CN109293466A - The method for preparing isooctane using isobutene - Google Patents
The method for preparing isooctane using isobutene Download PDFInfo
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- CN109293466A CN109293466A CN201811120103.6A CN201811120103A CN109293466A CN 109293466 A CN109293466 A CN 109293466A CN 201811120103 A CN201811120103 A CN 201811120103A CN 109293466 A CN109293466 A CN 109293466A
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- isobutene
- isooctane
- catalyst
- isooctene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/10—Catalytic processes with metal oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
- C07C2523/04—Alkali metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention belongs to technical field of petrochemical industry, more particularly to a kind of method for preparing isooctane using isobutene, including, (1) isobutene is passed into water-cooled shell-and-tube reactor together with activator, then it is passed into again in the catalytic distillation tower for being loaded with catalyst, activator is extracted and is recycled as side line material with other C4 hydrocarbon, and the isooctene of collection is transferred to the next step；(2) isooctene is added in reaction kettle, palladium/active catalyst is added, reaction kettle is closed to be placed in heating furnace, is heated to 120~150 DEG C, and then passing to hydrogen and keeping Hydrogen Vapor Pressure is 5~8Mpa, after hydrogenation reaction, reaction kettle is cooled to room temperature, Hydrogen Vapor Pressure is reduced to normal pressure, opens kettle cover, take out the mixture of palladium/active catalyst and product, the isolated isooctane；In the preparation method of isooctane provided by the invention, it is used to prepare the catalyst catalytic activity with higher and stability of isooctene, effectively reduces the preparation cost of isooctane.
Description
Technical field
The invention belongs to technical field of petrochemical industry, and in particular to a method of isooctane is prepared using isobutene.
Background technique
2,2,4- trimethylpentanes are commonly called as isooctane, are a kind of isomers of octane.In the prior art, isooctane
It is often used as gasoline additive, for improving the octane number of gasoline.Industrially, it can be obtained by way of mixed octene plus hydrogen
Obtain C8 paraffins mixture (such as China Patent Publication No. rich in isooctane
1381549, United States Patent (USP) US 08-975867).And mixed octene can be obtained by butene oligomerization, by being made
Catalyst and technique are different, the type and quantity of various isomers contained in mixed octene also not phase after butene oligomerization
Together, alkene in the branches such as trimethylpentene, dimethyhexenes, methyl heptenyl is mainly contained.
The thinking of indirect alkylation is to be prepared isooctane using isobutene as raw material through dimerization plus hydrogen, industrially made at present
Isobutene dimerization mainly uses cation exchange resin and solid phosphoric acid two major classes catalyst with catalyst, since MTBE is closed
At cation exchange resin is all made of, so cationic friendship can be continued to use by the process units that MTBE process units transform isooctane as
It is optimal for changing resin.But when cation exchange resin being used to produce isooctene as catalyst, the conversion ratio of isobutene is lower than
Conversion ratio when MTBE is produced, and very low to the dimerization activity of n-butene；In addition, having more impurity in product, with solid
Phosphoric acid loses activity compared to fouling is easier, and in order to obtain higher dimer selectivity, usually also needs using diluent.
Summary of the invention
The purpose of the present invention is to provide a kind of method for preparing isooctane using isobutene, the isobutene be converted into it is different
There is the advantages of olefine selective height, high conversion rate during octene, then add the method for hydrogen to be prepared by isooctene again
To isooctane, there is prospects for commercial application.
To achieve the goals above, the present invention is achieved by the following scheme:
A method of isooctane is prepared using isobutene, comprising the following steps:
(1) isobutene dimerization
Isobutene is passed into water-cooled shell-and-tube reactor together with activator, is then passed into again and is loaded with catalyst
In catalytic distillation tower, activator is extracted and is recycled as side line material with other C4 hydrocarbon, and the isooctene of collection is transferred to down
One step process；
(2) isooctene adds hydrogen
The isooctene being prepared in step (1) is added in reaction kettle, palladium/active catalyst is added, reaction kettle is close
Close and be placed in heating furnace, be heated to 120~150 DEG C, hydrogen is then passed through into reaction kettle and keep Hydrogen Vapor Pressure be 5~
After hydrogenation reaction, reaction kettle is cooled to room temperature by 8Mpa, is reduced Hydrogen Vapor Pressure to normal pressure, is opened kettle cover, take out palladium/work
Property catalyst and product mixture, the isolated isooctane.
