CN101962352B - Method for continuously producing p-menthane hydroperoxide by p-menthane and device thereof - Google Patents
Method for continuously producing p-menthane hydroperoxide by p-menthane and device thereof Download PDFInfo
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Abstract
The invention relates to a method for continuously producing p-menthane hydroperoxide by p-menthane and a device thereof. The method comprises the following steps of: 1, blowing an oxidizing gas into an oxidizing tower, adding a mixed solution comprising p-menthane and a catalyst radical initiator into the oxidizing tower to ensure that the gas is in fully contact with the p-menthane solution for carrying out oxidizing reaction; 2, carrying out gas-liquid separation on oxidation products, refluxing a part of p-menthane hydroperoxide products to the oxidizing tower, conveying the left p-menthane hydroperoxide products to a cooler from a discharging hole at the middle of a gas-liquid separator through the other branch pipeline, and entering an intermediate storage tank after cooled; and 3, sending the p-menthane hydroperoxide products in the intermediate storage tank into an evaporator for evaporating and concentrating as well as purifying, then cooling and sending into a product storage tank, and refluxing unoxidized products evaporated by the evaporator to a raw material mixing tank. The invention also relates to a device for implementing the method for continuously producing the p-menthane hydroperoxide by the p-menthane. The p-menthane hydroperoxide produced by using the method in the invention has the advantages of high purity, good quality, stable and safe production process and convenient operation.
Description
Technical field
The present invention relates to a kind of to the Meng alkane prepare continuous production method and the device thereof of hydrogen peroxide to alkane in the Meng.
Background technology
To the Meng alkane be important fine chemical product, generally make with the kautschin hydrogenation from afforestation product.
Hydrogen peroxide is a kind of olefinic polymerization initiator of excellent performance to alkane in the Meng (English name p-Menthane hydroperoxide is called for short PMHP), mainly is used as the initiator of polymerized sbr.Industrial production hydrogen peroxide is by to alkoxide preparation in the Meng to one of the important method of alkane in the Meng.
At present, industrial by to the Meng alkane to produce hydrogen peroxide mainly be batch production technology to what the Meng, alkane adopted, i.e. intermittent oxidation and evaporation concentration purifying technique intermittently.For example, the disclosed catalytic air oxidation of Chinese patent application CN101225067A to the Meng alkane prepare in the method for hydrogen peroxide to alkane in the Meng, introduced with batch technology add the catalyzer liquid-phase oxidation to the Meng alkane obtain the method for hydrogen peroxide to alkane in the Meng; Liu Xianzhang etc. [kautschin dehydrogenation cracking synchronous reaction and asynchronous reaction comparative study. forest chemical engineering communication, 1997, (1), 31] four-hole boiling flask of the 250mL that has reported a band stirring is in the reactor, adopt the rhythmic reaction working method, studied differing temps, different catalysts, the combination of different ratios oxygen air and different hydrogen peroxide to the Meng alkane composition etc. to the influence of oxidizing reaction.
There are the following problems to adopt batch production technology: (1) intermittent oxidation feeds intake usually at every turn and all needs to add catalyzer and just can reach and produce desired oxidation depth, because be liquid-phase oxidation, catalyzer is normally with the reaction product outflow reactor, on the one hand, reaction product just can enter next process after need removing catalyzer and impurity; On the other hand, catalyzer costs an arm and a leg, need to reclaim, therefore, the catalyst recovery equipment that need purchase special, and the catalyzer operation steps that removes in the reaction product is quite complicated, and the enterprise that is engaged in this products production both at home and abroad all needs to spend a large amount of inputs just may make catalyst removal in the reaction product; In addition, the discharge of wastewater that removes behind the catalyzer also can cause environmental pollution; (2) for improve product purity as far as possible, oxidation depth must strengthen, and therefore the schedule of operation complexity, exists many potential safety hazards in addition; (3) inconvenient automatization control, mainly by manual operation, except that labour intensity was big, control accuracy was also relatively poor, so general industrial scale is little; (4) hydrogen peroxide to the Meng alkane meet thermal capacitance and easily resolve into pure and mild oxygen, adopt intermittently evaporation concentration purifying technique, heated time is longer in evaporation concentrator, decomposes easily, and product color is deepened.
