Acrolein from propylene and oxygen from air [ ]

Transcription

1 Acrolein from propylene and oxygen from air [ ] CONTENTS OF FACTORY GATE TO FACTORY GATE LIFE CYCLE INVENTORY SUMMARY Chemistry... 2 Process Summary... 3 Summary of LCI Information... 5 Process Diagram or Boundary of LCI... 8 Mass Balance of Chemicals in Each Process Stream...13 Graph of Cumulative Chemical Losses through Manufacturing Process...21 Graph of Cumulative Contaminated Use / Emission through Manufacturing Process...23 Graph of Cumulative Non-Contaminated Use / Emission through Manufacturing Process...25 Energy Input for each Unit Process, Cumulative Energy Requirements, Cooling Requirements (exotherms), and Assumed Heat Recovery from Hot Streams Receiving Cooling...27 Graph of Cumulative Energy Requirements...29 Authors Peer reviews, name (date) Gtg report last modified on Additional notes Y. Li Reviewed by MR Overcash on : route, stoichiometry, and calculations reviewed and found to be representative. Reviewed by EM Griffing on : route and stoichiometry reviewed and found to be representative. Checked for database consistency on First gtg version finalized on Modification history, Author (date) EMG ( ) and YL ( ) Products Standard inputs Acrolein, Acrylic acid, Acetic acid oxygen from air, Propylene Methodology: Environmental Clarity gtg lci reports are based on industrial practice information, standard methods of engineering process design, and technical reviews. These reports are intended to be representative of industrial production based on the stated route. Terms of use: Environmental Clarity does not assume any liability due to use of these lci data. Integration of these data with lci data based on other methodologies is the responsibility of the user. Each report may be updated to improve model accuracy or representativeness. Users of this report should cite: E. Griffing and M. Overcash, Chemical Life Cycle Database, present. updated on 9/1/2016 1

2 Chemistry Primary reaction: CH 2 CHCH 3 + O 2 CH 2 CHCHO + H 2 O (1-1) Propylene Oxygen Acrolein Side reactions: CH 2 CHCH O 2 CH 2 CHCOOH + H 2 O (1-2) Propylene Oxygen Acrylic acid CH 2 CHCH O 2 CH 3 COOH + CH 2 O (1-3) Propylene Oxygen Acetic acid Formaldehyde CH 2 CHCH 3 + O 2 C2H4O + CH 2 O (1-4) Propylene Oxygen Acetaldehyde Formaldehyde updated on 9/1/2016 2

3 Process Summary Literature Acrolein is a colorless, volatile, toxic, and lacrimatory liquid with a powerful odor. The commercial production of acrolein by heterogeneously catalyzed gas-phase condensation of acetaldehyde and formaldehyde was established by Degussa in Today, acrolein is produced on a large commercial scale by heterogeneously catalyzed gas-phase oxidation of propene. 1 LCI design Propylene, air, and steam are compressed to 2 atm and then mixed at a molar ratio of 1:8:4 2. The gas mixture is fed to a multitubular fixed-bed reactor, which is operated at 350 o C and 2 atm 2. The conversion rate of propylene in this reactor is 95% 2. The effluent gas from the reactor is cooled to 250 o C and then fed into a gas washer. An aqueous stream and an organic liquid, 2-ethylhexanol, are used to wash the gas stream. The ratio of gas stream:aqueous stream:organic stream is 10.6:1.5:1 3. The residual gas leaves gas washer at 70 o C and is introduced to the bottom of a gas cooler. The liquid stream from the gas washer is pumped into series of distillation columns at 105 o C to recover byproducts acrylic acid and acetic acid 3. From the gas cooler, the residual gas stream leaves at 19 o C and is fed into another gas washer to recover residual acrolein. The organic phase from the bottom of the cooler is recycled to the first gas washer at 45 o C 3. Part of the aqueous phase is combined with the organic phase of the second gas washer and cooled to 16 o C and recycled to the gas cooler. Part of the aqueous phase from the gas cooler is recycled to the first gas washer. The second gas washer using water-2-ethylhexanol mixture to wash the residual gas at 2 o C 3. The aqueous phase is then combined with part of the aqueous phase from the gas cooler to recover acrolein product. 2-Ethylhexanol is also recovered and combined with makeup 2-ethylhexanol and water. This stream is cooled to 2 o C and fed into the second gas washer. Route review 2016 KO (2009), KO (2007), and KO (2015) confirm propylene oxide as only commercial route. Critical parameters Conversion / Yield information from both reactors Total conversion in reactor 1: (% of reactant entering the process that reacts) From mass balance Conversion of or Yield from Propylene Conversion of or Yield from Oxygen Total per pass conversion in reactor 1: From mass Acrolein and Methacrolein, Ullmann s Encyclopedia of Industrial Chemistry, online edition, pp 1 2 Acrolein and Methacrolein, Ullmann s Encyclopedia of Industrial Chemistry, online edition, pp US patent 3,926,744, Dec. 16, 1975 updated on 9/1/2016 3