In step (1), the activator is one of the tert-butyl alcohol or methyl tertiary butyl ether(MTBE).
In step (1), the preparation method of the catalyst the following steps are included:
S1: grinding after petroleum coke is stirred with attapulgite, crosses 40 meshes, obtains powder mixture；
S2: powder mixture is distributed in solvent, and metal salt is added, is stirred, ultrasonic disperse processing, then mistake
Filter, then filter cake is immersed into immersion treatment in phosphoric acid solution, it refilters, obtains pre-product；
S3: pre-product is placed in high temperature sintering furnace, calcination process, and cooled to room temperature is to get the catalyst.
In step S1, the weight ratio of the petroleum coke and attapulgite is 1:(0.35~0.6).
In step S2, the metal salt is selected from soluble at least one of halogen, nitrate or sulfate.
In step S2, the concentration of the phosphoric acid solution is 1.5~5mol/L；And/or
The time of filter cake immersion treatment in phosphoric acid solution is 3~7h.
In step S3, the condition of the calcination process includes that maturing temperature is 300~400 DEG C, and calcining time is 2~7h.
Compared with prior art, the present invention has following technical effect that
The method provided by the invention for preparing isooctane using isobutene can be obtained by the dimerization of isobutene, repeated hydrogenation
To isooctane, in the catalyst used in the dimerization of isobutene, by being mixed into petroleum coke in attapulgite, in height
Under the action of temperature, the carbon being rich in petroleum coke is ablated and itself pore structure is gradually reduced, to be coated on recessed
The surface of convex stick stone；In addition, the metal ion after displacement is in the layer chain structure of attapulgite and the pore structure of petroleum coke
In-situ oxidation, finally obtain inlay, the attapulgite of clad structure, further ensure that the catalyst being prepared is being catalyzed
High efficiency and stability when isobutene dimerization.To reduce the preparation cost of isooctane.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment.
Specific embodiment
In order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, tie below
Specific embodiment is closed, the present invention is furture elucidated.
The present invention provides a kind of methods for preparing isooctane using isobutene, comprising the following steps:
(1) isobutene dimerization
Isobutene is passed into water-cooled shell-and-tube reactor together with activator, is then passed into again and is loaded with catalyst
In catalytic distillation tower, activator is extracted and is recycled as side line material with other C4 hydrocarbon, and the isooctene of collection is transferred to down
One step process；
(2) isooctene adds hydrogen
The isooctene being prepared in step (1) is added in reaction kettle, palladium/active catalyst is added, reaction kettle is close
Close and be placed in heating furnace, be heated to 120~150 DEG C, hydrogen is then passed through into reaction kettle and keep Hydrogen Vapor Pressure be 5~
After hydrogenation reaction, reaction kettle is cooled to room temperature by 8Mpa, is reduced Hydrogen Vapor Pressure to normal pressure, is opened kettle cover, take out palladium/work
Property catalyst and product mixture, the isolated isooctane.
In step (1), the activator is one of the tert-butyl alcohol or methyl tertiary butyl ether(MTBE).
In step (1), the preparation method of the catalyst the following steps are included:
S1: grinding after petroleum coke is stirred with attapulgite, crosses 40 meshes, obtains powder mixture；
S2: powder mixture is distributed in solvent, and metal salt is added, is stirred, ultrasonic disperse processing, then mistake
Filter, then filter cake is immersed into immersion treatment in phosphoric acid solution, it refilters, obtains pre-product；
S3: pre-product is placed in high temperature sintering furnace, calcination process, and cooled to room temperature is to get the catalyst.
