
(1) it raffinates oil by first rectifying column, the isolated C5 of tower top and following components stream I, side line position are contained
Isohexane, n-hexane, methyl cyclopentane and benzene stream I I, feed following position and obtain C7 and the above component object containing hexamethylene
Flow III；
(2) the above-mentioned hydrogenated isomerization reactor of stream I I obtains stream I V；
(3) the isolated isohexane of above-mentioned stream I V, n-hexane, methyl cyclopentane, hexamethylene.
In above-mentioned technical proposal, it is preferred that in step (1) raw material raffinate oil in containing C5 and following components, preferably on a small quantity
C5 and following components.
In above-mentioned technical proposal, it is preferred that also contain C6 component in the isolated component of step (1) tower top；Preferably
A small amount of C6 component.
In above-mentioned technical proposal, it is preferred that also contain C6 component in the component obtained below step (1) feed entrance point；It is excellent
It is selected as a small amount of C6 component.
In above-mentioned technical proposal, it is preferred that C6 component main component is hexamethylene.
Since raw material is raffinated oil, middle component multiplicity is complicated, and there are a variety of azeotropic mixtures, especially hexamethylene and dimethyl pentane
(DMP) etc. there are azeotropisms for multiple components, therefore in first rectifying column, have lost the hexamethylene in raw material Aromatic raffinate
Alkane makes most of hexamethylene enter anti-isomerization unit from first rectifying column kettle, to reduce two in first rectifying column side-stream
The concentration of the azeotropic such as methylpentane (DMP) composition avoids the purity for influencing product hexamethylene.Simultaneously as benzene and n-hexane are total
Boiling, a part of benzene is from Second distillation column overhead extraction.Raw material raffinate oil in common azeotropic mixture enumerate such as table 1:
Table 1
| Azeotropic mixture | Azeotropic point (DEG C) |
| Hexamethylene and 2,2- dimethyl pentane | 78.9 |
| Hexamethylene and 2,4- dimethyl pentane | 80.29 |
| Hexamethylene and 2,2,3- triptane | 80.23 |
| N-hexane and benzene | 68.93 |
In above-mentioned technical proposal, it is preferred that C6 group lease making trans isomerism reactor, the methyl cyclopentane circulation reacted
Return first rectifying column.It is furthermore preferred that stream I II first passes through the mixture M 1 that de- heavy distillation column isolates the hexamethylene containing high concentration,
Mixture M 1 is entered back into after hexamethylene is converted methyl cyclopentane by trans isomerism unit and is recycled in first rectifying column, anteiso- structure
Changing reaction pressure is preferably 0.0~0.35MPag, and temperature is preferably 50~115 DEG C；The operating pressure of weight-removing column be 0.0~
0.4MPag, more preferably 0.0~0.25MPag.
In above-mentioned technical proposal, it is preferred that the mass concentration of isohexane is not less than the mass concentration of n-hexane in stream I I.
In isomerization reaction, isohexane and n-hexane also deposit balance reversible reaction.It therefore is raising product n-hexane
Yield, during first rectifying column and Second distillation column are cut, preferably the mass concentration of isohexane is not less than n-hexane
Mass concentration reduces the conversion of n-hexane.
In above-mentioned technical proposal, it is preferred that benzene and unsaturated hydrocarbons are removed in step (3) hydroisomerization reactor, by benzene
And other unsaturated hydrocarbons are converted into hexamethylene and saturated hydrocarbons, and convert hexamethylene for methyl cyclopentane.Hygrogenating isomerization reaction
The pressure of the pressure hydrogenator of device is preferably 0.3~4MPag, more preferably 1.5MPag~2.5MPag, and temperature is preferably
60~450 DEG C, more preferably 100~300 DEG C.
In above-mentioned technical proposal, it is preferred that step (3) methyl cyclopentane is recycled back to hydroisomerization reactor.
In above-mentioned technical proposal, it is preferred that step (3) is not less than 90% isohexane by isolated mass concentration,
And/or n-hexane of the mass concentration not less than 60% and/or mass concentration are not less than 99% hexamethylene, it is preferred that isolated
Mass concentration is not low not less than 80% n-hexane and/or mass concentration not less than 99% isohexane and/or mass concentration
In 99.9% hexamethylene.