4 (% of reactant entering the reactor that reacts) Total yield of reactor 1: (% yield acrolein produced in the reactor based on reactant input to process) Total yield of Process: (% yield produced by the overall process based on reactant input to process) Notes: balance From mass balance From mass balance Product purity Acrolein Used here 98.6% LiteratureSource Comments updated on 9/1/2016 4

5 Summary of LCI Information Inputs UID CAS Chemical Amount Purity (%) Units UIDO2FromAir Oxygen 100 [kg/hr] 7 from air Propylene Propylene [kg/hr] Total 1,715 [kg/hr] Comments Non-reacting inputs UID CAS Chemical Amount Purity (%) Units Comments UIDN2FromAir Nitrogen from air 49 [kg/hr] ,644 [kg/hr] UIDO2FromAir Oxygen from air 491 [kg/hr] Total non-reacting inputs 14,174 [kg/hr] Ancillary inputs UID CAS Chemical Amount Purity (%) Units Comments Ethylhexanol, [kg/hr] Total ancillary inputs 9 [kg/hr] Products UID CAS Chemical Amount Purity (%) Units Comments Acrolein 1, [kg/hr] Acrylic acid [kg/hr] Acetic acid [kg/hr] Total 1196 [kg/hr] Benign outflows UID CAS Chemical Amount Purity (%) Units Comments Nitrogen 4,9 [kg/hr] Oxygen 491 [kg/hr] ,6 [kg/hr] Total benign output flows [kg/hr] updated on 9/1/2016 5

6 Chemical Emissions UID CAS Chemical Amount Units Comments Gas Liquid Solid Solvent Acrylic acid [kg/hr] Acrolein [kg/hr] Propylene [kg/hr] Acetic acid [kg/hr] Formaldehyde [kg/hr] Acetaldehyde [kg/hr] Ethylhexanol, [kg/hr] Total [kg/hr] Mass Balance Difference -57 [kg/hr] Energy use Source Amount Units Comments Electricity 2045 [MJ/hr] Dowtherm 0 [MJ/hr] Heating steam [MJ/hr] 85% efficiency has been included to determine how much steam is needed for heating process fluid 2.10E+04 Direct fuel use in high [MJ/hr] temperature heating 0 Heating natural gas 0 [MJ/hr] Energy input requirement [MJ/hr] Electricity + steam + direct fuel oil + Dowtherm 2.31E+04 Cooling water - [MJ/hr] 1.92E+04 Cooling refrigeration 0 [MJ/hr] Potential Heat Recovery [MJ/hr] Net energy [MJ/hr] Energy input requirement minus potential heat 1.86E+04 recovery from cooling systems. updated on 9/1/2016 6

