# US 5,702,570 A · Process of producing sodium hydroxide from sodium sulphate in a pulp mill

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- Number: US 5,702,570 A
- Document ID: US5702570A
- Status: Granted
- Kind: A
- Application number: 08/273,628
- Filed: 1994-07-12
- Granted: 1997-12-30
- Earliest claimed: 1991-08-20
- Assignees: Thor Technology Corporation
- Inventors: James W. Smith; Hoc Nghia Tran
- Web page: https://patentgrep.com/patent/US5702570A

## CPC

- C01B 17/0404: {by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process}
- C01B 17/164: {Preparation by reduction of oxidic sulfur compounds}
- C01D 1/22: with carbonates or bicarbonates
- C01D 7/00: Carbonates of sodium, potassium or alkali metals in general
- C01D 7/10: Preparation of bicarbonates from carbonates (ammonia soda process C01D7/18)
- D21C 11/00: Regeneration of pulp liquors {or effluent waste waters}
- D21C 11/0014: {Combination of various pulping processes with one or several recovery systems (cross-recovery)}
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C01D: COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts of peroxyacids C01B15/00; sulfides C01B17/22; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds other than ammonia and cyanogen, containing nitrogen and other non-metals C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; phosphides C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; cyanides C01C3/08; salts of cyanic acid C01C3/14; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- D21C: PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR

## Abstract

Sodium hydroxide is formed from sodium sulphate by a three step operation comprising converting the sodium sulphate to sodium sulphide, converting the sodium sulphide to sodium bicarbonate, and converting the sodium bicarbonate to sodium hydroxide. The operations preferably are effected in conjunction with a bleached kraft pulp mill operation, so as to utilize by-product sodium sulphate from chlorine dioxide generation to produce useful sodium hydroxide as sulphur without co-producing chlorine.

## Claims

### Claim 1

A pulp mill process for the production of pulp wherein added sodium sulphate is introduced in an amount in excess of any amount required to make up soda and/or sulphur losses from the pulp mill process and is converted to sodium hydroxide and hydrogen sulphide as products of said pulp mill process, which comprises:
(a) digesting a cellulosic fibrous material in a pulping liquor comprising sodium sulphide and sodium hydroxide to form a pulp and spent pulping liquor,
(b) separating said pulp from said spent pulping liquor and feeding said spent pulping liquor to a spent pulping liquor regenerating operation to form a smelt comprising sodium sulphide and sodium carbonate,
(c) introducing said added sodium sulphate to the spent pulping liquor regenerating operation prior to the smelt-forming step thereof, thus producing a smelt comprising sodium sulphide and sodium carbonate,
(d) dissolving said smelt in water to form a smelt solution and dividing the smelt solution into a first smelt solution stream containing an amount of sodium sulphide corresponding to the molar amount of sodium ions and sulfur in said added sodium sulphate and a second smelt solution stream,
(e) contacting said first smelt solution stream with a carbon-dioxide containing gas stream to convert said sodium sulphide corresponding to the molar amount of sodium ions and sulfur in said added sodium sulphate simultaneously to solid-phase crystalline sodium bicarbonate, mother liquor, spent carbon dioxide-containing gas stream, and hydrogen sulfide,
(f) removing hydrogen sulfide from step (e) in gaseous admixture with said spent carbon dioxide-containing gas stream,
(g) separating said solid-phase crystalline sodium bicarbonate from said mother liquor from said contacting step,
(h) mixing said mother liquor following step (g) with said second smelt solution stream from step (d) to form a combined stream containing sodium sulphide and sodium carbonate,
(i) converting sodium carbonate and any sodium bicarbonate in said combined stream to sodium hydroxide by contact of said combined stream with calcium oxide and water to coproduce solid phase calcium carbonate and thereby form a pulping liquor comprising sodium sulphide and sodium hydroxide,
(j) removing said solid phase calcium carbonate from the pulping liquor,
(k) recycling said pulping liquor from step (j) to said digesting step (a),
(l) converting said sodium bicarbonate from step (g) to aqueous sodium hydroxide by contacting said sodium bicarbonate with calcium oxide and water to coproduce solid phase calcium carbonate,
(m) removing solid phase calcium carbonate from the aqueous sodium hydroxide formed in step (l),
(n) recovering said aqueous sodium hydroxide from step (m) as a product of the pulp mill process,
(o) calcining solid phase calcium carbonate from the solid phase calcium carbonate removal steps (k) and (m) to calcium oxide and to coproduce a carbon dioxide containing gas stream,
(p) forwarding said carbon dioxide containing gas stream from step (o), at least in part, to said sodium sulphide conversion step (e), and
(q) forwarding said calcium oxide produced in step (o) to steps (i) and (l),
whereby said added sodium sulphate is converted to produce aqueous sodium hydroxide and hydrogen sulfide while the balance of soda and sulfur values of the pulp mill process is maintained, said hydrogen sulfide is removed from the pulp mill process in a gas stream from calcination of calcium carbonate and the use of calcium oxide for recausticization to produce pulping liquor is minimized.

