B TR GIÁO D C VÀ ĐÀO T O NG Đ I H C BÁCH KHOA HÀ N I HÀ V NH H NG NGHIÊN C U Q TRÌNH HỊA TÁCH THU H I VÀNG T CH T TH I ĐI N T B NG H DUNG D CH AMONIAC-Đ NG(II)-THIOSUNPHAT Chuyên ngành: Công ngh môi tr ng ch t th i r n Mã s : 62.85.06.10 LU N ÁN TI N S CÔNG NGH NG IH MÔI TR NG D N KHOA H C: PGS TS Hu nh Trung H i PGS TS Ngô Th Nga Hà N i, 2012 NG L I C M ƠN Tơi xin bày t lịng bi t ơn sâu s c t i PGS TS Hu nh Trung H i, PGS TS Ngô Th Nga nh ng ng h ng cho nh ng b c quan tr ng đ i th y đ nh ng nghiên c u khoa h c, đ ng viên, chia s t o nh ng u ki n t t đ ti n hành nh ng nghiên c u lu n án Tôi xin c m ơn s giúp đ nhi t tình, h tr kinh phí t o u ki n thu n l i c a TS Jae-chun Lee, TS Jin-ki Jeong su t th i gian th c hi n nghiên c u lu n án t i Vi n Khoa h c Đ a ch t Tài ngun khống s n Hàn Qu c Tơi xin c m ơn gia đình nh ng ng i thân dành cho nh ng u ki n t t nh t đ tơi tồn tâm tồn ý nghiên c u khoa h c Tơi xin c m ơn nh ng đ ng nghi p Công ngh Môi tr Vi n Khoa h c ng – Đ i h c Bách khoa Hà N i, Vi n Khoa h c Đ a ch t Tài nguyên khoáng s n Hàn Qu c b n bè thân h u cung c p h tr nhi u tài li u, thông tin b ích giúp cho tơi hồn thành lu n án L I CAM ĐOAN Tôi xin cam đoan cơng trình nghiên c u c a b n thân Các k t qu công b lu n án trung th c, xác tơi xin hoàn toàn trách nhi m v s li u, n i dung trình bày lu n án NCS Hà V nh H ng M CL C DANH M C CÁC KÝ HI U VÀ CH VI T T T iv DANH M C B NG v DANH M C CÁC HÌNH V M Đ U VÀ Đ TH vi Ch ơng T NG QUAN TÀI LI U 1.1 HI N TR NG CH T TH I ĐI N T VÀ CÔNG NGH THU H I VÀNG 1.1.1 Hi n tr ng phát sinh ch t th i n t 1.1.2 Thành ph n ch t th i n t 1.1.3 T ng quan tình hình thu h i vàng t ch t th i n t hi n 11 1.1.4 Đánh giá l a ch n tác nhân hòa tách vàng t ch t th i n t 15 1.2 T NG QUAN PH ƠNG PHÁP THIOSUNPHAT 16 1.2.1 Đ c tính c a vàng 16 1.2.2 Nhi t đ ng h c c a hòa tách vàng h dung d ch amoniac – đ ng(II) - thiosunphat 19 1.2.3 Đ ng h c hòa tách vàng 22 1.2.3.1 nh h ng c a n ng đ thiosunphat 23 1.2.3.2 nh h ng c a n ng đ ion đ ng(II) 24 1.2.3.3 nh h ng c a n ng đ amoniac 25 1.2.3.4 nh h ng c a pH 26 1.2.3.5 nh h ng c a nhi t đ 27 1.3 NH NG V N Đ Ch ơng C N GI I QUY T 28 NGHIÊN C U TH C NGHI M 30 2.1 N I DUNG NGHIÊN C U 30 2.2 V T LI U NGHIÊN C U 31 i 2.2.1 M u nghiên c u 31 2.2.2 Hóa ch t, v t li u khác 32 2.3 MÔ HÌNH THI T B NGHIÊN C U 33 2.4 PH ƠNG PHÁP NGHIÊN C U 36 2.4.1 Quy trình thí nghi m hịa tách vàng 36 2.4.2 Ph ơng pháp quan tr c phân tích thơng s 39 2.4.3 Tính tốn x lý s li u 42 2.4.3.1 Ph ơng pháp xác đ nh hi u su t hòa tách vàng 42 2.4.3.2 Ph ơng pháp xác đ nh t c đ hòa tách vàng 43 2.4.4 Ch ơng Ph ơng pháp quy ho ch th c nghi m 44 K T QU VÀ TH O LU N 46 3.1 KH O SÁT HÌNH THÁI C A CÁC LO I M U