CN113563153B - Method for preparing monochloro-ortho-xylene by continuous chlorination of ortho-xylene - Google Patents
Method for preparing monochloro-ortho-xylene by continuous chlorination of ortho-xylene Download PDFInfo
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- 238000005660 chlorination reaction Methods 0.000 title claims abstract description 221
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 238000000034 method Methods 0.000 title claims abstract description 40
- NVLHGZIXTRYOKT-UHFFFAOYSA-N 1-chloro-2,3-dimethylbenzene Chemical group CC1=CC=CC(Cl)=C1C NVLHGZIXTRYOKT-UHFFFAOYSA-N 0.000 title claims abstract description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 102
- 239000000460 chlorine Substances 0.000 claims abstract description 102
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 102
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- 229940078552 o-xylene Drugs 0.000 claims abstract description 54
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000007872 degassing Methods 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000002841 Lewis acid Substances 0.000 claims abstract description 14
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 14
- 238000003860 storage Methods 0.000 claims abstract description 11
- 239000000376 reactant Substances 0.000 claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 109
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 18
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- -1 chloro compound Chemical class 0.000 claims description 6
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 claims description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 239000007769 metal material Substances 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 239000000523 sample Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 13
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000010907 mechanical stirring Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- UERPUZBSSSAZJE-UHFFFAOYSA-N 3-chlorophthalic anhydride Chemical compound ClC1=CC=CC2=C1C(=O)OC2=O UERPUZBSSSAZJE-UHFFFAOYSA-N 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000011552 falling film Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011344 liquid material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- DFOZLRWOCDRNDA-UHFFFAOYSA-N 4,5-dichloroisoindole-1,3-dione Chemical compound ClC1=CC=C2C(=O)NC(=O)C2=C1Cl DFOZLRWOCDRNDA-UHFFFAOYSA-N 0.000 description 1
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- 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
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present disclosure provides a method for preparing monochloro-ortho-xylene by continuous chlorination of ortho-xylene, comprising: (1) Adding dried o-xylene and Lewis acid into a batching kettle according to a proportion, and uniformly stirring; (2) Reactants in the batching kettle are introduced into the tower kettle combined chlorination reactor through a reaction tower in the tower kettle combined chlorination reactor, and dried chlorine is introduced into the tower kettle combined chlorination reactor, so that the ratio of o-xylene to chlorine is controlled to carry out continuous chlorination reaction; (3) And (3) delivering the chloride of the reaction product of the tower kettle combined chlorination reactor into a degassing tower, removing HCl and residual chlorine in the degassing tower, and delivering the chloride into a chloride storage tank. The method adopts the combination of the kettle reactor and the tower reactor, and can realize the purpose of safely and efficiently producing the chloro-o-xylene.
Description
Technical Field
The disclosure relates to the field of chemical production processes, in particular to a method for preparing monochloro-ortho-xylene by continuously chlorinating ortho-xylene.
Background
In recent years, with the rapid development of polyimide industry, the demand for dianhydride monomers is also increasing. The monochlorophthalic anhydride prepared by oxidizing monochloro-o-xylene is an ideal raw material for synthesizing a plurality of dianhydride monomers, and even polyimide can be directly synthesized by dichlorophthalimide and bisphenolate, so that the production cost of the polyimide is greatly reduced. Little research is currently done on monochloroortho-xylene, and only patent CN1080278A discloses an example of batch chlorination in a tank reactor. Similar to the o-xylene chlorination process, benzene chlorination to chlorobenzene and toluene chlorination to monochlorotoluene are two common industrial production schemes:
an intermittent chlorination process of a kettle reactor is quite similar to the orthoxylene disclosed in patent CN1080278A, has the same problems as low production efficiency, low chlorine utilization rate (less than 90 percent and only 82 percent), and large holding quantity of reaction equipment;
a continuous chlorination process using tower reactor features that no catalyst is added, a large number of iron rings are installed in reaction tower, and the water in toluene is used to react in chlorine state to generate FeCl 3 As a catalyst. The scheme realizes continuous production, but has larger potential safety hazard, and is specifically embodied as the following aspects: firstly, chlorine and water react to generate hypochlorous acid in the process of generating hydrochloric acid, and the hypochlorous acid generates atomic oxygen or oxygen with higher activity when heated; on the other hand, hydrochloric acid reacts with the iron ring to generate FeCl 2 Hydrogen is generated at the same time. Thus, chlorine, hydrogen, oxygen and explosive raw materials exist in the reaction system at the same time, and the production is at risk. The cause of the explosion which often occurs in the absorption of tail gases in the production of chlorobenzene and chlorotoluene is the result of this, which makes the chlorination of otherwise safer aromatic hydrocarbons dangerous in this case. Some chlorination safety accidents are also caused by explosion of chlorine, hydrogen and oxygen reactions. In addition, the tower reactor has the advantages of no stirring, poor heat transfer and easy occurrence of the condition of carbonization of materials caused by local overheating, and is called black materials in the industry. Such local overheating also presents a safety risk.
Monochloro-ortho-xylene is a feasible method for industrial production of monochlorophthalic anhydride compared with air oxidation, but literature for preparing chloro-ortho-xylene by using ortho-xylene as a raw material is rarely disclosed. Patent CN1080278A discloses a method in which o-xylene is used as a raw material, lewis acids such as ferric trichloride, aluminum trichloride, antimony trichloride, tin tetrachloride or the like or iodine, iron or the like are used as a catalyst in a stirred reactor, and chlorine is used for direct chlorination to obtain monochloro-o-xylene. The process is exposed to the following deficiencies in industrial practice:
(1) Because the heat exchange area of the jacket of the chlorination reactor is limited, the heat transfer of the reaction is not in time, the temperature of the system is increased, and polychloride is easy to generate.
