TWI606975B - Treating and Recycling Method of Fluorine Containing Dust - Google Patents
Treating and Recycling Method of Fluorine Containing Dust Download PDFInfo
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- TWI606975B TWI606975B TW105117895A TW105117895A TWI606975B TW I606975 B TWI606975 B TW I606975B TW 105117895 A TW105117895 A TW 105117895A TW 105117895 A TW105117895 A TW 105117895A TW I606975 B TWI606975 B TW I606975B
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- Prior art keywords
- fluoroantimonate
- sodium
- potassium
- water
- ammonium
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- 239000000428 dust Substances 0.000 title claims description 28
- 238000000034 method Methods 0.000 title claims description 24
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 14
- 229910052731 fluorine Inorganic materials 0.000 title claims description 14
- 239000011737 fluorine Substances 0.000 title claims description 14
- 238000004064 recycling Methods 0.000 title description 2
- 239000000243 solution Substances 0.000 claims description 53
- -1 ammonium fluoroantimonate Chemical compound 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000000926 separation method Methods 0.000 claims description 30
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 24
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 24
- LEJMMWQSCFZGGL-UHFFFAOYSA-N C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[F-].[NH4+].[NH4+].[NH4+].[NH4+] Chemical compound C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[F-].[NH4+].[NH4+].[NH4+].[NH4+] LEJMMWQSCFZGGL-UHFFFAOYSA-N 0.000 claims description 23
- 239000011734 sodium Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 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 claims description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 12
- 229960003975 potassium Drugs 0.000 claims description 12
- 229910052700 potassium Inorganic materials 0.000 claims description 12
- 239000011591 potassium Substances 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940086066 potassium hydrogencarbonate Drugs 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims 1
- 235000011181 potassium carbonates Nutrition 0.000 claims 1
- 239000001509 sodium citrate Substances 0.000 claims 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims 1
- 238000003756 stirring Methods 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- AEBBMWLXRUIOTF-UHFFFAOYSA-L FC1=C(C(C(=O)[O-])=CC=C1)C(=O)[O-].[Na+].[Na+] Chemical compound FC1=C(C(C(=O)[O-])=CC=C1)C(=O)[O-].[Na+].[Na+] AEBBMWLXRUIOTF-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 2
- 229910019975 (NH4)2SiF6 Inorganic materials 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910020440 K2SiF6 Inorganic materials 0.000 description 1
- 229910004883 Na2SiF6 Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- HDDMREWZGLZQMX-UHFFFAOYSA-N azanium;carbonofluoridate Chemical compound [NH4+].[O-]C(F)=O HDDMREWZGLZQMX-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DVJXIKZVQYWHMT-UHFFFAOYSA-N fluoro decanoate Chemical compound CCCCCCCCCC(=O)OF DVJXIKZVQYWHMT-UHFFFAOYSA-N 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000005495 investment casting Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
Description
本發明係關於一種含氟集塵灰的處理及回收方法，特別適用於平面顯示器(TFT - LCD)製程產生的集塵灰，用以製造純度高的氟矽酸鹽。The invention relates to a method for treating and recovering fluorine-containing dust ash, and is particularly suitable for dust collecting ash generated by a flat panel display (TFT-LCD) process for producing a high purity fluoroantimonate.
電子工業平面顯示器(TFT - LCD)玻璃基板薄膜製程為利用化學氣相沉積法之原理，將矽甲烷、三氟化氮、氨氣等氣體通入化學氣相沉積(CVD)機台後於一定之溫度、壓力等條件下沉積於玻璃基板並形成絕緣層。而未完全反應之氣體則由製程的燃燒器處理後形成懸浮微粒，再經廢氣處理程序之袋式集塵器收集而成為集塵灰，此集塵灰成分主要為氟矽酸銨與二氧化矽，國內一般當作廢棄物掩埋處理，，但掩埋仍然會造成環保問題。In the electronic industry, flat panel display (TFT-LCD) glass substrate film process is based on the principle of chemical vapor deposition, and the gas such as methane, nitrogen trifluoride and ammonia is introduced into the chemical vapor deposition (CVD) machine. It is deposited on a glass substrate under conditions of temperature, pressure, and the like to form an insulating layer. The gas that is not completely reacted is treated by the burner of the process to form suspended particles, and then collected by the bag dust collector of the exhaust gas treatment program to become dust collecting ash. The dust collecting ash component is mainly ammonium fluoroantimonate and dioxide. Hey, the country generally treats it as waste, but it still causes environmental problems.
