CN113831212A - Method for producing o-dichlorobenzene by using o-nitrochlorobenzene as raw material through one-pot method - Google Patents
Method for producing o-dichlorobenzene by using o-nitrochlorobenzene as raw material through one-pot method Download PDFInfo
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- CN113831212A CN113831212A CN202010510640.2A CN202010510640A CN113831212A CN 113831212 A CN113831212 A CN 113831212A CN 202010510640 A CN202010510640 A CN 202010510640A CN 113831212 A CN113831212 A CN 113831212A
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- dichlorobenzene
- nitrochlorobenzene
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- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 239000002994 raw material Substances 0.000 title claims abstract description 66
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 238000005580 one pot reaction Methods 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 94
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 239000000463 material Substances 0.000 claims abstract description 45
- 239000002131 composite material Substances 0.000 claims abstract description 35
- HVZWVEKIQMJYIK-UHFFFAOYSA-N nitryl chloride Chemical compound [O-][N+](Cl)=O HVZWVEKIQMJYIK-UHFFFAOYSA-N 0.000 claims abstract description 29
- -1 azo compound Chemical class 0.000 claims abstract description 26
- 150000002978 peroxides Chemical class 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000460 chlorine Substances 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 238000009833 condensation Methods 0.000 claims abstract description 6
- 230000005494 condensation Effects 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- 238000002791 soaking Methods 0.000 claims description 21
- 239000000853 adhesive Substances 0.000 claims description 16
- 230000001070 adhesive effect Effects 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 16
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000007605 air drying Methods 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910010293 ceramic material Inorganic materials 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 5
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 claims description 4
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical compound [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 229960004995 magnesium peroxide Drugs 0.000 claims description 3
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 claims description 2
- 229940105296 zinc peroxide Drugs 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 238000005660 chlorination reaction Methods 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000006193 diazotization reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- IZUKQUVSCNEFMJ-UHFFFAOYSA-N 1,2-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1[N+]([O-])=O IZUKQUVSCNEFMJ-UHFFFAOYSA-N 0.000 description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- GBDZXPJXOMHESU-UHFFFAOYSA-N 1,2,3,4-tetrachlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1Cl GBDZXPJXOMHESU-UHFFFAOYSA-N 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- BYBLEWFAAKGYCD-UHFFFAOYSA-N Miconazole Chemical compound ClC1=CC(Cl)=CC=C1COC(C=1C(=CC(Cl)=CC=1)Cl)CN1C=NC=C1 BYBLEWFAAKGYCD-UHFFFAOYSA-N 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229960002509 miconazole Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for producing o-dichlorobenzene by using o-nitrochlorobenzene as a raw material through a one-pot method. Based on a continuous reactor, the continuous reactor is a reaction device formed by communicating a reaction kettle and a catalyst packed tower, an opening of the reaction kettle is directly connected with an inlet at the bottom of a tower body, the reaction kettle is provided with a feeding port and a vent, a gas outlet is arranged at the top of the catalyst packed tower, o-nitrochlorobenzene and continuously introduced chlorine are used as raw materials, a composite catalyst of peroxide and an azo compound is used as a catalyst, the nitrochlorination reaction is carried out in the continuous reactor under the conditions of 225 plus materials and 255 ℃ and 0.11-0.15Mpa to generate o-dichlorobenzene and tail gas nitryl chloride, the o-dichlorobenzene and the tail gas nitryl chloride are led out from the outlet at the top of the tower together, liquid o-dichlorobenzene is obtained by condensation, and the o-dichlorobenzene and the tail gas nitryl chloride stay in the catalyst packed tower for 5-20 min. The method for synthesizing o-dichlorobenzene at high temperature in short time has the advantages of remarkably reducing energy consumption, few byproducts, no isomer and high conversion rate which can reach more than 95%.
Description
Technical Field
The invention relates to a method for producing o-dichlorobenzene, in particular to a method for producing o-dichlorobenzene by using o-nitrochlorobenzene as a raw material through a one-pot method.
