Raw material composition for preparing oxygen carrier particles, oxygen carrier particles prepared by using same, and method for preparing oxygen carrier particles

Patent metadata

Field	Value
Publication number	US-2019170346-A1
Application number	US-201716321821-A
Country	US
Kind code	A1
Filing date	Sep 22, 2017
Priority date	Sep 23, 2016
Publication date	Jun 6, 2019
Grant date	—

Abstract

A raw material composition for producing oxygen carriers includes a first component which is one or more of nickel oxide and nickel hydroxide and a second component which is one or more of boehmite, cerium oxide, cerium hydroxide, magnesium oxide, magnesium hydroxide, and titanium oxide, wherein, when the first component is nickel oxide, the second component includes cerium hydroxide. Such a raw material composition for producing oxygen carriers of the present invention is formed into oxygen carriers according to an oxygen carrier producing method, which will be described below, by adjusting the composition, formulation of raw materials, and degree of homogenization. Then, it is possible to produce oxygen carriers having physical properties such as a shape, a particle size, and a particle distribution suitable for a fluidized bed process or a high speed fluidized bed process and having improved wear-resistance, long-term durability, and oxygen transfer performance.

First claim

1 . A raw material composition for producing oxygen carriers, the raw material composition comprising a first component which is one or more of nickel oxide and nickel hydroxide and a second component which is one or more of boehmite, cerium oxide, cerium hydroxide, magnesium oxide, magnesium hydroxide, and titanium oxide,
wherein, when the first component is nickel oxide, the second component includes cerium hydroxide.

2 . The raw material composition of claim 1 , wherein the raw material composition comprises 55 parts by weight to 80 parts by weight nickel hydroxide, 15 parts by weight to 40 parts by weight boehmite, and 3 parts by weight to 15 parts by weight magnesium oxide or magnesium hydroxide.

3 . The raw material composition of claim 1 , wherein the raw material composition comprises 55 parts by weight to 75 parts by weight nickel oxide and 25 parts by weight to 45 parts by weight cerium hydroxide.

4 . The raw material composition of claim 1 , wherein the raw material composition comprises:
55 parts by weight to 80 parts by weight nickel hydroxide; 5 parts by weight to 35 parts by weight boehmite; 3 parts by weight to 20 parts by weight cerium oxide or cerium hydroxide; 3 parts by weight to 15 parts by weight magnesium oxide or magnesium hydroxide; and 0 parts by weight to 15 parts by weight titanium oxide.

5 . The raw material composition of claim 1 , wherein the nickel oxide or nickel hydroxide has an average particle size in the range of 0 to 5 μm and a purity of 98% or higher.

6 . The raw material composition of claim 1 , wherein the boehmite is in the form of a powder or sol and has an average particle size in the range of 0 to 5 μm and a purity of 98% or higher in a state in which the boehmite is dispersed in a solvent.

7 . The raw material composition of claim 1 , wherein the cerium oxide or cerium hydroxide has an average particle size in the range of 0 to 5 μm and a purity of 98% or higher.

8 . The raw material composition of claim 1 , wherein the magnesium oxide or magnesium hydroxide has an average particle size in the range of 0 to 5 μm and a purity of 97% or higher.

9 . The raw material composition of claim 1 , wherein the titanium oxide has an average particle size in the range of 0 to 5 μm and a purity of 95% or higher.

10 . Oxygen carriers formed from the raw material composition of claim 1 and comprising nickel oxide.

11 . The oxygen carriers of claim 10 , wherein the oxygen carriers are subjected to a wear test for 5 hours at a flow rate of 10.00 l/min (273.15 K, 1 bar) according to ASTM D5757-95 from the American Society for Testing Materials (ASTM) using a wear tester, and then a wear index indicated using Equation 1 below is 20% or lower.
AI (%)=[( W 2)/( W 1)]  [Equation 1]
In Equation 1, W1 represents a weight in g of a sample before the wear test, and W2 represents a weight in g of fine particles captured during the 5 hours of the wear test.