Also have now and adopt the fixed bed continuous production processes, but there are following two subject matters in production unit wherein: (1) oxidizing tower structure problem: adopt coil pipe (oxygen, air or oxygen and the air gas mixture) device of supplying gas in the oxidizing tower, on coil pipe, have the aperture of about 2 mm of diameter, portal as gas, the defective one that this structure exists is because pore is bigger, the bubble of discharging is big, and specific surface area is little, and gas effciency is low; The 2nd, because pore is bigger, cause in the outer liquid of pipe local gas excessive concentration or liquid to enter into easily to cause gas localized liquid excessive concentration in the pipe and reach the blast limit (under temperature and pressure alkoxide reaction setting in the Meng, the control hydrogen peroxide is no more than 20% just safer to the concentration of alkane in the Meng), cause potential safety hazard; (2) evaporation structure problem: hydrogen peroxide to the Meng alkane be heat-sensitive material, except the long decomposition easily of heated time, product color are deepened, the too high potential safety hazard of also bringing of partial concn, so be different from the evaporation of general material, the vaporizer of traditional structure can not effectively solve the safety and stability thickening problem of hydrogen peroxide to alkane in the Meng.
Summary of the invention
The objective of the invention is at existing to the Meng alkane prepare hydrogen peroxide to the problem that the Meng, alkane existed in producing, provide that a kind of product purity height, quality are good, production process safety and stability, easy to operate serialization produce method and the device thereof of hydrogen peroxide to alkane in the Meng.
The present invention to the Meng alkane prepare hydrogen peroxide to the Meng alkane continuous production method may further comprise the steps:
(1) to alkoxide in the Meng: the mixed gas of air or oxygen or air and oxygen is blasted in the oxidizing tower, will the mixing solutions that the Meng alkane and catalyzer are formed be joined in the oxidizing tower, make gas with to the Meng alkane solution fully contact, carry out oxidizing reaction;
Described catalyzer is a radical initiator, as cupric acetate, Cobaltous diacetate or manganese acetate etc., is disposable adding, add-on be to the Meng alkane raw material weight 0.01% ~ 0.1%, after reaction is normal, needn't add any catalyzer again;
The operational condition of oxidizing reaction is: gas flow rate 20 m that enter oxidizing tower
3/ h ~ 200 m
3/ h is 0.5 m to alkane material charging in Meng flow velocity
3/ h ~ 2.0m
3Temperature is 80 ℃ ~ 130 ℃ in the/h, oxidizing tower;
(2) gas-liquid separation: oxidation products is after the oxidizing tower discharge hole for discharge, enter gas-liquid separator, in gas-liquid separator, isolate gas and hydrogen peroxide to alkane product liquid in the Meng, a part hydrogen peroxide to the Meng alkane product be back in the oxidizing tower through a return line that links to each other with the oxidizing tower opening for feed by gas-liquid separator bottom discharge mouth, continue to finish automatic oxidation reaction with the material of Ta Neixin, the hydrogen peroxide of backflow to the Meng alkane product quantity be 30 m
3/ h ~ 100m
3/ h, remaining hydrogen peroxide to the Meng alkane product from gas-liquid separator middle part discharge hole for discharge, be delivered in the water cooler by another bye-pass and enter middle vessel after the cooling;
(3) evaporation concentration is purified: by fresh feed pump with the hydrogen peroxide in the middle vessel to the Meng alkane product send into vaporizer and carry out evaporation concentration and purify, product after evaporation concentration is purified enters the water cooler cooling again, the hydrogen peroxide of directly collecting after the cooling to the Meng alkane product enter product storage tank; The unoxidized feed back that evaporator evaporation goes out to the raw material mixing tank with new to alkane solution merging in the Meng;
The evaporation concentration purification step is preferably used double effect evaporator to carry out double evaporation-cooling and is concentrated, and is beneficial to improve the purity of reaction product hydrogen oxide to alkane in the Meng;
The operational condition of evaporation concentration is: the charging flow velocity that enters vaporizer is 0.5 m
3/ h ~ 2.0 m
3/ h, 50 ℃ ~ 100 ℃ of control one-level evaporator temperatures, the secondary steaming device is sent out 60 ℃ ~ 100 ℃ of temperature.
When treating the operation of system continous-stable, sampling analysis from oxidizing tower eject the material hydrogen peroxide to the Meng alkane resultant content be 15% ~ 20%, the hydrogen peroxide of secondary evaporimeter bottom discharge to the Meng alkane content be 50 ~ 60%.
Above production process, the disposable adding, other operation steps from feed product is added oxidizing tower, to constantly emitting hydrogen peroxide from the vaporizer discharge port to alkane product in the Meng, is all carried out continuously when being beginning except that catalyzer.
