Iron porphyrazines as efficient, catalytic and scalable method to produce chlorine dioxide

Patent metadata

Field	Value
Publication number	US-11242248-B2
Application number	US-201916400277-A
Country	US
Kind code	B2
Filing date	May 1, 2019
Priority date	Aug 23, 2010
Publication date	Feb 8, 2022
Grant date	Feb 8, 2022

Abstract

Methods, kits, cartridges, and compounds related to generating chlorine dioxide by exposing ClO 2 − to at least one of an iron porphyrin catalyst or an iron porphyrazine catalyst are described.

First claim

What is claimed is:

1. A cartridge comprising a housing and at least one of an iron porphyrin catalyst or an iron porphyrazine catalyst in the housing, wherein the cartridge is adapted to allow reactants to contact the at least one of an iron porphyrin catalyst or an iron porphyrazine catalyst, and the cartridge further comprises at least one of the reactants or a source of ClO 2 − in the housing, and the reactants comprise ClO 2 − .

2. The cartridge of claim 1 , wherein the iron porphyrin catalyst has a structure of formula I:

wherein the a is the oxidation state II, III or IV of the Fe and R 1 , R 2 , R 3 , and R 4 are independently selected from the group consisting of TM2PyP, TM4PyP, TDMImP, and TDMBImp, which have a structure of formulas II, III, IV, and V, respectively:

and at least one of R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are independently selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, CH 2 —(CH 2 ) n1 —CH 3 where n1=5-20, CH 2 —(CH 2 ) n2 —CH 2 —X where n2=0-20, —CH 2 (CO)—(CH 2 ) n3 —CH 2 —X where n3=0-20, —CH 2 —Ar—X, (CH 2 ) n —X, (CH 2 ) m Ar—X, (CH 2 ) m Ar—Y, (CH 2 ) n —Y, CH 2 CONH—Y; CH 2 COO—Y, CH 2 CO(CH 2 ) P —Y, (OCH 2 CH 2 ) m —Y, (OCH 2 CH 2 ) m —X; Y 2 —X, CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 3 , —CH 2 CO 2 CH 2 CH 3 , alkyl, CH 2 CH 2 OCH 3 , CH 2 CH 2 OCH 2 CH 2 OCH 3 , (CH 2 ) n —X, (CH 2 ) n —Y, (CH 2 ) n Ar—X, (CH 2 ) n Ar—Y, CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 3 , CH 2 CO 2 CH 2 CH 3 , (OCH 2 CH 2 ) m —X, (OCH 2 CH 2 ) m —Y, Y 2 —X, or Y 2 C(Z 1 ) 3 ; where Z 1 is CH 2 OCH 2 (CH 2 ) n X, CH 2 OCH 2 (CH 2 ) n Y, or (CH 2 ) n C(O)Y 2 C(Z 2 ) 3 ; Z 2 is CH 2 OCH 2 CH 2 C(O)Y 2 C(Z 4 ) 3 ; Z 4 is CH 2 OCH 2 CH 2 X or (CH 2 ) n C(O)—Y 2 —C(Z 5 ) 3 ; Z 5 is CH 2 OCH 2 CH 2 C(O)Y 2 C(Z 6 ) 3 ; Z 6 is CH 2 OCH 2 CH 2 C(O)O(CH 2 CH 2 O) m CH 2 CH 2 O, (CH 2 ) n OCH 2 C(CH 2 OH) 3 , (CH 2 ) n OCH 2 CH(CH 2 OH) 2 , (CH) n OCH 2 C(CH 2 OH) 2 (CH 3 ), (CH 2 ) n OCH 2 C[CH 2 OCH 2 C(CH 2 OH) 3 ] 3 , (CH 2 ) n OCH 2 C[CH 2 OCH 2 C(CH 2 O[CH 2 CH 2 O] m CH 2 CH 2 OX) 3 , CH 2 CONH—Y, CH 2 CO—Y, or CH 2 CO(CH 2 ) P —Y; where
Ar is substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, or substituted or unsubstituted naphthyl and when Ar is the phenyl in —CH 2 —Ar—X, (CH 2 ) m Ar—X, or (CH 2 ) m Ar—Y, the X or Y is attached ortho- meta- or para to the —CH 2 — attached to pyridoporphyrazine;
n is 1 to 10; m is 1 to 200; p is 1 or 2; X is COOH, COO(alkyl 1 ), CONH 2 , CONH(alkyl 1 ), CON(alkyl 1 ) 2 , CO(CH 2 ) P alkyl 1 , OPO 3 H 2 , PO 3 H 2 , SO 3 H, NH 2 , N(alkyl 1 ) 2 , or N(alkyl 1 ) 3 + , where alkyl 1 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl; Y is OH, (O—CH 2 CH 2 ) m —W 1 , or (CH 2 CH 2 ) m —W 2 , where W 1 is OH or (O—(CH 2 CH 2 ) m OH), and W 2 is O-alkyl; and Y 2 is —(CH 2 ) n O—, —(CH 2 ) n NH—, —(CH) n S—; CH 2 CONH—, CH 2 COO—, or CH 2 CO(CH 2 ) p —; and
L 1 and L 2 are, independently absent, halide, oxo, aquo, hydroxo, CN, OPO 3 H, or alcohol.