(2) The chlorine introduced into the bottom of the chlorination kettle is in contact with o-xylene for too short, so that insufficient reaction is caused, a part of chlorine escapes, the loss of raw materials is caused, and the trouble of tail gas aftertreatment and even pollution are brought.
(3) The chlorination reaction is a dangerous process, the kettle type chlorination reaction can only adopt intermittent reaction, and under the condition of the same productivity, compared with a continuous reaction device, the intermittent device has larger instant holding quantity, and the serious damage caused by accidents is larger.
(4) The intermittent reaction process device has more troublesome automatic control, more production operators and does not meet the requirements of modern chemical safety management.
Disclosure of Invention
In view of the above problems, the present disclosure provides a method for producing monochloro-ortho-xylene by continuous chlorination of ortho-xylene, comprising:
(1) Adding dried o-xylene and Lewis acid into a batching kettle according to a proportion, and uniformly stirring;
(2) Adding materials in a batching kettle into a tower kettle combined chlorination reactor from the upper part of a reaction tower, introducing dried chlorine into the tower kettle combined chlorination reactor, and controlling the ratio of o-xylene to chlorine so as to carry out continuous chlorination reaction;
(3) And (3) delivering the chloride of the reaction product of the tower kettle combined chlorination reactor into a degassing tower, removing HCl and residual chlorine in the degassing tower, and delivering the chloride into a chloride storage tank.
In a preferred embodiment, the chlorination reaction temperature is controlled between 0 and 80 ℃ to obtain the chloro compound.
In a preferred embodiment, the heat released by the chlorination reaction is removed by a combination of the circulating water outside the chlorination reactor and an off-tank cooler at the bottom of the column for better control of the chlorination reaction temperature and safety of the chlorination reaction system.
In a preferred embodiment, the purity of both o-xylene and chlorine is greater than 99.5% and the water content is less than 400ppm, preferably less than 100ppm.
In a preferred embodiment, in step (2), the combined reactor comprises a reaction tower directly mounted on the combined chlorination reactor, and also comprises a combined chlorination reactor and a reaction tower connected to the combined chlorination reactor through a pipe.
In a preferred embodiment, the material of the tower kettle combined reactor comprises a non-metallic material with a corrosion-resistant metal lining, such as enamel, polytetrafluoroethylene and the like; also included are corrosion resistant metallic materials such as titanium alloys, zirconium alloys, hastelloy, and the like.
In a preferred embodiment, in step (2), the combined column and vessel reactor comprises a single stage and multiple stages. The continuous chlorination operation can be realized by a single stage, and the effect is better by adopting a multi-stage series operation. In a preferred embodiment, in step (2), the combined column reactor may comprise a primary combined column reactor, a secondary combined column reactor. In a preferred embodiment, the structural form of the reaction tower of the tower kettle combined reactor comprises a packed tower, a sieve plate tower and a bubble cap tower.
In a preferred embodiment, the reaction columns of the multistage column bottoms combined reactor can be optionally combined from a variety of configurations.
In a preferred embodiment, the chlorination reaction temperature in the single stage bottoms combined reactor is controlled to be in the range of 0-80 ℃.
In a preferred embodiment, the chlorination reaction temperature of each stage of the multi-stage combined reactor is controlled to be 0-80 ℃; preferably, the chlorination reaction temperature of each stage of tower kettle combined reactor can be optionally selected within the range of 0-80 ℃, for example, the preferred range can be selected according to practical situations, such as: 0-40deg.C, 5-40deg.C, 10-25deg.C, 30-40deg.C, 30-70deg.C, etc.
In a preferred embodiment, in the step (2), the dried chlorine gas is introduced into the liquid material of the column-bottom combined chlorination reactor through a gas distributor at the lower part of the column-bottom combined chlorination reactor to carry out bubbling reaction, and the gas generated in the chlorination reaction is captured by a reaction column and a condenser at the upper part of the column-bottom combined chlorination reactor and then enters an HCl absorption process. Continuously extracting the reacted materials by a circulating pump below the tower kettle combined chlorination reactor, and directly entering a degassing tower in a single-stage tower kettle combined reactor device; in the multistage series tower kettle combined reactor device, the materials produced by the last stage tower kettle combined reactor are sent into a degassing tower by a circulating pump after entering the next stage tower kettle combined reactor through the top of the next stage reaction tower. After continuous chlorination is started, part of materials are circulated between the tower kettle combined chlorination reactor and the reaction tower through a circulating pump, and the part of materials added at the top of the tower react with chlorine escaping from the tower kettle combined chlorination reactor, so that the chlorine is fully utilized.
In a preferred embodiment, in step (2), the combined column reactor comprises a primary combined column reactor, a secondary combined column reactor, and a tertiary combined column reactor.
In a preferred embodiment, in step (2), a four-stage bottoms combined reactor is optionally also included.
In a preferred embodiment, in step (2), o-xylene is used as follows: the chlorine is introduced into the reactor with the molar ratio of 1:0.3-0.8.
In a preferred embodiment, in the first-stage bottoms combined reactor, ortho-xylene is reacted as: the chlorine is introduced into the reactor in a molar ratio of 1:0.5-0.8, and the chlorination reaction temperature is controlled to be 30-70 ℃. Preferably, in the primary tower kettle combined reactor, the chlorination reaction temperature is controlled to be 30-40 ℃.
