B GIO DC V O TO TRNG I HC BCH KHOA H NI - NGUYN TH THU NGHIấN CU Mễ PHNG D ON CN BNG PHA H CU T Cể TRONG QU TRèNH SN XUT NHIấN LIU SINH HC BIODIESEL S DNG Mễ HèNH NHIT NG GC-PC-SAFT Chuyờn ngnh : K thut hoỏ hc LUN VN THC S KHOA HC K THUT HO HC NGI HNG DN KHOA HC : TS Vn ỡnh Sn Th TS Nguyn Hunh ụng H NI - 2013 LI CAM OAN Bn lun thc s Ngnh k thut Hoỏ hc vi ti: Nghiờn cu mụ phng d oỏn cõn bng pha h cu t cú quỏ trỡnh sn xut nhiờn liu sinh hc biodiesel s dng mụ hỡnh nhit ng GC-PC-SAFT c hon thnh di s hng dn ca TS Vn ỡnh Sn Th - B mụn Cụng ngh Hu c - Húa du, Khoa Cụng ngh Húa hc, Trng i hc Bỏch khoa H Ni v TS Nguyn Hunh ụng - B mụn Lc Hoỏ du khoa Du khớ, Trng Cao ng ngh Du khớ Vng Tu Tụi xin cam oan õy l cụng trỡnh nghiờn cu ca riờng tụi Cỏc s liu, kt qu nờu lun l trung thc v ni dung ny cha tng c cụng b bt k cụng trỡnh nghiờn cu no trc ú H Ni, thỏng 09 nm 2013 Tỏc gi Nguyn Th Thu Trang LI CM N Tụi xin by t lũng bit n sõu sc n TS Vn ỡnh Sn Th v TS Nguyn Hunh ụng ó dy d, hng dn tn tỡnh v mt khoa hc giỳp tụi cú th hon thnh lun thc s ny c hc v nghiờn cu di s hng dn ca cỏc thy giỳp tụi tin b hn rt nhiu, c v mt kin thc v tỏc phong lm vic Tụi xin cỏm n ti HP TC QUC T V KHOA HC V CễNG NGH THEO NGH NH TH S: 10/2012/H-NT Tụi xin cm n cỏc Thy, Cụ giỏo ca trng i hc Bỏch khoa H Ni ó dy d v giỳp tụi sut thi gian hc Tụi cng xin cm n gia ỡnh v Ban giỏm hiu cng nh khoa Du khớ trng cao ng ngh Du khớ ó to iu kin, giỳp tụi sut quỏ trỡnh hc v hon thnh lun ny H Ni, thỏng 09 nm 2013 Tỏc gi Nguyn Th Thu Trang DANH MC CC K HIU, CC CH VIT TT Ký hiu/ Chỳ gii ch vit tt L t trng pha lng (liquid density) Pvap ỏp sut hi bo hũa (vapor pressure) CpL nhit dung pha lng (liquid heat capacity) Hvap nhit húa hi (heat of vaporization) VLE Cõn bng lng hi (Vaporliquid equilibria) LLE Cõn bng lng lng (Liquidliquid equilibria) EoS phng trỡnh trng thỏi (Equation of state) SAFT thuyt nhit ng thng kờ (statistical associating fluid theory) PC-SAFT perturbed chain SAFT asso association hc hard chain disp dispersion id Ideal hs hard sphere ahc thnh phn nng lng chun adisp nng lng lc London (nng lng tớnh n tng tỏc cỏc moment phõn cc tm thi) gõy aasso nng lng tớnh n cỏc liờn kt hydro aid nng lng t Helmholtz ca khớ lý tng ahs nng lng t Helmholtz ca thnh phn hard-sphere xi thnh phn mole ca cu t i mi s segments ca cu t i g ijhs hm phõn b cp ca segments ca cu t i d ng kớnh segment k hng s Boltzmann Trang T nhit tuyt i i ng kớnh cỏc segment i nng lng tng tỏc gia cỏc segment m chiu di phõn t kớch thc phõn t /k nng lng tng tỏc NAV s Avogadro t trng mole ca cu t AiNj thụng s c trng cho lc liờn kt hydro XAi phn mole ca phõn t i khụng cú liờn kt hydro ti v trớ site A Mi s v trớ sites trờn phõn t i cú liờn kt hydro nng lng tng tỏc ng kớnh segment m s segment cu phõn t/ chiu di phõn t kij thụng s tng tỏc hn hp, l h s hiu chnh K hng