It should be noted that, should be according to hydrogen peroxide bottom oxidizing tower top and the secondary evaporimeter to alkane discharging in Meng concentration, respectively the gas flow in the controlled oxidation tower, to the Meng alkane mass flow, hydrogen peroxide to the Meng alkane product loop back flow, the feed rate of one-level vaporizer, suitably regulate in the oxidizing tower and the temperature and pressure in the vaporizer, up to the resultant hydrogen peroxide to the Meng alkane product purity reach requirement;
The present invention's enforcement alkane in the described Meng prepare hydrogen peroxide to the Meng alkane continuous production method device comprise the raw material mixing tank, charge pump, the oxidizing gas basin, oxidizing tower, gas-liquid separator, the under meter I, the under meter II, the under meter III, the under meter IV, the water cooler I, the water cooler II, middle vessel, fresh feed pump, the one-level vaporizer, secondary evaporimeter, product storage tank and condenser, the discharge port of raw material mixing tank links to each other with the opening for feed of charge pump, the discharge port of charge pump links to each other with under meter I opening for feed, under meter I discharge port links to each other with oxidizing tower underfeed mouth, the air outlet of air reservoir and oxygen storage tank links to each other with the inlet mouth of under meter II with the under meter III respectively, the air outlet of under meter II and under meter III links to each other with oxidizing tower bottom inlet mouth, the top of oxidizing tower links to each other with the gas-liquid separator import by pipeline, the liquid material outlet of gas-liquid separator bottom links to each other with oxidizing tower underfeed mouth with the under meter IV by return line, form circulation loop, the liquid material outlet at gas-liquid separator middle part links to each other with the import of water cooler I by another bye-pass, the outlet of water cooler I links to each other with the middle vessel import, the middle vessel outlet links to each other with the fresh feed pump import by pipeline, the fresh feed pump outlet links to each other with one-level vaporizer top inlet by pipeline, the outlet of one-level base of evaporator directly links to each other with the secondary evaporimeter top inlet, the secondary evaporimeter outlet at bottom by hydrogen peroxide to the Meng alkane product discharge nozzle link to each other with the import of water cooler II, water cooler II outlet by hydrogen oxide to the Meng alkane product discharge nozzle link to each other with the product storage tank import, one-level vaporizer top links to each other with condenser inlet by unoxidized material delivery line, and condensator outlet links to each other with the import of raw material mixing tank through the reflux cycle pipeline; Oxidizing tower is provided with heat exchange jacket, and the heat exchange jacket import links to each other with heating medium pipe or heat-eliminating medium pipe by the pipeline that valve is housed; Be provided with temperature sensor and pressure transmitter in oxidizing tower, one-level vaporizer and the secondary evaporimeter.
The tower body of described oxidizing tower is preferably round shape, and diameter is preferably 500mm ~ 1500mm, and height is preferably 4000mm ~ 10000mm, and the tower inner bottom part is equipped with film pipe diffuser, and the film pore directly is preferably 2 μ m ~ 100 μ m, and diameter and length calculate according to required air input in the tower; Different heights all should be provided with temperature sensor in the oxidizing tower, and oxidizing tower inner bottom part and top also should be provided with pressure transmitter respectively.
Described gas-liquid separator can be selected broken foam gas-liquid separator of silk screen or whirlwind gas-liquid separator for use.
The preferred falling film evaporator of described vaporizer, and should be provided with two is one another in series, be that the outlet of one-level base of evaporator directly links to each other with the secondary evaporimeter top inlet, the all preferred double-sleeve structure of vaporizer, the little variable diameter structure in big bottom, the preferred top of inner sleeve, inner sleeve top is 1:1.5 ~ 3.0 with bottom reducing ratio.Adopting this variable diameter structure is thickness uniformity for the formed film of upper and lower material that guarantees evaporator wall; Should temperature sensor be set at different heights in the vaporizer, one-level vaporizer and secondary evaporimeter bottom and top all also should be provided with pressure transmitter respectively.
The raw material mixing tank is preferably the circle tube tank that has stirring that metal or non-metallic material are made, its effect be oxidizing reaction when beginning with raw material to the Meng alkane and catalyst mix even.
Charge pump and fresh feed pump can be liquid transporting apparatus such as toothed gear pump, reciprocal plunger metering pump, and the transport capacity of pump is determined according to the size of throughput.
Tubular heat exchanger or plate-type heat exchanger that condenser can be made for metal or non-metallic material, its heat interchanging area is determined by heat balance according to the size of throughput, is used for reclaiming the organism of oxidizing tower expellant gas.
