Methods for preparing diol

• US 10,464,870 B2
• Filed: 09/23/2015
• Issued: 11/05/2019
• Est. Priority Date: 09/28/2014
• Status: Active Grant

• Current Assignee: Changchun Meihe Science and Technology Development Co., LTD, The Coca-Cola Company
• Original Assignee: The Coca-Cola Company
• Inventors: Liu, Jing, Qi, Hongbin, Ren, Haiyu, Prakash, Indra, Shi, Yu
• Primary Examiner(s): Brooks, Clinton A
• Application Number:
  US15/514,980
• Publication Number:
  US 20170210687A1
• Time in Patent Office: 1,504 Days
• Field of Search: None
• CPC Class Codes: B01J 23/30 Tungsten
• CPC Class Codes: B01J 23/835 with germanium, tin or lead
• CPC Class Codes: B01J 23/888 Tungsten
• CPC Class Codes: B01J 23/8885 containing also molybdenum
• CPC Class Codes: B01J 25/02 Raney nickel
• CPC Class Codes: B01J 2523/00 Constitutive chemical elements of heterogeneous catalysts
• CPC Class Codes: B01J 2523/305 Boron
• CPC Class Codes: B01J 2523/31 Aluminium
• CPC Class Codes: B01J 2523/3706 Lanthanum
• CPC Class Codes: B01J 2523/3712 Cerium
• CPC Class Codes: B01J 2523/3737 Samarium
• CPC Class Codes: B01J 2523/43 Tin
• CPC Class Codes: B01J 2523/51 Phosphorus
• CPC Class Codes: B01J 2523/68 Molybdenum
• CPC Class Codes: B01J 2523/69 Tungsten
• CPC Class Codes: B01J 2523/847 Nickel
• CPC Class Codes: B01J 27/188 with chromium, molybdenum, tungsten or polonium
• CPC Class Codes: B01J 27/19 Molybdenum
• CPC Class Codes: B01J 35/19 Catalysts containing parts with different compositions
• CPC Class Codes: B01J 37/0081 Preparation by melting
• CPC Class Codes: B01J 37/04 : Mixing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: C07C 29/00 : Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
• CPC Class Codes: C07C 29/132 : by reduction of an oxygen containing functional group
• CPC Class Codes: C07C 29/60 : by elimination of -OH groups, e.g. by dehydration C07C29/34 takes precedence
• CPC Class Codes: C07C 31/202 : Ethylene glycol
• CPC Class Codes: C07C 31/205 : 1,3-Propanediol; 1,2-Propanediol
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts
• CPC Class Codes: Y02P 20/582 : Recycling of unreacted starting or intermediate materials

Abstract

Provided is a method for preparing a diol. In the method, a saccharide and hydrogen as raw materials are contacted with a catalyst in water to prepare the diol. The employed catalyst is a composite catalyst comprised of a main catalyst and a cocatalyst, wherein the main catalyst is a water-insoluble acid-resistant alloy; and the cocatalyst is a soluble tungstate and/or soluble tungsten compound. The method uses an acid-resistant, inexpensive and stable alloy needless of a support as a main catalyst, and can guarantee a high yield of the diol in the case where the production cost is relatively low.

Claims

1. A method for preparing a diol comprising contacting a sugar and hydrogen with a catalyst in water in a reactor to prepare a diol;

wherein the catalyst is a composite catalyst consisting of a main catalyst and a cocatalyst;

the main catalyst is a water-insoluble acid-resistant alloy comprising nickel, one or more rare earth elements, tin and aluminum; and

the cocatalyst is a soluble tungstic acid salt and/or an insoluble tungsten compound.

2. The method of claim 1, wherein the diol is ethylene glycol.

3. The method of claim 2, wherein the pH of the reactor is 1-7.

4. The method of claim 1, wherein the sugar is selected from the group consisting of one or more five-carbon monosaccharides, disaccharides, and oligosaccharides;

six-carbon monosaccharides, disaccharides and oligosaccharides;

soluble five-carbon polysaccharides and soluble six-carbon polysaccharides.

5. The method of claim 1, wherein the sugar is provided in the form of an aqueous sugar solution, wherein the aqueous sugar solution has a concentration of 5-60 wt %.

6. The method of claim 5, wherein the amount of the soluble cocatalyst used is 0.01-5 wt % of the aqueous sugar solution.

7. The method of claim 6, wherein the amount of the insoluble cocatalyst used is 0.5-50 wt % of the main catalyst.

8. The method for preparing a diol as claimed in claim 1, characterized in that the acid-resistant alloy comprises, in parts by weight, 10-90 parts nickel, 1-5 parts rare earth element, 1-60 parts tin and 5-9 parts aluminum.

9. The method of claim 1, wherein the acid-resistant alloy comprises, in parts by weight, 10-90 parts nickel, 1-5 parts rare earth element, 1-60 parts tin, 5-9 parts aluminum, 1-90 parts tungsten and 0.5-20 parts molybdenum.

10. The method of claim 1, wherein the soluble tungstic acid salt is selected from the group consisting of ammonium tungstate, sodium tungstate, sodium phosphotungstate and combinations thereof.

11. The method of claim 1, wherein the insoluble tungsten compound is selected from tungsten trioxide, tungstic acid and a combination thereof.

12. The method of claim 1, wherein the amount of the main catalyst used is 0.01-10 times the amount of sugar fed per hour.

13. The method of claim 1, wherein the reactor has a reaction pressure of 6-10 MPa, a reaction temperature of 180-250°

C., and a reaction time of 0.5-3 h.

14. The method of claim 1, wherein the method is continuous.

15. The method of claim 14, wherein the amount of main catalyst added is:

0.01-5 kg of main catalyst is added per 1000 kg of sugar fed.

16. The method of claim 1, further comprising separating the cocatalyst from the diol and then recycling the cocatylst in a subsequent method.

17. The method of claim 1, wherein the reactor is slurry bed reactor.