CN117304121A - Refining method and refining device of 5-chlorobenzotriazole - Google Patents
Refining method and refining device of 5-chlorobenzotriazole Download PDFInfo
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- CN117304121A CN117304121A CN202210705965.5A CN202210705965A CN117304121A CN 117304121 A CN117304121 A CN 117304121A CN 202210705965 A CN202210705965 A CN 202210705965A CN 117304121 A CN117304121 A CN 117304121A
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- chlorobenzotriazole
- refined
- mixed solution
- organic solvent
- powder
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- PZBQVZFITSVHAW-UHFFFAOYSA-N 5-chloro-2h-benzotriazole Chemical compound C1=C(Cl)C=CC2=NNN=C21 PZBQVZFITSVHAW-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 238000007670 refining Methods 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000012528 membrane Substances 0.000 claims abstract description 65
- 239000011259 mixed solution Substances 0.000 claims abstract description 60
- 239000000843 powder Substances 0.000 claims abstract description 58
- 238000001914 filtration Methods 0.000 claims abstract description 45
- 239000003960 organic solvent Substances 0.000 claims abstract description 41
- 239000000243 solution Substances 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 26
- 239000012535 impurity Substances 0.000 claims abstract description 17
- 238000005342 ion exchange Methods 0.000 claims abstract description 11
- 239000002923 metal particle Substances 0.000 claims abstract description 5
- 238000005341 cation exchange Methods 0.000 claims abstract description 4
- 239000011148 porous material Substances 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000001471 micro-filtration Methods 0.000 claims description 25
- 238000004821 distillation Methods 0.000 claims description 21
- 230000007246 mechanism Effects 0.000 claims description 21
- 238000004090 dissolution Methods 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 238000011084 recovery Methods 0.000 claims description 10
- 238000004378 air conditioning Methods 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 5
- 238000004891 communication Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 3
- 230000005484 gravity Effects 0.000 claims description 3
- 238000010923 batch production Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 description 39
- 239000002184 metal Substances 0.000 description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- 229910052791 calcium Inorganic materials 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 239000011651 chromium Substances 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- -1 Polypropylene Polymers 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229940023913 cation exchange resins Drugs 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- NEMFQSKAPLGFIP-UHFFFAOYSA-N magnesiosodium Chemical compound [Na].[Mg] NEMFQSKAPLGFIP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 206010042496 Sunburn Diseases 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a refining method and a refining device of 5-chlorobenzotriazole. The refining method comprises the following steps: dissolving the 5-chlorobenzotriazole crude powder in an organic solvent at the temperature of 50-60 ℃ for heating and dissolving for 3-4 hours to form a mixed solution, wherein the weight ratio of the 5-chlorobenzotriazole crude powder to the organic solvent is 1:4-1:5; filtering the mixed solution by a precise filtering membrane with the aperture of 40nm to remove impurities and metal particles; ion-exchanging the mixed solution subjected to the filtration treatment with a cation exchange resin at a temperature of 25 + -1 ℃ for at least 6 hours, and taking out part of the cation exchange to obtain a refined solution; heating the refining solution at a temperature of 135-145 ℃ for at least 12 hours to distill the organic solvent, leaving a bulk refined 5-chlorobenzotriazole; and crushing the blocky refined 5-chlorobenzotriazole to obtain refined 5-chlorobenzotriazole powder with the fineness grade of 2 mm.
Description
Technical Field
The present invention relates to a method and an apparatus for purifying an organic compound, and more particularly, to a method and an apparatus for purifying 5-chlorobenzotriazole.
Background
5-chlorobenzotriazole is an organic compound with wide application range. 5-chlorobenzotriazole is commonly used in organic synthesis with some compounds, as other downstream organic compounds, and also as electroplating additive. In addition, 5-chlorobenzotriazole is also used as an effective antifogging agent and stabilizer in photosensitive materials, so that the substance is widely applied to the production of photographic paper emulsion and developing solution.
The purity of commercially available 5-chlorobenzotriazole is not low, but is usually less than 99%. Impurities mixed in 5-chlorobenzotriazole powder are usually some metallic impurities such as iron, sodium, magnesium, calcium, potassium, copper, nickel, chromium, zinc, etc. If a more refined product is to be produced, the purity of the 5-chlorobenzotriazole is improved, and the purity is preferably between 99.5 and 99.9 percent. The content of the foregoing metal impurities is reduced. For example, the iron content is about 10ppm before refining and below 2ppm after refining; the content of calcium is about 5ppm before refining and is also below 2ppm after refining; the other small amounts of metal are also less than 1ppm after refining.