Water cooler I and water cooler II also can be tubular heat exchanger or the plate-type heat exchanger that metal or non-metallic material are made, and its heat interchanging area is determined by heat balance according to the size of throughput.
Compared with prior art, the present invention has following advantage: (1) adopts continuous autoxidation prepared hydrogen peroxide to alkane in the Meng, only when producing beginning disposable adding catalyzer as radical initiator, after reaction is normal, needn't add any catalyzer again, solved the quality problems that product causes because of catalyst residue, also saved simultaneously the operation of in product, removing catalyzer, simplify Production Flow Chart, improved production efficiency, got rid of the environmental pollution that causes because of catalyzer; (2) owing to improved the structure of oxidizing tower, to change the film pipe air supply plant of micrometer grade hole at the air supply plant that about 2mm pore left by coil pipe into, guaranteed the oxidising process security and stability, improved the utilization ratio of gas, can be under the constant situation of the same industrial scale of onesize equipment, the oxidation depth that logical oxygen just can reach in the original production, blowing air just can reach now, has reduced production cost; (3) will change the device of oxidation and evaporation coupling operate continuously into evaporation unit intermittently to alkane intermittent oxidation in the Meng, the separation of peroxide product is purified and is finished in same system, accurately the controlled oxidation degree of depth has been avoided because of safety problems such as oxidizing tower endoperoxide excessive concentration set off an explosion easily in safety range; (4) adopt the variable diameter falling-film evaporator, the technical problem of having avoided traditional falling-film evaporator to exist, except that evaporation material heated time is short, also make material film thickness on wall accurately remain on setting range, so both guaranteed the quality of the hydrogen peroxide of thermo-sensitivity, solved the safety problem that the evaporation back segment may cause vaporizer inner oxide excessive concentration to cause because of siccative again alkane product in the Meng; (5) because adopt the serialization production equipment, the convenient whole-process automatic control that adopts of full scale production process, the error that can avoid manual operation to cause uses manpower and material resources sparingly, and makes things convenient for large-scale production.
Description of drawings
Fig. 1 for the present invention to the Meng alkane prepare hydrogen peroxide to alkane serialization in Meng production equipment example structure synoptic diagram.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.
Embodiment 1: to the Meng alkane prepare hydrogen peroxide to alkane serialization in Meng production equipment embodiment
With reference to Fig. 1, present embodiment comprises raw material mixing tank 1, charge pump 2, air reservoir 4, oxygen storage tank 5, oxidizing tower 8, gas-liquid separator 9, under meter I 3, under meter II 6, under meter III 7, under meter IV 10, water cooler I 11 and water cooler II 16, middle vessel 13, fresh feed pump 13, one-level vaporizer 14, secondary evaporimeter 15, product storage tank 17 and condenser 18, the discharge port of raw material mixing tank 1 links to each other with the opening for feed of charge pump 2, the discharge port of charge pump 2 links to each other with under meter I 3 opening for feeds, under meter I 3 discharge ports link to each other with oxidizing tower 8 underfeed mouths, the air outlet of air reservoir 4 and oxygen storage tank 5 links to each other with the inlet mouth of under meter II 6 with under meter IV 7 respectively, the air outlet of under meter II 6 and under meter IV 7 links to each other with oxidizing tower 8 bottom inlet mouths, the top of oxidizing tower 8 links to each other with gas-liquid separator 9 imports by pipeline, the liquid material outlet of gas-liquid separator 9 bottoms links to each other with oxidizing tower 8 underfeed mouths with under meter III 10 by return line, form circulation loop, the liquid material outlet at gas-liquid separator 9 middle parts links to each other with 11 imports of oxidation material water cooler I by another bye-pass, 11 outlets of water cooler I link to each other with middle vessel 12 imports, middle vessel 12 outlets link to each other with fresh feed pump 13 imports, fresh feed pump 13 outlets link to each other with one-level vaporizer 14 top inlet, one-level vaporizer 14 outlet at bottoms directly link to each other with secondary evaporimeter 15 top inlet, secondary evaporimeter 15 outlet at bottoms by hydrogen peroxide to the Meng alkane product discharge nozzle link to each other with 16 imports of water cooler II, water cooler II 16 outlet by hydrogen oxide to the Meng alkane product discharge nozzle link to each other with product storage tank 17 imports, one-level vaporizer 14 tops link to each other with condenser 18 imports by unoxidized material delivery line, and condenser 18 outlets link to each other with 1 import of raw material mixing tank through the reflux cycle pipeline; Be provided with temperature sensor and pressure transmitter in oxidizing tower 8, one-level vaporizer 14 and the secondary evaporimeter 15.
