CN108033869A - A kind of method using production n-hexane of raffinating oil - Google Patents
A kind of method using production n-hexane of raffinating oil Download PDFInfo
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- CN108033869A CN108033869A CN201711462403.8A CN201711462403A CN108033869A CN 108033869 A CN108033869 A CN 108033869A CN 201711462403 A CN201711462403 A CN 201711462403A CN 108033869 A CN108033869 A CN 108033869A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
Abstract
The present invention provides a kind of method using production n-hexane of raffinating oil, include the following steps：(1) raffinate oil and carry out rectifying in weight tower is cut, six component of light dydrocarbon carbon in raffinating oil is distillated from tower top, and mixing seven carbon eightfold component of carbon is produced from bottom of towe；(2) the preheated rear feeding fixed bed reactors of six component of light dydrocarbon carbon described in step (1), under hydro condition, methyl cyclopentane carries out isomerization reaction or hydrocracking reaction on bifunctional catalyst；(3) reaction product obtained in step (2) is sent to gas-liquid separator, the gas-phase product isolated is back in fixed bed reactors as recycle hydrogen to be recycled, liquid product is sent to stabilizer, and a small amount of hydrogen and a small amount of cracking small molecule lighter hydrocarbons are distillated from tower top after processing.Method of the present invention using production n-hexane of raffinating oil changes into the methyl cyclopentane in raffinating oil differs larger chemical substance with n-hexane boiling point, greatly reduces the energy consumption of purification n-hexane.
Description
Technical field
The invention belongs to reforming raffinate oil recycling field, and production n-hexane of raffinating oil is utilized more particularly, to a kind of
Method.
Background technology
Reforming raffinate oil octane number is relatively low, and general only 60 or so, vehicle fuel oil use is not suitable as, as reconciliation
Oily usage amount is limited.But the impurity contents such as middle sulphur, nitrogen and heavy metal of raffinating oil are extremely low, it is adapted to the good solvent naphtha of production, height attached
Value added hexane oil and isohexane oil etc..But composition of raffinating oil is complicated, usually contains the methyl ring very close with n-hexane boiling point
Pentane.To obtain the n-hexane of high-purity, more theoretical cam curve and larger reflux ratio ability are needed by conventional distil-lation
N-hexane and methyl cyclopentane are separated, whole process energy consumption is very high.The methods for using extracting rectifying at present more, but it is molten
Agent is bigger, and energy consumption is higher.
But the reformed naphtha of the catalytic reforming unit of different refineries remaining PONA that raffinates oil after Aromatics Extractive Project
Race's composition difference is larger, and the content of the methyl cyclopentane in raffinating oil is also change.When methyl cyclopentane content is higher, build
Methyl cyclopentane in raffinating oil by isomerization reaction is converted into benzene and hexamethylene by view, react generation benzene and hexamethylene and
N-hexane has larger relative volatility, and separation is readily achieved by conventional distillation；It is different when methyl cyclopentane content is relatively low
Structure reaction and hydrocracking reaction, preferably hydrocracking reaction, it is small less than C6 that cracking reaction mainly generates C1-C5 etc.
Molecule lighter hydrocarbons, the C1-C5 small molecules lighter hydrocarbons of generation are more easy to realize separation, but the benzene of isomerization reaction generation with respect to isomerization reaction
There is the industrial value of higher with hexamethylene.
Methyl cyclopentane in raffinating oil is changed into and differs larger chemistry with n-hexane boiling point by the present invention by reaction
Material, greatly reduces the energy consumption of purification n-hexane.
The content of the invention
In view of this, the present invention is directed to propose a kind of utilize the method raffinated oil and produce n-hexane, by the first in raffinating oil
Cyclopentane, which is converted into hexamethylene and benzene of the industrial value with respect to higher or generation, the C1- of larger relative volatility with n-hexane
C5 small molecule lighter hydrocarbons, solve the problems, such as the difficult separation of methyl cyclopentane and n-hexane thing system, prepared high added value just oneself
Alkane solvents.