NGHIÊN C U 46 3.1.1 Phân tích SEM-EDX c a m u ph li u công nghi p n t 47 3.1.2 Phân tích SEM-EDX c a m u PCBs n tho i di đ ng 49 3.2 NH N D NG CÁC Y U T NH H NG Đ N Q TRÌNH HỊA TÁCH VÀNG 52 3.2.1 Xác đ nh kho ng n ng đ c a hóa ch t 52 3.2.1.1 Kh o sát hòa tách vàng h dung d ch amoniac – thiosunphat – đ ng(II) 52 3.2.1.2 Xác đ nh kho ng n ng đ hóa ch t 54 3.2.2 Các y u t nh h ng đ n q trình hịa tách vàng 57 3.2.2.1 nh h ng c a n ng đ oxy 57 3.2.2.2 nh h ng c a n ng đ ion clorua 61 3.2.2.3 nh h ng c a n ng đ thiosunphat 63 3.2.2.4 nh h ng c a n ng đ ion đ ng(II) 65 3.2.2.5 nh h ng c a n ng đ amoniac 66 3.2.2.6 nh h ng c a nhi t đ 70 3.3 T I 3.3.1 U HÓA CÁC ĐI U KI N Q TRÌNH HỊA TÁCH VÀNG 71 Xây d ng k ho ch th c nghi m 72 ii 3.3.2 Xác đ nh t c đ hòa tách vàng b ng th c nghi m 76 3.3.3 Xây d ng ph ơng trình h i quy 78 3.3.4 Đánh giá s nh h tác đ ng qua l i l n gi a y u t ng c a chúng đ n t c đ hòa tách vàng 80 3.3.5 T i u hóa u ki n c a q trình hịa tách vàng 87 3.3.6 Xác đ nh thông s đ ng h c c a q trình hịa tách vàng 87 3.3.6.1 Xác đ nh b c ph n ng đ i v i n ng đ hóa ch t 87 3.3.6.2 Xác đ nh l 3.3.7 ng ho t hóa hi u d ng 91 Hòa tách vàng t b n m ch in n tho i di đ ng 93 3.3.7.1 Hòa tách vàng t PCBs h dung d ch thiosunphat -đ ng(II)- amoniac 93 3.3.7.2 Nâng cao hi u qu hòa tách vàng 95 K T LU N VÀ KI N NGH 97 TÀI LI U THAM KH O 99 DANH M C CÁC CƠNG TRÌNH ĐÃ CÔNG B PH N PH C A LU N ÁN 111 L C 112 iii DANH M C CÁC KÝ HI U VÀ CH VI T T T AAS Quang ph h p th nguyên t BFRs Ch t làm ch m cháy brom CRT ng phóng tia n t DO Hàm l ng oxy hịa tan EDX Tán x l Eh Th ơxy hóa kh EU Liên minh châu Âu E-waste Ch t th i n t ng tia X N ng đ c a hóa ch t khơng khí GAS-RAT (LC50) có th gây ch t 50% s qua đ ng th sau gi ti p xúc LCD Màn hình tinh th l ng MSDS B ng an tồn c a v t li u Li u l ORL-RAT-LD50 cá th chu t ng ch t đ c gây ch t cho m t n a (50%) s cá th chu t qua đ ng mi ng ORP Th ơxy hóa kh PC Máy tính cá nhân PCBs B n m ch in RPM Vòng/phút SEM Hi n vi n t quét TV Ti vi Ch ơng trình môi tr ng Liên h p UNEP qu c URENCO Công ty môi tr US EPA C c b o v môi tr WEEE Thi t b n n t th i iv ng đô th ng M DANH M C B NG B ng 1.1 S l ng thi t b n, n t gia d ng th i n m 2006 B ng 1.2 Các thành ph n v t li u trung bình c a b n m ch in B ng 1.3 Thành ph n kim lo i PCBs c a m t s lo i ch t th i n t 10 B ng 1.4 Giá tr kinh t c a kim lo i PCBs c a m t s lo i ch t th i n t 10 B ng 1.5 Đ đ c c a tác nhân hòa tách vàng thu th p t MSDS 15 B ng 1.6 Tính ch t v t lý c a vàng 16 B ng 1.7 H ng s b n đ i v i ph c Au(I) Au(III) th ơxy hóa kh tiêu chu n đ i v i ph n ng t ơng ng B ng 1.8 nh h B ng 1.9 nh h B ng 1.10 B ng 1.11 ng c a n ng đ thiosunphat đ n hòa tách vàng 24 ng c a n