CN106316911B - Prepared by method and device of the hydrogen peroxide to Meng's alkane to Meng's alkane non-catalytic oxidation - Google Patents
Prepared by method and device of the hydrogen peroxide to Meng's alkane to Meng's alkane non-catalytic oxidation Download PDFInfo
- Publication number
- CN106316911B CN106316911B CN201510329339.0A CN201510329339A CN106316911B CN 106316911 B CN106316911 B CN 106316911B CN 201510329339 A CN201510329339 A CN 201510329339A CN 106316911 B CN106316911 B CN 106316911B
- Authority
- CN
- China
- Prior art keywords
- meng
- alkane
- hydrogen peroxide
- initiator
- air
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of liquid phases to generate the non-catalytic air oxidation of Meng's alkane method and device of the hydrogen peroxide to Meng's alkane.It is characterized in that using 0~3% product hydrogen peroxide to Meng's alkane as initiator, alkaline solution persistently washs air inlet, and oxidation reaction carries out under temperature 50 C~140 DEG C, 0 0.5MPa of pressure.This method does not use catalyst, and reaction speed is fast, product yield high, simplifies the purification process of follow-up complexity.
Description
Technical field
Prepared by method and device of the hydrogen peroxide to Meng's alkane to Meng's alkane non-catalytic oxidation the present invention relates to a kind of.
Background technology
Be to Meng's alkane (PM) it is fully saturated after hydrogenation monocyclic monoterpene compounds, generally add from afforestation product with dipentene
Hydrogen is made.
It is a kind of olefinic polymerization initiator of function admirable to Meng's alkane hydrogen peroxide (PMHP), such as butadiene and styrene
Polymerisation.Compared with other organic hydroperoxides, PMHP performances are good, and low-consuming and stability is excellent, is widely used as
The initiator of low temperature emulsion method polymerized sbr, industrial production is to Meng's alkane hydrogen peroxide mainly using to Meng's alkane air
Oxidation.
Catalytic air oxidation disclosed in Chinese patent application CN101225067A prepares Meng's alkane hydrogen peroxide to Meng's alkane
In method, describe and method of the hydrogen peroxide to Meng's alkane is obtained to Meng's alkane with batch technology addition catalyst liquid phase oxidation；China
It is disclosed in patent application CN101962352A and continuous producing method and its device of the hydrogen peroxide to Meng's alkane is prepared to Meng's alkane, but
Industrial production is not widely used in the serialization of Meng's alkoxide technique, large-scale industrial production is also mainly with non-catalytic oxygen
Based on the batch technology of change.
It is then that catalyst is added in or loaded using problem main existing for interval catalytic oxidation technique.Intermittent oxidation needs
Catalyst is added again before reaction raw materials are added in every time, if do not separated and recovered at the end of reaction, remaining catalyst
Just as mixed liquor flows into next workshop section, product purity is reduced, expensive catalyst is caused to be lost in, while the waste liquid discharged also can shadow
Ring environment.However abjection catalyst needs one section of huge separation process, step is also considerably complicated, needs to put into a large amount of manpower objects
Power financial resources.And also having the fixed bed reaction technique comprising gas-liquid-solid three-phase other than gas-liquid aoxidizes, this is reasonable to consersion unit
Using and the safety of production propose strict requirements, while the cleaning of catalyst is also a numerous and diverse step.
In view of the above problems, inventor summarizes previous achievement in research, from non-catalytic oxidation angle, pass through unstripped gas
Alkali cleaning neutralization reaction liquid in organic acid other impurities residual is had no to improve hydrogen peroxide to the selectivity of Meng's alkane.Develop profit
Method and its device of the hydrogen peroxide to Meng's alkane are synthesized as initiator, reaction air inlet alkali cleaning to Meng's alkane by the use of hydrogen peroxide.
Invention content
The object of the present invention is to provide a kind of simple process and low cost is honest and clean, hydrogen peroxide is selectively good to Meng to Meng's alkane
Oxidation process and device.
The invention discloses a kind of methods to Meng's alkoxide, it is characterised in that using principal product hydrogen peroxide to Meng's alkane to draw
Agent is sent out, unstripped gas alkali cleaning enters autoclave, under conditions of temperature is 50 DEG C 140 DEG C, pressure is 0.3MPa, according to peroxide
Change hydrogen to react Meng's alkane mass fraction in 0%~3% ratio.
In method provided by the invention, alkaline solution may include NH3·H2O、Na2CO3Solution, NaHCO3Solution aqueous solution etc.
