TWI825787B - Method and system for refining 5-chlorobenzotriazole - Google Patents
Method and system for refining 5-chlorobenzotriazole Download PDFInfo
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- TWI825787B TWI825787B TW111122507A TW111122507A TWI825787B TW I825787 B TWI825787 B TW I825787B TW 111122507 A TW111122507 A TW 111122507A TW 111122507 A TW111122507 A TW 111122507A TW I825787 B TWI825787 B TW I825787B
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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 121
- 238000007670 refining Methods 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000012528 membrane Substances 0.000 claims abstract description 70
- 238000001914 filtration Methods 0.000 claims abstract description 63
- 239000000843 powder Substances 0.000 claims abstract description 63
- 239000011259 mixed solution Substances 0.000 claims abstract description 57
- 239000011148 porous material Substances 0.000 claims abstract description 50
- 239000003960 organic solvent Substances 0.000 claims abstract description 41
- 239000000243 solution Substances 0.000 claims abstract description 40
- 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 28
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 239000012535 impurity Substances 0.000 claims abstract description 17
- 239000002923 metal particle Substances 0.000 claims abstract description 5
- 238000005341 cation exchange Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000004821 distillation Methods 0.000 claims description 22
- 238000000746 purification Methods 0.000 claims description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- 230000002378 acidificating effect Effects 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 10
- 238000005342 ion exchange Methods 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 230000005484 gravity Effects 0.000 claims description 3
- CVICEEPAFUYBJG-UHFFFAOYSA-N 5-chloro-2,2-difluoro-1,3-benzodioxole Chemical group C1=C(Cl)C=C2OC(F)(F)OC2=C1 CVICEEPAFUYBJG-UHFFFAOYSA-N 0.000 claims 1
- 238000010298 pulverizing process Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 41
- 239000002184 metal Substances 0.000 description 41
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 150000002739 metals Chemical class 0.000 description 17
- 239000007788 liquid Substances 0.000 description 14
- 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
- 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
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 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
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 150000002894 organic compounds Chemical class 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
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 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
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 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
- 239000000284 extract Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 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
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
Description
本發明關於一種有機化合物之精製方法及精製系統，特別是一種5-氯代苯並三氮唑之精製方法及精製系統。The present invention relates to a refining method and refining system for organic compounds, in particular to a refining method and refining system for 5-chlorobenzotriazole.
5-氯代苯並三氮唑是一種應用面廣的有機化合物。5-氯代苯並三氮唑常用於與一些化合物進行有機合成，成為其他的下游有機化合物，也用作電鍍添加劑。此外，感光材料中有效的防灰霧劑及穩定劑也使用到5-氯代苯並三氮唑，因而該物質也廣泛應用於照相紙乳劑和顯影液的生產中。5-Chlorobenzotriazole is an organic compound with a wide range of applications. 5-Chlorobenzotriazole is often used in organic synthesis with some compounds to become other downstream organic compounds, and is also used as an electroplating additive. In addition, 5-chlorobenzotriazole is also used as an effective anti-fog agent and stabilizer in photosensitive materials, so this substance is also widely used in the production of photographic paper emulsions and developers.
市場上銷售的5-氯代苯並三氮唑的純度不低，但通常低於99%。混雜在5-氯代苯並三氮唑粉體中的不純物通常是一些金屬雜質，比如、鐵、鈉、鎂、鈣、鉀、銅、鎳、鉻、鋅等。如果要製作較精良的產品，5-氯代苯並三氮唑的純度要提升，最好要達到99.5%~99.9%間。前述的金屬雜質的含量要降低。例如鐵的含量在精煉前在10 ppm左右，精煉後要達到2 ppm以下；鈣的含量在精煉前在5 ppm左右，精煉後也要達到2 ppm以下；其它少量金屬的含量在精煉後也要低於1 ppm。The purity of 5-chlorobenzotriazole sold on the market is not low, but usually less than 99%. The impurities mixed in 5-chlorobenzotriazole powder are usually some metal impurities, such as iron, sodium, magnesium, calcium, potassium, copper, nickel, chromium, zinc, etc. If you want to make a more sophisticated product, the purity of 5-chlorobenzotriazole needs to be improved, preferably between 99.5% and 99.9%. The content of the aforementioned metal impurities should be reduced. For example, the iron content is around 10 ppm before refining and should be below 2 ppm after refining; the calcium content is around 5 ppm before refining and should be below 2 ppm after refining; the content of other small amounts of metals should also be below 2 ppm after refining. Less than 1 ppm.
然而，目前針對5-氯代苯並三氮唑的精煉並沒有有效的方式。因此，本發明即是提出關於5-氯代苯並三氮唑之精製方法及精製系統。However, there is currently no effective method for refining 5-chlorobenzotriazole. Therefore, the present invention proposes a purification method and purification system for 5-chlorobenzotriazole.
本段文字提取和編譯本發明的某些特點。其它特點將被揭露於後續段落中。其目的在涵蓋附加的申請專利範圍之精神和範圍中，各式的修改和類似的排列。This text extracts and compiles certain features of the invention. Other features will be revealed in subsequent paragraphs. It is intended to cover various modifications and similar arrangements within the spirit and scope of the appended claims.
本發明揭露一種5-氯代苯並三氮唑之精製方法，包含步驟：加熱溶解步驟：在50-60℃的溫度下，將5-氯代苯並三氮唑粗製粉體溶解於一有機溶劑中，進行加熱溶解3-4小時，以形成一混合溶液，其中5-氯代苯並三氮唑粗製粉體與該有機溶劑的重量比為1:4~1:5；過濾步驟：以孔徑40nm的精密過濾膜對該混合溶液進行過濾處理，以除去雜質及金屬顆粒；離子交換步驟：在25±1℃的溫度下，以陽離子交換樹脂對過濾處理完成的該混合溶液進行離子交換至少6小時，將其中部分的陽離子交換取出，以獲得一精煉溶液；去溶劑步驟：在135-145℃的溫度下加熱該精煉溶液至少12小時，以將該有機溶劑蒸餾，留下塊狀精製5-氯代苯並三氮唑；以及粉碎步驟：粉碎該塊狀精製5-氯代苯並三氮唑，以獲得細度等級2mm之精製5-氯代苯並三氮唑粉體。The invention discloses a method for refining 5-chlorobenzotriazole, which includes the following steps: heating and dissolving step: dissolving the crude powder of 5-chlorobenzotriazole in an organic solvent at a temperature of 50-60°C. In the solvent, heat and dissolve for 3-4 hours to form a mixed solution, in which the weight ratio of the crude 5-chlorobenzotriazole powder and the organic solvent is 1:4~1:5; the filtration step: The mixed solution is filtered with a precision filter membrane with a pore size of 40 nm to remove impurities and metal particles; the ion exchange step: at a temperature of 25±1°C, use a cation exchange resin to ion exchange the filtered mixed solution for at least 6 hours, take out part of the cation exchange to obtain a refined solution; desolventization step: heat the refined solution at a temperature of 135-145°C for at least 12 hours to distill the organic solvent, leaving a block of refined 5 -Chlorobenzotriazole; and a crushing step: crush the massive refined 5-chlorobenzotriazole to obtain refined 5-chlorobenzotriazole powder with a fineness grade of 2 mm.