In the present invention, ash content≤1.0% of the petroleum coke, moisture≤5.0%, volatile matter≤15%, phosphorus content >=
90%；The attapulgite is a kind of crystalloid hydration alumina magnesia silicate, with unique layer chain structure feature,
There are crystal lattice in its structure, variable amount of Na is contained in crystal+、Ca2+、Fe3+、Al3+；Attapulgite has unique point
Good colloidal nature and the higher adsorption bleaching abilities such as scattered, high temperature resistant, salt resistance alkali, and there is certain plasticity and bonding
Power.
The petroleum coke is mixed to attapulgite in the present invention and is ground up, sieved processing, obtains powder mixture, so
The powder mixture is distributed in solvent afterwards, be added metal salt, mix by stirring and ultrasonic disperse processing mode,
On the one hand promote the metal ion in metal ion displacement attapulgite；On the other hand, promote the phase of petroleum coke and attapulgite
Mutually infiltration dispersion；Filtered filter cake is immersed into phosphoric acid solution Immersion treatment again and obtains the pre-product with catalytic activity；
Further, it is rich in petroleum coke under the action of high temperature by the way that the pre-product is carried out high temperature sintering
Carbon is ablated and itself pore structure is gradually reduced, to be coated on the surface of attapulgite；In addition, after displacement
Metal ion in-situ oxidation in the layer chain structure of attapulgite and the pore structure of petroleum coke, finally obtains and inlays, coats
The attapulgite of structure further ensures high efficiency and stabilization of the catalyst being prepared in catalyzing iso-butane alkene dimerization
Property.
Catalyst provided in the present invention, not only stability with higher, moreover, being inlayed in the attapulgite
Multimetal oxide has multiple catalytic sites, improves the selection performance of catalyst.
According to the present invention, in step S1, the weight ratio of the petroleum coke and attapulgite is 1:(0.35~0.6).
In the present invention, in step S2, in halogen, nitrate or sulfate of the metal salt selected from solubility at least
It is a kind of.For example, the halogen of the solubility in sodium chloride, potassium chloride, sodium bromide, potassium bromide, iron chloride, copper chloride extremely
Few one kind；The nitrate is selected from least one of sodium nitrate, potassium nitrate, ferric nitrate, copper nitrate；The sulfate choosing
From at least one of sodium sulphate, potassium sulfate, ferric sulfate, copper sulphate.
According to the present invention, the additive amount of the metal salt is the 0.5~3% of powder mixture weight.
In the present invention, in step S2, the concentration of the phosphoric acid solution is 1.5~5mol/L；
The time of filter cake immersion treatment in phosphoric acid solution is 3~7h.
According to the present invention, in step S3, for the pre-product before calcination process, it is 5 that mass fraction is added into pre-product
The polyvinyl alcohol water solution of~10wt%, stirring kneading make pre-product be in the graininess of 2~7mm of partial size.
According to the present invention, in step S3, the condition of the calcination process includes that maturing temperature is 300~400 DEG C, roasting
Time is 2~7h.
The preparation method provided by the invention for preparing isooctane using isobutene is made below by way of specific embodiment
Further instruction.
