CN106631688A - Method for preparing sec-butyl alcohol through butylene hydration - Google Patents
Method for preparing sec-butyl alcohol through butylene hydration Download PDFInfo
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- CN106631688A CN106631688A CN201710017523.0A CN201710017523A CN106631688A CN 106631688 A CN106631688 A CN 106631688A CN 201710017523 A CN201710017523 A CN 201710017523A CN 106631688 A CN106631688 A CN 106631688A
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- hydration
- hydrogen
- butyl alcohol
- deionized water
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing sec-butyl alcohol through butylene hydration. A hydrogen absorbing agent using fly ash as a base body is used; hydrogen generated in reaction is absorbed by the hydrogen absorbing agent in a hydration reactor at the high pressure of 10 to 25 MPa; the damage of the oxidation film coating on the surface of the hydration reactor made of titanium materials due to hydrogen embrittlement under the hydrogen existence condition is avoided.
Description
Technical field
The present invention relates to a kind of preparation method of sec-butyl alcohol, the method that particularly a kind of butylene hydration prepares sec-butyl alcohol.
Background technology
The traditional mode of production method of sec-butyl alcohol is n-butene and 80% sulfuric acid reaction to be generated into sulfuric ester and then hydrolysis and is obtained, positive fourth
The selectivity of the Transformation efficiency is up to 90 % of alkene, SBA is 95%, it is recycled before must consume big energy and carry out concentrate.Due to producing
Water content is higher in product other impurity, it is necessary to is further purified, causes equipment investment and observable index higher, therefore sec-butyl alcohol
Production cost and value of the product it is higher.With strong-acid ion exchange resin as catalyst, by the hydration of mixing n-butene one step
, it is not required to the ingredient requirement for just meeting MEK processed refined through specific purification.The shortcoming of technique is that conversion ratio is relatively low, conversion per pass
Rate about 10% or so, total conversion is 35%.
CN101395111 discloses the preparation method of sec-butyl alcohol, is characterised by the preparation method of sec-butyl alcohol, and the method is to make
With the heteropoly acid aqueous solution as catalyst, direct hydration n-butene, the method is characterized in that:Dissolved with oxygen used in raw water
Water.Raw water is preferably oxygen saturation water.The oxidation overlay film of titanium material surface can so be prevented because hydrogen occurs hydrogen embrittlement, and
Cause corrosion.
CN101289368 is related to a kind of process of continuously producing sec-butyl alcohol by direct hydration of n-butene, belongs to oil
Work technical field, in the presence of strong acid ion exchange resin catalyst, fresh n-butene raw material is mixed into circulation n-butene
Entering hydration reactor carries out hydration reaction, is separated subsequently into crude product separative element, sets up n-butene refined unit, by
The unreacted n-butene that crude product separative element is isolated a, part is back to hydration reactor and continues to join as circulation n-butene
Plus hydration reaction, another part sends to n-butene refined unit and refined, and removes butane, reclaims n-butene, continues as new
Fresh n-butene raw material is used.
Existing patent and technical literature use sulphur acid as catalyst, although n-butene conversion per pass is higher, but equipment
Seriously corroded, waste water is more, pollutes environment；Using strong acid ion exchange resin catalyst, there is n-butene conversion per pass again
Relatively low shortcoming；Using traditional heteropoly acid solution compositing catalyst, better catalytic activity, but deionized water need sudden and violent in an atmosphere
Reveal and incorporate oxygen, equipment corrosion occurs to avoid hydrogen catalysis.
The content of the invention
The technical problem to be solved is to overcome the deficiencies in the prior art, there is provided a kind of butylene hydration prepares Zhong Ding
The method of alcohol.
In order to solve above technical problem, following technical scheme is present invention employs：A kind of butylene hydration prepares Zhong Ding
The method of alcohol, comprises the following steps：
（1）The preparation of hydrogen absorbent
Flyash, the deionized water of flyash quality degree 500-1000, flyash quality hundred are added in a kettle.
Divide the double methylenephosphonic acids of 1,6- hexamethylene triamines five than content 0.01-0.1, add flyash quality degree 0.5-2's
Gamma-aminopropyl-triethoxy-silane (KH-550), in 40-80 DEG C of stirring reaction 10-20h, filters, and drying is obtained hydrogen absorbent.
（2）Hydration reaction
By deionized water, the heteropoly acid of deionized water quality degree 0.5-5, in 40-80 DEG C of stirring reaction 1-5h, it is obtained
Reaction water, by mixing carbon four, reaction water is entered in hydration reactor, and the mol ratio for mixing the n-butene in carbon four and water is 1:5-
15, the hydrogen absorbent of deionized water quality degree 0.5-2 is added, add deionized water quality degree 0.01-
0.1 aliphatic amine polyoxyethylene ether disulfonate, temperature 180-250 DEG C, pressure 10-25MPa, time of staying 0.5-5h, from anti-
Device top extraction sec-butyl alcohol crude product, unreacted water and catalyst is answered to be produced by reactor side.It is anti-that hydrogen absorbent stays in hydration
Answer in device and reuse.
