Process for the manufacture of diesel range hydrocarbons

Patent metadata

Field	Value
Publication number	US-10550332-B2
Application number	US-201816039210-A
Country	US
Kind code	B2
Filing date	Jul 18, 2018
Priority date	Jul 5, 2005
Publication date	Feb 4, 2020
Grant date	Feb 4, 2020

Abstract

The invention relates to a process for the manufacture of diesel range hydrocarbons wherein a feed is hydrotreated in a hydrotreating step and isomerised in an isomerisation step, and a feed comprising fresh feed containing more than 5 wt % of free fatty acids and at least one diluting agent is hydrotreated at a reaction temperature of 200-400° C., in a hydrotreating reactor in the presence of catalyst, and the ratio of the diluting agent/fresh feed is 5-30:1.

First claim

The invention claimed is:

1. A process for the manufacture of diesel range hydrocarbons comprising:
combining a fresh feed stream of biological origin containing more than 10 wt-% of free fatty acids and a stream of diluting agent containing hydrocarbons of biological origin to form a total feed stream with a ratio of diluting agent/fresh feed in the total feed stream of at least 5:1,
introducing the total feed stream to a hydrodeoxygenation step,
hydrodeoxygenating the total feed stream, in the hydrodeoxygenating step, at a reaction temperature between 280-340° C. to form a hydrodeoxygenated product containing n-paraffins in the diesel range and 0.5%-wt or less high molecular weight hydrocarbons,
introducing the hydrodeoxygenated product to an isomerization step, and
isomerizing the hydrodeoxygenated product in the isomerization step to form isoparaffins in the diesel range,
wherein the total feed stream contains less than 20 wt-% of the fresh feed stream of biological origin, less than 1 w-ppm alkali and alkaline earth metals, calculated as elemental alkali and alkaline earth metals, less than 1 w-ppm other metals, calculated as elemental metals, and less than 5 w-ppm phosphorous, calculated as elemental phosphorous.

2. The process according to claim 1 , wherein the ratio of diluting agent/fresh feed in the total feed stream ranges from 5:1 to 30:1.

3. The process according to claim 1 , wherein the ratio of diluting agent/fresh feed in the total feed stream ranges from 10:1 to 30:1.

4. The process according to claim 1 , wherein the ratio of diluting agent/fresh feed in the total feed stream ranges from 12:1 to 25:1.

5. The process according to claim 1 , wherein the fresh feed stream of biological origin is introduced to a pretreatment step to remove impurities.

6. The process according to claim 5 , wherein the pretreatment step is chosen from degumming, bleaching, and prehydrogenating.

7. The process according to claim 1 , wherein the fresh feed stream of biological origin has an acid number of at least 21.5 mg KOH/g.

8. The process according to claim 1 , wherein the fresh feed stream of biological origin contains 100 wt-% of free fatty acids.

9. The process according to claim 1 , wherein the hydrodeoxygenation conversion in the hydrodeoxygenating step is complete.

10. The process according to claim 1 , wherein the hydrodeoxygenated product contains an almost theoretical yield of n-paraffins in the diesel range.

11. The process according to claim 1 , wherein the hydrodeoxygenating step takes place on a hydrodeoxygenating catalyst bed system comprising one or more catalyst beds.

12. The process according to claim 11 , wherein one or more catalysts used in the hydrodeoxygenating catalyst bed system maintain stable operation for at least 9 months.

13. The process according to claim 11 , wherein hydrogen is introduced to each catalyst bed in the hydrodeoxygenating catalyst bed system.

14. The process according to claim 13 , wherein the hydrogen is introduced on top of each catalyst bed.

15. The process according to claim 11 , wherein the stream of diluting agent containing hydrocarbons of biological origin is a recycled stream from the hydrodeoxygenated product.

16. The process according to claim 1 , wherein the fresh feed stream of biological origin is selected from plant oils/fats, animal fats/oils, fish fats/oils, fats contained in plants bred by means of gene manipulation, recycled fats of the food industry, and mixtures thereof.