Background
O-dichlorobenzene is colorless liquid, aromatic, melting point-17 deg.C, insoluble in water, soluble in ethanol and ether, and soluble in organic solvent benzene. The o-dichlorobenzene can be used as an intermediate of the broad-spectrum antifungal drug miconazole, and the traditional synthetic method comprises the following steps: 1) phenylenediamine, sulfuric acid and sodium nitrite are subjected to diazotization reaction to prepare diazonium salt, and then chlorination is carried out to obtain the product; 2) the o-chloroaniline is prepared by diazotization and chlorination, and the diazotization method of the o-chloroaniline has low synthesis rate and low productivity; 3) direct catalytic chlorination of o-dinitrobenzene; 4) benzene chlorination method, which has the disadvantages of difficult process control conditions and low separation efficiency. Among them, the phenylenediamine diazotization method has a complex synthesis process and is eliminated. The o-dinitrobenzene chlorination method has the explosive o-dinitrobenzene, so that great potential safety hazards exist in the synthesis process.
The Chinese patent with publication number CN102976886A, 03 and 20 in 2013, discloses a method for synthesizing o-dichlorobenzene, which adopts an iron ring and fluorspar as catalysts, and compared with the traditional synthesis method, the method has the advantages that the raw material consumption is reduced, the total energy (including the sum of the productivity of p-dichlorobenzene, chlorobenzene and o-dichlorobenzene) is improved, but the consumption of the catalysts is large, the productivity of o-dichlorobenzene is not obviously improved, a large number of byproducts are produced, the production process cannot be continuously carried out, the production efficiency is low, and reaction residues cannot be effectively utilized. The present invention aims to solve this technical problem.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a method for producing o-dichlorobenzene by using o-nitrochlorobenzene as a raw material through a one-pot method, wherein o-nitrochlorobenzene is used as the raw material to synthesize o-dichlorobenzene at high temperature in a short time, so that the energy consumption is obviously reduced, byproducts are few, isomers are not generated, the conversion rate is high and can reach more than 95%, an additional purification step is not needed, and the purity controllability and the yield of the target product o-dichlorobenzene are good.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for producing ortho-dichlorobenzene by using ortho-nitrochlorobenzene as a raw material through a one-pot method is based on a continuous reactor, the continuous reactor is a reaction device formed by communicating a reaction kettle and a catalyst packed tower, an opening of the reaction kettle is directly connected with an inlet at the bottom of a tower body, the reaction kettle is provided with a feeding port and an air vent, the top of the catalyst packed tower is provided with a gas outlet, the method comprises the steps of taking o-nitrochlorobenzene and continuously introduced chlorine as raw materials, taking a compound catalyst of peroxide and an azo compound as a catalyst, carrying out a nitrochlorination reaction in a continuous reactor at the temperature of 225 plus 255 ℃ and under the pressure of 0.11-0.15Mpa to generate o-dichlorobenzene and tail gas nitryl chloride, leading the o-dichlorobenzene and the tail gas nitryl chloride out from a leading-out opening at the top of a tower together, condensing to obtain liquid o-dichlorobenzene, and keeping the o-dichlorobenzene and the tail gas nitryl chloride in a catalyst packed tower for 5-20 min.
Preferably, the catalyst filler is loaded by a three-dimensional porous fixed bed base material, and the preparation process comprises the following steps: fully coating or soaking a fixed bed base material in an aqueous adhesive, taking out the base material, and naturally air-drying the base material in a dust-free environment, wherein the fixed bed base material comprises three-dimensional structural foamed nickel, foamed aluminum or porous ceramic material, and the aqueous adhesive is prepared from the following raw materials in percentage by mass: 30-40% of ethyl orthosilicate, 3-5% of citric acid and the balance of deionized water, wherein the total amount of the raw materials is 100%; the air-dried fixed bed base material is coated with a soaking compound catalyst, and the compound catalyst comprises the following components in percentage by weight: 8-12% of peroxide, 10-25% of azo compound and the balance of absolute ethyl alcohol, wherein the total amount of the raw materials is 100%; after the process of soaking the composite catalyst is finished, drying the composite catalyst in an oven at the temperature of 280-320 ℃ for 1-1.5 h.