ng đ đ ng(II) đ n hòa tách vàng 25 nh h nh h 25oC 19 ng c a n ng đ amoniac đ n hòa tách vàng 26 ng c a pH đ n hòa tách vàng 27 B ng 2.1 Thành ph n kim lo i ch y u m u nghiên c u 32 B ng 2.2 Hóa ch t đ B ng 2.3 Các thi t b đ B ng 2.4 L c s d ng q trình thí nghi m 32 c s d ng q trình thí nghi m 33 ng amoniac bù áp su t bão hòa 38 B ng 2.5 Các thông s k thu t c a quy trình phân tích kim lo i 42 B ng 3.1 Ký hi u m c c a y u t nh h ng 74 B ng 3.2 Xây d ng ma tr n k ho ch th c nghi m theo bi n mã hóa 75 B ng 3.3 K t qu th c nghi m theo k ho ch 77 B ng 3.4 Các h s h i quy thu đ c t quy ho ch th c nghi m 79 B ng 3.5 N ng đ kim lo i dung d ch hòa tách 96 B ng A3.1 N ng đ hóa ch t dung d ch hòa tách 113 v DANH MỤC CÁC HÌNH VẼ VÀ ĐỒ THỊ Hình 1.1 S l n ng thi t b n, n t gia d ng s d ng c c qua năm Hình 1.2 S thuê bao n tho i di đ ng c n c Hình 1.3 dung d ch amoniac- Mơ hình ch hịa tách vàng h đ ng(II)-thiosunphat 20 Hình 1.4 Gi n đ 2- Eh-pH c a h Au(0)-Au(I)-Au(III)-NH3- S2O3 -H2O -5 + 25°C; [Au(I)]= 10 M, [Na2S2O3]= 0,1 M, [NH3+NH4 ]= M 21 Hình 1.5 Gi n đ Eh-pH c a h Cu-NH3-S-H2O 2- 25°C (0,5 mM Cu, 0,1 + M S2O3 , 0,1 M NH3/NH4 ) 22 Hình 1.6 Sơ đ cơng ngh hịa tách thu h i vàng t ch t th i n t 29 Hình 2.1 (a) M u ph li u (b) PCBs n tho i di đ ng th i đ c s d ng nghiên c u 31 Hình 2.2 Sơ đ h th ng thí nghi m hòa tách vàng t ch t th i n t 35 Hình 2.3 Sơ đ quy trình thí nghi m hịa tách vàng t m u ph li u PCBs 36 Hình 2.4 Ph UV/vis c a amoniacat đ ng(II) ph c thiosunphat đ ng(I) 39 Hình 2.5 Ph UV/vis c a h amoniac - đ ng(II) - thiosunphat sau 30 giây hịa tr n hóa ch t 40 Hình 2.6 Xây d ng đ đ ng(II) b ng chu n xác đ nh n ng đ ph c amoniacat c sóng 610 nm 40 Hình 3.1 Ph tán x l ng tia X c a b m t m u ph li u 48 Hình 3.2 Hình nh SEM c a m t c t ngang m u ph li u 48 Hình 3.3 T l ph n trăm b ph n c a n tho i di đ ng 50 Hình 3.4 PCBs n tho i di đ ng phân b kim lo i 50 Hình 3.5 Ph tán x l ng c a b m t v t li u PCBs 51 vi Hình 3.6 Hình nh phân tích SEM c a m t c t ngang c a m u PCBs 51 Hình 3.7 nh h ng c a th i gian đ n hi u su t hịa tách vàng 53 Hình 3.8 S thay đ i pH ORP dung d ch theo theo th i gian 53 Hình 3.9 N ng đ đ ng(II) theo th i gian th i gian hịa tách vàng 54 Hình 3.10 nh h ng c a hóa ch t tham gia ph n ng hịa tan vàng mơi tr ng n ng đ amoniac khác a) 0,1M; b) 0,2M; c) 0,3M; d) 0,4M (các u ki n khác: th i gian ti p xúc: gi , pH ban đ u = 10, nhi t đ phòng) 56 Hình 3.11 nh h ng c a n ng đ oxy đ n hi u su t hòa tách vàng u ki n 10 mM ion đ ng(II) 58 Hình 3.12 nh h ng c a n ng đ oxy đ n hi u su t hòa tách vàng u ki n khơng có ion đ ng(II) 58 Hình 3.13 nh h ng c a oxy đ n t c đ hòa tách ban đ u 58 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