In a secondary tower kettle combined reactor, o-xylene is mixed according to the following weight: the chlorine is introduced into the reactor in a molar ratio of 1:0.4-0.6, and the chlorination reaction temperature is controlled to be 5-40 ℃. Preferably, in the secondary tower kettle combined reactor, the chlorination reaction temperature is controlled to be 30-35 ℃.
In a three-stage tower kettle combined reactor, o-xylene is mixed according to the following ratio: the chlorine is introduced into the reactor in a molar ratio of 1:0.3-0.5, and the chlorination reaction temperature is controlled to be 0-40 ℃. Preferably, in the three-stage tower kettle combined reactor, the chlorination reaction temperature is controlled to be 10-25 ℃.
In a preferred embodiment, in step (1), the molar ratio of ortho-xylene to Lewis acid is from 100:0.01 to 1. Preferably, the molar ratio of ortho-xylene to Lewis acid is from 100:0.1 to 0.5.
In a preferred embodiment, the lewis acid is selected from one or a mixture of several of ferric trichloride, aluminum trichloride, antimony trichloride, tin tetrachloride.
In a preferred embodiment, the method further comprises:
and cooling the chloro compound which is a reaction product of the tower kettle combined chlorination reactor before the chloro compound is sent to the degassing tower.
In a preferred embodiment, the method further comprises:
and the degasser is used for removing hydrogen chloride gas and a small amount of chlorine in the materials.
In a preferred embodiment, the degasser is a continuous degasser. Preferably, the continuous degasser is a packed column.
In a preferred embodiment, the method further comprises:
the tail gas generated by the tower kettle combined chlorination reactor and the tail gas or flue gas of the degassing tower are converged and then enter an HCl absorber, a falling film absorber or other absorbers can be adopted for converting hydrogen chloride gas into hydrochloric acid, and the absorbed tail gas enters an alkaline washing tower for washing and purifying and then is discharged.
The method adopts the combination of the kettle reactor and the tower reactor, plays the advantages of the kettle reactor and the tower reactor, overcomes the defects of the kettle reactor and the tower reactor, and can realize the purpose of safely and efficiently producing chloro-o-xylene.
The advancement of the present disclosure has the following aspects:
1. the reactor is combined with the chlorination reactor to realize continuous chlorination reaction, and the reactor has high efficiency, less holding quantity per unit productivity and good safety compared with a single kettle reactor.
2. The materials added from the top of the reaction tower and the materials circulated by the circulating pump can react with the chlorine escaping from the tower kettle combined chlorination reactor in the reaction tower, so that the chlorine is effectively captured and utilized, the cost can be reduced, and the chlorination safety can be greatly improved.
3. Drying o-xylene and liquid chlorine to reduce hypochlorous acid generated by the reaction of chlorine and water so as to generate oxygen, and directly adding a catalyst; instead of the catalyst synthesized by the reaction of moisture in materials, chlorine and metallic iron, which is commonly used in the prior industry for aromatic chlorination, the generation of hydrogen is avoided, and the safety of a reaction system is improved.
4. For deacidification of chlorinated matters generated by the chlorination reaction, the invention adopts the degassing tower with higher efficiency, uses nitrogen to remove residual hydrogen chloride gas in the chlorinated matters, and enters the hydrogen chloride absorber together with the hydrogen chloride gas generated by the chlorination reaction to be converted into hydrochloric acid, and can adopt the falling film absorber to absorb HCl, and the residual tail gas is neutralized by the alkaline washing tower, so that continuous production can be conveniently realized, workshop operators can be reduced, waste utilization can be realized, and a large amount of waste water difficult to treat can be reduced.
5. The invention adds the external circulation heat exchanger, so that the reaction heat can be transferred through two channels of circulating water of the jacket outside the tower kettle combined chlorination reactor and a cooler outside the kettle, the temperature control is more accurate and convenient, the invention has important significance for reducing the generation of polychlorinated o-xylene, and the situations of carbonization of materials caused by local overhigh temperature rise due to poor heat transfer of the independent tower reactor and the safety risks caused by the situations can be avoided.
6. The o-xylene chlorination reaction is realized by single-stage and/or multi-stage tower kettle combined reactors, and the multi-stage tower kettle combined reactors connected in series have better effect on controlling the generation of polychloride by controlling different material mole ratios and temperatures of the reactors.
The catalyst for chloridizing o-xylene is Lewis acid, and o-xylene: the molar ratio of the Lewis acid is 100:0.01-1.
7. The reaction temperature of the o-xylene chlorination is 0-80 ℃.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the disclosure and together with the description serve to explain the principles of the disclosure.
Fig. 1 is a process flow diagram illustrating the continuous chlorination of the present disclosure to produce monochloro-ortho-xylene.
Reference numerals:
1: a batching kettle; 2: a chlorine surge tank; 3: a primary tower kettle combined chlorination reactor; 4: a second-stage tower kettle combined chlorination reactor; 5: a three-stage tower kettle combined chlorination reactor; 6. 7, 8: a reaction tower; 9. 10, 11: a cooler; 12. 13, 14, 19: a condenser; 15. 16, 17, 20: a condensate collection tank; 18: and (5) a degassing tower.
Detailed Description
The present disclosure is described in further detail below with reference to the drawings and the embodiments. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant content and not limiting of the present disclosure. It should be further noted that, for convenience of description, only a portion relevant to the present disclosure is shown in the drawings.
