CN105061215A - 2, 4-diaminotoluene purification method - Google Patents
2, 4-diaminotoluene purification method Download PDFInfo
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- CN105061215A CN105061215A CN201510550850.3A CN201510550850A CN105061215A CN 105061215 A CN105061215 A CN 105061215A CN 201510550850 A CN201510550850 A CN 201510550850A CN 105061215 A CN105061215 A CN 105061215A
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- 238000000034 method Methods 0.000 title claims abstract description 44
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000746 purification Methods 0.000 title claims abstract description 27
- 230000035900 sweating Effects 0.000 claims abstract description 42
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 73
- 239000000203 mixture Substances 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 230000003252 repetitive effect Effects 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000001816 cooling Methods 0.000 abstract description 3
- 210000004243 sweat Anatomy 0.000 abstract 1
- 208000008454 Hyperhidrosis Diseases 0.000 description 34
- 238000002156 mixing Methods 0.000 description 7
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 description 6
- 210000002837 heart atrium Anatomy 0.000 description 6
- 239000007789 gas Substances 0.000 description 4
- 238000009434 installation Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000005057 refrigeration Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000012041 food component Nutrition 0.000 description 1
- 239000005417 food ingredient Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002620 method output Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a 2, 4-diaminotoluene purification method. The method comprises the steps that an initial raw material composed of 2, 4-diaminotoluene and 2, 6-diaminotoluene is fed into a preheated crystallizer after being dissolved; the crystallizer is cooled at a preset cooling speed until crystals are dissolved out; heat is preserved until crystallizing layers grow up completely; residual liquor in the crystallizer is discharged, and temperature of the crystallizer is raised at a preset temperature raising speed for carrying out sweating processing on the crystallizing layers; sweat liquid is discharged from the crystallizer; the temperature of the crystallizer is raised so as to dissolve the crystallizing layers in the crystallizer completely, so that liquid 2, 4-diaminotoluene product is obtained. By meticulously designing all the technological steps, purification of 2, 4-diaminotoluene is practical for industrialization.
Description
Technical field
The present invention relates to a kind of technology from mixing diaminotoluene (TDA) purification 2,4 di amino toluene.
Background technology
2,4 di amino toluene is important dyestuff intermediate, is also the important raw and processed materials of producing tolylene diisocyanate (TDI) simultaneously.Methylbenzene nitration normally first obtains mixing dinitrotoluene (DNT) by the method for industrial synthesis TDA, mixing dinitrotoluene (DNT) in position between obtaining after the dinitrotoluene (DNT) of rectifying separation removing ortho position, restore and obtain mixing TDA, 2,4-TDA and 2,6-TDA content mainly contain 2 kinds of ratios (quality Isomer ratio): about 80:20 or about 65:35.Because the dyestuff better quality of pure 2,4-TDA synthesis, better by the use properties of polyurethane(s) of pure 2,4-TDA polymerizations, so, economical, efficiently 2, the 4-TDA that purifies there is wide industrial prospect.
At present, such as, although have the relevant report being prepared 2,4 di amino toluene by mixing TDA both at home and abroad, resin method, sieve method and derivatize crystallization process.But resin method, sieve method output are less, can not meet industrial needs, and derivatize crystallization process raffinate is difficult to process, easily causes secondary pollution.Therefore, environmental pollution is little, and production technique is simple, and the purification techniques of the 2,4 di amino toluene that energy consumption is low has high marketable value.
Summary of the invention
The object of the invention is for problems of the prior art, the purification techniques of simple 2,4 di amino toluene is efficiently provided.