17. The process according to claim 1 , wherein the fresh feed stream of biological origin contains animal fats/oils.

18. The process according to claim 1 , wherein the fresh feed stream of biological origin is selected from rapeseed oil, colza oil, canola oil, tall oil, sunflower oil, soybean oil, hempseed oil, olive oil, linseed oil, mustard oil, palm oil, peanut oil, castor oil, coconut oil, lard, tallow, train oil, and fats contained in milk.

19. The process according to claim 1 , wherein the fresh feed stream of biological origin comprises a mixture of a feed of biological origin and at least one hydrocarbon.

20. The process according to claim 1 , wherein the hydrodeoxygenating step is at a pressure in the range of 2-15 MPa.

21. The process according to claim 1 , wherein the reaction temperature in the hydrodeoxygenating step is between 280-305° C.

22. A process for the manufacture of diesel range hydrocarbons comprising:
combining fresh feed of biological origin containing more than 10 wt-% of free fatty acids and one or more diluting agents containing hydrocarbons of biological origin to form a total feed,
introducing the total feed to a hydrodeoxygenation step,
hydrodeoxygenating the total feed, in the hydrodeoxygenating step, at a reaction temperature between 280-340° C. on a hydrodeoxygenating catalyst bed system comprising one or more catalyst beds in series to form a hydrodeoxygenated product containing n-paraffins in the diesel range, to prevent the formation of high molecular weight hydrocarbons,
wherein the fresh feed of biological origin and one or more diluting agents containing hydrocarbons of biological origin are introduced on each catalyst bed in the hydrodeoxygenating catalyst bed system and the fresh feed of biological origin over each catalyst bed is present in a concentration less than 20 wt-%,
introducing the hydrodeoxygenated product to an isomerization step, and
isomerizing the hydrodeoxygenated product in the isomerization step to form isoparaffins in the diesel range,
wherein the total feed contains less than 1 w-ppm alkali and alkaline earth metals, calculated as elemental alkali and alkaline earth metals, less than 1 w-ppm other metals, calculated as elemental metals, and less than 5 w-ppm phosphorous, calculated as elemental phosphorous.

23. The process according to claim 22 , wherein at least one of the diluting agents introduced on a first catalyst bed in the hydrodeoxygentating catalyst bed system is a recycle stream of the hydrodeoxygenated product.

24. The process according to claim 22 , wherein at least one of the diluting agents introduced on each catalyst bed in the hydrodeoxygentating catalyst bed system is a quench liquid stream containing hydrocarbons of biological origin.

25. The process according to claim 24 , wherein the quench liquid stream containing hydrocarbons of biological origin is a recycled product from the hydrodeoxygenated product that is cooled in a heat exchanger.

26. The process according to claim 22 , wherein the fresh feed of biological origin and one or more diluting agents containing hydrocarbons of biological origin are introduced on top of each catalyst bed.

27. The process according to claim 22 , wherein a ratio of diluting agent/fresh feed in the total feed over each catalyst ranges from 5:1 to 30:1.

28. The process according to claim 22 , wherein a ratio of diluting agent/fresh feed in the total feed over each catalyst ranges from 10:1 to 30:1.

29. The process according to claim 22 , wherein a ratio of diluting agent/fresh feed in the total feed over each catalyst ranges from 12:1 to 25:1.

30. The process according to claim 22 , wherein the fresh feed stream of biological origin is introduced to a pretreatment step to remove impurities.

31. The process according to claim 30 , wherein the pretrea

Assignees

• Neste Oyj

Inventors

• Myllyoja Jukka
• Aalto Pekka
• Savolainen Pekka
• Purola Veli-Matti
• Alopaeus Ville
• Gronqvist Johan

Classifications

• C10G45/64

  containing crystalline alumino-silicates, e.g. molecular sieves · CPC title

• C10G3/47

  containing platinum group metals or compounds thereof · CPC title

• C10G45/62

  containing platinum group metals or compounds thereof · CPC title

• C10G2300/4081

  Recycling aspects · CPC title

• C10G2300/205

  Metal content · CPC title