However, there is currently no effective way to refine 5-chlorobenzotriazole. Accordingly, the present invention provides a method and an apparatus for purifying 5-chlorobenzotriazole.
Disclosure of Invention
The invention aims to provide a refining method and a refining device of 5-chlorobenzotriazole.
The invention provides a refining method of 5-chlorobenzotriazole, which comprises the following steps:
and (3) heating and dissolving: dissolving the 5-chlorobenzotriazole crude powder in an organic solvent at the temperature of 50-60 ℃ for heating and dissolving for 3-4 hours to form a mixed solution, wherein the weight ratio of the 5-chlorobenzotriazole crude powder to the organic solvent is 1:4-1:5;
and (3) filtering: filtering the mixed solution by a precise filtering membrane with the aperture of 40nm to remove impurities and metal particles;
ion exchange step: ion-exchanging the mixed solution subjected to the filtration treatment with a cation exchange resin at a temperature of 25 + -1 ℃ for at least 6 hours, and taking out part of the cation exchange to obtain a refined solution;
a solvent removal step: heating the refining solution at a temperature of 135-145 ℃ for at least 12 hours to distill the organic solvent, leaving a bulk refined 5-chlorobenzotriazole; and
crushing: the blocky refined 5-chlorobenzotriazole is crushed to obtain refined 5-chlorobenzotriazole powder with the fineness grade of 2 mm.
Preferably, the organic solvent is methanol, ethanol or isopropanol.
Preferably, a batch of the mixed solution is not more than 800 kg.
The invention also provides a refining device of the 5-chlorobenzotriazole, which comprises the following components:
a heating dissolution tank set for providing a temperature of 50-60 ℃, dissolving the 5-chlorobenzotriazole crude powder in an organic solvent, and heating and dissolving for 3-4 hours to form a mixed solution, wherein the weight ratio of the 5-chlorobenzotriazole crude powder to the organic solvent is 1:4-1:5;
a precision membrane filter in communication with the heated dissolution tank set for cyclically receiving and returning the mixed solution, comprising a 40nm pore size precision filtration membrane for cyclically filtering the mixed solution for at least 90 minutes each time;
an ion exchanger, which is communicated with the precise membrane filter and is provided with cation exchange resin, and the ion exchanger exchanges and takes out partial cations in the mixed solution which is circularly filtered at the temperature of 25+/-1 ℃ so as to obtain a refined solution;
a desolventizing mechanism for heating the refined solution at a temperature of 135-145 ℃ for at least 12 hours to distill the organic solvent to leave a bulk refined 5-chlorobenzotriazole; and
a crushing mechanism for crushing the blocky refined 5-chlorobenzotriazole to obtain refined 5-chlorobenzotriazole powder with the fineness grade of 2 mm.
Preferably, the organic solvent is methanol, ethanol or isopropanol.
Preferably, the precision membrane filter further comprises:
a 450nm pore size microfiltration membrane for at least 45 minutes of each cycle of filtering the mixed solution; a kind of electronic device with high-pressure air-conditioning system
A 200nm pore size microfiltration membrane for performing at least 45 minutes of each cycle of filtration of the mixed solution,
the execution sequence is the 450nm aperture precise filtration membrane, the 200nm aperture precise filtration membrane and the 40nm aperture precise filtration membrane in sequence.
Preferably, the cation exchange resin is a strong acid cation exchange resin or a weak acid cation exchange resin.
Preferably, the desolventizing mechanism further includes a recovery tank for recovering the organic solvent for reuse in the heated dissolution tank set.
Preferably, the desolventizing mechanism further comprises:
a condenser;
the distillation barrel comprises a cover body above and a barrel body combined with the cover body in an openable and closable manner, the barrel body is hermetically connected with the condenser, the refining solution is placed in the sealed distillation barrel and heated, the distilled organic solvent is led out of the distillation barrel by the condenser, and blocky refined 5-chlorobenzotriazole is left in the distillation barrel; a kind of electronic device with high-pressure air-conditioning system
An electrothermal heater receives electric power to generate heat and transmit the heat to the distillation barrel, and the temperature in the distillation barrel is kept between 135-145 ℃.