According to a first aspect of the invention, a kind of method adopting fused junction crystallization purification 2,4 di amino toluene is provided.The method comprising the steps of:
Will by 2, after the initial feed mixture that 4-diaminotoluene and 2,6-diaminotoluene form melts at 90-100 DEG C in the crystallizer that has been preheated of feeding, in initial feed mixture 2,4-diaminotoluene: 2,6-diaminotoluene is 75 ~ 85:25 ~ 15; And wherein crystallizer preheating temperature is consistent with the melt temperature of initial feed mixture;
With the predetermined rate of temperature fall decrease temperature crystalline device of 0.5-3 DEG C/h until the crystal Precipitation Temperature of 62-70 DEG C;
Keep above-mentioned crystal Precipitation Temperature 0.5-4 hour until crystallizing layer is grown up completely;
Raffinate in crystallizer is released, and with the predetermined sweating temperature of 2-8 DEG C/h of predetermined temperature rise rate intensification crystallizer to 80-90 DEG C to carry out sweating process to crystallizing layer;
Keep above-mentioned predetermined sweating temperature 0.5-4 hour;
Sweating is discharged from crystallizer;
Promote to melt the crystallizing layer of crystallizer inside completely about mould temperature to 100 DEG C, thus obtain liquid 2,4 di amino toluene product.
The present invention makes the purification of 2,4 di amino toluene (2,4-TDA) be able to industry by well-designed each processing step practical.
In a specific embodiment, method of the present invention can also comprise: with gained liquid 2,4 di amino toluene products substitution initial feed mixture to repeat each step above-mentioned.In this case, each step above-mentioned can also be repeated to the recirculation of gained liquid 2,4 di amino toluene product such as, until the liquid 2,4 di amino toluene product of gained reaches predetermined purity, more than 99%.Further, in recirculation repetitive process, gained sweating and/or raffinate also can be introduced crystallizer by as material composition again.Therefore, this embodiment can also minimize industrial wastes while raising product purity.
In another specific embodiment, method of the present invention can also comprise: repeat each step above-mentioned by after above-mentioned initial feed mixture and gained sweating mix.In this case, mix (or feed) ratio of initial feed mixture and gained sweating is preferably about 4:1.A large amount of practice shows, this mixing feed ratio can obtain best product yield with minimum process cost.
In another specific embodiment, method of the present invention can also comprise: the discharge port of heating crystalline device when crystallizer discharges corresponding material.In this case water vapour is preferably used to carry out the discharge port of heating crystalline device.Heating crystalline device discharge port can avoid material stagnant thus smooth and easy discharge material.
In another specific embodiment, water vapour type of heating also can be used to promote about mould temperature to 100 DEG C to melt the crystallizing layer of crystallizer inside completely.
In the above two embodiments, using water vapour to heat both can not superheated crystallizer, again convenient control Heating temperature.In addition, same vapour source can be used to perform the thawing heating of the heating of crystallizer discharge port and crystallization.
In a specific embodiment, method of the present invention can also comprise: remain nitrogen protection atmosphere in a crystallizer.Adopt nitrogen not only to save cost but also environmental protection as crystallization protective atmosphere, also improve quality product simultaneously.
According to a second aspect of the invention, provide a kind of purification system, for 2,4 di amino toluene of purifying from the initial feed mixture be made up of 2,4 di amino toluene and 2,6-diaminotoluene.This purification system comprises:
Crystallizer, has opening for feed and discharge port, and wherein crystallizer also comprises and arranging and temperature adjustment sleeve for changing its temperature around it, and temperature adjustment sleeve has circulating water intake and circulating water outlet;
Interchanger, for heating or cooling the recirculated water in temperature adjustment sleeve;
Head tank, is communicated with the opening for feed of crystallizer;
Product receiving tank, is communicated with the discharge port of crystallizer;
Sweating receiving tank, is communicated with the discharge port of crystallizer; And
Raffinate receiving tank, is communicated with the discharge port of crystallizer.
Purification system of the present invention can perform method of purification of the present invention or technique easily, and compact construction thus overall floor space is little.
