CN1185206C - Separation method of composition containing 4-aminodiamine and its equipment - Google Patents
Separation method of composition containing 4-aminodiamine and its equipment Download PDFInfo
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- CN1185206C CN1185206C CNB031481949A CN03148194A CN1185206C CN 1185206 C CN1185206 C CN 1185206C CN B031481949 A CNB031481949 A CN B031481949A CN 03148194 A CN03148194 A CN 03148194A CN 1185206 C CN1185206 C CN 1185206C
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- aminodiphenylamine
- water
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- separation method
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- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 238000000926 separation method Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 81
- 238000000605 extraction Methods 0.000 claims abstract description 57
- 239000011552 falling film Substances 0.000 claims abstract description 36
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 230000000694 effects Effects 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000012074 organic phase Substances 0.000 claims abstract description 14
- 238000001704 evaporation Methods 0.000 claims abstract description 12
- 230000008020 evaporation Effects 0.000 claims abstract description 12
- 239000012071 phase Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 229920000570 polyether Polymers 0.000 claims abstract description 5
- 238000005516 engineering process Methods 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000005984 hydrogenation reaction Methods 0.000 claims description 13
- 230000008676 import Effects 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 239000006200 vaporizer Substances 0.000 claims description 9
- 239000012141 concentrate Substances 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000284 extract Substances 0.000 claims description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 2
- 229920000151 polyglycol Polymers 0.000 claims description 2
- 239000010695 polyglycol Substances 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 4
- 238000010924 continuous production Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 4
- 241000282326 Felis catus Species 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- YHYKLKNNBYLTQY-UHFFFAOYSA-N 1,1-diphenylhydrazine Chemical compound C=1C=CC=CC=1N(N)C1=CC=CC=C1 YHYKLKNNBYLTQY-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000000998 batch distillation Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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Abstract
The present invention relates to a method for continuously separating a composition containing 4-aminodiphenylamine, aniline, a composite base catalyst containing tetraalkylamine hydroxide, etc. and a relevant device. The method comprises the sequential technical operation of extraction, concentration and evaporation. A gas aided flow type falling film evaporator is designed. The water phase of the composite base catalyst containing tetraalkylamine hydroxide is rapidly condensed, water is used as an extracting agent, and polyethers are adopted as an extraction aiding agent. In this way, the effective continuous separation of the composite is realized. The separating technology has the advantages of continuous process, short period, convenient operation, no pollution caused by three wastes, high production efficiency and favorable separating effect. The recovery rate of the composite base catalyst containing tetraalkylamine hydroxide reaches 99.7%, and the extraction rate of organic phases can reach 97%.
Description
Technical field
The present invention relates to a kind of separation method and equipment thereof of composition, be specifically related to mainly to contain the separation method and the equipment thereof of the composition of 4-aminodiphenylamine.
Background technology
Be in the process of raw material production 4-aminodiphenylamine with oil of mirbane and aniline, the composition after the hydrogenation contains the 4-aminodiphenylamine, contains compound alkaline catalysts, aniline and the hydrogenation solvent etc. of hydroxide tetra-allkylammonium.The general at present intermittently water extracts composition that adopts adopts the batch still formula to concentrate the aqueous solution of tetraalkylammonium hydroxide and the method for batch distillation is separated said composition.The shortcoming of these methods is that operation is discontinuous, complex procedures, extraction institute water consumption is bigger, percentage extraction is relatively low, extraction and concentrated cycle are long, and the compound alkaline catalysts rate of recovery that contains the hydroxide tetra-allkylammonium in the concentration process is low, not the compound alkaline catalysts contaminate environment that contains the hydroxide tetra-allkylammonium of Hui Shouing, production efficiency is low, is unsuitable for large-tonnage and produces the 4-aminodiphenylamine.
