CN106365971A - Method for continuously producing glutaraldehyde - Google Patents
Method for continuously producing glutaraldehyde Download PDFInfo
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- CN106365971A CN106365971A CN201610732599.7A CN201610732599A CN106365971A CN 106365971 A CN106365971 A CN 106365971A CN 201610732599 A CN201610732599 A CN 201610732599A CN 106365971 A CN106365971 A CN 106365971A
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- glutaraldehyde
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- dihydropyran
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/60—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in six-membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/79—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for continuously producing glutaraldehyde and belongs to the field of fine chemical intermediate chemical engineering and technologies. Water, 2-methoxy-3,4-dihydropyran and a sodium dihydrogen phosphate saturated solution continuously enter a tanks-in-series reactor and are hydrolyzed at certain temperature to obtain an aqueous solution of glutaraldehyde and methyl alcohol, hydrolysate enters a continuous rectifying tower, methyl alcohol is generated on a tower top, and a qualified glutaraldehyde aqueous solution is generated by a tower bottom. The method has the advantages of being high in production efficiency, stable in process and very suitable for being used in large-scale production devices.
Description
Technical field
The present invention relates to a kind of continuous method producing glutaraldehyde, belong to Chemical Engineering and Technology field.
Background technology
Glutaraldehyde is mainly used as oil-field flooding antibacterial and leather retanning agent, and the sterilization of health field in the market
Agent.
Cn1064665c is a kind of 2- methoxyl group -3 of basf company application, the method for hydrolysis of 4- dihydropyran, the method
Can also can be continuous as intermittent reaction technique, which depict 2- methoxyl group -3,4- dihydropyran, water are being filled with microporous solids
In the tubular reactor of catalyst, hydrolysis obtains glutaraldehyde and corresponding alcohol, and above-mentioned solid acid is homemade for carrier with beta-zeolite
Micropore halogen solid catalyst, this catalyst processing technology is numerous and diverse, and consumptive material is many, and does not refer in literary composition that using of catalyst is all
Phase, 2- methoxyl group -3 under this technique, 4- dihydropyran conversion ratio is higher, but side reaction is more, creates the contracting such as a large amount of acetals
Compound, has had a strong impact on ultimate yield and the quality of product glutaraldehyde.
Cn102992975a discloses a kind of method and apparatus continuously preparing glutaraldehyde, this method describes 2- methoxy
Base -3,4- dihydropyran, water, phosphoric acid continuously enter double tube reactor after static mixer mixing, and double tube reactor goes out
Material is directly entered the rectifying column being filled with solid acid filler or acidic resins, and rectifying tower top continuously produces corresponding alcohol, tower reactor
Continuous acquisition glutaraldehyde water solution.Under this technique, the first partial hydrolysiss in double tube reactor of 2- methoxyl group -3,4- dihydropyran become
Glutaraldehyde and corresponding alcohol, 2- methoxyl group -3 of non-complete hydrolysis, 4- dihydropyran enters rectifying column to be continued in acid condition
Hydrolysis.2- methoxyl group -3,4- dihydropyran is poor with the intersolubility of water, such as wants to reach preferable conversion ratio, the set of double tube reactor
Pipe is necessary for long enough, hydrolysis temperature is necessary sufficiently high or hydrolyzed solution acid number is sufficiently low, but above variable is also impact finally product
Being incremented by of the factor of quality, one of the above or multiple variable all can make end product quality be deteriorated.
Content of the invention
In order to overcome drawbacks described above, the invention provides a kind of disclosure satisfy that the market demand and the continuous life of high-quality glutaraldehyde
Product method.
A kind of continuous produce glutaraldehyde method it is characterised in that: by water, 2- methoxyl group -3,4- dihydropyran, di(2-ethylhexyl)phosphate
Hydrogen sodium saturated solution presses (250～2500): (50～1250): 1 mass ratio enters series connection tank reactor, in 30-150 DEG C of temperature
Under obtain the aqueous solution of glutaraldehyde, methanol, this mixed aqueous solution enters the continuous rectifying tower being filled with cation exchange resin, tower
The methanol of top output by-product, the qualified glutaraldehyde water solution of tower reactor output, color number < 30#, yield 94-96%；Described series connection autoclave is anti-
Device is answered to be multiple reactor series connection, in production process, the concentration of each reactor discharging is stable, and 2- methoxyl group -3,4-
The content of dihydropyran is decline trend.