Preferably, the molar ratio of the composite catalyst to the raw material o-nitrochlorobenzene is 2: 3-100.
Preferably, the molar ratio of the composite catalyst to the raw material o-nitrochlorobenzene is 3-100.
Preferably, the peroxide is any one of sodium peroxide, potassium peroxide, magnesium peroxide and zinc peroxide, and the azo compound is azobisisobutyronitrile or azobisisovaleronitrile.
Preferably, the peroxide is sodium peroxide or potassium peroxide, and the azo compound is azobisisobutyronitrile.
Preferably, the reaction temperature is 240-245 ℃, the reaction pressure is 0.12-0.13Mpa, and the retention time is 10-15 min.
Preferably, the reaction temperature is 242 ℃, the reaction pressure is 0.12MPa, and the retention time is 15 min.
Preferably, the aqueous adhesive is prepared by processing the following raw materials in percentage by mass: 35% of ethyl orthosilicate, 4% of citric acid and the balance of deionized water.
Preferably, the composite catalyst comprises the following components in percentage by weight: 10% of peroxide, 20% of azo compound and the balance of absolute ethyl alcohol.
The invention has the beneficial effects that:
the invention realizes continuous production of o-dichlorobenzene, the production scale can be adjusted according to requirements, different production requirements are met, the complex catalyst is adopted for catalytic chlorination, the reaction conditions are high temperature, low pressure and short time, the process operation is simple, the synthetic route is short, the reaction selectivity is good, and the product purity reaches more than 99.8%. The problem that the monochlorobenzene, the o-and p-dichlorobenzene, the trichlorobenzene and even the tetrachlorobenzene in the reaction products in the prior art are difficult to separate is solved. The nitryl chloride tail gas can be well treated based on the treatment means in the prior art, the environmental pollution is avoided, and the three wastes are less.
In addition, the fixed bed substrate of the composite catalyst has larger specific surface area, better penetrability and medium circulation. Particularly, the composite catalyst is attached to a three-dimensional porous fixed bed substrate, so that a large catalytic chlorination contact surface is provided, the catalytic reaction efficiency is high, and the selectivity is good.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples.
In examples 1 to 5 of the present invention, all the crystallizers used were commercially available conventional crystallizers, and each of the raw materials was a commercially available conventional raw material.
Example 1:
the method for producing the o-dichlorobenzene by the one-pot method by taking the o-nitrochlorobenzene as the raw material is based on a continuous reactor, the continuous reactor is a reaction device formed by communicating a reaction kettle and a catalyst packed tower, an opening of the reaction kettle is directly connected with an inlet at the bottom of a tower body, the reaction kettle is provided with a feeding port and an air vent, the top of the catalyst packed tower is provided with an air outlet, the o-nitrochlorobenzene and continuously introduced chlorine are taken as raw materials, a composite catalyst of peroxide and an azo compound is taken as a catalyst, the nitrochlorination reaction is carried out in the continuous reactor under the condition of 220 ℃ and 0.11MPa to generate the o-dichlorobenzene and tail gas nitryl chloride, the o-dichlorobenzene and the tail gas nitryl chloride are led out from the outlet at the top of the tower together with the tail gas nitryl chloride, liquid o-dichlorobenzene is obtained by condensation, the o-dichlorobenzene and the tail gas nitryl chloride stay for 5min in the catalyst packed tower, the catalyst packed material is loaded by a three-dimensional porous fixed bed base material, the preparation process comprises the following steps: fully coating or soaking a fixed bed base material in an aqueous adhesive, taking out the base material, and naturally air-drying the base material in a dust-free environment, wherein the fixed bed base material comprises three-dimensional structural foamed nickel, foamed aluminum or porous ceramic material, and the aqueous adhesive is prepared from the following raw materials in percentage by mass: 30% of ethyl orthosilicate, 3% of citric acid and the balance of deionized water, wherein the total amount of the raw materials is 100%; the air-dried fixed bed base material is coated with a soaking compound catalyst, and the compound catalyst comprises the following components in percentage by weight: 8% of peroxide, 10% of azo compound and the balance of absolute ethyl alcohol, wherein the total amount of the raw materials is 100%; and (3) after the process of soaking the composite catalyst is finished, drying the composite catalyst in an oven at 280 ℃ for 1h, wherein the molar ratio of the composite catalyst to the raw material o-nitrochlorobenzene is 2: 100, the peroxide is sodium peroxide, and the azo compound is azobisisobutyronitrile.