Existing vaporizer, comprise shell side, tube side, be installed in the steam inlet of shell side upper end, be installed in the vapor condensation water out of shell side lower end, be installed in the lower concentration water import at tube side top, be installed in the high density water outlet of tube side bottom, the lower concentration water for the treatment of concentration and evaporation enters tube side from the lower concentration water import at tube side top, steam enters shell side from the steam inlet that is installed in the shell side upper end, the lower concentration water flows in the tube side of vaporizer from top to down, owing to be subjected to the heating of shell side steam, the low boiling substance evaporation, during to the bottom, water is condensed into higher concentration.This equipment is used to heat the concentrated compound alkaline catalysts that contains tetraalkylammonium hydroxide, its heating is abundant inadequately, and the evaporation time of water is wayward, if the temperature of heating is low excessively, spissated concentration does not reach requirement, if Heating temperature is too high, can cause thermolysis, the compound alkaline catalysts rate of recovery that contains tetraalkylammonium hydroxide descends, the consuming cost that contains the compound alkaline catalysts of tetraalkylammonium hydroxide in the production cost rises, this water that just requires how to contain as far as possible the compound alkaline catalysts heat-sensitive substance of hydroxide tetra-allkylammonium concentrates continuously fast, both guarantee spissated concentration, kept containing the compound alkaline catalysts heat-sensitive substance low decomposition ratio of hydroxide tetra-allkylammonium again.
Summary of the invention
Technical problem to be solved by this invention provides a kind of 4-of containing aminodiphenylamine, contain the continuous separation method of composition of compound alkaline catalysts, aniline and the hydrogenation solvent of tetraalkylammonium hydroxide, and provides continuous rapid evaporation spissated key equipment.
The present invention selects successively through extraction, concentrates, the technical process of evaporation, relevant operational condition, and the gas that has designed a kind of continuous rapid evaporation helps the stream falling-film evaporator, realizes that the continuous effective of said composition is separated.
Hydrogenation solvent of the present invention is an alcohols or/and water, and wherein alcohols is preferably methyl alcohol or ethanol or Virahol.Hydrogenation solvent is pure time-like, need separate and recycled, and when hydrogenation solvent was water, the water after the extraction only need concentrate and promptly get the compound alkaline catalysts that contains the hydroxide tetra-allkylammonium.
Contain hydroxide tetra-allkylammonium (N in the composition isolated of the present invention
+R
4OH
-) compound alkaline catalysts in each alkyl (R) be the alkyl of representing to contain 1-4 carbon atom independently.
Concrete separating step of the present invention is: will mainly contain the 4-aminodiphenylamine, the catalyzer that contains the hydroxide tetra-allkylammonium, the composition of aniline and hydrogenation solvent, with water is extraction agent, the ratio of it and composition is 0.5: 1-5: 1 (volume), preferred proportion is 0.8: 1-1.2: 1 (volume), with the polyethers organism for helping extraction agent, preferred polyglycol ether, polypropylene glycol ether, fatty alcohol-polyoxyethylene ether, polyethylene oxide dimethyl, the ratio of its consumption and extraction agent water is 0.01: 1-0.05: 1 (volume), in the process of continuous extraction, help extraction agent to improve extraction efficiency by adding, reduce the water yield of extraction, make interface debonding more obvious; To help extraction agent etc. to enter continuously and extract in the extraction tower as raw material combination thing and extraction agent water by power-driven pump, the mode of entrance of extraction agent and feedstock composition can take and stream, adverse current, cross-flow or segmentation enter.Keep tower internal pressure (absolute pressure) be 0.005-0.1 (MPa), temperature 0-80 (℃), extract time 2-5 (hour).Be divided into two-layerly in the tower of extraction back, the upper strata is a water after the discharging, and lower floor is an organic phase, contains aniline and 4-aminodiphenylamine.
In order to make alcohols and the compound alkaline catalysts that contains the hydroxide tetra-allkylammonium all fully are extracted into aqueous phase and to separate with aniline with the 4-aminodiphenylamine, improve percentage extraction effectively, the present invention adopts the extraction agent that helps of polyethers to make the easy layering of extraction, aspect is clear, change in the interrupted extraction process because of repeatedly extracting the defective that causes the water yield many, thereby realization continuous extraction, the percentage extraction of organic phase have also brought up to 97% from 93% of interrupted extraction.