In the first specific embodiment of purification system of the present invention, crystallizer can be riser type crystallizer, and opening for feed is positioned at the top of crystallizer and discharge port is positioned at the bottom of crystallizer; Temperature adjustment sleeve can be the riser type temperature adjustment sleeve arranged around crystallizer, and circulating water intake is positioned at the top that the bottom of temperature adjustment sleeve and circulating water outlet are positioned at temperature adjustment sleeve; And interchanger can comprise well heater and the water cooler of upper and lower arranged in series, and the circulating water line that the circulating water intake of temperature adjustment sleeve is communicated with circulating water outlet is extended respectively through well heater and water cooler.Formation/the thawing of this import and export of the present invention and the very applicable crystal of arranged in series design also can optimizing heat exchange efficiency.
In the purification system of the first specific embodiment, further, well heater can be positioned on water cooler, and well heater has superposed steam inlet and is positioned at the condensation-water drain of bottom, and water cooler has superposed refrigeration cycle water out and is positioned at the refrigeration cycle water inlet of bottom.This import and export design optimizes heat exchange further.
In the purification system of the first specific embodiment, again further, can also comprise: circulation water pot, jointly form circulating water loop with circulating water line and temperature adjustment sleeve; And water circle device, for the water in the water loop of pump circulation flow circuit.Circulation water pot is equivalent to reservoir and plays the dash adjustment effect to recirculated water.
In the second embodiment of purification system of the present invention, the discharge port of crystallizer can be communicated with the house steward at least partly to downward-extension by valve such as check valve, product receiving tank, sweating receiving tank and raffinate receiving tank are communicated with house steward respectively by corresponding arm, and each arm are provided with valve such as check valve.Valve and house steward/arm with the use of making each processing step independently to perform easily.
In the purification system of the second specific embodiment, further, head tank can have material inlet and material outlet, can be provided with pumping installation in the raw material feed pipeline be communicated with the opening for feed of crystallizer by the material outlet of head tank.In this case, house steward can also by valve such as check valve and the raw material feed pipeline connection being positioned at pumping installation upstream.This structure design of the present invention makes raffinate/sweating/product directly selectivity can participate in recirculation crystallisation process.
In the purification system of the 3rd specific embodiment of the present invention, head tank, product receiving tank, sweating receiving tank and raffinate receiving tank can be respectively equipped with the inlet mouth for receiving nitrogen.This design of the present invention can build corresponding low-cost environmental-protecting inert protective atmosphere.
In the purification system of the 4th specific embodiment of the present invention, head tank can also be provided with feedback outlet, and product receiving tank, sweating receiving tank can have with raffinate receiving tank the discharge gate be communicated with the feedback outlet of head tank by valve such as check valve respectively.This structure design of the present invention makes raffinate/sweating/product can participate in recirculation crystallisation process by indirect selective.
In the purification system of the 5th specific embodiment of the present invention, rotary type crystallizer is provided with in crystallizer, the bottom of crystallizer is also provided with the atria be communicated with crystallizer and the indirect heating cover arranged around atria, and indirect heating puts and is respectively equipped with steam-gas inlet and condensation-water drain.This structure design of the present invention can avoid material lagging phenomenon easily.
Accompanying drawing explanation
Fig. 1 is the structural representation of purification system of the present invention; And
Fig. 2 is fusion-crystallization process flow diagram of the present invention.
Embodiment
Method of purification of the present invention and system is described in detail below in conjunction with accompanying drawing.It should be appreciated by those skilled in the art that the following detailed description just for a better understanding of the present invention, is not limited to the present invention.
See Fig. 1, purification system of the present invention mainly can be used for purifying 2,4 di amino toluene from the initial feed mixture be made up of 2,4 di amino toluene and 2,6-diaminotoluene.This purification system mainly comprises crystallizer 100, interchanger (well heater 210 and water cooler 220), head tank 300, raffinate receiving tank 400, sweating receiving tank 500 and product receiving tank 600.
Shown crystallizer 100 is (erecting) tubular mold, the temperature adjustment sleeve 140 comprise rotary type (or radiator type) crystallizer 110, arranging around crystallizer 110.Crystallizer 100 also has top cover 130, top cover 130 offers opening for feed 131 and inlet mouth 132.The funneling atria 120 be communicated with crystallizer 110 is formed on crystallizer bottom or bottom, and discharge port 121 is formed on the bottom of atria 120.Indirect heating cover 150 around atria 120 is respectively equipped with steam-gas inlet 151 and condensation-water drain 152, and shown condensation-water drain 152 is positioned at below steam-gas inlet 151, contiguous discharge port 121.In the embodiment shown, crystallizer 110 neither stretches into atria 120 and does not also stretch into top cover 130 inside.