In addition, embodiments of the present disclosure and features of the embodiments may be combined with each other without conflict. The present disclosure will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.
The present application discloses a process for the continuous production of chloro-ortho-xylene wherein both ortho-xylene and chlorine have a purity of greater than 99.5% and a water content of less than 400ppm, preferably less than 100ppm.
Ortho-xylene: lewis acid=100:0.01 to 1, preferably ortho-xylene: lewis acid=100:0.1-0.5.
The application discloses a method for continuously producing chloro-o-xylene. The three-stage column bottom combined chlorination reactor will be described as an example.
1.1 batching: ortho-xylene and catalyst are mixed according to ortho-xylene: adding Lewis acid=100:0.01-1 into the batching kettle 1, and uniformly stirring;
1.2 initial charge: and (3) opening cooling water of a condensate collecting tank 15, adding the mixed materials into the primary tower kettle combined chlorination reactor 3 from the batching kettle 1 through the reaction tower 6, stopping feeding when the liquid level reaches 30%, starting feeding to the primary tower kettle combined chlorination reactor 3, and starting a circulating pump to carry out intermittent chlorination reaction while introducing chlorine. When the chlorine flow reaches 50-60% of the mole fraction of o-xylene in the primary tower kettle combined chlorination reactor 3, a primary circulating pump and cooling water of a cooler 9 are started.
1.3 first stage Chlorination
And (3) recovering the charging of the chlorination system, wherein the charging amount is controlled to be the molar ratio of o-xylene to chlorine according to the set proportion according to the chlorination reaction speed, and the molar ratio is: chlorine = 1:0.4 to 0.8, and starting the first-stage continuous chlorination reaction. The reaction temperature is 30-40 ℃. When the liquid level of the primary tower kettle combined chlorination reactor reaches 60, the flow rate of circulation and extraction is controlled by a flow meter, so that the material quantity entering the secondary tower kettle combined chlorination reactor 4 is equal to the material quantity entering the primary tower kettle combined chlorination reactor 3, and the material inlet and outlet balance of the primary tower kettle combined chlorination reactor 3 is achieved.
1.4 two-stage Chlorination
When the material amount added into the secondary tower kettle combined chlorination reactor 4 reaches 30% of the liquid level, starting a secondary circulating pump and a cooler 10, starting a condenser 13, and simultaneously introducing chlorine into the secondary tower kettle combined chlorination reactor 4, wherein about 50% of o-xylene is unreacted at the moment, and the chlorine introducing flow is that of o-xylene: chlorine = 1: 0.1-0.4, and the reaction temperature is controlled between 30 ℃ and 35 ℃. When the liquid level of the second-stage tower kettle combined chlorination reactor 4 reaches 60%, the flow rate of circulation and extraction is controlled through a flow meter, so that the amount of materials entering the third-stage tower kettle combined chlorination reactor 5 is equal to the amount of materials entering the first-stage tower kettle combined chlorination reactor 3 at the moment, and the balance of the materials entering and exiting the first-stage tower kettle combined chlorination reactor and the second-stage tower kettle combined chlorination reactor is achieved.
1.5 three stage Chlorination
When the material quantity added into the three-stage tower kettle combined chlorination reactor 5 reaches 30% of the liquid level, starting a three-stage circulating pump and a cooler 11, starting a condenser 14, and simultaneously introducing chlorine into the three-stage tower kettle combined chlorination reactor 5, wherein about 20-40% of o-xylene is unreacted at the moment, and the chlorine introducing flow is that of the o-xylene: chlorine = 1: 0.1-0.3, and the reaction temperature is controlled at 10-25 ℃. When the liquid level of the second-stage tower kettle combined chlorination reactor 4 reaches 60%, the flow rate of circulation and extraction is controlled through a flow meter, so that the amount of materials entering the degassing tower 18 is equal to the amount of materials entering the first-stage tower kettle combined chlorination reactor 3 at the moment, and the balance of the materials entering and exiting the first-stage, second-stage and third-stage tower kettle combined chlorination reactors is achieved.
After the operation is finished, the continuous chlorination process is conducted, and continuous chlorination operation is carried out. The degasser 18 is continuously degasified by nitrogen, and the chloride is stripped by nitrogen to remove residual HCl and chlorine in the liquid material, and then enters a chloride storage tank, and then enters the following working procedures.
The invention simplifies the process by directly chlorinating with chlorine without solvent, has high yield of monochloro-o-xylene, less byproducts, and the unreacted o-xylene can be recycled, and the degassed chloro-compound also has a trace amount of residual HCl and can be removed in the subsequent distillation operation.
Examples
Example 1 batch chlorination of a Tower bottom Combined reactor
(1) Preparing materials, namely, o-xylene according to the mass ratio: aluminum trichloride = 100:0.2 formulation. 4kg of aluminum trichloride with the water content of less than 100ppm of o-xylene 2124kg and the average particle size of 200 microns is added into a batching kettle 1 after nitrogen replacement and stirred for one hour for later use.
(2) Feeding, namely starting a jacket of a primary tower kettle combined chlorination reactor and cooling circulating water of a condenser 12 at the top of the tower, adding 600kg of materials into a reaction tower 6, and controlling o-xylene: the total molar ratio of chlorine is 1:0.8, starting a mechanical stirring and primary circulating pump of the primary tower kettle combined chlorination reactor 3, starting an HCl absorption and alkali absorption unit, simultaneously starting cooling water of a cooler 9, setting the chlorine introducing speed to be 50kg/h, starting chlorine introducing reaction, controlling the kettle temperature to be 35 ℃, and ending chlorine introducing to complete the chlorination reaction when chlorine introducing is carried out to 321 kg. The mixture was fed into the degassing column 18 by a primary circulation pump to be degassed, and the flow rate of the material fed into the degassing column 18 was 72L/h. The degassed material enters a chloride storage tank. The degassed material was sampled and analyzed for reactant composition and chlorine utilization.