7 Process Diagram Interpretation Sheet 1) As much as possible, standard symbols are used for all unit processes. 2) Only overall input and output chemicals are labeled on these diagrams. All intermediate information is given on the attached Process Mass Balance sheet 3) The physical state of most streams is shown (gas, g; liquid, l; solid, s) 4) The process numbering is as follows, generally numbers progress from the start to the end of the process numbers are used for process streams C i, i = 1,..n are used for all cooling non-contact streams S j, j = 1,...n are used for all steam heating non-contact streams 5) Recycle streams are shown with dotted lines For most streams, the temperature and pressure are shown, if the pressures are greater than 1 atm updated on 9/1/2016 7

8 Process Diagram or Boundary of LCI Steam enters the process as a gas at 207 o C and leaves as a liquid at 207 o C. Cooling water enters at 20 o C and leaves at 50 o C. Unless otherwise indicated, all processes are at 1 atm. Fugitive Losses makeup (Total) 19.2 kg Propylene 1 (g) 960 kg Propylene Cmp 1 2 (g) 52.0 o C 2.0 atm F 3c (g) 101 o C 5 (g) 49 kg Nitrogen 1226 kg Oxygen Cmp 2 Cmp 3 4 (g) o C 2.0 atm 6 (g) 89.9 o C 2.0 atm Mx 1 7 (g) o C 2.0 atm C1 8 (g) o C 2.0 atm R1 T: 350 o C P: 2 atm C2 C3 B 20e (g) 70 o C HX 2 H E 28a (l) 45.0 o C 23 (l) 45.0 o C Washer 1 9 (g) o C 2.0 atm C4 A 11 (l) 105 o C P2 S13 10 (l) 105 o C S14 updated on 9/1/2016 8

9 A 11 (l) 105 o C C5 Di 1 C6 12 (l) 100 o C 14 (l) 100 o C P3 Ambient cooling 13 (l) kg kg Acrolein 4.04 kg Nitrogen kg Acrylic acid kg Oxygen kg Propylene kg Acetic acid 0.05 kg Ethylhexanol, kg Formaldehyde kg Acetaldehyde S3 S4 15 (l) 100 o C I B E 23 (l) 45.0 o C 29 (g) 44.5 kg Nitrogen kg Oxygen 47.5 kg Propylene 26.8 kg Formaldehyde kg Acetaldehyde 20e (g) 70 o C P9 Gas cooler 22 (l) 45.0 o C 24 (l) 45.0 o C 21 (g) 19.0 o C 27 (l) 16 o C P10 P4 C14 25 (l) 45.0 o C Ambient heating C13 Refrigeration 1 26 (l) 44.3 o C Gas washer 34 (l) 14 o C 36 (l) 14 o C 55 (l) 2.0 o C 37 (l) 14 o C 35 (l) 25a (l) 14 o C 45.0 o 28b (l) C K Mx o C P11 28 (l) 45.0 o C P12 28a (l) 45.0 o C G D H updated on 9/1/2016 9

10 K D 37 (l) 14 o C S11 HX 4 38 (l) 28b (l) 45.0 o C 38a (l) 33.5 o C G/L separator 40 (g) 14.7 kg Acetaldehyde kg Formaldehyde Mx 4 S12 41 (l) 33.5 o C C17 C18 43 (l) 57 o C 44 (l) 57 o C L P13 42 (l) 33.5 o C Di 4 46 (l) 57 o C P14 47 (l) 57 o C C21 HX 6 48 (l) 45e (l) M G 55 (l) 2 o C C24 S9 C23 Refrigeration 2 54 (l) 28.9 o C updated on 9/1/ S10 Mx3 53 (l) 8000 kg 9.00 kg Ethylhexanol, 2 P15 52 (l) P17 20d (l) 139 o C 51 (l) C22 48a (l) Decanter 1 49 (l) P16 50 (l) 9598 kg 41 kg Acrolein 5.51 kg Ethylhexanol, E-05 kg Acetic acid J