本發明提供一種關於一種含氟集塵灰的處理及回收方法，特別適用於平面顯示器(TFT - LCD)製程產生的集塵灰，用以製造純度高的氟矽酸鹽，包括溶解段，將含氟矽酸銨與二氧化矽之集塵灰與水混合，將水可溶解性之氟矽酸銨溶解出來。第一分離段，溶解段得到之混濁溶液，經過固液分離，得到含氟矽酸銨之澄清溶液，與不溶解性的固体二氧化矽。置換段，第一分離段得到之氟矽酸銨溶液，加入含鈉或鉀之鹽類，產生氟矽酸鈉或氟矽酸鉀的氟矽酸鹽沉澱物。第二分離段，將置換段得到之混濁溶液，經過固液分離，得到氟矽酸鈉或氟矽酸鉀的氟矽酸鹽。The invention provides a method for treating and recovering fluorine-containing dust ash, which is particularly suitable for collecting dust generated by a flat panel display (TFT-LCD) process, and is used for manufacturing a high purity fluoroantimonate, including a dissolution section, The dust-collecting ash of ammonium fluoride citrate and cerium oxide is mixed with water to dissolve the water-soluble ammonium fluoroantimonate. The first separation section, the turbid solution obtained in the dissolution section, is subjected to solid-liquid separation to obtain a clear solution of ammonium fluoride citrate and insoluble solid cerium oxide. The replacement section, the ammonium fluoroantimonate solution obtained in the first separation stage, is added with a salt containing sodium or potassium to produce a fluoroantimonate precipitate of sodium fluoroantimonate or potassium fluoroantimonate. In the second separation stage, the turbid solution obtained in the replacement section is subjected to solid-liquid separation to obtain sodium fluoroantimonate or potassium fluoroantimonate.
本發明方法可以回收含氟集塵灰，得到純度高的氟矽酸鹽，達到廢棄物回收及再利用目的。The method of the invention can recover the fluorine-containing dust ash and obtain the fluoroantimonate with high purity to achieve the purpose of waste recycling and reuse.
依據圖式顯示，本發明提供一種含氟集塵灰的處理及回收方法（如第１圖所示），其程序步驟包括溶解段S1、第一分離段S2、置換段S3、第二分離段S4，其中 :According to the drawings, the present invention provides a method for treating and recovering fluorine-containing dust ash (as shown in FIG. 1), and the program steps include a dissolution section S1, a first separation section S2, a replacement section S3, and a second separation section. S4, where:
溶解段S1，將含氟矽酸銨（(NH4)2SiF6）與二氧化矽（SiO2）之集塵灰與水混合，水將可溶解性之氟矽酸銨溶解出來並得到第一混濁溶液。Dissolving the segment S1, mixing the fluorine-containing ammonium citrate ((NH4)2SiF6) with the dust ash of cerium oxide (SiO2) and water, and dissolving the soluble ammonium fluoroantimonate in water to obtain a first turbid solution.
第一分離段S2，溶解段得到之混濁溶液經過固液分離，得到含氟矽酸銨之澄清溶液，與不溶解性的粉狀二氧化矽。In the first separation section S2, the turbid solution obtained in the dissolution section is subjected to solid-liquid separation to obtain a clear solution of ammonium fluoride citrate and insoluble powdery cerium oxide.
置換段S3，第一分離段得到之含氟矽酸銨之澄清溶液，加入含鈉或含鉀之鹽類，產生氟矽酸鈉（Na2SiF6）或氟矽酸鉀（K2SiF6）的氟矽酸鹽沉澱物以及第二混濁溶液。Substituting section S3, a clear solution of ammonium fluoride citrate obtained in the first separation stage, adding sodium or potassium-containing salts to produce sodium fluorophthalate (Na2SiF6) or potassium fluoroantimonate (K2SiF6) fluoroantimonate a precipitate and a second turbid solution.
