Process for converting feeds derived from renewable sources with pre-treatment of feeds by hot dephosphatation

Patent metadata

Field	Value
Publication number	US-9447334-B2
Application number	US-96835410-A
Country	US
Kind code	B2
Filing date	Dec 15, 2010
Priority date	Dec 16, 2009
Publication date	Sep 20, 2016
Grant date	Sep 20, 2016

Abstract

The invention concerns a process for the pre-treatment of an unrefined vegetable or animal oil, consisting of passing said oil through a reactor comprising at least one fixed bed of at least one adsorbent comprising a porous refractory oxide which is free of catalytic metals, at a temperature in the range 130° C. to 320° C., at a pressure in the range 0.1 to 7 MPa and with a residence time for said oil on said fixed bed in the range 0.1 to 1 hour. The invention concerns a process for pre-treatment of a semi-refined vegetable or animal oil, integrated upstream of a hydrotreatment step for the production of green gas oil.

First claim

The invention claimed is:

1. A process for the production of middle distillate bases, comprising:
a) pre-treating of a semi-refined vegetable or animal oil, comprising passing said oil through a reactor comprising at least one fixed bed of at least one adsorbent comprising 100% porous refractory oxide that is optionally activated alumina, or silica-alumina, which porous refractory oxide is free of catalytic metals from group 6 and groups 8 to 12, at a temperature in the range of 130° C. to 320° C., at a pressure in the range of 0.1 to 7 MPa and with a residence time for said oil on said fixed bed in the range of 0.1 to 1 hour; said adsorbent having a macroporous volume, measured by mercury intrusion, of pores with a mean diameter of 500 Å of more than 0.1 ml/g, a total pore volume of more than 0.60 ml/g, and a specific surface area, expressed as the SBET, of 30 m2/g to 320 m2/g,
b) hydrotreating, in the presence of at least one fixed bed catalyst, of the pre-treated effluent from a) at a temperature in the range 200° C. to 450° C., at a pressure in the range 1 MPa to 10 MPa, at an hourly space velocity in the range 0.1 h −1 to 10 h −1 and in the presence of a total quantity of hydrogen mixed with the feed such that the hydrogen/feed ratio is in the range 70 to 1000 Nm 3 of hydrogen/m 3 of feed;
c) separating from the hydrotreated effluent derived from b), of the hydrogen, the gases and at least one middle distillate base,
in which said semi-refined vegetable or animal oil is obtained by pre-refining an unrefined vegetable or animal oil before the pre-treatment process, the pre-refining comprising:
degumming, comprising eliminating at least a portion of the phospholipids or gums by precipitation in the presence of acidulated water;
neutralizing, in the presence of a sodium hydroxide solution, of the degummed oil in order to neutralize at least a portion of the free fatty acids present in the oil;
washing with water to eliminate traces of sodium salts; and
vacuum drying.

2. A process in accordance with claim 1 , in which the unrefined vegetable or animal oil subject to the pre-refining comprises 95-98% by weight of triglycerides and 2% to 5% by weight of free fatty acids, mono- and di-glycerides, and any of phospholipids, tocopherols, sterols, natural colorants as well as odorizing compounds and compounds of phosphorus, magnesium, calcium, iron and/or zinc in quantities of up to 2500 ppm, in the form of phospholipids and/or sterols in the case of phosphorus, magnesium and calcium or present in pigments in the case of magnesium and in the form of sterols and/or soaps in the case of iron and/or zinc.

3. A process for producing middle distillate bases in accordance with claim 1 , in which said adsorbents have a spherical or extruded shape, with a diameter in the range 0.5 to 10 mm.

4. A process for producing middle distillate bases in accordance with claim 1 , in which said pre-treatment is carried out at a temperature in the range 160° C. to 250° C., at a pressure in the range 0.3 to 1 MPa and with a residence time in the range 0.2 to 1.5 hours.

5. A process for producing middle distillate bases in accordance with claim 1 , in which said pre-treatment is carried out in a reactor comprising several fixed beds placed in parallel, and which can be switched.

6. A process for producing middle distillate bases in accordance with claim 1 , in which the fixed bed catalyst used in hydrotreatment step b) is a hydrotreatment catalyst comprising a hydrodehydrogenating function comprising at least one metal from group VIII and/or group VIB, used alone or as a mixture, and a support selected from the group formed by alumina, silica, silica-aluminas, magnesia, clays and mixtures of at least two of said minerals.