Shown temperature adjustment sleeve 140 is riser type sleeve, and top has circulating water outlet 141, and bottom has circulating water intake 142.In addition, the middle part of shown temperature adjustment sleeve 140 is also provided with and is added to the mouth of a river 143.Be added to the mouth of a river 143 and be usually in closing condition, only when circulating water heating/speed of cooling is inadequate for introducing extra water.In addition, the sidewall of shown temperature adjustment sleeve 140 also offers viewing window 144.
Interchanger shown in Fig. 1 is made up of the well heater 210 of upper and lower arranged in series and water cooler 220.The circulating water line 200 that the circulating water intake 142 of temperature adjustment sleeve 140 is communicated with circulating water outlet 141 is extended respectively through well heater 210 and water cooler 220, thus forms circulating water loop.In the embodiment shown in fig. 1, can also arrange the circulation water pot 230 with water-in 231 and water outlet 232, water outlet 232 is communicated with the circulating water intake 142 of temperature adjustment sleeve by circulating water line 200, water-in 231 communication loop water outs 141.Like this, circulation water pot 230 forms circulating water loop jointly with circulating water line 200 and temperature adjustment sleeve 140.In addition, although do not illustrate, water circle device such as water pump can also be set in circulating water loop, produce for making circulating water loop and force current.
In the embodiment shown in fig. 1, the circulating water line 200 of adjacent cycle water inlet 142 is also provided with valve 201 (such as check valve) so that carry out selective control.Circulation water pot 230 top is also provided with pressure release valve 233.Although do not illustrate more valve, as further described as follows, system of the present invention can also arrange all kinds of valve as required.
As shown in Figure 1, well heater 210 is positioned on water cooler 220.Well heater 210 has superposed steam inlet 211 and is positioned at the condensation-water drain 212 of bottom.Water cooler 220 has superposed refrigeration cycle water out 221 and is positioned at the refrigeration cycle water inlet 222 of bottom.
Although do not illustrate further, the steam inlet 151 that steam-gas inlet 211 and the indirect heating of well heater 210 overlap 150 can be communicated with by means of the arm (and by same supervisor) respectively with valve and shares source of water vapor; The condensation-water drain 152 of the condensation-water drain 212 of well heater 210 and indirect heating cover 150 can be communicated with shared condensate receiver by means of the arm (and by same supervisor) respectively with valve equally.
Shown head tank 300 has material inlet 301, material outlet 302, feedback outlet 303 and (nitrogen) inlet mouth 304.Material inlet 301 receives the TDA mixing raw material in supplied materials direction shown in Fig. 1 left arrow.Material outlet 302 is communicated with the opening for feed 131 of crystallizer by raw material feed pipeline 310.Although do not illustrate, in raw material feed pipeline 310, corresponding pumping installation can also be set.
Raffinate receiving tank 400 has receiving port 401, discharge gate 402 and inlet mouth 403.Sweating receiving tank 500 has receiving port 501, discharge gate 502 and inlet mouth 503.Product receiving tank 600 has receiving port 601, discharge gate 602 and inlet mouth 603.
The discharge port 121 of shown crystallizer 100 can pass through valve (not shown, such as check valve) and be communicated with the discharge header pipe 160 at least partly to downward-extension.Raffinate receiving tank 400 such as, is communicated with discharge header pipe 160 by the arm 404 being provided with valve (not shown, check valve); Sweating receiving tank 500 such as, is communicated with discharge header pipe 160 by the arm 504 being provided with valve (not shown, check valve); Product receiving tank 600 such as, is communicated with discharge header pipe 160 by the arm 604 being provided with valve (not shown, check valve).