Preferably, the pulverizing mechanism further comprises:
an input groove for receiving the block-shaped refined 5-chlorobenzotriazole and releasing the block-shaped refined 5-chlorobenzotriazole from the high position;
the two rollers are adjustable in distance and relatively rotate, and the blocky refined 5-chlorobenzotriazole falling onto the upper parts of the two rollers from the input end by gravity is ground by the two rollers to form refined 5-chlorobenzotriazole powder with the fineness level of 2mm and falls down; a kind of electronic device with high-pressure air-conditioning system
A receiving tank for receiving the dropped refined 5-chlorobenzotriazole powder.
According to the refining method and the refining device disclosed by the invention, the purity of the 5-chlorobenzotriazole can be ensured to be higher than 99.5%, and the method and the device are superior to the existing commodity sold in the market.
Drawings
FIG. 1 is a schematic diagram showing components of a refining apparatus for 5-chlorobenzotriazole according to the present invention.
FIG. 2 is a flow chart of a method for refining 5-chlorobenzotriazole according to the present invention.
Reference numerals illustrate:
a refining device of 1-5-chlorobenzotriazole; 10-heating a dissolution tank group;
11-an organic solvent supply; 111-a first switch valve; 112-a second switch valve;
12-dissolving tank body; 121-opening holes; 13-heating the tank body; 131-a recovery line; 132-priming line;
14-5-chlorobenzotriazole coarse powder supply source; 20-a precise membrane filter;
201-a liquid inlet pipeline; 202-a liquid outlet line; 203-a first control valve; 204-a second control valve;
a precise filtering membrane with the aperture of 21-450 nm; a microfiltration membrane of 22-200nm pore size;
a 23-40nm pore size microfiltration membrane; 24-a third control valve; 25-discharge line; 26-purifying barrel
30-ion exchange; 31-cation exchange resin; 32-an auxiliary filter; 33-a flow direction control valve;
341-a refining solution barrel 1; 342-refined solution barrel 2; 35-circulating pipe; 40-a solvent removal mechanism;
41-a condenser; 42-a distillation barrel; 421-cover; 422-a tub; 43-an electrothermal heater;
44-a recovery tank; 50-a crushing mechanism; 51-an input slot; 52-rolling wheels; 53-a receiving slot;
b-refining 5-chlorobenzotriazole in a blocky manner; f-refining 5-chlorobenzotriazole powder;
h-mixed solution; p1-a first pump; p2-a second pump; p3-a third pump; r-refining solution
Detailed Description
The invention will be further described with reference to specific embodiments, and advantages and features of the invention will become apparent from the description. These examples are merely exemplary and do not limit the scope of the invention in any way. It will be understood by those skilled in the art that various changes and substitutions of details and forms of the technical solution of the present invention may be made without departing from the spirit and scope of the present invention, but these changes and substitutions fall within the scope of the present invention.
Reference is made to FIG. 1, which is a schematic diagram showing the components of a refining apparatus 1 for 5-chlorobenzotriazole according to the present invention. The refining apparatus 1 of 5-chlorobenzotriazole comprises a heating dissolution tank group 10, a precision membrane filter 20, an ion exchanger 30, a desolventizing mechanism 40 and a pulverizing mechanism 50. The aspects, functions and operation of the devices described above will be described in detail below.
The heating dissolution tank set 10 is used for providing a temperature of 50-60 ℃, dissolving 5-chlorobenzotriazole coarse powder in an organic solvent, and heating and dissolving for 3-4 hours to form a mixed solution H. The purity of the 5-chlorobenzotriazole coarse powder is less than 99 percent, and is generally about 98 percent. Too many impurities and impurities cause a lot of trouble to subsequent processing operations, and further reduction is required. The detailed apparatus of the heating dissolution tank set 10 comprises an organic solvent supply source 11, a dissolution tank body 12, a heating tank body 13 and a 5-chlorobenzotriazole crude powder supply source 14. According to the present invention, the organic solvent may be an alcohol such as methanol, ethanol or isopropanol. In the following examples, ethanol is used as an example, and the purity is greater than 99.5%. Since the alcohols are liquids, the organic solvent supply 11 may be a storage tank or a line connecting an external alcohol recovery source, such as a storage tank. The organic solvent may be injected into the dissolution tank 12 in various ways, for example, directly into the dissolution tank 12 by controlling a first switch valve 111; the mixed solution H filtered by the circulation is also fed by the control of a second switch valve 112.