s Boltzmann d kớch thc trung bỡnh ca segment v momen dipole ca cu t xp phn phõn cc cú trờn phõn t x thnh phn mole ca cu t ni s nhúm i phõn t lm nờn nhng nhúm khỏc nnhúm Si h s khụng cu ca phõn nhúm Trang MC LC LI CAM OAN LI CM N DANH MC CC K HIU, CC CH VIT TT DANH MC CC BNG DANH MC CC HèNH Chng 1: BIO-DIESEL NGUYấN LIU V CễNG NGH SN XUT 17 1.1 Gii thiu chung 17 1.2 Nguyờn liu sn xut Bio-diesel 22 1.3 Cỏc cu t hin din quỏ trỡnh sn xut bio-diesel 27 1.4 Quy trỡnh sn xut bio-diesel 31 1.4.1 Phng phỏp este húa cú s dng xỳc tỏc baz 32 1.4.2 Phng phỏp este húa cú s dng xỳc tỏc axit 32 1.4.3 Phng phỏp chuyn hoỏ du thnh acid, v sau ú este húa thnh bio-diesel 32 1.4.4 Phng phỏp khụng s dng cht xỳc tỏc 33 1.5 Cỏc c tớnh yờu cu cho quỏ trỡnh sn xut Bio-diesel 33 Chng 2: GII THIU V Mễ HèNH NHIT NG GC-PC-SAFT 37 2.1 Cỏc mụ hỡnh nhit ng ng dng cụng nghip 37 2.2 Phng trỡnh nhit ng PC-SAFT 43 2.3 Phng trỡnh nhit ng GC-PC-SAFT ỏp dng cho cu t phõn cc 48 Chng 3: PHNG PHP Mễ PHNG 50 3.1 Cỏc cu t, phõn nhúm v thụng s cn thit mụ phng quỏ trỡnh sn xut bio-diesel 50 3.2 La chn d liu thc nghim 52 3.3 Ti u cỏc thụng s phõn nhúm v cỏc cu t c bit 53 3.4 Xỏc nh thụng s cu t tinh khit v phõn nhúm 54 Chng 4: KT QU Mễ PHNG 56 4.1 Kt qu mụ phng thu c, thụng s phõn nhúm 56 4.2 Kt qu mụ phng cu t tinh khit 58 4.2.1 Cu t c bit: glycerol, methanol, ethanol 58 4.2.2 Ankanes 59 4.2.3 Alkene 61 4.2.4 Alcohols 62 4.2.5 Esters 64 Trang 4.3 D oỏn cõn bng pha ca cu t tinh khit nng v so sỏnh vi cỏc mụ hỡnh nhit ng khỏc 66 4.4 Mụ phng cõn bng pha hn hp 72 4.4.1 Cõn bng pha lng hi, h hai cu t 72 4.4.2 Cõn bng pha lng lng, h hai cu t 80 4.4.3 Cõn bng pha h ba cu t 85 4.4.4 D oỏn t trng pha lng ca hn hp bio-diesel 90 Chng : KT LUN KIN NGH 97 Trang DANH MC CC BNG Bng 1: So sỏnh nhiờn liu bio-diesel v nhiờn liu diesel 18 Bng 2: Mc gim khớ thi s dng bio-diesel so vi diesel du m 19 Bng 3: c tớnh ca mt s loi du thc vt so sỏnh vi du diesel 23 Bng 1.4: Cỏc thnh phn axit bộo ca cỏc loi du thc vt 24 Bng 1.5: Mt s ngun nguyờn liu c s dng sn xut bio-diesel 26 Bng 1.6: Axit bộo mt s Du khụng n c (Non-edible Oils) 30 Bng 1.7: Tờn v cụng thc húa hc ca cỏc axit bộo cú du v m 31 Bng 1.8: Cỏc thnh phn axit bộo ca cỏc loi du thc vt 31 Bng 1.9: Cỏc thụng s nhit ng quan trng cn cú mụ phng quỏ trỡnh sn xut Bio-diesel 35 Bng 1: D liu cõn bng pha cn thit thit k mt s trng hp c th 38 Bng 2: Nhng phng trỡnh trng thỏi Cubic (cubic EoS) v cỏch c in c tớnh cỏc thụng s ca chỳng 41 Bng 3: Mt s bin th ni ting ca mụ hỡnh SAFT 42 Bng 1: Cỏc phõn nhúm cn thit mụ phng cỏc cu t cú h bio-diesel .51 Bng 2: Cỏc thụng s cn thit cho cỏc phõn nhúm ca tng cu t 51 Bng 1: Thụng s cu t tinh khit thu c cho cỏc phõn nhúm 57 Bng 2: Thụng s phõn cc v liờn kt hydro thu c cho cỏc phõn nhúm 57 Bng 3: Kt qu ti u d liu s dng xỏc nh thụng s phõn nhúm [CH3] v [CH2] ca