最好，該有機溶劑甲醇、乙醇或異丙醇。Preferably, the organic solvent is methanol, ethanol or isopropyl alcohol.
最好，一批量處理的該混合溶液不超過800公斤。Preferably, the mixed solution processed in one batch does not exceed 800 kilograms.
本發明亦揭露一種5-氯代苯並三氮唑之精製系統，包含：一加熱溶解槽組，用以提供50-60℃的溫度，將5-氯代苯並三氮唑粗製粉體溶解於一有機溶劑中，進行加熱溶解3-4小時，以形成一混合溶液，其中5-氯代苯並三氮唑粗製粉體與該有機溶劑的重量比為1:4~1:5；一精密膜過濾機，與該加熱溶解槽組連通以循環地接收及回送該混合溶液，包含一40nm孔徑精密過濾膜，用以對該混合溶液進行每次至少90分鐘的循環過濾；一離子交換機，與該精密膜過濾機連通並具有陽離子交換樹脂，在25±1℃的溫度下交換取出完成循環過濾的該混合溶液中部分的陽離子，以獲得一精煉溶液；一去溶劑機構，將該精煉溶液在135-145℃的溫度下加熱至少12小時，以將該有機溶劑蒸餾，留下塊狀精製5-氯代苯並三氮唑；以及一粉碎機構，粉碎該塊狀精製5-氯代苯並三氮唑，以獲得細度等級2mm之精製5-氯代苯並三氮唑粉體。The invention also discloses a refining system for 5-chlorobenzotriazole, which includes: a heating and dissolving tank group for providing a temperature of 50-60°C to dissolve the crude powder of 5-chlorobenzotriazole. In an organic solvent, heat and dissolve for 3-4 hours to form a mixed solution, in which the weight ratio of the crude 5-chlorobenzotriazole powder and the organic solvent is 1:4~1:5; A precision membrane filter connected to the heated dissolution tank group to receive and return the mixed solution cyclically, including a 40nm pore size precision filter membrane for cyclic filtering of the mixed solution for at least 90 minutes each time; an ion exchanger, It is connected to the precision membrane filter and has a cation exchange resin, which exchanges and removes part of the cations in the mixed solution that has completed the cyclic filtration at a temperature of 25±1°C to obtain a refined solution; a solvent removal mechanism removes the refined solution Heating at a temperature of 135-145°C for at least 12 hours to distill the organic solvent, leaving a block of refined 5-chlorobenzotriazole; and a crushing mechanism to crush the block of refined 5-chlorobenzotriazole. benzotriazole to obtain refined 5-chlorobenzotriazole powder with a fineness grade of 2mm.
最好，該有機溶劑甲醇、乙醇或異丙醇。Preferably, the organic solvent is methanol, ethanol or isopropyl alcohol.
依照本發明，該精密膜過濾機可進一步包含：一450nm孔徑精密過濾膜，用以對該混合溶液進行每次至少45分鐘的循環過濾；及一200nm孔徑精密過濾膜，用以對該混合溶液進行每次至少45分鐘的循環過濾，執行順序依次為該450nm孔徑精密過濾膜、該200nm孔徑精密過濾膜及該40nm孔徑精密過濾膜。According to the present invention, the precision membrane filter may further comprise: a 450nm pore size precision filtration membrane, used to circulate the mixed solution for at least 45 minutes each time; and a 200nm pore size precision filtration membrane, used to filter the mixed solution The cyclic filtration is performed for at least 45 minutes each time, and the order of execution is the 450nm pore size precision filtration membrane, the 200nm pore size precision filtration membrane, and the 40nm pore size precision filtration membrane.
最好，該陽離子交換樹脂為強酸性陽離子交換樹脂或弱酸性陽離子交換樹脂。Preferably, the cation exchange resin is a strongly acidic cation exchange resin or a weakly acidic cation exchange resin.
最好，該去溶劑機構可進一步包含一回收槽，用以回收該有機溶劑，重新用於該加熱溶解槽組中。Preferably, the solvent removal mechanism may further include a recovery tank for recovering the organic solvent and reusing it in the heated dissolution tank group.
依照本發明，該去溶劑機構可進一步包含：一冷凝器；一蒸餾桶，包含上方一蓋體及與該蓋體可開合地結合之一桶體，該桶體密接該冷凝器，該精煉溶液置於密閉的該蒸餾桶中被加熱，蒸餾出的該有機溶劑由冷凝器導出該蒸餾桶，塊狀精製5-氯代苯並三氮唑遺留於該蒸餾桶中；及一電熱加熱器，接收電力以產生熱量，並將熱量傳導至該蒸餾桶，保持該蒸餾桶內溫度在135-145℃之間。According to the present invention, the solvent removal mechanism may further include: a condenser; a distillation barrel, including an upper cover and a barrel that can be opened and closed with the cover, the barrel is closely connected to the condenser, and the refining barrel is The solution is placed in the sealed distillation barrel and heated, the distilled organic solvent is led out of the distillation barrel from the condenser, and the block refined 5-chlorobenzotriazole is left in the distillation barrel; and an electric heater , receives electricity to generate heat, conducts the heat to the distillation barrel, and maintains the temperature in the distillation barrel between 135-145°C.