In addition, product receiving tank 600, sweating receiving tank 500 also can be (not shown respectively by being provided with respective valves with the discharge gate of raffinate receiving tank 400, such as check valve) arm be communicated with returning charge house steward 360, returning charge house steward 360 is communicated with the feedback outlet 303 of head tank 300 again.
Although Fig. 1 does not specifically illustrate, discharge header pipe 160 directly can also be communicated with the material inlet 301 of the raw material feed pipeline 310 or head tank 300 that are positioned at pumping installation upstream by the arm (not shown) being provided with valve such as check valve.
Referring to Fig. 1 and Fig. 2, purifying technique of the present invention or method are described.
First, from (initially) batching of Fig. 2.Send into (one-level) crystallizer 100 be preheated from head tank 300 after first the initial feed mixture be made up of 2,4 di amino toluene and 2,6-diaminotoluene can being melted at 90-100 DEG C.2,4 di amino toluene in initial feed mixture: 2,6-diaminotoluene (mass ratio) is 75 ~ 85:25 ~ 15.Crystallizer 100 preheating temperature is consistent with the melt temperature of initial feed mixture is very important.
Then, (one-level) fusion-crystallization of Fig. 2 is performed.Namely utilize water cooler 220 with the predetermined rate of temperature fall decrease temperature crystalline device 100 of 0.5-3 DEG C/h until the crystal Precipitation Temperature of 62-70 DEG C, keep above-mentioned crystal Precipitation Temperature 0.5-4 hour until crystallizing layer is grown up completely (first degree crystalline product).
Next, raffinate (or can be described as " one-level mother liquor ") in crystallizer 100 is discarded to (one-level) raffinate receiving tank 400, and utilizes well heater 210 with the predetermined sweating temperature of 2-8 DEG C/h of predetermined 100 to 80-90 DEG C, temperature rise rate intensification crystallizer to carry out sweating process to the crystallizing layer in crystallizer 100.Keep above-mentioned predetermined sweating temperature 0.5-4 hour.
One-level sweating is discharged to (one-level) sweating receiving tank 500 from crystallizer 100.
Again utilize well heater 210 to promote to melt the crystallizing layer of crystallizer 100 inside completely about crystallizer 100 temperature to 100 DEG C, thus obtain liquid 2,4 di amino toluene product.The finished product obtained the direction of arrow can outwards send (one-level) product receiving tank 600 shown on the right side of such as Fig. 1.
In above process, nitrogen can be passed into all the time to produce protective atmosphere in crystallizer 110 by inlet mouth 132.In addition, nitrogen can also be passed into wherein by the inlet mouth that head tank 300, raffinate receiving tank 400, sweating receiving tank 500 and product receiving tank 600 are respective to produce protective atmosphere equally.
In addition, secondary fusion-crystallization shown in Figure 2.In the present invention, can also with first degree crystalline product directly (shown in Fig. 2) or indirectly (come from product receiving tank 600, can see Fig. 1) participate in batching (such as substituting initial feed mixture) and carry out improving product purity, until such as more than 99% to repeat each step above-mentioned in (secondary) crystallizer 100.Further, gained secondary sweating in recirculation repetitive process---can be temporary in (secondary) sweating receiving tank 500, and/or secondary raffinate (or can be described as " secondary mother liquor ")---can be temporary in (secondary) raffinate receiving tank 400, even secondary crystallization product---can be temporary in (secondary) product receiving tank 600, also all can again be introduced head tank 300 by as food ingredient.In the present invention, first degree crystalline device and secondary crystal device can be identical or different; One-level raffinate receiving tank and secondary raffinate receiving tank, one-level sweating receiving tank and secondary sweating receiving tank, first class product receiving tank and secondary product receiving tank as the same.
In addition, as shown in Figure 2, each step above-mentioned can be repeated by after the one-level sweating received in such as sweating receiving tank 500 and above-mentioned initial feed mixture mix.In this case, it is best when the mix ratio of initial feed mixture and sweating is about 4:1.