The extraction equipment that the present invention adopts can be mixer-settlers, the pulse-column of external energy, centrifugal extractor, packing tower, stirring packing tower, gas bubble tower, rotating disc contactor, spray column, sieve-tray tower etc.
Water after extraction is because of containing a large amount of hydrogenation solvents and the compound alkaline catalysts that contains the hydroxide tetra-allkylammonium, and the compound alkaline catalysts that contains the hydroxide tetra-allkylammonium is a kind of material of thermo-sensitivity, be in for a long time under the higher temperature and decompose easily, the compound alkaline catalysts that contains the hydroxide tetra-allkylammonium after the extraction is extracted into aqueous phase and causes it low excessively in aqueous phase concentration, need a large amount of water and other low boiling substances sloughed, be condensed into higher concentration.For this reason, the present invention has designed gas and has helped this concentrating unit of rapid evaporation continuously of stream falling-film evaporator, it comprises shell side, tube side, be installed in the shell side upper end steam inlet, be installed in the shell side lower end the vapor condensation water out, be installed in the tube side top the import of lower concentration water, be installed in the tube side bottom the outlet of high density water, be installed in the distributing disc that the import of tube side overhead vapor promptly helps head piece, is installed in lower concentration water import below, the steam inlet that is installed in the tube side top promptly helps head piece, and its quantity is not limit.
Gas of the present invention helps the stream falling-film evaporator, and shell side adopts steam heating, and water is walked tube side, another part steam is by the steam port at the top of an effect falling-film evaporator, promptly help head piece, enter tube side, water helps the lower concentration water import of stream falling-film evaporator to enter in the tube side from gas.With steam is power-assist power, steam and water direction of motion are in the same way, in falling-film evaporator, under the drive of steam, water is membranaceous from top to bottom and flows by distributing disc in inside tube, the control residence time is 2-60 second, after evaporation concentration becomes the high density water, flow out from the outlet of high density water.With steam is power-assist power, reduces high-temperature residence time as much as possible.Make material in membranaceous flow, not only be subjected to the heating of the shell side pipe outside, and be subjected to the inboard vapour of tube side and help the stream heating, the mode that all heat both sides is evaporated low boiling substance in large quantities, is condensed into higher concentration during to the bottom.Its temperature of reaction can be controlled at 60-150 (℃), pressure (absolute pressure) 0.005-0.1 (MPa), help the stream falling-film evaporator by having designed gas, simultaneously under higher temperature of reaction, the low boiling substance of aqueous phase is evaporated in large quantities, controlled the residence time again, thereby can reduce the decomposition of the compound alkaline catalysts that contains the hydroxide tetra-allkylammonium to greatest extent, become intermittence into continuously, solved the continuous quick spissated difficult problem of water of the compound alkaline catalysts that contains the hydroxide tetra-allkylammonium.
Concentrated employing of the present invention one is imitated or multiple-effect gas helps the stream falling-film evaporator to carry out one or more levels to concentrate, and the heating agent that is used for concentrating water can be the secondary steam of water, water vapor or last effect, its Controllable Temperature be made as 60-150 (℃).The loss that its whole enrichment process contains the compound alkaline catalysts of hydroxide tetra-allkylammonium is no more than 0.3 (weight %).
Help the gas phase at stream falling-film evaporator top through gas, obtain the mixed solution of alcohols and water after the condensation, enter the rectifying tower separation continuously with pump after, at the available alcohols of cat head, its content is greater than 99 (weight %).Can recycled.Be water at the bottom of the tower, use gas chromatographic detection, its alcohols content is few.
Organic phase after extraction enters continuously to evaporate in the vaporizer and isolates most of aniline, and its working pressure (absolute pressure) is 0.005-0.1 (MPa), the temperature of evaporated liquor be 120-320 (℃), gas phase temperature be 60-190 (℃).After the gas-liquid separator separates of vaporizer top, aniline content is up to 99 (weight %) in condensed liquid for gas phase, and the bottom remainder is 4-aminodiphenylamine and minor amounts of aniline and organic impurity.
