Search

CN-121986151-A - Method for purifying biological oils

CN121986151ACN 121986151 ACN121986151 ACN 121986151ACN-121986151-A

Abstract

Method for purifying biological oils the present invention relates to a method for purifying biological oils and to a unit for carrying out said method. The invention further relates to a purified bio-oil obtainable or obtained by said method.

Inventors

  • O. Pilarsky
  • F. Hulsman
  • A. Languede Oliveira
  • HIEBER GISELA
  • D. Kupke
  • M. Hagg
  • M. Feiyan
  • M. SCHREIBER
  • A. MELZER
  • S. MILLER

Assignees

  • 巴斯夫欧洲公司

Dates

Publication Date
20260505
Application Date
20240926
Priority Date
20231006

Claims (15)

  1. 1. A method for purifying a biological oil, the method comprising: (i) Providing a stream F0 comprising the bio-oil, wherein preferably the bio-oil is obtained from biomass by performing mechanical and physical operations as well as chemical methods; (ii) Subjecting the stream F0 provided in (i) to extraction in at least one extraction zone Z E , obtaining a stream F1 comprising extracted bio-oil, wherein (ii) comprises: (ii.1) introducing F0 into an extraction unit UM1 contained in Z E ; (ii.2) contacting F0 with water and a base B in UM1 at a temperature T1 in the range of 10 ℃ to 200 ℃ to obtain a mixture M1 comprising an aqueous phase P A (1) and an organic phase P O (1), the pH of this aqueous phase P A (1) of M1 being in the range of 7.5 to 11; (ii.3) passing the mixture M1 obtained according to (ii.2) into a liquid-liquid separation unit US1 comprised in Z E -US 1 being located downstream of UM1, obtaining a stream F A (1) comprising P A (1) and a stream F1 comprising P O (1) being the extracted bio-oil; (ii.4) removing F1 from Z E ; (iii) Subjecting the stream F1 provided in (ii) to washing in at least one washing zone Z W -Z W is located downstream of Z E , obtaining a stream F2 comprising purified bio-oil, and (V) Introducing the F2 comprising the bio-oil obtained according to (iii) into at least one storage unit SU and storing said bio-oil in SU.
  2. 2. The method of claim 1, wherein (ii.2) comprises (Ii.2.1) introducing water into UM1 contained in Z E ; (ii.2.2) contacting, preferably mixing, F0 with water in UM1 to obtain a mixture PM1 comprising water and the bio-oil; (ii.2.3) introducing B into UM1 and contacting, preferably mixing, B in UM1 with the mixture PM1 obtained in (ii.2.2) to obtain a mixture M1 comprising an aqueous phase P A (1) and an organic phase P O (1), the pH of the aqueous phase P A (1) of M1 being in the range of 7.5 to 11, preferably in the range of 8 to 10; Preferably, (ii.2) comprises (Ii.2.1) introducing water into UM1 contained in Z E ; (ii.2.2) contacting, more preferably mixing, F0 with water in UM1 to obtain a mixture PM1 comprising water and the bio-oil, wherein the aqueous phase of PM1 has a pH value pH (PM 1), more preferably measured by a pH sensor in UM 1; (ii.2.3) adjusting the pH of the aqueous phase of PM1 by introducing B into UM1 by contacting, preferably mixing, B with M1 obtained in (ii.2.2) in UM1, a mixture M1 comprising aqueous phase P A (1) and organic phase P O (1) is obtained, the pH of the aqueous phase P A (1) of M1 > pH (PM 1), the pH of P A (1) being in the range of 7.5 to 11, more preferably in the range of 8 to 10.