The dissolution tank 12 is a main location for forming the mixed solution H. The dissolution tank 12 is provided with a plurality of openings 121, and the mixed solution H is circulated through the openings 121 for heating and recovery. The heating tank 13 sucks the cooled mixed solution H from one opening 121 through a recovery line 131 by using a first pump P1, heats the cooled mixed solution H, and then returns the heated mixed solution H to the other opening 121 through a liquid injection line 132. The direction of circulation of the mixed solution H is indicated by the solid line arrow in FIG. 1. The heating tank 13 can heat the mixed solution H at a temperature ranging from 50 to 60 ℃, and heat carried by the mixed solution H may be lost in the pipeline, so long as the temperature in the dissolution tank 12 is ensured to be 30 to 40 ℃. The 5-chlorobenzotriazole crude powder supply 14 may be fed into the dissolution tank 12 to be mixed with the organic solvent in accordance with a specific weight. It is to be noted that, according to the present invention, the weight ratio of the crude powder of 5-chlorobenzotriazole to the organic solvent should be 1:4 to 1:5. Taking 20% by weight as an example, 120kg of crude 5-chlorobenzotriazole powder can be mixed with 480kg of ethanol to prepare 600kg of mixed solution H.
The function of the precision membrane filter 20 is to circularly filter the mixed solution H to remove impurities and impurities (e.g., metal particles) in the crude powder of 5-chlorobenzotriazole. The precision membrane filter 20 may be in communication with the heated dissolving tank set 10 to cyclically receive and return the mixed solution H. To achieve the above objective, the precision membrane filter 20 can suck the mixed solution H through a liquid inlet line 201 (indicated by the arrow with a diagonal bottom) by a second pump P2, and discharge the mixed solution back to the dissolution tank 12 through a liquid outlet line 202 (indicated by the arrow with a diagonal bottom) after the cyclic filtration, thus repeatedly circulating. In addition, a first control valve 203 may be mounted to the inlet line 201 for discharging (as indicated by solid arrows) residual waste material from the recirculation filter when emptying the dissolution tank 12. A second control valve 204 may also be mounted on the outlet line 202 for switching the mixed solution H after the completion of the loop filtration to the next processing unit. The precision membrane filter 20 includes a plurality of precision filtration membranes: a 450nm pore size microfiltration membrane 21, a 200nm pore size microfiltration membrane 22 and a 40nm pore size microfiltration membrane. The mixed solution H can be selectively flowed to one of the third control valves 24 by the on-off control of the plurality of third control valves 24. The 450nm pore size microfiltration membrane 21 may be used to perform at least 45 minutes (e.g., 60 minutes) of the mixed solution H at a time, the 200nm pore size microfiltration membrane 22 may be used to perform at least 45 minutes (e.g., 60 minutes) of the mixed solution H at a time, and the 40nm pore size microfiltration membrane 23 may be used to perform at least 90 minutes (e.g., 120 minutes) of the mixed solution H at a time. Microfiltration membranes of different pore sizes can physically remove impurities greater than or equal to this pore size. Although the micro-filtration membrane with small pore size can remove almost all impurities, the flow-through and filtration speed is low, and the filtration efficiency is low. Thus, each of the microfiltration membranes was used sequentially, and the order of execution was 450nm pore size microfiltration membrane 21, 200nm pore size microfiltration membrane 22 and 40nm pore size microfiltration membrane 23. The cyclic filtration may be performed several times for each microfiltration membrane. The microfiltration membranes used in the subsequent examples were MEP-0.45, MEP-0.2 and MES-0.04, manufactured by Asahi International Co., ltd, and were made of Polypropylene (PP) and Polyethersulfone (PES). The mixed solution H after the circulated filtration can flow out through a discharge line 25 and is temporarily stored in a purifying tank 26. Before the determination of the discharge of the purification vessel 26, the concentration of the metal component in the mixed solution H can be measured by an inductively coupled plasma mass spectrometer (ICP-MS) at the outlet of the precise filtration membrane 23 with a pore diameter of 40nm, so as to ensure that the amount of impurities such as metal can be effectively reduced by the precise membrane filter 20.
