CN106316911A - Method and apparatus for preparation of hydrogen peroxide p-menthane by non-catalytic oxidation of p-menthane - Google Patents
Method and apparatus for preparation of hydrogen peroxide p-menthane by non-catalytic oxidation of p-menthane Download PDFInfo
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- CN106316911A CN106316911A CN201510329339.0A CN201510329339A CN106316911A CN 106316911 A CN106316911 A CN 106316911A CN 201510329339 A CN201510329339 A CN 201510329339A CN 106316911 A CN106316911 A CN 106316911A
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Abstract
The invention relates to a method and apparatus for non-catalytic air oxidation of liquid phase p-menthane to generate hydrogen peroxide p-menthane. The method is characterized in that: 0-3% of the product hydrogen peroxide p-menthane is adopted as the initiator, an alkaline solution is employed for continuous washing of inflow gas, and oxidation reaction is carried out at a temperature of 50DEG C-140DEG C and under a pressure of 0-0.5MPa. The method has the advantages of no use of catalyst, fast reaction speed, high product yield, and simplifies the follow-up complicated purification process.
Description
Technical field
The present invention relates to a kind of prepared by alkane non-catalytic oxidation in the Meng hydrogen peroxide method and device to alkane in the Meng.
Background technology
To alkane in the Meng (PM) be fully saturated after hydrogenation monocyclic monoterpene compounds, typically obtain with dipentene Hydrogenation from afforestation product.
Being the olefinic polymerization initiator of a kind of function admirable to alkane hydrogen peroxide in the Meng (PMHP), such as butadiene and styrene polymerization react.Compared with other organic hydroperoxide, PMHP serviceability is good, low-consuming and stability is excellent, is widely used as the initiator of low temperature emulsion method polymerized sbr, and alkane hydrogen peroxide in the Meng is mainly used alkane air oxidation in the Meng by industrial production.
Alkane in the Meng is prepared in the hydrogen peroxide method to alkane in the Meng by catalytic air oxidation disclosed in Chinese patent application CN101225067A, describes and adds catalyst liquid phase oxidation with batch technology alkane in the Meng obtains the hydrogen peroxide method to alkane in the Meng；Chinese patent application CN101962352A discloses and hydrogen peroxide is prepared by alkane in the Meng to the continuous producing method of alkane in the Meng and device thereof, but the serialization to alkoxide technique in the Meng is not widely used in commercial production, large-scale industrial production is also mainly based on the batch technology of non-catalytic oxidation.
The main problem using interval catalytic oxidation technique to exist is then that catalyst adds or filling.Intermittent oxidation needs again to add catalyst before adding reaction raw materials every time, if do not separated and recovered at the end of reaction, remaining catalyst just flows into next workshop section along with mixed liquor, reduces product purity, causing expensive catalyst to run off, the waste liquid simultaneously discharged also can affect environment.But abjection catalyst needs one section of huge separation circuit, step is the most considerably complicated, needs to put into a large amount of manpower, material resources and financial resources.And also having, in addition to gas-liquid aoxidizes, the fixed bed reaction technique comprising gas-liquid-solid three-phase, this proposes strict requirements to the safety of consersion unit Appropriate application and production, and the cleaning of catalyst simultaneously is also a numerous and diverse step.
For problem above, inventor sums up conventional achievement in research, from non-catalytic oxidation angle, by the selectivity of alkane in the Meng being there is no other impurities left with organic acid in reactant liquor to improve hydrogen peroxide in the alkali cleaning of unstripped gas.Develop utilize hydrogen peroxide to alkane in the Meng as initiator, reaction air inlet alkali cleaning to synthesize hydrogen peroxide to the method for alkane in the Meng and device thereof.
Summary of the invention
It is an object of the invention to provide a kind of technique simple, with low cost, hydrogen peroxide to alkane selectivity in the Meng good to oxidation process in the Meng and device.
The invention discloses a kind of method to alkoxide in the Meng, it is characterized in that with principal product hydrogen peroxide to alkane in the Meng as initiator, unstripped gas alkali cleaning enters autoclave, temperature be 50 DEG C 140 DEG C, under conditions of pressure is 0.3MPa, according to hydrogen peroxide to the Meng alkane mass fraction 0%～3% ratio react.
In the method that the present invention provides, alkaline solution can include NH3·H2O、Na2CO3Solution, NaHCO3The alkalescent system such as solution water solution, highly basic enters system not only etching apparatus more can cause the hydrogen peroxide decomposition to alkane in the Meng, reaches reverse effect.The mass fraction of the weak caustic solution used should control within the specific limits.