The tower body of described oxidizing tower 8 is a round shape, and diameter is 500mm ~ 1500mm, and height is 4000mm ~ 10000mm, and the tower inner bottom part is equipped with film pipe diffuser, film pore footpath 2 μ m ~ 100 μ m, and diameter and length calculate according to required air input in the tower; Different heights is provided with temperature sensor in the oxidizing tower 7, and bottom and top are provided with pressure transmitter; Oxidizing tower 7 is provided with heat exchange jacket, and the heat exchange jacket import links to each other with heating medium pipe or heat-eliminating medium pipe by the pipeline that valve is housed.
Described gas-liquid separator 9 is the broken foam gas-liquid separator of silk screen.
One-level vaporizer 14 and secondary evaporimeter 15 are falling film evaporator, double-sleeve structure, the little variable diameter structure in big bottom, the preferred top of inner sleeve, the reducing proportional range is 1.5 ~ 3.0:1 up and down, and adopting this variable diameter structure is thickness uniformity for the formed film of upper and lower material that guarantees evaporator wall; Different heights is provided with temperature sensor in the vaporizer, and one-level vaporizer and secondary evaporimeter bottom and top are respectively equipped with pressure transmitter.
Following examples be to the Meng alkane prepare hydrogen peroxide to alkane continuous production method embodiment in the Meng.Wherein embodiment 2 is operation steps embodiment, and embodiment 3-14 is operating procedure actual conditions embodiment.
Embodiment 2
With catalyst acetic acid cobalt, cupric acetate or manganese acetate is radical initiator, comprises following concrete operations step:
(1) oxidizing reaction: with air (or gas mixture of oxygen or air and oxygen) from air reservoir 4(or oxygen storage tank 5, or air reservoir 4 and oxygen storage tank 5) through under meter II 6(or/and under meter III 7) and oxidizing tower 8 bottom inlet mouths blast in the oxidizing tower 8, open the chuck heating, when temperature reaches 80 ℃ ~ 130 ℃ in oxidizing tower 8, open charge pump 2, with 0.5 m
3/ h ~ 2.0 m
3/ h flow will join the oxidizing tower 8 from Yangization Ta 8 bottoms the mixing solutions that the Meng alkane and catalyzer are formed, make air with to the Meng alkane solution fully contact, carry out oxidizing reaction, controlled oxidation tower 8 top discharge hydrogen peroxide to the Meng alkane concentration be 10% ~ 20%; (2) gas-liquid separation: oxidation products is after oxidizing tower 8 discharge hole for discharge, enter gas-liquid separator 9, in gas-liquid separator 9, isolate gas and hydrogen peroxide to alkane product liquid in the Meng, a part hydrogen peroxide to the Meng alkane product be back in the oxidizing tower 8 through a return line that links to each other with oxidizing tower 7 opening for feeds and under meter IV 10 by gas-liquid separator 9 bottom discharge mouths, proceed automatic oxidation reaction with materials new in the oxidizing tower 8, hydrogen peroxide to the Meng alkane product quantity of reflux be 10 m
3/ h ~ 100 m
3/ h; Another part hydrogen peroxide to the Meng alkane product from gas-liquid separator 9 middle part discharge hole for discharge, enter water cooler I 11 cooling by another pipeline after, enter middle vessel 12 again; (3) evaporation concentration is purified: open one-level vaporizer 14 and secondary evaporimeter 15 heating medium terminal valves, keeping the interior temperature of one-level vaporizer is 50 ℃ ~ 100 ℃, temperature is 60 ℃ ~ 100 ℃ in the secondary evaporimeter, the hydrogen peroxide in the middle vessel 12 to the Meng alkane product by fresh feed pump 13 with 0.5 m
3/ h ~ 2.0 m
3The flow of/h is sent into one-level vaporizer 14 and is carried out the evaporation concentration purification, the unoxidized material that one-level vaporizer 14 tops steam is back to raw material mixing tank 1 after condenser 18 condensations, with new to the Meng alkane solution merge, return in the oxidizing tower 8 through charge pump 2, under meter 3 again, proceed automatic oxidation reaction; Reaction product after one-level vaporizer 14 concentrates purification enters secondary evaporimeter 15 and concentrates purification once more, reaction product after the purification is from secondary evaporimeter 15 bottom discharges, enter water cooler 16, through water cooler 16 cooled products, enter product storage tank 17, products obtained therefrom is hydrogen peroxide to alkane in the Meng.