The vaporizer that the present invention uses can be jacketed type, coil pipe type, natural recirculating type, vertical lift type, fixedly scraper-type, movable scraping plate formula and the vaporizer that gets rid of forms such as disc type.
It is extraction agent that the present invention selects water, and polyethers can make the easy layering of extraction for helping extraction agent, and aspect is clear, has changed extraction several times in the interrupted extraction process, and the defective that the water yield is big has realized continuous extraction.The percentage extraction of organic phase also brings up to 97% from 93% of interrupted extraction; Adopt gas to help the stream falling-film evaporator, overcome the continuous quick spissated difficult problem of water of the compound alkaline catalysts that contains the hydroxide tetra-allkylammonium, make the rate of recovery of the compound alkaline catalysts that contains the hydroxide tetra-allkylammonium bring up to 99.7% from 90% of traditional method; Through above-mentioned extraction, concentrate, evaporate each technological operation, having realized containing the continuous effective of the composition of a plurality of components such as 4-aminodiphenylamine separates, and technology is continuous, simple to operate, the cycle short, and labour intensity is low, production efficiency is high, three-waste free pollution, continuous good separating effect.
Description of drawings
Fig. 1 is the schema that contains the separation method of 4-ADP amine composition.
Fig. 2 is the synoptic diagram that gas helps the stream falling-film evaporator
1-water 2-organic phase
3-gas phase 4-liquid phase
5-hydrogenation solvent 6-contains the compound alkaline catalysts of hydroxide tetra-allkylammonium
7-aniline 8-4-aminodiphenylamine crude product
9-shell side 10-tube side
11-lower concentration water import 12-steam inlet
13-steam inlet 14-vapor condensation water out
15-high density water outlet 16-distributing disc
Embodiment
Embodiment 1
Is the water of 580 liter/hour and same traffic respectively be conveyed into the cat head and tower of extraction tower at the bottom of with composition (wherein hydrogenation solvent is a methyl alcohol) with flow with volume pump, help extraction agent to select polypropylene glycol ether for use, enter extraction tower continuously with 6 liters/hour flows, extraction tower is the packing tower of atmospheric pressure state, temperature is 30-50 ℃, water after the extraction and organic phase enter water basin and organic phase basin respectively, the water flow that obtains is 767 liters/hour, the organic phase flow is 393 liters/hour, the organic phase that can take a morsel equal-volume deionized water thorough washing, after treating standing demix, the pH value that records water layer gets final product less than 9, and the percentage extraction of organic phase is 97.1% by analysis
767 liters of/hour waters are preheated to 80 ℃, enter normal pressure one effect gas and help stream falling-film evaporator top, gas helps stream falling-film evaporator shell side to heat with 120 ℃ of water vapors, the tube side material distributes through sparger, and under air-flow drives, be the membranaceous gas that flows to and help stream falling-film evaporator bottom, about 10 seconds of the residence time of material in vaporizer, the liquid-vapor mixture temperature that helps the stream falling-film evaporator to come out from an effect gas is 100-105 ℃, after an effect vapour liquid separator separated, a flow of imitating concentrated solution was about 300 liters/hour then.Take a morsel an effect concentrated solution through gas chromatographic detection, do not detect methyl alcohol.One effect concentrated solution is entered the effect of two under the 0.03Mpa pressure (absolute pressure) gas continuously help the stream falling-film evaporator, two imitate gas helps the shell side of stream falling-film evaporator to heat with a vapour phase of imitating after vapour liquid separator separates, two imitate gas helps stream falling-film evaporator tube side material also to distribute through sparger, and under air-flow drives, be membranaceous flow direction bottom, 10 seconds residence time in vaporizer of material, from two imitate that gas help that the stream falling-film evaporator comes out vapour-liquid composition temperature be 80-95 ℃, then after two effect vapour liquid separators separate, obtain containing the compound alkaline catalysts of hydroxide tetramethyl-ammonium, two imitate the flow of finishing liquid is about 150 liters/hour.The compound alkaline catalysts rate of recovery that whole enrichment process contains the hydroxide tetra-allkylammonium can reach 99.7%, and water has obtained concentrating.