EXAMPLE 2 Single stage continuous chlorination
(1) Preparing materials, namely, o-xylene according to the mass ratio: aluminum trichloride = 100:0.2 formulation. 4kg of aluminum trichloride with the water content of less than 100ppm of o-xylene 2124kg and the average particle size of 200 microns is added into a batching kettle 1 after nitrogen replacement and stirred for one hour for later use.
(2) And (3) starting the initial feeding, starting a jacket of the primary tower kettle combined chlorination reactor and cooling circulating water of the tower top condenser 12, and stopping feeding after 204L of materials are added into the reaction tower 6. Starting mechanical stirring and a primary circulating pump of the primary tower kettle combined chlorination reactor 3, starting the chlorine introducing reaction of the primary tower kettle combined chlorination reactor, starting cooling water of the cooler 9, and entering the next continuous chlorination operation when 96kg of chlorine is introduced.
(3) Continuous chlorination
The recovery batching kettle 1 feeds materials to the primary tower kettle combined chlorination reactor 3 through the reaction tower 6, and the ortho-xylene is controlled according to the set molar ratio: the molar ratio of chlorine is 1:0.8, the feeding speed is that the flow of the dimethylbenzene is 72L/h, the flow of the chlorine is controlled at 33.91kg/h, the primary continuous chlorination reaction is started, and the reaction temperature is controlled at 40 ℃ through a tower kettle combined chlorination reactor jacket and a cooler. When the total amount of the added xylenes in the first-stage tower kettle combined chlorination reactor 3 is 600L, the circulation and the extracted flow are controlled through a flowmeter, the extracted materials enter the degassing tower 18, the extracted materials are 72L/h, and the extracted materials are equal to the materials entering the first-stage tower kettle combined chlorination reactor 3, so that the continuous chlorination of the o-xylene is realized. The degassed material enters a chloride storage tank. The degassed material was sampled and analyzed for reactant composition and chlorine utilization.
EXAMPLE 3 two-stage tandem continuous chlorination
(1) Preparing materials, namely, o-xylene according to the mass ratio: aluminum trichloride = 100:0.2 formulation. 4kg of aluminum trichloride with the water content of less than 100ppm of o-xylene 2124kg and the average particle size of 200 microns is added into a batching kettle 1 after nitrogen replacement and stirred for one hour for later use.
(2) The method comprises the steps of initially feeding, starting a jacket of a tower kettle combined chlorination reactor and cooling circulating water at the top of a reaction tower, adding 180kg of materials into a 1000L tower kettle combined chlorination reactor provided with a DN150 reaction tower (glass lining material and ceramic pore plate corrugated structured packing), starting a mechanical stirring and circulating pump, starting a chlorine introducing reaction, starting a cooler at the outlet of the circulating pump, stopping until 60kg of chlorine is introduced, and entering the next continuous chlorination operation.
(3) Continuous chlorination
Control o-xylene: the total molar ratio of chlorine is 1:0.8, feeding the recovered batching kettle 1 into the primary tower kettle combined chlorination reactor 3 through a reaction tower 6, and controlling o-xylene in the primary tower kettle combined chlorination reactor 3 according to a set molar ratio: chlorine = 1:0.6, the feeding speed is that the flow of the dimethylbenzene is 72L/h, the flow of the chlorine is controlled at 25.43kg/h, the primary continuous chlorination reaction is started, and the reaction temperature is controlled to be 40 ℃ through a jacket of a primary tower kettle combined chlorination reactor and a cooler 9. When the total mass of the added xylene of the first-stage tower kettle combined chlorination reactor 3 is 600L, the flow rate of circulation and extraction is controlled through a flow meter, so that the amount of the material entering the second-stage tower kettle combined chlorination reactor 4 is 72L/h, and the amount of the material entering the first-stage tower kettle combined chlorination reactor 3 is equal to the amount of the material entering the first-stage tower kettle combined chlorination reactor 3, and the balance of the material inlet and outlet of the first-stage tower kettle combined chlorination reactor 3 is achieved. And simultaneously, chlorine is introduced into the secondary tower kettle combined chlorination reactor 4, and the chlorine flow is controlled at 12.71kg/h. When the material quantity added into the secondary tower kettle combined chlorination reactor 4 reaches 68L, the secondary circulating pump and the cooler 10 are started, the condenser 13 is started, and meanwhile, chlorine is introduced into the secondary tower kettle combined chlorination reactor 4, and the reaction temperature is controlled at 35 ℃. When the total material amount added into the two-stage tower kettle combined chlorination reactor 4 reaches 600L, the circulation and the extracted flow are controlled through a flowmeter, the extracted material enters the degassing tower 18, and the extracted material amount is 72L/h and is equal to the material entering the tower kettle combined chlorination reactor 4. The degassed material enters a chloride storage tank. The degassed material was sampled and analyzed for reactant composition and chlorine utilization.
EXAMPLE 4 three-stage series continuous chlorination
(1) Preparing materials, namely, o-xylene according to the mass ratio: aluminum trichloride = 100:0.2 formulation. 4kg of aluminum trichloride with the water content of less than 100ppm of o-xylene 2124kg and the average particle size of 200 microns is added into a batching kettle 1 after nitrogen replacement and stirred for one hour for later use.