The system that treats is stable, sampling analysis from oxidizing tower eject the material hydrogen peroxide to the Meng alkane resultant content be 15% ~ 20%, the hydrogen peroxide of secondary evaporimeter bottom discharge to the Meng alkane content be 50 ~ 60%.
Reach continous-stable operation required time from the system of driving, with the film pore footpath size of film pipe diffuser and vaporizer inner sleeve top and bottom reducing than relevant, be generally 6-9h.For example, when oxidizing tower 8 inlet pipe are the film pipe diffuser in 2 μ m apertures, vaporizer inner sleeve top and bottom reducing are than for 1:2.5 the time, and reaching continuous and stable production from the system of driving needs 6 h approximately; The oxidizing tower inlet pipe is the film pipe diffuser in 10 μ m apertures, and the vaporizer inner sleeve is that top and bottom reducing ratio are 1:1.5, and reaching continuous and stable production from the system of driving needs 6.5 h approximately; The oxidizing tower inlet pipe is the film pipe diffuser in 50 μ m apertures, and the vaporizer inner sleeve is that top and bottom reducing ratio are 1:3, and reaching continuous and stable production from the system of driving needs 8.0h approximately; The oxidizing tower air inlet is the film pipe diffuser in 100 μ m apertures, and the vaporizer inner sleeve is that top and bottom reducing ratio are 1:2, and reaching continuous and stable production from the system of driving needs 9 h approximately.
Embodiment 3 ~ 6
60 ℃ of step (1) oxidizing reaction temperatures; Setting oxygen gas flow rate respectively is 20 m
3/ h, 80 m
3/ h, 140 m
3/ h, 200 m
3/ h is 0.5 m to alkane material charging in Meng flow velocity
3/ h, 1.0 m
3/ h, 1. 5 m
3/ h, 2.0 m
3/ h; Catalyst acetic acid cobalt add-on be to the Meng alkane raw material weight 0.01%, 0.04%, 0.07%, 0.1%; Step (2) hydrogen peroxide to the Meng alkane product quantity of reflux be respectively 30 m
3/ h, 50 m
3/ h, 70 m
3/ h, 100 m
3/ h; Step (3) one-level vaporization temperature is controlled at 50 ℃, and the dual evaporation temperature is controlled at 80 ℃, sets hydrogen peroxide respectively the flow velocity that the Meng, the alkane product entered the one-level vaporizer is respectively 0.5 m
3/ h, 1.0 m
3/ h, 1.5 m
3/ h, 2.0 m
3/ h, surplus with embodiment 2.
The system that treats is stable, sampling analysis at the bottom of the oxidizing tower hydrogen peroxide the discharging to the Meng alkane product content be respectively 10.2%, 12.5%, 14.8%, 16.7%, the hydrogen peroxide of secondary evaporimeter bottom discharge to the Meng alkane content be respectively 59.2%, 57.5%, 53.7%, 50.1%.
Embodiment 7 ~ 10
Step (1) oxidizing reaction temperature is controlled at 80 ℃, and setting air and oxygen mixture rate of flow of fluid are 30 m respectively
3/ h, 90 m
3/ h, 150 m
3/ h, 200 m
3/ h(air and oxygen mix ratio are 1:0.3), be 0.5 m to alkane material charging in Meng flow velocity
3/ h, 1.0 m
3/ h, 1. 5 m
3/ h, 2.0 m
3/ h, the catalyzer cupric acetate, add-on be to the Meng alkane raw material weight 0.02%, 0.04%, 0.06%, 0.1%; Step (2) hydrogen peroxide to the Meng alkane product quantity of reflux be respectively 30 m
3/ h, 50 m
3/ h, 70 m
3/ h, 100 m
3/ h; Step (3) one-level vaporization temperature is controlled at 100 ℃, and the dual evaporation temperature is controlled at 100 ℃, and setting hydrogen peroxide respectively is 0.5 m to the flow velocity that the Meng, the alkane product entered the one-level vaporizer
3/ h, 1.0 m
3/ h, 1.4 m
3/ h, 2.0 m
3/ h.Surplus with embodiment 2.
The system that treats is stable, sampling analysis at the bottom of the oxidizing tower hydrogen peroxide the discharging to the Meng alkane product content be 14.2%, 16.9%, 17.3%, 18.5%, the hydrogen peroxide of secondary evaporimeter bottom discharge to the Meng alkane content be 59.7%, 56.5%, 54.3%, 50.9%.