Step（2）Described heteropoly acid is by hetero atom（Such as P, Si, Fe, Co）And polyatom（Such as Mo, W, V, Nb, Ta
Deng）By the oxygen-containing polyacid of a class that certain structure is consisted of oxygen atom ligand bridging, 12 phosphotungstic acids are optimized for, molybdophosphate,
For commercially available prod.
Described flyash, double methylenephosphonic acids of 1,6- hexamethylene triamines five, gamma-aminopropyl-triethoxy-silane (KH-
550), aliphatic amine polyoxyethylene ether disulfonate is commercially available prod.
Compared with prior art, the invention has the advantages that：
Jing this patents adopt heteropoly acid for catalyst, it is not necessary to which deionized water exposes in an atmosphere and incorporates oxygen, to avoid hydrogen from urging
Change and equipment corrosion occurs, this patent adopts the hydrogen absorbent based on flyash, in hydration reactor, pressure 10-25MPa's
Under high pressure, react the hydrogen for producing and absorbed by hydrogen absorbent, it is to avoid the oxidation overlay film on the hydration reactor surface of titanium matter because
It is destroyed for hydrogen embrittlement hydrogen occurs, the hydrogen raw sorbent that the method is adopted is cheap and easy to get, simple to operate, hydration reactor
Titanium material does not absorb hydrogen substantially.The addition of aliphatic amine polyoxyethylene ether disulfonate also improves the reaction conversion of butylene hydration one way
Rate.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is further elucidated, but these embodiments are only used for explaining of the invention, and not
It is for limiting the scope of the present invention.
Embodiment 1
Step 1：The preparation of hydrogen absorbent
100Kg flyash, the deionized water of 700Kg, double 1,6- hexamethylene triamines five of 0.05Kg are added in 2000L reactors
Methylenephosphonic acid, the gamma-aminopropyl-triethoxy-silane (KH-550) of 1Kg, in 60 DEG C of stirring reactions 11h, is filtered, and drying is obtained hydrogen
Absorbent.
Step 2：Hydration reaction
By 100Kg deionized waters, the heteropoly acid of 2Kg, in 60 DEG C of stirring reactions 3h, reaction water is obtained, by mixing carbon four, reaction water
Into in the titanium matter hydration reactor that volume is 2 cubic centimetres, the mol ratio for mixing the n-butene in carbon four and water is 1:8 add
Enter the hydrogen absorbent of 1Kg, the aliphatic amine polyoxyethylene ether disulfonate of 0.05Kg, 220 DEG C of temperature, pressure 19MPa, the time of staying
2h, is produced from reactor top extraction sec-butyl alcohol crude product, unreacted water and catalyst by reactor side.Hydrogen absorbent is stayed in
Reuse in hydration reactor.
Embodiment 2
Step 1：The preparation of hydrogen absorbent
100Kg flyash, the deionized water of 500Kg, double 1,6- hexamethylene triamines five of 0.05Kg are added in 2000L reactors
Methylenephosphonic acid, the gamma-aminopropyl-triethoxy-silane (KH-550) of 0.5Kg, in 40 DEG C of stirring reactions 10h, is filtered, and drying is obtained
Hydrogen absorbent.
Step 2：Hydration reaction
By 100Kg deionized waters, the heteropoly acid of 0.5Kg, in 40 DEG C of stirring reactions 1h, reaction water is obtained, by mixing carbon four, reaction
Into in the titanium matter hydration reactor that volume is 1 cubic centimetre, the mol ratio for mixing the n-butene in carbon four and water is 1 to water:
5, add the hydrogen absorbent of 0.5Kg, the aliphatic amine polyoxyethylene ether disulfonate of 0.01Kg, 180 DEG C of temperature, pressure 10MPa to stop
Time 0.5h is stayed, is produced by reactor side from reactor top extraction sec-butyl alcohol crude product, unreacted water and catalyst.Hydrogen is inhaled
Receive agent and stay in reuse in hydration reactor.
Embodiment 3
Step 1：The preparation of hydrogen absorbent
100Kg flyash, the deionized water of 1000Kg, double 1,6- hexamethylene triamines five of 0.1Kg are added in 2000L reactors
Methylenephosphonic acid, the gamma-aminopropyl-triethoxy-silane (KH-550) of 2Kg, in 80 DEG C of stirring reactions 20h, is filtered, and drying is obtained hydrogen
Absorbent.
Step 2：Hydration reaction
By 100Kg deionized waters, the heteropoly acid of 5Kg, in 80 DEG C of stirring reactions 5h, reaction water is obtained, by mixing carbon four, reaction water
Into in the titanium matter hydration reactor that volume is 5 cubic centimetres, the mol ratio for mixing the n-butene in carbon four and water is 1:15,
Add the hydrogen absorbent of 2Kg, the aliphatic amine polyoxyethylene ether disulfonate of 0.1Kg, 250 DEG C of temperature, pressure 25MPa, during stop
Between 5h, from reactor top extraction sec-butyl alcohol crude product, unreacted water and catalyst are produced by reactor side.Hydrogen absorbent is stayed
Reuse in hydration reactor.
