CN105461571B - A kind of cleaning procedure for being continuously synthesizing to 2,6 dichloro paranitroanilinum - Google Patents
A kind of cleaning procedure for being continuously synthesizing to 2,6 dichloro paranitroanilinum Download PDFInfo
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- CN105461571B CN105461571B CN201510578026.9A CN201510578026A CN105461571B CN 105461571 B CN105461571 B CN 105461571B CN 201510578026 A CN201510578026 A CN 201510578026A CN 105461571 B CN105461571 B CN 105461571B
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- hydrochloric acid
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- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 19
- 238000004140 cleaning Methods 0.000 title abstract description 8
- 125000003963 dichloro group Chemical group Cl* 0.000 title abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 141
- 239000012452 mother liquor Substances 0.000 claims abstract description 93
- 239000007789 gas Substances 0.000 claims abstract description 70
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 26
- 238000003860 storage Methods 0.000 claims abstract description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000460 chlorine Substances 0.000 claims abstract description 16
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 16
- 239000012065 filter cake Substances 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000012360 testing method Methods 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 7
- -1 2,6 dichloro p-nitrophenyl Chemical group 0.000 claims abstract 3
- 238000003756 stirring Methods 0.000 claims abstract 3
- 238000010521 absorption reaction Methods 0.000 claims description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 12
- PEMGGJDINLGTON-UHFFFAOYSA-N n-(3-aminophenyl)acetamide Chemical compound CC(=O)NC1=CC=CC(N)=C1 PEMGGJDINLGTON-UHFFFAOYSA-N 0.000 claims description 10
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 239000006096 absorbing agent Substances 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 5
- 238000005360 mashing Methods 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- 206010000060 Abdominal distension Diseases 0.000 claims 2
- 208000024330 bloating Diseases 0.000 claims 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- 238000004128 high performance liquid chromatography Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 9
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 8
- 229940018564 m-phenylenediamine Drugs 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000011017 operating method Methods 0.000 description 6
- 238000004064 recycling Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 4
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical group ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- VGKYEIFFSOPYEW-UHFFFAOYSA-N 2-methyl-4-[(4-phenyldiazenylphenyl)diazenyl]phenol Chemical compound Cc1cc(ccc1O)N=Nc1ccc(cc1)N=Nc1ccccc1 VGKYEIFFSOPYEW-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000004816 dichlorobenzenes Chemical class 0.000 description 1
- NJXPQVNXQNPYRT-UHFFFAOYSA-L disodium;3-amino-4-[[4-[4-[[4-(4-methylphenyl)sulfonyloxyphenyl]diazenyl]phenyl]phenyl]diazenyl]naphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].C1=CC(C)=CC=C1S(=O)(=O)OC1=CC=C(N=NC=2C=CC(=CC=2)C=2C=CC(=CC=2)N=NC=2C3=CC=C(C=C3C=C(C=2N)S([O-])(=O)=O)S([O-])(=O)=O)C=C1 NJXPQVNXQNPYRT-UHFFFAOYSA-L 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical group [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
One kind is continuously synthesizing to the cleaning procedure of 2,6 dichloro paranitroanilinum, and the technique is：Using the reactor of plural serial stage,Continuously by paranitroanilinum,Hydrochloric acid and chlorine addition are into first order reaction kettle,Stirring is lower to carry out chlorination reaction,Material in upper level reactor is partly into autoreactivity kettle by pump to be circulated,It is partly into next stage reactor and continues chlorination reaction,Tail gas caused by upper level reactor, which enters, continues chlorination reaction in next stage reactor,Material in final stage reactor is partly into autoreactivity kettle by pump to be circulated,After testing after reaction completely,A part of continuous discharge filtering,The filter cake of gained is 2,6 dichloro p-nitrophenyl amine products,Filter mother liquid obtained into disposing mother liquor groove,Mother liquor drum air into disposing mother liquor groove,The hydrogen chloride tail gas reuse that bulging comes,Mother liquor is driven into mother liquor storage tank when rousing air to certain acidity,Mother liquor in mother liquor storage tank substitutes hydrochloric acid recycled.
Description
(1) technical field
The present invention relates to a kind of cleaning procedure of synthesis 2,6- dichloro paranitroanilinum, especially one kind is continuously synthesizing to 2,
The cleaning procedure of 6- dichloro paranitroanilinum.
