CN205099599U - Device that ethanol was retrieved in production of hexanitro bibenzyl - Google Patents
Device that ethanol was retrieved in production of hexanitro bibenzyl Download PDFInfo
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- CN205099599U CN205099599U CN201520867648.9U CN201520867648U CN205099599U CN 205099599 U CN205099599 U CN 205099599U CN 201520867648 U CN201520867648 U CN 201520867648U CN 205099599 U CN205099599 U CN 205099599U
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Abstract
The utility model relates to a device that ethanol was retrieved in production of hexanitro bibenzyl. Including crystallizer (4), stills (5) that connect gradually, the entry of back, the feed liquid side of relinking to infiltration vaporization separation unit (9) is connected again in proper order in the distillate of stills (5) export with pans (6), evaporimeter (8), export relinking to the product jar (13) of the feed liquid side of infiltration vaporization separation unit (9). The utility model discloses the dewatering does not have other discarded objects emissions outward among the recovery process, and the rate of recovery is high, and process is simple, and energy utilization is high, and no third component is added.
Description
Technical field
The utility model relates to the device that in the production of a kind of hexanitrobibenzyl, ethanol reclaims, and particularly relates to the device that a kind of pervaporation method reclaims ethanol in hexanitrobibenzyl production, belongs to infiltrating and vaporizing membrane Application Areas.
Background technology
Hexanitrobibenzyl i.e. two picryl ethane, fusing point 212 DEG C, pale yellow powder, are a kind of important source material of two step synthesis high temperature powder hexanitro-Stilbene.
First dissolved in ethanol by raw material TNT in hexanitrobibenzyl oxidative coupling reaction workshop section, then add clorox, after oxidative coupling reaction, feed liquid obtains hexanitrobibenzyl finished product through filtration, washing, crystallization.In said process, ethanol and water and other minor component form solution, if do not carry out ethanol recovery, cannot recycle, and directly sell and cause cost to raise, as directly discharge causes ethanol lose, while contaminate environment.In order to make ethanol recycle, water must be removed, requiring that the water-content of reuse ethanol is less than less than 5/1000ths.
At present, ethanol recovery process many employings extractive distillation with salt in hexanitrobibenzyl production, general using ethylene glycol as extraction agent, extractive distillation with salt is double tower process, and steam consumption is large, and occupation area of equipment is large, environmental pollution is serious, and product easily introduces three components, cause product purity low, three components consumption is large, cost recovery is high.
Summary of the invention
The purpose of this utility model is to propose the device that in the production of a kind of hexanitrobibenzyl, ethanol reclaims.Have technological process simple, occupation area of equipment is little, and safety coefficient is high, and energy consumption is low, and the ethanol rate of recovery is high, the feature of cleanliness without any pollution.
The method that in hexanitrobibenzyl production, ethanol reclaims, comprises the steps:
1st step: distill being prepared the ethanol mother liquor obtained in hexanitrobibenzyl by oxidative coupling reaction, ethanol is steamed, obtains overhead product;
2nd step: adopt infiltrating and vaporizing membrane to dewater to overhead product, be recycled ethanol retaining side.
In the 1st described step, ethanol mother liquor refers to: the ethanol mother liquor that the reactant in hexanitrobibenzyl obtains after filtration, crystallization prepared by oxidative coupling reaction.
Water content (mass percent) in the 1st described step in ethanol mother liquor is 5 ~ 30%.
In distillation and concentration, material liquid volume is concentrated into 15% ~ 30% in the 1st described step, optimum is 20%.
In the 2nd described step, when doing infiltration evaporation separation to overhead product, after first charging being heated with vaporizer, then the aqueous ethanol steamed by vaporizer sends into infiltration evaporation separation.As preferably, the temperature of aqueous ethanol is 50 ~ 150 DEG C.
As improvement, described charging can be carried out heat exchange by the recovery alcohol vapour of the feed liquid side with infiltration evaporation, make feeding temperature be increased to 50 ~ 100 DEG C before sending into vaporizer.
In the 2nd described step, the gauge pressure of the feed liquid side of infiltrating and vaporizing membrane is 0 ~ 0.5MPa; Per-meate side is connected with vacuum system, per-meate side absolute pressure 100 ~ 3000Pa.