To reach above-mentioned purpose, the technical proposal of the invention is realized in this way：
A kind of method using production n-hexane of raffinating oil, includes the following steps：
(1) raffinate oil and carry out rectifying in weight tower is cut, six component of light dydrocarbon carbon in raffinating oil is distillated from tower top, mixes carbon seven
Carbon eightfold component is produced from bottom of towe；
(2) the preheated rear feeding fixed bed reactors of six component of light dydrocarbon carbon described in step (1), under hydro condition,
Methyl cyclopentane carries out isomerization reaction or hydrocracking reaction on bifunctional catalyst；
(3) reaction product obtained in step (2) is sent to gas-liquid separator, the gas-phase product isolated is as recycle hydrogen
It is back in fixed bed reactors and recycles, liquid product is sent to stabilizer, a small amount of hydrogen and is cracked on a small quantity small after processing
Molecule lighter hydrocarbons are distillated from tower top, and remaining six component of light dydrocarbon carbon is produced from bottom of towe；
(4) obtained remaining six component of light dydrocarbon carbon of step (3) is sent to light tower is cut, boiling point is less than the lighter hydrocarbons of n-hexane
(including 3- methylpentanes) distillates from tower top, and the material rich in n-hexane produces (tower reactor is mainly C6 mixtures) from bottom of towe；
(5) the obtained material rich in n-hexane of step (4) is sent to hexane treating column, tower top and obtains n-hexane.
Further, the bifunctional catalyst of the progress isomerization reaction in the step (2) is Pt/HZSM-5, Pd/
NaY、Pt/SiO2/Al2O3, Pt/HM, HY+Pd/NaY or Pt/SiO2One kind in+HZSM-5.
Preferably, the bifunctional catalyst of the progress isomerization reaction is Pt/HZSM-5.
Further, the bifunctional catalyst for hydrocracking reaction being carried out in the step (2) is Pt/HM or Pt/Al2O3
In one kind.
Further, in the step (2) isomery is carried out when the mass percent of methyl cyclopentane is more than or equal to 10%
Change reaction, when the mass percent of methyl cyclopentane is 5%-10%, carries out isomerization reaction or hydrocracking reaction, work as first
When the mass percent of cyclopentane is less than or equal to 5%, hydrocracking reaction is carried out.The weight of the continuous reformer of different refineries
Whole naphtha remaining PONA races composition of raffinating oil after Aromatics Extractive Project is not quite similar, and the methyl cyclopentane in raffinating oil contains
Amount is also ever-changing.
Further, the pressure for cutting weight tower in the step (1) is 40KPA-150KPA, reflux ratio 2-8；It is preferred that
, the pressure for cutting weight tower in the step (1) is 45KPA-80KPA, reflux ratio 3-5.
Further, the operation temperature that fixed bed reactors during isomerization reaction are carried out in the step (2) is 230-380
DEG C, hydrogen-hydrocarbon ratio 2.0-10.0, operating pressure 0-0.5MPaG；Preferably, isomerization reaction is carried out in the step (2)
When fixed bed reactors operation temperature be 250-350 DEG C, hydrogen-hydrocarbon ratio 4.0-6.0, operating pressure 0.3-0.5MPaG；Institute
The operation temperature of fixed bed reactors is 250-350 DEG C when hydrocracking reaction is carried out in the step of stating (2), hydrogen-hydrocarbon ratio 2.0-
10.0, operating pressure 0-0.5MPaG；Preferably, fixed bed reactors during hydrocracking reaction are carried out in the step (2)
Operation temperature be 260-320 DEG C, hydrogen-hydrocarbon ratio 4.0-6.0, operating pressure 0.3-0.5MPaG.Generation isomerization reaction or
Hydrocracking reaction is determined by raw material and catalyst property；Autotomying six component of mixing light dydrocarbon carbon that weight tower top distillates, first warp efficiently changes
Hot device specifies operation temperature to send to fixed bed reactors with being heated to after reaction product heat exchange through reaction heating furnace, when methyl ring penta
When alkane content is higher, it is proposed that selection isomerization reaction, under hydro condition, methyl cyclopentane is difunctional in noble metal/solid acid
Isomerization reaction generation hexamethylene and benzene occur on catalyst.Raffinated oil according to raw material and urged (noble metal/solid acid) is difunctional
Agent response characteristic, when operation temperature is at 250-275 DEG C, the selectivity of hexamethylene is more than benzene；When operation temperature is in 285-350
DEG C when, the selectivity of benzene is more than hexamethylene；When operation temperature is at 280 DEG C or so, the selectivity of benzene and hexamethylene is substantially suitable,
Reaction temperature can be adjusted according to user demand, added value of product can be improved to greatest extent.It is different when methyl cyclopentane content is relatively low
Structure reaction or hydrocracking reaction may be selected, preferably hydrocracking reaction, and under hydro condition, cracking reaction mainly generates
C1-C5 etc. is less than the small molecule lighter hydrocarbons of C6.