依照本發明，該粉碎機構可進一步包含：一輸入槽，用以盛接該塊狀精製5-氯代苯並三氮唑並將該塊狀精製5-氯代苯並三氮唑自高處釋放；二滾輪，彼此間距可調整並相對地旋轉，藉由重力由該輸入端掉落到該二滾輪上方的該塊狀精製5-氯代苯並三氮唑受該二滾輪研磨，形成細度等級2mm之精製5-氯代苯並三氮唑粉體並向下方掉落；及一接收槽，接收掉落的精製5-氯代苯並三氮唑粉體。According to the present invention, the crushing mechanism may further include: an input chute for receiving the block-shaped refined 5-chlorobenzotriazole and discharging the block-shaped refined 5-chlorobenzotriazole from a height Release; the two rollers can adjust the distance between each other and rotate relatively, and the block of refined 5-chlorobenzotriazole dropped from the input end to the top of the two rollers by gravity is ground by the two rollers to form fine particles. The refined 5-chlorobenzotriazole powder with a density of 2mm falls downward; and a receiving tank receives the fallen refined 5-chlorobenzotriazole powder.
依照本發明揭露的精製方法與精製系統，可確保5-氯代苯並三氮唑的純度可高於99.5%，優於市場上販售之現有商品。According to the purification method and purification system disclosed in the present invention, the purity of 5-chlorobenzotriazole can be ensured to be higher than 99.5%, which is superior to existing products sold on the market.
為了使揭露內容的敘述更加詳盡及完備，以下針對本發明的實施態樣與具體實施例提出了說明性的描述。In order to make the description of the disclosure more detailed and complete, an illustrative description is provided below for implementation modes and specific examples of the present invention.
請見圖1，該圖為依照本發明的一種5-氯代苯並三氮唑之精製系統1的元件示意圖。5-氯代苯並三氮唑之精製系統1包含了一加熱溶解槽組10、一精密膜過濾機20、一離子交換機30、一去溶劑機構40及一粉碎機構50。前述諸元件的態樣、功能以及系統的運作，將於下方詳述之。Please see Figure 1, which is a schematic diagram of the components of a purification system 1 for 5-chlorobenzotriazole according to the present invention. The refining system 1 for 5-chlorobenzotriazole includes a heating and dissolving tank group 10, a precision membrane filter 20, an ion exchanger 30, a solvent removal mechanism 40 and a crushing mechanism 50. The appearance, function and operation of the system will be described in detail below.
加熱溶解槽組10的功用是用以提供50-60℃的溫度，將5-氯代苯並三氮唑粗製粉體溶解於一有機溶劑中，進行加熱溶解3-4小時，以形成一混合溶液H。5-氯代苯並三氮唑粗製粉體的純度小於99%，一般在98%左右。雜質與不純物太多，對後續的加工作業造成了不少的困擾，需要進一步減少。加熱溶解槽組10的細部裝置包含了一有機溶劑供應源11、溶解槽體12、加熱槽體13及5-氯代苯並三氮唑粗製粉體供應源14。依照本發明，有機溶劑可以是醇類，比如甲醇、乙醇或異丙醇。在下列的實施中以乙醇為例來說明，其純度大於99.5%。由於醇類是液體，有機溶劑供應源11可以是個儲存槽或是連通外部醇類可回收來源，如儲存罐的管線。有機溶劑注入溶解槽體12的方式可以多樣，比如通過一第一開關閥門111的控制，直接注入溶解槽體12中；也可以通過一第二開關閥門112的控制，注入循環過濾的混合溶液H中補充。The function of the heating and dissolving tank group 10 is to provide a temperature of 50-60°C to dissolve the crude 5-chlorobenzotriazole powder in an organic solvent and heat and dissolve it for 3-4 hours to form a mixture. Solution H. The purity of 5-chlorobenzotriazole crude powder is less than 99%, generally around 98%. There are too many impurities and impurities, which cause a lot of troubles to subsequent processing operations and need to be further reduced. The detailed device of the heating and dissolving tank group 10 includes an organic solvent supply source 11, a dissolving 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 alcohols, such as methanol, ethanol or isopropyl alcohol. In the following implementation, ethanol is taken as an example, and its purity is greater than 99.5%. Since alcohol is a liquid, the organic solvent supply source 11 can be a storage tank or a pipeline connected to an external alcohol recovery source, such as a storage tank. The organic solvent can be injected into the dissolving tank 12 in various ways. For example, it can be directly injected into the dissolving tank 12 through the control of a first switching valve 111; it can also be injected into the circulating filtered mixed solution H under the control of a second switching valve 112. Supplement.
溶解槽體12是形成該混合溶液H的主要處所。溶解槽體12開設數個開孔121，開孔121流通混合溶液H以進行加熱及回收。加熱槽體13利用一第一泵浦P1透過一回收管線131從一開孔121將已冷卻的混合溶液H吸取，加熱後，再將已加熱的混合溶液H通過一注液管線132，回注另一開孔121中。混合溶液H的循環方向如圖1中實心線段箭號標示。加熱槽體13可以加熱混合溶液H的溫度範圍在50-60℃，混合溶液H攜帶的熱量可能會在管線中損失，只要確保溶解槽體12內的溫度在30-40℃即可。5-氯代苯並三氮唑粗製粉體供應源14可以依照特定重量，將5-氯代苯並三氮唑粗製粉體投入溶解槽體12中與有機溶劑混合。要注意的是，依照本發明，5-氯代苯並三氮唑粗製粉體與有機溶劑的重量比有其限制，應為1:4~1:5。以重量濃度20%為例，可將120kg的5-氯代苯並三氮唑粗製粉體與480kg的乙醇混合製成為600kg的混合溶液H。The dissolution tank 12 is the main place where the mixed solution H is formed. The dissolving tank body 12 is provided with several openings 121, and the openings 121 circulate the mixed solution H for heating and recovery. The heating tank 13 uses a first pump P1 to suck the cooled mixed solution H from an opening 121 through a recovery line 131. After heating, the heated mixed solution H is then injected back into the liquid injection line 132 through a liquid injection line 132. in another opening 121. The circulation direction of mixed solution H is marked by the solid line arrow in Figure 1. The heating tank 13 can heat the mixed solution H to a temperature range of 50-60°C. The heat carried by the mixed solution H may be lost in the pipeline, so long as the temperature in the dissolving tank 12 is ensured to be 30-40°C. The 5-chlorobenzotriazole crude powder supply source 14 can put the 5-chlorobenzotriazole crude powder into the dissolving tank 12 and mix it with the organic solvent according to a specific weight. It should be noted that according to the present invention, the weight ratio of the crude 5-chlorobenzotriazole powder and the organic solvent is limited and should be 1:4~1:5. Taking the weight concentration of 20% as an example, 120kg of 5-chlorobenzotriazole crude powder and 480kg of ethanol can be mixed to make 600kg of mixed solution H.