Embodiment 1
A method of isooctane is prepared using isobutene, comprising the following steps:
(1) isobutene dimerization
Isobutene is passed into water-cooled shell-and-tube reactor together with the tert-butyl alcohol, is then passed into again and is loaded with catalyst
In catalytic distillation tower, activator is extracted and is recycled as side line material with other C4 hydrocarbon, and the isooctene of collection is transferred to down
One step process；
The preparation method of the catalyst the following steps are included:
S1: with attapulgite be by weight by petroleum coke 1:0.45 be stirred mix after grind, cross 40 meshes, obtain powder
Body mixture；
S2: powder mixture is distributed in deionized water, and 2% sodium chloride of powder mixture weight, stirring is added
Mixing, ultrasonic disperse processing, is then filtered, then filter cake is immersed into immersion treatment 4h in phosphoric acid solution (concentration 3mol/L),
It refilters, obtains pre-product；
S3: the polyvinyl alcohol water solution that mass fraction is 7wt% being added into pre-product, and stirring kneading makes pre-product in grain
Diameter is the graininess of 5mm；
Then it is placed in high temperature sintering furnace, calcination process, maturing temperature is 350 DEG C, calcining time 5h, then naturally cold
But to room temperature to get the catalyst；
(2) isooctene adds hydrogen
The isooctene being prepared in step (1) is added in reaction kettle, palladium/active catalyst is added, reaction kettle is close
Close and be placed in heating furnace, be heated to 120~150 DEG C, hydrogen is then passed through into reaction kettle and keep Hydrogen Vapor Pressure be 5~
After hydrogenation reaction, reaction kettle is cooled to room temperature by 8Mpa, is reduced Hydrogen Vapor Pressure to normal pressure, is opened kettle cover, take out palladium/work
Property catalyst and product mixture, the isolated isooctane.
Embodiment 2
Such as the method for preparing isooctane using isobutene provided in embodiment 1, unlike, in the preparation side of catalyst
In method, in step S1, the weight ratio of petroleum coke and attapulgite is 1:0.35；Remaining is constant, and the catalyst is prepared.
Embodiment 3
Such as the method for preparing isooctane using isobutene provided in embodiment 1, unlike, in the preparation side of catalyst
In method, in step S1, the weight ratio of petroleum coke and attapulgite is 1:0.6；Remaining is constant, and the catalyst is prepared.
Comparative example 1
Such as the method for preparing isooctane using isobutene provided in embodiment 1, unlike, in the preparation side of catalyst
In method, in step S1, petroleum coke is not contained, in specific preparation method:
S1: attapulgite is ground, and is crossed 40 meshes, is obtained powdery attapulgite stone；
S2: powdery attapulgite stone is distributed in deionized water, and 2% sodium chloride of powdery attapulgite stone weight is added,
It is stirred, ultrasonic disperse processing is then filtered, then filter cake is immersed into immersion treatment in phosphoric acid solution (concentration 3mol/L)
4h is refiltered, and obtains pre-product；
S3: the polyvinyl alcohol water solution that mass fraction is 7wt% being added into pre-product, and stirring kneading makes pre-product in grain
Diameter is the graininess of 5mm；
Then it is placed in high temperature sintering furnace, calcination process, maturing temperature is 350 DEG C, calcining time 5h, then naturally cold
But to room temperature to get the catalyst.
The yield of isooctene in test above-described embodiment 1-3, comparative example 1, and the corresponding catalyst used are using 2
The yield of isooctene, tests the yield of isooctane, test result is recorded in table 1 after month.
Table 1:
| Isooctene yield (%) | Isooctane yield (%) | Isooctene yield (%) after 2 months | |
| Embodiment 1 | 89.3 | 92.9 | 87.5 |
| Embodiment 2 | 88.7 | 92.3 | 86.5 |
| Embodiment 3 | 88.5 | 92.7 | 85.9 |
| Comparative example 1 | 56.4 | 92.8 | 35.9 |
Basic principles and main features and the features of the present invention of the invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement is both fallen in the range of claimed invention.The scope of protection of present invention is by appended claims
And its equivalent thereof.
Claims (7)
1. a kind of method for preparing isooctane using isobutene, it is characterised in that: the following steps are included:
(1) isobutene dimerization
Isobutene is passed into water-cooled shell-and-tube reactor together with activator, is then passed into the catalysis for being loaded with catalyst again
In destilling tower, activator is extracted and is recycled as side line material with other C4 hydrocarbon, and the isooctene of collection is transferred in next step
Process；
(2) isooctene adds hydrogen
The isooctene being prepared in step (1) is added in reaction kettle, palladium/active catalyst is added, after reaction kettle is closed
It is placed in heating furnace, is heated to 120~150 DEG C, it is 5~8Mpa that hydrogen is then passed through into reaction kettle and keeps Hydrogen Vapor Pressure,
After hydrogenation reaction, reaction kettle is cooled to room temperature, Hydrogen Vapor Pressure is reduced to normal pressure, opens kettle cover, take out palladium/active catalytic
The mixture of agent and product, the isolated isooctane.