(2) background technology
2,6- dichloro paranitroanilinum are important dyestuff intermediates, for disperse yellow brown 3GL, the yellowish-brown 2RFL of decomposition, are divided
The synthesis of the disperse dyes such as brown 3R, disperse brown 5R is dissipated, its synthetic method mainly has following several：
(1) direct chlorination method
Paranitroanilinum obtains under the conditions of hydrochloric acid in 35 DEG C and chlorine reaction.Although this method raw material is cheap and easy to get, receive
Rate 95%, purity >=98%, but hydrogen chloride tail gas need to be recycled.
(2) sodium chlorate method
Paranitroanilinum reacts at 20 DEG C~25 DEG C and obtained with sodium chlorate under the conditions of hydrochloric acid.This method cost of material is high,
Complex process, yield 90%, cost are high.
(3) dichloro sulfonyl method
Paranitroanilinum reacts at 80 DEG C and obtained with dichloro sulfonyl under the conditions of dichloro-benzenes.This method raw material dichloro sulfonyl
Transport difficult, self-produced dichloro sulfonyl is needed, and produce substantial amounts of sulfur dioxide and hydrogen chloride gas, three-protection design is difficult, yield
92.1%, purity >=98%.
(4) hypochlorous acid method
Paranitroanilinum reacts at 30 DEG C and obtained with hypochlorous sulfuric acid solution under the conditions of sulfuric acid.This method needs to consume
Substantial amounts of sulfuric acid and sodium hypochlorite, spent acid discharge capacity is big in production, yield 85%, purity >=96%.
(5) hydrogen peroxide method
Paranitroanilinum obtains under the conditions of 40 DEG C~50 DEG C with hydrogen peroxide and hydrochloric acid reaction.The production that the reaction obtains
Product yield 82%, purity >=99%, but substantial amounts of hydrogen peroxide and hydrochloric acid need to be consumed.
Pass through the contrast of above-mentioned five kinds of production methods, it is believed that direct chlorination method is better than other four kinds, such as publication
Using serialization direct chlorination method production 2,6- dichloro paranitroanilinum in CN101423480A, by the reactor of multiple large volumes
It is sequentially connected logical, and tail gas absorber is connected with last reactor, then by completely reacted material from reactor
In pump out, through press filtration, washing to neutrality, drying product.The production technology can improve yield, reduce production cost, but
The mother liquor after hydrogen chloride gas and material press filtration in tail gas absorber also needs subsequent treatment.
(3) content of the invention
In order to solve the above problems, the present invention provides the cleaner that one kind is continuously synthesizing to 2,6- dichloro paranitroanilinum
Skill, the process recovery ratio is high, and obtained product purity is high, and is produced without waste water, really realizes the clean manufacturing of wastewater zero discharge.
The technical solution adopted by the present invention is as follows：
One kind is continuously synthesizing to the cleaning procedure of 2,6- dichloro paranitroanilinum, and the technique is as follows：Using plural serial stage
Reactor, according to paranitroanilinum, hydrochloric acid, chlorine raw materials components mole ratio be 1：(9~15)：The proportioning of (1.8~2.0), even
Continuous ground paranitroanilinum, hydrochloric acid and chlorine addition into first order reaction kettle, are stirred into lower progress chlorination reaction, upper level reaction
Material in kettle is partly into autoreactivity kettle by pump to be circulated, and it is anti-to be partly into continuation chlorination in next stage reactor
Should, tail gas caused by upper level reactor (hydrogen chloride and the complete chlorine of unreacted) enters and continues chlorination in next stage reactor
Reaction, controls material of the chlorination reaction temperature of reactors at different levels in 5 DEG C~65 DEG C, final stage reactor to enter by a pump part
Enter in autoreactivity kettle and circulate, after testing after reaction completely, a part of continuous discharge is filtered or centrifuged, and obtains 2,6- dichloros
P-nitrophenyl amine product, and mother liquor, mother liquor enter disposing mother liquor groove, the mother liquor drum air into disposing mother liquor groove, bloat what is come
Hydrogen chloride tail gas reuse, mother liquor are driven into mother liquor storage tank when rousing air to certain acidity, and the mother liquor in mother liquor storage tank substitutes salt
Sour recycled.