11 3 (l) 1644 kg P1 3a (l) 25 o C S1 HX 1 S2 3b (l) 100 o C F C8 I C7 15 (l) 100 o C S5 Di 2 S6 16 (l) 118 o C 18 (l) 118 o C P5 P6 19 (l) 118 o C C9 Ambient cooling Di 3 C10 20 (l) 139 o C P7 20a (l) 139 o C 17 (l) 33.6 kg Acetic acid 7.4 kg Acrylic acid 10 kg Ethylhexanol, kg HX 3 C11 C12 20b (l) kg Acrylic acid 4.89 kg Ethylhexanol, kg Acetic acid Fugitive Losses (Total) (g) kg Acrolein 19.2 kg Propylene kg Acetic acid kg Formaldehyde kg Acetaldehyde S7 S8 20c (l) 139 o C P8 20d (l) 139 o C J updated on 9/1/

12 C21 C19 C20 45 (l) 57 o C 45a (l) 57 o C HX 5 C22 45b (l) 986 kg Acrolein 13.8 kg kg Acetaldehyde 7.21E-06 kg Acetic acid L 44 (l) 57 o C Di 5 P18 45c (l) 57 o C S15 S16 P19 C27 45d (l) 57 o C HX 7 45e (l) 25 o C M C28 updated on 9/1/

13 Comments Streams Temp [C] P, atm Phase Total Flow Acrylic acid Oxygen Acrolein Propylene Acetic acid Formaldehyde Nitrogen Acetaldehyde Ethylhexanol, 2 Steam Mass Balance of Chemicals in Each Process Stream All flow rates are given in kg / hr Physical state of chemical losses: Gas Liquid Solid Input g g Input l a l b g g Input g g g R1 787 kg Propylene is converted in rxn 1 ( 82.0 % of reactor input) 86.4 kg Propylene is lost in rxn kg Propylene is lost in rxn Propylene is lost in rxn 4 Input to reactor : R1 Reaction Coefficient : R1 Conversion 1 [kg/hr] : R1 Conversion 1 [kgmol/hr] : R1 Reaction Coefficient : R1 Conversion 2 [kg/hr] : R1 Conversion 2 [kgmol/hr] : R1 Reaction Coefficient : R1 Conversion 3 [kg/hr] : 1.37E R1 Conversion 3 [kgmol/hr] : updated on 9/1/

14 Comments Streams Temp [C] P, atm Phase Total Flow Acrylic acid Oxygen Acrolein Propylene Acetic acid Formaldehyde Nitrogen Acetaldehyde Ethylhexanol, 2 Steam R1 Reaction Coefficient : R1 Conversion 4 [kg/hr] : R1 Conversion 4 : [kgmol/hr] Flow out of reactor : Primary product : Acrolein Total conversion : NA 60.0 NA 95.0 NA NA -0 NA -0 Per pass conversion : NA 60.0 NA 95.0 NA NA NA -0 NA Total yield from reactor : 81.4 NA g g Stream 28a:Recycle input Stream 28a:Recycle calculated Stream 28a:Recycle residue Stream 23:Recycle input Stream 23:Recycle calculated Stream 23:Recycle residue l l Feed l streamphase l g g g g l g g g l Di <1> percentage of input in distillate : percentage of input in : bottoms Boiling Temperature (Tb) [oc] : Distillate l streamphase l g g g l l g g g l Bottoms l streamphase l g g g l l g g g l l Waste l updated on 9/1/

15 Comments Streams Temp [C] P, atm Phase Total Flow Acrylic acid Oxygen Acrolein Propylene Acetic acid Formaldehyde Nitrogen Acetaldehyde Ethylhexanol, 2 Steam l l Feed l streamphase l g g g l l g g g l Di <2> percentage of input in : distillate percentage of input in : bottoms Boiling Temperature (Tb) [oc] : Distillate l streamphase l g g g l l g g g l Bottoms 17a l streamphase l g g g l l g g g l l By-product l l l Feed l streamphase l g g g g l g g g l Di <3> percentage of input in : distillate percentage of input in : bottoms Boiling Temperature (Tb) [oc] : Distillate l streamphase l g g g g g g g g l Bottoms 20c l streamphase l g g g g g g g g l l a l By-product 20b l d l e g Stream 27:Recycle input 3.84E E E Stream 27:Recycle 3.84E E E updated on 9/1/

