Copper, iron, and nitrogen treated sorbent and method for making same

Patent metadata

Field	Value
Publication number	US-2022062861-A1
Application number	US-202117446555-A
Country	US
Kind code	A1
Filing date	Aug 31, 2021
Priority date	Aug 31, 2020
Publication date	Mar 3, 2022
Grant date	—

Abstract

Carbonaceous material that is activated to form precursor activated carbon is further enhanced by doping with copper, iron, and nitrogen and calcining. The carbonaceous material includes those obtained from coal, wood, or coconut shells. Methods of doping the activated carbon are described. The described treatment processes result in a sorbent material that has excellent performance in removing chloramine and similar compounds from fluids such as water that is intended for drinking.

First claim

1 . A sorbent material formed from a carbonaceous material that is activated to form a precursor activated carbon, the sorbent material comprising:
about 2 wt. % to about 20 wt. % nitrogen as measured on a dry precursor activated carbon basis; about 0.1 wt. % to about 4 wt. % iron and copper as measured on a dry precursor activated carbon basis; wherein the sorbent material has a chloramine destruction number (CDN) of about 5 to about 75.

2 . The sorbent material of claim 1 , wherein the chloramine destruction number is about 20 to about 75.

3 . The sorbent material of claim 1 , wherein the sorbent material has a peroxide number of less than about 20 minutes.

4 . The sorbent material of claim 3 , wherein the sorbent material has a peroxide number of about 1 minute to about 10 minutes.

5 . The sorbent material of claim 1 , wherein the amount of nitrogen is about 2.5 wt. % to about 5 wt. %.

6 . The sorbent material of claim 1 , wherein the amount of nitrogen is about 1.4 wt. % to about 3.0 wt. %.

7 . The sorbent material of claim 1 , wherein the sorbent material is formed from a carbonaceous material that is formed from one or more of coal, wood, and coconut.

8 . The sorbent material of claim 7 , wherein at least part of the carbonaceous material is formed from coconut.

9 . The sorbent material of claim 1 , wherein the weight ratio of iron and copper is about 25:75 to about 75:25.

10 . The sorbent material of claim 9 , wherein the weight ratio of iron and copper is about 50:50.

11 . A method of manufacturing a sorbent material, the method comprising:
providing a carbonaceous material; activating the carbonaceous material to form a precursor activated carbon; optionally oxidizing the precursor activated carbon; doping the precursor activated carbon by contacting the precursor activated carbon with one or more compounds that are a copper source, an iron source, and a nitrogen source to thereby form a doped precursor activated carbon; calcining the doped precursor activated carbon by heating to a temperature of at least about 950° C. in a calcining atmosphere that does not cause any substantial oxidation or activation of the doped precursor activated carbon to thereby form a sorbent material.

12 . The method of claim 11 , wherein a single compound is the copper source, the iron source, and the nitrogen source.

13 . The method of claim 11 , wherein a first compound is the copper source and the iron source, and a second compound is the nitrogen source.

14 . The method of claim 11 , wherein a first compound is the copper source and the nitrogen source, and a second compound is the iron source.

15 . The method of claim 11 , wherein a first compound is the iron source and the nitrogen source, and a second compound is the copper source.

16 . The method of claim 11 , wherein a first compound is the copper source, a second compound is the iron source, and a third compound is the nitrogen source.

17 . The method of claim 11 , wherein doping the precursor activated carbon is performed in a single stage process, the single stage process including contacting the precursor activated carbon in an aqueous solution that contains the copper source, the iron source, and the nitrogen source.

