公开(公告)号：US10519086B2

公开(公告)日：2019-12-31

申请号：US16328085

申请日：2017-08-30

Applicant: SHELL OIL COMPANY

Inventor： Duraisamy Muthusamy ,  Viet Quoc Nguyen

IPC: C07C29/76 ,  B01J23/00 ,  B01J25/00 ,  B01J23/30 ,  B01J25/04 ,  B01J35/00 ,  B01J38/72 ,  C07C29/141 ,  C07C31/20

Abstract: Implementations of the disclosed subject matter provide a process for producing ethylene glycol from a carbohydrate feed. The process may include contacting, in a reactor under hydrogenation conditions, the carbohydrate feed with a bi-functional catalyst system which may include a heterogeneous hydrogenation catalyst including a magnetically active metal, and a soluble retro-Aldol catalyst including tungstate. A liquid effluent stream may be obtained from the reactor and may include hydrogenation catalyst particles and tungsten oxide precipitate particles. The hydrogenation catalyst particles may be magnetically separated from the tungsten oxide precipitate particles in the liquid effluent stream using a magnet in a separation vessel. The separated hydrogenation catalyst particles may be retained in a separation zone in the separation vessel and may be subsequently removed from the separation zone. A liquid product stream may be obtained from the separation vessel and may include the tungsten oxide precipitate particles and ethylene glycol.

公开(公告)号：US10294181B2

公开(公告)日：2019-05-21

申请号：US16060221

申请日：2016-12-07

Applicant: SHELL OIL COMPANY

Inventor： Leslie Andrew Chewter ,  Jean Paul Andre Marie Joseph Ghislain Lange ,  Duraisamy Muthusamy ,  Timothy Michael Nisbet ,  Evert Van Der Heide ,  Pieter Huizenga

IPC: C07C29/60 ,  C07C31/00 ,  B01J19/00 ,  C07C29/132 ,  B01J8/20 ,  B01J8/22 ,  B01J10/00 ,  B01J16/00 ,  B01J19/18 ,  B01J19/24 ,  C07C31/20

Abstract: The invention provides a continuous process for the preparation of ethylene glycol and 1, 2-propylene glycol from starting material comprising one or more saccharides, said process being carried out in a reactor system comprising a reactor vessel equipped with an external recycle loop and said process comprising the steps of: i) providing the starting material in a solvent, via an inlet, to the external recycle loop and contacting it therein with a retro-aldol catalyst composition to provide an intermediate stream; ii) then contacting said intermediate stream with hydrogen in the presence of a hydrogenation catalyst composition in the reactor vessel; iii) withdrawing a product stream comprising glycols from the reactor vessel; iv) providing a portion of said product stream, via an outlet, for separation and purification of the glycols contained therein; and v) recycling the remainder of said product stream via the external recycle loop.

公开(公告)号：US11485693B2

公开(公告)日：2022-11-01

申请号：US17275570

申请日：2019-09-10

Applicant: SHELL OIL COMPANY

Inventor： Dionysius Jacobus Maria De Vlieger ,  Pieter Huizenga ,  Munro Mackay ,  Lucas Petrus Simon Keyzer ,  Duraisamy Muthusamy

IPC: C07C29/132 ,  B01J21/18 ,  B01J23/30 ,  B01J23/46

Abstract: The invention provides a start-up method for a process for the preparation of glycols from a starting material comprising one or more saccharides in the presence of hydrogen and a catalyst system comprising one or more retro-aldol catalysts comprising tungsten and one or more catalytic species suitable for hydrogenation in a reactor, said method comprising introducing the one or more retro-aldol catalysts to the reactor whilst also in the presence of one or more agents suitable to suppress tungsten precipitation.

公开(公告)号：US10752567B2

公开(公告)日：2020-08-25

申请号：US16336140

申请日：2017-09-28

Applicant: SHELL OIL COMPANY

Inventor： Duraisamy Muthusamy ,  Viet Quoc Nguyen

IPC: C07C29/00 ,  B01J25/00 ,  B01J31/00 ,  C07C29/132 ,  B01J25/02 ,  B01J31/04 ,  C07C31/20

Abstract: Implementations of the disclosed subject matter provide methods for producing ethylene glycol from a carbohydrate feed which may include conditioning a heterogeneous hydrogenation catalyst by treatment with a protic acid resulting in an acid-conditioned heterogeneous hydrogenation catalyst. Next, in a reactor under hydrogenation conditions, the carbohydrate feed may be contacted with a bi-functional catalyst system comprising the acid-conditioned heterogeneous hydrogenation catalyst, and a soluble retro-Aldol catalyst. An intermediate product stream may be obtained from the reactor including ethylene glycol.

公开(公告)号：US10654782B2

公开(公告)日：2020-05-19

申请号：US15768964

申请日：2016-10-18

Applicant: SHELL OIL COMPANY

Inventor： Duraisamy Muthusamy ,  Viet Quoc Nguyen ,  Pieter Huizenga

IPC: C07C29/132 ,  C07C29/60 ,  B01J23/30 ,  B01J25/02 ,  B01J35/00

Abstract: Implementations of the disclosed subject matter provide methods for producing ethylene glycol from a carbohydrate feed may include contacting, in a first reactor under hydrogenation conditions, the carbohydrate feed with a bi-functional catalyst system. The bi-functional catalyst system may include a heterogeneous hydrogenation catalyst, and a soluble retro-Aldol catalyst. The carbohydrate feed may include a concentration of carbohydrate, in the total solution entering the first reactor, of 5-40 wt % in a solvent. An intermediate product stream may be obtained from the first reactor including ethylene glycol. The hydrogenation conditions may include a temperature in the range of from 180-250° C.

公开(公告)号：US10450255B2

公开(公告)日：2019-10-22

申请号：US15763714

申请日：2016-09-27

Applicant: SHELL OIL COMPANY

Inventor： Duraisamy Muthusamy

IPC: C07C29/60 ,  C07C29/132

Abstract: A process for the preparation of glycols from a saccharide-containing feedstock comprising the steps of: (a) preparing a reaction mixture in a reactor vessel comprising the saccharide-containing feedstock, a solvent, a catalyst component with retro-aldol catalytic capabilities and a first hydrogenation catalyst comprising an element selected from groups 8, 9 and 10 of the periodic table; (b) supplying hydrogen gas to the reaction mixture in the reactor vessel; (c) monitoring the activity of the first hydrogenation catalyst; (d) preparing a second hydrogenation catalyst by contacting in a reactor a catalyst precursor comprising one or more elements selected from chromium and groups 8, 9, 10 and 11 of the periodic table with hydrazine to convert the catalyst precursor into the second hydrogenation catalyst; (e) when the hydrogenation activity declines, supplying the second hydrogenation catalyst to the reactor vessel to supplement the declined hydrogenation activity in the reactor vessel.