The ion exchanger 30 is in communication with the precision membrane filter 20 (either through the purification tank 26 or directly in practice) and has a cation exchange resin for exchanging and removing a part of cations (metal ions) in the mixed solution H subjected to the cyclic filtration at a temperature of 25±1 ℃ (room temperature) to obtain a refined solution R. The ion exchanger 30 has a plurality of cation exchange resins 31 (two cation exchange resins 31 are illustrated in fig. 1 as an example), a third pump P3, an auxiliary filter 32, four flow direction control valves 33, two refining solution tanks 341 and 342, and a circulation pipe 35. The cation exchange resin 31 may be a strong acid cation exchange resin or a weak acid cation exchange resin according to the present invention. The strong acid cation exchange resin contains strong acid sulfonic acid exchange group (-SO) 3 H) The weak acid cation exchange resin is a polymer containing weak acidFunctional groups such as carboxyl groups (-COOH) as exchange groups. The cation exchange resin 31 used in the subsequent examples was a strongly acidic cation exchange resin manufactured by Mitsubishi chemical corporation under the brand name DIAION SK1BH, and was used in an amount of about 100L (about 80 kg) at a time. The third pump P3 sucks the mixed solution H in the purifying tank 26 through a pipeline, and makes the refined solution R (marked with light gray color in FIG. 1) flow into the refined solution tank 341 for temporary storage through the cation exchange resin 31 and the auxiliary filter 32, and the speed can reach 3.3kg/min. The auxiliary filter 32 is for filtering strong acid cation exchange resin chips carried by the mixed solution H flowing through the cation exchange resin 31 to prevent contamination of the refining solution R. The auxiliary filter 32 is a microfiltration membrane made of Polyethersulfone (PES) manufactured by the company of the international corporation of sunburn. The four flow direction control valves 33 can control the flow direction of the mixed solution H, and allow the inflowing mixed solution H to perform the repeated cycle ion exchange through the circulation pipe 35. Refining solution R may be moved to desolventizing mechanism 40 for processing by moving refining solution barrel 342. Determining whether to become the refining solution R may be performed by measuring the concentration of the metal component in the mixed solution H at the outlet of the auxiliary filter 32 by means of an inductively coupled plasma mass spectrometer to determine that there is a significant reduction in the metal component in the refining solution R. After the refining solution R is obtained, the repeated cycle ion exchange is ended. The ion exchanger 30 was operated for about 6 hours for 600kg of the mixed solution H.
The desolventizing mechanism 40 is a device for recovering the organic solvent in the refining solution R. Desolventizing mechanism 40 heats refining solution R at a temperature of 135-145℃ (e.g., about 140℃) for at least 12 hours to distill the organic solvent, leaving a block of refined 5-chlorobenzotriazole B. The desolventizing mechanism 40 includes a condenser 41, a distillation tank 42, an electrothermal heater 43, and a recovery tank 44. The condenser 41 cools the vaporized organic solvent to form a liquid organic solvent, and conveys it to the recovery tank 44. The recovery tank 44 is used to recover the organic solvent for reuse in the heating dissolution tank set 10. The distillation barrel 42 includes a cover 421 disposed above and a barrel 422 coupled to the cover 421 in a retractable manner. The barrel 422 is hermetically connected with the condenser 41, and the refining solution R is placed in the sealed distillation barrel 42 to be heated. The distilled organic solvent is led out of the distillation barrel 42 from the condenser 41, and the refined 5-chlorobenzotriazole B in the form of a block is left in the distillation barrel 42. The electric heater 43 may receive electric power to generate heat and conduct the heat to the distillation tub 42, and maintain the temperature in the distillation tub 42 between 135-145 ℃ to perform the distillation operation of the organic solvent.
Since distilled bulk-refined 5-chlorobenzotriazole B is not powdery and is difficult to use for industry, pulverization is necessary, and the pulverizing mechanism 50 is a tool for performing this operation. The pulverizing mechanism 50 may pulverize the bulk-refined 5-chlorobenzotriazole B to obtain refined 5-chlorobenzotriazole powder F having a fineness level of 2 mm. The crushing mechanism 50 includes an input slot 51, two rollers 52 and a receiving slot 53. The input tank 51 serves to receive the bulk purified 5-chlorobenzotriazole B and release the bulk purified 5-chlorobenzotriazole B from above. The two rollers 52 are under the input slot 51, the distance between the rollers 52 can be adjusted and rotate relatively (along the arrow direction of the arc curve in fig. 1), and the friction function generated by the same rotation speed between the two rollers 52 is utilized to achieve the effect of grinding materials. The block-shaped refined 5-chlorobenzotriazole B which falls onto the upper parts of the two rollers 52 from the input end 51 by gravity is ground by the two rollers 52 to form refined 5-chlorobenzotriazole powder F with the fineness level of 2mm and falls downwards. A receiving groove 53 is provided below the roller 52 for receiving the dropped purified 5-chlorobenzotriazole powder F. The refined 5-chlorobenzotriazole powder F is a finished product which can be used for industry, and the purity of the refined 5-chlorobenzotriazole powder F can reach more than 99.5 percent.