第二分離段S4，將置換段得到之第二混濁溶液，經過固液分離，得到氟矽酸鈉或氟矽酸鉀的氟矽酸鹽。In the second separation section S4, the second turbid solution obtained in the replacement section is subjected to solid-liquid separation to obtain sodium fluoroantimonate or potassium fluoroantimonate fluoroantimonate.
本發明方法在溶解段S1中，將含氟矽酸銨與二氧化矽之集塵灰與水混合，水將可溶解性之氟矽酸銨溶解出來。氟矽酸銨在水中之溶解度於 20℃時為 186g/L，30℃時為 250g/L，水的溶解量只要超過氟矽酸銨在水中的溶解度，具體地說，水的容量與集塵灰的質量比值介於4.6:1~2.3:1，即可將固体集塵灰中之氟矽酸銨全部溶解出來並得到第一混合溶液，溶解時的水溫度沒有特別限制，但溫度愈高溶解度愈高。In the method of the present invention, in the dissolution section S1, the dust-collecting ash of ammonium fluoride citrate and cerium oxide is mixed with water, and the water dissolves the soluble ammonium fluoroantimonate. The solubility of ammonium fluoroantimonate in water is 186 g/L at 20 ° C and 250 g / L at 30 ° C. The solubility of water exceeds the solubility of ammonium fluorocarbonate in water, specifically, the capacity and dust collection of water. When the mass ratio of ash is between 4.6:1 and 2.3:1, the ammonium fluoroantimonate in the solid dust ash can be completely dissolved and the first mixed solution can be obtained. The water temperature during dissolution is not particularly limited, but the temperature is higher. The higher the solubility.
本發明方法在第一分離段S2，溶解段得到之第一混濁溶液，經過固液分離，得到含氟矽酸銨之澄清溶液，與水不溶解性的二氧化矽。使用的固液分離設備例如離心機或壓濾機等，將水不溶解性的二氧化矽自第一混濁溶液中分離出來並取得含氟矽酸銨之澄清溶液，分離出來的二氧化矽，可以使用水洗，將雜質洗掉，得到二氧化矽，直接出售或進行乾燥後出售。In the first separation section S2, the first turbid solution obtained in the dissolution section is subjected to solid-liquid separation to obtain a clear solution of ammonium fluoride citrate and water-insoluble cerium oxide. The solid-liquid separation device used, such as a centrifuge or a filter press, separates the water-insoluble ceria from the first turbid solution and obtains a clear solution of ammonium fluoride citrate, and the separated cerium oxide, It can be washed with water, the impurities are washed away, and cerium oxide is obtained, sold directly or dried and sold.
本發明方法在置換段S3中，第一分離段得到之含氟矽酸銨之澄清溶液，加入含鈉或鉀之鹽類，產生氟矽酸鈉或氟矽酸鉀的氟矽酸鹽沉澱物。含鈉或鉀之鹽類可以是碳酸鈉(Na 2CO 3)、碳酸鉀(K 2CO 3)、碳酸氫鈉(NaHCO 3)、碳酸氫鉀(KHCO 3)、硫酸鈉(Na 2SO 4)、硫酸鉀(K 2SO 4)、氯化鈉(NaCl)、氯化鉀(KCl)、硝酸鈉(NaNO 3)、硝酸鉀(KNO 3)等其中任意一種鹽類，純度沒有特別限制，最好大於95wt.%，加入的型態沒有特別限制，可以固態或加水配成液態加入。 In the method of the present invention, in the replacement section S3, the clear solution of the ammonium fluoride-containing ammonium citrate obtained in the first separation stage is added with a salt containing sodium or potassium to produce a fluoroantimonate precipitate of sodium fluoroantimonate or potassium fluoroantimonate. . The salt containing sodium or potassium may be sodium carbonate (Na 2 CO 3 ), potassium carbonate (K 2 CO 3 ), sodium hydrogencarbonate (NaHCO 3 ), potassium hydrogencarbonate (KHCO 3 ), sodium sulfate (Na 2 SO 4 ). ), potassium sulfate (K 2 SO 4 ), sodium chloride (NaCl), potassium chloride (KCl), sodium nitrate (NaNO 3 ), potassium nitrate (KNO 3 ), and the like, and the purity thereof is not particularly limited. It is preferably more than 95 wt.%, and the type to be added is not particularly limited, and it may be added in a liquid state in a solid state or in addition to water.