Further, described paranitroanilinum, hydrochloric acid, the mol ratio of chlorine are preferably 1：(11~13)：(1.82~
1.98)。
Further, the mass fraction of hydrochloric acid is 28~35%, preferably 28%~33%.
Further, described chlorination reaction temperature is preferably 25 DEG C~45 DEG C.
Further, paranitroanilinum and hydrochloric acid are first added in mashing kettle and mixed, then are continuously added to one-level by pump
In reactor.
Further, the mother liquor drum air into disposing mother liquor groove, the hydrochloric acid mass fraction into mother liquor is 28%~35%
Stop air-blowing when (being preferably 28%~33%), mother liquor enters mother liquor storage tank.
Further, all connect an injector on reactors at different levels, in reactor a part of material by pump via injection
Device circulated in autoreactivity kettle, while caused negative pressure may be inhaled tail gas caused by chlorine or upper level in injector, from
And fluid and gas enter reactor after being sufficiently mixed in injector, be advantageous to the progress of chlorination reaction in reactor.
Further, preferably 2~4 grades series connection of the reactor.
Further, final stage reactor is provided with detection mouth, is detected with KI test paper and then judges that reaction is complete without color change.
Further, the filtering or centrifugation refer in general physical filtering or mechanically decoupled, can such as use filter press mistake
Filter or centrifuge separation, to reach being continuously removed for material, preferably filter press or centrifuge is multiple parallel connections, i.e. final stage reactor
Material out after filter press or centrifuge saturation, switches to other into one in filter press or centrifuge in parallel
Filter press or centrifuge are to ensure being continuously removed for material.The filter press or centrifuge preferably 3~5 parallel connections.
Further, to reach being continuously removed for mother liquor, the disposing mother liquor groove can be multiple parallel connections, filter press filter out or from
The mother liquor that the heart is isolated continuously enters one in the disposing mother liquor groove of parallel connection, when reaching setting liquid level, switches to other dead slots
To ensure being continuously removed for mother liquor.The disposing mother liquor groove preferably 2 or 3 parallel connections.
Further, by hydrogen chloride tail gas reuse caused by final stage reactor.
Further, the hydrogen chloride tail come is bloated in hydrogen chloride tail gas caused by the final stage reactor and disposing mother liquor groove
The reuse of gas, the synthesis that hydrogen chloride tail gas can be used for 3-acetylaminoaniline is referred specifically to, such as can be according to publication
Method described in CN101328133A or the like synthesizes；Or hydrogen chloride tail gas enters exhaust treatment system recovery salt
Acid, the exhaust treatment system are the tail gas absorbers using plural serial stage, and hydrogen chloride tail gas is sprayed into first grade absorption tower by water
Leaching absorbs, and unabsorbed hydrogen chloride tail gas enters next stage absorption tower and continues to be absorbed by Water spray in previous stage absorption tower, inhales
Receive liquid and circulation continuation absorbing hydrogen chloride tail gas in own absorption tower, the absorbing by liquid caustic soda previous stage suction of final stage absorption tower are entered by pump
The hydrogen chloride tail gas escaped on a small quantity in tower is received, absorbing liquid is entered in own absorption tower by pump to be circulated, the tail gas on final stage absorption tower
Qualified rear discharge after testing, when the mass fraction of hydrochloric acid in first grade absorption tower reaches setting value, reclaims hydrochloric acid, next stage is inhaled
The absorbing liquid received in tower (in addition to final stage absorption tower) is pumped into previous stage absorption tower, and is supplemented to penultimate stage absorption tower
Water, when the absorbing liquid pH value≤10 on final stage absorption tower, enter Waste Water Treatment, and liquid caustic soda is supplemented to final stage absorption tower.
Further, the tail gas absorber is preferably 3~5 grades of series connection.
Further, the mass fraction of hydrochloric acid reaches setting value in the first order absorption tower, setting value will be generally above or
Equal to 25%.Further, the liquid caustic soda mass fraction is preferably 5~15%.