Example 2:
the method for producing the o-dichlorobenzene by the one-pot method by taking the o-nitrochlorobenzene as the raw material is based on a continuous reactor, the continuous reactor is a reaction device formed by communicating a reaction kettle and a catalyst packed tower, an opening of the reaction kettle is directly connected with an inlet at the bottom of a tower body, the reaction kettle is provided with a feeding port and an air vent, the top of the catalyst packed tower is provided with an air outlet, the o-nitrochlorobenzene and continuously introduced chlorine are taken as raw materials, a composite catalyst of peroxide and an azo compound is taken as a catalyst, the nitrochlorination reaction is carried out in the continuous reactor under the condition of 255 ℃ and 0.15MPa to generate the o-dichlorobenzene and tail gas nitryl chloride, the o-dichlorobenzene and the tail gas nitryl chloride are led out from the outlet at the top of the tower together with the tail gas nitryl chloride, liquid o-dichlorobenzene is obtained by condensation, the o-dichlorobenzene and the tail gas nitryl chloride stay for 20min in the catalyst packed tower, the catalyst packed material is loaded by a three-dimensional porous fixed bed base material, the preparation process comprises the following steps: fully coating or soaking a fixed bed base material in an aqueous adhesive, taking out the base material, and naturally air-drying the base material in a dust-free environment, wherein the fixed bed base material comprises three-dimensional structural foamed nickel, foamed aluminum or porous ceramic material, and the aqueous adhesive is prepared from the following raw materials in percentage by mass: 40% of ethyl orthosilicate, 5% of citric acid and the balance of deionized water, wherein the total amount of the raw materials is 100%; the air-dried fixed bed base material is coated with a soaking compound catalyst, and the compound catalyst comprises the following components in percentage by weight: 12% of peroxide, 25% of azo compound and the balance of absolute ethyl alcohol, wherein the total amount of the raw materials is 100%; and after the process of soaking the composite catalyst is finished, drying the composite catalyst in a drying oven at 320 ℃ for 1.5 hours, wherein the molar ratio of the composite catalyst to the raw material o-nitrochlorobenzene is 3-100, the peroxide is potassium peroxide, and the azo compound is azobisisovaleronitrile.