Further, it is 200KPG-800KPG to stablize pressure tower in the step (3)；Preferably, the step (3)
Middle stable pressure tower is 500kPaG-700KPG.
Further, the pressure for light tower being cut in the step (4) is 80KPA-140KPA, reflux ratio 6-14；Preferably,
The pressure that light tower is cut in the step (4) is 20KPA- normal pressures, reflux ratio 6-9.
Further, the operating pressure of hexane treating column is 40kPaA-110KPA, reflux ratio 3- in the step (5)
9；Preferably, the operating pressure of hexane treating column is 45kPaA-70KPA, reflux ratio 3-6 in the step (5).
Raffinate oil and refer generally to C5-C8 components in the reformate that naphtha is generated through catalytic reforming after Aromatics Extractive Project, it is remaining
Under lower alkanes hydrocarbons, 35-120 DEG C of boiling point range, preferably 60-100 DEG C, it also may be preferable for No. 6 solvent naphthas are excellent as raw material
Select substitute.
No matter methyl cyclopentane selects that isomerization reaction or hydrocracking reaction occurs, and institute's general character, both needs
To react under hydro condition and on (noble metal/solid acid) bifunctional catalyst, except that used in two reactions
(noble metal/solid acid) bifunctional catalyst it is different.
Under hydro condition ring expansion occurs for methyl cyclopentane, and according to thermodynamic analysis, its ring expansion may occur
Three main chemical reactions it is as follows：
MCP (methyl cyclopentane) → CH (hexamethylene)；
MCP (methyl cyclopentane) → Bz (benzene)+3H2；
CH (hexamethylene) → Bz (benzene)+3H2。
Under hydro condition hydrocracking reaction occurs for methyl cyclopentane, mainly generates the small molecule that C1-C5 etc. is less than C6
Lighter hydrocarbons.
When under hydro condition isomerization reaction occurs for methyl cyclopentane, tower reactor is mainly hexamethylene, methyl cyclopentane
And the mixture of benzene；When hydrocracking reaction occurs under hydro condition for methyl cyclopentane, tower reactor is mainly C6 mixtures, hexamethylene
The content of alkane or benzene is similar with raw material.
Relative to the prior art, the method for the present invention using production n-hexane of raffinating oil has the advantage that：
It is of the present invention using raffinate oil production n-hexane method by the methyl cyclopentane in raffinating oil change into
N-hexane boiling point differs larger chemical substance, greatly reduces the energy consumption of purification n-hexane., will when isomerization reaction occurs
Methyl cyclopentane changes into the benzene and hexamethylene for more having industrial utility value, both solves and separates methyl using traditional rectification process
The problem of pentamethylene and n-hexane high energy consumption, it also avoid using extracting rectifying can introduce novel substance, Solvent quantity it is big and
Difference raffinate oil selection of the composition on extractant, solvent than selection influence the problem of big, while the present invention raffinates oil difference
The characteristics of composition is also adaptable wide.
Brief description of the drawings
Fig. 1 be the embodiment of the present invention described in utilization raffinate oil production n-hexane method schematic diagram.