Compared with prior art, the cleaning procedure of the present invention for being continuously synthesizing to 2,6- dichloro paranitroanilinum, its
Have the beneficial effect that：1st, using the reactor of plural serial stage, partial material and tail gas in upper level reactor enter down
Continue chlorination reaction in first order reaction kettle, realize continuous production while it also avoid exhaust emissions；2nd, final stage reactor produces
Hydrogen chloride tail gas and disposing mother liquor groove bulging come hydrogen chloride tail gas be used for 3-acetylaminoaniline synthesis or through tail gas at
Hydrochloric acid is reclaimed after the processing of reason system, Recycling Mother Solution is applied mechanically, and non-wastewater discharge decreases hydrochloric acid dosage simultaneously, is realized tail gas and is given up
The effective processing and comprehensive utilization of resources of water；3rd, with the method for the invention prepare 2,6- dichloro paranitroanilinum purity >=
98%th, yield >=96%.
In summary, the cleaning procedure of the present invention for being continuously synthesizing to 2,6- dichloro paranitroanilinum, realize tail gas and
The effective processing and comprehensive utilization of resources of waste water, emission-free and waste water produce, and are a kind of really serialization process for cleanly preparing,
With significant economic benefit and social benefit.
(4) illustrate
Fig. 1 is that one kind that the embodiment of the present invention uses is continuously synthesizing to process chart, wherein 1 is to be beaten kettle, 2,3,4 points
Not Wei one-level, two level, third-order reaction kettle, 5,6,7 be injector, and 8,9,10 be pressure filter, and 11,12 be disposing mother liquor groove,
13 be mother liquor storage tank；
Fig. 2 is that the another kind that the embodiment of the present invention uses is continuously synthesizing to process chart, wherein 1 is to be beaten kettle, 2,3,4
Respectively one-level, two level, third-order reaction kettle, 5,6,7 be injector, and 8,9,10 be pressure filter, and 11,12 be disposing mother liquor
Groove, 13 be mother liquor storage tank；
Fig. 3 is the exhaust treatment system flow chart that the embodiment of the present invention 5,6 uses, wherein 14,15,16,17 be respectively one
Level, two level, three-level, level Four tail gas absorber.
(5) embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited to
This.
Embodiment 1
It is continuously synthesizing to：
Such as Fig. 1, using the reactor (2,3,4) of thtee-stage shiplock, three filter presses (8,9,10) in parallel and two parallel connections
Disposing mother liquor groove (11,12), the volume of one, two, three reactor is 50m3, 40~45 DEG C of chlorination temperature is controlled, mother liquor returns
It is 50m to receive groove volume3, filter press volume is 400m3, mother liquor storage tank volume is 100m3, disposing mother liquor tank liquor position is set as volume
90%.
Raw material is continuously squeezed into mashing kettle (1) simultaneously to be beaten, the charging rate for controlling paranitroanilinum is
690kg/h, the charging rate of 31% hydrochloric acid is 7065kg/h, and the material in mashing kettle (1) is entered with 7755kg/h speed again
First order reaction kettle (2)；Chlorine is passed through in first order reaction kettle (1) by injector (5) with 674kg/h flow velocity, first order reaction kettle
(2) material in enters second order reaction kettle (3) by a part of self-loopa of pump, a part with 8429kg/h flow velocity, and one-level is anti-
Answer the tail gas of kettle (2) to be drawn onto by injector (6) in second order reaction kettle (3) and continue chlorination reaction；Material in second order reaction kettle (3)
By a part of self-loopa of pump, a part enters third-order reaction kettle (4), the tail of second order reaction kettle (3) with 8429kg/h flow velocity
Gas is drawn onto in third-order reaction kettle (4) by injector (7) continues chlorination reaction；Material in third-order reaction kettle (4) passes through pump one
Point self-loopa, (detected with KI test paper after reaction completely after testing and then judge that reaction is complete without color change), a part with
8429kg/h flow velocity squeezes into filter press filtering and (the advanced filter press of material (8), switches to filter press after filter press (8) saturation
(9), while filter press (8) removes filter cake, standby；Filter press (10), while filter press (9) are switched to after filter press (9) saturation
Filter cake is removed, it is standby；Filter press (8) is switched to after filter press (10) saturation, while filter press (10) removes filter cake, it is standby；According to
Secondary circulation is gone down)；Filter press come out mother liquor with 5781kg/h flow velocity enter disposing mother liquor groove in (mother liquor be introduced into mother liquor return
Groove (11) is received, disposing mother liquor groove (12), while the drum air into disposing mother liquor groove (11), drum are switched to when liquid level is to setting value
Hydrogen chloride gas out is directly used in the synthesis of 3-acetylaminoaniline after collecting, stop drum when drum to concentration of hydrochloric acid is 31%
Air, mother liquor enter mother liquor storage tank (13)；The liquid level of disposing mother liquor groove (12) to switching to disposing mother liquor groove again during setting value
(11) air, while into disposing mother liquor groove (12) is roused, bloats after the hydrogen chloride gas come is collected and is directly used in a glycyl
The synthesis of aniline, stops drum air when drum to concentration of hydrochloric acid is 31%, mother liquor enters mother liquor storage tank (13)；Circulation is gone down successively)；
The alternative hydrochloric acid of mother liquor in mother liquor storage tank (13), recycled.