Alkalescent system, highly basic enters system, and not only etching apparatus but will cause decomposition of the hydrogen peroxide to Meng's alkane, reach reverse effect.
The mass fraction of used weak caustic solution should control in a certain range.
In method provided by the invention, unstripped gas selected as air or air and oxygen mixture.
In method provided by the invention, reaction can carry out under the conditions of existing for no catalyst, and raw material is to Meng's alkane with drawing
Agent hydrogen peroxide is sent out to Meng's alkane with mass fraction 100:1、50:1、40:1 ratio adds in reaction kettle, while in caustic treater 1-14
The weak caustic solution of middle implantation quality score 0%~5%, whole process heat up under nitrogen protection, and heating terminates to switch to air at once.
Method provided by the invention to Meng's alkoxide overcomes the low production efficiency of traditional non-catalytic production technology, production
The shortcomings that object is selectively low, while in turn avoid that catalysis oxidation flow is complicated, separation costs are high and the problems such as noxious emission.This
Invention is flowed through alkaline bath and brings a small amount of lye into reaction system, removed in material liquid and add itself product mistake with air oxidant
Hydrogen oxide to Meng's alkane as initiator outside, without adding any inhibitor or catalyst, production process is simple, is easy to control, mistake
Hydrogen oxide is to Meng's alkane high selectivity, and oxygen effective rate of utilization is high, CO and CO in tail gas2Volume fraction is less than 0.4%.
Description of the drawings
Fig. 1 shows a kind of liquid phases to the semicontinuous reaction unit of Meng's alkane air oxidation, and the apparatus structure is as follows：
The flow controller of flow and motor-driven valve (3,4) are accurately controlled, the motor stirring dress of full and uniform mixing can be carried out
(6) are put, for the coil pipe water cooler (7) of condensation reaction mixture, online magnetic force tail oxygen analyzer (9), online infrared C O2、
CO analyzers (10,11), the computer (12) of program control and data storage, accurately measure the thermocouple (13) of temperature, can hold
The stainless steel surge tank (14) of continuous alkali cleaning air inlet provides the electric heating cover of stable heat and can bear high pressure, acid-alkali-corrosive-resisting
Alloy reaction kettle (15) by the emperor himself.
Reaction unit is semicontinuous system, and raw material disposably adds in high pressure to Meng's alkane and initiator hydrogen peroxide to Meng's alkane
Kettle, air or air are continuously added into oxygen mixture by compressor or steel cylinder by alkaline bath 14.
Specific embodiment
Following embodiment will be further described the present invention, but the content being not intended to limit the present invention.
Embodiment 1
In the case where temperature is 100 DEG C and pressure is 0.3MPa, using oxygen as oxidant, alkali wash water NaCO3The quality of solution point
Number for 2%, ventilatory capacity 3L/min, will to Meng's alkane and hydrogen peroxide to Meng's alkane according to 50：It is reacted under 1 molar ratio.Instead
The result for answering 5 hours is as follows：It is 24% to Meng's alkane conversion ratio；Hydrogen peroxide is 19% to the mass fraction of Meng's alkane.
Embodiment 2
In the case where temperature is 110 DEG C and pressure is 0.3MPa, using oxygen as oxidant, alkali wash water NaCO3The quality of solution point
Number for 2%, ventilatory capacity 3L/min, will to Meng's alkane and hydrogen peroxide to Meng's alkane according to 50：It is reacted under 1 molar ratio.Instead
The result for answering 5 hours is as follows：It is 30% to Meng's alkane conversion ratio；Hydrogen peroxide is 20% to the mass fraction of Meng's alkane.
Embodiment 3
In the case where temperature is 120 DEG C and pressure is 0.3MPa, using oxygen as oxidant, initiator hydrogen peroxide is to the matter of Meng's alkane
Measure score be 2%, ventilatory capacity 3L/min, will to Meng's alkane and hydrogen peroxide to Meng's alkane according to 50：It is carried out under 1 molar ratio anti-
It should.The result of reaction 5 hours is as follows：It is 33% to Meng's alkane conversion ratio；Hydrogen peroxide is 23% to the mass fraction of Meng's alkane.
Embodiment 4
In the case where temperature is 130 DEG C and pressure is 0.3MPa, using oxygen as oxidant, alkali wash water NaCO3The quality of solution point
Number for 1%, ventilatory capacity 3L/min, will to Meng's alkane and hydrogen peroxide to Meng's alkane according to 50：It is reacted under 1 molar ratio.Instead
The result for answering 5 hours is as follows：It is 47% to Meng's alkane conversion ratio；Hydrogen peroxide is 27% to the mass fraction of Meng's alkane, and at this
The hydrogen peroxide that alkaline cleaning procedure is added without under part only has 22% to the mass fraction of Meng's alkane.