本發明方法在置換段S3中，含鈉或鉀之鹽類與溶液中之氟矽酸銨((NH 4) 2SiF 6)反應，產生氟矽酸鈉(Na 2SiF 6)或氟矽酸鉀(K 2SiF 6)之沉澱物以及第二混濁溶液，鈉(Na)或鉀(K)與氟矽酸根(SiF 6 -2)之反應理論摩爾比為 2 : 1，反應時摩爾比沒有特別限制，摩爾比過高表示含鈉或鉀之鹽類加入量多，對操作成本不利，摩爾比過低表示含鈉或鉀之鹽類加入量少，沒有反應的氟矽酸增根多，氟矽酸鈉(Na 2SiF 6)或氟矽酸鉀(K 2SiF 6)之回收量減少。 In the method of the present invention, in the replacement section S3, a salt containing sodium or potassium is reacted with ammonium fluoroantimonate ((NH 4 ) 2 SiF 6 ) in a solution to produce sodium fluorophthalate (Na 2 SiF 6 ) or fluoroantimonic acid. The precipitate of potassium (K 2 SiF 6 ) and the second turbid solution, the theoretical molar ratio of sodium (Na) or potassium (K) to fluoroantimonate (SiF 6 -2 ) is 2: 1, the molar ratio at the time of reaction is not In particular, the high molar ratio means that the sodium or potassium-containing salt is added in a large amount, which is unfavorable for the operation cost. If the molar ratio is too low, the sodium or potassium-containing salt is added in a small amount, and the unreacted fluoroantimonic acid has a large amount. The recovery amount of sodium fluoroantimonate (Na 2 SiF 6 ) or potassium fluoroantimonate (K 2 SiF 6 ) is reduced.
本發明方法在第二分離段S4中，將置換段得到之第二混濁溶液，經過固液分離，得到氟矽酸鈉或氟矽酸鉀的氟矽酸鹽，可以利用固-液分離設備，例如離心機、壓濾機等，將氟矽酸鈉或氟矽酸鉀沉澱物自第二混濁溶液中分離出來，分離出的氟矽酸鈉或氟矽酸鉀，可以使用水洗，將雜質洗掉直接出售，或進行乾燥後得到純度高的產品出售。另外分離出氟矽酸鈉或氟矽酸鉀後可得到含銨之鹽類溶液，可以做其他用途使用（例如在含銨之鹽類溶液中加入氯化鈉可以得到氯化銨溶液，進一步濃縮結晶可以得到氯化銨產品，作為製造電池、蓄電池、銨鹽、精密鑄造、鞣革，電鍍、照相或粘合劑等）。In the second separation section S4, the second turbid solution obtained in the replacement section is subjected to solid-liquid separation to obtain a sodium fluoroantimonate or a potassium fluoroantimonate fluoroantimonate, and a solid-liquid separation device can be used. For example, a centrifuge, a filter press, etc., the sodium fluoroantimonate or potassium fluoroantimonate precipitate is separated from the second turbid solution, and the separated sodium fluoroantimonate or potassium fluoroantimonate can be washed with water to wash the impurities. Directly sold, or dried to obtain a product with high purity for sale. In addition, sodium fluoroantimonate or potassium fluoroantimonate can be isolated to obtain an ammonium-containing salt solution, which can be used for other purposes (for example, sodium chloride solution can be obtained by adding sodium chloride to the ammonium-containing salt solution, and further concentrated. Crystallization can be obtained as an ammonium chloride product as a battery, battery, ammonium salt, precision casting, tanning, electroplating, photographic or adhesive, etc.).
