WO1993002249A1 - Method for recovery of chemicals and energy from spent liquor - Google Patents
Method for recovery of chemicals and energy from spent liquor Download PDFInfo
- Publication number
- WO1993002249A1 WO1993002249A1 PCT/SE1992/000477 SE9200477W WO9302249A1 WO 1993002249 A1 WO1993002249 A1 WO 1993002249A1 SE 9200477 W SE9200477 W SE 9200477W WO 9302249 A1 WO9302249 A1 WO 9302249A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gas
- particles
- reactor
- process according
- temperature
- Prior art date
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/12—Combustion of pulp liquors
- D21C11/125—Decomposition of the pulp liquors in reducing atmosphere or in the absence of oxidants, i.e. gasification or pyrolysis
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/06—Treatment of pulp gases; Recovery of the heat content of the gases; Treatment of gases arising from various sources in pulp and paper mills; Regeneration of gaseous SO2, e.g. arising from liquors containing sulfur compounds
- D21C11/063—Treatment of gas streams comprising solid matter, e.g. the ashes resulting from the combustion of black liquor
- D21C11/066—Separation of solid compounds from these gases; further treatment of recovered products
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/12—Heat utilisation in combustion or incineration of waste
Definitions
- the present invention relates to a process for the extraction of chemicals and energy from cellulose spent liquors, primarily for the extraction of chemicals and energy from the gas stream from a reactor for black liquor gasification.
- the recovery process comprises a heating stage, a reactor, where the organic molecular chains are broken down by pyrolysis and incineration to energy-rich gas and the inorganic content mainly forms finely divided particles of chemical melt which can be recovered.
- the pyrolysis in combination with the incineration thus liberates heat energy, usually the temperature is about 1000°C in the reactor, and produces a combustible gas. It is desirable to extract the liberated heat and also exploit the combustible gas by means of further incineration.
- SE-B-448 173 describes a method for the recovery of chemicals and energy from black liquor. According to SE-B-448 173 it has been possible to recover the sensible heat in the gas and simultaneously avoid settling problems by means of directly allowing the gases to pass through a liquid bath. Besides the melt particles being taken up by the said liquid, which is green liquor, the gas is simultaneously cooled. The gas which leaves the liquid bath and which has been freed from melt particles thereby achieves a temperature which in an unpressurised system only amounts to the order of 80°- 90°C, which also corresponds to the approximate temperature in the green liquor bath. Thus, in this unpressurised system, a melt-free gas flow is obtained at about 90°C, as is a liquid bath, consisting of green liquor, at about 90°C. Even if the process according to SE-B-448 173 is carried out at as high a pressure as 150 bar, heat recovery can at best take place by the generation of 300°C saturated steam.
- the gas is cooled down to a temperature in the region of 100-300°C, which limits the possibility for efficient energy recovery. It is evident from the,above reasoning that it would be desirable to be able to extract the heat at a higher temperature, so that it can be recovered in the form of superheated steam.
- a process is previously known from SE-B-182 336 for the extraction of chemicals and energy from cellulose spent liquors, preferably black liquor obtained in the sulphate cellulose process, wherein the spent liquor is conducted into a gasification reactor (1) for pyrolysis and partial incineration, wherein an energy-rich gas is formed containing particles of inorganic chemical melt, the said gas mixture is conveyed out of the reactor (1) and is thereby cooled by injection of a finely-divided cooling medium (cold gas) , in connection with departure from the reactor (1) , the said mixture of gas and non-adhesive chemical particles is conducted from a cooling chamber (2) , arranged in connection with the ' gasification reactor (1) , where they have at least partially solidified and been transformed into solid phase, so that the particles included in the gas mixture become non-adhesive, and thence to a separating arrangement (3) , preferably a cyclone, where the non-adhesive chemical particles are separated from the gas, the gas stream, which has been essentially cleaned
- a first object of the invention is thus to offer a process and an arrangement whereby it is possible to make use of the heat from a gas stream containing both melt particles and gas, without drastically lowering the temperature level of the gas before the heat exchange takes place, at the same time as settling problems are avoided.