### Claim 2 (depends on 1)

The process of claim 1 wherein said co-produced hydrogen sulphide is converted to sulphur.

### Claim 3 (depends on 2)

The process of claim 2 wherein said hydrogen sulphide is converted to sulphur by oxidation and any residual hydrogen sulphide and/or other sulphur-based acid gas is scrubbed from a tail gas stream from said oxidation in a liquor from said pulp mill process.

### Claim 4 (depends on 3)

The process of claim 3 wherein said oxidation is effected using air comprising a foul air stream arising from said pulp mill process.

### Claim 5 (depends on 3)

The process of claim 3 wherein said liquor from said pulp mill process comprises green liquor or white liquor.

### Claim 6

A pulp mill process for the production of pulp wherein added sodium sulphate is introduced in an amount in excess of any amount required to make up soda and/or sulphur losses from the pulp mill process and is converted to sodium hydroxide and hydrogen sulphide as products of said pulp mill process, which comprises:
(a) digesting a cellulosic fibrous material in a pulping liquor comprising sodium sulphide and sodium hydroxide to form a pulp and spent pulping liquor,
(b) separating said pulp from said spent pulping liquor and feeding said spent pulping liquor to a spent pulping liquor regenerating operation to form a smelt comprising sodium sulphide and sodium carbonate,
(c) introducing said added sodium sulphate to the spent pulping liquor regenerating operation prior to the smelt-forming step thereof, thus producing a smelt comprising sodium sulphide and sodium carbonate,
(d) subjecting said smelt to fractionation by selectively dissolving all the sodium sulphide and a portion of said sodium carbonate from the smelt to form a leach solution of sodium sulphide and sodium carbonate and leave sodium carbonate in solid form in an amount corresponding to at least the molar quantity of sodium ions introduced by said added sodium sulphate,
(e) converting at least a portion of said sodium carbonate in solid form and corresponding to the molar amount of said sodium ions introduced by said added sodium sulphate to aqueous sodium hydroxide and calcium carbonate solids by contacting said sodium carbonate with calcium oxide and water,
(f) removing solid phase calcium carbonate from the aqueous sodium hydroxide,
(g) recovering said aqueous sodium hydroxide from step (f) as a product of the pulp mill process,
(h) introducing any residual solid phase sodium carbonate produced in step (e) to said spent pulping liquor regeneration operation,
(i) converting a portion of said sodium sulphide in said leach solution of sodium sulfide formed in step (d) and corresponding to the molar amount of sulfur introduced by said added sodium sulphate simultaneously to sodium bicarbonate, spent carbon dioxide containing gas stream, and hydrogen sulfide by contacting said aqueous solution of sodium sulfide with a carbon dioxide containing gas stream,
(j) removing hydrogen sulfide from step (i) in gaseous admixture with said spent carbon dioxide containing gas stream,
(k) forming a combined stream comprising residual aqueous sodium sulphide solution from step (i), said sodium bicarbonate and the remaining portion of sodium carbonate in said smelt not converted to sodium hydroxide,
(l) converting sodium carbonate and sodium bicarbonate in said combined stream to sodium hydroxide by contact of said combined stream with calcium oxide and water to coproduce solid phase calcium carbonate and thereby form a pulping liquor comprising sodium sulphide and sodium hydroxide,
(m) removing said solid phase calcium carbonate from the pulping liquor,
(n) recycling said pulping liquor from step (m) to said digesting step (a),
(o) calcining solid phase calcium carbonate from the solid phase calcium carbonate removal steps (f) and (m) to calcium oxide and to coproduce a carbon dioxide containing gas stream,
(p) forwarding said carbon dioxide containing gas stream from step (o), at least in part, to said sodium sulphide conversion step (i), and
(q) forwarding said calcium oxide produced in step (o) to steps (e) and (l),
whereby said added sodium sulphate is converted to product aqueous sodium hydroxide and hydrogen sulfide while the balance of soda and sulfur values of the pulp mill process is maintained, said hydrogen sulfide is removed from the pulp mill process in a gas stream from calcination of calcium carbonate and the use of calcium oxide for recausticization to produce pulping liquor is minimized.