18 . The method of claim 11 , wherein:
the copper source is one or more of copper(II) sulfate pentahydrate (CuSO 4 ·5H 2 O), copper(II) chloride (CuCl 2 ), copper(II) chloride dihydrate (CuCl 2 2H 2 O), copper(II) nitrate (Cu(NO 3 ) 2 ), copper(II) nitrate monohydrate (Cu(NO 3 ) 2 ·H 2 O), copper(II) nitrate sesquihydrate (Cu(NO 3 ) 2 ·1.5H 2 O), copper(II) nitrate hemipentahydrate (Cu(NO 3 ) 2 2.5H 2 O), copper(II) nitrate trihydrate (Cu(NO 3 ) 2 3H 2 O), copper(II) nitrate hexahydrate (([Cu(H 2 O) 6 ](NO 3 ) 2 )), copper(II) acetate (Cu(CH 3 COO) 2 ), copper(II) acetate monohydrate (Cu(CH 3 COO) 2 H 2 O), Copper (II) formate tetrahydrate, Cu(NH 3 ) 6 +2 , copper (II) carbonate hydroxide, (Cu 2 (OH) 2 CO 3 ) compounds thereof, or mixtures thereof; the iron source is one or more of iron(III) chloride hexahydrate (FeCl 3 ·6H 2 O), iron(II) chloride tetrahydrate (FeCl 2 ·4H 2 O), ammonium iron(III) sulfate dodecahydrate (NH 4 Fe(SO 4 )·12H 2 O), iron(II) sulfate heptahydrate (Fe 2 SO 4 ·7H 2 O), ammonium iron(III) oxalate trihydrate ((NH 4 ) 3 Fe(C 2 O 4 ) 3 ·3H 2 O), ammonium hexacyanoferrate(II) hydrate ((NH 4 ) 4 [Fe(CN) 6 ]·xH 2 O), ammonium iron(III) citrate ((NH 4 ) 5 [Fe(C 6 H 4 O 7 ) 2 ]), sodium ferrocyanide decahydrate (Na 4 Fe(CN) 6 ·10H 2 O), sodium ferrioxalate (Na 3 Fe(C 2 O 4 ) 3 ), potassium ferrocyanide trihydrate (K 4 [Fe(CN) 6 ]·3H 2 O), potassium ferricyanide (K 3 [Fe(CN) 6 ]), potassium ferrooxalate (K 2 [Fe(C 2 O 4 ) 2 ]), or iron(II) acetate tetrahydrate ((CH 3 COO) 2 Fe·4H 2 O), ferrous lactate dihydrate, ferrous lacate trihydrate, compounds thereof, or mixtures thereof; and the nitrogen source is one or more compounds where nitrogen has a −3 oxidation state.

19 . The method of claim 11 , wherein calcining is performed at a temperature of about 800° C. to about 1050° C. in a N 2 atmosphere.

20 . The method of claim 11 , wherein the oxidizing is required and is performed.

21 . The method of claim 11 , wherein the oxidizing is not performed.

22 . The method of claim 18 , wherein the copper source is copper(II) sulfate pentahydrate copper(II) sulfate pentahydrate (CuSO 4 ·5H 2 O), the iron source is iron(III) chloride hexahydrate (FeCl 3 ·6H 2 O), and the nitrogen source is one or more of urea or dicyandiamide (DCD).

23 . The method of claim 11 , wherein calcining is performed at a temperature of about 400° C. to about 1050° C. in a N 2 atmosphere.

24 . The method of claim 19 , wherein calcining is performed at a temperature of about 925° C. to about 975° C. in a N 2 atmosphere.

25 . A method of removing chlorine, chloramine, or both chlorine and chloramine from a fluid, the method comprising:
providing a sorbent material, the sorbent material being formed from a carbonaceous material that is activated to form a precursor activated carbon, said sorbent material comprising about 2 wt. % to about 20 wt. % nitrogen as measured on a dry precursor activated carbon basis, about 0.1 wt. % to about 4 wt. % iron and copper as measured on a dry precursor activated carbon basis, and wherein the sorbent material has a chloramine destruction number (CDN) of about 5 to about 75; and contacting the sorbent material with a fluid.

26 . The method of claim 25 , wherein the fluid is liquid water.

27 . The method of claim 25 , wherein the water or the sorbent material has previously undergone a disinfecting step.

Assignees

• Calgon Carbon Corp

Inventors

• Mazzoccoli Jason P
• Walker Ryan W
• Tramposch Walter G

Classifications

• C02F2303/185

  The treatment agent being halogen or a halogenated compound · CPC title

• C02F2101/36

  containing halogen · CPC title

• C02F2101/322

  Volatile compounds, e.g. benzene · CPC title

• C02F2101/12

  Halogens or halogen-containing compounds · CPC title

• C02F1/288

  using composite sorbents, e.g. coated, impregnated, multi-layered · CPC title