Example 3:
the method for producing the o-dichlorobenzene by the one-pot method by taking the o-nitrochlorobenzene as the raw material is based on a continuous reactor, the continuous reactor is a reaction device formed by communicating a reaction kettle and a catalyst packed tower, an opening of the reaction kettle is directly connected with an inlet at the bottom of a tower body, the reaction kettle is provided with a feeding port and an air vent, the top of the catalyst packed tower is provided with an air outlet, the o-nitrochlorobenzene and continuously introduced chlorine are taken as raw materials, a composite catalyst of peroxide and an azo compound is taken as a catalyst, the nitrochlorination reaction is carried out in the continuous reactor at 230 ℃ and 0.12MPa to generate the o-dichlorobenzene and tail gas nitryl chloride, the o-dichlorobenzene is led out from the outlet at the top of the tower along with the tail gas nitryl chloride, liquid o-dichlorobenzene is obtained by condensation, the o-dichlorobenzene and the tail gas nitryl chloride stay for 10min in the catalyst packed tower, the catalyst packed is loaded by a three-dimensional porous fixed bed base material, the preparation process comprises the following steps: fully coating or soaking a fixed bed base material in an aqueous adhesive, taking out the base material, and naturally air-drying the base material in a dust-free environment, wherein the fixed bed base material comprises three-dimensional structural foamed nickel, foamed aluminum or porous ceramic material, and the aqueous adhesive is prepared from the following raw materials in percentage by mass: 35% of ethyl orthosilicate, 4% of citric acid and the balance of deionized water, wherein the total amount of the raw materials is 100%; the air-dried fixed bed base material is coated with a soaking compound catalyst, and the compound catalyst comprises the following components in percentage by weight: 10% of peroxide, 20% of azo compound and the balance of absolute ethyl alcohol, wherein the total amount of the raw materials is 100%; and (3) after the process of soaking the composite catalyst is finished, drying the composite catalyst in an oven at 300 ℃ for 1h, wherein the molar ratio of the composite catalyst to the raw material o-nitrochlorobenzene is 3-100, the peroxide is magnesium peroxide, and the azo compound is azobisisobutyronitrile.
Example 4:
the method for producing the o-dichlorobenzene by the one-pot method by taking the o-nitrochlorobenzene as the raw material is based on a continuous reactor, the continuous reactor is a reaction device formed by communicating a reaction kettle and a catalyst packed tower, an opening of the reaction kettle is directly connected with an inlet at the bottom of a tower body, the reaction kettle is provided with a feeding port and an air vent, a gas outlet is arranged at the top of the catalyst packed tower, the o-nitrochlorobenzene and continuously introduced chlorine are taken as raw materials, a composite catalyst of peroxide and an azo compound is taken as a catalyst, nitrochlorination reaction is carried out in the continuous reactor under the conditions of 240 ℃ and 255 ℃ and 0.12MPa to generate the o-dichlorobenzene and tail gas nitryl chloride, the o-dichlorobenzene and the tail gas nitryl chloride are led out from the outlet at the top of the tower together with the tail gas nitryl chloride and condensed to obtain liquid o-dichlorobenzene, and the retention time of the o-dichlorobenzene and the tail gas nitryl chloride in the catalyst packed tower is 10 min.
Preferably, the catalyst filler is loaded by a three-dimensional porous fixed bed base material, and the preparation process comprises the following steps: fully coating or soaking a fixed bed base material in an aqueous adhesive, taking out the base material, and naturally air-drying the base material in a dust-free environment, wherein the fixed bed base material comprises three-dimensional structural foamed nickel, foamed aluminum or porous ceramic material, and the aqueous adhesive is prepared from the following raw materials in percentage by mass: 35% of ethyl orthosilicate, 4% of citric acid and the balance of deionized water, wherein the total amount of the raw materials is 100%; the air-dried fixed bed base material is coated with a soaking compound catalyst, and the compound catalyst comprises the following components in percentage by weight: 10% of peroxide, 20% of azo compound and the balance of absolute ethyl alcohol, wherein the total amount of the raw materials is 100%; and (3) after the process of soaking the composite catalyst is finished, drying the composite catalyst in a drying oven at 280 ℃ for 1.5 hours, wherein the molar ratio of the composite catalyst to the raw material o-nitrochlorobenzene is 3-100, the peroxide is sodium peroxide, and the azo compound is azobisisobutyronitrile.