In the method that the present invention provides, unstripped gas is chosen as air or air and oxygen mixture.
In the method that the present invention provides; reaction can be carried out under conditions of existing without catalyst; raw material adds reactor to alkane in the Meng with the ratio of mass fraction 100:1,50:1,40:1 with initiator hydrogen peroxide to alkane in the Meng; the weak caustic solution of implantation quality mark 0%～5% in caustic treater 1-14 simultaneously; whole process heats up under nitrogen protection, heats up and terminates to switch to air at once.
The method to alkoxide in the Meng that the present invention provides, the production efficiency overcoming traditional non-catalytic production technology is low, the shortcoming that selectivity of product is low, turn avoid the problems such as catalysis oxidation flow process complexity, separation costs height and noxious emission simultaneously.The present invention is with air oxidant, flow through alkaline bath and bring a small amount of alkali liquor into reaction system, in material liquid except add self product hydrogen peroxide to alkane in the Meng as initiator in addition to, without adding any inhibitor or catalyst, production process is simple, is easily controlled, and hydrogen peroxide is high to alkane selectivity in the Meng, oxygen effective rate of utilization is high, CO and CO in tail gas2Volume fraction is less than 0.4%.
Detailed description of the invention
The present invention will be further described by below example, but and be not so limited present disclosure.
Embodiment 1
Being 100 DEG C in temperature is under 0.3MPa with pressure, with oxygen as oxidant, and alkali wash water NaCO3The mass fraction of solution is 2%, and ventilation is 3L/min, will react alkane in the Meng and hydrogen peroxide under the alkane in the Meng mol ratio according to 50:1.The result reacting 5 hours is as follows: be 24% to alkane conversion ratio in the Meng；Hydrogen peroxide is 19% to the mass fraction of alkane in the Meng.
Embodiment 2
Being 110 DEG C in temperature is under 0.3MPa with pressure, with oxygen as oxidant, and alkali wash water NaCO3The mass fraction of solution is 2%, and ventilation is 3L/min, will react alkane in the Meng and hydrogen peroxide under the alkane in the Meng mol ratio according to 50:1.The result reacting 5 hours is as follows: be 30% to alkane conversion ratio in the Meng；Hydrogen peroxide is 20% to the mass fraction of alkane in the Meng.
Embodiment 3
Being 120 DEG C and pressure is under 0.3MPa in temperature, with oxygen as oxidant, initiator hydrogen peroxide is 2% to the mass fraction of alkane in the Meng, and ventilation is 3L/min, will react alkane in the Meng and hydrogen peroxide under the alkane in the Meng mol ratio according to 50:1.The result reacting 5 hours is as follows: be 33% to alkane conversion ratio in the Meng；Hydrogen peroxide is 23% to the mass fraction of alkane in the Meng.
Embodiment 4
Being 130 DEG C in temperature is under 0.3MPa with pressure, with oxygen as oxidant, and alkali wash water NaCO3The mass fraction of solution is 1%, and ventilation is 3L/min, will react alkane in the Meng and hydrogen peroxide under the alkane in the Meng mol ratio according to 50:1.The result reacting 5 hours is as follows: be 47% to alkane conversion ratio in the Meng；Hydrogen peroxide is 27% to the mass fraction of alkane in the Meng, and the mass fraction of alkane in the Meng is only had 22% by the hydrogen peroxide being added without alkaline cleaning procedure with this understanding.
Embodiment 5
Being 130 DEG C in temperature is under 0.3MPa with pressure, with oxygen as oxidant, and alkali wash water NaCO3The mass fraction of solution is 5%, and ventilation is 3L/min, will react alkane in the Meng and hydrogen peroxide under the alkane in the Meng mol ratio according to 50:1.The result reacting 5 hours is as follows: be 53% to alkane conversion ratio in the Meng；Hydrogen peroxide is 28% to the mass fraction of alkane in the Meng, and the mass fraction of alkane in the Meng is only had 23% by the hydrogen peroxide being added without alkaline cleaning procedure with this understanding.
Embodiment 6
Being 130 DEG C in temperature is under 0.3MPa with pressure, with oxygen as oxidant, and alkali wash water NaCO3The mass fraction of solution is 2%, and ventilation is 3L/min, will react alkane in the Meng and hydrogen peroxide under the alkane in the Meng mol ratio according to 50:1.The result reacting 5 hours is as follows: be 53% to alkane conversion ratio in the Meng；Hydrogen peroxide is 28% to the mass fraction of alkane in the Meng, and the selectivity of alkane in the Meng is only had 22% by the hydrogen peroxide being added without alkaline cleaning procedure with this understanding.