Description of reference numerals：
1- cuts weight tower；2- high-performance heat exchangers；3- reaction heating furnaces；4- fixed bed reactors；5- gas-liquid separators；6- water coolings
Device；7- stabilizers；8- cuts light tower；9- hexane treating columns.
Embodiment
In addition to being defined, technical term used has universal with those skilled in the art of the invention in following embodiments
The identical meanings of understanding.Test reagent used, is routine biochemistry reagent unless otherwise specified in following embodiments；It is described
Experimental method, is conventional method unless otherwise specified.
With reference to embodiment and attached drawing, the present invention will be described in detail.
A kind of method using production n-hexane of raffinating oil, includes the following steps：
(1) raffinate oil and carry out rectifying in weight tower is cut, six component of light dydrocarbon carbon in raffinating oil is distillated from tower top, mixes carbon seven
Carbon eightfold component is produced from bottom of towe；
(2) the preheated rear feeding fixed bed reactors of six component of light dydrocarbon carbon described in step (1), under hydro condition,
Methyl cyclopentane carries out isomerization reaction or hydrocracking reaction on bifunctional catalyst；
(3) reaction product obtained in step (2) is sent to gas-liquid separator, the gas-phase product isolated is as recycle hydrogen
It is back in fixed bed reactors and recycles, liquid product is sent to stabilizer, a small amount of hydrogen and is cracked on a small quantity small after processing
Molecule lighter hydrocarbons are distillated from tower top, and remaining six component of light dydrocarbon carbon is produced from bottom of towe；
(4) obtained remaining six component of light dydrocarbon carbon of step (3) is sent to light tower is cut, boiling point is less than the lighter hydrocarbons of n-hexane
(including 3- methylpentanes) distillates from tower top, and the material rich in n-hexane produces (tower reactor is mainly C6 mixtures) from bottom of towe；
(5) the obtained material rich in n-hexane of step (4) is sent to hexane treating column, tower top is obtaining high-purity just
Hexane, kettle material composition is determined by reaction type, when under hydro condition isomerization reaction occurs for methyl cyclopentane, tower reactor
The predominantly mixture of hexamethylene, methyl cyclopentane and benzene；When under hydro condition hydrocracking reaction occurs for methyl cyclopentane,
Tower reactor is mainly C6 mixtures, and the content of hexamethylene or benzene is similar with raw material.
The bifunctional catalyst of progress isomerization reaction in the step (2) is Pt/HZSM-5, Pd/NaY, Pt/
SiO2/Al2O3, Pt/HM, HY+Pd/NaY or Pt/SiO2One kind in+HZSM-5.
The bifunctional catalyst that hydrocracking reaction is carried out in the step (2) is Pt/HM or Pt/Al2O3In one
Kind.
In the step (2) when the mass percent of methyl cyclopentane is more than or equal to 10%, isomerization reaction is carried out,
When the mass percent of methyl cyclopentane is 5%-10%, isomerization reaction or hydrocracking reaction are carried out, when methyl ring penta
When the mass percent of alkane is less than or equal to 5%, hydrocracking reaction is carried out.
The pressure for cutting weight tower in the step (1) is 40KPA-150KPA, reflux ratio 2-8.The step (2)
The middle operation temperature for carrying out fixed bed reactors during isomerization reaction is 230-380 DEG C, hydrogen-hydrocarbon ratio 2.0-10.0, operating pressure
For 0-0.5MPaG；The operation temperature that fixed bed reactors during hydrocracking reaction are carried out in the step (2) is 250-350
DEG C, hydrogen-hydrocarbon ratio 2.0-10.0, operating pressure 0-0.5MPaG.It is 200KPG- to stablize pressure tower in the step (3)
800KPG.The pressure that light tower is cut in the step (4) is 80KPA-140KPA, reflux ratio 6-14.In the step (5)
The operating pressure of hexane treating column is 40kPaA-110KPA, reflux ratio 3-9.
Due to the complexity of reforming raffinate oil PONA races composition, three kinds of compositions of more typically raffinating oil are have chosen,
With the verification present invention to the adaptability that forms of raffinating oil.
