Desulfurized tall oil and derivatives thereof

Patent metadata

Field	Value
Publication number	US-11041095-B2
Application number	US-202015929779-A
Country	US
Kind code	B2
Filing date	May 21, 2020
Priority date	May 22, 2019
Publication date	Jun 22, 2021
Grant date	Jun 22, 2021

Abstract

A process for reducing or removing at least 90% of sulfur in a tall oil composition, e.g., to a level of 15 ppm or less is disclosed. The process employs at least a first desulfurization and a second desulfurization treatment in parallel or in series. The first treatment comprises adsorptive desulfurization, wherein the adsorbent material comprises silica adsorbent having an average pore size between 50-200 Å, BET surface area of at least 300 m2/g, pore volume of 1.20 to 3.00 cc/g, and a silanol [Si—OH] level of 0.5 to 5 unit/nm2. The second desulfurization treatment is selected from adsorptive treatment, heat treatment, distillation, extraction, oxidation, reduction, hydrogenation, and sulfur scavenging for a reduced sulfur content.

First claim

The invention claimed is:

1. A process for desulfurizing a tall oil feedstock having a first sulfur content and an initial odor intensity, comprising:
contacting the tall oil feedstock with two adsorbent beds in series, a first adsorbent bed containing a first adsorbent material and a second adsorbent bed containing a second adsorbent material, obtaining a desulfurized tall oil composition having a reduced sulfur content;
wherein at least one of the first adsorbent material and the second adsorbent material comprises silica adsorbent having an average pore size between 50-200 Å, BET surface area of 300-1000 m 2 /g, pore volume of 1.00 to 3.00 cc/g, a silanol [Si—OH] level of 0.5 to 5 unit/nm 2 , and an equilibrium sulfur loading capacity of at least 1 mg S/g of adsorbent material;
wherein the wherein the adsorbent bed comprising silica adsorbent is operated at an adsorption temperature of 20-30° C., at one bar pressure, and at a superficial velocity (V) of at least 0.3 ft/hr;
wherein the reduced sulfur content is less than 50% of the first sulfur content
wherein the desulfurized tall oil has an odor intensity reduction of at least 1 unit on odor intensity scale of Offensive Odor Control Act as compared to the initial odor intensity of the tall oil feedstock;
wherein the silica adsorbent is regenerated adsorbent material.

2. The process of claim 1 , wherein the first adsorbent bed and the second adsorbent bed are in same adsorbent column or different adsorbent columns.

3. A process for desulfurizing a tall oil feedstock having a first sulfur content and an initial odor intensity, comprising:
a) providing an adsorbent material;
b) subjecting the tall oil feedstock to a first desulfurization treatment by contacting the adsorbent material in an adsorbent bed,
wherein the adsorbent material adsorbs a portion of the first sulfur content,
wherein the adsorbent bed is operated at an adsorption temperature of 20-30° C., at one bar pressure, and at a superficial velocity (V) of at least 0.3 ft/hr;

c) subjecting the tall oil after the first desulfurization treatment to at least a second desulfurization treatment selected from adsorptive treatment, heat treatment, distillation, extraction, oxidation, reduction, hydrogenation, and sulfur scavenging, obtaining a desulfurized tall oil composition having a reduced sulfur content;
d) collecting the adsorbent material after the first desulfurization treatment;
e) regenerating the collected adsorbent material by passing a solvent over the collected adsorbent material for a sufficient period of time for desorption of at least a portion of the first sulfur content from the collected adsorbent material;
wherein the first desulfurization treatment is before or after the second desulfurization treatment;
wherein the reduced sulfur content is less than 50% of the first sulfur content;
wherein the adsorbent material comprises silica adsorbent having an average pore size between 50-200 Å, a BET surface area of 300-1000 m 2 /g, pore volume of 1.00 to 3.00 cc/g, a silanol [Si—OH] level of 0.5 to 5 unit/nm 2 , and an equilibrium sulfur loading capacity in the range of 5-20 mg S/g of adsorbent;
wherein the desulfurized tall oil has an odor intensity reduction of at least 1 unit on odor intensity scale of Offensive Odor Control Act as compared to the initial odor intensity of the tall oil feedstock; and
wherein the adsorbent material in step a) is regenerated adsorbent material.

4. The method of claim 1 , wherein the desulfurized tall oil has an odor intensity of reduction of at least 2 units on odor intensity scale of Offensive Odor Control Act as compared to the initial odor intensity of the tall oil feedstock.

5. The process of claim 3 , wherein the adsorption bed is operated at a superficial velocity (V) of at least 1 ft/hr.

6. The process of claim 3 , wherein the solvent used for regenerating the adsorbent material is selected from methanol, ethanol, acetone and mixtures thereof.

7. The process of claim 3 , wherein the second desulfurization treatment is an adsorptive treatment.

8. The process of claim 7 , wherein the adsorptive treatment comprises using an adsorbent material comprising any of activated carbon, clay, hydrated alumina, zeolite, calcium exchanged zeolite, a zinc exchanged zeolite, a manganese compound, copper oxide, iron oxide, zinc oxide, silver salt, copper salt, zeolite doped with a metal salt, alumina doped with a metal salt, and mixtures thereof.

9. The process of claim 3 , wherein the first desulfurization treatment comprises using multi-staged adsorbent system with at least two adsorbent beds in series, each containing same or different adsorbent materials.

10. The process of claim 3 , wherein the second desulfurization treatment is an adsorptive treatment employing a reagent or catalyst on a support carrier, and wherein the support carrier is selected from activated carbon, clay, acid activated clay, mineral, zeolite, silica, alumina, ion exchange material, polystyrene, and combinations thereof.

11. The process of claim 3 , wherein the tall oil feedstock comprises any of crude sulfate turpentine, a crude tall oil, depitched tall oil, a composition derived from crude tall oil, and mixtures thereof.

12. The process of claim 3 , wherein the silica adsorbent particles has a surface area of at least 500 m 2 /g, based on the Brunauer-Em-mett-Teller (BET) measurement technique.

Assignees

• Kraton Polymers Llc

Inventors

• Ding Ruidong
• Tian Jason
• Reiter Chad

Classifications

• C09F1/04

  Chemical modification, e.g. esterification (resin soaps C11D) · CPC title

• B01J20/103

  comprising silica · CPC title

• C11B13/005

  of residues of the fabrication of wood-cellulose (in particular tall-oil) · CPC title

• Y02W30/74

  Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes · CPC title

• C11C1/08

  Refining · CPC title