EP0693145A1 - Procede de conversion du sulfate de sodium - Google Patents

Procede de conversion du sulfate de sodium

Info

Publication number
EP0693145A1
EP0693145A1 EP94912988A EP94912988A EP0693145A1 EP 0693145 A1 EP0693145 A1 EP 0693145A1 EP 94912988 A EP94912988 A EP 94912988A EP 94912988 A EP94912988 A EP 94912988A EP 0693145 A1 EP0693145 A1 EP 0693145A1
Authority
EP
European Patent Office
Prior art keywords
sodium
stage
separated
waste liquor
stripping
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP94912988A
Other languages
German (de)
English (en)
Other versions
EP0693145B1 (fr
Inventor
Michael Bobik
Dieter Chybin
Alfred Glasner
Karin Taferner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Austrian Energy and Environment AG and Co KG
Austrian Energy and Environment SGP Waagner Biro GmbH
Original Assignee
Austrian Energy and Environment AG and Co KG
Austrian Energy and Environment SGP Waagner Biro GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Austrian Energy and Environment AG and Co KG, Austrian Energy and Environment SGP Waagner Biro GmbH filed Critical Austrian Energy and Environment AG and Co KG
Publication of EP0693145A1 publication Critical patent/EP0693145A1/fr
Application granted granted Critical
Publication of EP0693145B1 publication Critical patent/EP0693145B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • 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
    • D21C11/0064—Aspects concerning the production and the treatment of green and white liquors, e.g. causticizing green liquor
    • D21C11/0071—Treatment of green or white liquors with gases, e.g. with carbon dioxide for carbonation; Expulsion of gaseous compounds, e.g. hydrogen sulfide, from these liquors by this treatment (stripping); Optional separation of solid compounds formed in the liquors by this treatment
    • 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
    • D21C11/04—Regeneration of pulp liquors or effluent waste waters of alkali lye
    • 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
    • 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
    • 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
    • D21C11/127—Decomposition of the pulp liquors in reducing atmosphere or in the absence of oxidants, i.e. gasification or pyrolysis with post-combustion of the gases

