CN106187711A - Method for preparing 2, 5-dichlorophenol by tubular diazotization and special device - Google Patents
Method for preparing 2, 5-dichlorophenol by tubular diazotization and special device Download PDFInfo
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- CN106187711A CN106187711A CN201610538837.0A CN201610538837A CN106187711A CN 106187711 A CN106187711 A CN 106187711A CN 201610538837 A CN201610538837 A CN 201610538837A CN 106187711 A CN106187711 A CN 106187711A
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- tubular reactor
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- acid
- diazotising
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- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000006193 diazotization reaction Methods 0.000 title abstract description 8
- RANCECPPZPIPNO-UHFFFAOYSA-N 2,5-dichlorophenol Chemical compound OC1=CC(Cl)=CC=C1Cl RANCECPPZPIPNO-UHFFFAOYSA-N 0.000 title abstract 2
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 44
- 230000007062 hydrolysis Effects 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- AVYGCQXNNJPXSS-UHFFFAOYSA-N 2,5-dichloroaniline Chemical compound NC1=CC(Cl)=CC=C1Cl AVYGCQXNNJPXSS-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 71
- 238000006243 chemical reaction Methods 0.000 claims description 56
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical group [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 54
- 239000001117 sulphuric acid Substances 0.000 claims description 45
- 239000002253 acid Substances 0.000 claims description 38
- 235000011149 sulphuric acid Nutrition 0.000 claims description 35
- 235000010288 sodium nitrite Nutrition 0.000 claims description 27
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 12
- 208000035126 Facies Diseases 0.000 claims description 10
- 238000005452 bending Methods 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000012954 diazonium Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims description 5
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 230000010349 pulsation Effects 0.000 abstract 2
- 238000002360 preparation method Methods 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 25
- 239000007864 aqueous solution Substances 0.000 description 13
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 7
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 4
- 239000011736 potassium bicarbonate Substances 0.000 description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IWEDIXLBFLAXBO-UHFFFAOYSA-N dicamba Chemical compound COC1=C(Cl)C=CC(Cl)=C1C(O)=O IWEDIXLBFLAXBO-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- YJJYGKTWCPEFMD-UHFFFAOYSA-N 2,5-dichloroaniline;sulfuric acid Chemical compound OS(O)(=O)=O.NC1=CC(Cl)=CC=C1Cl YJJYGKTWCPEFMD-UHFFFAOYSA-N 0.000 description 1
- XJCVRTZCHMZPBD-UHFFFAOYSA-N 3-nitroaniline Chemical compound NC1=CC=CC([N+]([O-])=O)=C1 XJCVRTZCHMZPBD-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- ZAOCWQZQPKGTRN-UHFFFAOYSA-N nitrous acid;sodium Chemical compound [Na].ON=O ZAOCWQZQPKGTRN-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/045—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of a group bound to the ring by nitrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/20—Diazonium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 2, 5-dichlorophenol by tubular diazotization and a special device, wherein the special device comprises a mixer, a tubular reactor and a hydrolysis kettle which are sequentially connected by a pipeline, and the mixer is respectively connected with input 2, 5-dichloroaniline and H2SO4The first batching kettle for inputting diazotization reagent is connected with the second batching kettle for inputting diazotization reagent, a first safety valve, a first metering pump and a first flowmeter are sequentially connected between the first batching kettle and the mixer through a first bottom valve, and a second safety valve, a second metering pump and a second flowmeter are sequentially connected between the second batching kettle and the mixer through a second bottom valve; the first metering pump and the first flowmeter as well as the second metering pump and the second flowmeter form a feedback loop respectively. The inlet of the hydrolysis kettle is communicated with the outlet of the tubular reactor; a water separator is arranged on the hydrolysis kettle; and a first pulsation damper and a second pulsation damper are respectively arranged on pipelines between the first batching kettle and the tubular reactor and between the second batching kettle and the tubular reactor.