The film that described infiltrating and vaporizing membrane adopts is preferential water permeable membrane, and can be molecular screen membrane, soft silica film, PVA film, optimum be molecular screen membrane.
In 2nd step infiltrating and vaporizing membrane per-meate side feed liquid condensation after return still kettle.
According to another aspect of the present utility model, the device that in a kind of hexanitrobibenzyl production, ethanol reclaims, include the crystallizer, the still kettle that connect successively, after the overhead product of still kettle exports and is connected with tundish, vaporizer successively, then be connected to the entrance that infiltration evaporation is separated the feed liquid side of unit; The outlet that infiltration evaporation is separated the feed liquid side of unit is connected to products pot again.
The pipeline being separated the outlet of the feed liquid side of unit at infiltration evaporation will form heat exchange and be connected with the pipeline entering vaporizer.
The pipeline entering products pot arranges product condenser.
The per-meate side being separated unit at infiltration evaporation is also connected with penetrating fluid condenser and vacuum pump.
The per-meate side that infiltration evaporation is separated unit can also be connected in still kettle.
It is connected by 1 ~ 100 Pervaporation membrane separator series, parallel or series-parallel connection that infiltration evaporation is separated unit.
Also include the oxidative coupling reaction still, pressure filter, the material liquid tank that connect successively in device, material liquid tank is connected to crystallizer.
Beneficial effect
With extractive distillation with salt method reclaim hexanitrobibenzyl produce in compared with ethanol, method of the present utility model has following features:
1. the utility model adopts the dehydration of infiltration evaporation membrane separator group, and do not limit by azeotropic, technological process is simple;
2. the utility model infiltration evaporation membrane separator group level of automation is high, easy and simple to handle, and occupation area of equipment is few;
3. present method adopts the mode of first distilling again infiltration evaporation, does not introduce three components, has both saved reagent consumption, ensured product purity again;
4. penetrating fluid returns to still kettle recycling by the utility model, decreases the quantity discharged of ethanol, adds the rate of recovery of ethanol;
5. the utility model utilizes product heat to carry out preheating to entering the aqueous ethanol feed liquid before vaporizer, improves system self-energy utilization ratio, reduce further production energy consumption;
6. the ethanol recovery process that provides of the utility model, the water-content in ethanol is little, can be reduced to 0.01%, and energy consumption reduces by 40 ~ 60%.
Accompanying drawing explanation
Fig. 1 is the setting drawing that during hexanitrobibenzyl is produced, ethanol reclaims;
Wherein 1, oxidative coupling reaction still; 2, pressure filter; 3, material liquid tank; 4, crystallizer; 5, still kettle; 6, tundish; 7, preheater; 8, vaporizer; 9, infiltration evaporation is separated unit; 10, penetrating fluid condenser; 11, vacuum pump; 12, product condenser; 13, products pot.
Embodiment
The purpose of this utility model is that the ethanol mother liquor that in producing for hexanitrobibenzyl, oxidative coupling technique produces carries out ethanol dehydration recovery, adopt TNT as starting raw material in the oxidative coupling technique of hexanitrobibenzyl, dissolved in ethanol, add clorox again to react, after reaction terminates, filter out solid reaction product, and reaction solvent is as filtrate, filtrate is carried out crystallization, reaction product is wherein separated out, just ethanol mother liquor is obtained after filtration, in mother liquor, containing a large amount of unreacted, raw material is (such as: TNT completely, clorox), by product, impurity, water.After it is distilled, then by infiltrating and vaporizing membrane, dewatering of ethanol is separated.
The topmost object of ethanol mother liquor being carried out to distillation and concentration carries out preliminary purification to it, the heavy constituent such as raw material, by product and a part of water are stayed at the bottom of still kettle completely can to make unreacted, such one side can avoid heavy constituent to enter to the feed liquid side of infiltration evaporation separator, have influence on the purity of final recovery ethanol, a part of water can also be removed, alleviate the area of infiltrating and vaporizing membrane, make its treatment capacity, product water content is improved.In general, the water content in ethanol mother liquor is at about 5 ~ 30wt%, and what be more suitable for this technique is at about 15wt%.In addition, in the process of this distillation, if enrichment factor is not high, can causes can not being distilled out of completely at a part of ethanol, have influence on the yield of technique; But if when enrichment factor is too high, can cause the still bed material liquid overrich of still kettle, some heavy constituents, impurity also can enter in steam along with the process of distillation, finally can have influence on the purity reclaiming ethanol.Preferably material liquid volume is concentrated into 15 ~ 30%; Be 20% in the embodiment of optimum.