The filter cake that filter press comes out obtains 2,6- dichloros paranitroanilinum of the present invention, measured after washing and drying
Purity (HPLC) 98.8%, yield 97.3%.
Recycling tail gas：
M-acetamidoaniline mother liquor 660Kg is taken, wherein containing：Hydrochloric acid 33Kg, acetic acid 59.4Kg, m-acetamidoaniline
30Kg, m-phenylene diamine (MPD) 50Kg, a diacetylamino aniline 60Kg, the HCl gas of above-mentioned collection is passed through by difference assay at normal temperatures
Body 30Kg, m-phenylene diamine (MPD) 88g and glacial acetic acid 56Kg (percentage amount) is added, after being warming up to 96~104 DEG C of reaction 20h, be cooled to 35
Filtered below DEG C, after obtained filter cake is drained, add 20Kg water washings, obtain the m-acetamino benzene that purity (HPLC) is 99%
Amine.
Embodiment 2
By the operating method described in embodiment 1, simply hydrochloric acid is changed into mother liquor in mother liquor storage tank, what filter press came out
Filter cake obtains 2,6- dichloros paranitroanilinum of the present invention after washing and drying, measures purity (HPLC) 98.4%, yield
96.9%.The HCl gases of collection are used for the synthesis of m-acetamidoaniline, and can obtain purity (HPLC) is acetyl ammonia between 99%
Base aniline.
Embodiment 3
It is continuously synthesizing to：
Operating method is continuously synthesizing to by described in embodiment 1, the difference is that the flow velocity of raw material：Paranitroanilinum enters
Material speed is 552kg/h, and the charging rate of 29% hydrochloric acid is 5790kg/h, is beaten the material in kettle again with 6342kg/h speed
Into first order reaction kettle；Chlorine is passed through in first order reaction kettle by injector with 525kg/h flow velocity, the thing of upper level reactor
Material is passed through next stage reactor with 6867kg/h flow velocity；Filter press filtering, filter press are squeezed into 6867kg/h flow velocity again
Disposing mother liquor groove is entered with 6867kg/h flow velocity；Drum air in disposing mother liquor groove, stops when drum to concentration of hydrochloric acid is 29%
Drum air, mother liquor enters mother liquor storage tank, while collects hydrogen chloride tail gas；The alternative hydrochloric acid of mother liquor in mother liquor storage tank, circulating sleeve
With.
The filter cake that filter press comes out obtains 2,6- dichloros paranitroanilinum of the present invention, measured after washing and drying
Purity (HPLC) 98.9%, yield 97.2%.
Recycling tail gas：
M-acetamidoaniline mother liquor 660Kg is taken, wherein containing：Hydrochloric acid 59.4Kg, acetic acid 105Kg, m-acetamidoaniline
44Kg, m-phenylene diamine (MPD) 63Kg, a diacetylamino aniline 80Kg, the HCl gas of above-mentioned collection is passed through by difference assay at normal temperatures
Body 25Kg, m-phenylene diamine (MPD) 88Kg and glacial acetic acid 56Kg (percentage amount) is added, after being warming up to 96~104 DEG C of reaction 20h, be cooled to 35
Filtered below DEG C, after obtained filter cake is drained, add 30Kg water washings, obtain the m-acetamino benzene that purity (HPLC) is 99%
Amine.
Embodiment 4
By the operating method that is continuously synthesizing to described in embodiment 3, simply hydrochloric acid is changed into mother liquor in mother liquor storage tank, press
The filter cake that filter comes out obtains 2,6- dichloros paranitroanilinum of the present invention, measures purity (HPLC) after washing and drying
98.5%th, yield 96.7%.