Embodiment 1
Composition is shown in Table 1 to certain petro-chemical corporation's catalytic reforming unit reforming raffinate oil entirely.The said firm raffinates oil containing more
C5 is formed and containing a certain amount of heavy constituent.The full composition raffinated oil according to table 1, methyl cyclopentane content is higher, preferably selects isomerization
It is reacted to give hexamethylene and benzene of the industrial value with respect to higher.
As shown in Figure 1, the process flow diagram for embodiment 1.It is sent into after raffinating oil and cutting the kettle material heat exchange of weight tower
Weight tower is cut, six component of light dydrocarbon carbon is distillated from tower top, and the heavy constituent such as seven carbon eight of carbon is produced from bottom of towe.
Cut weight column overhead distillate six component of light dydrocarbon carbon first mixed with recycle hydrogen, then again with isomerization product heat exchange.Change
The reacted heating furnace of raw material after heat is preheated to reaction temperature and is sent into fixed bed reactors on Pt/HZSM-5 bifunctional catalysts
Generation isomerization reaction, isomerization reaction product first exchange heat with raw material, and the isomerization product after heat exchange is sent into water cooler and is cooled to
40 DEG C, into gas-liquid separator, the gas phase that gas-liquid separator separates is recycled back into isomerization fixed bed reaction as recycle hydrogen
Device；Liquid phase is sent to stabilizer, and the small molecule lighter hydrocarbons self-stabilization tower top of a small amount of hydrogen and a small amount of cracking generation distillates；Six groups of light dydrocarbon carbon
Point being sent from bottom of towe extraction to cutting light tower, the lighter hydrocarbons (including 3- methylpentanes) less than n-hexane boiling point are autotomyed light column overhead and are distillated,
Rich in the discharging of the tower reactor of n-hexane and hexamethylene the outflow of light tower tower reactor is autotomyed to send to hexane treating column lower part, 97% n-hexane from
Hexane refines column overhead and distillates, and hexane refines the mixture that tower reactor is mainly hexamethylene, methyl cyclopentane and benzene.
Pressure that cutting weight tower in the step (1) is 47KPA, reflux ratio 4.
The operation temperature that fixed bed reactors during isomerization reaction are carried out in the step (2) is 270 DEG C, and hydrogen-hydrocarbon ratio is
5.0, operating pressure 0.2MPaG；
It is 650KPG to stablize pressure tower in the step (3).
The pressure that light tower is cut in the step (4) is 91KPA, reflux ratio 7.
The operating pressure of hexane treating column is 47KPA in the step (5), reflux ratio 5.
1 reforming raffinate oil of table forms entirely
| Component | Mass fraction/% | Boiling point/DEG C | Component | Mass fraction/% | Boiling point/DEG C |
| Isopentane | 1.57 | 27.85 | 2- methyl hexanes | 1.02 | 90.05 |
| Pentane | 8.62 | 36.07 | Cis- 1,3- dimethylcyclopentanes | 1.32 | 90.77 |
| Pentamethylene | 18.18 | 49.26 | Trans- 1,3- dimethylcyclopentanes | 0.95 | 91.73 |
| 2- methylpentanes | 9.07 | 60.27 | Trans- 1,2- dimethylcyclopentanes | 1.25 | 91.87 |
| N-hexane | 8.11 | 68.74 | Normal heptane | 3.31 | 98.43 |
| Methyl cyclopentane | 21.16 | 71.81 | Hexahydrotoluene | 5.27 | 100.93 |
| Benzene | 0.62 | 80.10 | Ethyl cyclopentane | 3.35 | 103.50 |
| Hexamethylene | 5.80 | 80.74 | Heavy constituent | 10.40 | 122.82 |
Embodiment 2
Certain catalytic reforming unit reforming raffinate oil PONA race of China Petrochemical Industry Company composition is shown in Table 2.The composition of raffinating oil of the said firm
Mainly it is made of C6-C7 isoparaffins and n-alkane, is substantially free of alkene and aromatic hydrocarbons, wherein n-hexane accounts for n-alkane and always contains
The 93.7% of amount.The PONA races to be raffinated oil according to table 2 form, and methyl cyclopentane content is relatively low, preferably using hydrocracking reaction, splits
Change the small molecule lighter hydrocarbons that reaction mainly generates C1-C5, the relative volatility with bigger, is more easy to realize the separation with n-hexane,
The implementation process of lower hydrocracking reaction is described below.