Embodiment 5
In the case where temperature is 130 DEG C and pressure is 0.3MPa, using oxygen as oxidant, alkali wash water NaCO3The quality of solution point
Number for 5%, ventilatory capacity 3L/min, will to Meng's alkane and hydrogen peroxide to Meng's alkane according to 50：It is reacted under 1 molar ratio.Instead
The result for answering 5 hours is as follows：It is 53% to Meng's alkane conversion ratio；Hydrogen peroxide is 28% to the mass fraction of Meng's alkane, and at this
The hydrogen peroxide that alkaline cleaning procedure is added without under part only has 23% to the mass fraction of Meng's alkane.
Embodiment 6
In the case where temperature is 130 DEG C and pressure is 0.3MPa, using oxygen as oxidant, alkali wash water NaCO3The quality of solution point
Number for 2%, ventilatory capacity 3L/min, will to Meng's alkane and hydrogen peroxide to Meng's alkane according to 50：It is reacted under 1 molar ratio.Instead
The result for answering 5 hours is as follows：It is 53% to Meng's alkane conversion ratio；Hydrogen peroxide is 28% to the mass fraction of Meng's alkane, and at this
The hydrogen peroxide that alkaline cleaning procedure is added without under part only has 22% to the selectivity of Meng's alkane.
Embodiment 7
In the case where temperature is 130 DEG C and pressure is 0.3MPa, using oxygen as oxidant, alkali wash water Na2CO3The quality of solution point
Number for 2%, ventilatory capacity 1L/min, will to Meng's alkane and hydrogen peroxide to Meng's alkane according to 50：It is reacted under 1 molar ratio.Instead
The result for answering 5 hours is as follows：It is 49% to Meng's alkane conversion ratio；Hydrogen peroxide is 23% to the mass fraction of Meng's alkane, and at this
When ventilatory capacity is 3L/min under part, hydrogen peroxide is 28% to the mass fraction of Meng's alkane.
Embodiment 8
In the case where temperature is 130 DEG C and pressure is 0.3MPa, using oxygen as oxidant, alkali wash water Na2CO3The quality of solution point
Number for 2%, ventilatory capacity 6L/min, will to Meng's alkane and hydrogen peroxide to Meng's alkane according to 50：It is reacted under 1 molar ratio.Instead
The result for answering 5 hours is as follows：It is 54% to Meng's alkane conversion ratio；Hydrogen peroxide is 28% to the mass fraction of Meng's alkane.
Embodiment 9
In the case where pressure is 0.3MPa, using oxygen as oxidant, alkali wash water Na2CO3The mass fraction of solution is 0.5%, ventilation
Measure as 3L/min, will to Meng's alkane and hydrogen peroxide to Meng's alkane according to 200：It is reacted under 1 mass ratio.Temperature is anti-for 130 DEG C
2 hours are answered, it is then that the result of temperature to 120 DEG C of reactions 3 hours is as follows：It is 50% to Meng's alkane conversion ratio；Hydrogen peroxide is to Meng
The mass fraction of alkane is 27%.
Embodiment 10
In the case where pressure is 0.3MPa, using oxygen as oxidant, alkali wash water Na2CO3The mass fraction of solution is 2%, ventilatory capacity
For 3L/min, will to Meng's alkane and hydrogen peroxide to Meng's alkane according to 50：It is reacted under 1 molar ratio.Temperature is 130 DEG C of reactions 2
It is a hour, then that the result of temperature to 120 DEG C of reactions 3 hours is as follows：It is 52% to Meng's alkane conversion ratio；Hydrogen peroxide is to Meng's alkane
Mass fraction is 30%.
Claims (2)
1. a kind of liquid phase produces the non-catalytic air oxidation of Meng's alkane method of the hydrogen peroxide to Meng's alkane, it is characterised in that with principal product
Hydrogen peroxide is initiator to Meng's alkane, and the initiator is 1 with the molar ratio to Meng's alkane:50, it is anti-that unstripped gas alkali cleaning enters high pressure
Kettle is answered, is reacted under conditions of temperature is 50~140 DEG C, pressure is 0.3MPa, the reaction time is 5 hours；
For unstripped gas by entering back into reaction kettle after caustic treater in a manner of bubbling, caustic treater neutral and alkali solution includes NH3·H2O、
Na2CO3Aqueous solution or NaHCO3Aqueous solution, the mass concentration of the alkaline solution is 1%~5%.