3. The cartridge of claim 2 , wherein the alkyl is selected from straight-chain or branched-chain alkyl radicals containing from 1 to 22 carbon atoms, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and eicosyl.

4. The cartridge of claim 2 , wherein R 1 , R 2 , R 3 , and R 4 are TDMBImp.

5. The cartridge of claim 2 , wherein R 1 , R 2 , R 3 , and R 4 are TM2PyP or R 1 , R 2 , R 3 and R 4 are TM4PyP.

6. The cartridge of claim 1 , wherein the iron porphyrazine catalyst has a structure of formula VI:

wherein a is the oxidation state II, III or IV of the Fe and each of A 1 , A 2 , A 3 , A 4 , B 1 , B 2 , B 3 , B 4 , C 1 , C 2 , C 3 , C 4 , D 1 , D 2 , D 3 , and D 4 are independently selected from N + —R n , N, C—H, C—X, and C—R n ;
when N + —R n is selected, only one in each set of A 1 , B 1 , C 1 , and D 1 ; A 2 , B 2 , C 2 , and D 2 ; A 3 , B 3 , C 3 , and D 3 ; or A 4 , B 4 , C 4 , and D 4 is N + —R n ;
when N is selected, only one in each set of A 1 , B 1 , C 1 , and D 1 ; A 2 , B 2 , C 2 , and D 2 ; A 3 , B 3 , C 3 , and D 3 ; or A 4 , B 4 , C 4 , and D 4 is N;
each R, is independently selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, CH 2 —(CH 2 ) n1 —CH 3 where n1=5-20, CH 2 —(CH 2 ) n2 —CH 2 —X where n2=0-20, CH 2 (CO)—(CH 2 ) n3 —CH 2 —X where n3=0-20, CH 2 —Ar—X, (CH 2 ) n —X; (CH 2 ) m Ar—X, (CH 2 ) m Ar—Y, (CH 2 ) n —Y, CH 2 CONH—Y; CH 2 COO—Y, CH 2 CO—Y, CH 2 CO(CH 2 ) P —Y, (OCH 2 CH 2 ) m —Y, (OCH 2 CH 2 ) m —X, Y 2 —X, CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 3 , CH 2 CO 2 CH 2 CH 3 , CH 2 CH 2 OCH 3 , CH 2 CH 2 OCH 2 CH 2 OCH 3 , (CH 2 ) n —Y, (CH 2 ) n Ar—X, (CH 2 ) n Ar—Y, and Y 2 C(Z 1 ) 3 ; Z 1 is CH 2 OCH 2 (CH 2 ) n X, CH 2 OCH 2 (CH 2 ) n Y, or (CH 2 ),C(O)Y 2 C(Z 2 ) 3 ; Z 2 is CH 2 OCH 2 CH 2 C(O)Y 2 C(Z 3 ) 3 ; Z 3 is CH 2 OCH 2 CH 2 X or (CH 2 ) n C(O)—Y 2 —C(Z 4 ) 3 ; Z 4 is CH 2 OCH 2 CH 2 C(O)Y 2 C(Z 5 ) 3 ; and Z 5 is CH 2 OCH 2 CH 2 C(O)O(CH 2 CH 2 O) m CH 2 CH 2 O, (CH 2 ) n OCH 2 C(CH 2 OH) 3 , (CH 2 ) n OCH 2 CH(CH 2 OH) 2 , (CH 2 ) n OCH 2 C(CH 2 OH) 2 (CH 3 ), (CH 2 ) n OCH 2 C[CH 2 OCH 2 C(CH 2 OH) 3 ] 3 , (CH 2 ) n OCH 2 C[CH 2 OCH 2 C(CH 2 O[CH 2 CH 2 O] m CH 2 CH 2 OX) 3 , CH 2 CONH—Y, CH 2 CO—Y, or CH 2 CO(CH 2 ) P —Y; where