- An additional object of the invention is to solve this in an optimal manner, in connection with application to gas turbines and in relation to the use of a cooling or scrubbing medium.
- the abovementioned objects are achieved by the melt particles, which leave the reactor in the gas mixture, being cooled to a temperature not exceeding 700°C and the said finely-divided cooling medium being composed of water, together with the gas being washed after the heat exchange by being conducted through a washing arrangement (5) , a so-called wet scrubber (5) , for the washing out of remaining chemicals in solid form and gas form and by the separated solidified melt particles, which are removed at the bottom (31) of the separating arrangement (3) , being conducted to a receptacle (6) in which the particles are dissolved, wherein at least parts of the alkaline solution formed in this way are exploited for washing the gas in the said wet scrubber (5) .
- a reactor 1 is shown to which is conducted black liquor via a first conduit 10 and air via a second conduit 11.
- the black liquor is gasified by pyrolysis and partial incineration and thereby forms a gas/melt mixture, where the melt drops are present in finely suspended form, at a tempera- ture of about 1000°C.
- a number of combustible gases are formed such as H 2 , CO, CH 4 , etc.
- the melt particles contain mainly Na 2 C0 3 and NaS.
- a cooling chamber 2 is arranged inside which are dis ⁇ tributed a number of spray nozzles 14 which are fed with water and/or cooled gas via conduits 15. With the aid of the nozzles 14 the water and/or gas is finely divided and comes into contact with the hot exhaust gases from the reactor 1. Thereby the exhaust gases are cooled to a temperature of about 650°C. This cooling results in the melt particles being converted into solid phase and thereby becoming non-adhesive. From the cooling chamber 2, which is located in connection with the reactor 1, the gas is conducted with its content of solidified chemical particles onwards through a conduit 4 which leads to a cyclone separator 3.
- the solid and non-adhesive particles are separated from the gas and the gas leaves the cyclone via an upper conduit 30 while the crystalline particles are taken out through a lower conduit 31.
- the gas phase in the conduit 30 still retains a temperature of about 650°C and is conducted in direct connection thereto into a heat exchanger unit 7 for the generation of superheated steam. Due to the purity of the gas, heat exchange can now take place without interfering deposition on the convection surfaces in the heat ex ⁇ changer.
- the heat exchanger unit 7 comprises preferably a steam dome 70, a first heat exchanger core 71 for feed water which leads to the steam dome 70, a second coil 72 for production of saturated steam which leads back to the steam dome 70 and a third heat exchanger core 73 for generation of superheated steam, with a temperature of 300-600°C and a pressure of 20-150 bar, which is taken out via a conduit 74, preferably for the generation of electrical energy in a steam turbine according to the back pressure or condensing procedure.
- This washing arrangement comprises a cylindrical casing 51 to which at a first level 52 is brought an alkaline solution by means of the spray nozzles in order to eliminate remaining chemicals from the gas, primarily H 2 S.
- This alkaline solution can be obtained partly via a recirculating conduit 53 and partly from a receptacle 6.
- this re ⁇ eptacle 6 contains green liquor which has been prepared by dissolving the chemicals that were separated off in the cyclone 3 in water or so-called weak liquor. This green liquor has thus been obtained by dissolution of the chemical particles that were recovered from the separator 3.
- the liquor from the last-named receptacle 6 like that from the washer 5 is led away in conduits 60 and 55 for collection in receptacles (not shown) and for further processing in a causticisation stage for the production of white liquor which is reused in the digestion process.
- the gas which is led away via a conduit 56 at the top of the gas washer 5 is exploited for the production of steam and/or electricity via gas and/or steam turbines.
- the steam which is produced in the super ⁇ heated section can have a variable temperature preferably between 400°-600°C and the pressure can vary within a wide range up to about 160 bar.
- the heat of the gas can be used to produce preheated air for the reactor.
- the gas temperature after the boiler can also be varied, suitably within the range 150°-300°C.
- the gas that is taken out of the top of the separator has in the preferred case a temperature of 500°-700°C.
- the temperature in the reactor is suitably above 800°C and can reach up to 1500°C.