Embodiment 7
Being 130 DEG C in temperature is under 0.3MPa with pressure, with oxygen as oxidant, and alkali wash water Na2CO3The mass fraction of solution is 2%, and ventilation is 1L/min, will react alkane in the Meng and hydrogen peroxide under the alkane in the Meng mol ratio according to 50:1.The result reacting 5 hours is as follows: be 49% to alkane conversion ratio in the Meng；Hydrogen peroxide is 23% to the mass fraction of alkane in the Meng, and when ventilation is 3L/min with this understanding, hydrogen peroxide is 28% to the mass fraction of alkane in the Meng.
Embodiment 8
Being 130 DEG C in temperature is under 0.3MPa with pressure, with oxygen as oxidant, and alkali wash water Na2CO3The mass fraction of solution is 2%, and ventilation is 6L/min, will react alkane in the Meng and hydrogen peroxide under the alkane in the Meng mol ratio according to 50:1.The result reacting 5 hours is as follows: be 54% to alkane conversion ratio in the Meng；Hydrogen peroxide is 28% to the mass fraction of alkane in the Meng.
Embodiment 9
Under pressure is 0.3MPa, with oxygen as oxidant, alkali wash water Na2CO3The mass fraction of solution is 0.5%, and ventilation is 3L/min, will react alkane in the Meng and hydrogen peroxide under the alkane in the Meng mass ratio according to 200:1.Temperature is 130 DEG C and reacts 2 hours, then temperature to 120 DEG C is reacted the result of 3 hours as follows: be 50% to alkane conversion ratio in the Meng；Hydrogen peroxide is 27% to the mass fraction of alkane in the Meng.
Embodiment 10
Under pressure is 0.3MPa, with oxygen as oxidant, alkali wash water Na2CO3The mass fraction of solution is 2%, and ventilation is 3L/min, will react alkane in the Meng and hydrogen peroxide under the alkane in the Meng mol ratio according to 50:1.Temperature is 130 DEG C and reacts 2 hours, then temperature to 120 DEG C is reacted the result of 3 hours as follows: be 52% to alkane conversion ratio in the Meng；Hydrogen peroxide is 30% to the mass fraction of alkane in the Meng.
Claims (10)
1. a liquid phase produces the hydrogen peroxide method to alkane in the Meng to alkane on-catalytic air oxidation in the Meng, it is characterised in that the product hydrogen peroxide using 0%～3% to alkane in the Meng as initiator.
2. according to the method for claim 1, it is characterised in that feeding gas enters back into reactor in bubbling mode by after caustic treater, and caustic treater neutral and alkali solution includes NH3•H2O、Na2CO3Aqueous solution, NaHCO3One in aqueous solution etc., mass concentration is in 0%～5%.
3. according to the method for claim 1, it is characterised in that temperature maintains 50 DEG C～10 DEG C.
4. according to the method for claim 1, it is characterised in that reaction pressure is maintained at 0 ~ 0.3MPa.
5. according to the method for claim 1, it is characterised in that selected unstripped gas is air or air and oxygen mixture.
6. a liquid phase is to the semicontinuous reaction unit of alkane air oxidation in the Meng, this device includes: provide the electric heating cover (1) stablizing heat, the motor agitating device (2) of full and uniform mixing can be carried out, the titanium alloy reactor (3) of high pressure, acid-alkali-corrosive-resisting can be born, the rustless steel surge tank (4) of sustainable alkali cleaning air inlet, accurately control flow controller and the electrodynamic valve (5) of flow, the computer (6) that programme-control stores with data, online magnetic force tail oxygen analyzer (7), online infrared C O2, CO analyser (8) accurately measure the thermocouple (10) of temperature for the coil pipe water cooler (9) of condensation reaction mixture.
7. device as claimed in claim 6, it is characterized in that, described oxidation reaction apparatus is semicontinuous system, and raw material disposably adds autoclave, air or air to alkane in the Meng and initiator hydrogen peroxide to alkane in the Meng and is continuously added into through alkaline bath 14 by compressor or steel cylinder with oxygen mixture.
8. device as claimed in claim 6, it is characterised in that increase online gas analyzer for O2 9, measure scope 0%～21% (molar percentage), through calibrating gas calibrated error in allowed band.
9. device as claimed in claim 6, it is characterised in that increase online infrared CO2Analyser 10, measures scope 0%～5% (molar percentage), through calibrating gas calibrated error in allowed band.
10. device as claimed in claim 6, it is characterised in that increase online infrared CO analyser 11, measure scope 0%～2% (molar percentage), through calibrating gas calibrated error in allowed band.
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