本發明係依據上述含氟集塵灰的處理及回收方法，假設符合所述之方法的條件下的實例作說明，但請瞭解本發明並不為具體實施例所述之條件及內容所限：The present invention is based on the above-described method for treating and recovering the fluorine-containing dust ash, and is assumed to be an example under the conditions of the method described, but it should be understood that the present invention is not limited by the conditions and contents described in the specific embodiments:
實施例1：來自平面顯示器(TFT - LCD)製程產生集塵灰，其成份如下：68.5%的氟矽酸銨((NH 4) 2SiF 6)、29.5%的二氧化矽(SiO 2) 、以及2.0%的水份(H 2O)，在容積5公升的攪拌桶內，加入3,560毫升的水，倒入1,000公克的集塵灰，攪拌1小時後停止得到第一混濁溶液，由於二氧化矽不溶於水，因此取出桶內的第一混濁溶液進行過濾後，可得到的濕的二氧化矽以700毫升的含氟矽酸銨之澄清溶液，將濕的二氧化矽以水加以清洗，並且將清洗二氧化矽的水洗液與含氟矽酸銨之澄清溶液混合，最後得到含氟矽酸銨之澄清溶液4,445公克及濕的二氧化矽800公克，分析含氟矽酸銨之澄清溶液測得氟矽酸銨((NH 4) 2SiF 6)含量13.9 %。將此含氟矽酸銨之澄清溶液移入容積5公升的攪拌桶內，一面攪拌，一面慢慢加入食鹽(NaCl) 406公克，攪拌1小時後停止取得第二混濁溶液，取出桶內的第二混濁溶液過濾，得到的濕的氟矽酸鈉以及以500毫升的含銨之鹽類溶液，將濕的氟矽酸鈉加以水洗後，置於烘箱內100℃乾燥2小時，獲得620公克的乾燥氟矽酸鈉，經分析測得氟矽酸鈉純度為98.1%。 Example 1: A process for producing dust from a flat panel display (TFT-LCD) process, the composition of which is as follows: 68.5% ammonium fluoroantimonate ((NH 4 ) 2 SiF 6 ), 29.5% cerium oxide (SiO 2 ), And 2.0% water (H 2 O), in a 5 liter mixing tank, add 3,560 ml of water, pour 1,000 grams of dust ash, stir for 1 hour and then stop to get the first turbid solution, due to dioxide矽 is insoluble in water, so after removing the first turbid solution in the barrel for filtration, the obtained wet cerium oxide is washed with 700 ml of a clear solution of ammonium fluoride citrate, and the wet cerium oxide is washed with water. And the washing liquid of the cleaned cerium oxide is mixed with the clear solution of ammonium fluoride citrate, and finally, 4,445 grams of a clear solution of ammonium fluoride citrate and 800 g of wet cerium oxide are obtained, and a clear solution of ammonium fluoride citrate is analyzed. The content of ammonium fluoroantimonate ((NH 4 ) 2 SiF 6 ) was measured to be 13.9%. The clear solution of ammonium fluoride citrate was transferred into a stirring tank having a volume of 5 liters, and while stirring, slowly adding 406 g of salt (NaCl), stirring for 1 hour, stopping to obtain the second turbid solution, and taking out the second inside the barrel. The turbid solution was filtered, and the obtained wet sodium fluoroantimonate and 500 ml of an ammonium-containing salt solution were washed with water, and then dried in an oven at 100 ° C for 2 hours to obtain 620 g of dried. Sodium fluoroantimonate, the purity of sodium fluoroantimonate was determined to be 98.1%.