dóy alkanes, s dng ỏp sup hi bóo hũa ca cu t t propane (C3) n decane (C10) 60 Bng 4: Kt qu ti u d liu s dng xỏc nh thụng s phõn nhúm [CH3] v [CH2] ca dóy alkanes, s dng t trng pha lng ca cu t t propane (C3) n decane (C10) 60 Bng 5: Kt qu ti u d liu s dng xỏc nh thụng s phõn nhúm [CH=] ca dóy alkenes, s dng t trng pha lng ca cu t t 1- butene (C4) n 1decene (C10) 62 Bng 6: Kt qu ti u thu c trờn ỏp sut hi ca cỏc alcohols 62 Trang Bng 7: Kt qu ti u thu c trờn t trng pha lng ca cỏc alcohols 63 Bng 8: Kt qu ti u thu c trờn ỏp sut hi ca cỏc esters 64 Bng 9: Kt qu ti u thu c trờn t trng pha lng ca cỏc esters 65 Bng 10: Kt qu d oỏn ỏp sut hi ca cỏc cỏc alkanes nng khụng s dng quỏ trỡnh ti u, xỏc nh thụng s phõn nhúm 66 Bng 11: Kt qu d oỏn t trng pha lng ca cỏc cỏc alkanes nng khụng s dng quỏ trỡnh ti u, xỏc nh thụng s phõn nhúm 67 Bng 12: So sỏnh kt qu d oỏn ỏp sut hi bóo hũa cu t nng gia GC-sPCSAFT v mGC-PC-SAFT 68 Bng 13: So sỏnh kt qu d oỏn ỏp sut hi bóo hũa ca alkane nng gia SAFT- [160] v mGC-PC-SAFT 68 Bng 14: Kt qu d oỏn ỏp sut hi ca cỏc cỏc alcohols nng 69 Bng 15: Kt qu d oỏn t trng pha lng ca cỏc cỏc alcohols nng 69 Bng 16 So sỏnh kt qu d oỏn ỏp sut hi bóo hũa ca alkane nng gia GCSAFT-VR [162] v mGC-PC-SAFT 70 Bng 17: Sai s tng i ỏp sut sụi ca hn hp thu c t tớnh toỏn v thc nghim ca hn hp Methanol ester 72 Bng 18: Sai s tng i ỏp sut sụi ca hn hp thu c t tớnh toỏn v thc nghim ca hn hp Ethanol ester 73 Bng 19: Sai s tng i ỏp sut sụi ca hn hp thu c t tớnh toỏn v thc nghim ca hn hp Glycerol Methanol v Glycerol Ethanol 74 Bng 20: Thnh phn ca cỏc bio-diesel c nghiờn cu bi lun vn, theo phn trm lng 90 Bng 21: Khi lng phõn t ca cỏc bio-diesel 91 Bng 22: Kt qu d oỏn d oỏn t trng pha lng ca hn hp bio-diesel ti ỏp sut hi bóo ho 92 Bng 23: Kt qu d oỏn t trng pha lng ca hn hp bio-diesel ti ỏp sut 0.145 MPa 93 Trang DANH MC CC HèNH Hỡnh Nhúm cỏc thụng s tng tỏc hin cú ca UNIFAC chnh sa (Modified UNIFAC) cung cp bi DDBST (Dortmund Data Bank Software & Separation Technology), nm 2011 40 Hỡnh 2: Phõn t c xut bao gm cỏc chui v cú liờn kt hydro 43 Hỡnh 3: Quỏ trỡnh hỡnh thnh mt phõn t mụ hỡnh SAFT 44 Hỡnh 4: Chiu di phõn t m, kớch thc phõn t v nng lng tng tỏc /k ca cu t tinh khit khụng phõn cc 46 Hỡnh 5: Mụ t phõn t phõn cc, hin cú nhiu thuyt phõn cc khỏc nhng thuyt ca Jog v Chapman (phi) vi gi thuyt mụ men phõn cc ca phõn t ch phõn b trờn phõn nhúm phõn cc, c nhiu tỏc gi chp nhn v cho kt qu mụ phng tt nht 48 Hỡnh 1: Chiu di phõn t m, kớch thc phõn t v nng lng tng tỏc /k ca Butane 52 Hỡnh 2: Chiu di phõn t m, kớch thc phõn t nng lng tng tỏc /k v th tớch vựng cú kh nng to liờn kt hydro AB ca 2-Pentanol 52 Hỡnh 1: S liờn kt hydro ca alcohols mụ phng theo mụ hỡnh 3B 56 Hỡnh 2: S liờn kt hydro ca methanol v ethanol mụ phng theo mụ hỡnh 2B 56 Hỡnh 3: S liờn kt hydro ca Glycerols mụ phng theo