Through a gas phase of imitating after vapour liquid separator separates, after imitating the condensation of falling-film evaporator heat exchange condensers with two, obtain containing methyl alcohol-aqueous solution of methyl alcohol about 28 (weight %), after entering rectifying tower continuously and separate with pump, cat head obtains the methyl alcohol greater than 99 (weight %), the tower still is a water, surveys tower still water with gas-chromatography, and methanol content is less than 0.3 (weight %).
The organic phase that extracting and separating is obtained, send into shell and tube climbing-film evaporator separating most aniline continuously with pump, the working pressure of climbing-film evaporator (absolute pressure) is 0.01Mpa, shell side is with 180 ℃ of steam heating, obtain 75-105 ℃ gas phase and 160 ℃ liquid phase through the separation of climbing-film evaporator top vapour liquid separator, detect condensed gaseous phase materials with chromatogram, record aniline content and reach 99 (weight %), the crude product of liquid phase material 4-aminodiphenylamine is 78.1 (weight %) for containing the 4-aminodiphenylamine, aniline 20.1 (weight %), remainder is other organic impuritys.
Embodiment 2
The present invention adopts two effect gas to help the stream falling-film evaporator, every effect gas help the stream falling-film evaporator comprise shell side 9, tube side 10, be installed in shell side 9 upper ends steam inlet 13, be installed in shell side 9 lower ends vapor condensation water out 14, be installed in tube side 10 tops lower concentration water import 11, be installed in the high density water outlet 15 of tube side 10 bottoms, five steam inlets 12 are evenly installed at top at tube side 10, promptly help head piece, distributing disc 16 is installed in the below of lower concentration water import 11.
The two effect gas that the present invention adopts help the stream falling-film evaporator, its shell side 9 adopts steam heating, water is walked tube side 10, also have the steam port 12 of one road steam by the top of an effect falling-film evaporator, promptly help head piece, enter tube side 10, water helps the lower concentration water import 11 of stream falling-film evaporator to enter in the tube side 10 from gas.With steam is power-assist power, steam and water direction of motion are in the same way, in falling-film evaporator, under the drive of steam, the low concentration of water distributing disc 16 that communicated is membranaceous from top to bottom and flows in tube side 10 inboards, the control residence time, evaporation concentration becomes the high density water, promptly one imitates concentrated solution, flows out falling-film evaporator from high density water outlet 15.One effect concentrated solution enters two effect gas continuously and helps the stream falling-film evaporator, two imitate gas helps the gas phase that shell side 9 usefulness one of stream falling-film evaporator are imitated after vapour liquid separator separates to heat, two imitate gas helps stream falling-film evaporator tube side material also to distribute through distributing disc 16, and under air-flow drives, be membranaceous flow direction bottom, flow out from high density water outlet 15.
Gas of the present invention helps the stream falling-film evaporator, and material is heated by shell side not only in membranaceous flowing, and is subjected to the gentle heating that helps the stream both sides of tube side side, and low boiling substance is evaporated in large quantities, is condensed into higher concentration during to the bottom.Adopt two effect gas to help the stream falling-film evaporator, utilized the superheated vapo(u)r of an effect steam, make that the ultimate density after the material evaporation concentration is higher, overcome the continuous quick spissated difficult problem of water of the catalyzer that contains the hydroxide tetra-allkylammonium simultaneously.
Claims (11)
1. separation method that contains the composition of 4-aminodiphenylamine, composition is to be in the process of raw material production 4-aminodiphenylamine with oil of mirbane and aniline, gained contains the 4-aminodiphenylamine behind the hydrogenation, the compound alkaline catalysts that contains the hydroxide tetra-allkylammonium, the mixing liquid of aniline and hydrogenation solvent, it is characterized in that sepn process is successively through extraction, concentrate with evaporation technology and carry out, make extraction agent with water, polyethers helps extraction agent, the organic phase that obtains after the extraction contains aniline and 4-aminodiphenylamine, organic phase after extraction enters vaporizer continuously, evaporate to separate and obtain 4-aminodiphenylamine and aniline, the water of extraction back gained, help the stream falling-film evaporator to carry out the compound alkaline catalysts that concentrating and separating obtains hydrogenation solvent respectively and contains the hydroxide tetra-allkylammonium by an effect or multiple-effect gas, separate and carry out continuously.