實施例2：來自平面顯示器(TFT - LCD)製程產生集塵灰，其成份如下：68.5%的氟矽酸銨((NH 4) 2SiF 6)、29.5%的二氧化矽(SiO 2) 、以及2.0%的水份(H 2O)，在容積5公升的攪拌桶內，加入3,600毫升的水，倒入1,000公克的集塵灰，攪拌1小時後停止得到第一混濁溶液，由於二氧化矽不溶於水，因此取出桶內的第一混濁溶液進行過濾後，可得到的濕的二氧化矽以及700毫升的含氟矽酸銨之澄清溶液，將濕的二氧化矽以水加以清洗，並且將清洗二氧化矽的水洗液與含氟矽酸銨之澄清溶液合併，最後得到含氟矽酸銨之澄清溶液4,510公克及濕的二氧化矽780公克，分析含氟矽酸銨之澄清溶液測得氟矽酸銨((NH 4) 2SiF 6)含量13.5 %。將此含氟矽酸銨之澄清溶液移入容積5公升的攪拌桶內，一面攪拌，一面慢慢加入硫酸鈉(Na 2SO 4) 485公克，攪拌1小時後停止取得第二混濁溶液，取出桶內第二混濁溶液過濾，得到的濕的氟矽酸鈉以及500毫升的含銨之鹽類溶液，將濕的氟矽酸鈉加以水洗後，置於烘箱內100℃乾燥2小時，獲得615公克的乾燥氟矽酸鈉，經分析測得氟矽酸鈉純度為98.2%。 Example 2: A process from a flat panel display (TFT-LCD) produces dust collecting ash having the following composition: 68.5% ammonium fluoroantimonate ((NH 4 ) 2 SiF 6 ), 29.5% cerium oxide (SiO 2 ), And 2.0% water (H 2 O), in a 5 liter mixing tank, add 3,600 ml of water, pour 1,000 grams of dust ash, stir for 1 hour and then stop to get the first turbid solution, due to dioxide矽 is insoluble in water, so after removing the first turbid solution in the barrel for filtration, the obtained wet cerium oxide and 700 ml of a clear solution of ammonium fluoride citrate are used to wash the wet cerium oxide with water. And the washing liquid of the cerium dioxide cleaning and the clear solution of ammonium fluoride citrate are combined, and finally, 4,510 grams of a clear solution of ammonium fluoride citrate and 780 grams of wet cerium oxide are obtained, and a clear solution of ammonium fluoride citrate is analyzed. The content of ammonium fluoroantimonate ((NH 4 ) 2 SiF 6 ) was measured to be 13.5%. The clear solution of the ammonium fluoride citrate was transferred into a stirring tank having a volume of 5 liters, and while stirring, slowly adding 485 g of sodium sulfate (Na 2 SO 4 ), stirring for 1 hour, stopping to obtain the second turbid solution, and taking out the barrel. The second turbid solution was filtered, and the obtained wet sodium fluoroantimonate and 500 ml of an ammonium-containing salt solution were washed with water, and then dried in an oven at 100 ° C for 2 hours to obtain 615 g. The dried sodium fluoroantimonate was analyzed and found to have a purity of 98.2%.
實施例3：來自平面顯示器(TFT - LCD)製程產生集塵灰，其成份如下：70.3%的氟矽酸銨((NH 4) 2SiF 6)、28.5%的二氧化矽(SiO 2) 、以及1.2%的水份(H 2O)，在容積5公升的攪拌桶內，加入3,600毫升的水，倒入1,000公克的集塵灰，攪拌1小時後停止得到第一混濁溶液，由於二氧化矽不溶於水，因此取出桶內第一混濁溶液過濾後，可得到的濕的二氧化矽以700毫升的水，將二氧化矽以水加以清洗，並且將清洗二氧化矽的水洗液與含氟矽酸銨之澄清溶液混合，最後得到含氟矽酸銨之澄清溶液4,490公克及二氧化矽790公克，分析含氟矽酸銨之澄清溶液測得氟矽酸銨((NH 4) 2SiF 6)含量14.8%。將此含氟矽酸銨之澄清溶液移入容積5公升的攪拌桶內，一面攪拌，一面慢慢加入氯化鉀(KCl)557公克，攪拌1小時後停止取得第二混濁溶液，取出桶內的第二混濁溶液過濾後，得到的氟矽酸鉀以及500毫升的含銨之鹽類溶液，將氟矽酸鉀以水加以清洗後，置於烘箱內100℃乾燥2小時，獲得620公克乾燥的氟矽酸鉀，經分析測得氟矽酸鉀純度為98.3%。 Example 3: A process from a flat panel display (TFT-LCD) produces dust collecting ash having the following composition: 70.3% ammonium fluoroantimonate ((NH 4 ) 2 SiF 6 ), 28.5% cerium oxide (SiO 2 ), And 1.2% water (H 2 O), in a 5 liter mixing tank, add 3,600 ml of water, pour 1,000 grams of dust ash, stir for 1 hour and then stop to get the first turbid solution, due to dioxide矽 is insoluble in water, so after the first turbid solution in the barrel is filtered, the obtained wet cerium oxide is washed with water in 700 ml of water, and the washing liquid of cerium oxide is washed and contained. The clear solution of ammonium fluoroantimonate was mixed, and finally, 4,490 g of a clear solution of ammonium fluoride citrate and 790 g of cerium oxide were obtained. The ammonium fluoroantimonate ((NH 4 ) 2 SiF was determined by analyzing the clear solution of ammonium fluoride citrate. 6 ) The content is 14.8%. The clear solution of ammonium fluoride citrate was transferred into a stirred tank of 5 liters in volume, and while stirring, 557 grams of potassium chloride (KCl) was slowly added, and after stirring for 1 hour, the second turbid solution was stopped, and the inside of the barrel was taken out. After the second turbid solution was filtered, the obtained potassium fluoroantimonate and 500 ml of an ammonium-containing salt solution were washed with water, and then dried in an oven at 100 ° C for 2 hours to obtain 620 g of dried. Potassium fluoroantimonate, the purity of potassium fluoroantimonate was 98.3%.