  3. 3. The method of claim 1, wherein (ii.2) comprises (Ii.2.1') mixing water and B to obtain a mixture M0 of water and B having a pH (M0) in the range 12 to 14; (ii.2.2 ') introducing M0 obtained according to (ii.2.1') into UM1 and contacting, preferably mixing, F0 with M0 in UM1 to obtain a mixture M1 comprising an aqueous phase P A (1) and an organic phase P O (1), the pH of this aqueous phase P A (1) of M1 being in the range from 7.5 to 11, preferably in the range from 8 to 10.
  4. 4. A process according to any one of claims 1 to 3, wherein contacting, preferably mixing, according to (ii.2) is carried out at a temperature T1 in the range of 10 ℃ to 95 ℃, preferably in the range of 15 ℃ to 85 ℃, more preferably in the range of 20 ℃ to 80 ℃, more preferably in the range of 20 ℃ to 50 ℃.
  5. 5. The process according to any one of claims 1 to 4, wherein no organic solvent is used in (ii).
  6. 6. The method of any one of claims 1 to 5, wherein (iii) comprises: (iii.1) introducing F1 into a washing unit UM2 contained in Z W ; (iii.2) contacting F1 with water in UM2 at a temperature T2 in the range of 10 ℃ to 95 ℃ to obtain a mixture M2 comprising an aqueous phase P A (2) and an organic phase P O (2), the pH of this aqueous phase P A (2) of M2 being in the range of 7.5 to 11, the pH of P A (2) being < the pH of P A (1); (iii.3) passing the mixture M2 obtained according to (iii.2) into a liquid-liquid separation unit US2 contained in Z W -US 2 being located downstream of UM2, obtaining a stream F A (2) comprising P A (2) and a stream F2 comprising P O (2) being the purified bio-oil, Wherein preferably the washing unit UM2 is one or more of a stirring vessel, a mixing pump and a static mixer, more preferably a stirring vessel, and Wherein preferably the liquid-liquid separation unit US2 is one or more of a hydrocyclone, a settling tank, a centrifuge and an extraction column, more preferably a hydrocyclone, a settling tank or a centrifuge, more preferably a settling tank or a centrifuge.
  7. 7. The method of any one of claims 1 to 5, wherein (iii) comprises: (iii.1') introducing F1 into an extraction column UM+US contained in Z W ; (iii.2') introducing water into UM+US; (iii.3 ') contacting F1 with water in um+us at a temperature T2' in the range of 10 ℃ to 95 ℃ to obtain a stream F A (2) comprising an aqueous phase P A (2), the pH of the aqueous phase P A (2) of M2 being in the range of 7.5 to 11, the pH of P A (2) being < the pH of P A (1), and to obtain a stream F2 comprising the purified bio-oil.
  8. 8. The method of any one of claims 6 to 7, wherein the weight ratio of water to F1 according to (iii.2) or (iii.3') is in the range of 0.05:1 to 2:1, preferably in the range of 0.1:1 to 1.5:1, more preferably in the range of 0.1:1 to 1.2:1, more preferably in the range of 0.1:1 to 0.5:1.
  9. 9. The method of any one of claims 6 to 8, further comprising Recycling at least a portion of the water contained in F A (2) obtained according to (iii.3) and/or (iii.2) in (ii.2), or Recycling at least a portion of the water contained in F A (2) obtained according to (iii.3 ') and/or (iii.2') in (ii.2).
  10. 10. The method of any one of claims 1 to 9, further comprising, when scale is formed in US1 at the interface of P A (1) and P O (1), cleaning the scale from US1, preferably a settling tank.