In the present invention, indirect heating cover 150 can be utilized the discharge port of heating crystalline device is carried out when crystallizer discharges corresponding material.Material so just can be avoided stagnant thus smooth and easy discharge material.
Below three examples that method and system according to the present invention carries out.
Example 1
2,4 and 2,6-diaminotoluene mixture (Isomer ratio is: 2,4:2,6=80:20) 500kg is melted at temperature 90 DEG C, is pumped in the crystallizer of same preheating 90 DEG C; Regulate the circulating water temperature in temperature adjustment sleeve, slowly reduce (rate of temperature fall 2 DEG C/h) mould temperature to 65 DEG C, and raffinate was released after half an hour by constant temperature at this temperature; Regulate the circulating water temperature in temperature adjustment sleeve slowly to raise (temperature rise rate 4 DEG C/h), constant temperature half an hour after 86 DEG C, sweating collected in intensification separates with raffinate to be deposited; Promote mould temperature to 100 DEG C, after materials inside is all melted, product is released.Obtain 2,4 di amino toluene and 2,6-diaminotoluene mixture (Isomer ratio 95:5) 250kg.
Embodiment 2
Product 250kg in embodiment 1 is melted at temperature 100 DEG C, is pumped in the crystallizer of 95 DEG C; Regulate the circulating water temperature in temperature adjustment sleeve, slowly reduce mould temperature (1.5 DEG C/h) to 75 DEG C, and raffinate was released after half an hour by constant temperature at this temperature; Regulate the circulating water temperature in temperature adjustment sleeve slowly to raise (2 DEG C/h), constant temperature half an hour after 98 DEG C, sweating collected in intensification separates with raffinate to be deposited; Promote mould temperature to 100 DEG C, after materials inside is all melted, product is released.Obtain 2,4 di amino toluene 200kg, the purity (GC method) of product is 99.1%.
Embodiment 3
2,4 and 2,6-diaminotoluene mixture (Isomer ratio is: 2,4:2,6=80:20) 400kg is mixed with the sweating 100kg in embodiment 1, melts at temperature 90 DEG C, be pumped in the crystallizer of 90 DEG C; Regulate the circulating water temperature in temperature adjustment sleeve, slowly reduce mould temperature (1.5 DEG C/h) to 75 DEG C, and raffinate was released after half an hour by constant temperature at this temperature; Regulate the circulating water temperature in temperature adjustment sleeve slowly to raise (2 DEG C/h), constant temperature half an hour after 98 DEG C, sweating collected in intensification separates with raffinate to be deposited; Promote mould temperature to 100 DEG C, after materials inside is all melted, product is released.Obtain 2,4 di amino toluene and 2,6-diaminotoluene mixture (Isomer ratio 95:5) 280kg.
Generally speaking, the present invention at least also has the following advantages:
1, the present invention adopts fused junction crystallization to purify to mix diaminotoluene for raw material, makes the 2,4 di amino toluene content in product up to more than 99.0%, can be better than 98.5% of chemical industry standard (HG/T3395-2010).
2, the present invention does not add any new solvent in purification process, thus avoids secondary pollution.
3, the present invention utilizes the heat of crystallization of material, and comparing vaporization heat has had and significantly reduce, and effectively can reduce energy consumption cost, thus be suitable for industrialization.
Claims (10)
1. adopt a method for fused junction crystallization purification 2,4 di amino toluene, comprise step:
Will by 2, after the initial feed mixture that 4-diaminotoluene and 2,6-diaminotoluene form melts at 90-100 DEG C in the crystallizer that has been preheated of feeding, in initial feed mixture 2,4-diaminotoluene: 2,6-diaminotoluene=75 ~ 85:25 ~ 15; And wherein crystallizer preheating temperature is consistent with the melt temperature of initial feed mixture;
With the predetermined rate of temperature fall decrease temperature crystalline device of 0.5-3 DEG C/h until the crystal Precipitation Temperature of 62-70 DEG C;
Keep above-mentioned crystal Precipitation Temperature 0.5-4h until crystallizing layer is grown up completely;
Raffinate in crystallizer is released, and with the predetermined sweating temperature of 2-8 DEG C/h predetermined temperature rise rate intensification crystallizer to 80-90 DEG C to carry out sweating process to crystallizing layer;
Keep above-mentioned predetermined sweating temperature 0.5-4h;
Sweating is discharged from crystallizer;
Promote to melt the crystallizing layer of crystallizer inside completely about mould temperature to 100 DEG C, thus obtain liquid 2,4 di amino toluene product.