Ar is substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, or substituted or unsubstituted naphthyl and when Ar is the phenyl in —CH 2 —Ar—X, (CH 2 ) m Ar—X, or (CH 2 ) m Ar—Y, the X or Y is attached ortho- meta- or para to the —CH 2 — attached to pyridoporphyrazine;
n is 1 to 10; m is 1 to 200; p is 1 or 2; X is COOH, COO(alkyl 1 ), CONH 2 , CONH(alkyl 1 ), CON(alkyl 1 ) 2 , CO(CH 2 ) P alkyl 1 , OPO 3 H 2 , PO 3 H 2 , SO 3 H, NH 2 , N(alkyl 1 ) 2 , or N(alkyl 1 ) 3 + , where alkyl 1 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl; Y is OH, (O—CH 2 CH 2 ) m —W 1 , or (CH 2 CH 2 ) m —W 2 ; W 1 is OH or (O—(CH 2 CH 2 ) m OH); W 2 is O-alkyl; and Y 2 is —(CH 2 ) n O—, —(CH 2 ) n NH—, —(CH 2 ) n S—; CH 2 CONH—, CH 2 COO—, or CH 2 CO(CH 2 ) p —; and
L 1 and L 2 are independently absent, halide, oxo, aquo, hydroxo, CN, OPO 3 H, or alcohol.

7. The cartridge of claim 6 , wherein in the O-alkyl the alkyl is selected from straight-chain or branched-chain alkyl radicals containing from 1 to 22 carbon atoms, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and eicosyl.

8. The cartridge of claim 1 , wherein the cartridge comprises the reactants, and the reactants.

9. The cartridge of claim 8 , wherein the ClO 2 − is in the form of at least one substance selected from the group consisting of chlorite salts.

10. The cartridge of claim 8 , wherein the ClO 2 − is in the form of at least one substance selected from the group consisting of sodium chlorite, potassium chlorite, calcium chlorite and magnesium chlorite.

11. The cartridge of claim 8 , wherein the ClO 2 − is mixed with a solid filler.

12. The cartridge of claim 8 , wherein the ClO 2 − is adsorbed on at least one substance selected from the group consisting of clay, silica, alumina and organic polymers.

Assignees

• Univ Princeton

Inventors

• Groves John T
• Xiao Roy

Classifications

• B01J2531/842

  Iron · CPC title

• B01J31/183

  with more than one complexing nitrogen atom, e.g. phenanthroline · CPC title

• C01B11/024 Primary

  from chlorites · CPC title

• D21C9/14

  with ClO2 or chlorites · CPC title

• C07F15/025

  without a metal-carbon linkage · CPC title