(2) The method comprises the steps of initially feeding, starting a jacket of a tower kettle combined chlorination reactor and cooling circulating water at the top of a reaction tower, adding 180kg of materials into a 1000L tower kettle combined chlorination reactor provided with a DN150 reaction tower (glass lining material and ceramic pore plate corrugated structured packing), starting a mechanical stirring and circulating pump, starting a chlorine introducing reaction, starting a cooler at the outlet of the circulating pump, stopping until 60kg of chlorine is introduced, and entering the next continuous chlorination operation.
(3) Continuous chlorination
Control o-xylene: the total molar ratio of chlorine is 1:0.8, feeding the recovered batching kettle 1 into the primary tower kettle combined chlorination reactor 3 through a reaction tower 6, and controlling o-xylene in the primary tower kettle combined chlorination reactor 3 according to a set molar ratio: chlorine = 1:0.6, the feeding speed is that the flow of the dimethylbenzene is 72L/h, the flow of the chlorine is controlled at 25.43kg/h, the primary continuous chlorination reaction is started, and the reaction temperature is controlled to be 40 ℃ through a jacket of a primary tower kettle combined chlorination reactor 3 and a cooler 9. When the total mass of the added xylene in the first-stage tower kettle combined chlorination reactor 3 is 600L, circulating and extracted flow is controlled through a flow meter, extracted materials enter a second-stage reaction tower 7 and enter the second-stage tower kettle combined chlorination reactor 4 through the second-stage reaction tower 7. The flow rate of the extracted material is 72L/h, which is equal to the amount of the material entering the primary tower kettle combined chlorination reactor 3. And simultaneously, chlorine is introduced into the secondary tower kettle combined chlorination reactor 4, and the chlorine flow is controlled at 12.71kg/h. When the amount of the material added into the secondary tower kettle combined chlorination reactor 4 reaches 68L, the secondary circulating pump and the cooler 10 are started, the condenser 13 is started, and the reaction temperature is controlled at 35 ℃. When the total material quantity added into the two-stage tower kettle combined chlorination reactor reaches 600L, the circulation and the extracted flow are controlled through a flowmeter, the extracted material enters the three-stage tower kettle combined chlorination reactor 5 through the three-stage reaction tower 8, and the extracted material flow is 72L/h. And simultaneously, chlorine is introduced into the three-stage tower kettle combined chlorination reactor 5, and the flow of the chlorine is 4.24Kg/h, so that the balance of feeding and discharging is achieved. When the material amount added into the secondary tower kettle combined chlorination reactor 4 reaches 68L, the tertiary circulation pump and the cooler 11 are started, the condenser 14 is started, and the reaction temperature is controlled at 20 ℃. When the total material amount added into the combined chlorination reactor of the second-stage tower kettle reaches 600L, the circulation and the extracted flow rate are controlled by a flowmeter, the extracted material enters the degassing tower 18, and the extracted material flow rate is 72L/h. The amount of the material entering the degassing tower 18 is equal to that of the material entering the three-stage tower kettle combined chlorination reactor 5. The degassed material enters a chloride storage tank. The degassed material was sampled and analyzed for reactant composition and chlorine utilization.
EXAMPLE 5 two-stage tandem continuous chlorination
(1) Preparing materials, namely, o-xylene according to the mass ratio: antimony trichloride = 100:0.4 formulation. 4kg of antimony trichloride with the water content of less than 100ppm of o-xylene 2124kg and the average particle size of 250 micrometers is added into a batching kettle 1 after nitrogen replacement and stirred for one hour for later use.
(2) The method comprises the steps of initially feeding, starting a jacket of a tower kettle combined chlorination reactor and cooling circulating water at the top of a reaction tower, adding 180kg of materials into a 1000L tower kettle combined chlorination reactor provided with a DN150 reaction tower (glass lining material and ceramic pore plate corrugated structured packing), starting a mechanical stirring and circulating pump, starting a chlorine introducing reaction, starting a cooler at the outlet of the circulating pump, stopping until 60kg of chlorine is introduced, and entering the next continuous chlorination operation.
(3) Continuous chlorination
Control o-xylene: the total molar ratio of chlorine is 1:0.8, feeding the recovered batching kettle 1 into the primary tower kettle combined chlorination reactor 3 through a reaction tower 6, and controlling o-xylene in the primary tower kettle combined chlorination reactor 3 according to a set molar ratio: chlorine = 1:0.5, the feeding speed is that the flow of the dimethylbenzene is 72L/h, the flow of the chlorine is controlled at 21.19kg/h, the primary continuous chlorination reaction is started, and the reaction temperature is controlled to be 40 ℃ by a jacket of a combined chlorination reactor of a tower kettle and a cooler. When the total mass of the added xylene of the first-stage tower kettle combined chlorination reactor 3 is 600L, the flow rate of circulation and extraction is controlled through a flow meter, so that the amount of the material entering the second-stage tower kettle combined chlorination reactor 4 is 72L/h, and the amount of the material entering the first-stage tower kettle combined chlorination reactor 3 is equal to the amount of the material entering the first-stage tower kettle combined chlorination reactor 3, and the balance of the material inlet and outlet of the first-stage tower kettle combined chlorination reactor 3 is achieved. And simultaneously, chlorine is introduced into the secondary tower kettle combined chlorination reactor 4, and the chlorine flow is controlled at 10.59kg/h. When the material quantity added into the secondary tower kettle combined chlorination reactor 4 reaches 68L, the secondary circulating pump and the cooler 10 are started, the condenser 13 is started, and meanwhile, chlorine is introduced into the secondary tower kettle combined chlorination reactor 4, and the reaction temperature is controlled at 35 ℃. When the total material amount added into the secondary tower kettle combined chlorination reactor 4 reaches 600L, the circulation and the extracted flow are controlled through a flowmeter, the extracted material enters the degassing tower 18, and the extracted material amount is 72L/h and is equal to the material entering the secondary tower kettle combined chlorination reactor 4. The degassed material enters a chloride storage tank. The degassed material was sampled and analyzed for reactant composition and chlorine utilization.