According to the embodiment of improvement of the present utility model, for the overhead product distilling generation from still kettle, after preferably it being heated with vaporizer, enter to infiltration evaporation separator in vapour form, this mainly can improve infiltration evaporation membrane separation efficiency, and the temperature of steam is preferably 50 ~ 150 DEG C, in order to utilize waste heat better, before being sent into vaporizer, first can carry out preheating with the alcohol vapour of infiltration evaporation separator feed liquid side, be warming up to 50 ~ 100 DEG C.
According to of the present utility model one preferred embodiment, the infiltrating and vaporizing membrane adopted is molecular screen membrane, the mould material similar relative to other, such as: the membrane flux in the high and sepn process of the purity of recovery ethanol that soft silica film, PVA film, molecular screen membrane obtain after being separated is larger.In another one embodiment, also can carry out pre-treatment to adding in ethanol mother liquor S-WAT, neutralizing unreacted chlorine residue completely.
According to above-mentioned method, the apparatus structure adopted in the utility model as shown in Figure 1, is connected with pressure filter 2 in the outlet of oxidative coupling reaction still 1, and the material liquid outlet of pressure filter 2 is connected with material liquid tank 3, crystallizer 4 more successively; The effect of oxidative coupling reaction still 1 is reacted, the effect of pressure filter 2 carries out solid-liquid separation to reactant, solvent slop reaction produced separately, the effect of material liquid tank 3 is solvent slops that storage press filtration obtains, the effect of crystallizer 4 is after carrying out crystallization to solvent slop, make the precipitations such as reaction product wherein, make it recycle and make the impurity in solvent reduce simultaneously.The outlet of crystallizer 4 is connected with still kettle 5 again, after the overhead product of still kettle 5 exports and is connected with tundish 6, vaporizer 8 successively, then is connected to the entrance that infiltration evaporation is separated the feed liquid side of unit 9; The outlet that infiltration evaporation is separated the feed liquid side of unit 9 is connected to products pot 13 again, and the effect of products pot 13 is the recovery ethanol accepting to obtain; In addition, the pipeline being separated the outlet of the feed liquid side of unit 9 at infiltration evaporation will form heat exchange and be connected with the pipeline entering vaporizer 8, its effect is that the waste heat of recovery ethanol is utilized, incoming stock temperature is improved, also product condenser 12 can be set on the pipeline entering products pot 13, after making evaporative condenser, enter products pot 13.The per-meate side being separated unit 9 at infiltration evaporation is also connected with penetrating fluid condenser 10 and vacuum pump 11, and the effect of penetrating fluid condenser 12 forms liquid by after penetrant condensation, and the effect of vacuum pump 11 is to provide negative pressure; In addition, infiltration evaporation is separated the per-meate side of unit 9 and can also be connected in still kettle 5, makes penetrant again be recycled a small amount of ethanol wherein.
Embodiment 1
The method that in hexanitrobibenzyl production, ethanol reclaims, the device adopted as shown in Figure 1, operating process comprises the following steps: the mother liquor will obtained from hexanitrobibenzyl oxidative coupling reaction workshop section, be introduced into pressure filter 2 to filter, filtrate enters material liquid tank 3 again, finally enter crystallizer 4 crystallization, upper strata mother liquor (about water content 20wt%) is sent into still kettle 5 and is concentrated, distillation ethanol is collected in tundish 6, in still-process, mother liquor volume is decreased to about 25%, and in tundish 6, water-content is the ethanolic soln of 15wt%.It is that 900kg/h is transported to preheater 7 that feed liquid in tundish 6 is controlled flow, by product steam, 80 DEG C are preheated to this feed liquid, then enter in vaporizer 8 and heat, feed liquid is heated to 110 DEG C and enters into by 10 molecular screen membrane assemblies that (every grade of membrane module area is 10m in vapour form
2) infiltration evaporation membrane separator group 9 in series carry out dehydration be separated.Feed liquid wall pressure is 0.2MPa, and osmotic lateral pressure controls at 1500Pa.Feed liquid water-content can be reduced significantly by infiltration evaporation membrane separator, is recycled ethanol, and it enters products pot 13 through product condenser 12 condensation after flowing through preheater 7 pairs of feed liquid preheatings again.After the penetrating fluid condensation that per-meate side obtains, be back to still kettle 5 and process.