- a preferred range is however 800°-1300°C. Neither is the invention limited to a reactor with an outlet at the lower end of the reactor, which in certain cases can create problems (in particular deposition problems) if the size of the melt particles varies widely.
- a reactor with an upper outlet preferably a reactor of the Kopper-Totzek type, resulting in larger melt particles being collected in a melt bath at the bottom of the reactor and the melt particles departing from the reactor with the gas stream being guaranteed to have a relatively small and therefore a relatively uniform size, and thereby to ensure that all departing particles are cooled to a temperature below the solidification temperature.
- a filter appropriately a textile filter, can be used.
Landscapes
- Engine Equipment That Uses Special Cycles (AREA)
- Paper (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Processing Of Solid Wastes (AREA)
- Industrial Gases (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU23327/92A AU655063B2 (en) | 1991-07-16 | 1992-06-29 | Recovery of chemicals and energy from spent liquor |
EP92915696A EP0660896A1 (en) | 1991-07-16 | 1992-06-29 | Method for recovery of chemicals and energy from spent liquor |
BR9206271A BR9206271A (en) | 1991-07-16 | 1992-06-29 | Process for the extraction of chemical components and energy from used cellulose liquors |
JP5502439A JPH07500150A (en) | 1991-07-16 | 1992-06-29 | Method for extracting chemicals and energy from cellulose waste liquid |
FI940145A FI940145A (en) | 1991-07-16 | 1994-01-12 | Method for recovering chemicals and energy from cellulosic waste liquors |
NO940149A NO940149L (en) | 1991-07-16 | 1994-01-14 | Procedure for recovery of chemicals and heat from waste |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE9102186-5 | 1991-07-16 | ||
SE9102186A SE470066B (en) | 1991-07-16 | 1991-07-16 | Extraction of chemicals and energy from cellulose wastes by gasification |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1993002249A1 true WO1993002249A1 (en) | 1993-02-04 |
Family
ID=20383335
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/SE1992/000477 WO1993002249A1 (en) | 1991-07-16 | 1992-06-29 | Method for recovery of chemicals and energy from spent liquor |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0660896A1 (en) |
JP (1) | JPH07500150A (en) |
AU (1) | AU655063B2 (en) |
BR (1) | BR9206271A (en) |
CA (1) | CA2112563A1 (en) |
FI (1) | FI940145A (en) |
NO (1) | NO940149L (en) |
SE (1) | SE470066B (en) |
WO (1) | WO1993002249A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994020677A1 (en) * | 1993-03-11 | 1994-09-15 | Kvaerner Pulping Technologies Ab | A method of separating sulphur compounds |
WO1996014465A1 (en) * | 1994-11-04 | 1996-05-17 | Kvaerner Pulping Ab | Evaporation of bleach filtrate in the gas cooling system of a plant for gasifying black liquor |
GB2318131A (en) * | 1996-10-12 | 1998-04-15 | Krc Umwelttechnik Gmbh | Method of regenerating black liquor during wood pulping, whilst simultaneously recovering energy |
DE19718131A1 (en) * | 1997-04-29 | 1998-11-05 | Krc Umwelttechnik Gmbh | Regeneration of black liquor from wood digester |
US20110226997A1 (en) * | 2010-03-19 | 2011-09-22 | Air Products And Chemicals, Inc. | Method And System Of Gasification |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3073672A (en) * | 1959-04-15 | 1963-01-15 | Stora Kopparbergs Bergslags Ab | Method of gasifying sulphurous cellulose waste liquors |
US3323858A (en) * | 1964-08-21 | 1967-06-06 | Lummus Co | Process for recovering the alkali metal content of spent pulping liquor |