Description
Technical field
The present invention relates to a kind of tubular type diazotising and prepare method and the special purpose device of 2,5-chlorophenesic acid.
Background technology
2,5-chlorophenesic acids are the raw materials of synthesis Mediben (3,6-bis-chloro-2-methoxybenzoic acid), and its synthetic method is led to
Being often with 2,5-dichloroaniline is initiation material, generates diazol through diazo-reaction, then obtains through pyrohydrolysis.Diazotising is anti-
Should be the mode of operation of batch tank, there is many defects in this method: diazol is unstable, is heated and easily decomposes, therefore, and diazonium
Change reaction and must strictly control reaction temperature (generally about 0 DEG C)；Diazo-reaction is strong exothermal reaction, must in course of reaction
Must strictly control the rate of addition of sodium nitrite；Tradition diazonium turns to Batch Process mode, when diazol stops in reactor
Between long, increase the side reaction occurrence probability such as coupling, decomposition；Tradition diazonium turns to low-temp reaction, and ammonium salt is many in solid precipitation state,
Being now solid-liquid reaction system, its mass transfer effect is poor, and sodium nitrite solution instills in ammonium salt mixture and cannot be rapidly reached point
The mix homogeneously of sub-yardstick, increases side reaction, and easily causes security incident.Easily produce a large amount of burnt during pyrohydrolysis
Oily waste residue, adds post-processing difficulty and environmental protection pressure.
The method of 2,5-chlorophenesic acid is prepared in the diazol hydrolysis reported at present to be had: (1) with sodium nitrite in aqueous solution is
Diazotization agent is to 2, and 5-dichloroaniline sulfate carries out diazotising, and the diazotizing reactant of part is pre-loaded with the end through pipeline addition
Being hydrolyzed (Chemical Manufacture and technology, 2010,17 (2): 16-17) in acid the hydrolysis kettle that heats up, hydrolytic process uses steam
Product is taken in distillation out of, and part diazotising operation difficulty controls, and is unfavorable for amplifying；(2) with sodium nitrite solid for diazotization agent to molten
In the 2 of 98% sulphuric acid, 5-dichloroaniline sulfate carries out diazotising, and gained diazo liquid is added dropwise to be pre-loaded with end acid and heats up
Be hydrolyzed in hydrolysis kettle (CN1830943), and the method concentrated sulphuric acid is difficult to recycle and large usage quantity；(3) with nitrous acid
Sodium solution be diazotization agent to 2,5-dichloroaniline sulfate carries out diazotising in pipeline, and gained diazo liquid enters another pipeline
Middle pyrohydrolysis (synthesis chemistry, 2014,22 (1): 88～90), yield is only 85.8%, and the method hydrolytic process is coal-tar middle oil many,
Easily block pipeline, it is difficult to produce continuously.
Summary of the invention
In order to overcome existing diazol to hydrolyze preparation 2, the drawbacks described above that the method for 5-chlorophenesic acid exists, the present invention provides
A kind of tubular type diazotising prepares method and the special purpose device of 2,5-chlorophenesic acid.
For achieving the above object, the present invention adopts the following technical scheme that
Tubular type diazotising prepares 2, the method for 5-chlorophenesic acid, it is characterised in that: described method is:
(1), by raw material 2,5-dichloroaniline and H2SO4Mixed liquor and diazo reagent be separately stored in the first dispensing
In still and the second batching kettle, and respectively by the first dosing pump conveyer device being connected with the first batching kettle and the second dispensing
The second dosing pump conveyer device that still is connected is delivered continuously in blender mixing, enters tubular reactor immediately and carries out diazotising
Reaction, described 2,5-dichloroaniline, described H2SO4In sulphuric acid and described diazo reagent in diazo-reaction
The ratio of molar flow be 1:2.5～15:0.95～1.3；The ratio of described 2,5-dichloroaniline and organic solvent be 1:1～
20kg/L；
(2) mixed reaction solution that the step (1) described in obtains enters tubular reactor and carries out diazo-reaction, reaction temperature
Being 10～150 DEG C, reaction time is 1～60s, obtains diazo-reaction liquid；
(3) the diazo-reaction liquid that the step (2) described in obtains entered equipped with sulphuric acid by the outlet of tubular reactor and
Organic solvent is also hydrolyzed reaction in being warming up to the hydrolysis kettle of backflow in advance, by fraction water device water-dividing in course of reaction, hydrolyzes
Reaction is rear continues backflow 1～2h, after having reacted, collects organic facies, and alkali cleaning, to neutrality, distillating recovering solvent, i.e. obtains
2,5-chlorophenesic acid crude product.