Based on the operation of the above-mentioned 5-chlorobenzotriazole purification apparatus 1, the present invention also proposes a method for purifying 5-chlorobenzotriazole (hereinafter referred to as a purification method). Please refer to fig. 2, which is a flow chart of the refining method. The refining method comprises the following steps: a heating and dissolving step (S01), a filtering step (S02), an ion exchange step (S03), a desolventizing step (S04) and a crushing step (S05). The heating and dissolving steps are as follows: dissolving the crude 5-chlorobenzotriazole powder in an organic solvent (any one of methanol, ethanol or isopropanol) at the temperature of 50-60 ℃ for heating and dissolving for 3-4 hours to form a mixed solution, wherein the weight ratio of the crude 5-chlorobenzotriazole powder to the organic solvent is 1:4-1:5. The filtering steps are as follows: the mixed solution was subjected to filtration treatment with a microfiltration membrane having a pore size of 40nm to remove impurities and metal particles. Although the precise membrane filter 20 comprises a 450nm pore size precise filter membrane 21, a 200nm pore size precise filter membrane 22 and a 40nm pore size precise filter membrane 23, impurities and impurities above 40nm are filtered out mainly by the 40nm pore size precise filter membrane 23, and the 450nm pore size precise filter membrane 21 and the 200nm pore size precise filter membrane 22 are only used for accelerating the filtering speed. The ion exchange steps are as follows: ion-exchanging the mixed solution after the filtration treatment with a cation exchange resin at a temperature of 25.+ -. 1 ℃ for at least 6 hours, and taking out a part of the cation exchange to obtain a refined solution. The solvent removing step comprises the following steps: the refining solution is heated at a temperature of 135-145 ℃ for at least 12 hours to distill the organic solvent, leaving a bulk refined 5-chlorobenzotriazole. The crushing steps are as follows: the blocky refined 5-chlorobenzotriazole is crushed to obtain refined 5-chlorobenzotriazole powder with the fineness grade of 2 mm. It is preferable that the mixed solution to be processed in a batch is not more than 800 kg for the purpose of better quality, limited to the apparatus.
The following were taken out 120kg of each of 5-chlorobenzotriazole crude powders having various components of metal impurities (including particulate and ionic states), 480kg of ethanol was mixed to prepare 600kg of 5-chlorobenzotriazole crude powders, and the above-mentioned 5-chlorobenzotriazole refining apparatus 1 was used to see the change in the components of the refined 5-chlorobenzotriazole powders.
Example 1
Please see table one, which lists various metal concentrations of a first 5-chlorobenzotriazole crude powder, various metal concentrations in the mixed solution at the outlet of the 40nm pore size precision filtration membrane, various metal concentrations in the refined solution at the outlet of the auxiliary filter, and various metal concentrations of the refined 5-chlorobenzotriazole powder.
List one
| Metal species | Aluminum (Al) | Iron (Fe) | Sodium salt | Magnesium (Mg) | Calcium | Potassium | Copper (Cu) | Nickel (Ni) | Chromium (Cr) | Zinc alloy |
| Crude powder of 5-chlorobenzotriazole | 0.36 | 1.96 | 0.58 | 1.03 | 2.62 | 0.21 | <0.1 | 0.21 | 0.16 | 0.13 |
| Precise filtration with 40nm pore diameterAt the membrane outlet | 0.15 | 0.63 | 0.58 | 0.94 | 1.91 | 0.21 | <0.1 | 0.17 | <0.1 | 0.13 |
| Auxiliary filter outlet | <0.1 | 0.40 | <0.1 | <0.1 | 0.58 | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 |
| Refined 5-chlorobenzotriazole powder | <0.1 | 0.44 | <0.1 | <0.1 | 0.53 | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 |
Units: ppm of
From the results, it was found that the concentration of metal components such as aluminum, iron, and calcium was greatly reduced after the solution passed through a 40nm pore size microfiltration membrane. The sodium and magnesium which are not removed and which flow out are removed in the ion exchange resin (at the outlet of the auxiliary filter). The concentration of the metal components such as sodium and magnesium was reduced to a level less than the analysis upper limit (< 0.1 ppm), and it was confirmed that the metal components were removed by the ion exchanger. The metal concentration of the refined 5-chlorobenzotriazole powder is less than 1ppm of iron and calcium, the other metals are less than 0.1ppm, and the purity of the finished product after refining is more than 99.9 percent, thereby meeting the requirements.