Step (1) is controlled at 120 ℃ with oxidizing reaction temperature, and the flow velocity of setting air is 20 m respectively
3/ h, 60 m
3/ h, 120 m
3/ h, 200 m
3/ h is 0.5 m to alkane material charging in Meng flow velocity
3/ h, 1.0 m
3/ h, 1.6 m
3/ h, 2.0 m
3/ h, the catalyzer manganese acetate, add-on be to the Meng alkane raw material weight 0.02%, 0.05%, 0.07%, 0.1%; Step (2) hydrogen peroxide to the Meng alkane product quantity of reflux be respectively 30 m
3/ h, 50 m
3/ h, 70 m
3/ h, 100 m
3/ h; Step (3), one-level vaporization temperature are controlled at 70 ℃, and the dual evaporation temperature is controlled at 90 ℃, and setting hydrogen peroxide respectively is 0.5 m to the flow velocity that the Meng, the alkane product entered the one-level vaporizer
3/ h, 1.0 m
3/ h, 1.4 m
3/ h, 2.0 m
3/ h.Surplus with embodiment 2
The system that treats is stable, sampling analysis at the bottom of the oxidizing tower hydrogen peroxide the discharging to the Meng alkane product content be 15.6%, 17.3%, 18.9%, 19.8%, the hydrogen peroxide of secondary evaporimeter bottom discharge to the Meng alkane content be 59.5%, 58.5%, 56.6%, 55.3%.
Claims (6)
- One kind to the Meng alkane prepare the continuous production method of hydrogen peroxide to alkane in the Meng, it is characterized in that, may further comprise the steps:(1) to alkoxide in the Meng: the mixed gas of air or oxygen or air and oxygen is blasted in the oxidizing tower, will the mixing solutions that the Meng alkane and catalyzer are formed be joined in the oxidizing tower, make gas with to the Meng alkane solution fully contact, carry out oxidizing reaction;Described catalyzer is radical initiator cupric acetate, Cobaltous diacetate or manganese acetate, is disposable adding, and add-on is the 0.01%-0.1% to alkane raw material weight in the Meng;The operational condition of oxidizing reaction is: gas flow rate 20 m that enter oxidizing tower 3/ h-200 m 3/ h is 0.5 m to alkane material charging in Meng flow velocity 3/ h-2.0m 3Temperature is 80 ℃-130 ℃ in the/h, oxidizing tower;(2) gas-liquid separation: oxidation products is after the oxidizing tower discharge hole for discharge, enter gas-liquid separator, in gas-liquid separator, isolate gas and hydrogen peroxide to alkane product liquid in the Meng, a part hydrogen peroxide to the Meng alkane product be back in the oxidizing tower through a return line that links to each other with the oxidizing tower opening for feed by gas-liquid separator bottom discharge mouth, continue to finish automatic oxidation reaction with the material of Ta Neixin, the hydrogen peroxide of backflow to the Meng alkane product quantity be 30 m 3/ h-100m 3/ h, remaining hydrogen peroxide to the Meng alkane product from gas-liquid separator middle part discharge hole for discharge, be delivered in the water cooler by another bye-pass and enter middle vessel after the cooling;(3) evaporation concentration is purified: by fresh feed pump with the hydrogen peroxide in the middle vessel to the Meng alkane product send into vaporizer and carry out evaporation concentration and purify, product after evaporation concentration is purified enters the water cooler cooling again, the hydrogen peroxide of directly collecting after the cooling to the Meng alkane product enter product storage tank; The unoxidized feed back that evaporator evaporation goes out to the raw material mixing tank with new to alkane solution merging in the Meng;Described evaporation concentration purification is adopted double effect evaporator to carry out double evaporation-cooling and is concentrated, and the operational condition of evaporation concentration is: the charging flow velocity that enters vaporizer is 0.5 m 3/ h-2.0 m 3/ h, 50 ℃-100 ℃ of control one-level evaporator temperatures, the secondary steaming device is sent out 60 ℃-100 ℃ of temperature.