Implementation process is implemented according to the process flow diagram of embodiment 1, the difference is that the fixed bed of embodiment 1 is anti-
It is isomerization fixed bed reactors to answer device, and what embodiment 2 used is hydrocracked fixed bed reactors；Two reactions your gold used
Category/solid acid bifunctional catalyst is also different.
The operation temperature of fixed bed reactors is 300 DEG C when hydrocracking reaction is carried out in the step (2), hydrogen-hydrocarbon ratio
For 5.0, operating pressure 0.2MPaG；
The bifunctional catalyst that hydrocracking reaction is carried out in the step (2) is Pt/Al2O3。
2 reforming raffinate oil PONA races of table form
| Project | P | IP | O | N | A | It is total |
| C5 | 1.49 | 1.15 | -- | 3.91 | -- | 6.55 |
| C6 | 24.24 | 36.99 | -- | 3.98 | 0.02 | 65.23 |
| C7 | 0.14 | 27.64 | -- | 0.42 | -- | 28.20 |
| It is total | 25.87 | 65.78 | 0 | 8.31 | 0.02 | 99.98 |
Note：P represents alkane, IP represents isoparaffin, O represents alkene, N represents cycloalkane, A represents aromatic hydrocarbons.
Embodiment 3
The full composition of No. 6 solvent naphthas is shown in Table 3.According to table 3, methyl cyclopentane content is higher, preferably selects isomerization reaction
To obtain hexamethylene and benzene of the industrial value with respect to higher.Implementation process is implemented according to the process flow diagram of embodiment 1, Gu
The operation temperature of fixed bed reactor is 270 DEG C, and under this operation temperature, the selectivity of hexamethylene is more than benzene.
3 No. 6 solvent naphthas of table form entirely
| Component | Mass fraction/% | Boiling point/DEG C | Component | Mass fraction/% | Boiling point/DEG C |
| ≦C4 | 0.010 | Hexamethylene | 0.374 | 80.7 | |
| Isopentane | 0.060 | 9.40 | 2,2,3- triptanes | 0.289 | 80.8 |
| Pentane | 0.105 | 36.0 | 3,3- dimethyl pentanes | 1.264 | 86.1 |
| Pentamethylene | 0.290 | 49.2 | 1,1- dimethylcyclopentanes | 0.012 | 87.5 |
| 2,2- dimethylbutanes | 1.527 | 49.7 | 2,3- dimethyl pentanes | 2.285 | 89.7 |
| 2,3- dimethylbutanes | 4.202 | 58.0 | 2- methyl hexanes | 5.997 | 90.1 |
| 2- methylpentanes | 19.640 | 60.3 | 3- methyl hexanes | 5.764 | 91.9 |
| 3- methylpentanes | 17.150 | 63.3 | Cis- 1,3- dimethylcyclopentanes | 0.188 | 90.8 |
| N-hexane | 24.980 | 68.7 | Trans- 1,3- dimethylcyclopentanes | 0.164 | 91.7 |
| Methyl cyclopentane | 9.888 | 71.8 | 3- ethylpentanes | 0.419 | 93.5 |
| 2,2- dimethyl pentanes | 1.938 | 79.2 | Trans- 1,2- dimethylcyclopentanes | 0.191 | 92.0 |
| Benzene | 0.147 | 80.1 | Normal heptane | 1.039 | 98.4 |
| 2,4- dimethyl pentanes | 2.030 | 80.5 | Hexahydrotoluene | 0.001 | 100 |
Embodiment 4
Raw material composition is same as Example 3, and selective hydrocracking reaction, cracking reaction mainly generates the small molecule of C1-C5
Lighter hydrocarbons, have the relative volatility of bigger, are more easy to realize the separation with n-hexane.