mụ hỡnh 4C 56 Hỡnh 4: p sut hi bóo hũa v t trng pha lng ca glycerol So sỏnh gia s liu thc nghim v kt qu thu c bi lun ny 58 Hỡnh 5: p sut hi bóo hũa v t trng pha lng ca methanol So sỏnh gia s liu thc nghim v kt qu thu c bi lun ny 59 Hỡnh 6: p sut hi bóo hũa v t trng pha lng ca ethanol So sỏnh gia s liu thc nghim v kt qu thu c bi lun ny 59 Hỡnh 7: Kt qu ti u ỏp sut hi (trỏi) v t trng pha lng (phi) ca alkanes s dng lm c s d liu xỏc nh thụng s phõn nhúm [CH3] v [CH2] im l Trang Chng : KT LUN KIN NGH Sau mt thi gian nghiờn cu ti liu, tng hp lý thuyt v cỏc mụ hỡnh nhit ng, c bit l mụ hỡnh nhit ng thng kờ PC-SAFT Lun ó hon thnh c mc tiờu nghiờn cu c bn, c th nh sau: Túm tt thc trng nghiờn cu v tim nng s dng bio-diesel tng lai vi nhng thụng tin v nguyờn liu, sn phm, cụng ngh sn xut Xỏc nh yờu cu cp thit v tớnh thc t v mụ phng nhit ng ca cỏc h cú quỏ trỡnh sn xut bio-diesel; ó tỡm hiu cỏc mụ hỡnh nhit ng ng dng cụng nghip húa cht núi chung, mụ phng tớnh cht nhit ng h phc núi riờng v c bit l mụ hỡnh nhit ng thng kờ Trờn c s phõn tớch tng hp nhng kt qu nghiờn cu ca nhiu nhúm tỏc gi khỏc nhau, lun ó minh chng c s la chn mụ hỡnh nhit ng mGC-PC-SAFT l ỳng n; ó ngh phng phỏp ci tin kh nng d oỏn tớnh cht nhit ng ca cỏc cu t nng thụng qua vic s dng h s hiu chnh s khụng cu tuyt i ca phõn nhúm cụng thc tớnh toỏn chiu di phõn t Vi ci tin ny, mGC-PC-SAFT ó ci thin c sai s kt qu d oỏn so vi s liu thc nghim t khong 20% [132] xung cũn 4-8% Kt qu d oỏn ỏp sut hi bo hũa, t trng pha lng ca cỏc cu t tinh khit nng thu c vi mGC-PC-SAFT u cho sai s 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[6]) có tính đến các liên kết phân cực, liên kết hydro của từng cấu tử Luận văn này tập trung vào đánh giá, sử dụng mô hình nhiệt động GC- SAFT một cách phù hợp nhất, tối ƣu các thông số cấu tử tinh khiết để thu đƣợc Trang 15 kết quả mô phỏng các đặc tính cân bằng pha cấu tử và các hỗn hợp có trong quá trình sản xuất nhiên liệu sinh học biodiesel Mục tiêu nghiên cứu chính của luận văn là tối ƣu, dự đoán. .. bio-diesel (bên phải) xét trong hệ đẳng nhiệt, so sánh giữa dữ liệu thực nghiệm và dự đoán bằng hệ nhiệt động mGC -PC- SAFT 95 Trang 13 Hình 4 48: Tỷ trọng pha lỏng của Soybean bio-diesel xét trong hệ đẳng nhiệt, so sánh giữa dữ liệu thực nghiệm, dự đoán bằng hệ nhiệt động mGC -PC- SAFT và dữ liệu tính toán với hệ nhiệt động CPA 95 Trang 14 MỞ ĐẦU Từ thực trạng nguồn nhiên liệu hoá thạch đƣợc khai... số của mô hình nhiệt động để cho phép dự đoán cân bằng pha các hỗn hợp có trong quá trình sản xuất bio-diesel Các thông số của mô hình nhiệt động đƣợc tối ƣu thông qua dữ liệu thực nghiệm đƣợc công bố trên các tạp chí khoa học Cấu trúc luận văn bao gồm các nội dung chính nhƣ sau: Chương 1: Cung cấp những thông tin tóm tắt, tổng quan về nguyên liệu sử dụng trong quá trình sản xuất nhiên liệu