Comparative example 1
Step（1）It is added without double methylenephosphonic acids of 1,6- hexamethylene triamines five, the other the same as in Example 1.
Comparative example 2
Step（2）It is added without hydrogen absorbent, the other the same as in Example 1.
Comparative example 3
Step（2）It is added without aliphatic amine polyoxyethylene ether disulfonate, the other the same as in Example 1.
Comparative example 4
Step（2）Aliphatic amine polyoxyethylene ether disulfonate is added without, hydrogen absorbent, the other the same as in Example 1 is also added without.
Embodiment 4
The hydration reaction of embodiment 1-8 and comparative example 1-4 is reruned 50 batches, is closed by JIS H1619-1995 titaniums and titanium
The hydrogen concentration of the titanium material of the assay method detection titanium matter hydration reactor of hydrogen in gold.
And using each component content of gas chromatographic detection sec-butyl alcohol crude product, calculate conversion per pass.
Table 1：The hydrogen concentration of the titanium material of the conversion per pass and hydration reactor of embodiment 1-3 and comparative example 1-4.
| Embodiment | Conversion per pass % | Hydrogen concentration ppm of titanium material |
| Embodiment 1 | 43 | 24 |
| Embodiment 2 | 41 | 27 |
| Embodiment 3 | 46 | 23 |
| Comparative example 1 | 38 | 36 |
| Comparative example 2 | 38 | 53 |
| Comparative example 3 | 33 | 29 |
| Comparative example 4 | 29 | 58 |
| Unused titanium material | 21 |
Claims (4)
1. a kind of method that butylene hydration prepares sec-butyl alcohol, it is characterised in that comprise the following steps：
（1）The preparation of hydrogen absorbent
Flyash, the deionized water of flyash quality degree 500-1000, flyash quality hundred are added in a kettle.
Divide the double methylenephosphonic acids of 1,6- hexamethylene triamines five than content 0.01-0.1, add flyash quality degree 0.5-2's
Gamma-aminopropyl-triethoxy-silane (KH-550), in 40-80 DEG C of stirring reaction 10-20h, filters, and drying is obtained hydrogen absorbent;
（2）Hydration reaction
By deionized water, the heteropoly acid of deionized water quality degree 0.5-5, in 40-80 DEG C of stirring reaction 1-5h, it is obtained
Reaction water, by mixing carbon four, reaction water is entered in hydration reactor, adds the hydrogen of deionized water quality degree 0.5-2
Absorbent, adds the aliphatic amine polyoxyethylene ether disulfonate of deionized water quality degree 0.01-0.1, temperature 180-
250 DEG C, pressure 10-25MPa, time of staying 0.5-5h, from reactor top extraction sec-butyl alcohol crude product, unreacted water and catalysis
Agent is produced by reactor side.
2. the method that a kind of butylene hydration according to claim 1 prepares sec-butyl alcohol, it is characterised in that described heteropoly acid
It is by hetero atom（Such as P, Si, Fe, Co）And polyatom（Such as Mo, W, V, Nb, Ta）Matched somebody with somebody by oxygen atom by certain structure
The oxygen-containing polyacid of one class of position bridging composition.
3. the method that a kind of butylene hydration according to claim 1 prepares sec-butyl alcohol, it is characterised in that described hydrogen absorbs
Agent is stayed in hydration reactor and reused.
4. the method that a kind of butylene hydration according to claim 1 prepares sec-butyl alcohol, it is characterised in that described mixing carbon
The mol ratio of n-butene and deionized water in four is 1:5-15.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710017523.0A CN106631688A (en) | 2017-01-11 | 2017-01-11 | Method for preparing sec-butyl alcohol through butylene hydration |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710017523.0A CN106631688A (en) | 2017-01-11 | 2017-01-11 | Method for preparing sec-butyl alcohol through butylene hydration |
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| CN201710017523.0A Pending CN106631688A (en) | 2017-01-11 | 2017-01-11 | Method for preparing sec-butyl alcohol through butylene hydration |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1210847A (en) * | 1997-09-10 | 1999-03-17 | 中国石油化工总公司 | Process for producing low carbon alcohol by directly hydrating low carbon olefines |
| CN101395111A (en) * | 2006-03-02 | 2009-03-25 | 出光兴产株式会社 | Process for the preparation of sec-butanol |
-
2017
- 2017-01-11 CN CN201710017523.0A patent/CN106631688A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1210847A (en) * | 1997-09-10 | 1999-03-17 | 中国石油化工总公司 | Process for producing low carbon alcohol by directly hydrating low carbon olefines |
| CN101395111A (en) * | 2006-03-02 | 2009-03-25 | 出光兴产株式会社 | Process for the preparation of sec-butanol |
Non-Patent Citations (1)
| Title |
|---|
| 吴承明等: "仲丁醇合成工艺研究进展", 《化学工程师》 * |
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Address after: The new school district 322000 town Zhejiang city Yiwu province 5 Building 1 unit 201 room Applicant after: Wang Yilin Address before: 402, building 19, building three, garden community, 324004 Garden Street, Zhejiang, Quzhou Applicant before: Wang Yilin |
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Application publication date: 20170510 |
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