Example 5:
the method for producing the o-dichlorobenzene by the one-pot method by taking the o-nitrochlorobenzene as the raw material is based on a continuous reactor, the continuous reactor is a reaction device formed by communicating a reaction kettle and a catalyst packed tower, an opening of the reaction kettle is directly connected with an inlet at the bottom of a tower body, the reaction kettle is provided with a feeding port and an air vent, the top of the catalyst packed tower is provided with an air outlet, the o-nitrochlorobenzene and continuously introduced chlorine are taken as raw materials, a composite catalyst of peroxide and an azo compound is taken as a catalyst, the nitrochlorination reaction is carried out in the continuous reactor at 245 ℃ and 0.13MPa to generate the o-dichlorobenzene and tail gas nitryl chloride, the o-dichlorobenzene is led out from the outlet at the top of the tower along with the tail gas nitryl chloride, liquid o-dichlorobenzene is obtained by condensation, the o-dichlorobenzene and the tail gas nitryl chloride stay for 10min in the catalyst packed tower, the catalyst packed is loaded by a three-dimensional porous fixed bed base material, the preparation process comprises the following steps: fully coating or soaking a fixed bed base material in an aqueous adhesive, taking out the base material, and naturally air-drying the base material in a dust-free environment, wherein the fixed bed base material comprises three-dimensional structural foamed nickel, foamed aluminum or porous ceramic material, and the aqueous adhesive is prepared from the following raw materials in percentage by mass: 35% of ethyl orthosilicate, 4% of citric acid and the balance of deionized water, wherein the total amount of the raw materials is 100%; the air-dried fixed bed base material is coated with a soaking compound catalyst, and the compound catalyst comprises the following components in percentage by weight: 10% of peroxide, 20% of azo compound and the balance of absolute ethyl alcohol, wherein the total amount of the raw materials is 100%; and (3) after the process of soaking the composite catalyst is finished, drying the composite catalyst in an oven at 300 ℃ for 1h, wherein the molar ratio of the composite catalyst to the raw material o-nitrochlorobenzene is 3-100, the peroxide is potassium peroxide, and the azo compound is azobisisovaleronitrile.
In examples 1 to 5, the purity and yield of o-dichlorobenzene produced by using o-nitrochlorobenzene as a raw material through a one-pot method are as follows:
note: molecular weight of o-nitrochlorobenzene: 157.5545, molecular weight of o-dichlorobenzene: 147
| Examples | O-nitrochlorobenzene (kg) | O-dichlorobenzene (kg) | Purity (%, GC method) | Molar yield (%) |
| Example 1 | 1575.54（10kmol） | 1403.85（9.55kmol） | 99.89% | 95.5% |
| Example 2 | 1575.54（10kmol） | 1417.08（9.64kmol） | 99.85% | 96.4% |
| Example 3 | 1575.54（10kmol） | 1411.2（9.6kmol） | 99.9% | 96.0% |
| Example 4 | 1575.54（10kmol） | 1417.67（9.644kmol） | 99.87% | 96.44% |
| Example 5 | 1575.54（10kmol） | 1417.08（9.64kmol） | 99.80% | 96.4% |
The invention realizes continuous production of o-dichlorobenzene, the production scale can be adjusted according to requirements, different production requirements are met, the complex catalyst is adopted for catalytic chlorination, the reaction conditions are high temperature, low pressure and short time, the process operation is simple, the synthetic route is short, the reaction selectivity is good, and the product purity reaches more than 99.8%. The problem that the monochlorobenzene, the o-and p-dichlorobenzene, the trichlorobenzene and even the tetrachlorobenzene in the reaction products in the prior art are difficult to separate is solved. The nitryl chloride tail gas can be well treated based on the treatment means in the prior art, the environmental pollution is avoided, and the three wastes are less. In addition, the fixed bed substrate of the composite catalyst has larger specific surface area, better penetrability and medium circulation. Particularly, the composite catalyst is attached to a three-dimensional porous fixed bed substrate, so that a large catalytic chlorination contact surface is provided, the catalytic reaction efficiency is high, and the selectivity is good.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (10)
1. A method for producing o-dichlorobenzene by a one-pot method by taking o-nitrochlorobenzene as a raw material is based on a continuous reactor, the continuous reactor is a reaction device formed by communicating a reaction kettle and a catalyst packed tower, the opening of the reaction kettle is directly connected with the inlet at the bottom of the tower body, the reaction kettle is provided with a feed inlet and an air vent, the top of the catalyst packed tower is provided with a gas outlet, the method is characterized in that o-nitrochlorobenzene and continuously introduced chlorine are used as raw materials, a compound catalyst of peroxide and an azo compound is used as a catalyst, nitrochlorination reaction is carried out in a continuous reactor at the temperature of 225 plus 255 ℃ and the pressure of 0.11-0.15Mpa to generate o-dichlorobenzene and tail gas nitryl chloride, the o-dichlorobenzene and the tail gas nitryl chloride are led out from a leading-out opening at the top of the tower together, liquid o-dichlorobenzene is obtained by condensation, and the retention time of the o-dichlorobenzene and the tail gas nitryl chloride in a catalyst packed tower is 5-20 min.