When adopting different mould materials, the data such as recovery ethanol, penetrating fluid, flux of gained are as shown in table 1.
Table 1
As can be seen from the table, molecular screen membrane is particularly suitable for the processed of this recovery ethanol, and the treatment capacity of gained, permeation flux are better than the mould material of other kind, and the water-content of penetrating fluid is also better than other several mould materials.
Embodiment 2
The method that in hexanitrobibenzyl production, ethanol reclaims, the device adopted as shown in Figure 1, operating process comprises the following steps: the mother liquor will obtained from hexanitrobibenzyl oxidative coupling reaction workshop section, be introduced into pressure filter 2 to filter, filtrate enters material liquid tank 3 again, finally enter crystallizer 4 crystallization, upper strata mother liquor (about water content 20wt%) is sent into still kettle 5 and is concentrated, distillation ethanol is collected in tundish 6, in still-process, concentrated liquid integration is not decreased to 10%, 15%, 20%, 25%, 30%, about 35% (mass percent), in tundish 6, water-content is the ethanolic soln of 12wt%.Be that 1200kg/h is transported to preheater 7 by the flow control in tundish 6, by product steam, 75 DEG C are preheated to this feed liquid, then enter in vaporizer 8 and heat, feed liquid is heated to 125 DEG C and enters into by 12 NaA molecular sieve infiltration vaporization membrane modules that (every grade of membrane module area is 10m in vapour form
2) infiltration evaporation membrane separator group 9 in series carry out dehydration be separated.Feed liquid wall pressure is 0.4MPa, and osmotic lateral pressure controls at 1000Pa.Feed liquid water-content can be reduced significantly by infiltration evaporation membrane separator, is recycled ethanol, and it enters products pot 13 through product condenser 12 condensation after flowing through preheater 7 pairs of feed liquid preheatings again.After the penetrating fluid condensation that per-meate side obtains, be back to still kettle 5 and process.
When adopting different concentrated per-cent, the data such as recovery ethanol, penetrating fluid, flux of gained are as shown in table 2.
Table 2
As can be seen from the table, the concentration ratio of still kettle is controlled when suitable scope, can effectively to make in mother liquor impurity etc. enter in steam, the purity being separated flux and reclaiming ethanol can be improved.
Embodiment 3
The method that in hexanitrobibenzyl production, ethanol reclaims, the device adopted as shown in Figure 1, operating process comprises the following steps: the mother liquor will obtained from hexanitrobibenzyl oxidative coupling reaction workshop section, be introduced into pressure filter 2 to filter, filtrate enters material liquid tank 3 again, finally enters crystallizer 4 crystallization, and upper strata mother liquor (about water content 15wt%) is sent into still kettle 5 and concentrated, distillation ethanol is collected in tundish 6, and in tundish 6, water-content is the ethanolic soln of 10wt%.It is that 1000kg/h is transported to preheater 7 that ethanol in tundish 6 is controlled flow, by product steam, 85 DEG C are preheated to this feed liquid, then enter in vaporizer 8 and heat, feed liquid is heated to 110 DEG C and enters into by 15 NaA molecular sieve infiltration vaporization membrane modules that (every grade of membrane module area is 10m in vapour form
2) infiltration evaporation membrane separator group 9 in series carry out dehydration be separated.Feed liquid wall pressure is 0.2MPa, and osmotic lateral pressure controls at 1000Pa.Feed liquid water-content can be reduced significantly by infiltration evaporation membrane separator, and the purity being recycled ethanol is approximately 99.1wt%, and its water flux is about 0.66kg/m
2h, water content is about 0.1wt%, and it enters products pot 13 through product condenser 12 condensation after flowing through preheater 7 pairs of feed liquid preheatings again.After the penetrating fluid condensation that per-meate side obtains, water-content is 91.65%, is back to still kettle 5 and processes.