16 Comments Streams Temp [C] P, atm Phase Total Flow Acrylic acid Oxygen Acrolein Propylene Acetic acid Formaldehyde Nitrogen Acetaldehyde Ethylhexanol, 2 Steam calculated Stream 27:Recycle residue g l l l 4.14E E E l 4.14E E E a l 3.74E E E Stream 35:Recycle input Stream 35:Recycle calculated Stream 35:Recycle residue l 3.84E E E l 3.84E E E l a l b l Stream 55:Recycle input Stream 55:Recycle calculated E Stream 55:Recycle residue E Waste g l l l E l E l E a l 1.08E E g/l separation <1> percentage of input in vapor phase percentage of input in liquid phase : : updated on 9/1/

17 Comments Streams Temp [C] P, atm Phase Total Flow Acrylic acid Oxygen Acrolein Propylene Acetic acid Formaldehyde Nitrogen Acetaldehyde Ethylhexanol, 2 Steam Boiling Temperature (Tb) [oc] : Waste g l 1.08E E l 1.08E E Feed l E streamphase l g l g l l g g g l Di <4> percentage of input in : distillate percentage of input in : bottoms Boiling Temperature (Tb) [oc] : Distillate l E streamphase l g l g l l g g g l Bottoms l E streamphase l g l g l l g g g l l E l E Feed l E streamphase l g l g l l g g g l Di <5> percentage of input in distillate : percentage of input in : bottoms Boiling Temperature (Tb) [oc] : Distillate l streamphase l l g Bottoms 45c l E updated on 9/1/

18 Comments Streams Temp [C] P, atm Phase Total Flow Acrylic acid Oxygen Acrolein Propylene Acetic acid Formaldehyde Nitrogen Acetaldehyde Ethylhexanol, 2 Steam 06 streamphase l l l l l a l Main product 45b l c l E d l E e l E l E l E e l E Decanter 1 percentage in oil phase : percentage in aqueous : phase l E Waste l E l E Input l l E l E Product purity (%) Main product Acrolein Overall Rxn coefficients Total yield of process (from reactant) 46.3 NA 76.3 NA Waste Fugitive Losses (Total) g Input Sum 1.59E Fugitive Replacement of updated on 9/1/

19 Comments Streams Temp [C] P, atm Phase Total Flow Acrylic acid Oxygen Acrolein Propylene Acetic acid Formaldehyde Nitrogen Acetaldehyde Ethylhexanol, 2 Steam Reactants Total Input (Input + Fugitive 1.59E Replacement) Product Sum Main product flow Net Input Input C l 3.81E E+04 Cooling out C l E E+04 Input C l Cooling out C l Input C l Cooling out C l Input C l Cooling out C l Input C l Cooling out C l Input C l Cooling out C l Input C l 2.64E E+04 Cooling out C l E E+04 Input C l 5.68E E+04 Cooling out C l E E+04 Input C l Cooling out C l Input C l Cooling out C l Input C l Cooling out C l Input C l Cooling out C l Input C l Cooling out C l Input S g Steam out S l updated on 9/1/

20 Comments Streams Temp [C] P, atm Phase Total Flow Acrylic acid Oxygen Acrolein Propylene Acetic acid Formaldehyde Nitrogen Acetaldehyde Ethylhexanol, 2 Steam Input S g Steam out S l Input S g Steam out S l Input S g Steam out S l Input S g Steam out S l Input S g Steam out S l Input S g Steam out S l Input S g Steam out S l updated on 9/1/

21 Graph of Cumulative Chemical Losses through Manufacturing Process Cumulative Chemical Loss a c 20 20a 20b 20d 20e a a 28b a c 45 45a 45b 45c 45d 45e e Fu kg chemical loss / hr a 3b Process Stream updated on 9/1/