In the above technical solution, it is preferred that isohexane, n-hexane, methyl cyclopentane and hexamethylene are respectively from isohexane
Off-take point the extraction more than feed entrance point of tower, n-hexane tower, methyl cyclopentane tower and hexamethylene tower；It is furthermore preferred that isohexane
Tower and n-hexane tower use divided wall column, and isohexane is from divided wall column overhead extraction, and n-hexane is from divided wall column side take-off, ring containing methyl
The mixture of pentane, hexamethylene enters methyl cyclopentane tower from the extraction of divided wall column tower reactor.
Since product isohexane and n-hexane separation accuracy are of less demanding, isohexane is methylpentane containing 2-, 3- methylpent
The mixture of alkane, n-hexane is the mixture of mass concentration > 60%, using divided wall column, while reaching product requirement, can be had
Effect reduces energy consumption.
In the above technical solution, it is preferred that first rectifying column, isohexane tower, n-hexane tower, methyl cyclopentane tower and ring
The operating pressure of hexane tower is 0.0~0.8MPag, more preferably 0.0~0.3MPag；The operating pressure of divided wall column be 0.0~
0.35MPag,.
The present invention raffinates oil raw material through first rectifying column by the cutting of C5 and C7 component and to key component isohexane,
The concentration of n-hexane, methyl cyclopentane and hexamethylene controls, and benzene is converted hexamethylene, and methyl ring by hydrogenated isomerization unit
Conversion of pentane is hexamethylene, isohexane and n-hexane equilibrium conversion, eventually by the isolated isohexane of rectifying, n-hexane and ring
Hexane product, and by first rectifying column kettle liquid cyclohexane trans isomerism, the hexamethylene in raw material is then converted to methyl ring penta
Alkane recycles, and effectively prevents the loss of raw material Aromatic raffinate cyclohexane, other materials can still act as cracking and
Reformer feed greatly improves the added value of Aromatic raffinate, can operate in industrialized production.
The present invention will be further described below by way of examples, but these embodiments are not anyway to this hair
Bright range is construed as limiting.
Detailed description of the invention
Fig. 1 is that a kind of raffinate oil prepares the process flow diagram of hexane.Containing isohexane, n-hexane, methyl cyclopentane, hexamethylene
The Aromatic raffinate F of alkane and benzene enters first rectifying column, obtains from first rectifying column top containing C5 and following components stream I, side line
Position obtains the stream I I containing isohexane, n-hexane, methyl cyclopentane and benzene, feed following position obtain C7 containing hexamethylene and
The hydrogenated isomerization reactor of the above component streams III, stream I I obtains stream I V, and stream I V is isolated to isohexane, just
Hexane, methyl cyclopentane, hexamethylene, wherein methyl cyclopentane is recycled to isomerization reactor.
As shown in figure 1, F is Aromatic raffinate raw material, and I is the mixture of component containing C5 and a small amount of C6 component, and II is containing different
The mixture of hexane, n-hexane, methyl cyclopentane and benzene, IV are the reaction product after II hydroisomerization, and III is containing hexamethylene
Boiling point is more than or equal to the mixture of hexamethylene under alkane, DMP and normal pressure.1 is first rectifying column, and 2 be hydroisomerization unit, and 3 are
Separative unit.
Fig. 2 is hydroisomerised product stream I V by 4 rectifying columns from feeding the above position successively isolated dissident
Alkane, n-hexane, methyl cyclopentane and hexamethylene.
In Fig. 2, IV is the reaction product after hydroisomerization, and S1 is isohexane, and S2 is n-hexane, and S3 is methyl ring penta
Alkane, S4 are hexamethylene, and S5 is the mixture that boiling point is more than or equal to hexamethylene under normal pressure.7 be isohexane tower, 8 be n-hexane tower, 9
It is hexamethylene tower for methyl cyclopentane tower, 10.
Fig. 3 is that hydroisomerised product stream I V first passes through divided wall column respectively, obtains isohexane, side line position from tower top position
It sets to obtain n-hexane, divided wall column tower bottoms enters methyl cyclopentane tower, and it is isolated to feed the above position from methyl cyclopentane tower
Methyl cyclopentane, the tower bottoms of methyl cyclopentane tower enter hexamethylene tower, feed the above isolated ring in position from hexamethylene tower
Hexane.