Further, in technique scheme, described raw water, 2- methoxyl group -3,4- dihydropyran, biphosphate
The mass ratio of sodium saturated solution is preferred (250～1250): (150～1000): 1.
Further, in technique scheme, described series connection tank reactor is the reactor of 2-10 10-5000l
Series connection, material is fed by first kettle, last kettle discharging.
Further, in technique scheme, the reaction temperature of described series connection 2-n reactor of tank reactor is
40-120 DEG C, the reaction temperature of the (n-1)th 0 reactors is 50-80 DEG C；Described n-th reactor is one of 2-9.
Further, in technique scheme, for promoting 2- methoxyl group -3 of micro not thoroughly hydrolysis, 4- dihydropyran
Complete hydrolysis, described continuous rectifying tower is plate column.
Specific embodiment
Embodiment 1
The experiment of this group uses the reactor of 5 10l pilot scale reactors and 1 50l.
Raw material 2- methoxyl group -3,4- dihydropyran is entered with 11kg/h, water 17kg/h, sodium dihydrogen phosphate saturated solution 22g/h
Enter 1# reactor, saturated solution at wherein sodium dihydrogen phosphate saturated solution refers to 20-25 DEG C, material be sequentially connected in series entrance 1#, 3#,
4#, 5#, 6# reactor, 1-5# reactor controlling reaction temperature is 92 DEG C, 0.02mpa, and 6# reactor controlling reaction temperature is 70
DEG C, detection methanol 16-22%, methoxyl group pyrans 0.4-2.7%, glutaraldehyde 72-80%(gas phase color are sampled by 6# reactor discharging opening
Spectrometry testing result), this hydrolyzed solution enters rectifying column and is continuously separated, and tower top obtains the methanol aqueous solution of 27-38% weight,
Gas phase is not detected by methoxyl group pyrans, tower reactor obtain 52.3-54% weight glutaraldehyde water solution, the methanol of 0.3-1.7% weight, 0.3%
The final color number of methoxyl group pyrans below weight, product < 30#(platinum-cobalt method), product ultimate yield 95.4%.
Embodiment 2
The experiment of this group uses the reactor of 7 10l pilot scale reactors and 1 50l.
Raw material 2- methoxyl group -3,4- dihydropyran is entered with 19kg/h, water 24kg/h, sodium dihydrogen phosphate saturated solution 30g/h
Enter 1# reactor, saturated solution at wherein sodium dihydrogen phosphate saturated solution refers to 20-25 DEG C.Material is sequentially connected in series entrance 1#-8#
Reactor, 1-7# reactor controlling reaction temperature is 85 DEG C, and 8# reactor controlling reaction temperature is 60 DEG C, by 8# reactor discharging
Mouth sampling detection methanol 16-20%, methoxyl group pyrans 0.3-1.2%, glutaraldehyde 72-77%(gas chromatography testing result), this water
Solution liquid enters rectifying column and is continuously separated, and tower top obtains the methanol aqueous solution of 23-30% weight, and gas phase is not detected by first substantially
Epoxide pyrans, tower reactor obtains 52-54% weight glutaraldehyde water solution, the methanol of 0.3-1.7% weight, the methoxyl group below 0.3% weight
Pyrans, and color number < 30#(platinum-cobalt method), product ultimate yield 94.1%.
Embodiment 3
This group uses the reactor of 4 150l pilot scale reactors and 1 300l.
Raw material 2- methoxyl group -3,4- dihydropyran enters 1# with 210kg/h, water 315kg/h, sodium dihydrogen phosphate 0.4kg/h
Reactor, saturated solution at wherein sodium dihydrogen phosphate saturated solution refers to 20-25 DEG C, material is sequentially connected in series entrance 1#-5# reaction
Kettle, 1-4# reactor controlling reaction temperature is 90 DEG C, and 5# reactor controlling reaction temperature is 60 DEG C, is taken by 5# reactor discharging opening
Sample detection methanol 16-20%, methoxyl group pyrans 0.3-2.5%, glutaraldehyde 70-75%(gas chromatography testing result), hydrolyzed solution enters
Enter plate distillation column to be continuously separated, tower top obtains the methanol aqueous solution of 25-40% weight, gas phase is not detected by methoxyl group pyrrole
Mutter, tower reactor obtains 51-53% weight glutaraldehyde water solution, the methanol of 0.3-1.7% weight, the methoxyl group pyrans below 0.3% weight,
Color number < 30#(platinum-cobalt method), product ultimate yield 94.8%.