2. method according to claim 1, also comprises:
With gained liquid 2,4 di amino toluene products substitution initial feed mixture to repeat each step above-mentioned.
3. method according to claim 2, wherein repeats each step above-mentioned until the liquid 2,4 di amino toluene product of gained reaches predetermined purity to the recirculation of gained liquid 2,4 di amino toluene product.
4. method according to claim 3, in wherein recirculation repetitive process, gained sweating and/or raffinate are also introduced crystallizer again by as material composition.
5. method according to claim 1, also comprises:
Each step above-mentioned is repeated by after above-mentioned initial feed mixture and gained sweating mix.
6. method according to claim 5, by above-mentioned initial feed mixture and gained sweating to repeat each step above-mentioned after the weight ratio mix of about 4:1.
7. method according to claim 1, also comprises:
The discharge port of heating crystalline device when crystallizer discharges corresponding material.
8. method according to claim 7, wherein uses water vapour to carry out the discharge port of heating crystalline device.
9. method according to claim 1, wherein uses water vapour type of heating to promote about mould temperature to 100 DEG C to melt the crystallizing layer of crystallizer inside completely.
10. method according to claim 1, also comprises:
Remain nitrogen protection atmosphere in a crystallizer.
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| CN107903178A (en) * | 2017-11-28 | 2018-04-13 | 沧州众赫科技有限责任公司 | The method and apparatus for being separated in toluenediamine mixture and purifying 2,4 diaminotoluenes |
| CN109761775A (en) * | 2019-01-21 | 2019-05-17 | 湖北海力环保科技股份有限公司 | The method of 4- acetyl group -1- methyl naphthalene is purified in a kind of acetylmethyl naphthalene mixtures |
| CN111494980A (en) * | 2020-04-20 | 2020-08-07 | 湖北东方化工有限公司 | System and method for nitrotoluene melt crystallization |
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| CN101250113A (en) * | 2008-03-28 | 2008-08-27 | 上海安诺芳胺化学品有限公司 | Method for refining p-phenylene diamine |
| CN104402732A (en) * | 2014-12-16 | 2015-03-11 | 沧州丰源环保科技有限公司 | Technology for purifying 2, 4-diaminotoluene by recrystallization method |
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| CN101250113A (en) * | 2008-03-28 | 2008-08-27 | 上海安诺芳胺化学品有限公司 | Method for refining p-phenylene diamine |
| CN104402732A (en) * | 2014-12-16 | 2015-03-11 | 沧州丰源环保科技有限公司 | Technology for purifying 2, 4-diaminotoluene by recrystallization method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107903178A (en) * | 2017-11-28 | 2018-04-13 | 沧州众赫科技有限责任公司 | The method and apparatus for being separated in toluenediamine mixture and purifying 2,4 diaminotoluenes |
| CN109761775A (en) * | 2019-01-21 | 2019-05-17 | 湖北海力环保科技股份有限公司 | The method of 4- acetyl group -1- methyl naphthalene is purified in a kind of acetylmethyl naphthalene mixtures |
| CN109761775B (en) * | 2019-01-21 | 2022-02-01 | 湖北海力环保科技股份有限公司 | Method for purifying 4-acetyl-1-methylnaphthalene from acetyl methylnaphthalene mixture |
| CN111494980A (en) * | 2020-04-20 | 2020-08-07 | 湖北东方化工有限公司 | System and method for nitrotoluene melt crystallization |
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| CN105061215B (en) | 2017-06-20 |
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