7. The process of claim 1 , wherein the fixed bed catalyst for the hydrotreating step b) comprises at least one metal from Group VIII or Group IVB or at least one metal from each of Group VIII and Group IVB.

8. The process of claim 1 , wherein the fixed bed catalyst for the hydrotreating step b) comprises at least one metal selected from nickel and cobalt and at least one metal selected from molybdenum and tungsten.

9. The process of claim 1 , wherein the fixed bed catalyst for the hydrotreating step b) comprises a nickel oxide content in the range 0.5% to 10% by weight and a molybdenum trioxide content in the range 1% to 30% by weight, the percentages being expressed as a % by weight with respect to the total catalyst mass.

10. A process for the production of middle distillate bases, comprising:
a) pre-treating of an unrefined vegetable or animal oil, comprising passing said oil through a reactor comprising at least one fixed bed of at least one adsorbent comprising 100% porous refractory oxide that is optionally activated alumina, or silica-alumina, which porous refractory oxide is free of catalytic metals from group 6 and groups 8 to 12, at a temperature in the range of 130° C. to 320° C., at a pressure in the range of 0.1 to 7 MPa and with a residence time for said oil on said fixed bed in the range of 0.1 to 2 hours; said adsorbent having a macroporous volume, measured by mercury intrusion, of pores with a mean diameter of 500 Å of more than 0.1 ml/g, a total pore volume of more than 0.60 ml/g, and a specific surface area, expressed as the SBET, of 30 m2/g to 320 m2/g,
b) hydrotreating, in the presence of at least one fixed bed catalyst, of the pre-treated effluent from a) at a temperature in the range 200° C. to 450° C., at a pressure in the range 1 MPa to 10 MPa, at an hourly space velocity in the range 0.1 h −1 to 10 h −1 and in the presence of a total quantity of hydrogen mixed with the feed such that the hydrogen/feed ratio is in the range 70 to 1000 Nm 3 of hydrogen/m 3 of feed;
c) separating from the hydrotreated effluent derived from b), of the hydrogen, the gases and at least one middle distillate base.

11. A process in accordance with claim 10 , in which the unrefined vegetable or animal oil comprises 95-98% by weight of triglycerides and 2% to 5% by weight of free fatty acids, mono- and di-glycerides, and any of phospholipids, tocopherols, sterols, natural colorants as well as odorizing compounds and compounds of phosphorus, magnesium, calcium, iron and/or zinc in quantities of up to 2500 ppm, in the form of phospholipids and/or sterols in the case of phosphorus, magnesium and calcium or present in pigments in the case of magnesium and in the form of sterols and/or soaps in the case of iron and/or zinc.

12. A process for producing middle distillate bases in accordance with claim 10 , in which said adsorbents have a spherical or extruded shape, with a diameter in the range 0.5 to 10 mm.

13. A process for producing middle distillate bases in accordance with claim 10 , in which said pre-treatment is carried out at a temperature in the range 160° C. to 250° C., at a pressure in the range 0.3 to 1 MPa and with a residence time in the range 0.2 to 1.5 hours.

14. A process for producing middle distillate bases in accordance with claim 10 , in which said pre-treatment is carried out in a reactor comprising several fixed beds placed in parallel, and which can be switched.

15. A process for producing middle distillate bases in accordance with claim 10 , in which the fixed bed catalyst used in hydrotreatment step b) is a hydrotreatment catalyst comprising a hydrodehydrogenating function comprising at least one metal from group VIII and/or group VIB, used alone or as a mixture, and a support selected from the group formed by alumina, silica, silica-aluminas, magnesia, clays and mixtures of at least two of said minerals.

Assignees

• Dandeu Aurelie
• Coupard Vincent
• Chapus Thierry
• Ifp Energies Now

Inventors

• Dandeu Aurelie
• Coupard Vincent
• Chapus Thierry

Classifications

• C10G2300/1018

  of animal origin · CPC title

• C10G3/46

  in combination with chromium, molybdenum, tungsten metals or compounds thereof · CPC title

• C10G2300/4018

  Spatial velocity, e.g. LHSV, WHSV · CPC title

• C10G2300/4012

  Pressure · CPC title

• Y02P30/20

  using bio-feedstock · CPC title