The HCl gases of collection are used for the synthesis of m-acetamidoaniline, and can obtain purity (HPLC) is acetyl between 99%
Amino aniline.
Embodiment 5
It is continuously synthesizing to：
Such as Fig. 2, operating method is continuously synthesizing to by described in embodiment 1, the difference is that the flow velocity of raw material：P-nitrophenyl
The charging rate of amine is 552kg/h, and the charging rate of 29% hydrochloric acid is 5790kg/h, is beaten the material in kettle again with 6342kg/h
Speed enter first order reaction kettle；Chlorine is passed through in first order reaction kettle by injector with 525kg/h flow velocity, upper level reaction
The material of kettle is passed through next stage reactor with 6867kg/h flow velocity, collects caused hydrogen chloride tail gas in third-order reaction kettle (4)；
Filter press filtering is squeezed into 6867kg/h flow velocity again, filter press also enters disposing mother liquor groove with 6867kg/h flow velocity；Mother liquor
Drum air in accumulator tank, stop drum air when drum to concentration of hydrochloric acid is 29%, mother liquor enters mother liquor storage tank, while collects chlorination
Hydrogen tail gas；The alternative hydrochloric acid of mother liquor in mother liquor storage tank, recycled.
The filter cake that filter press comes out obtains 2,6- dichloros paranitroanilinum of the present invention, measured after washing and drying
Purity (HPLC) 98.9%, yield 97.2%.
Recycling tail gas：
Exhaust treatment system as shown in Figure 3, using the tail gas absorber (14,15,16,17) of 4 grades of series connection, absorption tower is straight
Footpath 1m, height 7.8m, first grade absorption tower (14), two-level absorption tower (15) and three-level absorption tower (16) add water to volume
75%, level Four absorption tower (17) add 10% liquid caustic soda to the 75% of volume：The hydrogen chloride tail gas of above-mentioned collection is continuously entered
First grade absorption tower (14) is absorbed by Water spray, and absorbing liquid carries out self-loopa by pump and continues absorbing hydrogen chloride tail gas, first order absorption
Unabsorbed hydrogen chloride tail gas continues to absorb into two-level absorption tower (15) by Water spray in tower (14), and absorbing liquid is entered by pump
Row self-loopa, unabsorbed hydrogen chloride tail gas continues to inhale into three-level absorption tower (16) by Water spray in two-level absorption tower (15)
Receive, absorbing liquid carries out self-loopa by pump, and the hydrogen chloride tail gas escaped on a small quantity in three-level absorption tower (16) enters level Four absorption tower
(17) by liquid caustic soda spray-absorption, air is discharged into through blower fan after tail gas in level Four absorption tower (17) is qualified after testing.When one-level is inhaled
When receiving the hydrochloric acid mass fraction of absorbing liquid in tower (14) and being reached for 28%, hydrochloric acid is reclaimed, and by the absorption of two-level absorption tower (15)
Liquid pump enters in first grade absorption tower (14), and the absorbing liquid of three-level absorption tower (16) is pumped into two-level absorption tower (15), while to three-level
Water is added in absorption tower (16) to the 75% of volume；As the absorbing liquid pH value ＜ 10 in level Four absorption tower (17), company is pumped into
Waste Water Treatment, while 10% liquid caustic soda is added to the 75% of volume.
Embodiment 6
By the operating method that is continuously synthesizing to described in embodiment 5, simply hydrochloric acid is changed into mother liquor in mother liquor storage tank, press
The filter cake that filter comes out obtains 2,6- dichloros paranitroanilinum of the present invention, measures purity (HPLC) after washing and drying
98.5%th, yield 96.7%.
The HCl gases of collection also by the recycling tail gas operating method described in embodiment 5, simply change 10% liquid caustic soda into
8% liquid caustic soda, when the hydrochloric acid mass fraction of absorbing liquid in first grade absorption tower (14) is reached for 31%, reclaim hydrochloric acid.