EXAMPLE 6 two-stage tandem continuous chlorination
(1) Preparing materials, namely, o-xylene according to the mass ratio: ferric trichloride = 100:0.1 formulation. 4kg of ferric trichloride with the water content of less than 100ppm of o-xylene 2124kg and the average particle size of 150 microns is added into a batching kettle 1 after nitrogen replacement and stirred for one hour for standby.
(2) The method comprises the steps of initially feeding, starting a jacket of a tower kettle combined chlorination reactor and cooling circulating water at the top of a reaction tower, adding 180kg of materials into a 1000L tower kettle combined chlorination reactor provided with a DN150 reaction tower (glass lining material and ceramic pore plate corrugated structured packing), starting a mechanical stirring and circulating pump, starting a chlorine introducing reaction, starting a cooler at the outlet of the circulating pump, stopping until 60kg of chlorine is introduced, and entering the next continuous chlorination operation.
(3) Continuous chlorination
Control o-xylene: the total molar ratio of chlorine is 1:0.8, feeding the recovered batching kettle 1 into the primary tower kettle combined chlorination reactor 3 through a reaction tower 6, and controlling o-xylene in the primary tower kettle combined chlorination reactor 3 according to a set molar ratio: chlorine = 1:0.7, the feeding speed is that the flow of the dimethylbenzene is 72L/h, the flow of the chlorine is controlled at 29.67kg/h, the primary continuous chlorination reaction is started, and the reaction temperature is controlled to be 40 ℃ by a jacket of a combined chlorination reactor of a tower kettle and a cooler. When the total mass of the added xylene of the first-stage tower kettle combined chlorination reactor 3 is 600L, the flow rate of circulation and extraction is controlled through a flow meter, so that the amount of the material entering the second-stage tower kettle combined chlorination reactor 4 is 72L/h, and the amount of the material entering the first-stage tower kettle combined chlorination reactor 3 is equal to the amount of the material entering the first-stage tower kettle combined chlorination reactor 3, and the balance of the material inlet and outlet of the first-stage tower kettle combined chlorination reactor 3 is achieved. And simultaneously, chlorine is introduced into the secondary tower kettle combined chlorination reactor 4, and the chlorine flow is controlled at 14.82kg/h. When the material quantity added into the secondary tower kettle combined chlorination reactor 4 reaches 68L, the secondary circulating pump and the cooler 10 are started, the condenser 13 is started, and meanwhile, chlorine is introduced into the secondary tower kettle combined chlorination reactor 4, and the reaction temperature is controlled at 35 ℃. When the total material amount added into the secondary tower kettle combined chlorination reactor 4 reaches 600L, the circulation and the extracted flow are controlled through a flowmeter, the extracted material enters the degassing tower 18, and the extracted material amount is 72L/h and is equal to the material entering the secondary tower kettle combined chlorination reactor 4. The degassed material enters a chloride storage tank. The degassed material was sampled and analyzed for reactant composition and chlorine utilization.
Comparative example 1 batch reaction in a conventional tank chlorination reactor
The same procedure and equipment as in example 1 were used, except that the chlorination reactor was a conventional kettle-type chlorination reactor, the materials were directly fed into the reactor, and the inside of the reactor was subjected to chlorination by introducing chlorine, without circulation outside the reactor.
(1) Preparing materials, namely, o-xylene according to the mass ratio: ferric trichloride = 100:0.25 formulation. 15kg of ferric trichloride with the water content of less than 100ppm and 600kg of o-xylene and the average particle size of 300 microns is added into a batching kettle 1 after nitrogen replacement and stirred for one hour for standby.
(2) Feeding, namely opening cooling circulating water of a jacket of the kettle-type chlorination reactor, adding 615kg of prepared materials into the kettle-type chlorination reactor, starting mechanical stirring, starting an HCl absorption and alkali absorption unit, and controlling o-xylene: the total molar ratio of chlorine is 1: and 0.8, setting the chlorine introducing speed to be 50kg/h, starting the chlorine introducing reaction, controlling the kettle temperature to be 35-50 ℃, and ending the chlorine introducing reaction to complete the chlorination reaction when the chlorine introducing speed is 321 kg. The deaeration was carried out in the deaeration column 18 by means of a circulation pump, and the flow rate of the material fed into the deaeration column 18 was 72L/h. The degassed material enters a chloride storage tank. The degassed material was sampled and analyzed for reactant composition and chlorine utilization.
Table 1 reactant compositions and chlorine utilization in examples 1-6 and comparative example 1.
The total molar ratio of o-xylene to chlorine feed in the above reactions was all 1:0.8, test and calculation data indicate:
(1) The tower and kettle combined chlorination reactor is used for obtaining higher effective utilization rate of chlorine compared with the traditional reaction kettle in batch chlorination, whether the tower and kettle combined chlorination reactor is used for batch chlorination or single-stage continuous chlorination and multistage continuous chlorination;
(2) The multi-stage serial use of the tower and kettle combined chlorination reactor can effectively improve the chloro-o-xylene conversion rate and reduce the production of polychlorinated o-xylene.