Embodiment 4
The method that in hexanitrobibenzyl production, ethanol reclaims, the device adopted as shown in Figure 1, operating process comprises the following steps: the mother liquor will obtained from hexanitrobibenzyl oxidative coupling reaction workshop section, be introduced into pressure filter 2 to filter, filtrate enters material liquid tank 3 again, the S-WAT accounting for filtrate weight 1% is also added in material liquid tank, finally enter crystallizer 4 crystallization, upper strata mother liquor (about water content 15wt%) is sent into still kettle 5 and is concentrated, distillation ethanol is collected in tundish 6, and in tundish 6, water-content is the ethanolic soln of 10wt%.It is that 1000kg/h is transported to preheater 7 that ethanol in tundish 6 is controlled flow, by product steam, 85 DEG C are preheated to this feed liquid, then enter in vaporizer 8 and heat, feed liquid is heated to 110 DEG C and enters into by 15 NaA molecular sieve infiltration vaporization membrane modules that (every grade of membrane module area is 10m in vapour form
2) infiltration evaporation membrane separator group 9 in series carry out dehydration be separated.Feed liquid wall pressure is 0.2MPa, and osmotic lateral pressure controls at 1000Pa.Feed liquid water-content can be reduced significantly by infiltration evaporation membrane separator, and the purity being recycled ethanol is approximately 99.9wt%, and its water flux is about 0.83kg/m
2h, water content is about 0.1wt%, and it enters products pot 13 through product condenser 12 condensation after flowing through preheater 7 pairs of feed liquid preheatings again.After the penetrating fluid condensation that per-meate side obtains, water-content is 93.47%, is back to still kettle 5 and processes.Can find out, after carrying out pre-treatment to reaction feed liquid, can get rid of wherein unreacted oxidizing agent sodium hypochlorite completely, the purity that ethanol removal process can be made to obtain is higher, and can prevent the chlorine generated from having an impact to infiltration evaporation membrane sepn.
Claims (8)
1. the device that in a hexanitrobibenzyl production, ethanol reclaims, it is characterized in that: include the crystallizer (4), the still kettle (5) that connect successively, after the overhead product of still kettle (5) exports and is connected with tundish (6), vaporizer (8) successively, then be connected to the entrance that infiltration evaporation is separated the feed liquid side of unit (9); The outlet that infiltration evaporation is separated the feed liquid side of unit (9) is connected to products pot (13) again.
2. the device that in hexanitrobibenzyl production according to claim 1, ethanol reclaims, is characterized in that: the pipeline being separated the outlet of the feed liquid side of unit (9) at infiltration evaporation will form heat exchange and be connected with the pipeline entering vaporizer (8).
3. the device that in hexanitrobibenzyl production according to claim 1, ethanol reclaims, is characterized in that: on the pipeline entering products pot (13), arrange product condenser (12).
4. the device that in hexanitrobibenzyl production according to claim 1, ethanol reclaims, is characterized in that: the per-meate side being separated unit (9) at infiltration evaporation is also connected with penetrating fluid condenser (10) and vacuum pump (11).
5. the device that in hexanitrobibenzyl production according to claim 1, ethanol reclaims, is characterized in that: the per-meate side that infiltration evaporation is separated unit (9) can also be connected in still kettle (5).
6. the device that in hexanitrobibenzyl production according to claim 1, ethanol reclaims, is characterized in that: it is connected by 1 ~ 100 Pervaporation membrane separator series, parallel or series-parallel connection that infiltration evaporation is separated unit (9).
7. the device that in hexanitrobibenzyl production according to claim 1, ethanol reclaims, it is characterized in that: also include the oxidative coupling reaction still (1), pressure filter (2), the material liquid tank (3) that connect successively in device, material liquid tank (3) is connected to crystallizer (4).
8. the device that in hexanitrobibenzyl production according to claim 1, ethanol reclaims, is characterized in that: the film that described infiltration evaporation separation unit (9) adopts is preferential water permeable membrane; Described preferential water permeable membrane is molecular screen membrane, soft silica film or PVA film.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201520867648.9U CN205099599U (en) | 2015-11-03 | 2015-11-03 | Device that ethanol was retrieved in production of hexanitro bibenzyl |
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| CN201520867648.9U CN205099599U (en) | 2015-11-03 | 2015-11-03 | Device that ethanol was retrieved in production of hexanitro bibenzyl |
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