Claims (13)
1. one kind is continuously synthesizing to the technique of 2,6- dichloro paranitroanilinum, the technique is：Using the reactor of plural serial stage,
Raw materials components mole ratio according to paranitroanilinum, hydrochloric acid, chlorine is 1：(9~15)：The proportioning of (1.8~2.0), continuously will be to nitre
Base aniline, hydrochloric acid and chlorine addition are into first order reaction kettle, progress chlorination reaction under stirring, the material in upper level reactor
It is partly into autoreactivity kettle and is circulated by pump, is partly into next stage reactor and continues chlorination reaction, upper level
Tail gas caused by reactor, which enters, continues chlorination reaction in next stage reactor, control the chlorination reaction temperature of reactors at different levels
Material in 5 DEG C~65 DEG C, final stage reactor is partly into autoreactivity kettle by pump to be circulated, and reaction is complete after testing
Afterwards, a part of continuous discharge filtering, the filter cake of gained is 2,6- dichloro p-nitrophenyl amine products, is filtered mother liquid obtained into female
Liquid accumulator tank, the mother liquor drum air into disposing mother liquor groove, bloats the hydrogen chloride tail gas reuse come, and mother liquor rouses air into mother liquor
Hydrochloric acid mass fraction be driven into mother liquor storage tank when being 28%~35%, mother liquor in mother liquor storage tank substitutes hydrochloric acid circulating sleeve
With, also, by hydrogen chloride tail gas reuse caused by final stage reactor.
2. one kind is continuously synthesizing to the technique of 2,6- dichloro paranitroanilinum, the technique is：Using the reactor of plural serial stage,
Raw materials components mole ratio according to paranitroanilinum, hydrochloric acid, chlorine is 1：(9~15)：The proportioning of (1.8~2.0), continuously will be to nitre
Base aniline, hydrochloric acid and chlorine addition are into first order reaction kettle, progress chlorination reaction under stirring, the material in upper level reactor
It is partly into autoreactivity kettle and is circulated by pump, is partly into next stage reactor and continues chlorination reaction, upper level
Tail gas caused by reactor, which enters, continues chlorination reaction in next stage reactor, control the chlorination reaction temperature of reactors at different levels
Material in 5 DEG C~65 DEG C, final stage reactor is partly into autoreactivity kettle by pump to be circulated, and reaction is complete after testing
Afterwards, a part of continuous discharge is centrifuged, and obtains 2,6- dichloro p-nitrophenyl amine products and mother liquor, and mother liquor returns into mother liquor
Groove is received, the mother liquor drum air into disposing mother liquor groove, bloats the hydrogen chloride tail gas reuse come, mother liquor rouses the salt in air to mother liquor
Sour mass fraction is driven into mother liquor storage tank when being 28%~35%, and the mother liquor in mother liquor storage tank substitutes hydrochloric acid recycled, and
And by hydrogen chloride tail gas reuse caused by final stage reactor.
3. technique as claimed in claim 1 or 2, it is characterised in that：Paranitroanilinum and hydrochloric acid are first added in mashing kettle and mixed
Close, then be continuously added in first order reaction kettle by pump.
4. technique as claimed in claim 1 or 2, it is characterised in that：Described paranitroanilinum, hydrochloric acid, the mol ratio of chlorine
For 1：(11~13)：(1.82~1.98).
5. technique as claimed in claim 1 or 2, it is characterised in that：Chlorination reaction temperature is 25 DEG C~45 DEG C.
6. technique as claimed in claim 1 or 2, it is characterised in that：Hydrochloric acid mass fraction is 28~35%.
7. technique as claimed in claim 1 or 2, it is characterised in that：An injector, reactor are all connected on reactors at different levels
Interior a part of material via injector circulate in autoreactivity kettle by pump, while caused negative pressure may be inhaled in injector
Tail gas caused by chlorine or upper level.
8. technique as claimed in claim 1 or 2, it is characterised in that：The reactor is using 2~4 grades of series connection.
9. technique as claimed in claim 1, it is characterised in that：Described filtering uses multiple filter presses in parallel.
10. technique as claimed in claim 2, it is characterised in that：Described centrifugation uses multiple centrifuges in parallel.
11. technique as claimed in claim 1 or 2, it is characterised in that：Described disposing mother liquor groove uses multiple parallel connections.
12. technique as claimed in claim 1 or 2, it is characterised in that：Hydrogen chloride tail gas caused by final stage reactor and mother liquor return
Receive the synthesis that the hydrogen chloride tail gas for bloating to come in groove is used for 3-acetylaminoaniline.