2. the method according to claim 1 for preparing isooctane using isobutene, it is characterised in that: described in step (1)
Activator be one of the tert-butyl alcohol or methyl tertiary butyl ether(MTBE).
3. the method according to claim 1 for preparing isooctane using isobutene, it is characterised in that: described in step (1)
The preparation method of catalyst the following steps are included:
S1: grinding after petroleum coke is stirred with attapulgite, crosses 40 meshes, obtains powder mixture；
S2: powder mixture is distributed in solvent, and metal salt is added, is stirred, and ultrasonic disperse processing is then filtered, then
Filter cake is immersed into immersion treatment in phosphoric acid solution, refilters, obtains pre-product；
S3: pre-product is placed in high temperature sintering furnace, calcination process, and cooled to room temperature is to get the catalyst.
4. the method according to claim 3 for preparing isooctane using isobutene, it is characterised in that: described in step S1
The weight ratio of petroleum coke and attapulgite is 1:(0.35~0.6).
5. the method according to claim 3 for preparing isooctane using isobutene, it is characterised in that: described in step S2
Metal salt be selected from soluble at least one of halogen, nitrate or sulfate.
6. the method according to claim 3 for preparing isooctane using isobutene, it is characterised in that: described in step S2
Phosphoric acid solution concentration be 1.5~5mol/L；And/or
The time of filter cake immersion treatment in phosphoric acid solution is 3~7h.
7. the method according to claim 3 for preparing isooctane using isobutene, it is characterised in that: described in step S3
The condition of calcination process includes that maturing temperature is 300~400 DEG C, and calcining time is 2~7h.
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Citations (7)
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| CN1394194A (en) * | 2000-01-14 | 2003-01-29 | 阿科化学技术公司 | Selective olefin oligomerization |
| US20060241326A1 (en) * | 2005-04-22 | 2006-10-26 | Zak Thomas S | Diisobutylene process |
| US20100145122A1 (en) * | 2008-12-04 | 2010-06-10 | Zak Thomas S | Diisobutylene process |
| CN102046567A (en) * | 2008-05-29 | 2011-05-04 | 利安德化学技术有限公司 | Diisobutylene process |
| US20140121430A1 (en) * | 2012-10-31 | 2014-05-01 | Archer Daniels Midland Company | Renewable para-xylene from acetic acid |
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2018
- 2018-09-25 CN CN201811120103.6A patent/CN109293466A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1279661A (en) * | 1997-11-21 | 2001-01-10 | 阿科化学技术公司 | Process for oligomerization of isobutylene |
| CN1330619A (en) * | 1998-10-16 | 2002-01-09 | 福图石油及煤气公司 | Process for dimerizing olefinic hydrocarbon feedstock and producing fuel component |
| CN1394194A (en) * | 2000-01-14 | 2003-01-29 | 阿科化学技术公司 | Selective olefin oligomerization |
| US20060241326A1 (en) * | 2005-04-22 | 2006-10-26 | Zak Thomas S | Diisobutylene process |
| CN102046567A (en) * | 2008-05-29 | 2011-05-04 | 利安德化学技术有限公司 | Diisobutylene process |
| US20100145122A1 (en) * | 2008-12-04 | 2010-06-10 | Zak Thomas S | Diisobutylene process |
| US20140121430A1 (en) * | 2012-10-31 | 2014-05-01 | Archer Daniels Midland Company | Renewable para-xylene from acetic acid |
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Application publication date: 20190201 |