In Fig. 3, IV is the reaction product after hydroisomerization, and S6 is isohexane, and S7 is n-hexane, and S8 is methyl ring penta
Alkane, S9 are hexamethylene, and S10 is the mixture that boiling point is more than or equal to hexamethylene under normal pressure；11 be divided wall column, and 12 be methyl cyclopentane
Tower, 13 be hexamethylene tower.
Fig. 4 is that first rectifying column tower bottoms stream I II first passes through weight-removing column, and it is isolated to feed the above position from weight-removing column
Mixture containing hexamethylene enters trans isomerism reaction member, and in trans isomerism reaction member, hexamethylene is converted into methyl ring
Pentane, trans isomerism reaction product will be back to first rectifying column.
In Fig. 4, III is the mixture for being more than or equal to hexamethylene containing boiling point under hexamethylene, DMP and normal pressure, and M1 is containing ring
The mixture of hexane, M2 are the mixture containing hexamethylene and methyl cyclopentane, and M3 is that boiling point is more than or equal to hexamethylene under normal pressure
Mixture；14 be weight-removing column, and 15 be trans isomerism reaction member.
Specific embodiment
[embodiment 1]
The method that a kind of Aromatic raffinate as shown in Figure 1 prepares hexane.0.5wt%C5 and following components will be contained,
15wt% isohexane, 15wt% n-hexane, the F warp of raffinating oil of 20wt% methyl cyclopentane, 20wt% hexamethylene and 0.2wt% benzene
First rectifying column is crossed, is obtained from first rectifying column top containing C5 and following components stream I, side line position obtains containing isohexane, just oneself
The stream I I of alkane, methyl cyclopentane and benzene feeds following position and obtains C7 and the above component streams III containing hexamethylene, logistics
C6 group lease making trans isomerism reactor in III, the methyl cyclopentane reacted are recycled back to first rectifying column, and stream I I is hydrogenated
Isomerization reactor obtains stream I V, the isolated isohexane of stream I V, n-hexane, methyl cyclopentane, hexamethylene, such as Fig. 2 institute
Show, wherein methyl cyclopentane is recycled to isomerization reactor.
First rectifying column, isohexane tower, n-hexane tower, methyl cyclopentane tower, hexamethylene tower operating pressure is atmospheric tower.
The operating pressure of hydroisomerization reactor is 2.5MPag, and reaction temperature is 320 DEG C, benzene conversion ratio > 99.5%,
Methyl cyclopentane conversion ratio > 60%, selectivity > 99% of hexamethylene.
Purity > 98.5wt% of obtained product isohexane, purity > 70wt% of product n-hexane, product hexamethylene
Purity>99.9wt%, wherein methyl cyclopentane mass concentration<150ppm, reaches the standard of high-class product；
[embodiment 2]
Embodiment is similar to Example 1.To contain 0.5wt%C5 and following components, 15wt% isohexane, 15wt% just oneself
Alkane, the F that raffinates oil of 20wt% methyl cyclopentane, 20wt% hexamethylene and 0.2wt% benzene is by first rectifying column, from the first rectifying
Tower top is obtained containing C5 and following components stream I, and side line position obtains the logistics containing isohexane, n-hexane, methyl cyclopentane and benzene
II, it is anti-that the following position of charging obtains C6 group lease making trans isomerism in C7 and the above component streams III, stream I II containing hexamethylene
Device is answered, the methyl cyclopentane reacted is recycled back to first rectifying column, and the hydrogenated isomerization reactor of stream I I obtains stream I V,
The isolated isohexane of stream I V, n-hexane, methyl cyclopentane, hexamethylene, as shown in Fig. 2, wherein methyl cyclopentane is recycled to
Isomerization reactor.
Except that the change of operating parameter:
N-hexane tower, methyl cyclopentane tower, hexamethylene tower operating pressure is atmospheric tower；
First rectifying column and isohexane tower operating pressure are 0.26MPag；
The operating pressure of hydroisomerization reactor is 3.8MPag, and reaction temperature is 320 DEG C, benzene conversion ratio > 99%, first
Cyclopentane conversion ratio > 65%, selectivity > 99.2% of hexamethylene.
Purity > 92.5wt% of product isohexane, purity > 65wt% of product n-hexane, the purity of product hexamethylene >
99wt%.
[embodiment 3]
Embodiment is similar to Example 1.To contain 10wt%C5 and following components, 15wt% isohexane, 15wt% just oneself
Alkane, the F that raffinates oil of 20wt% methyl cyclopentane, 20wt% hexamethylene and 0.03wt% benzene is by first rectifying column, from the first essence
It evaporates tower top to obtain containing C5 and following components stream I, side line position obtains the object containing isohexane, n-hexane, methyl cyclopentane and benzene
II is flowed, following position is fed and obtains C6 group lease making trans isomerism in C7 and the above component streams III, stream I II containing hexamethylene
Reactor, the methyl cyclopentane reacted are recycled back to first rectifying column, and the hydrogenated isomerization reactor of stream I I obtains logistics
The isolated isohexane of IV, stream I V, n-hexane, methyl cyclopentane, hexamethylene, as shown in Fig. 2, wherein methyl cyclopentane recycles
To isomerization reactor.
Except that the change of operating parameter:
First rectifying column, isohexane tower, n-hexane tower operating pressure is atmospheric tower；
The operating pressure of methyl cyclopentane tower and hexamethylene tower is 0.31MPag；
The operating pressure of hydroisomerization reactor is 1.4MPag, and reaction temperature is 130 DEG C, benzene conversion ratio > 98%, first
Cyclopentane conversion ratio > 52%, selectivity > 99.5% of hexamethylene.
Purity > 93wt% of product isohexane, purity > 60wt% of product n-hexane, the purity of product hexamethylene >
99.5wt%.
[embodiment 4]
Embodiment is similar to Example 1.To contain 0.5wt%C5 and following components, 15wt% isohexane, 15wt% just oneself
Alkane, the F that raffinates oil of 20wt% methyl cyclopentane, 20wt% hexamethylene and 0.2wt% benzene is by first rectifying column, from the first rectifying
Tower top is obtained containing C5 and following components stream I, and side line position obtains the logistics containing isohexane, n-hexane, methyl cyclopentane and benzene
II, it is anti-that the following position of charging obtains C6 group lease making trans isomerism in C7 and the above component streams III, stream I II containing hexamethylene
Device is answered, the methyl cyclopentane reacted is recycled back to first rectifying column, and the hydrogenated isomerization reactor of stream I I obtains stream I V,
The isolated isohexane of stream I V, n-hexane, methyl cyclopentane, hexamethylene, as shown in Fig. 2, wherein methyl cyclopentane is recycled to
Isomerization reactor.
Except that the change of operating parameter:
First rectifying column, isohexane tower, methyl cyclopentane tower, hexamethylene tower operating pressure is atmospheric tower；
N-hexane tower operating pressure is 0.36MPag；
The operating pressure of hydroisomerization reactor is 0.2MPag, and reaction temperature is 100 DEG C, benzene conversion ratio > 98%, first
Cyclopentane conversion ratio > 45%, selectivity > 99% of hexamethylene.
Purity > 95wt% of product isohexane, purity > 65wt% of product n-hexane, the purity of product hexamethylene >
99.5wt%.
[embodiment 5]
Embodiment is similar to Example 1.To contain 0.5wt%C5 and following components, 15wt% isohexane, 15wt% just oneself
Alkane, the F that raffinates oil of 20wt% methyl cyclopentane, 20wt% hexamethylene and 0.2wt% benzene is by first rectifying column, from the first rectifying
Tower top is obtained containing C5 and following components stream I, and side line position obtains the logistics containing isohexane, n-hexane, methyl cyclopentane and benzene
II, it is anti-that the following position of charging obtains C6 group lease making trans isomerism in C7 and the above component streams III, stream I II containing hexamethylene
Device is answered, the methyl cyclopentane reacted is recycled back to first rectifying column, and the hydrogenated isomerization reactor of stream I I obtains stream I V,
The isolated isohexane of stream I V, n-hexane, methyl cyclopentane, hexamethylene, wherein methyl cyclopentane is recycled to isomerization reaction
Device.
Except that isohexane tower and n-hexane tower are replaced using a divided wall column as shown in figure 3, divided wall column behaviour
Making pressure is 0.06MPag, and other operating parameters are constant.
First rectifying column, methyl cyclopentane tower, hexamethylene tower operating pressure is atmospheric tower.
The operating pressure of hydroisomerization reactor is 2.5MPag, and reaction temperature is 320 DEG C, benzene conversion ratio > 99.5%,
Methyl cyclopentane conversion ratio > 60%, selectivity > 99% of hexamethylene.
Purity > 98.5wt% of obtained product isohexane, purity > 70wt% of product n-hexane, product hexamethylene
Purity>99.9wt%, wherein methyl cyclopentane mass concentration<150ppm, reaches the standard of high-class product；
After divided wall column, compared to two towers of isohexane tower and n-hexane are used in embodiment 1, energy consumption saves about 17%.
[embodiment 6]
Embodiment is similar to Example 1.To contain 0.5wt%C5 and following components, 15wt% isohexane, 15wt% just oneself
Alkane, the F that raffinates oil of 20wt% methyl cyclopentane, 20wt% hexamethylene and 0.2wt% benzene is by first rectifying column, from the first rectifying
Tower top is obtained containing C5 and following components stream I, and side line position obtains the logistics containing isohexane, n-hexane, methyl cyclopentane and benzene
II, it is anti-that the following position of charging obtains C6 group lease making trans isomerism in C7 and the above component streams III, stream I II containing hexamethylene
Device is answered, the methyl cyclopentane reacted is recycled back to first rectifying column, and the hydrogenated isomerization reactor of stream I I obtains stream I V,
The isolated isohexane of stream I V, n-hexane, methyl cyclopentane, hexamethylene, wherein methyl cyclopentane is recycled to isomerization reaction
Device.
Except that isohexane tower and n-hexane tower are replaced using a divided wall column as shown in figure 3, divided wall column behaviour
Making pressure is 0.29MPag, and other operating parameters are constant.
First rectifying column, methyl cyclopentane tower, hexamethylene tower operating pressure is atmospheric tower.
The operating pressure of hydroisomerization reactor is 2.5MPag, and reaction temperature is 320 DEG C, benzene conversion ratio > 99.5%,
Methyl cyclopentane conversion ratio > 60%, selectivity > 99% of hexamethylene.
Purity > 98.5wt% of obtained product isohexane, purity > 70wt% of product n-hexane, product hexamethylene
Purity>99.9wt%, wherein methyl cyclopentane mass concentration<150ppm, reaches the standard of high-class product；
After divided wall column, compared to two towers of isohexane tower and n-hexane are used in embodiment 1, energy consumption saves about 15%.
[embodiment 7]
It will contain 0.5wt%C5 and following components, 10wt% isohexane, 15wt% n-hexane, 20wt% methyl cyclopentane,
The F that raffinates oil of 20wt% hexamethylene and 0.2wt% benzene is obtained from first rectifying column top containing C5 and with the following group by first rectifying column
Divide stream I, side line position obtains the stream I I containing isohexane, n-hexane, methyl cyclopentane and benzene, feeds following position and is contained
C6 group lease making trans isomerism reactor in the C7 of hexamethylene and the above component streams III, stream I II, the methyl ring reacted
Pentane is recycled back to first rectifying column, and the hydrogenated isomerization reactor of stream I I obtains stream I V, the isolated isohexane of stream I V,
N-hexane, methyl cyclopentane, hexamethylene, as shown in Fig. 2, wherein methyl cyclopentane is recycled to isomerization reactor.
Operating parameter is same as Example 1.
First rectifying column, isohexane tower, n-hexane tower, methyl cyclopentane tower, hexamethylene tower operating pressure is atmospheric tower.
The operating pressure of hydroisomerization reactor is 2.5MPag, and reaction temperature is 320 DEG C, benzene conversion ratio > 99.5%,
Methyl cyclopentane conversion ratio > 60%, selectivity > 99% of hexamethylene.
Purity > 98.5wt% of obtained product isohexane, purity > 70wt% of product n-hexane, product hexamethylene
Purity>99.9wt%, wherein methyl cyclopentane mass concentration<150ppm, reaches the standard of high-class product；
Compared to embodiment 1, normal hexane product yield reduces 17%.
[embodiment 8]
It will contain 0.5wt%C5 and following components, 12wt% isohexane, 18wt% n-hexane, 20wt% methyl cyclopentane,
The F that raffinates oil of 20wt% hexamethylene and 0.2wt% benzene is obtained from first rectifying column top containing C5 and with the following group by first rectifying column
Divide stream I, side line position obtains the stream I I containing isohexane, n-hexane, methyl cyclopentane and benzene, feeds following position and is contained
C6 group lease making trans isomerism reactor in the C7 of hexamethylene and the above component streams III, stream I II, the methyl ring reacted
Pentane is recycled back to first rectifying column, and the hydrogenated isomerization reactor of stream I I obtains stream I V, the isolated isohexane of stream I V,
N-hexane, methyl cyclopentane, hexamethylene, as shown in Fig. 2, wherein methyl cyclopentane is recycled to isomerization reactor.
Operating parameter is same as Example 1.
First rectifying column, isohexane tower, n-hexane tower, methyl cyclopentane tower, hexamethylene tower operating pressure is atmospheric tower.
The operating pressure of hydroisomerization reactor is 2.5MPag, and reaction temperature is 320 DEG C, benzene conversion ratio > 99.5%,
Methyl cyclopentane conversion ratio > 60%, selectivity > 99% of hexamethylene.
Purity > 98.5wt% of obtained product isohexane, purity > 70wt% of product n-hexane, product hexamethylene
Purity>99.9wt%, wherein methyl cyclopentane mass concentration<150ppm, reaches the standard of high-class product；
Normal hexane product yield reduces 17%.
[embodiment 9]
It will contain 0.001wt%C5 and following components, 15wt% isohexane, 15wt% n-hexane, 24wt% methyl cyclopentane,
The F that raffinates oil of 20wt% hexamethylene and 0.2wt% benzene is obtained from first rectifying column top containing C5 and with the following group by first rectifying column
Divide stream I, side line position obtains the stream I I containing isohexane, n-hexane, methyl cyclopentane and benzene, feeds following position and is contained
C6 group lease making trans isomerism reactor in the C7 of hexamethylene and the above component streams III, stream I II, the methyl ring reacted
Pentane is recycled back to first rectifying column, and the hydrogenated isomerization reactor of stream I I obtains stream I V, the isolated isohexane of stream I V,
N-hexane, methyl cyclopentane, hexamethylene, as shown in Fig. 2, wherein methyl cyclopentane is recycled to isomerization reactor.
Operating parameter is same as Example 1.
First rectifying column, isohexane tower, n-hexane tower, methyl cyclopentane tower, hexamethylene tower operating pressure is atmospheric tower.
The operating pressure of hydroisomerization reactor is 2.5MPag, and reaction temperature is 320 DEG C, benzene conversion ratio > 99.5%,
Methyl cyclopentane conversion ratio > 60%, selectivity > 99% of hexamethylene.
Purity > 98.5wt% of obtained product isohexane, purity > 70wt% of product n-hexane, product hexamethylene
Purity>99.9wt%, wherein methyl cyclopentane mass concentration<150ppm, reaches the standard of high-class product；
Compared to embodiment 1, cyclohexane product yield increases by 20%.
[embodiment 10]
Embodiment is similar to Example 1.To contain 0.5wt%C5 and following components, 15wt% isohexane, 15wt% just oneself
Alkane, the F that raffinates oil of 20wt% methyl cyclopentane, 20wt% hexamethylene and 0.2wt% benzene is by first rectifying column, from the first rectifying
Tower top is obtained containing C5 and following components stream I, and side line position obtains the logistics containing isohexane, n-hexane, methyl cyclopentane and benzene
II, it is anti-that the following position of charging obtains C6 group lease making trans isomerism in C7 and the above component streams III, stream I II containing hexamethylene
Device is answered, the methyl cyclopentane reacted is recycled back to first rectifying column, and the hydrogenated isomerization reactor of stream I I obtains stream I V,
The isolated isohexane of stream I V, n-hexane, methyl cyclopentane, hexamethylene, as shown in Fig. 2, wherein methyl cyclopentane is recycled to
Isomerization reactor.
Operating parameter is same as Example 1.
First rectifying column, isohexane tower, n-hexane tower, methyl cyclopentane tower, hexamethylene tower operating pressure is atmospheric tower.
The operating pressure of hydroisomerization reactor is 2.5MPag, and reaction temperature is 320 DEG C, benzene conversion ratio > 99.5%,
Methyl cyclopentane conversion ratio > 60%, selectivity > 99% of hexamethylene.