本發明自含氟集塵灰的處理及回收方法，可以得到純度高的氟矽酸鈉或氟矽酸鉀產品以及二氧化矽（可當作水玻璃的原料，也可作為廢氫氟酸溶液回收氟製造氟矽酸鹽之原料使用），如此提高集塵灰的經濟價值。The method for treating and recovering fluorine-containing dust ash of the invention can obtain high purity sodium fluoroantimonate or potassium fluoroantimonate product and cerium oxide (can be used as raw material of water glass, and can also be used as waste hydrogen fluoride solution). The use of recycled fluorine to produce fluorodecanoate raw materials), thus increasing the economic value of dust ash.
由於說明書揭示的本創作可在未脫離本創作精神或大體特徵的其它特定形式來實施，且這些特定形式的一些形式已經被指出，所以，說明書揭示的實施例應視為舉例說明而非限制。本創作的範圍是由所附的申請專利範圍界定，而不是由上述說明所界定，對於落入申請專利範圍的均等意義與範圍的所有改變仍將包含在其範圍之內。The present invention disclosed in the specification is to be considered as illustrative and not restrictive. The scope of the present invention is defined by the scope of the appended claims, and is not intended to be limited by the scope of the invention.
S1‧‧‧溶解段S1‧‧‧dissolved section
S2‧‧‧第一分離段S2‧‧‧ first separation section
S3‧‧‧置換段S3‧‧‧ replacement section
S4‧‧‧第二分離段S4‧‧‧Second separation
第１圖顯示本發明含氟集塵灰的處理及回收方法的簡要流程圖。Fig. 1 is a schematic flow chart showing a method of treating and recovering fluorine-containing dust ash according to the present invention.
以下說明僅便於解釋本發明基本教導而已，圖式說明中將對構成較佳實施例之成份、使用量、操作條件、及其他相關延伸將有所說明，在閱讀及了解本發明的敎導後相關之變化實施屬於業界技能。另外，在閱讀及了解本發明敎導後，配合特定設備、作用濃度、作用溫度及類似要求之改變亦屬業界技能。The following description is merely illustrative of the basic teachings of the present invention, and the description of the components, the amount of use, the operating conditions, and other related extensions of the preferred embodiments will be explained, after reading and understanding the teachings of the present invention. Related changes are implemented in industry skills. In addition, changes in the combination of specific equipment, concentration of action, temperature of action, and the like are also within the skill of the art after reading and understanding the teachings of the present invention.
S1‧‧‧溶解段 S1‧‧‧dissolved section
S2‧‧‧第一分離段 S2‧‧‧ first separation section
S3‧‧‧置換段 S3‧‧‧ replacement section
S4‧‧‧第二分離段 S4‧‧‧Second separation
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| CN104071820A (en) * | 2014-07-21 | 2014-10-01 | 扬州百德光电有限公司 | Method for producing calcium fluoride by waste LCD panel glass etching liquid |
| TW201604144A (en) * | 2014-07-28 | 2016-02-01 | Climax Applied Materials Co Ltd | Method for recycling waste liquid containing hydrofluoric acid and fluosilicic acid |
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| CN104071820A (en) * | 2014-07-21 | 2014-10-01 | 扬州百德光电有限公司 | Method for producing calcium fluoride by waste LCD panel glass etching liquid |
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