The mass concentration of the described sulphuric acid mixed with 2,5-dichloroaniline is 30%～98%.
Described diazo reagent is sodium nitrite or nitrosyl sulfuric acid.
The mass concentration of described diazo reagent is 6%～50%.
The mixed reaction solution that described step (1) obtains enters tubular reactor and carries out diazo-reaction, and reaction temperature is
30～80 DEG C.
The concentration of the described sulphuric acid in hydrolysis kettle is 30%～70%.
Described organic solvent is one or more combinations in aromatic hydrocarbons or alkane or ether or alcohol；Such as toluene, dimethylbenzene, ring
One or more combinations in hexane, methyl tertiary butyl ether(MTBE), isoamyl alcohol.
Alkali for the organic facies of alkali cleaning collection is inorganic weak bases.
Described inorganic weak bases can be sodium carbonate, sodium bicarbonate, potassium carbonate or potassium bicarbonate；Obtain after having reacted
Dilute sulfuric acid adds concentrated sulphuric acid to initial acid after filtering the inorganic salt of precipitation, get final product recovery.
A kind of tubular type diazotising as described above prepares 2, the special purpose device of 5-chlorophenesic acid method, it is characterised in that:
Described special purpose device includes passing sequentially through the blender of pipeline connection, tubular reactor, hydrolysis kettle, and described blender is respectively
With input 2,5-dichloroaniline and H2SO4Mixed liquor the first batching kettle, input diazo reagent second batching kettle connect,
It is sequentially connected with the first relief valve, the first dosing pump, first-class by the first bottom valve between described the first batching kettle and blender
Gauge, between described the second batching kettle and blender by the second bottom valve be sequentially connected with the second relief valve, the second dosing pump,
Two effusion meters；The first described dosing pump is not formed with second flow score with first-class gauge and the second described dosing pump
Feedback circuit.Described hydrolysis kettle entrance and the outlet of tubular reactor；On described hydrolysis kettle, water knockout drum is installed；Institute
On pipeline between the first batching kettle and the tubular reactor stated and between described the second batching kettle and tubular reactor point
It is not provided with the first ripple damper and the second ripple damper.
Described tubular reactor is single tube tubular reactor or multitube tubular reactor composes in parallel；Described tubular type is anti-
The reacting pipe answering device is shaped as straight tube or bending pipeline, bending angle >=45 ° of bending pipeline.
Described blender is two pipelines, embeds another pipeline in the middle part of one of them pipeline, and the opening of another pipeline is towards thing
Direction of flow is arranged, and open front is divided and had undergauge structure；Another pipeline is connected with the pipeline equipped with diazo reagent.
Described tubular reactor pipe range is 1～30m, and pipe diameter is 1～30mm.
Preparation method of the present invention, wherein, can be flowed by control when material is delivered in blender by dosing pump
Speed reaches to react required rate of charge.
Described in tubular reactor, carry out diazo-reaction before, generally beforehand through chuck be heated and maintained at 10～
The reaction temperature of 150 DEG C, the preferably described temperature carrying out diazo-reaction in tubular reactor is 30～80 DEG C.