Example two
Please see table two, which lists various metal concentrations of a second 5-chlorobenzotriazole crude powder, various metal concentrations in the mixed solution at the outlet of the 40nm pore size precision filtration membrane, various metal concentrations in the refined solution at the outlet of the auxiliary filter, and various metal concentrations of the refined 5-chlorobenzotriazole powder.
Watch II
Units: ppm of
The concentration of aluminum, iron, sodium, magnesium, calcium and zinc in the second 5-chlorobenzotriazole coarse powder is 3.08 times, 2.06 times, 2.09 times, 0.43 times, 1.46 times and 1.38 times of the same components of the first 5-chlorobenzotriazole coarse powder in the first embodiment respectively, the concentration of nickel is lower, and the concentration of the rest metals is not greatly changed. From the results, it was found that the concentration of metal components such as aluminum, iron, and calcium was greatly reduced after the liquid passed through the 40nm pore size microfiltration membrane. The sodium and magnesium which are not removed and which flow out are removed in the ion exchange resin. The concentration of the metal components such as sodium and magnesium was reduced to a level lower than the analysis upper limit, and it was confirmed that the metal components were removed by the ion exchanger. The metal concentration of the refined 5-chlorobenzotriazole powder is less than 1ppm of iron, calcium and chromium, the other metals are less than 0.1ppm, and the purity of the finished product after refining is more than 99.9 percent, which also meets the requirements.
Example III
Please see table three, which lists various metal concentrations of a third 5-chlorobenzotriazole crude powder, various metal concentrations in the mixed solution at the outlet of the 40nm pore size precision filtration membrane, various metal concentrations in the refined solution at the outlet of the auxiliary filter, and various metal concentrations of the refined 5-chlorobenzotriazole powder.
Watch III
| Metal species | Aluminum (Al) | Iron (Fe) | Sodium salt | Magnesium (Mg) | Calcium | Potassium | Copper (Cu) | Nickel (Ni) | Chromium (Cr) | Zinc alloy |
| Crude powder of 5-chlorobenzotriazole | 1.14 | 8.24 | 1.82 | 1.05 | 3.97 | 0.16 | 0.47 | 0.11 | 0.18 | 0.25 |
| 40nm aperture precision filter membrane outlet | 0.45 | 1.94 | 1.80 | 1.00 | 2.84 | 0.14 | 0.41 | <0.1 | 0.14 | 0.24 |
| Auxiliary filter outlet | 0.20 | 1.23 | <0.1 | <0.1 | 0.39 | <0.1 | 0.15 | <0.1 | 0.13 | <0.1 |
| Refined 5-chlorobenzotriazole powder | 0.22 | 1.26 | <0.1 | <0.1 | 0.32 | <0.1 | 0.16 | <0.1 | 0.14 | <0.1 |
Units: ppm of
The third crude powder of 5-chlorobenzotriazole and the second crude powder of 5-chlorobenzotriazole are similar in that the concentration of metals such as aluminum, iron, sodium, calcium, copper, zinc and the like is much higher than that of the first crude powder of 5-chlorobenzotriazole, the concentration of nickel is same lower, and the concentration of the other metals is not changed much. From the results, it was found that the concentration of metal components such as aluminum, iron, and calcium was greatly reduced after the liquid passed through the 40nm pore size microfiltration membrane. The sodium and magnesium which are not removed and which flow out are removed in the ion exchange resin. The concentration of the metal components such as sodium and magnesium was reduced to a level lower than the analysis upper limit, and it was confirmed that the metal components were removed by the ion exchanger. The metal concentration of the refined 5-chlorobenzotriazole powder is less than 1ppm of aluminum, calcium, copper and chromium, the iron is less than 2ppm, the other metals are less than 0.1ppm, and the purity of the finished product after refining is more than 99.9 percent, which also meets the requirements.
Claims (10)
1. A refining method of 5-chlorobenzotriazole is characterized by comprising the following steps:
and (3) heating and dissolving: dissolving the 5-chlorobenzotriazole crude powder in an organic solvent at the temperature of 50-60 ℃ for heating and dissolving for 3-4 hours to form a mixed solution, wherein the weight ratio of the 5-chlorobenzotriazole crude powder to the organic solvent is 1:4-1:5;
and (3) filtering: filtering the mixed solution by a precise filtering membrane with the aperture of 40nm to remove impurities and metal particles;
ion exchange step: ion-exchanging the mixed solution subjected to the filtration treatment with a cation exchange resin at a temperature of 25 + -1 ℃ for at least 6 hours, and taking out part of the cation exchange to obtain a refined solution;
a solvent removal step: heating the refining solution at a temperature of 135-145 ℃ for at least 12 hours to distill the organic solvent, leaving a bulk refined 5-chlorobenzotriazole; and
crushing: the blocky refined 5-chlorobenzotriazole is crushed to obtain refined 5-chlorobenzotriazole powder with the fineness grade of 2 mm.