精密膜過濾機20的作用是對混合溶液H進行循環過濾，以取出5-氯代苯並三氮唑粗製粉體中的雜質與不純物（如金屬顆粒）。精密膜過濾機20可與加熱溶解槽組10連通以循環地接收及回送混合溶液H。為了達成前述目的，精密膜過濾機20可透過一第二泵浦P2，將混合溶液H經由一入液管線201吸入接收（如斜線底箭號標示），並在循環過濾後，由一出液管線202排出回送至溶解槽體12中（如空心箭號標示），如此反覆循環。此外，入液管線201上可安裝一第一控制閥門203，用來在清空溶解槽體12時，將殘餘廢料排出（如實心箭號標示）而不進入循環過濾中。出液管線202上也可安裝一第二控制閥門204，用來在完成循環過濾時，將完成循環過濾的混合溶液H切換輸送到下一個處理裝置中。精密膜過濾機20內包含了多個精密過濾膜：一450nm孔徑精密過濾膜21、一200nm孔徑精密過濾膜22與一40nm孔徑精密過濾膜。透過多個第三控制閥門24的開關控制，混合溶液H可以選擇性地流向其中一個第三控制閥門24。450nm孔徑精密過濾膜21可用以對混合溶液H進行每次至少45分鐘（比如60分鐘）的循環過濾，200nm孔徑精密過濾膜22可用以對混合溶液H進行每次至少45分鐘（比如60分鐘）的循環過濾，40nm孔徑精密過濾膜23可用以對混合溶液H進行每次至少90分鐘（比如120分鐘）的循環過濾。不同孔徑的精密過濾膜可以物理性地除去該孔徑長度以上的不純物。雖然孔徑小的精密過濾膜可以除去幾乎所有的不純物，但其流通與過濾速度慢，過濾效率低。因此，每個精密過濾膜是依次地使用，執行順序依次為450nm孔徑精密過濾膜21、200nm孔徑精密過濾膜22及40nm孔徑精密過濾膜23。對每一精密過濾膜可執行數次的循環過濾。在後續實施例中使用的精密過濾膜為旭然國際股份有限公司生產的型號MEP-0.45、MEP-0.2與MES-0.04，材質為聚丙烯（Polypropylene，PP）與聚醚碸（Polyethersulfone，PES）。完成循環過濾的混合溶液H可由一排出管線25流出，暫儲於一純化桶26中。在決定可以放流純化桶26前，可於40nm孔徑精密過濾膜23出口處，以感應耦合電漿質譜儀（ICP-MS）量測混合溶液H中金屬成分的濃度，以確保金屬等不純物的量能有效為精密膜過濾機20降低。The function of the precision membrane filter 20 is to circulate and filter the mixed solution H to remove impurities and impurities (such as metal particles) in the crude 5-chlorobenzotriazole powder. The precision membrane filter 20 can be connected to the heated dissolution tank group 10 to receive and return the mixed solution H cyclically. In order to achieve the aforementioned purpose, the precision membrane filter 20 can use a second pump P2 to inhale and receive the mixed solution H through an inlet pipeline 201 (as indicated by an arrow with a diagonal bottom), and after circulating filtration, it can be discharged through an outlet The discharge from the pipeline 202 is returned to the dissolving tank 12 (as indicated by the hollow arrow), and this cycle repeats. In addition, a first control valve 203 can be installed on the liquid inlet line 201 to discharge the residual waste (as indicated by the solid arrow) when the dissolving tank 12 is emptied without entering the circulating filtration. A second control valve 204 can also be installed on the liquid outlet line 202 to switch and transport the mixed solution H that has completed the cycle filtration to the next treatment device when the cycle filtration is completed. The precision membrane filter 20 contains a plurality of precision filtration membranes: a 450nm pore size precision filtration membrane 21, a 200nm pore size precision filtration membrane 22, and a 40nm pore size precision filtration membrane. Through the switch control of a plurality of third control valves 24, the mixed solution H can selectively flow to one of the third control valves 24. The 450nm pore size precision filter membrane 21 can be used to filter the mixed solution H for at least 45 minutes (such as 60 minutes) at a time. ), the 200nm pore size precision filtration membrane 22 can be used to cycle the mixed solution H for at least 45 minutes (such as 60 minutes) each time, and the 40nm pore size precision filtration membrane 23 can be used to cycle the mixed solution H for at least 90 minutes each time. (e.g. 120 minutes) cycle filtration. Precision filtration membranes with different pore sizes can physically remove impurities above the pore length. Although the precision filtration membrane with small pore size can remove almost all impurities, its circulation and filtration speed are slow and the filtration efficiency is low. Therefore, each precision filtration membrane is used in sequence, and the order of execution is the 450nm pore size precision filtration membrane 21, the 200nm pore size precision filtration membrane 22, and the 40nm pore size precision filtration membrane 23. Several cycles of filtration can be performed on each precision filtration membrane. The precision filtration membranes used in subsequent examples are models MEP-0.45, MEP-0.2 and MES-0.04 produced by Xuran International Co., Ltd., and their materials are polypropylene (PP) and polyethersulfone (PES). . The mixed solution H that has completed cyclic filtration can flow out from a discharge line 25 and be temporarily stored in a purification barrel 26 . Before deciding to discharge the purification barrel 26, the concentration of metal components in the mixed solution H can be measured with an inductively coupled plasma mass spectrometer (ICP-MS) at the outlet of the 40nm pore size precision filter membrane 23 to ensure the amount of impurities such as metals. It can effectively reduce the precision membrane filter by 20%.