Except that stream I II first passes through weight-removing column, the mixture M 1 containing hexamethylene is obtained from tower top, then through anteiso- structure
Change, converts methyl cyclopentane for hexamethylene, obtain the logistics M2 containing methyl cyclopentane and hexamethylene, be recycled to the first rectifying
Tower, as shown in Figure 4.
Trans isomerism operation pressure is 0.23MPag, and reaction temperature is 80 DEG C, conversion ratio > 35%, selectivity >
99%；
The operating pressure of weight-removing column is 0.04MPag；
Purity > 98.5wt% of obtained product isohexane, purity > 70wt% of product n-hexane, product hexamethylene
Purity>99.9wt%, wherein methyl cyclopentane mass concentration<150ppm, reaches the standard of high-class product；
Compared with Example 1, cyclohexane product yield increases by 50%.
[embodiment 11]
Embodiment is similar to Example 10.0.5wt%C5 and following components will be contained, 15wt% isohexane, 15wt% is just
Hexane, the F that raffinates oil of 20wt% methyl cyclopentane, 20wt% hexamethylene and 0.2wt% benzene is by first rectifying column, from the first essence
It evaporates tower top to obtain containing C5 and following components stream I, side line position obtains the object containing isohexane, n-hexane, methyl cyclopentane and benzene
II is flowed, following position is fed and obtains C6 group lease making trans isomerism in C7 and the above component streams III, stream I II containing hexamethylene
Reactor, the methyl cyclopentane reacted are recycled back to first rectifying column, and the hydrogenated isomerization reactor of stream I I obtains logistics
The isolated isohexane of IV, stream I V, n-hexane, methyl cyclopentane, hexamethylene, as shown in Fig. 2, wherein methyl cyclopentane recycles
To isomerization reactor.
Operating parameter is same as Example 1.
First rectifying column, isohexane tower, n-hexane tower, methyl cyclopentane tower, hexamethylene tower operating pressure is atmospheric tower.
The operating pressure of hydroisomerization reactor is 2.5MPag, and reaction temperature is 320 DEG C, benzene conversion ratio > 99.5%,
Methyl cyclopentane conversion ratio > 60%, selectivity > 99% of hexamethylene.
Stream I II first passes through weight-removing column, the mixture M 1 containing hexamethylene is obtained from tower top, then through trans isomerism, by hexamethylene
Alkane is converted into methyl cyclopentane, obtains the logistics M2 containing methyl cyclopentane and hexamethylene, is recycled to first rectifying column, such as Fig. 4 institute
Show.
The difference is that the operating parameter of trans isomerism reaction and weight-removing column changes:
Trans isomerism operation pressure is 0.02MPag, and reaction temperature is 50 DEG C, conversion ratio > 20%, selectivity >
99%；
The operating pressure of weight-removing column is 0.27MPag；
Purity > 98.5wt% of obtained product isohexane, purity > 70wt% of product n-hexane, product hexamethylene
Purity>99.9wt%, wherein methyl cyclopentane mass concentration<150ppm, reaches the standard of high-class product；
Compared with Example 1, cyclohexane product yield increases by 46%.
[embodiment 12]
Embodiment is similar to Example 10.0.5wt%C5 and following components will be contained, 15wt% isohexane, 15wt% is just
Hexane, the F that raffinates oil of 20wt% methyl cyclopentane, 20wt% hexamethylene and 0.2wt% benzene is by first rectifying column, from the first essence
It evaporates tower top to obtain containing C5 and following components stream I, side line position obtains the object containing isohexane, n-hexane, methyl cyclopentane and benzene
II is flowed, following position is fed and obtains C6 group lease making trans isomerism in C7 and the above component streams III, stream I II containing hexamethylene
Reactor, the methyl cyclopentane reacted are recycled back to first rectifying column, and the hydrogenated isomerization reactor of stream I I obtains logistics
The isolated isohexane of IV, stream I V, n-hexane, methyl cyclopentane, hexamethylene, as shown in Fig. 2, wherein methyl cyclopentane recycles
To isomerization reactor.
Operating parameter is same as Example 1.
First rectifying column, isohexane tower, n-hexane tower, methyl cyclopentane tower, hexamethylene tower operating pressure is atmospheric tower.