2, the separation method that contains the composition of 4-aminodiphenylamine according to claim 1 is characterized in that the extraction agent that helps that is adopted is polyglycol ether or polypropylene glycol ether or fatty alcohol-polyoxyethylene ether or polyethylene oxide dimethyl.
3, the separation method that contains the composition of 4-aminodiphenylamine according to claim 1 and 2 is characterized in that helping the volume ratio of extraction agent and extraction agent is 0.01: 1-0.05: 1.
4, the separation method that contains the composition of 4-aminodiphenylamine according to claim 1 is characterized in that extraction agent water and the volume ratio that contains the composition of 4-aminodiphenylamine are 0.5: 1-5: 1.
5, the separation method that contains the composition of 4-aminodiphenylamine according to claim 4 is characterized in that extraction agent water and the volume ratio that contains the composition of 4-aminodiphenylamine are 0.8: 1-1.2: 1.
6, the separation method that contains the composition of 4-aminodiphenylamine according to claim 1 is characterized in that the temperature that extracts is 0-80 ℃.
7, the separation method that contains the composition of 4-aminodiphenylamine according to claim 1 is characterized in that being used for the secondary steam that spissated heating agent is water or water vapour or last effect, and the temperature of spissated heating agent is 60-150 ℃.
8, the separation method that contains the composition of 4-aminodiphenylamine according to claim 1 is characterized in that spissated pressure is absolute pressure 0.005-0.1Mpa, and the residence time is 2-60 second.
9, the separation method that contains the composition of 4-aminodiphenylamine according to claim 1 is characterized in that the pressure that evaporates is absolute pressure 0.005-0.1MPa, and liquidus temperature is 120-320 ℃, and gas phase temperature is 60-190 ℃.
10, a kind of separation gas of containing the composition of 4-aminodiphenylamine helps the stream falling-film evaporator, comprise shell side (9), tube side (10), be installed in shell side (9) upper end steam inlet (13), be installed in shell side (9) lower end vapor condensation water out (14), be installed in tube side (10) top lower concentration water import (11), be installed in the high density water outlet (15) of tube side (10) bottom, it is characterized in that, steam inlet (12), the below distributing disc (16) of lower concentration water import (11) are installed in top at tube side (10).
11, the separation according to claim 10 gas that contains the composition of 4-aminodiphenylamine helps the stream falling-film evaporator, it is characterized in that the quantity of the steam inlet (12) at tube side (10) top is not limit.
Priority Applications (31)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031481949A CN1185206C (en) | 2003-07-04 | 2003-07-04 | Separation method of composition containing 4-aminodiamine and its equipment |
| EA200501647A EA009395B1 (en) | 2003-07-04 | 2004-07-02 | A process for preparing 4-aminodiphenylamine |
| PCT/CN2004/000734 WO2005003079A1 (en) | 2003-07-04 | 2004-07-02 | A method for producing 4-aminodiphenylamine |
| ES04738332T ES2373720T3 (en) | 2003-07-04 | 2004-07-02 | METHOD FOR THE PRODUCTION OF 4-AMINODYPHENYLAMINE. |
| DE602004010234T DE602004010234T2 (en) | 2003-07-04 | 2004-07-02 | PROCESS FOR THE PREPARATION OF 4-AMINODIPHENYLAMINE |
| ES04738331T ES2298762T3 (en) | 2003-07-04 | 2004-07-02 | PROCESS TO PREPARE 4-AMINODYPHENYLAMINE. |