離子交換機30與精密膜過濾機20連通（可透過純化桶26，實作上也可直接連通）並具有陽離子交換樹脂，可在25±1℃的溫度（室溫）下交換取出完成循環過濾的混合溶液H中部分的陽離子（金屬離子），以獲得一精煉溶液R。離子交換機30內部具有數個陽離子交換樹脂31（圖1中以2個陽離子交換樹脂31為例來說明）、一第三泵浦P3、一輔助過濾器32、四個流向控制閥33、兩個精煉溶液桶341與342及一循環管35。依照本發明，陽離子交換樹脂31可以是強酸性陽離子交換樹脂或弱酸性陽離子交換樹脂。強酸性陽離子交換樹脂是含強酸性磺酸交換基（-SO 3H）之苯乙烯高分子聚合物，弱酸性陽離子交換樹脂是含弱酸性官能基，如羧基－COOH，作為交換基之樹脂。在後續實施例中使用的陽離子交換樹脂31為強酸性陽離子交換樹脂，由三菱化學股份有限公司製作，廠牌型號為DIAION SK1BH，一次使用的量約100L（約80kg）。第三泵浦P3通過管線吸取純化桶26中的混合溶液H，通過陽離子交換樹脂31與輔助過濾器32，製成了精煉溶液R（圖1中以淺灰底色標註）流入到精煉溶液桶341暫存，其速率可達3.3kg/min。輔助過濾器32是用來過濾流經陽離子交換樹脂31的混合溶液H所帶出的強酸性陽離子交換樹脂碎屑，避免汙染精煉溶液R。輔助過濾器32為旭然國際股份有限公司製作，材質為聚醚碸（Polyethersulfone，PES）的精密過濾膜。四個流向控制閥33可以控制混合溶液H的流向，讓流入的混合溶液H通過循環管35進行重複循環離子交換。精煉溶液R可藉由移動精煉溶液桶342而移到去溶劑機構40進行處理。決定是否成為精煉溶液R，可於輔助過濾器32出口處，以感應耦合電漿質譜儀量測混合溶液H中金屬成分的濃度，以確定精煉溶液R中的金屬成分有明顯的降低。成為精煉溶液R後，就會結束重複循環離子交換。離子交換機30對600kg混合溶液H的執行時間約6小時。 The ion exchanger 30 is connected to the precision membrane filter 20 (can pass through the purification barrel 26, and can also be directly connected in practice) and has a cation exchange resin, which can be exchanged and taken out at a temperature of 25±1°C (room temperature) to complete the cycle filtration. Mix part of the cations (metal ions) in solution H to obtain a refined solution R. The ion exchanger 30 has several cation exchange resins 31 inside (two cation exchange resins 31 are used as an example in Figure 1 for illustration), a third pump P3, an auxiliary filter 32, four flow direction control valves 33, two Refining solution barrels 341 and 342 and a circulation pipe 35. According to the present invention, the cation exchange resin 31 may be a strongly acidic cation exchange resin or a weakly acidic cation exchange resin. Strongly acidic cation exchange resin is a styrene polymer containing a strong acidic sulfonic acid exchange group (-SO 3 H). Weakly acidic cation exchange resin is a resin containing weakly acidic functional groups, such as carboxyl-COOH, as an exchange group. The cation exchange resin 31 used in subsequent embodiments is a strongly acidic cation exchange resin produced by Mitsubishi Chemical Co., Ltd. with the brand name DIAION SK1BH and a single use volume of approximately 100L (approximately 80kg). The third pump P3 draws the mixed solution H in the purification barrel 26 through the pipeline, passes through the cation exchange resin 31 and the auxiliary filter 32, and makes the refining solution R (marked with a light gray background in Figure 1) and flows into the refining solution barrel. 341 temporary storage, its rate can reach 3.3kg/min. The auxiliary filter 32 is used to filter the strongly acidic cation exchange resin debris brought out by the mixed solution H flowing through the cation exchange resin 31 to avoid contaminating the refining solution R. The auxiliary filter 32 is manufactured by Xuran International Co., Ltd. and is made of polyethersulfone (PES) precision filtration membrane. The four flow direction control valves 33 can control the flow direction of the mixed solution H, allowing the inflowing mixed solution H to pass through the circulation pipe 35 for repeated circulation of ion exchange. The refining solution R can be moved to the solvent removal mechanism 40 by moving the refining solution barrel 342 for processing. To determine whether to become the refining solution R, the concentration of metal components in the mixed solution H can be measured with an inductively coupled plasma mass spectrometer at the outlet of the auxiliary filter 32 to confirm that the metal components in the refining solution R have been significantly reduced. After becoming the refining solution R, the repeated cycle of ion exchange ends. The execution time of the ion exchanger 30 for 600kg mixed solution H is about 6 hours.
去溶劑機構40是用來將精煉溶液R中有機溶劑回收的裝置。去溶劑機構40將精煉溶液R在135-145℃的溫度下（比如約在140℃）加熱至少12小時，以將有機溶劑蒸餾，留下塊狀精製5-氯代苯並三氮唑B。去溶劑機構40包含了一冷凝器41、一蒸餾桶42、一電熱加熱器43與一回收槽44。冷凝器41是將汽化的有機溶劑降溫以形成液態的有機溶劑，並將之傳送到回收槽44。回收槽44用以回收該有機溶劑，重新用於加熱溶解槽組10中。蒸餾桶42包含上方的一蓋體421及與該蓋體421可開合地結合之一桶體422。桶體422密接冷凝器41，精煉溶液R置於密閉的蒸餾桶42中被加熱。蒸餾出的有機溶劑由冷凝器41導出蒸餾桶42，塊狀精製5-氯代苯並三氮唑B則遺留於蒸餾桶42中。電熱加熱器43可接收電力以產生熱量，並將熱量傳導至蒸餾桶42，保持蒸餾桶42內溫度在135-145℃之間，以進行有機溶劑的蒸餾作業。The solvent removal mechanism 40 is a device for recovering the organic solvent in the refining solution R. The solvent removal mechanism 40 heats the refining solution R at a temperature of 135-145°C (eg, about 140°C) for at least 12 hours to distill the organic solvent, leaving the refined 5-chlorobenzotriazole B in bulk. The solvent removal mechanism 40 includes a condenser 41 , a distillation barrel 42 , an electric heater 43 and a recovery tank 44 . The condenser 41 cools the vaporized organic solvent to form a liquid organic solvent and sends it to the recovery tank 44 . The recovery tank 44 is used to recover the organic solvent and reuse it in the heating and dissolving tank group 10 . The distillation barrel 42 includes an upper cover 421 and a barrel 422 that is releasably combined with the cover 421 . The barrel 422 is closely connected to 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 from the condenser 41 to the distillation barrel 42 , and the block of refined 5-chlorobenzotriazole B is left in the distillation barrel 42 . The electric heater 43 can receive electricity to generate heat and conduct the heat to the distillation barrel 42 to maintain the temperature in the distillation barrel 42 between 135-145°C to perform the distillation operation of organic solvents.