2. The method for producing o-dichlorobenzene by using o-nitrochlorobenzene as a raw material through a one-pot method according to claim 1, wherein a catalyst filler is loaded by a three-dimensional porous fixed bed base material, and the preparation process comprises the following steps: fully coating or soaking a fixed bed base material in an aqueous adhesive, taking out the base material, and naturally air-drying the base material in a dust-free environment, wherein the fixed bed base material comprises three-dimensional structural foamed nickel, foamed aluminum or porous ceramic material, and the aqueous adhesive is prepared from the following raw materials in percentage by mass: 30-40% of ethyl orthosilicate, 3-5% of citric acid and the balance of deionized water, wherein the total amount of the raw materials is 100%; the air-dried fixed bed base material is coated with a soaking compound catalyst, and the compound catalyst comprises the following components in percentage by weight: 8-12% of peroxide, 10-25% of azo compound and the balance of absolute ethyl alcohol, wherein the total amount of the raw materials is 100%; after the process of soaking the composite catalyst is finished, drying the composite catalyst in an oven at the temperature of 280-320 ℃ for 1-1.5 h.
3. The method for producing o-dichlorobenzene by using o-nitrochlorobenzene as a raw material through a one-pot method according to claim 1, wherein the molar ratio of the composite catalyst to the raw material o-nitrochlorobenzene is 2: 3-100.
4. The method for producing o-dichlorobenzene by using o-nitrochlorobenzene as a raw material through a one-pot method according to claim 3, wherein the molar ratio of the composite catalyst to the raw material o-nitrochlorobenzene is 3-100.
5. The method for producing o-dichlorobenzene by using o-nitrochlorobenzene as a raw material through a one-pot method according to claim 1, wherein the peroxide is any one of sodium peroxide, potassium peroxide, magnesium peroxide and zinc peroxide, and the azo compound is azobisisobutyronitrile or azobisisovaleronitrile.
6. The method for producing o-dichlorobenzene by using o-nitrochlorobenzene as a raw material through a one-pot method according to claim 5, wherein the peroxide is sodium peroxide or potassium peroxide, and the azo compound is azobisisobutyronitrile.
7. The method for producing o-dichlorobenzene by using o-nitrochlorobenzene as a raw material through a one-pot method according to claim 1, wherein the reaction temperature is 240-.
8. The method for producing o-dichlorobenzene by using o-nitrochlorobenzene as a raw material through a one-pot method according to claim 7, wherein the reaction temperature is 242 ℃, the reaction pressure is 0.12MPa, and the retention time is 15 min.
9. The method for producing o-dichlorobenzene by using o-nitrochlorobenzene as a raw material through a one-pot method according to claim 2, wherein the water-based adhesive is prepared by processing the following raw materials in percentage by mass: 35% of ethyl orthosilicate, 4% of citric acid and the balance of deionized water.
10. The method for producing o-dichlorobenzene by using o-nitrochlorobenzene as a raw material through a one-pot method according to claim 2, wherein the composite catalyst comprises the following components in percentage by weight: 10% of peroxide, 20% of azo compound and the balance of absolute ethyl alcohol.
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| Title |
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| 中华人民共和国物资管理部制订: "《物资技术保管规程 试行本 第四分册 化工和轻工》", 广州：广东科技出版社 * |
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