### Claim 7 (depends on 6)

The process of claim 6 wherein said portion of said sodium sulphide in said smelt is converted to sodium bicarbonate by converting to sodium bicarbonate a portion of the leach solution of sodium sulphide and sodium carbonate resulting from said selective dissolution corresponding to the molar amount of sulphur in said added sodium sulphate.

### Claim 8 (depends on 6)

The process of claim 6 wherein said hydrogen sulphide is converted to sulphur.

### Claim 9 (depends on 8)

The process of claim 8 wherein said hydrogen sulphide is converted to sulphur by oxidation and any residual hydrogen sulphide and/or other sulphur-based acid gas is scrubbed from a tail gas stream from said oxidation in a liquor from said pulp mill process.

### Claim 10 (depends on 9)

The process of claim 9 wherein said oxidation is effected using air comprising a foul air stream arising from said pulp mill process.

### Claim 11 (depends on 9)

The process of claim 9 wherein said liquor from said pulp mill process comprises green liquor or white liquor.

### Claim 12

A pulp mill process for the production of pulp wherein added sodium sulphate is introduced in an amount in excess of any amount required to make up soda and/or sulphur losses from the pulp mill process and is converted to sodium hydroxide and hydrogen sulphide as products of said pulp mill process, which comprises:
(a) digesting a cellulosic fibrous material in a pulping liquor comprising sodium sulphide and sodium hydroxide to form a pulp and spent pulping liquor,
(b) separating said pulp from said spent pulping liquor and feeding said spent pulping liquor regenerating operation to form a smelt comprising sodium sulphide and sodium carbonate,
(c) introducing said added sodium sulphate to the spent pulping liquor regenerating operation prior to the smelt-forming step thereof, thus producing a smelt comprising sodium sulphide and sodium carbonate,
(d) subjecting said smelt to fractionation by subjecting a portion of said smelt to selective dissolution of sodium sulphide therefrom in an amount corresponding to the molar amount of sulphur in said added sodium sulphate to form a first aqueous sodium sulphide solution and leave sodium carbonate in solid form and by dissolving the remaining portion of the smelt to form a second aqueous solution of sodium sulphide,
(e) converting at least a portion of said sodium carbonate in solid form and corresponding to the molar amount of said sodium ions introduced by said added sodium sulphate to aqueous sodium hydroxide and calcium carbonate solids by contacting said sodium carbonate with calcium oxide and water,
(f) removing solid phase calcium carbonate from the aqueous sodium hydroxide,
(g) recovering said aqueous sodium hydroxide from step (f) as a product of the pulp mill process,
(h) introducing any residual solid phase sodium carbonate produced in step (e) to said spent pulping liquor regeneration operation,
(i) converting the dissolved sodium sulphide in said first aqueous solution of sodium sulphide formed in step (d) and corresponding to the molar amount of sulphur introduced by said added sodium sulphate simultaneously to sodium bicarbonate, spent carbon dioxide containing gas stream, and hydrogen sulphide by contacting said aqueous solution of sodium sulphide with a carbon dioxide containing gas stream,
(j) removing hydrogen sulphide from step (i) in gaseous admixture with said spent carbon dioxide containing gas stream,
(k) forming a combined stream comprising residual aqueous sodium sulphide solution from step (i), said sodium bicarbonate and the remaining portion of sodium carbonate in said smelt not converted to sodium hydroxide and contained in said second aqueous solution of sodium sulphide,
(l) converting sodium carbonate and sodium bicarbonate in said combined stream to sodium hydroxide by contact of said combined stream with calcium oxide and water to coproduce solid phase calcium carbonate and thereby form a pulping liquor comprising sodium sulphide and sodium hydroxide,
(m) removing said solid phase calcium carbonate from the pulping liquor,
(n) recycling said pulping liquor from step (m) to said digesting step (a),
(o) calcining solid phase calcium carbonate from the solid phase calcium carbonate removal steps (f) and (m) to calcium oxide and to coproduce a carbon dioxide containing gas stream,
(p) forwarding said carbon dioxide containing gas stream from step (o), at least in part, to said sodium sulphide conversion step (i), and
(q) forwarding said calcium oxide produced in step (o) to steps (e) and (l),
whereby said added sodium sulphate is converted to product aqueous sodium hydroxide and hydrogen sulphide while the balance of soda and sulphur values of the pulp mill process is maintained, said hydrogen sulphide is removed from the pulp mill process in a gas stream from calcination of calcium carbonate and the use of calcium oxide for recausticization to produce pulping liquor is minimized.

### Claim 13 (depends on 12)

The process of claim 12 wherein said portion of said sodium sulphide in said smelt is converted to sodium bicarbonate by converting the dissolved sodium sulphide in said first aqueous sodium sulphide solution from said selective dissolution to sodium bicarbonate.