由於蒸餾過的塊狀精製5-氯代苯並三氮唑B並非粉狀，難以供工業使用，必須進行粉碎化，粉碎機構50就是執行這作業的工具。粉碎機構50可粉碎該塊狀精製5-氯代苯並三氮唑B，以獲得細度等級2mm之精製5-氯代苯並三氮唑粉體F。粉碎機構50包含了一輸入槽51、二滾輪52與一接收槽53。輸入槽51用以盛接塊狀精製5-氯代苯並三氮唑B並將該塊狀精製5-氯代苯並三氮唑B自高處釋放。二滾輪52在輸入槽51下方，滾輪52彼此的間距可調整並相對地旋轉（順著圖1中圓弧曲線的箭頭方向），運用二滾輪52間相同轉速下產生的磨擦功能，來達到物料研磨的效果。藉由重力由輸入端51掉落到二滾輪52上方的塊狀精製5-氯代苯並三氮唑B受該二滾輪52研磨，形成細度等級2mm之精製5-氯代苯並三氮唑粉體F並向下方掉落。接收槽53在滾輪52下方，用來接收掉落的精製5-氯代苯並三氮唑粉體F。精製5-氯代苯並三氮唑粉體F是可供工業用的精製過的成品，其純度可達99.5%以上。Since the distilled block-shaped refined 5-chlorobenzotriazole B is not in powder form and is difficult for industrial use, it must be pulverized. The pulverizing mechanism 50 is a tool for performing this operation. The crushing mechanism 50 can crush the massive refined 5-chlorobenzotriazole B to obtain the refined 5-chlorobenzotriazole powder F with a fineness grade of 2 mm. The crushing mechanism 50 includes an input slot 51 , two rollers 52 and a receiving slot 53 . The input tank 51 is used to receive the bulk refined 5-chlorobenzotriazole B and release the bulk refined 5-chlorobenzotriazole B from a high place. The two rollers 52 are below the input groove 51. The distance between the rollers 52 can be adjusted and they rotate relatively (following the arrow direction of the arc curve in Figure 1). The friction function generated between the two rollers 52 at the same rotation speed is used to achieve the material removal. Grinding effect. The block-shaped refined 5-chlorobenzotriazole B dropped from the input end 51 to the top of the two rollers 52 by gravity is ground by the two rollers 52 to form refined 5-chlorobenzotriazole B with a fineness grade of 2 mm. Azole powder F and falls downward. The receiving groove 53 is below the roller 52 and is used to receive the fallen refined 5-chlorobenzotriazole powder F. Refined 5-chlorobenzotriazole powder F is a refined finished product available for industrial use, with a purity of over 99.5%.
基於以上的5-氯代苯並三氮唑之精製系統1之操作，本發明也提出了一種5-氯代苯並三氮唑之精製方法（以下簡稱精製方法）。請見圖2，該圖為該精製方法的流程圖。精製方法包含步驟：加熱溶解步驟（S01）、過濾步驟（S02）、離子交換步驟（S03）、去溶劑步驟（S04）與粉碎步驟（S05）。加熱溶解步驟為：在50-60℃的溫度下，將5-氯代苯並三氮唑粗製粉體溶解於一有機溶劑（甲醇、乙醇或異丙醇中的任一種）中，進行加熱溶解3-4小時，以形成一混合溶液，其中5-氯代苯並三氮唑粗製粉體與該有機溶劑的重量比為1:4~1:5。過濾步驟為：以孔徑40nm的精密過濾膜對該混合溶液進行過濾處理，以除去雜質及金屬顆粒。雖然精密膜過濾機20內包含了450nm孔徑精密過濾膜21、200nm孔徑精密過濾膜22與40nm孔徑精密過濾膜23，但主要還是要靠40nm孔徑精密過濾膜23來過濾掉40nm以上的雜質與不純物，450nm孔徑精密過濾膜21與200nm孔徑精密過濾膜22只是用來加快過濾速度。離子交換步驟為：在25±1℃的溫度下，以陽離子交換樹脂對過濾處理完成的該混合溶液進行離子交換至少6小時，將其中部分的陽離子交換取出，以獲得一精煉溶液。去溶劑步驟為：在135-145℃的溫度下加熱該精煉溶液至少12小時，以將該有機溶劑蒸餾，留下塊狀精製5-氯代苯並三氮唑。粉碎步驟為：粉碎該塊狀精製5-氯代苯並三氮唑，以獲得細度等級2mm之精製5-氯代苯並三氮唑粉體。受限於設備，為了要有較佳的品質，最好一批量處理的混合溶液不超過800公斤。Based on the above operation of the 5-chlorobenzotriazole refining system 1, the present invention also proposes a refining method of 5-chlorobenzotriazole (hereinafter referred to as the refining method). Please see Figure 2, which is a flow chart of the refining method. The purification method includes steps: heating and dissolving step (S01), filtration step (S02), ion exchange step (S03), solvent removal step (S04) and crushing step (S05). The heating and dissolving step is: dissolving the crude 5-chlorobenzotriazole powder in an organic solvent (any one of methanol, ethanol or isopropyl alcohol) at a temperature of 50-60°C, and heating and dissolving. 3-4 hours to form a mixed solution, in which the weight ratio of the crude 5-chlorobenzotriazole powder and the organic solvent is 1:4~1:5. The filtration step is: filter the mixed solution with a precision filter membrane with a pore size of 40 nm to remove impurities and metal particles. Although the precision membrane filter 20 contains a 450nm pore size precision filtration membrane 21, a 200nm pore size precision filtration membrane 22 and a 40nm pore size precision filtration membrane 23, the 40nm pore size precision filtration membrane 23 is mainly relied upon to filter out impurities and impurities above 40nm. , the 450nm pore size precision filter membrane 21 and the 200nm pore size precision filter membrane 22 are only used to speed up the filtration speed. The ion exchange step is as follows: using a cation exchange resin to ion exchange the filtered mixed solution for at least 6 hours at a temperature of 25±1°C, and taking out part of the cation exchange to obtain a refined solution. The solvent removal step is to heat the refined solution at a temperature of 135-145°C for at least 12 hours to distill the organic solvent, leaving behind a block of refined 5-chlorobenzotriazole. The crushing step is: crush the massive refined 5-chlorobenzotriazole to obtain refined 5-chlorobenzotriazole powder with a fineness grade of 2 mm. Due to equipment limitations, in order to have better quality, it is best to process no more than 800 kilograms of mixed solution in one batch.
以下茲取數個金屬不純物（包含顆粒態與離子態）不同成分的5-氯代苯並三氮唑粗製粉體各120kg，分別混合480kg乙醇來製成數個600kg的5-氯代苯並三氮唑粗製粉體，通過以上的5-氯代苯並三氮唑之精製系統1，來看精製5-氯代苯並三氮唑粉體的成分變化。The following is to take 120kg of 5-chlorobenzotriazole crude powder with different components of several metal impurities (including particulate and ionic states), and mix 480kg of ethanol respectively to prepare several 600kg of 5-chlorobenzotriazole. Crude triazole powder, through the above 5-chlorobenzotriazole purification system 1, look at the composition changes of the refined 5-chlorobenzotriazole powder.