  11. 11. The process of any one of claims 1 to 10, wherein the stream F2 comprising the purified bio-oil obtained according to (iii) has a Total Acid Number (TAN) lower than the TAN of the bio-oil provided in (i); wherein preferably the stream F2 comprising the purified bio-oil obtained according to (iii) has an oxygen content equal to or lower than, more preferably lower than, the oxygen content of the bio-oil provided in (i).
  12. 12. A method for purifying a biological oil, the method comprising: (i) Any of the preceding claims; (II) according to any of the preceding claims; (III) according to any of the preceding claims; (iv) Subjecting at least a portion of this stream F2 obtained according to (iii) to one or more subsequent washes in Z W , wherein (iv) comprises: (iv.1) optionally introducing at least a portion of the F2 obtained according to (iii), preferably F2, into a washing unit UM3 comprised in Z W , UM3 being located downstream of US 2; Contacting at least a portion of the F2, preferably F2, with water in UM3 at a temperature T3 in the range of 10 ℃ to 95 ℃ to obtain a mixture M3 comprising an aqueous phase P A (3) and an organic phase P O (3), the pH of P A (3) being in the range of 7.5 to 11 < the pH of P A (1); Passing the mixture M3 into a liquid-liquid separation unit US3 comprised in Z W -US 3 being located downstream of UM3, obtaining a stream F A (3) comprising P A (3) and a stream F3 comprising P O (3) being the purified bio-oil; (iv.2) introducing at least a portion of the F2 obtained according to (iii), preferably F2 or at least a portion of the F3 obtained according to (iv.1), into a washing unit UM4 contained in Z W , UM4 being located downstream of US 3; (iv.3) contacting at least a portion of the F2 or at least a portion of the F3 with water in UM4 at a temperature T4 in the range of 10 ℃ to 95 ℃ to obtain a mixture M4 comprising an aqueous phase P A (4) and an organic phase P O (4), the pH of the aqueous phase P A (4) of M4 being in the range of 7.5 to 11, the pH of P A (4) being < the pH of P A (1); (iv.4) passing the mixture M4 obtained according to (iv.3) into a liquid-liquid separation unit US4 contained in Z W -US 4 being located downstream of UM4, obtaining a stream F A (4) comprising P A (4) and a stream F4 comprising P O (4) being the purified bio-oil, and (V) Introducing the F4 obtained according to (iv) into at least one storage unit SU and storing the bio-oil in SU.
  13. 13. The method according to claim 1 to 12, Wherein the storage unit SU is a tank, preferably made of one or more of steel and stainless steel, more preferably carbon steel and stainless steel.
  14. 14. A unit for carrying out the method for purifying bio-oil according to any one of claims 1 to 13, the unit comprising At least one extraction zone Z E comprising an extraction unit UM1 and a liquid-liquid separation unit US1, UM1 being located upstream of US 1; -inlet means for introducing F0 into Z E ; -outlet means for removing F1 from Z E ; -inlet means for introducing F0 into UM 1; -outlet means for removing M1 from UM 1; inlet means for introducing M1 into US 1; -outlet means for removing F1 from US 1; -at least one washing zone Z W downstream of Z E ; -inlet means for introducing F1 into Z W ; An outlet device for removing F2 from Z W , and -A reservoir.
  15. 15. A purified bio-oil obtained by the method of any one of claims 1 to 14, wherein preferably the purified bio-oil of the invention has a Total Acid Number (TAN) in the range of 0 to 10mg KOH/g (oil), more preferably in the range of 0 to 4 mg KOH/g (oil).