biodiesel, ... sánh kết quả mô phỏng trong luận văn này và kết quả sử dụng mô hình NRTL có trong phần mềm Hysys 78 Hình 4.25: Cân bằng pha lỏng hơi hệ ethanol +methyl butanoate (trái) và (phải) So sánh kết quả mô phỏng trong luận văn này và kết quả sử dụng mô hình NRTL có trong phần mềm Hysys 79 Hình 4.26: Cân bằng pha lỏng hơi hệ methanol + glycerol (trái) và so sánh kết quả mô phỏng trong luận văn... trọng pha lỏng (phải) của các alcohols so sánh giữa phƣơng trình nhiệt động mGC -PC- SAFT đang sử dụng trong bài luận văn Điểm là dữ liệu thực nghiệm lấy từ DIPPR và đƣờng liên tục là kết quả tính toán sử dụng mGC -PC- SAFT 63 Hình 4.11: Kết quả tối ƣu thu đƣợc trên áp suất hơi của Hexanol so sánh giữa phƣơng trình nhiệt động mGC -PC- SAFT đang sử dụng trong bài luận văn, hệ nhiệt động NRTL trong. .. thiết kế quá trình sản xuất nhiên liệu sinh học [3] Theo các nghiên cứu tổng hợp của các nhóm nghiên cứu trong lĩnh vực sản xuất nhiên liệu bio-diesel từ các loại nhiên liệu khác nhau, nhiều nhóm tác giả đã khẳng định sự cần thiết phải xây dựng một mô hình nhiệt động đáng tin cậy để mô phỏng quá trình thiết kế, tính toán công nghệ Sự thiếu hụt thông tin hoặc sai số tính toán lớn hơn cho phép có thể gây... hiện tƣợng xuất hiện các pha không mong muốn trong hỗn hợp phản ứng nhƣ lỏng-hơi, lỏng-lỏng, lỏnglỏng-hơi [4] Do đó, phát triển mô hình nhiệt động có thể mô tả chính xác cân bằng pha và cân bằng phản ứng cho các hỗn hợp có trong hệ là rất quan trọng [5] Hiện nay, có rất nhiều mô hình nhiệt động đã đƣợc đề nghị sử dụng để tính toán các đặc tính của hệ sản xuất biodiesel (bao gồm các cấu tử: nƣớc, axit... kết quả mô phỏng trong luận văn này với các mô hình nhiệt động khác nhau 83 Hình 4.31: Cân bằng pha lỏng – lỏng hệ glycerol + methyl-hexanoate So sánh số liệu thực nghiệm (điểm) và mGC -PC- SAFT (đƣờng liền) 83 Hình 4.32: Cân bằng pha lỏng – lỏng hệ glycerol + methyl-octanoate So sánh số liệu thực nghiệm (điểm) và mGC -PC- SAFT (đƣờng liền) 84 Hình 4.33: Cân bằng pha lỏng – lỏng hệ glycerol... bio-diesel (bên phải) xét trong hệ đẳng nhiệt, so sánh giữa dữ liệu thực nghiệm và dự đoán bằng hệ nhiệt động mGC -PC- SAFT 94 Hình 4 45: Tỷ trọng pha lỏng của Soybean + Rapeseed bio-diesel (bên trái) và Rapeseed + Palm bio-diesel (bên phải) xét trong hệ đẳng nhiệt, so sánh giữa dữ liệu thực nghiệm và dự đoán bằng hệ nhiệt động mGC -PC- SAFT 94 Hình 4 46: Tỷ trọng pha lỏng của Soybean + Palm... nêu trên, có 3 vùng phân tách có trong quá trình công nghệ sản xuất bio-diesel, bao gồm quá trình tách pha (2 pha lỏng) trong thiết bị phản ứng và trong hai tháp chƣng cất để tiến hành tinh khiết glycerol và FAMEs Việc thiết kế các thiết bị tách yêu cầu các thông số nhiệt động chính xác về đặc tính vật lý, cân bằng pha của các cấu tử có trong hệ, theo đó, cân bằng pha lỏng – lỏng và cân bằng pha lỏng