DE2027094B2 (en) * | 1969-06-03 | 1975-02-20 | Svenska Cellulosa Ab, Sundsvall (Schweden) | Process and plant for the recovery of chemicals in the waste liquor from the digestion of lignocellulosic material |
US4808264A (en) * | 1985-06-03 | 1989-02-28 | Kignell Jean Erik | Process for chemicals and energy recovery from waste liquors |
-
1991
- 1991-07-16 SE SE9102186A patent/SE470066B/en not_active IP Right Cessation
-
1992
- 1992-06-29 AU AU23327/92A patent/AU655063B2/en not_active Ceased
- 1992-06-29 WO PCT/SE1992/000477 patent/WO1993002249A1/en not_active Application Discontinuation
- 1992-06-29 BR BR9206271A patent/BR9206271A/en not_active Application Discontinuation
- 1992-06-29 EP EP92915696A patent/EP0660896A1/en not_active Withdrawn
- 1992-06-29 JP JP5502439A patent/JPH07500150A/en active Pending
- 1992-06-29 CA CA 2112563 patent/CA2112563A1/en not_active Abandoned
-
1994
- 1994-01-12 FI FI940145A patent/FI940145A/en not_active Application Discontinuation
- 1994-01-14 NO NO940149A patent/NO940149L/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3073672A (en) * | 1959-04-15 | 1963-01-15 | Stora Kopparbergs Bergslags Ab | Method of gasifying sulphurous cellulose waste liquors |
US3323858A (en) * | 1964-08-21 | 1967-06-06 | Lummus Co | Process for recovering the alkali metal content of spent pulping liquor |
DE2027094B2 (en) * | 1969-06-03 | 1975-02-20 | Svenska Cellulosa Ab, Sundsvall (Schweden) | Process and plant for the recovery of chemicals in the waste liquor from the digestion of lignocellulosic material |
US4808264A (en) * | 1985-06-03 | 1989-02-28 | Kignell Jean Erik | Process for chemicals and energy recovery from waste liquors |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994020677A1 (en) * | 1993-03-11 | 1994-09-15 | Kvaerner Pulping Technologies Ab | A method of separating sulphur compounds |
US5556605A (en) * | 1993-03-11 | 1996-09-17 | Chemrec Aktiebolag | Method of seperating sulphur compounds |
CN1044929C (en) * | 1993-03-11 | 1999-09-01 | 卡瓦纳碎浆处理公司 | A method of separating sulphur compounds |
WO1996014465A1 (en) * | 1994-11-04 | 1996-05-17 | Kvaerner Pulping Ab | Evaporation of bleach filtrate in the gas cooling system of a plant for gasifying black liquor |
GB2318131A (en) * | 1996-10-12 | 1998-04-15 | Krc Umwelttechnik Gmbh | Method of regenerating black liquor during wood pulping, whilst simultaneously recovering energy |
US5855737A (en) * | 1996-10-12 | 1999-01-05 | Noell-Krc Energie Und Umwelttechnik Niederlassung Freiberg | Process for regenerating a liquid created in the kraft process for pulping wood, while simultaneously obtaining high energy efficiency |
GB2318131B (en) * | 1996-10-12 | 2001-05-02 | Krc Umwelttechnik Gmbh | Method of regenerating a fluid,which accumulates during the power process to pulpwood,whilst simultaneously recovering energy |
DE19718131A1 (en) * | 1997-04-29 | 1998-11-05 | Krc Umwelttechnik Gmbh | Regeneration of black liquor from wood digester |
DE19718131C2 (en) * | 1997-04-29 | 1999-10-14 | Krc Umwelttechnik Gmbh | Method and device for the regeneration of a liquid obtained in the power process for the digestion of wood by gasification |
US20110226997A1 (en) * | 2010-03-19 | 2011-09-22 | Air Products And Chemicals, Inc. | Method And System Of Gasification |
Also Published As
Publication number | Publication date |
---|---|
NO940149D0 (en) | 1994-01-14 |
AU655063B2 (en) | 1994-12-01 |
AU2332792A (en) | 1993-02-23 |
SE9102186D0 (en) | 1991-07-16 |
BR9206271A (en) | 1995-10-10 |
SE470066B (en) | 1993-11-01 |
CA2112563A1 (en) | 1993-02-04 |
EP0660896A1 (en) | 1995-07-05 |
NO940149L (en) | 1994-01-14 |
JPH07500150A (en) | 1995-01-05 |
SE9102186L (en) | 1993-01-17 |
FI940145A0 (en) | 1994-01-12 |
FI940145A (en) | 1994-01-12 |
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