2. The method for purifying 5-chlorobenzotriazole as claimed in claim 1, wherein: the organic solvent is methanol, ethanol or isopropanol.
3. The method for purifying 5-chlorobenzotriazole as claimed in claim 1, wherein: the mixed solution is not more than 800 kg in a batch process.
4. A purification apparatus for 5-chlorobenzotriazole, comprising:
a heating dissolution tank set for providing a temperature of 50-60 ℃, dissolving the 5-chlorobenzotriazole crude powder in an organic solvent, and heating and dissolving for 3-4 hours to form a mixed solution, wherein the weight ratio of the 5-chlorobenzotriazole crude powder to the organic solvent is 1:4-1:5;
a precision membrane filter in communication with the heated dissolution tank set for cyclically receiving and returning the mixed solution, comprising a 40nm pore size precision filtration membrane for cyclically filtering the mixed solution for at least 90 minutes each time;
an ion exchanger, which is communicated with the precise membrane filter and is provided with cation exchange resin, and the ion exchanger exchanges and takes out partial cations in the mixed solution which is circularly filtered at the temperature of 25+/-1 ℃ so as to obtain a refined solution;
a desolventizing mechanism for heating the refined solution at a temperature of 135-145 ℃ for at least 12 hours to distill the organic solvent to leave a bulk refined 5-chlorobenzotriazole; and
a crushing mechanism for crushing the blocky refined 5-chlorobenzotriazole to obtain refined 5-chlorobenzotriazole powder with the fineness grade of 2 mm.
5. The apparatus for purifying 5-chlorobenzotriazole as claimed in claim 4, wherein: the organic solvent is methanol, ethanol or isopropanol.
6. The apparatus for purifying 5-chlorobenzotriazole as claimed in claim 4, wherein: the precision membrane filter further comprises:
a 450nm pore size microfiltration membrane for at least 45 minutes of each cycle of filtering the mixed solution; a kind of electronic device with high-pressure air-conditioning system
A 200nm pore size microfiltration membrane for performing at least 45 minutes of each cycle of filtration of the mixed solution,
the execution sequence is the 450nm aperture precise filtration membrane, the 200nm aperture precise filtration membrane and the 40nm aperture precise filtration membrane in sequence.
7. The apparatus for purifying 5-chlorobenzotriazole as claimed in claim 4, wherein: the cation exchange resin is a strong acid cation exchange resin or a weak acid cation exchange resin.
8. The apparatus for purifying 5-chlorobenzotriazole as claimed in claim 4, wherein: the desolventizing mechanism further includes a recovery tank for recovering the organic solvent for reuse in the heated dissolution tank set.
9. The apparatus for purifying 5-chlorobenzotriazole as claimed in claim 4, wherein: the desolventizing mechanism further includes:
a condenser;
the distillation barrel comprises a cover body above and a barrel body combined with the cover body in an openable and closable manner, the barrel body is hermetically connected with the condenser, the refining solution is placed in the sealed distillation barrel and heated, the distilled organic solvent is led out of the distillation barrel by the condenser, and blocky refined 5-chlorobenzotriazole is left in the distillation barrel; a kind of electronic device with high-pressure air-conditioning system
An electrothermal heater receives electric power to generate heat and transmit the heat to the distillation barrel, and the temperature in the distillation barrel is kept between 135-145 ℃.
10. The apparatus for purifying 5-chlorobenzotriazole as claimed in claim 4, wherein: the pulverizing mechanism further comprises:
an input groove for receiving the block-shaped refined 5-chlorobenzotriazole and releasing the block-shaped refined 5-chlorobenzotriazole from the high position;
the two rollers are adjustable in distance and relatively rotate, and the blocky refined 5-chlorobenzotriazole falling onto the upper parts of the two rollers from the input end by gravity is ground by the two rollers to form refined 5-chlorobenzotriazole powder with the fineness level of 2mm and falls down; a kind of electronic device with high-pressure air-conditioning system
A receiving tank for receiving the dropped refined 5-chlorobenzotriazole powder.
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