Beneficial effects of the present invention is embodied in:
1, described diazo-reaction is continuous process, and the blended device of reaction mass enters pipe reaction after quickly mixing
Device, controls raw material 2,5-dichloroaniline, H by strict2SO4, the charge proportion of diazotization agent, it is achieved that each cuts in pipeline
The reaction mass ratio in face keeps constant, axially without back-mixing in reactor, overcomes the local concentration inequality that prior art exists
The problem such as even；Improve heat exchange efficiency, reduce energy consumption, reduce diazo-reaction improves safety at line volume；
2, in hydrolytic process, by introducing solvent, situ extracting product, it is allowed to separate with diazol, it is to avoid side reaction
Generation, decrease the generation of tar；The addition of organic solvent makes the 2,5-chlorophenesic acid generated be extracted by organic facies rapidly
Thus suppress it to send out into side reaction with unreacted diazol and form tarry waste residue.
3, of the present invention 2,5-chlorophenesic acid preparation method is easy to operate, and post processing is simple, and product yield is good, purity
Height, is suitable for industrialized production.
Accompanying drawing explanation
Fig. 1 is the flow chart of 2,5-chlorophenesic acid preparation method of the present invention；
In figure, 1-the first batching kettle, 2-the second batching kettle, 3-the first bottom valve, 4-the second bottom valve, 5-the first dosing pump, 6-
Second dosing pump, 7-the first relief valve, 8-the second relief valve, 9-the first ripple damper, 10-the second ripple damper, 11-
Flow meters, 12-second gauge, 13-blender, 14-tubular reactor, 15-chuck, 16-hydrolysis kettle, 17-water knockout drum.
Fig. 2 is the structure diagram of blender of the present invention.
Detailed description of the invention
Below by way of specific embodiment, technical scheme is described, but protection scope of the present invention is not limited to this.
The present invention's
Tubular type diazotising prepares 2, and the special purpose device of 5-chlorophenesic acid method, described special purpose device includes passing sequentially through pipe
Road connect blender 13, tubular reactor 14, hydrolysis kettle 16, described blender 13 respectively with input 2,5-dichloroaniline with
H2SO4The first batching kettle 1 of mixed liquor, the second batching kettle 2 of input diazo reagent connect, described first batching kettle 1 with
It is sequentially connected with first relief valve the 7, first dosing pump 5, first-class gauge 11 by the first bottom valve 3 between blender 13, described
It is sequentially connected with second relief valve the 8, second dosing pump 6, second by the second bottom valve 4 between second batching kettle 2 and blender 13
Gauge 12；The first described dosing pump 5 and first-class gauge 11 and the second described dosing pump 6 are with second gauge 12 respectively
Form feedback circuit.Described hydrolysis kettle 16 entrance and the outlet of tubular reactor 14；Install on described hydrolysis kettle 16
There is water knockout drum 17；Between described the first batching kettle 1 and tubular reactor 14 and described the second batching kettle 2 and pipe reaction
The first ripple damper 9 and the second ripple damper 10 it is respectively arranged with on pipeline between device 14.Described tubular reactor
The outer cover of 14 is provided with chuck 15.
Described tubular reactor 14 is single tube tubular reactor or multitube tubular reactor composes in parallel；Described tubular type
The reacting pipe of reactor 14 is shaped as straight tube or bending pipeline, bending angle >=45 ° of bending pipeline.
Described blender 13 is two pipelines, embeds another pipeline in the middle part of one of them pipeline, the opening court of another pipeline
Flow of Goods and Materials direction is arranged, and open front is divided and had undergauge structure；Another pipeline is with the pipeline equipped with diazo reagent even
Connect.
As above, except for the difference that tubular reactor 14 pipe range is 1～30m to the reaction unit structure of following example, and pipeline is straight
Footpath is 1～30mm to be specifically shown in following example.
Embodiment 1
Reaction unit structure such as Fig. 1, tubular reactor pipe range 10m, pipe diameter is 1mm.
Operating procedure is as follows:
Preparation 2,5-dichloroaniline aqueous sulfuric acid: 2,5-dichloroanilines (1620g, 10mol), 98wt% sulphuric acid
(5004g, wherein containing H2SO450mol), water 2002g；
Preparation sodium nitrite in aqueous solution: sodium nitrite (759g, 11mol), water 1139g；
Sulphuric acid in configuration hydrolysis kettle: (5004g, wherein containing H for 98wt% sulphuric acid2SO450mol), water 2002g；
Toluene (32400g, 352mol)；
Chuck 15 is utilized tubular reactor 14 to be preheated and is incubated at 80 DEG C, by 2,5-dichloroaniline aqueous sulfuric acid, Asia
Sodium nitrate aqueous solution is prepared respectively in first batching kettle the 1, second batching kettle 2, and is counted by the first dosing pump 5, second respectively
In the amount continuous input mixer 15 of pump 6, coutroi velocity make the molar flow of meta nitro aniline and sodium nitrite ratio for 1:1.1,
Enter tubular reactor 14 in blender 13 after mixing, in tubular reactor 14, carry out diazo-reaction in 80 DEG C, through 1s
The time of staying after be directly entered in hydrolysis kettle 16, be stirred at reflux in hydrolysis kettle after 1h and stand separatory, aqueous phase discarded, sodium carbonate
Wash and boil off toluene after toluene takes mutually and obtain 2,5-chlorophenesic acid 1771g, crude yield 105%, content 66%.
Embodiment 2
Reaction unit structure such as Fig. 1, tubular reactor pipe range 30m, pipe diameter is 4mm.
Preparation 2,5-dichloroaniline aqueous sulfuric acid: 2,5-dichloroanilines (1620g, 10mol), 98wt% sulphuric acid
(5004g, wherein containing H2SO450mol), water 2002g；
Preparation sodium nitrite in aqueous solution: sodium nitrite (690g, 10mol), water 2760g；
Sulphuric acid in configuration hydrolysis kettle: (3002g, wherein containing H for 98wt% sulphuric acid2SO430mol), water 1201g；
Toluene (16200g, 176mol)；Carrying out diazo-reaction in 30 DEG C in tubular reactor 14, the time of staying is
60s；At hydrolysis kettle 16 internal reflux 2h；
Other modes of operation are same as in Example 1, finally give 2,5-chlorophenesic acid 1651g, and crude yield 101% contains
Amount 81%.
Embodiment 3
Reaction unit structure such as Fig. 1, tubular reactor pipe range 20m, pipe diameter is 8mm.
Preparation 2,5-dichloroaniline aqueous sulfuric acid: 2,5-dichloroanilines (1620g, 10mol), 10008g, Qi Zhonghan
H2SO4100mol), water 9608g；
Preparation sodium nitrite in aqueous solution: sodium nitrite (656g, 9.5mol), water 3717g；
Sulphuric acid in configuration hydrolysis kettle: (1001g, wherein containing H for 98wt% sulphuric acid2SO410mol), water 961g；
Toluene (12960g, 141mol)；Carrying out diazo-reaction in 40 DEG C in tubular reactor 14, the time of staying is
30s；At hydrolysis kettle 16 internal reflux 2h；
Other operations, with embodiment 1, finally give 2,5-chlorophenesic acid 1607g, crude yield 99%, content 73%.
Embodiment 4
Reaction unit structure such as Fig. 1, tubular reactor pipe range 6m, pipe diameter is 30mm.
Preparation 2,5-dichloroaniline aqueous sulfuric acid: 2,5-dichloroanilines (1620g, 10mol), (15010g, Qi Zhonghan
H2SO4150mol), water 34030g；
Preparation sodium nitrite in aqueous solution: sodium nitrite (897g, 13mol), water 14053g；
Sulphuric acid in configuration hydrolysis kettle: (2002g, wherein containing H for 98wt% sulphuric acid2SO420mol), water 4537g；
Toluene (19440g, 211mol)；
Carrying out diazo-reaction in 40 DEG C in tubular reactor 14, the time of staying is 45s；At hydrolysis kettle 16 internal reflux
1.2h；
Other operations, with embodiment 1, finally give 2,5-chlorophenesic acid 1453g crude yield 89%, content 91%.
Embodiment 5
Reaction unit structure such as Fig. 1, tubular reactor pipe range 4m, pipe diameter is 20mm.
Preparation 2,5-dichloroaniline aqueous sulfuric acid: 2,5-dichloroanilines (1620g, 10mol), 98wt% sulphuric acid
(3002g, wherein containing H2SO430mol), water 1286g；
Preparation sodium nitrite in aqueous solution: sodium nitrite (828g, 12mol), water water 1932g；
Sulphuric acid in configuration hydrolysis kettle: (2002g, wherein containing H for 98wt% sulphuric acid2SO420mol), water 4537g；
Isoamyl alcohol (1620g, 18mol)；
Carrying out diazo-reaction in 50 DEG C in tubular reactor 14, the time of staying is 20s；At hydrolysis kettle 16 internal reflux
1.5h；
Other operations, with embodiment 1, finally give 2,5-chlorophenesic acid 1632g, crude yield 100%, content 76%.
Embodiment 6
Reaction unit structure such as Fig. 1, tubular reactor pipe range 16m, pipe diameter is 10mm.
Preparation 2,5-dichloroaniline aqueous sulfuric acid: 2,5-dichloroanilines (1620g, 10mol), 98wt% sulphuric acid
(10008g, wherein containing H2SO4100mol), water 6338g；
Preparation sodium nitrite in aqueous solution: sodium nitrite (724g, 10.5mol), water 1632g；
Sulphuric acid in configuration hydrolysis kettle: (2002g, wherein containing H for 98wt% sulphuric acid2SO420mol), water 4537g；
Dimethylbenzene (25920g, 244.5mol)；
Carrying out diazo-reaction in 60 DEG C in tubular reactor 14, the time of staying is 30s；At hydrolysis kettle 16 internal reflux
1.8h；Organic facies potassium carbonate removes residual sulphuric acid；
Other operations, with embodiment 1, finally give 2,5-chlorophenesic acid 1677g, crude yield 103%, content 96%.
Embodiment 7
Reaction unit structure such as Fig. 1, tubular reactor: pipe range 1m, pipe diameter is 1mm.
Preparation 2,5-dichloroaniline aqueous sulfuric acid: 2,5-dichloroanilines (1620g, 10mol), 98wt% sulphuric acid
(121010g, wherein containing H2SO4120mol), water 4804g；
Preparation sodium nitrite in aqueous solution: sodium nitrite (759g, 11mol), water 1771g；
Sulphuric acid in configuration hydrolysis kettle: (4003g, wherein containing H for 98wt% sulphuric acid2SO440mol), water 1602g；
Methyl tertiary butyl ether(MTBE) (6480g, 73.6mol)；
At hydrolysis kettle 16 internal reflux 2h；
Other operations, with embodiment 1, finally give 2,5-chlorophenesic acid 1656g, crude yield 102%, content 80%.
Embodiment 8
Reaction unit structure such as Fig. 1, tubular reactor pipe range 12m, pipe diameter is 16mm.
Preparation 2,5-dichloroaniline aqueous sulfuric acid: 2,5-dichloroanilines (1620g, 10mol), 98wt% sulphuric acid
(3002g, wherein containing H2SO430mol), water 2002g；
Preparation nitrosyl sulfuric acid aqueous solution: nitrosyl sulfuric acid (1398g g, 11mol), water 2097g；
Sulphuric acid in configuration hydrolysis kettle: (2002g, wherein containing H for 98wt% sulphuric acid2SO420mol), water 4537g；
Toluene (9720g, 105.7mol)；
Carrying out diazo-reaction in 30 DEG C in tubular reactor 14, the time of staying is 15s；；At hydrolysis kettle 16 internal reflux
2h；Organic facies potassium carbonate removes residual sulphuric acid；
Other operations, with embodiment 1, finally give 2,5-chlorophenesic acid 1620g, crude yield 99%, content 97%.
Embodiment 9
Reaction unit structure such as Fig. 1, tubular reactor pipe range 24m, pipe diameter is 8mm.
Preparation 2,5-dichloroaniline aqueous sulfuric acid: 2,5-dichloroanilines (1620g, 10mol), 98wt% sulphuric acid
(8006g, wherein containing H2SO480mol), water 11609g；
Preparation sodium nitrite in aqueous solution: sodium nitrite 862g, 12.5mol), water 862g；
Sulphuric acid in configuration hydrolysis kettle: (3002g, wherein containing H for 98wt% sulphuric acid2SO430mol), water 4503g；
Isoamyl alcohol-toluene (16200g, 90.5mol)；
Carrying out diazo-reaction in 35 DEG C in tubular reactor 14, the time of staying is 50s；At hydrolysis kettle 16 internal reflux
1.5h；Organic facies potassium bicarbonate removes residual sulphuric acid；
Other operations, with embodiment 1, finally give 2,5-chlorophenesic acid 1643g, crude yield 101%, content 81%.
Embodiment 10
Reaction unit structure such as Fig. 1, tubular reactor: by two groups of pipe range 10m, pipe diameter is that 10mm is formed in parallel.
Preparation 2,5-dichloroaniline aqueous sulfuric acid: 2,5-dichloroanilines (1620g, 10mol), 98wt% sulphuric acid
(8006g, wherein containing H2SO480mol), water 3202g；
Preparation sodium nitrite in aqueous solution: sodium nitrite (759g, 11mol), water 6831g；
Sulphuric acid in configuration hydrolysis kettle: (3002g, wherein containing H for 98wt% sulphuric acid2SO430mol), water 1286g；
Methyl tertiary butyl ether(MTBE) (8100g, 92mol)；
Carrying out diazo-reaction in 60 DEG C in tubular reactor 14, the time of staying is 20s；At hydrolysis kettle 16 internal reflux
1.5h；Organic facies potassium bicarbonate removes residual sulphuric acid；
Other operations, with embodiment 1, finally give 2,5-chlorophenesic acid 1620g, crude yield 99%, content 88%.
Embodiment 11
Reaction unit structure such as Fig. 1, tubular reactor pipe range 16m, pipe diameter is 12mm.
Preparation 2,5-dichloroaniline aqueous sulfuric acid: 2,5-dichloroanilines (1620g, 10mol), passing through of 50wt% process
Spent acid (19620g, wherein containing H2SO4100mol)；
Preparation sodium nitrite in aqueous solution: sodium nitrite (724g, 10.5mol), water 4368g；
(5886g, wherein containing H for the treated spent acid of the sulphuric acid in configuration hydrolysis kettle: 50wt%2SO430mol)；
Hexamethylene (16200g, 192.8mol)；
Carrying out diazo-reaction in 30 DEG C in tubular reactor 14, the time of staying is 40s；At hydrolysis kettle 16 internal reflux
2h；Organic facies potassium bicarbonate removes residual sulphuric acid；
Other operations, with embodiment 1, finally give 2,5-chlorophenesic acid 1623g, crude yield 100%, content 93%.
Claims (10)
1. tubular type diazotising prepares 2, the method for 5-chlorophenesic acid, it is characterised in that: described method is:
(1), by raw material 2,5-dichloroaniline and H2SO4Mixed liquor and diazo reagent be separately stored in the first batching kettle and
In second batching kettle, and respectively by the first dosing pump conveyer device being connected with the first batching kettle and the second batching kettle phase
The second dosing pump conveyer device even is delivered continuously in blender mixing, and to carry out diazotising anti-for entrance tubular reactor immediately
Should, described 2,5-dichloroaniline, described H2SO4In sulphuric acid and described diazo reagent in diazo-reaction
The ratio of molar flow is 1:2.5～15:0.95～1.3；The ratio of described 2,5-dichloroaniline and organic solvent be 1:1～
20kg/L；
(2) mixed reaction solution that the step (1) described in obtains enters tubular reactor and carries out diazo-reaction, and reaction temperature is 10
～150 DEG C, reaction time is 1～60s, obtains diazo-reaction liquid；
(3) the diazo-reaction liquid that the step (2) described in obtains is entered equipped with sulphuric acid and organic by the outlet of tubular reactor
Solvent is also hydrolyzed reaction in being warming up to the hydrolysis kettle of backflow in advance, passes through fraction water device water-dividing, hydrolysis in course of reaction
Rear continue to reflux 1～2h, after having reacted, collection organic facies, alkali cleaning, to neutrality, distillating recovering solvent, i.e. obtains 2,5-
Chlorophenesic acid crude product.
2. tubular type diazotising as claimed in claim 1 prepares 2, the method for 5-chlorophenesic acid, it is characterised in that: described with 2,
The mass concentration of the sulphuric acid of 5-dichloroaniline mixing is 30%～98%.
3. tubular type diazotising as claimed in claim 1 prepares 2, the method for 5-chlorophenesic acid, it is characterised in that: described diazonium
Changing reagent is sodium nitrite or nitrosyl sulfuric acid.
4. tubular type diazotising as claimed in claim 1 prepares 2, the method for 5-chlorophenesic acid, it is characterised in that: described diazonium
The mass concentration changing reagent is 6%～50%.
5. tubular type diazotising as claimed in claim 1 prepares 2, the method for 5-chlorophenesic acid, it is characterised in that: described hydrolysis
The concentration of the sulphuric acid in still is 30%～70%.
6. tubular type diazotising as claimed in claim 1 prepares 2, the method for 5-chlorophenesic acid, it is characterised in that: described is organic
Solvent is one or more combinations in aromatic hydrocarbons or alkane or ether or alcohol.
7. tubular type diazotising as claimed in claim 1 prepares 2, the method for 5-chlorophenesic acid, it is characterised in that: receive for alkali cleaning
The alkali of the organic facies integrated is as inorganic weak bases.
8. a tubular type diazotising as claimed in claim 1 prepares 2, and the special purpose device of 5-chlorophenesic acid method, its feature exists
In: described special purpose device includes passing sequentially through the blender of pipeline connection, tubular reactor, hydrolysis kettle, described blender
Respectively with input 2,5-dichloroaniline and H2SO4The first batching kettle of mixed liquor, input diazo reagent the second batching kettle even
Connect, between described the first batching kettle and blender by the first bottom valve be sequentially connected with the first relief valve, the first dosing pump, first
Effusion meter, between described the second batching kettle and blender by the second bottom valve be sequentially connected with the second relief valve, the second dosing pump,
Second gauge；The first described dosing pump and first-class gauge and the second described dosing pump and second flow are scored other shape
Become feedback circuit.Described hydrolysis kettle entrance and the outlet of tubular reactor；On described hydrolysis kettle, water knockout drum is installed；
On pipeline between described the first batching kettle and tubular reactor and between described the second batching kettle and tubular reactor
It is respectively arranged with the first ripple damper and the second ripple damper.
9. special purpose device as claimed in claim 8, it is characterised in that: described tubular reactor be single tube tubular reactor or
Multitube tubular reactor composes in parallel；The reacting pipe of described tubular reactor is shaped as straight tube or bending pipeline, bending tube
Bending angle >=45 ° in road.
10. special purpose device as claimed in claim 9, it is characterised in that: described blender is two pipelines, one of them pipeline
Middle part embeds another pipeline, and the opening of another pipeline is arranged towards Flow of Goods and Materials direction, and open front is divided and had undergauge structure；
Another pipeline is connected with the pipeline equipped with diazo reagent.
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| CN201610538837.0A CN106187711A (en) | 2016-07-06 | 2016-07-06 | Method for preparing 2, 5-dichlorophenol by tubular diazotization and special device |
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