Description

Method for purifying biological oils The present invention relates to a process for purifying biological oils and to a unit for carrying out said process. The invention further relates to a purified bio-oil obtainable or obtained by said method. Bio-oils obtained from different types of biomass are becoming increasingly important as renewable raw materials for industrial as well as fuel applications. An important technique for producing bio-oil is pyrolysis of biomass, which is thermal degradation in an inert atmosphere. Bio-oil obtained from pyrolysis or other methods, if not purified, may damage containers made of steel, particularly containers made of carbon steel and low alloy steel, which serve as means for storing, transporting, guiding or handling the bio-oil, due to corrosion. Therefore, purified high quality bio-oil is preferred as a feedstock to prevent corrosion problems during storage and in downstream refining processes. US 2021/0277324 A1 discloses the purification of pyrolysis oil by treating the pyrolysis oil with sodium hydroxide at a temperature of 240 ℃. WO 2014/165859 A1 discloses a method for purifying pyrolysis oil by reducing the content of contaminants (e.g. acids, metals). Furthermore, WO 2020/178599 A1 discloses a process for upgrading pyrolysis oil comprising washing the pyrolysis oil with water, followed by washing the pyrolysis oil with alkanes, and treating the obtained organic phase with an upgrading solution comprising a polar organic solvent. However, there remains a need to provide improved methods for purifying bio-oils obtained from biomass. In particular, there remains a need to provide improved methods that allow for reduced corrosion in downstream processes and/or storage. Accordingly, it is desirable to provide a process for purifying bio-oils (particularly by reducing the total acid number and oxygen content). Indeed, there is a need to provide high value purified bio-oil while using economical methods. Accordingly, the present invention relates to a process for purifying a bio-oil, the process comprising: (i) Providing a stream F0 comprising bio-oil; (ii) Subjecting the stream F0 provided in (i) to extraction in at least one extraction zone Z E, obtaining a stream F1 comprising extracted bio-oil, wherein (ii) comprises: (ii.1) introducing F0 into an extraction unit UM1 contained in Z E; (ii.2) contacting F0 with water and a base B in UM1 at a temperature T1 in the range of 10 ℃ to 200 ℃ to obtain a mixture M1 comprising an aqueous phase P A (1) and an organic phase P O (1), the pH of this aqueous phase P A (1) of M1 being in the range of 7.5 to 11; (ii.3) passing the mixture M1 obtained according to (ii.2) into a liquid-liquid separation unit US1 comprised in Z E -US 1 being located downstream of UM1, obtaining a stream F A (1) comprising P A (1) and a stream F1 comprising P O (1) being the extracted bio-oil; (ii.4) removing F1 from Z E; (iii) Subjecting the stream F1 provided in (ii) to washing in at least one washing zone Z W -Z W is located downstream of Z E, obtaining a stream F2 comprising purified bio-oil, and optionally (V) Introducing the F2 comprising the bio-oil obtained according to (iii) into at least one storage unit SU and storing said bio-oil in SU. Typically, F0 of 1 to 100 weight-% or 5 to 100 weight-% or 10 to 100 weight-% or 20 to 100 weight-% or 30 to 100 weight-% or 40 to 100 weight-% or 50 to 100 weight-% or 60 to 100 weight-% or 70 to 100 weight-% or 80 to 100 weight-% or 90 to 100 weight-% may consist of bio-oil. Preferably, 95 to 100 wt-%, more preferably 98 to 100 wt-%, more preferably 99 to 100 wt-% of F0 consists of bio-oil. It is possible that 99.5 to 100 wt-% or 99.8 to 100 wt-% or 99.9 wt-% of F0 consists of bio-oil. Preferably, the bio-oil according to (i) has a Total Acid Number (TAN) in the range of 0 to 200 mg (KOH)/gram F0 (mg (KOH)/g (F0)), such as 50 to 200 mg (KOH)/g (F0) or 100 to 200 mg (KOH)/g (F0), 0 To 150 mg (KOH)/g (F0), for example 50 to 150 mg (KOH)/g (F0) or 100 to 150 mg (KOH)/g (F0), 0 To 100 mg (KOH)/g (F0), for example 50 to 100 mg (KOH)/g (F0) or 70 to 100 mg (KOH)/g (F0), Preferably 0 to 70 mg (KOH)/g (F0), for example greater than 60 mg (KOH)/g (F0) and not greater than 70 mg (KOH)/g (F0), Preferably 0.5 to 60 mg KOH/g (F0), more preferably 1 to 40 mg KOH/g (F0), preferably in the range of 3 to 20 mg KOH/g (F0), as determined in reference example 3. In the context of the present invention, the bio-oil to be purified may have any oxygen content. Preferably, the bio-oil according to (i) has an oxygen content in the range of 0.5 to 70 g (O)/100 g (F0), for example greater than 25 to not greater than 70 g (O)/100 g (F0), Preferably 0.5 to 50 g (O)/100 g (F0), for example greater than 15 to no greater than 50 g (O)/100 g (F0), preferably 25 to 50 g (O)/100 g (F0), or 0.5 To 15g (O)/100 g (F0), more preferably in the range of 0.5 to 10 g (O)/100 g (F0), more preferably in the range of 0.5 to 5g (O)/100 g (F0), more p