In the description of the present specification, reference to the terms "one embodiment/manner," "some embodiments/manner," "example," "specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment/manner or example is included in at least one embodiment/manner or example of the present application. In this specification, the schematic representations of the above terms are not necessarily for the same embodiment/manner or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments/modes or examples. Furthermore, the various embodiments/modes or examples described in this specification and the features of the various embodiments/modes or examples can be combined and combined by persons skilled in the art without contradiction.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present application, the meaning of "plurality" is at least two, such as two, three, etc., unless explicitly defined otherwise.
It will be appreciated by those skilled in the art that the above-described embodiments are merely for clarity of illustration of the disclosure, and are not intended to limit the scope of the disclosure. Other variations or modifications will be apparent to persons skilled in the art from the foregoing disclosure, and such variations or modifications are intended to be within the scope of the present disclosure.
Claims (10)
1. A process for the continuous chlorination of ortho-xylene to mono-chloro-ortho-xylene comprising:
(1) Adding dried o-xylene and Lewis acid into a batching kettle according to a proportion, and uniformly stirring;
(2) Reactants in the batching kettle are introduced into a tower kettle combined chlorination reactor through a reaction tower in the tower kettle combined chlorination reactor, dried chlorine is introduced into the tower kettle combined chlorination reactor, the ratio of o-xylene to the chlorine is controlled so as to carry out continuous chlorination reaction, heat released by the chlorination reaction is removed through circulating water of a jacket outside the tower kettle combined chlorination reactor and a cooler outside the tower kettle, wherein the reaction tower is directly arranged at the top of the tower kettle combined chlorination reactor or is connected above the tower kettle combined chlorination reactor through a pipeline, and the chlorination reaction temperature is 0-80 ℃;
(3) And (3) delivering the chloride of the reaction product of the tower kettle combined chlorination reactor into a degassing tower, removing HCl and residual chlorine in the degassing tower, and delivering the chloride into a chloride storage tank.
2. The method according to claim 1, wherein the structural form of the reaction tower of the tower kettle combined reactor comprises a packed tower, a sieve plate tower or a bubble cap tower.
3. The method of claim 1, wherein the material of the combined reactor comprises a non-metallic material with a metallic liner that is corrosion resistant.
4. The method according to claim 1, wherein in the step (2), the tower kettle combined reactor can be used for realizing continuous chlorination reaction independently in a single stage or can be used for realizing continuous chlorination reaction in a multi-stage series connection.
5. The method of claim 4, wherein in step (2), the combined column reactor comprises a primary combined column reactor, a secondary combined column reactor, and a tertiary combined column reactor.
6. The process of claim 5, wherein in step (2) a four-stage bottoms combined reactor is optionally included.
7. The method of claim 5, wherein the step of determining the position of the probe is performed,
in the first-stage tower kettle combined reactor, o-xylene is mixed according to the following ratio: introducing chlorine gas in the molar ratio of 1:0.5-0.8, and controlling the chlorination reaction temperature to be 30-70 ℃;
in a secondary tower kettle combined reactor, o-xylene is mixed according to the following weight: introducing chlorine gas in the molar ratio of 1:0.4-0.6, and controlling the chlorination reaction temperature to be 5-40 ℃;
in a three-stage tower kettle combined reactor, o-xylene is mixed according to the following ratio: the chlorine is introduced into the reactor in a molar ratio of 1:0.3-0.5, and the chlorination reaction temperature is controlled to be 0-40 ℃.
8. The process according to claim 1, wherein in step (1) the molar ratio of ortho-xylene to Lewis acid is from 100:0.01 to 1.
9. The method according to claim 1, wherein the lewis acid is selected from one or a mixture of several of ferric trichloride, aluminum trichloride, antimony trichloride, and tin tetrachloride.
10. The method as recited in claim 1, further comprising:
and cooling the chloro compound which is a reaction product of the tower kettle combined chlorination reactor before the chloro compound is sent to the degassing tower.
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| CN1080278A (en) * | 1992-06-17 | 1994-01-05 | 中国科学院长春应用化学研究所 | Preparation method of monochloro-o-xylene |
| JP2003342206A (en) * | 2002-05-28 | 2003-12-03 | Toray Ind Inc | METHOD FOR PRODUCING 4-CHLORO-o-XYLENE |
| CN1944408A (en) * | 2006-06-30 | 2007-04-11 | 衢州恒顺化工有限公司 | Process for preparing symmetric tetrachloro pyridine |
| CN101397234A (en) * | 2007-09-30 | 2009-04-01 | 浙江省常山长盛化工有限公司 | Method for preparing dichlorobenzene |
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| CN1080278A (en) * | 1992-06-17 | 1994-01-05 | 中国科学院长春应用化学研究所 | Preparation method of monochloro-o-xylene |
| JP2003342206A (en) * | 2002-05-28 | 2003-12-03 | Toray Ind Inc | METHOD FOR PRODUCING 4-CHLORO-o-XYLENE |
| CN1944408A (en) * | 2006-06-30 | 2007-04-11 | 衢州恒顺化工有限公司 | Process for preparing symmetric tetrachloro pyridine |
| CN101397234A (en) * | 2007-09-30 | 2009-04-01 | 浙江省常山长盛化工有限公司 | Method for preparing dichlorobenzene |
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