實施例一Embodiment 1
請見表一，該表表列一第一5-氯代苯並三氮唑粗製粉體的各類金屬濃度、在40nm孔徑精密過濾膜出口處混合溶液中各類金屬濃度、在輔助過濾器出口處精煉溶液中各類金屬濃度，及精製5-氯代苯並三氮唑粉體的各類金屬濃度。
根據結果得知，觀察到溶液通過40nm孔徑精密過濾膜後，鋁、鐵、鈣等金屬成分的濃度大幅的減少。未去除而流出的鈉與鎂，在離子交換樹脂當中（輔助過濾器出口處）被去除。就鈉、鎂等金屬成分而言，其濃度已降至分析上限值（＜0.1 ppm）以下的水準，可確認藉由離子交換機被去除。精製5-氯代苯並三氮唑粉體其金屬濃度，鐵與鈣小於1ppm，其它金屬小於0.1ppm，精製後成品純度＞99.9%，符合要求。According to the results, it was observed that after the solution passed through a 40nm pore size precision filtration membrane, the concentration of metal components such as aluminum, iron, and calcium was significantly reduced. The sodium and magnesium that flowed out without being removed are removed in the ion exchange resin (at the outlet of the auxiliary filter). For metal components such as sodium and magnesium, the concentration has dropped below the upper limit of analysis (<0.1 ppm), and it can be confirmed that they have been removed by the ion exchanger. The metal concentration of the refined 5-chlorobenzotriazole powder is less than 1ppm for iron and calcium, and less than 0.1ppm for other metals. The purity of the refined product is >99.9%, which meets the requirements.
實施例二Embodiment 2
請見表二，該表表列一第二5-氯代苯並三氮唑粗製粉體的各類金屬濃度、在40nm孔徑精密過濾膜出口處混合溶液中各類金屬濃度、在輔助過濾器出口處精煉溶液中各類金屬濃度，及精製5-氯代苯並三氮唑粉體的各類金屬濃度。
第二5-氯代苯並三氮唑粗製粉體中的鋁、鐵、鈉、鎂、鈣與鋅的濃度，分別為實施例一中的第一5-氯代苯並三氮唑粗製粉體的相同成分的3.08倍、2.06倍、2.09倍、0.43倍、1.46倍與1.38倍，鎳的濃度偏低，其餘金屬濃度變化不大。根據結果得知，觀察到液體通過40nm孔徑精密過濾膜後，鋁、鐵、鈣等金屬成分的濃度大幅的減少。未去除而流出的鈉與鎂，在離子交換樹脂當中被去除。就鈉、鎂等金屬成分而言，其濃度已降至分析上限值以下的水準，可確認藉由離子交換機被去除。精製5-氯代苯並三氮唑粉體其金屬濃度，鐵、鈣與鉻小於1ppm，其它金屬小於0.1ppm，精製後成品純度＞99.9%，亦符合要求。The concentrations of aluminum, iron, sodium, magnesium, calcium and zinc in the second 5-chlorobenzotriazole crude powder are respectively the first 5-chlorobenzotriazole crude powder in Example 1 The concentrations of nickel are 3.08 times, 2.06 times, 2.09 times, 0.43 times, 1.46 times and 1.38 times that of the same composition of the body. The concentration of nickel is low, and the concentrations of other metals do not change much. According to the results, it was observed that after the liquid passed through the 40nm pore size precision filtration membrane, the concentration of metal components such as aluminum, iron, and calcium was significantly reduced. The sodium and magnesium that flowed out without being removed are removed in the ion exchange resin. As for metal components such as sodium and magnesium, their concentrations have dropped to levels below the upper limit of analysis, and it can be confirmed that they have been removed by the ion exchanger. The metal concentration of the refined 5-chlorobenzotriazole powder is less than 1ppm for iron, calcium and chromium, and less than 0.1ppm for other metals. The purity of the refined product is >99.9%, which also meets the requirements.
實施例三Embodiment 3
請見表三，該表表列一第三5-氯代苯並三氮唑粗製粉體的各類金屬濃度、在40nm孔徑精密過濾膜出口處混合溶液中各類金屬濃度、在輔助過濾器出口處精煉溶液中各類金屬濃度，及精製5-氯代苯並三氮唑粉體的各類金屬濃度。
第三5-氯代苯並三氮唑粗製粉體和第二5-氯代苯並三氮唑粗製粉體相似處在於鋁、鐵、鈉、鈣、銅、鋅等金屬濃度皆較第一5-氯代苯並三氮唑粗製粉體中的多很多，且鎳的濃度相同地偏低，其餘金屬濃度變化不大。根據結果得知，觀察到液體通過40nm孔徑精密過濾膜後，鋁、鐵、鈣等金屬成分的濃度大幅的減少。未去除而流出的鈉與鎂，在離子交換樹脂當中被去除。就鈉、鎂等金屬成分而言，其濃度已降至分析上限值以下的水準，可確認藉由離子交換機被去除。精製5-氯代苯並三氮唑粉體其金屬濃度，鋁、鈣、銅與鉻小於1ppm，鐵小於2ppm，其它金屬小於0.1ppm，精製後成品純度＞99.9%，亦符合要求。The third 5-chlorobenzotriazole crude powder is similar to the second 5-chlorobenzotriazole crude powder in that the concentrations of aluminum, iron, sodium, calcium, copper, zinc and other metals are all higher than those of the first 5-chlorobenzotriazole crude powder. There is much more 5-chlorobenzotriazole in the crude powder, and the concentration of nickel is also low, and the concentrations of other metals do not change much. According to the results, it was observed that after the liquid passed through the 40nm pore size precision filtration membrane, the concentration of metal components such as aluminum, iron, and calcium was significantly reduced. The sodium and magnesium that flowed out without being removed are removed in the ion exchange resin. As for metal components such as sodium and magnesium, their concentrations have dropped to levels below the upper limit of analysis, and it can be confirmed that they have been removed by the ion exchanger. The metal concentration of the refined 5-chlorobenzotriazole powder is less than 1ppm for aluminum, calcium, copper and chromium, less than 2ppm for iron, and less than 0.1ppm for other metals. The purity of the refined product is >99.9%, which also meets the requirements.