13. technique as claimed in claim 1 or 2, it is characterised in that：Hydrogen chloride tail gas caused by final stage reactor and mother liquor return
Receive the hydrogen chloride tail gas for bloating to come in groove and enter exhaust treatment system recovery hydrochloric acid；
The exhaust treatment system is the tail gas absorber using plural serial stage, and hydrogen chloride tail gas is sprayed into first grade absorption tower by water
Leaching absorbs, and unabsorbed hydrogen chloride tail gas enters next stage absorption tower and continues to be absorbed by Water spray in previous stage absorption tower, inhales
Receive liquid and circulation continuation absorbing hydrogen chloride tail gas in own absorption tower, the absorbing by liquid caustic soda previous stage suction of final stage absorption tower are entered by pump
The hydrogen chloride tail gas escaped on a small quantity in tower is received, absorbing liquid is entered in own absorption tower by pump to be circulated, the tail gas on final stage absorption tower
Qualified rear discharge after testing, when the mass fraction of hydrochloric acid in first grade absorption tower reaches setting value, reclaims hydrochloric acid, will be except final stage
The absorbing liquid in next stage absorption tower outside absorption tower is pumped into previous stage absorption tower, and is supplemented to penultimate stage absorption tower
Water, when the absorbing liquid pH value≤10 on final stage absorption tower, enter Waste Water Treatment, and liquid caustic soda is supplemented to final stage absorption tower.
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| CN201510578026.9A Active CN105461571B (en) | 2014-12-29 | 2015-09-11 | A kind of cleaning procedure for being continuously synthesizing to 2,6 dichloro paranitroanilinum |
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| CN108586264B (en) * | 2018-04-08 | 2020-12-15 | 苏州市罗森助剂有限公司 | Production process of 2, 6-dichloro-p-nitroaniline |
| CN110590564B (en) * | 2019-10-25 | 2022-09-06 | 湖南比德生化科技股份有限公司 | Method for synthesizing 2, 4-dichloroaniline by continuous chlorination process |
| CN111704553B (en) * | 2020-06-22 | 2021-05-14 | 清华大学 | Cyclic synthesis method of nitroaniline chloride |
| CN112645894B (en) * | 2020-11-30 | 2022-04-15 | 江苏中旗科技股份有限公司 | Method for preparing sulpirazole intermediate 5, 5-dimethyl-4, 5-dihydroisoxazole-3-thiocarboxamidine hydrochloride |
| CN114539076A (en) * | 2022-03-28 | 2022-05-27 | 苏州市晶协高新电子材料有限公司 | Continuous synthesis device and process of dimethyl diallyl ammonium chloride |
| CN115385798A (en) * | 2022-09-19 | 2022-11-25 | 苏州市罗森助剂有限公司 | Method for directly preparing o-chloro-p-nitroaniline through chlorination reaction |
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| AU6067098A (en) * | 1997-04-07 | 1998-10-08 | Cfpi Nufarm | Preparation process for 3,4-disubstituted dinitroanilines |
| CN100347148C (en) * | 2004-07-28 | 2007-11-07 | 上海世景国际贸易有限公司 | Preparation of 2,5-dihalogenated p-phenylene diamine, catalyst utilized and preparation method |
| CN101328133B (en) * | 2008-07-26 | 2012-02-01 | 浙江龙盛染料化工有限公司 | Synthetic method of m-amino acetanilide |
| CN101423480A (en) * | 2008-11-27 | 2009-05-06 | 苏州市罗森助剂有限公司 | Production method of 2, 6-dichloro-p-nitroaniline and special reaction kettle thereof |
| CN103539680B (en) * | 2013-10-23 | 2015-05-20 | 浙江闰土研究院有限公司 | Clean production process of 6-chloro-2,4-dinitroaniline |
| CN103787891A (en) * | 2014-01-23 | 2014-05-14 | 安徽华润涂料有限公司 | Production technology of synthesizing 6-bromo-2,4-dinitroaniline |
| CN104003888B (en) * | 2014-06-05 | 2016-09-14 | 浙江洪翔化学工业有限公司 | 2,4-dinitro-6-chloroaniline preparation method |
| CN104610071B (en) * | 2015-01-07 | 2016-03-16 | 山东昌邑灶户盐化有限公司 | A kind of chlorine direct chlorination and hydrogen peroxide oxidation chlorination are prepared the method for 2,6-Dichloro-4-nitroaniline simultaneously |
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