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 hydr
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.
대표청구항▼
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,introducing the total
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,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, to prevent the formation of high molecular weight hydrocarbons,introducing the hydrodeoxygenated product to an isomerization step, andisomerizing 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 a ratio of diluting agent/fresh feed in the total feed stream is 5-30:1. 3. The process according to claim 1, wherein a ratio of diluting agent/fresh feed in the total feed stream is 10-30:1. 4. The process according to claim 1, wherein a ratio of diluting agent/fresh feed in the total feed stream is 12-25:1. 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 the group consisting of degumming, bleaching, or 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 of catalyst bed. 15. The process according to claim 1, 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 or 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 having an acid number of at least 21.5 mg KOH/g and 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,introducing the hydrodeoxygenated product to an isomerization step, andisomerizing 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 the 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 is 5-30:1. 28. The process according to claim 22, wherein a ratio of diluting agent/fresh feed in the total feed over each catalyst is 10-30:1. 29. The process according to claim 22, wherein a ratio of diluting agent/fresh feed in the total feed over each catalyst is 12-25:1. 30. The process according to claim 22, wherein the fresh feed of biological origin is introduced to a pretreatment step to remove impurities. 31. The process according to claim 30, wherein the pretreatment step is chosen from the group consisting of degumming, bleaching, or prehydrogenating. 32. The process according to claim 22, wherein the fresh feed of biological origin contains 100 wt-% of free fatty acids. 33. The process according to claim 22, wherein the hydrodeoxygenation conversion in the hydrodeoxygenating step is complete. 34. The process according to claim 22, wherein the hydrodeoxygenated product contains an almost theoretical yield of n-paraffins in the diesel range. 35. The process according to claim 22, wherein one or more catalysts used in the hydrodeoxygenating catalyst bed system maintain stable operation for at least 9 months. 36. The process according to claim 22, wherein hydrogen is introduced to each catalyst bed in the hydrodeoxygenating catalyst bed system. 37. The process according to claim 36, wherein the hydrogen is introduced on top of each of catalyst bed. 38. The process according to claim 22, wherein the diluting agent containing hydrocarbons of biological origin is a recycled stream from the hydrodeoxygenated product. 39. The process according to claim 22, wherein the fresh feed 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. 40. The process according to claim 22, wherein the fresh feed of biological origin contains animal fats/oils. 41. The process according to claim 22, wherein the fresh feed 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 or fats contained in milk. 42. The process according to claim 22, wherein the fresh feed of biological origin comprises a mixture of a feed of biological origin and at least one hydrocarbon. 43. The process according to claim 22, wherein the hydrodeoxygenating step is at a pressure in the range of 2-15 MPa. 44. The process according to claim 22, wherein the reaction temperature in the hydrodeoxygenating step is between 280-305° C.
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