Implementation process is implemented according to embodiment 2, the difference is that the bifunctional catalyst that embodiment 2 uses is Pt/
Al2O3, the bifunctional catalyst that embodiment 4 uses is Pt/HM.
Comparative example 1
Raw material composition is same as Example 3 with implementation process, the difference is that the operation temperature of fixed bed reactors is
320 DEG C, under this operation temperature, the selectivity of benzene is more than hexamethylene.
Comparative example 2
Raw material composition is same as Example 3 with implementation process, the difference is that the operation temperature of fixed bed reactors is
280 DEG C, under this operation temperature, the selectivity of hexamethylene and benzene is substantially suitable.
Technological parameter in embodiment 1-4 and comparative example 1-2 is see table 4, and product separating effect is see table 5.
4 process operation parameter of table
5 product separating effect of table
Note：MCP represents methyl cyclopentane, CH represents hexamethylene, Bz represents benzene, HX represents n-hexane.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on, should all be included in the protection scope of the present invention god.
Claims (10)
- A kind of 1. method using production n-hexane of raffinating oil, it is characterised in that：Include the following steps：(1) raffinate oil and carry out rectifying in weight tower is cut, six component of light dydrocarbon carbon in raffinating oil is distillated from tower top, mixes seven carbon eight of carbon Heavy constituent is produced from bottom of towe；(2) the preheated rear feeding fixed bed reactors of six component of light dydrocarbon carbon described in step (1), under hydro condition, methyl Pentamethylene carries out isomerization reaction or hydrocracking reaction on bifunctional catalyst；(3) reaction product obtained in step (2) is sent to gas-liquid separator, the gas-phase product isolated is returned as recycle hydrogen Recycled into fixed bed reactors, liquid product is sent to stabilizer, and a small amount of hydrogen and small molecule is cracked on a small quantity after processing Lighter hydrocarbons are distillated from tower top, and remaining six component of light dydrocarbon carbon is produced from bottom of towe；(4) obtained remaining six component of light dydrocarbon carbon of step (3) is sent to cutting light tower, boiling point less than n-hexane lighter hydrocarbons from tower Top distillates, and the material rich in n-hexane is produced from bottom of towe；(5) the obtained material rich in n-hexane of step (4) is sent to hexane treating column, tower top and obtains n-hexane.
- 2. the method according to claim 1 using production n-hexane of raffinating oil, it is characterised in that：The step (2) In the bifunctional catalyst of progress isomerization reaction be Pt/HZSM-5, Pd/NaY, Pt/SiO2/Al2O3、Pt/HM、HY+Pd/ NaY or Pt/SiO2One kind in+HZSM-5.
- 3. the method according to claim 2 using production n-hexane of raffinating oil, it is characterised in that：The carry out isomery The bifunctional catalyst for changing reaction is Pt/HZSM-5.
- 4. the method according to claim 1 or 2 using production n-hexane of raffinating oil, it is characterised in that：The step (2) bifunctional catalyst that hydrocracking reaction is carried out in is Pt/HM or Pt/Al2O3In one kind.
- 5. the method according to claim 1 using production n-hexane of raffinating oil, it is characterised in that：The step (2) In when methyl cyclopentane mass percent be more than or equal to 10% when, carry out isomerization reaction, when the quality hundred of methyl cyclopentane During point than be 5%-10%, carry out isomerization reaction or hydrocracking reaction, when methyl cyclopentane mass percent less than etc. When 5%, hydrocracking reaction is carried out.
- 6. the method according to claim 1 using production n-hexane of raffinating oil, it is characterised in that：The step (1) In cut weight tower pressure be 40KPA-150KPA, reflux ratio 2-8；Preferably, the pressure for cutting weight tower in the step (1) Power is 45KPA-80KPA, reflux ratio 3-5.