12 . The oxygen carriers of claim 10 , wherein the oxygen carriers may have a shape of spherical non-blowholes, an average particle size in the range of 60 μm to 150 μm, a particle size distribution in the range of 30 μm to 400 μm, and a packing density in the range of 1.0 g/ml to 4.0 g/ml.

13 . The oxygen carriers of claim 10 , wherein an oxygen transfer capacity of the oxygen carriers is in the range of 8 parts by weight to 25 parts by weight based on the total weight of the oxygen carriers.

14 . A method of producing oxygen carriers, the method comprising:
(A) producing a slurry for producing oxygen carriers by mixing a solvent with the raw material composition of claim 1 ; (B) stirring the slurry to produce a homogenized slurry; (C) spray-drying the homogenized slurry to form solid particles; and (D) drying and baking the formed solid particles to produce oxygen carriers.

15 . The method of claim 14 , wherein, in the (A) producing of the slurry for producing oxygen carriers, the solvent and the raw material composition for producing oxygen carriers are mixed at a weight ratio of 15 to 60:40 to 85, and the solvent is water.

16 . The method of claim 14 , wherein, in the (A) producing of the slurry for producing oxygen carriers, the slurry further comprises one or more additives of a dispersant, a defoamer, and an organic binder.

17 . The method of claim 16 , wherein the dispersant includes one or more of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant.

18 . The method of claim 17 , wherein the anionic surfactant includes one or more of a poly-carboxylate salt and a poly-carboxylate amine salt.

19 . The method of claim 16 , wherein the defoamer includes one or more of a silicone-based defoamer, a metal soap-based defoamer, an amide-based defoamer, a polyether-based defoamer, a polyester-based defoamer, a polyglycol-based defoamer, and an alcohol-based defoamer.

20 . The method of claim 16 , wherein the organic binder includes one or more of a polyvinyl alcohol, polyethylene glycol, and methylcellulose.

21 . The method of claim 16 , wherein:
the additives include all of the dispersant, the defoamer, and the organic binder; and as the additives, 0.01 to 5.0 parts by weight of the dispersant, 0.01 to 1.0 parts by weight of the defoamer, and 1.0 to 5.0 parts by weight of the organic binder are included based on 100 parts by weight of the raw material composition for producing oxygen carriers.

22 . The method of claim 14 , wherein the (B) stirring of the slurry to produce the homogenized slurry further comprises removing foreign substances from the stirred and milled slurry.

23 . The method of claim 14 , wherein the (C) spray-drying of the homogenized slurry to form the solid particles comprises injecting the homogenized slurry into a spray-dryer and then spraying the homogenized slurry while maintaining an inlet temperature in the range of 260° C. to 300° C. and an outlet temperature in the range of 90° C. to 150° C. to form the solid particles.

24 . The method of claim 14 , wherein the (D) drying and baking of the formed solid particles to produce oxygen carriers comprises drying the formed solid particles at 110° C. to 150° C. for 2 to 24 hours, injecting the dried solid particles into a high-temperature baking furnace, and elevating a temperature therein to a temperature in the range of 1000° C. to 1450° C. at a speed in the range of 1° C./min to 5° C./min to bake the dried solid particles for 2 to 10 hours.

25 . A chemical looping combustion (CLC) method including causing the oxygen carriers of claim 10 to react with a fuel so that the oxygen carriers are reduced and the fuel is combusted, and causing the reduced oxygen carriers to react with oxygen so that the oxygen carriers are regenerated.

Assignees

• Korea Electric Power Corp

Inventors

• Kim Ui Sik
• Baek Jeom In
• Lee Joong Beom
• Eom Tae Hyoung
• Jo Hyun Geun

Classifications

• C08L71/08

  Polyethers derived from hydroxy compounds or from their metallic derivatives (C08L71/02 takes precedence) · CPC title

• C08L1/28

  Alkyl ethers · CPC title

• F23J2215/50

  Carbon dioxide · CPC title

• C04B2235/3279

  Nickel oxides, nickalates, or oxide-forming salts thereof · CPC title

• C04B2235/3218

  Aluminium (oxy)hydroxides, e.g. boehmite, gibbsite, alumina sol · CPC title