These are only the present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto, any
Those familiar with the art in the technical scope of present disclosure, technology according to the present invention scheme and its invention
Design in addition equivalent or change, all should be included within the scope of the present invention.
Claims (5)
1. a kind of continuous produce glutaraldehyde method it is characterised in that: by water, 2- methoxyl group -3,4- dihydropyran, biphosphate
Sodium presses (250～2500): (50～1250): 1 mass ratio enters series connection tank reactor, obtains penta 2 at a temperature of 30-150 DEG C
Aldehyde, the aqueous solution of methanol, this mixed aqueous solution enters the continuous rectifying tower being filled with cation exchange resin, tower top output by-product
Methanol, the qualified glutaraldehyde water solution of tower reactor output, color number < 30#, yield 94-96%；Described series connection tank reactor is multiple
Reactor is connected, and in production process, the concentration of each reactor discharging is stable, and 2- methoxyl group -3,4- dihydropyran
Content is decline trend.
2. according to claim 1 a kind of continuous produce glutaraldehyde method it is characterised in that: described raw water, 2- methoxy
Base -3,4- dihydropyran, the mass ratio of sodium dihydrogen phosphate are preferably (250～1250): (150～1000): 1.
3. according to claim 1 a kind of continuous produce glutaraldehyde method it is characterised in that: described series connection tank reactor
Reactor series connection for 2-10 10-5000l, material is fed by first kettle, last kettle discharging.
4. according to claim 1 or 3 a kind of continuous produce glutaraldehyde method it is characterised in that: described series connection autoclave anti-
The reaction temperature answering 2-n reactor of device is 40-120 DEG C, and the reaction temperature of the (n-1)th 0 reactors is 50-80 DEG C；Described
N-th reactor is one of 2-9.
5. according to claim 1 a kind of continuous produce glutaraldehyde method it is characterised in that: described continuous rectifying tower is
Plate column.
Priority Applications (1)
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| CN201610732599.7A CN106365971A (en) | 2016-08-27 | 2016-08-27 | Method for continuously producing glutaraldehyde |
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| CN201610732599.7A CN106365971A (en) | 2016-08-27 | 2016-08-27 | Method for continuously producing glutaraldehyde |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115872846A (en) * | 2023-01-06 | 2023-03-31 | 武汉有机实业有限公司 | Method for decoloring glutaraldehyde aqueous solution |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5600018A (en) * | 1994-08-18 | 1997-02-04 | Basf Aktiengesellschaft | Preparation of glutaraldehyde |
| CN102066302A (en) * | 2008-06-19 | 2011-05-18 | 陶氏环球技术公司 | Preparation of glutaraldehyde |
| CN102292975A (en) * | 2009-02-05 | 2011-12-21 | 松下电器产业株式会社 | Solid state imaging element, camera system and method for driving solid state imaging element |
-
2016
- 2016-08-27 CN CN201610732599.7A patent/CN106365971A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5600018A (en) * | 1994-08-18 | 1997-02-04 | Basf Aktiengesellschaft | Preparation of glutaraldehyde |
| CN102066302A (en) * | 2008-06-19 | 2011-05-18 | 陶氏环球技术公司 | Preparation of glutaraldehyde |
| CN102292975A (en) * | 2009-02-05 | 2011-12-21 | 松下电器产业株式会社 | Solid state imaging element, camera system and method for driving solid state imaging element |
Non-Patent Citations (2)
| Title |
|---|
| 杨兴楷: "《石油化工中试装置实训》", 31 January 2008, 中国石化出版社 * |
| 王守庆: "戊二醛的合成方法及应用", 《天津化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115872846A (en) * | 2023-01-06 | 2023-03-31 | 武汉有机实业有限公司 | Method for decoloring glutaraldehyde aqueous solution |
| CN115872846B (en) * | 2023-01-06 | 2024-03-08 | 武汉有机实业有限公司 | Decoloring method for glutaraldehyde aqueous solution |
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