- 7. the method according to claim 1 using production n-hexane of raffinating oil, it is characterised in that：The step (2) The middle operation temperature for carrying out fixed bed reactors during isomerization reaction is 230-380 DEG C, hydrogen-hydrocarbon ratio 2.0-10.0, operating pressure For 0-0.5MPaG；Preferably, the operation temperature of fixed bed reactors is when isomerization reaction is carried out in the step (2) 250-350 DEG C, hydrogen-hydrocarbon ratio 4.0-6.0, operating pressure 0.3-0.5MPaG；Carry out being hydrocracked in the step (2) anti- The operation temperature of seasonable fixed bed reactors is 250-350 DEG C, hydrogen-hydrocarbon ratio 2.0-10.0, operating pressure 0-0.5MPaG；It is excellent Choosing, the operation temperature of fixed bed reactors is 260-320 DEG C when hydrocracking reaction is carried out in the step (2), hydrogen hydrocarbon Than for 4.0-6.0, operating pressure 0.3-0.5MPaG.
- 8. the method according to claim 1 using production n-hexane of raffinating oil, it is characterised in that：The step (3) Middle stable pressure tower is 200KPG-800KPG；Preferably, it is 500kPaG-700KPG to stablize pressure tower in the step (3).
- 9. the method according to claim 1 using production n-hexane of raffinating oil, it is characterised in that：The step (4) In to cut the pressure of light tower be 80KPA-140KPA, reflux ratio 6-14；Preferably, the pressure of light tower is cut in the step (4) For 20KPA- normal pressures, reflux ratio 6-9.
- 10. the method according to claim 1 using production n-hexane of raffinating oil, it is characterised in that：The step (5) The operating pressure of middle hexane treating column is 40kPaA-110KPA, reflux ratio 3-9；Preferably, hexane in the step (5) The operating pressure for the treatment of column is 45kPaA-70KPA, reflux ratio 3-6.
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| CN110669550A (en) * | 2018-07-03 | 2020-01-10 | 中国石油化工股份有限公司 | Isomerization method of aromatic raffinate oil |
| CN112225633A (en) * | 2020-10-29 | 2021-01-15 | 洛阳金达石化有限责任公司 | Production method of normal hexane containing heptane raw material |
| CN115287106A (en) * | 2022-08-08 | 2022-11-04 | 山东中油胜利石化有限公司 | Gasoline fuel for compression ignition engine |
| CN116410790A (en) * | 2021-12-31 | 2023-07-11 | 中国石油天然气股份有限公司 | Method for producing solvent oil by reforming raffinate oil |
| CN116410791A (en) * | 2021-12-31 | 2023-07-11 | 中国石油天然气股份有限公司 | Method for treating reforming raffinate oil |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110669550A (en) * | 2018-07-03 | 2020-01-10 | 中国石油化工股份有限公司 | Isomerization method of aromatic raffinate oil |
| CN110669550B (en) * | 2018-07-03 | 2021-11-12 | 中国石油化工股份有限公司 | Isomerization method of aromatic raffinate oil |
| CN112225633A (en) * | 2020-10-29 | 2021-01-15 | 洛阳金达石化有限责任公司 | Production method of normal hexane containing heptane raw material |
| CN116410790A (en) * | 2021-12-31 | 2023-07-11 | 中国石油天然气股份有限公司 | Method for producing solvent oil by reforming raffinate oil |
| CN116410791A (en) * | 2021-12-31 | 2023-07-11 | 中国石油天然气股份有限公司 | Method for treating reforming raffinate oil |
| CN116410790B (en) * | 2021-12-31 | 2024-04-09 | 中国石油天然气股份有限公司 | Method for producing solvent oil by reforming raffinate oil |
| CN116410791B (en) * | 2021-12-31 | 2024-04-09 | 中国石油天然气股份有限公司 | Method for treating reforming raffinate oil |
| CN115287106A (en) * | 2022-08-08 | 2022-11-04 | 山东中油胜利石化有限公司 | Gasoline fuel for compression ignition engine |
| CN115287106B (en) * | 2022-08-08 | 2023-09-22 | 山东京博新能源控股发展有限公司 | Gasoline fuel for compression ignition engine |
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