雖然本發明已以實施方式揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作些許之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field can make some modifications and modifications without departing from the spirit and scope of the present invention. Therefore, The protection scope of the present invention shall be determined by the appended patent application scope.
1:5-氯代苯並三氮唑之精製系統1:5-Chlorobenzotriazole purification system
10:加熱溶解槽組10: Heating and dissolving tank group
11:有機溶劑供應源11: Organic solvent supply source
111:第一開關閥門111: First switch valve
112:第二開關閥門112: Second switch valve
12:溶解槽體12:Dissolution tank
121:開孔121:Opening
13:加熱槽體13: Heating tank
131:回收管線131:Recovery line
132:注液管線132: Liquid injection line
14:5-氯代苯並三氮唑粗製粉體供應源14:5-Chlorobenzotriazole crude powder supply source
20:精密膜過濾機20:Precision membrane filter
201:入液管線201: Liquid inlet line
202:出液管線202:Liquid outlet line
203:第一控制閥門203: First control valve
204:第二控制閥門204: Second control valve
21:450nm孔徑精密過濾膜21: 450nm pore size precision filter membrane
22:200nm孔徑精密過濾膜22: 200nm pore size precision filter membrane
23:40nm孔徑精密過濾膜23:40nm pore size precision filtration membrane
24:第三控制閥門24:Third control valve
25:排出管線25: Discharge line
26:純化桶26:Purification barrel
30:離子交換機30:Ion exchanger
31:陽離子交換樹脂31:Cation exchange resin
32:輔助過濾器32: Auxiliary filter
33:流向控制閥33: Flow control valve
341:精煉溶液桶1341: Refining solution barrel 1
342:精煉溶液桶2342: Refining solution barrel 2
35:循環管35: Circulation pipe
40:去溶劑機構40: Solvent removal mechanism
41:冷凝器41:Condenser
42:蒸餾桶42:Distillation barrel
421:蓋體421: Cover
422:桶體422: Barrel body
43:電熱加熱器43:Electric heater
44:回收槽44:Recycling tank
50:粉碎機構50: Crushing mechanism
51:輸入槽51:Input slot
52:滾輪52:Roller
53:接收槽53:Receive slot
B:塊狀精製5-氯代苯並三氮唑B: Refined 5-chlorobenzotriazole in block form
F:精製5-氯代苯並三氮唑粉體F: Refined 5-chlorobenzotriazole powder
H:混合溶液H: mixed solution
P1:第一泵浦P1: first pump
P2:第二泵浦P2: Second pump
P3:第三泵浦P3: The third pump
R:精煉溶液R: Refining solution
圖1為依照本發明的一種5-氯代苯並三氮唑之精製系統的元件示意圖。 圖2為依照本發明的一種5-氯代苯並三氮唑之精製方法的流程圖。 Figure 1 is a schematic diagram of the components of a purification system for 5-chlorobenzotriazole according to the present invention. Figure 2 is a flow chart of a purification method of 5-chlorobenzotriazole according to the present invention.
1:5-氯代苯並三氮唑之精製系統 1:5-Chlorobenzotriazole purification system
10:加熱溶解槽組 10: Heating and dissolving tank group
11:有機溶劑供應源 11: Organic solvent supply source
111:第一開關閥門 111: First switch valve
112:第二開關閥門 112: Second switch valve
12:溶解槽體 12:Dissolution tank
121:開孔 121:Opening
13:加熱槽體 13: Heating tank
131:回收管線 131:Recovery line
132:注液管線 132: Liquid injection line
14:5-氯代苯並三氮唑粗製粉體供應源 14:5-Chlorobenzotriazole crude powder supply source
20:精密膜過濾機 20:Precision membrane filter
201:入液管線 201: Liquid inlet line
202:出液管線 202:Liquid outlet line
203:第一控制閥門 203: First control valve
204:第二控制閥門 204: Second control valve
21:450nm孔徑精密過濾膜 21: 450nm pore size precision filter membrane
22:200nm孔徑精密過濾膜 22:200nm pore size precision filter membrane
23:40nm孔徑精密過濾膜 23:40nm pore size precision filtration membrane
24:第三控制閥門 24:Third control valve
25:排出管線 25: Discharge line
26:純化桶 26:Purification barrel
30:離子交換機 30:Ion exchanger
31:陽離子交換樹脂 31:Cation exchange resin
32:輔助過濾器 32: Auxiliary filter
33:流向控制閥 33: Flow control valve
341:精煉溶液桶1 341: Refining solution barrel 1
342:精煉溶液桶2 342: Refining solution barrel 2
35:循環管 35: Circulation pipe
40:去溶劑機構 40: Solvent removal mechanism
41:冷凝器 41:Condenser
42:蒸餾桶 42:Distillation barrel
421:蓋體 421: Cover
422:桶體 422: Barrel body
43:電熱加熱器 43:Electric heater
44:回收槽 44:Recycling tank
50:粉碎機構 50: Crushing mechanism
51:輸入槽 51:Input slot
52:滾輪 52:Roller
53:接收槽 53:Receive slot
B:塊狀精製5-氯代苯並三氮唑 B: Refined 5-chlorobenzotriazole in block form
F:精製5-氯代苯並三氮唑粉體 F: Refined 5-chlorobenzotriazole powder
H:混合溶液 H: mixed solution
P1:第一泵浦 P1: first pump
P2:第二泵浦 P2: Second pump
P3:第三泵浦 P3: The third pump
R:精煉溶液 R: Refining solution
Claims (10)
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| TW111122507A TWI825787B (en) | 2022-06-16 | 2022-06-16 | Method and system for refining 5-chlorobenzotriazole |
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| TW111122507A TWI825787B (en) | 2022-06-16 | 2022-06-16 | Method and system for refining 5-chlorobenzotriazole |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108033925A (en) * | 2017-12-27 | 2018-05-15 | 温州大学 | A kind of benzotriazole compound and preparation method thereof |
| CN108329278A (en) * | 2018-02-02 | 2018-07-27 | 肖志才 | A kind of high-efficiency synthesis method of 5- Chloro-Benzotriazoles |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108033925A (en) * | 2017-12-27 | 2018-05-15 | 温州大学 | A kind of benzotriazole compound and preparation method thereof |
| CN108329278A (en) * | 2018-02-02 | 2018-07-27 | 肖志才 | A kind of high-efficiency synthesis method of 5- Chloro-Benzotriazoles |
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