| JP2006517937A JP4546958B2 (en) | 2003-07-04 | 2004-07-02 | Method for producing 4-aminodiphenylamine |
| US10/882,677 US7176333B2 (en) | 2003-07-04 | 2004-07-02 | Process for preparing 4-aminodiphenylamine |
| EP04738331A EP1591438B1 (en) | 2003-07-04 | 2004-07-02 | A process for preparing 4-aminodiphenylamine |
| KR1020040051541A KR100612922B1 (en) | 2003-07-04 | 2004-07-02 | A process for producing 4-aminodiphenylamine |
| JP2006500463A JP4500302B2 (en) | 2003-07-04 | 2004-07-02 | Method for producing 4-aminodiphenylamine |
| EP04738332A EP1645555B1 (en) | 2003-07-04 | 2004-07-02 | A method for producing 4-aminodiphenylamine |
| EA200600052A EA009396B1 (en) | 2003-07-04 | 2004-07-02 | A method for producing 4-aminodiphenylamine |
| AT04738332T ATE526305T1 (en) | 2003-07-04 | 2004-07-02 | METHOD FOR PRODUCING 4-AMINODIPHENYLAMINE |
| CA2531074A CA2531074C (en) | 2003-07-04 | 2004-07-02 | Process for preparing 4-aminodiphenylamine |
| PCT/CN2004/000733 WO2005003078A1 (en) | 2003-07-04 | 2004-07-02 | A process for preparing 4-aminodiphenylamine |
| PT04738332T PT1645555E (en) | 2003-07-04 | 2004-07-02 | A method for producing 4-aminodiphenylamine |
| CA2515238A CA2515238C (en) | 2003-07-04 | 2004-07-02 | Process for preparing 4-aminodiphenylamine |
| US10/883,042 US7084302B2 (en) | 2003-07-04 | 2004-07-02 | Process for preparing 4-aminodiphenylamine |
| MXPA05013788A MXPA05013788A (en) | 2003-07-04 | 2004-07-02 | A process for preparing 4-aminodiphenylamine. |
| BRPI0412101-5A BRPI0412101A (en) | 2003-07-04 | 2004-07-02 | process for the preparation of 4-aminodiphenylamine |
| PL04738332T PL1645555T3 (en) | 2003-07-04 | 2004-07-02 | A method for producing 4-aminodiphenylamine |
| KR1020040051932A KR100612923B1 (en) | 2003-07-04 | 2004-07-05 | A process for preparing 4-aminodiphenylamine |
| US11/477,954 US7235694B2 (en) | 2003-07-04 | 2006-06-30 | Process for preparing 4-aminodiphenylamine |
| US11/757,277 US20080039657A1 (en) | 2003-07-04 | 2007-06-01 | Process for preparing 4-aminodiphenylamine |
| US11/759,897 US8293673B2 (en) | 2003-07-04 | 2007-06-07 | Process for preparing 4-aminodiphenylamine |
| US11/759,901 US20070227675A1 (en) | 2003-07-04 | 2007-06-07 | Process for preparing 4-aminodiphenylamine |
| US12/195,371 US7989662B2 (en) | 2003-07-04 | 2008-08-20 | Process for preparing 4-aminodiphenylamine |
| US12/900,459 US8486223B2 (en) | 2003-07-04 | 2010-10-07 | Falling film evaporator |
| US13/104,900 US8686188B2 (en) | 2003-07-04 | 2011-05-10 | Process for preparing 4-aminodiphenylamine |
| US13/620,588 US9029603B2 (en) | 2003-07-04 | 2012-09-14 | Process for preparing alkylated p-phenylenediamines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031481949A CN1185206C (en) | 2003-07-04 | 2003-07-04 | Separation method of composition containing 4-aminodiamine and its equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1475476A CN1475476A (en) | 2004-02-18 |
| CN1185206C true CN1185206C (en) | 2005-01-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031481949A Expired - Lifetime CN1185206C (en) | 2003-07-04 | 2003-07-04 | Separation method of composition containing 4-aminodiamine and its equipment |
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| Country | Link |
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| CN (1) | CN1185206C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100336796C (en) * | 2004-07-15 | 2007-09-12 | 王农跃 | Process for preparing 4-amino diphenylamine |
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