2. according to the method described in claim 1, it is characterized in that the unstripped gas is air or air and oxygen mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510329339.0A CN106316911B (en) | 2015-06-15 | 2015-06-15 | Prepared by method and device of the hydrogen peroxide to Meng's alkane to Meng's alkane non-catalytic oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510329339.0A CN106316911B (en) | 2015-06-15 | 2015-06-15 | Prepared by method and device of the hydrogen peroxide to Meng's alkane to Meng's alkane non-catalytic oxidation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106316911A CN106316911A (en) | 2017-01-11 |
| CN106316911B true CN106316911B (en) | 2018-06-12 |
Family
ID=57733339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510329339.0A Active CN106316911B (en) | 2015-06-15 | 2015-06-15 | Prepared by method and device of the hydrogen peroxide to Meng's alkane to Meng's alkane non-catalytic oxidation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106316911B (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2302466A (en) * | 1941-03-19 | 1942-11-17 | Newport Ind Inc | Process of oxidizing cymenes |
| DE2444389C3 (en) * | 1973-09-17 | 1980-06-12 | Osrodek Badawczo Rozwojowy Kauczukow I Tworzyw Winylowych, Oswiencim (Polen) | Process for the production of hydroperoxides from turpentine hydrocarbons |
| CN101225067B (en) * | 2007-01-19 | 2011-12-07 | 湖南大学 | Method for preparing hydroperoxidation p-menthane by catalytic air oxidation p-menthane |
| CN101962352B (en) * | 2010-09-17 | 2011-08-31 | 湖南松源化工有限公司 | Method for continuously producing p-menthane hydroperoxide by p-menthane and device thereof |
| CN103819380A (en) * | 2014-02-26 | 2014-05-28 | 吉林化工学院 | New method for producing p-menthane hydroperoxide with series connection of multiple bubbling-tower reactors |
| CN104151224A (en) * | 2014-08-13 | 2014-11-19 | 广西梧松林化集团有限公司 | Method for synthesizing pinane superoxide by oxidizing pinane |
-
2015
- 2015-06-15 CN CN201510329339.0A patent/CN106316911B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106316911A (en) | 2017-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102936201B (en) | Production apparatus and production method for methyl nitrite | |
| CN111606790B (en) | System and method for continuously producing high-quality high-selectivity benzaldehyde and benzoic acid by using jet loop reactor | |
| CN111295238B (en) | NOx abatement method for precious metal refining and recycling processes | |
| CN101885712B (en) | Method for producing propylene oxide | |
| CN106316911B (en) | Prepared by method and device of the hydrogen peroxide to Meng's alkane to Meng's alkane non-catalytic oxidation | |
| CN102675147B (en) | Method for preparing lemonile by using citral | |
| CN1834078A (en) | Cyclohexane liquid phase oxidation technique | |
| CN101531337B (en) | Method and device for low-pressure processing of coal coking gas | |
| CN112456450A (en) | System and method for resource utilization of waste sulfuric acid containing organic matters | |
| CN1982273A (en) | Production of anone by cyclohexane liquid-phase oxidation | |
| CN110903181B (en) | Method for preparing p-benzoquinone compound by double-catalytic system | |
| CN101993423A (en) | Method for producing epoxy chloropropane | |
| CN107400038B (en) | Method for preparing cyclohexanone and cyclohexanol by decomposing cyclohexyl hydroperoxide | |
| CN104447263A (en) | Method for realizing one-step synthesis of carvone through catalytic oxidation | |
| CN103214365B (en) | Method for producing cyclohexyl acetate through benzene | |
| CN103864575A (en) | Method for preparing 1,2-pentanediol | |
| CN106831661A (en) | Method for preparing epoxypropane by using micro-reaction device | |
| CN106905127B (en) | Method for synthesizing 2, 5-hexanedione by oxidative dehydrogenation coupling of acetone | |
| CN102838569B (en) | Method for synthesizing peach aldehyde by using microreactor device | |
| CN105524022A (en) | Preparation method for epoxypropane | |
| CN112174790A (en) | Reinforcing system and process for producing cyclohexanone by cyclohexane oxidation method | |
| CN210683639U (en) | Cyclohexane oxidation reaction device | |
| CN108863789A (en) | A kind of low-purity isobutene prepares the production system and method for methyl methacrylate | |
| CN102976912B (en) | Method for preparing acetophenone | |
| CN115007156B (en) | Calcium-cobalt composite oxide catalyst, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |