CN109734551A - A kind of oriented chlorination of toluene prepares the production technology of p-chlorotoluene - Google Patents
A kind of oriented chlorination of toluene prepares the production technology of p-chlorotoluene Download PDFInfo
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- CN109734551A CN109734551A CN201910021511.4A CN201910021511A CN109734551A CN 109734551 A CN109734551 A CN 109734551A CN 201910021511 A CN201910021511 A CN 201910021511A CN 109734551 A CN109734551 A CN 109734551A
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- chlorotoluene
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 213
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000005660 chlorination reaction Methods 0.000 title claims abstract description 81
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- 238000005516 engineering process Methods 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 84
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 239000000460 chlorine Substances 0.000 claims abstract description 40
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 40
- 238000004587 chromatography analysis Methods 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 238000010992 reflux Methods 0.000 claims abstract description 17
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 82
- 239000007789 gas Substances 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 229910052757 nitrogen Inorganic materials 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 39
- 239000012267 brine Substances 0.000 claims description 38
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 38
- 238000002425 crystallisation Methods 0.000 claims description 37
- 230000008025 crystallization Effects 0.000 claims description 37
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 19
- 239000011780 sodium chloride Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 17
- 230000001376 precipitating effect Effects 0.000 claims description 16
- 229910021536 Zeolite Inorganic materials 0.000 claims description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 15
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 15
- 239000010457 zeolite Substances 0.000 claims description 15
- 230000000694 effects Effects 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 239000003426 co-catalyst Substances 0.000 claims description 10
- 239000008213 purified water Substances 0.000 claims description 10
- 239000012159 carrier gas Substances 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 8
- 238000002309 gasification Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003039 volatile agent Substances 0.000 claims description 8
- 239000002826 coolant Substances 0.000 claims description 7
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 claims description 7
- 150000003568 thioethers Chemical class 0.000 claims description 5
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 4
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000003317 industrial substance Substances 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 239000000575 pesticide Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000012320 chlorinating reagent Substances 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- RMOGWMIKYWRTKW-UONOGXRCSA-N (S,S)-paclobutrazol Chemical compound C([C@@H]([C@@H](O)C(C)(C)C)N1N=CN=C1)C1=CC=C(Cl)C=C1 RMOGWMIKYWRTKW-UONOGXRCSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 239000005985 Paclobutrazol Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QHTQREMOGMZHJV-UHFFFAOYSA-N Thiobencarb Chemical compound CCN(CC)C(=O)SCC1=CC=C(Cl)C=C1 QHTQREMOGMZHJV-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 150000001989 diazonium salts Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OSOUNOBYRMOXQQ-UHFFFAOYSA-N 1-chloro-3-methylbenzene Chemical compound CC1=CC=CC(Cl)=C1 OSOUNOBYRMOXQQ-UHFFFAOYSA-N 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- -1 adjacent Chemical compound 0.000 description 1
- 238000005267 amalgamation Methods 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GSSJSUKUYXXPME-UHFFFAOYSA-N benzene;chloromethane Chemical compound ClC.C1=CC=CC=C1 GSSJSUKUYXXPME-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000675 fabric finishing Substances 0.000 description 1
- 238000009962 finishing (textile) Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229940089536 indocin Drugs 0.000 description 1
- CGIGDMFJXJATDK-UHFFFAOYSA-N indomethacin Chemical compound CC1=C(CC(O)=O)C2=CC(OC)=CC=C2N1C(=O)C1=CC=C(Cl)C=C1 CGIGDMFJXJATDK-UHFFFAOYSA-N 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to industrial chemicals preparation technical fields, the production technology of p-chlorotoluene is prepared more particularly to a kind of oriented chlorination of toluene, include the following steps: chlorination: catalyst is added in reaction vessel, toluene is added in reaction vessel again, the air being passed through in inert gas discharge reaction vessel, then will be put into thermostat after reaction vessel shading treatment, then be passed through in chlorine thermostat and carry out chlorination reaction, to judge reaction end, the mixture for obtaining chlorination is stand-by for chromatography；Rectifying: adjusting reflux ratio is 10:1, and collecting temperature is 158 ~ 162 DEG C of fraction, obtains that adjacent, p-chlorotoluene mixed liquor is stand-by；Primary purifying；It is secondarily purified.The present invention solves the problems, such as that chlorination toluene directional selectivity is poor in the prior art and higher cost, provides that a kind of p-chlorotoluene high income, high conversion rate, contraposition M8003 line be preferable and the reasonable production technology of process costs.
Description
Technical field
The present invention relates to industrial chemicals preparation technical fields, and in particular to a kind of oriented chlorination of toluene prepares p-chlorotoluene
Production technology.
Background technique
P-chlorotoluene is the important source material and intermediate of pesticide, medicine, dyestuff and other fine Organic chemical products.Pass through
Chlorination, oxidation, ammoxidation on p-chlorotoluene side chain and the chlorination on ring, nitrification, sulfonation, Friedel-Crafts reaction, chlorine
The reaction such as methylation, can derive a series of important fine-chemical intermediate, can develop 100 by these intermediates
Multiple Pesticides, medicine, dye product.Such as pesticide benthiocarb, paclobutrazol, trefanocide, quasi- weeding chrysanthemum ester insecticide；Medical anti-inflammatory
Bitterly；Dyestuff water dye dyeing base etc..P-chlorotoluene is important among fine chemical material and the very extensive organic chemical industry of purposes
Body.On pesticide, it is production benthiocarb, paclobutrazol, pyrethroid that p-chlorotoluene, which is production speed come the required raw material of pesticides such as killing,
The key intermediate of ester pesticide and trefanocide etc..It in medicine, is the important source material for producing the key intermediate of indocin.
On dyestuff, water metachromia dye base can be prepared, is the raw material for producing nearly hundred kinds of dyestuffs；Textile fabric finishing agent can be prepared,
With performances such as fire-retardant, the resistance to pressing, the waterproofs that improve fabric.
The traditional production method of p-chlorotoluene is diazonium salt to be generated through diazotising, then in chlorine using para-totuidine as raw material
In the presence of changing cuprous catalysis agent, diazonium salt is reacted with concentrated hydrochloric acid generates p-chlorotoluene.This method high production cost, wastewater flow rate is big,
Equipment corrosion and seriously polluted, " three wastes " are mostly and poor product quality.
Major industrialized production method is chlorine direct chlorination toluene method both at home and abroad at present, and new production method is with toluene
It is obtained in the presence of a catalyst with chlorine direct chlorination for raw material.If but toluene ring chlorination non-selectivity catalyst is deposited
, and lewis acid catalyst is only used, para-selectivity is generally very poor.Usual p-chlorotoluene accounts for 35%~45%, ortho-chlorotolu'ene
55%~65% is accounted for, m-chlorotoluene is less than 1%.Such as in the presence of FeCl3, in the obtained amalgamation chlorotoluene of chlorination toluene,
Ortho-chlorotolu'ene/p-chlorotoluene=1.9.Since the purposes of p-chlorotoluene is big more than ortho-chlorotolu'ene.
In all chlorinating agents of chlorination toluene, the price of chlorine is generally the least expensive, and source is most abundant, and technique is also most simple, so
Chlorine is selected to make the chloridising of chlorinating agent both at home and abroad at present.Mainly have two with the chloridising used catalyst that chlorine makees chlorinating agent
Class: (1) with lewis acid catalyst add the catalyst system of sulfur-bearing co-catalyst；(2) zeolite molecular sieve catalyst system.First
It is that directional selectivity is preferable the characteristics of catalyst in class, resource has obtained reasonable utilization, and at low cost, the three wastes are less, equipment utilization
Rate is higher, and depth of chlorination is big, and energy consumption is relatively low.The disadvantage is that with two kinds of catalyst, the especially preparation difficulty of co-catalyst
Larger, directional selectivity is not good enough.The advantages of second class catalyst is that para-selectivity is high, depth of chlorination is big, product point
From being relatively easy to.The disadvantage is that at high cost (more much higher than FeCl3 chloridising), service life is short after regenerating molecular sieve.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of oriented chlorination of toluene to prepare p-chlorotoluene
Production technology solves the problems, such as that chlorination toluene directional selectivity is poor in the prior art and higher cost, provides one kind
M8003 line is preferable and the reasonable production technology of process costs for p-chlorotoluene high income, high conversion rate, contraposition.
The purpose of the present invention is achieved through the following technical solutions:
A kind of oriented chlorination of toluene prepares the production technology of p-chlorotoluene, includes the following steps:
Step 1: chlorination: catalyst being added in reaction vessel, then toluene is added in reaction vessel, is passed through indifferent gas
The air in reaction vessel is discharged in body, then will be put into thermostat after reaction vessel shading treatment, by dry chlorine with
Nitrogen, which is mixed to form to be passed through again in thermostat after chloridating gas, carries out chlorination reaction, and reaction end gas absorbs to be formed using purified water
Aqueous solution is carried out chromatography to judge reaction end by aqueous solution, and the mixture for obtaining chlorination is stand-by；
Step 2: rectifying: the mixture of chlorination in step 1 is added in rectifying column and carries out rectifying, adjusting reflux ratio is 2:
1, which collects temperature, is 109~113 DEG C of front-end volatiles, then adjusting reflux ratio is 10:1, collects the fraction that temperature is 158~162 DEG C,
Obtain that adjacent, p-chlorotoluene mixed liquor is stand-by；
Step 3: primary purifying: adjacent, p-chlorotoluene mixed liquor in step 2 being fitted into crystallizing tower, crystallizing tower outer wall twines
Around crystallizer, wherein crystallizing tank, which is passed through cooling medium, makes material decrease temperature crystalline in container, send in crystallization process to crystallizing tower drum
Gas, material gradually form crystallizing layer in crystallization inner wall of tower, lower section liquid are discharged, and stop cooling when no longer precipitating crystal；
Step 4: secondarily purified: after temperature warms naturally to 10 DEG C in crystallizing tower, crystallizer is passed through cooling medium again
Make the material decrease temperature crystalline in container, supply gas body in crystallization process to crystallizing tower drum, material gradually forms knot in crystallization inner wall of tower
Lower section liquid is discharged crystal layer, when no longer precipitating crystal stop cooling, collect crystallizing layer solid, purified to chloromethane
Benzene.
Oriented chlorination of toluene is prepared in the chlorination process of p-chlorotoluene, using inert gas filling and shading treatment, is reduced
The generation of chlorination side reaction improves the conversion ratio that toluene conversion is p-chlorotoluene, and wherein thermostat temperature control is 30~40
DEG C, reaction rate is very fast at this time and side reaction is less, and it is higher to purify more convenient and yield；Reaction end is monitored using gas phase,
Conducive to judging reaction end；Hydrochloride aqueous solution is formed using the hydrogen chloride that purified water absorbing reaction generates, it can also be used to produce
Preparation uses, and improves the utilization rate of material；The process that is passed through of chlorine is first dried, and mixes after dry with nitrogen, slows down chlorine
After the flow of gas, the generation of by-product is not only reduced, and improves selectivity of the chlorination toluene in contraposition selection.
Further, the molar ratio of toluene and chlorine is 1:(0.6~0.7 in the step 1)；It is urged in the step 1
The mass ratio of agent and toluene is 1:(120~130)；The reaction temperature of thermostat is 20~50 DEG C in the step 1.
It is further preferred that the mass ratio of catalyst and toluene is 1:(123~125 in the step 1), the step
The reaction temperature of thermostat is 30~40 DEG C in one.
Further, in the step 1 catalyst be natural activity zeolite and co-catalyst mass ratio be 1:(1.5~
2.0)。
Catalyst is formed using natural activity zeolite and co-catalyst, and wherein natural activity zeolite is a kind of environmental-friendly urges
Agent, catalytic activity with higher and catalytic selectivity improve the production of p-chlorotoluene for the M8003 line of chlorination toluene
The conversion ratio of rate and toluene；Natural activity zeolite is reusable, improves the overall utilization rate of material, reduce technique at
This.
It is further preferred that co-catalyst is thioether, sulfur monochloride, sulfur dichloride, benzenethiol or sulphur in the step 1
One of alcohol.
Oriented chlorination of toluene is prepared in the production process of p-chlorotoluene, and using chlorine as chlorinating agent, cost is relatively low,
Co-catalyst in catalyst reduces catalyst using one of thioether, sulfur monochloride, sulfur dichloride, benzenethiol or mercaptan
Cost so that integrated artistic cost reduces, but will not reduce the selectivity of M8003 line p-chlorotoluene, whole production technology first
The purity is high of benzene high conversion rate, the yield height of p-chlorotoluene, p-chlorotoluene.
Further, chlorine is dry using the concentrated sulfuric acid in the step 1；Chloridating gas is passed through speed in the step 1
Rate is 0.5~0.6L/min, and it according to volume ratio is 1:(0.8~1.0 that wherein chloridating gas, which is chlorine and nitrogen) it mixes.
Further, the chromatograph of the chromatography is 102G gas chromatograph, and chromatography is conductance cell detection, color
The carrier gas of spectrum analysis is nitrogen, and the column temperature of chromatography is 90 DEG C, and gasification room temperature is 210 DEG C.
Further, cooling medium is brine ice in the step 3, and the gas that crystallizing tower drum is sent in the step 3 is
Nitrogen；Cooling medium is brine ice in the step 4；The gas that crystallizing tower drum is sent in the step 4 is nitrogen.
It is further preferred that the mass fraction of sodium chloride is 21~24% in brine ice in the step 3；The step
The mass fraction of sodium chloride is 21~24% in brine ice in four.
In the production technology that oriented chlorination of toluene prepares p-chlorotoluene, adjacent, p-chlorotoluene mixed liquor is passed through into crystallization
Mode separates, and wherein the crystallization temperature of p-chlorotoluene is much higher than ortho-chlorotolu'ene, and the two may be implemented solid under the cooling of brine ice
Liquid separates, and the mass fraction of sodium chloride is 21~24% in brine ice, and the temperature of brine ice is -20~-5 DEG C at this time, warm herein
The lower p-chlorotoluene that is conducive to of degree crystallizes, and ortho-chlorotolu'ene does not crystallize at this time, the two separative efficiency height；Once after purification heating so that
Remaining ortho-chlorotolu'ene discharge under the advertising of nitrogen in solid, ortho-chlorotolu'ene liquefaction separate it with p-chlorotoluene solid, make
The purity is high of standby obtained p-chlorotoluene.
The beneficial effects of the present invention are:
1. oriented chlorination of toluene is prepared in the production process of p-chlorotoluene, using chlorine as chlorinating agent, cost compared with
Low, the co-catalyst in catalyst reduces catalysis using one of thioether, sulfur monochloride, sulfur dichloride, benzenethiol or mercaptan
Agent cost so that integrated artistic cost reduces, but will not reduce the selectivity of M8003 line p-chlorotoluene, whole production technology
Toluene conversion is high, p-chlorotoluene yield is high, p-chlorotoluene purity is high；
2. catalyst is formed using natural activity zeolite and co-catalyst, wherein natural activity zeolite is a kind of environmental-friendly
Catalyst, catalytic activity with higher and catalytic selectivity improve p-chlorotoluene for the M8003 line of chlorination toluene
The conversion ratio of yield and toluene；Natural activity zeolite is reusable, improves the overall utilization rate of material, reduces technique
Cost；
3. adjacent, p-chlorotoluene mixed liquor is passed through crystallization in the production technology that oriented chlorination of toluene prepares p-chlorotoluene
Mode separate, wherein the crystallization temperature of p-chlorotoluene is much higher than ortho-chlorotolu'ene, and the two may be implemented under the cooling of brine ice
It is separated by solid-liquid separation, the mass fraction of sodium chloride is 21~24% in brine ice, and the temperature of brine ice is -20~-5 DEG C at this time, herein
At a temperature of be conducive to p-chlorotoluene and crystallize, and ortho-chlorotolu'ene does not crystallize at this time, and the two separative efficiency is high；Make once heating up after purification
Ortho-chlorotolu'ene discharge under the advertising of nitrogen remaining in solid is obtained, ortho-chlorotolu'ene liquefaction separates it with p-chlorotoluene solid,
The purity is high for the p-chlorotoluene being prepared；
4. oriented chlorination of toluene is prepared in the chlorination process of p-chlorotoluene, using inert gas filling and shading treatment, subtract
The generation for having lacked chlorination side reaction improves the conversion ratio that toluene conversion is p-chlorotoluene, wherein thermostat temperature control 30~
40 DEG C, reaction rate is very fast at this time and side reaction is less, and it is higher to purify more convenient and yield；Reaction is monitored eventually using gas phase
Point is conducive to judge reaction end；Hydrochloride aqueous solution is formed using the hydrogen chloride that purified water absorbing reaction generates, it can also be used to raw
It produces preparation to use, improves the utilization rate of material；The process that is passed through of chlorine is first dried, and mixes, slows down with nitrogen after dry
After the flow of chlorine, the generation of by-product is not only reduced, and improves selectivity of the chlorination toluene in contraposition selection.
Specific embodiment
Technical solution of the present invention is described in further detail combined with specific embodiments below, but protection scope of the present invention is not
It is confined to as described below.
Embodiment 1
A kind of oriented chlorination of toluene prepares the production technology of p-chlorotoluene, includes the following steps:
Step 1: chlorination: catalyst being added in reaction vessel, then toluene is added in reaction vessel, is passed through indifferent gas
The air in reaction vessel is discharged in body, then will be put into thermostat after reaction vessel shading treatment, wherein toluene and chlorine
Molar ratio is 1:0.6, and the mass ratio of catalyst and toluene is 1:120, and the reaction temperature of thermostat is 20 DEG C, by the concentrated sulfuric acid
Dry chlorine and nitrogen are mixed to form to be passed through again in thermostat after chloridating gas carries out chlorination reaction, wherein chloridating gas
Being passed through rate is 0.5L/min, and it according to volume ratio is that 1:0.8 is mixed that wherein chloridating gas, which is chlorine and nitrogen, reaction end gas
It absorbs to form aqueous solution using purified water, aqueous solution is subjected to chromatography to judging reaction end, wherein chromatography
Chromatograph is 102G gas chromatograph, and chromatography is conductance cell detection, and the carrier gas of chromatography is nitrogen, the column of chromatography
Temperature is 90 DEG C, and gasification room temperature is 210 DEG C, and the mixture for obtaining chlorination is stand-by；
Step 2: rectifying: the mixture of chlorination in step 1 is added in rectifying column and carries out rectifying, adjusting reflux ratio is 2:
1, which collects temperature, is 109~113 DEG C of front-end volatiles, then adjusting reflux ratio is 10:1, collects the fraction that temperature is 158~162 DEG C,
Obtain that adjacent, p-chlorotoluene mixed liquor is stand-by；
Step 3: primary purifying: adjacent, p-chlorotoluene mixed liquor in step 2 being fitted into crystallizing tower, crystallizing tower outer wall twines
Around crystallizer, wherein crystallizing tank, which is passed through brine ice, makes material decrease temperature crystalline in container, wherein in brine ice sodium chloride quality
Score is 21%, send nitrogen to crystallizing tower drum in crystallization process, material gradually forms crystallizing layer in crystallization inner wall of tower, by lower section liquid
Body discharge, stops cooling when no longer precipitating crystal；
Step 4: secondarily purified: after temperature warms naturally to 10 DEG C in crystallizing tower, crystallizer is passed through brine ice again to be made
Material decrease temperature crystalline in container, wherein the mass fraction of sodium chloride is 21% in brine ice, to crystallizing tower drum in crystallization process
Nitrogen is sent, material gradually forms crystallizing layer in crystallization inner wall of tower, lower section liquid is discharged, is stopped when no longer precipitating crystal cold
But, crystallizing layer solid, the p-chlorotoluene purified are collected.
Specifically, it is 1:1.5 that catalyst, which is the mass ratio of natural activity zeolite and thioether, in the step 1.
Embodiment 2
A kind of oriented chlorination of toluene prepares the production technology of p-chlorotoluene, includes the following steps:
Step 1: chlorination: catalyst being added in reaction vessel, then toluene is added in reaction vessel, is passed through indifferent gas
The air in reaction vessel is discharged in body, then will be put into thermostat after reaction vessel shading treatment, wherein toluene and chlorine
Molar ratio is 1:0.7, and the mass ratio of catalyst and toluene is 1:130, and the reaction temperature of thermostat is 50 DEG C, by the concentrated sulfuric acid
Dry chlorine and nitrogen are mixed to form to be passed through again in thermostat after chloridating gas carries out chlorination reaction, wherein chloridating gas
Being passed through rate is 0.6L/min, and it according to volume ratio is that 1:1.0 is mixed that wherein chloridating gas, which is chlorine and nitrogen, reaction end gas
It absorbs to form aqueous solution using purified water, aqueous solution is subjected to chromatography to judging reaction end, wherein chromatography
Chromatograph is 102G gas chromatograph, and chromatography is conductance cell detection, and the carrier gas of chromatography is nitrogen, the column of chromatography
Temperature is 90 DEG C, and gasification room temperature is 210 DEG C, and the mixture for obtaining chlorination is stand-by；
Step 2: rectifying: the mixture of chlorination in step 1 is added in rectifying column and carries out rectifying, adjusting reflux ratio is 2:
1, which collects temperature, is 109~113 DEG C of front-end volatiles, then adjusting reflux ratio is 10:1, collects the fraction that temperature is 158~162 DEG C,
Obtain that adjacent, p-chlorotoluene mixed liquor is stand-by；
Step 3: primary purifying: adjacent, p-chlorotoluene mixed liquor in step 2 being fitted into crystallizing tower, crystallizing tower outer wall twines
Around crystallizer, wherein crystallizing tank, which is passed through brine ice, makes material decrease temperature crystalline in container, wherein in brine ice sodium chloride quality
Score is 24%, send nitrogen to crystallizing tower drum in crystallization process, material gradually forms crystallizing layer in crystallization inner wall of tower, by lower section liquid
Body discharge, stops cooling when no longer precipitating crystal；
Step 4: secondarily purified: after temperature warms naturally to 10 DEG C in crystallizing tower, crystallizer is passed through brine ice again to be made
Material decrease temperature crystalline in container, wherein the mass fraction of sodium chloride is 24% in brine ice, to crystallizing tower drum in crystallization process
Nitrogen is sent, material gradually forms crystallizing layer in crystallization inner wall of tower, lower section liquid is discharged, is stopped when no longer precipitating crystal cold
But, crystallizing layer solid, the p-chlorotoluene purified are collected.
Specifically, it is 1:2.0 that catalyst, which is the mass ratio of natural activity zeolite and sulfur dichloride, in the step 1.
Embodiment 3
A kind of oriented chlorination of toluene prepares the production technology of p-chlorotoluene, includes the following steps:
Step 1: chlorination: catalyst being added in reaction vessel, then toluene is added in reaction vessel, is passed through indifferent gas
The air in reaction vessel is discharged in body, then will be put into thermostat after reaction vessel shading treatment, wherein toluene and chlorine
Molar ratio is 1:0.6, and the mass ratio of catalyst and toluene is 1:123, and the reaction temperature of thermostat is 30 DEG C, by the concentrated sulfuric acid
Dry chlorine and nitrogen are mixed to form to be passed through again in thermostat after chloridating gas carries out chlorination reaction, wherein chloridating gas
Being passed through rate is 0.6L/min, and it according to volume ratio is that 1:0.9 is mixed that wherein chloridating gas, which is chlorine and nitrogen, reaction end gas
It absorbs to form aqueous solution using purified water, aqueous solution is subjected to chromatography to judging reaction end, wherein chromatography
Chromatograph is 102G gas chromatograph, and chromatography is conductance cell detection, and the carrier gas of chromatography is nitrogen, the column of chromatography
Temperature is 90 DEG C, and gasification room temperature is 210 DEG C, and the mixture for obtaining chlorination is stand-by；
Step 2: rectifying: the mixture of chlorination in step 1 is added in rectifying column and carries out rectifying, adjusting reflux ratio is 2:
1, which collects temperature, is 109~113 DEG C of front-end volatiles, then adjusting reflux ratio is 10:1, collects the fraction that temperature is 158~162 DEG C,
Obtain that adjacent, p-chlorotoluene mixed liquor is stand-by；
Step 3: primary purifying: adjacent, p-chlorotoluene mixed liquor in step 2 being fitted into crystallizing tower, crystallizing tower outer wall twines
Around crystallizer, wherein crystallizing tank, which is passed through brine ice, makes material decrease temperature crystalline in container, wherein in brine ice sodium chloride quality
Score is 22%, send nitrogen to crystallizing tower drum in crystallization process, material gradually forms crystallizing layer in crystallization inner wall of tower, by lower section liquid
Body discharge, stops cooling when no longer precipitating crystal；
Step 4: secondarily purified: after temperature warms naturally to 10 DEG C in crystallizing tower, crystallizer is passed through brine ice again to be made
Material decrease temperature crystalline in container, wherein the mass fraction of sodium chloride is 22% in brine ice, to crystallizing tower drum in crystallization process
Nitrogen is sent, material gradually forms crystallizing layer in crystallization inner wall of tower, lower section liquid is discharged, is stopped when no longer precipitating crystal cold
But, crystallizing layer solid, the p-chlorotoluene purified are collected.
Specifically, it is 1:2.0 that catalyst, which is the mass ratio of natural activity zeolite and benzenethiol, in the step 1.
Embodiment 4
A kind of oriented chlorination of toluene prepares the production technology of p-chlorotoluene, includes the following steps:
Step 1: chlorination: catalyst being added in reaction vessel, then toluene is added in reaction vessel, is passed through indifferent gas
The air in reaction vessel is discharged in body, then will be put into thermostat after reaction vessel shading treatment, wherein toluene and chlorine
Molar ratio is 1:0.7, and the mass ratio of catalyst and toluene is 1:125, and the reaction temperature of thermostat is 40 DEG C, by the concentrated sulfuric acid
Dry chlorine and nitrogen are mixed to form to be passed through again in thermostat after chloridating gas carries out chlorination reaction, wherein chloridating gas
Being passed through rate is 0.6L/min, and it according to volume ratio is that 1:0.9 is mixed that wherein chloridating gas, which is chlorine and nitrogen, reaction end gas
It absorbs to form aqueous solution using purified water, aqueous solution is subjected to chromatography to judging reaction end, wherein chromatography
Chromatograph is 102G gas chromatograph, and chromatography is conductance cell detection, and the carrier gas of chromatography is nitrogen, the column of chromatography
Temperature is 90 DEG C, and gasification room temperature is 210 DEG C, and the mixture for obtaining chlorination is stand-by；
Step 2: rectifying: the mixture of chlorination in step 1 is added in rectifying column and carries out rectifying, adjusting reflux ratio is 2:
1, which collects temperature, is 109~113 DEG C of front-end volatiles, then adjusting reflux ratio is 10:1, collects the fraction that temperature is 158~162 DEG C,
Obtain that adjacent, p-chlorotoluene mixed liquor is stand-by；
Step 3: primary purifying: adjacent, p-chlorotoluene mixed liquor in step 2 being fitted into crystallizing tower, crystallizing tower outer wall twines
Around crystallizer, wherein crystallizing tank, which is passed through brine ice, makes material decrease temperature crystalline in container, wherein in brine ice sodium chloride quality
Score is 23%, send nitrogen to crystallizing tower drum in crystallization process, material gradually forms crystallizing layer in crystallization inner wall of tower, by lower section liquid
Body discharge, stops cooling when no longer precipitating crystal；
Step 4: secondarily purified: after temperature warms naturally to 10 DEG C in crystallizing tower, crystallizer is passed through brine ice again to be made
Material decrease temperature crystalline in container, wherein the mass fraction of sodium chloride is 23% in brine ice, to crystallizing tower drum in crystallization process
Nitrogen is sent, material gradually forms crystallizing layer in crystallization inner wall of tower, lower section liquid is discharged, is stopped when no longer precipitating crystal cold
But, crystallizing layer solid, the p-chlorotoluene purified are collected.
Specifically, it is 1:1.8 that catalyst, which is the mass ratio of natural activity zeolite and mercaptan, in the step 1.
Embodiment 5
A kind of oriented chlorination of toluene prepares the production technology of p-chlorotoluene, includes the following steps:
Step 1: chlorination: catalyst being added in reaction vessel, then toluene is added in reaction vessel, is passed through indifferent gas
The air in reaction vessel is discharged in body, then will be put into thermostat after reaction vessel shading treatment, wherein toluene and chlorine
Molar ratio is 1:0.7, and the mass ratio of catalyst and toluene is 1:124, and the reaction temperature of thermostat is 35 DEG C, by the concentrated sulfuric acid
Dry chlorine and nitrogen are mixed to form to be passed through again in thermostat after chloridating gas carries out chlorination reaction, wherein chloridating gas
Being passed through rate is 0.6L/min, and it according to volume ratio is that 1:0.9 is mixed that wherein chloridating gas, which is chlorine and nitrogen, reaction end gas
It absorbs to form aqueous solution using purified water, aqueous solution is subjected to chromatography to judging reaction end, wherein chromatography
Chromatograph is 102G gas chromatograph, and chromatography is conductance cell detection, and the carrier gas of chromatography is nitrogen, the column of chromatography
Temperature is 90 DEG C, and gasification room temperature is 210 DEG C, and the mixture for obtaining chlorination is stand-by；
Step 2: rectifying: the mixture of chlorination in step 1 is added in rectifying column and carries out rectifying, adjusting reflux ratio is 2:
1, which collects temperature, is 109~113 DEG C of front-end volatiles, then adjusting reflux ratio is 10:1, collects the fraction that temperature is 158~162 DEG C,
Obtain that adjacent, p-chlorotoluene mixed liquor is stand-by；
Step 3: primary purifying: adjacent, p-chlorotoluene mixed liquor in step 2 being fitted into crystallizing tower, crystallizing tower outer wall twines
Around crystallizer, wherein crystallizing tank, which is passed through brine ice, makes material decrease temperature crystalline in container, wherein in brine ice sodium chloride quality
Score is 23%, send nitrogen to crystallizing tower drum in crystallization process, material gradually forms crystallizing layer in crystallization inner wall of tower, by lower section liquid
Body discharge, stops cooling when no longer precipitating crystal；
Step 4: secondarily purified: after temperature warms naturally to 10 DEG C in crystallizing tower, crystallizer is passed through brine ice again to be made
Material decrease temperature crystalline in container, wherein the mass fraction of sodium chloride is 23% in brine ice, to crystallizing tower drum in crystallization process
Nitrogen is sent, material gradually forms crystallizing layer in crystallization inner wall of tower, lower section liquid is discharged, is stopped when no longer precipitating crystal cold
But, crystallizing layer solid, the p-chlorotoluene purified are collected.
Specifically, it is 1:1.5 that catalyst, which is the mass ratio of natural activity zeolite and sulfur dichloride, in the step 1.
Embodiment 6
A kind of oriented chlorination of toluene prepares the production technology of p-chlorotoluene, includes the following steps:
Step 1: chlorination: catalyst being added in reaction vessel, then toluene is added in reaction vessel, is passed through indifferent gas
The air in reaction vessel is discharged in body, then will be put into thermostat after reaction vessel shading treatment, wherein toluene and chlorine
Molar ratio is 1:0.7, and the mass ratio of catalyst and toluene is 1:125, and the reaction temperature of thermostat is 35 DEG C, by the concentrated sulfuric acid
Dry chlorine and nitrogen are mixed to form to be passed through again in thermostat after chloridating gas carries out chlorination reaction, wherein chloridating gas
Being passed through rate is 0.6L/min, and it according to volume ratio is that 1:0.8 is mixed that wherein chloridating gas, which is chlorine and nitrogen, reaction end gas
It absorbs to form aqueous solution using purified water, aqueous solution is subjected to chromatography to judging reaction end, wherein chromatography
Chromatograph is 102G gas chromatograph, and chromatography is conductance cell detection, and the carrier gas of chromatography is nitrogen, the column of chromatography
Temperature is 90 DEG C, and gasification room temperature is 210 DEG C, and the mixture for obtaining chlorination is stand-by；
Step 2: rectifying: the mixture of chlorination in step 1 is added in rectifying column and carries out rectifying, adjusting reflux ratio is 2:
1, which collects temperature, is 109~113 DEG C of front-end volatiles, then adjusting reflux ratio is 10:1, collects the fraction that temperature is 158~162 DEG C,
Obtain that adjacent, p-chlorotoluene mixed liquor is stand-by；
Step 3: primary purifying: adjacent, p-chlorotoluene mixed liquor in step 2 being fitted into crystallizing tower, crystallizing tower outer wall twines
Around crystallizer, wherein crystallizing tank, which is passed through brine ice, makes material decrease temperature crystalline in container, wherein in brine ice sodium chloride quality
Score is 21%, send nitrogen to crystallizing tower drum in crystallization process, material gradually forms crystallizing layer in crystallization inner wall of tower, by lower section liquid
Body discharge, stops cooling when no longer precipitating crystal；
Step 4: secondarily purified: after temperature warms naturally to 10 DEG C in crystallizing tower, crystallizer is passed through brine ice again to be made
Material decrease temperature crystalline in container, wherein the mass fraction of sodium chloride is 21% in brine ice, to crystallizing tower drum in crystallization process
Nitrogen is sent, material gradually forms crystallizing layer in crystallization inner wall of tower, lower section liquid is discharged, is stopped when no longer precipitating crystal cold
But, crystallizing layer solid, the p-chlorotoluene purified are collected.
Specifically, it is 1:1.5 that catalyst, which is the mass ratio of natural activity zeolite and sulfur dichloride, in the step 1.
Toluene conversion, adjacency pair ratio, dichloride and purity is such as during the preparation process for 1~embodiment of above-described embodiment 6
Shown in table 1:
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 |
| Toluene conversion/% | 99.6 | 99.7 | 99.8 | 99.8 | 99.8 | 99.7 |
| Adjacency pair ratio | 0.83 | 0.82 | 0.81 | 0.81 | 0.80 | 0.81 |
| Dichloride/% | 1.5 | 1.4 | 1.3 | 1.3 | 1.2 | 1.3 |
| Purity/% | 99 | 99 | 99 | 99 | 99 | 99 |
Table 1
The above is only a preferred embodiment of the present invention, it should be understood that the present invention is not limited to described herein
Form should not be regarded as an exclusion of other examples, and can be used for other combinations, modifications, and environments, and can be at this
In the text contemplated scope, modifications can be made through the above teachings or related fields of technology or knowledge.And those skilled in the art institute into
Capable modifications and changes do not depart from the spirit and scope of the present invention, then all should be in the protection scope of appended claims of the present invention
It is interior.
Claims (9)
1. the production technology that a kind of oriented chlorination of toluene prepares p-chlorotoluene, which comprises the steps of:
Step 1: chlorination: catalyst being added in reaction vessel, then toluene is added in reaction vessel, is passed through inert gas row
Air in reaction vessel out, then will be put into thermostat after reaction vessel shading treatment, by dry chlorine and nitrogen
Be mixed to form to be passed through again in thermostat after chloridating gas and carry out chlorination reaction, reaction end gas using purified water absorb to be formed it is water-soluble
Aqueous solution is carried out chromatography to judge reaction end by liquid, and the mixture for obtaining chlorination is stand-by；
Step 2: rectifying: the mixture of chlorination in step 1 being added in rectifying column and carries out rectifying, adjusts reflux ratio as 2:1 receipts
Collect temperature and be 109 ~ 113 DEG C of front-end volatiles, then adjusting reflux ratio is 10:1, collects the fraction that temperature is 158 ~ 162 DEG C, obtains
Neighbour, p-chlorotoluene mixed liquor are stand-by；
Step 3: primary purifying: adjacent, p-chlorotoluene mixed liquor in step 2 being fitted into crystallizing tower, crystallizing tower outer wall winding knot
Crystalline substance pipe, wherein crystallizing tank, which is passed through cooling medium, makes material decrease temperature crystalline in container, supplies gas in crystallization process to crystallizing tower drum
Body, material gradually form crystallizing layer in crystallization inner wall of tower, lower section liquid are discharged, and stop cooling when no longer precipitating crystal；
Step 4: secondarily purified: after temperature warms naturally to 10 DEG C in crystallizing tower, crystallizer is passed through cooling medium again to be made to hold
Material decrease temperature crystalline in device, supplies gas body to crystallizing tower drum in crystallization process, and material gradually forms crystallization in crystallization inner wall of tower
Layer, lower section liquid is discharged, and stops cooling when no longer precipitating crystal, and collects crystallizing layer solid, the p-chlorotoluene purified.
2. the production technology that a kind of oriented chlorination of toluene according to claim 1 prepares p-chlorotoluene, which is characterized in that institute
Stating the molar ratio of toluene and chlorine in step 1 is 1:(0.6 ~ 0.7)；The mass ratio of catalyst and toluene is in the step 1
1:(120 ~ 130)；The reaction temperature of thermostat is 20 ~ 50 DEG C in the step 1.
3. a kind of oriented chlorination of toluene according to claim 1 or 2 prepares the production technology of p-chlorotoluene, feature exists
In the mass ratio of catalyst and toluene is 1:(123 ~ 125 in the step 1), the reaction temperature of thermostat in the step 1
Degree is 30 ~ 40 DEG C.
4. a kind of oriented chlorination of toluene according to claim 1 or 2 prepares the production technology of p-chlorotoluene, feature exists
In it is 1:(1.5 ~ 2.0 that catalyst, which is the mass ratio of natural activity zeolite and co-catalyst, in the step 1).
5. the production technology that a kind of oriented chlorination of toluene according to claim 4 prepares p-chlorotoluene, which is characterized in that institute
Stating co-catalyst in step 1 is one of thioether, sulfur monochloride, sulfur dichloride, benzenethiol or mercaptan.
6. according to claim 1, a kind of 2 or 4 described in any item oriented chlorination of toluene prepare the production technology of p-chlorotoluene,
It is characterized in that, chlorine is dry using the concentrated sulfuric acid in the step 1；In the step 1 chloridating gas be passed through rate be 0.5 ~
0.6L/min, it according to volume ratio is 1:(0.8 ~ 1.0 that wherein chloridating gas, which is chlorine and nitrogen) it mixes.
7. according to claim 1, a kind of 2 or 4 described in any item oriented chlorination of toluene prepare the production technology of p-chlorotoluene,
It is characterized in that, the chromatograph of the chromatography is 102G gas chromatograph, and chromatography is conductance cell detection, chromatography
Carrier gas is nitrogen, and the column temperature of chromatography is 90 DEG C, and gasification room temperature is 210 DEG C.
8. the production technology that a kind of oriented chlorination of toluene according to claim 1 prepares p-chlorotoluene, which is characterized in that institute
Stating cooling medium in step 3 is brine ice, and the gas that crystallizing tower drum is sent in the step 3 is nitrogen；It is cold in the step 4
But medium is brine ice；The gas that crystallizing tower drum is sent in the step 4 is nitrogen.
9. the production technology that a kind of oriented chlorination of toluene according to claim 8 prepares p-chlorotoluene, which is characterized in that institute
The mass fraction for stating sodium chloride in brine ice in step 3 is 21 ~ 24%；The quality of sodium chloride is divided in brine ice in the step 4
Number is 21 ~ 24%.
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| CN116052789A (en) * | 2023-03-29 | 2023-05-02 | 河北大景大搪化工设备有限公司 | Toluene chlorination parameter automatic optimization system based on deep learning |
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| CN112194554A (en) * | 2020-11-05 | 2021-01-08 | 湖北山水化工有限公司 | Preparation process and production process system of (o) p-chlorotoluene |
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