The operating pressure of hydroisomerization reactor is 2.5MPag, and reaction temperature is 320 DEG C, benzene conversion ratio > 99.5%,
Methyl cyclopentane conversion ratio > 60%, selectivity > 99% of hexamethylene.
Stream I II first passes through weight-removing column, the mixture M 1 containing hexamethylene is obtained from tower top, then through trans isomerism, by hexamethylene
Alkane is converted into methyl cyclopentane, obtains the logistics M2 containing methyl cyclopentane and hexamethylene, is recycled to first rectifying column, such as Fig. 4 institute
Show.
The difference is that the operating parameter of trans isomerism reaction and weight-removing column changes:
Trans isomerism operation pressure is 0.17MPag, and reaction temperature is 96 DEG C, conversion ratio > 35%, selectivity >
99.5%；The operating pressure of weight-removing column is 0.11MPag；
Purity > 98.5wt% of obtained product isohexane, purity > 70wt% of product n-hexane, product hexamethylene
Purity>99.9wt%, wherein methyl cyclopentane mass concentration<150ppm, reaches the standard of high-class product；
Unlike, cyclohexane product yield increases by 48%.
Claims (10)
1. a kind of method for preparing hexane of raffinating oil, comprising the following steps:
(1) it raffinates oil by first rectifying column, the isolated C5 of tower top and following components stream I, side line position is obtained containing dissident
Alkane, n-hexane, methyl cyclopentane and benzene stream I I, feed following position and obtain C7 and the above component streams containing hexamethylene
III；
(2) the above-mentioned hydrogenated isomerization reactor of stream I I obtains stream I V；
(3) the isolated isohexane of above-mentioned stream I V, n-hexane, methyl cyclopentane, hexamethylene.
2. method according to claim 1 that prepare hexane of raffinating oil, it is characterised in that during raw material is raffinated oil in step (1)
Containing C5 and following components, preferably a small amount of C5 and following components.
3. method according to claim 1 that prepare hexane of raffinating oil, it is characterised in that step (1) tower top is isolated
Also contain C6 component in component；Preferably a small amount of C6 component.
4. method according to claim 1 that prepare hexane of raffinating oil, it is characterised in that below step (1) feed entrance point
To component in also contain C6 component；Preferably a small amount of C6 component.
5. method according to claim 4 that prepare hexane of raffinating oil, it is characterised in that the reaction of C6 group lease making trans isomerism
Device, the methyl cyclopentane reacted are recycled back to first rectifying column.
6. method according to claim 1 that prepare hexane of raffinating oil, it is characterised in that the quality of isohexane in stream I I
Concentration is not less than the mass concentration of n-hexane.
7. method according to claim 1 that prepare hexane of raffinating oil, it is characterised in that step (2) hygrogenating isomerization reaction
Benzene and unsaturated hydrocarbons are removed in device.
8. method according to claim 1 that prepare hexane of raffinating oil, it is characterised in that step (2) hygrogenating isomerization reaction
Equilibrium conversion occurs for n-hexane and isohexane in device, and equilibrium conversion occurs for methyl cyclopentane and hexamethylene.
9. method according to claim 1 that prepare hexane of raffinating oil, it is characterised in that step (3) methyl cyclopentane circulation
Return isomerization reactor.
10. method according to claim 1 that prepare hexane of raffinating oil, it is characterised in that step (3) is by isolated
Mass concentration is not low not less than 60% n-hexane and/or mass concentration not less than 90% isohexane and/or mass concentration
In 99% hexamethylene, it is preferred that isohexane of the isolated mass concentration not less than 99% and/or mass concentration are not less than
80% n-hexane and/or mass concentration is not less than 99.9% hexamethylene.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110256190A (en) * | 2019-06-20 | 2019-09-20 | 山东京博石油化工有限公司 | A kind of production method of food-grade n-hexane |
| CN110724023A (en) * | 2019-11-07 | 2020-01-24 | 岳阳金瀚高新技术股份有限公司 | Preparation method of 2-methylpentane, 3-methylpentane and n-hexane |
| CN113736515A (en) * | 2020-05-27 | 2021-12-03 | 中国石油化工股份有限公司 | Method for producing high-octane gasoline components from C5-C6 alkane raw materials |
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