- One kind implement claim 1 described to the Meng alkane prepare the device of hydrogen peroxide to alkane continuous production method in the Meng, it is characterized in that, comprise raw material mixing tank, charge pump, oxidizing gas basin, oxidizing tower, gas-liquid separator, under meter, under meter, under meter, under meter IV, water cooler, water cooler, middle vessel, fresh feed pump, one-level vaporizer, secondary evaporimeter, product storage tank and condenser, the discharge port of raw material mixing tank links to each other with the opening for feed of charge pump, the discharge port of charge pump links to each other with the under meter opening for feed, the under meter discharge port links to each other with oxidizing tower underfeed mouth, the air outlet of air reservoir and oxygen storage tank respectively with under meter and under meter
Inlet mouth link to each other under meter and under meter
The air outlet link to each other with oxidizing tower bottom inlet mouth, the top of oxidizing tower links to each other with the gas-liquid separator import by pipeline, the liquid material outlet of gas-liquid separator bottom links to each other with oxidizing tower underfeed mouth with the under meter IV by return line, form circulation loop, the liquid material outlet at gas-liquid separator middle part links to each other with cooler inlet by another bye-pass, cooler outlet links to each other with the middle vessel import, the middle vessel outlet links to each other with the fresh feed pump import by pipeline, the fresh feed pump outlet links to each other with one-level vaporizer top inlet by pipeline, the outlet of one-level base of evaporator directly links to each other with the secondary evaporimeter top inlet, the secondary evaporimeter outlet at bottom by hydrogen peroxide to the Meng alkane product discharge nozzle link to each other with cooler inlet, cooler outlet by hydrogen oxide to the Meng alkane product discharge nozzle link to each other with the product storage tank import, one-level vaporizer top links to each other with condenser inlet by unoxidized material delivery line, and condensator outlet links to each other with the import of raw material mixing tank through the reflux cycle pipeline; Oxidizing tower is provided with heat exchange jacket, and the heat exchange jacket import links to each other with heating medium pipe or heat-eliminating medium pipe by the pipeline that valve is housed; Be provided with temperature sensor and pressure transmitter in oxidizing tower, one-level vaporizer and the secondary evaporimeter;
The tower body of described oxidizing tower is a round shape, and diameter is 500mm-1500mm, and height is 4000mm-10000mm, and the tower inner bottom part is equipped with film pipe diffuser, and the film pore directly is 2 μ m-100 μ m;Described one-level vaporizer and secondary evaporimeter are falling film evaporator, double-sleeve structure, the variable diameter structure that big bottom, inner sleeve top is little. - As described in the claim 2 to the Meng alkane prepare the device of hydrogen peroxide to alkane continuous production method in the Meng, it is characterized in that described raw material mixing tank is the circle tube tank that has stirring that metal or non-metallic material are made.
- , as described in the claim 2 to the Meng alkane prepare the device of hydrogen peroxide to alkane continuous production method in the Meng, it is characterized in that described charge pump and fresh feed pump are toothed gear pump or reciprocal plunger metering pump.
- , as described in the claim 2 to the Meng alkane prepare the device of hydrogen peroxide to alkane continuous production method in the Meng, it is characterized in that described condenser is tubular heat exchanger or the plate-type heat exchanger that metal or non-metallic material are made.
- As described in the claim 2 to the Meng alkane prepare the device of hydrogen peroxide to alkane continuous production method in the Meng, it is characterized in that water cooler and water cooler are tubular heat exchanger or the plate-type heat exchanger that metal or non-metallic material are made.
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| CN102211986A (en) * | 2011-04-19 | 2011-10-12 | 中南林业科技大学 | Process and device for extracting citral from Litsea cubeba oil |
| CN102557849B (en) * | 2011-12-13 | 2014-09-24 | 浙江新和成股份有限公司 | Continuous reaction method |
| CN102911102B (en) * | 2012-10-26 | 2014-06-25 | 崇左森隆林化科技有限公司 | Method and device for producing pinane hydrogen peroxide |
| CN106316911B (en) * | 2015-06-15 | 2018-06-12 | 华东理工大学 | Prepared by method and device of the hydrogen peroxide to Meng's alkane to Meng's alkane non-catalytic oxidation |
| CN108101818A (en) * | 2016-11-24 | 2018-06-01 | 湖南松源化工有限公司 | A kind of method that p-menthane hydroperoxide is produced under lower pressure |
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Effective date of registration: 20230614 Address after: No. 89, Huacheng Road, Tongguan Industrial Park, Wangcheng Economic and Technological Development Zone, Changsha, Hunan 410299 Patentee after: Hunan Songyuan Biotechnology Co.,Ltd. Address before: 410137 Huanghua Industrial Community, Huanglong New Village, Huanghua Town, Changsha County, Changsha, Hunan Province Patentee before: HUNAN SONGYUAN CHEMICAL Co.,Ltd. |