22 updated on 9/1/

23 Graph of Cumulative Contaminated Use / Emission through Manufacturing Process Cumulative Contaminated Use 12,000 10,000 8,000 6,000 4,000 2, a 3b a c 20 20a 20b 20d 20e a a 28b a c 45 45a 45b 45c 45d 45e e kg contaminated water / hr Process Stream updated on 9/1/

24 updated on 9/1/

25 C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C17 C18 C19 C20 C21 C22 C23 C24 C23 C24 C25 C26 C27 C28 S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 S11 S12 S13 S14 S15 S16 kg non-contaminated water / hr Graph of Cumulative Non-Contaminated Use / Emission through Manufacturing Process Cumulative Non-Contamintated Use 200, , , , , ,000 80,000 60,000 40,000 20,000 0 Process Stream updated on 9/1/

26 updated on 9/1/

27 Process Diagram Label Unit Energy input [MJ / 1000 kg Product] Cumulative energy [MJ / 1000 kg Product] To [C] (Used to determine Energy Type Process diagram label Unit Energy Loss Cumulative cooling water energy Tef [C] (for recovery efficiency) Recovery Efficiency Energy Recovered Cumulative recovered [MJ / 1000 kg Product] Energy Input for each Unit Process, Cumulative Energy Requirements, Cooling Requirements (exotherms), and Assumed Heat Recovery from Hot Streams Receiving Cooling Energy Input [MJ / hr] Cooling Requirements [MJ / hr] Cmp1 Compressor E R1 Reactor Cmp2 Compressor E Hx2 Heat exchanger Cmp3 Compressor E Di1 Distillation condenser 1 P1 Pump E Di2 Distillation condenser 2 Hx1 Heat exchanger S Di3 Distillation condenser 3 P2 Pump E E Hx3 Heat exchanger Di1 Distillation reboiler S Hx5 Heat exchanger P3 Pump E E Hx6 Heat exchanger P4 Pump E E Di4 Distillation condenser Di2 Distillation reboiler S Di5 Distillation condenser P5 Pump E E P6 Pump E E Di3 Distillation reboiler S P7 Pump E E P8 Pump E P9 Pump E E P10 Pump E P11 Pump E Ref1 Refrigerator elect E P12 Pump E P13 Pump E Di4 Distillation reboiler E S P14 Pump E- 1.67E+04 E P15 Pump E+04 E updated on 9/1/

28 P16 Pump E- 1.67E+04 E P17 Pump E+04 E Ref2 Refrigerator elect E+04 0 E Hx4 Heat exchanger E S : Washer E+04 0 S Di5 Distillation reboiler E S P18 Pump E+04 E P19 Pump E+04 E Potential recovery E+04 Net energy 1.55E+04 Potential recovery: Electricity 2045 E [MJ/hr] DowTherm 0 D [MJ/hr] Heating steam 1.79E+04 S [MJ/hr] Direct fuel use 0 F [MJ/hr] Heating natural gas 0 G [MJ/hr] Energy input 1.99E+04 [MJ/hr] requirement Cooling water -1.92E+04 [MJ/hr] Cooling refrigeration [MJ/hr] Potential heat [MJ/hr] recovery Net energy 1.55E+04 [MJ/hr] updated on 9/1/

29 Start Compressor 1 Compressor 2 Compressor 3 Pump 1 Heat exchanger 1 Pump 2 Distillation reboiler 1 Pump 3 Pump 4 Distillation reboiler 2 Pump 5 Pump 6 Distillation reboiler 3 Pump 7 Pump 8 Pump 9 Pump 10 Pump 11 Refrigerator elect. 1 Pump 12 Pump 13 Distillation reboiler 4 Pump 14 Pump 15 Pump 16 Pump 17 Refrigerator elect. 2 Heat exchanger 4 Washer 1 Distillation reboiler 5 Pump 18 Pump 19 Potential recovery MJ / hr Graph of Cumulative Energy Requirements Cumulative Energy Input 25,000 20,000 15,000 10,000 5,000 0 Process Unit updated on 9/1/