Definitions

  • the invention relates to a process for converting sodium sulfite and carbonate-containing waste liquor with sulfate and thiosulfate impurities into sodium sulfite and sodium carbonate-containing cooking liquor for a pulping process based on Na, such as, for. B. asam, basic or acidic sodium sulfite process, in which the waste liquor is burned in a lye combustion boiler with liquid slag and a multi-stage exhaust gas purification with recovery of the sodium-sulfur compounds.
  • the ASAM process (alkaline sulfite process with anthraquinone and methanol addition) is a further development of the neutral or alkali sulfite process, which has been known for decades and has been used in industry.
  • the really new thing about the ASAM process is the addition of methanol to the digestion solution.
  • the ASAM process has the advantage that no gaseous sulfur compounds occur during the digestion and that the pulps are bleached to the highest whiteness without the use of chlorine-containing bleaching agents.
  • AT-B 351 359 discloses the removal of NaCl from the digestion liquid without incorporating the solid residues from the exhaust gas purification.
  • EP-B1 223 821 discloses a pyrolysis process for the waste liquor, in which a part of the combustible components formed during the pyrolysis are burned and the inorganic residues are obtained in the molten state and are quenched. Here, too, the solid residues from exhaust gas cleaning are not introduced into the melt.
  • the object of the invention is to close the chemical recovery via the cycle of converting the waste liquor to the cooking liquor.
  • the recovery plants have two main functions: the recovery of the inorganic digestion chemicals from the waste liquor for the preparation of the cooking liquor and the use of the energy contained in the organic substance as high pressure steam. The value of the recovered chemicals exceeds the value of the steam energy required.
  • the invention solves the stated problem and is characterized in that the exhaust gases leaving the caustic pot are first dedusted dry and then washed in one stage, preferably in at least two stages by different washing liquids, the separated dusts, in particular the separated Na2S04, with the to be burned liquor is mixed, and the liquid slag from the liquor combustion kettle is dissolved in water and the dissolved sodium compounds, especially the formed Na2S, can be converted into aHC ⁇ 3, Na2C ⁇ 3 and NaHS by carbonation with part of the cleaned exhaust gas, and then in a multi-stage stripping of H2S and CO2 and a subsequent absorption CO2 at> 1 bar the H2S gas is expelled from the solution and after the condensation of water vapor is burned in an H2S muffle. Further refinements of the invention are specified in subclaims 2-11.
  • the invention is shown in the connected figures 1 to 3 in the form of circuit diagrams, for example.
  • FIG. 1 shows an overall circuit diagram
  • FIGS. 2 and 3 each show a partial circuit diagram.
  • the waste liquor (black liquor) from the evaporation plant is mixed together with the recycled sodium sulfate from the basic flue gas scrubber 5 and the ash from the electrostatic filter 2 in a caustic tank 7 and then fed to the caustic combustion boiler 1.
  • CaSO4 can already be excreted as an insoluble sludge, which reduces the fiber.
  • the waste liquor is mixed with separated solids in a lye tank 7 and burned in a leaching bed in a reduction bed analogously to the sulphate process in the lye combustion boiler 1, the resulting melt is drawn off from the lye combustion chamber floor and the resulting gases by supplying air through secondary and tertiary air nozzles burned.
  • the chemical reactions taking place are essentially as follows:
  • the melt is dissolved in a container 6 with H2O and condensates from the conversion, and then subjected to a blowdown 8.
  • the vapors of the melt dissolving reaction are fed to the caustic combustion boiler 1.
  • the Na2-S. Green liquor containing NaHS and Na2C03 is after the blowdown 8 in a multi-stage wash 9 with CO 2 -containing Pre-carbonized boiler flue gas, forming NaHC03.
  • the following chemical reactions take place:
  • This CO 2 absorption preferably takes place at higher pressures and low temperature, the pressure side being limited to approximately 1050-1060 m bar.
  • the lower temperature limit can be seen in the solubility of sodium bicarbonate and should be in the range of 30 ° - 45 ° C. Due to possible deposit reactions that can cause faults due to the precipitation of silicates, it makes sense to design this apparatus as a multi-stage scrubber.
  • the precarbonated liquor is further carbonated with CO 2 -containing exhaust gas from the SO2 scrub 15 after the H2S muffle 3 in the carbonation 10.
  • the following chemical reactions take place:
  • the thiosulfate content in the lye does not interfere with the cooking process in the alkaline environment, but it does contribute to undesired inactivation of the digestion chemicals.
  • a sensible procedure for the H2S stripping makes it necessary to divide the H2S stripping 11 into several apparatuses (FIG. 2). Since sodium carbonate is formed in the stripping stage in question due to the two simultaneous desorption reactions, it is therefore necessary to carry out an intermediate strengthening with CO2 after each stripping stage in order to convert the carbonate back to the bicarbonate and thus to raise the H2S partial pressure that determines the mass transport.
  • the two desorption reactions with H2S and CO2 are as follows:
  • H2S partial pressure in the gas phase must be kept low, for which purpose H2O steam and / or CO 2 can be used as the medium, H2O steam is advantageously used. Since CO2 can only be used to a limited extent from the sulfitization, the H2S can thus be obtained for the muffle 13 in highly concentrated form after condensation of the water vapor. If, in contrast to other processes, the stripping is carried out without CO 2 circulation with concentrated CO2, it is not possible to carry out the process without splitting bicarbonate during the stripping because of the very similar behavior of the carbonic acid and the hydrogen sulfide. Partial splitting of the bicarbonate promotes mass transfer.
  • This CO 2 absorption takes place preferably at higher pressures (> 1 bar) and low temperatures. If one wants to absorb the carbon dioxide at higher temperatures, specifically higher pressures are required.
  • the CO 2 source used is that from the decarbonation 12 after condensation of the steam and that of the sulfitization.
  • the intermediate fortification with CO2 takes place under increased pressure and increasing temperature.
  • the pressure is generated via the geodetic gradient from stripping to intermediate reinforcement, the process being led downwards from the previous stripping.
  • the absorption of the carbon dioxide is carried out in hydraulic compressors 18, 19, 29, 21 (see FIGS. 2 and 3) in order to ensure a sufficient dissolving reaction through a further pressure increase (approx. 2 bar absolute) and a long residence time of the CO 2 in the liquid , the CO 2 gas and the carbonate, bicarbonate solution being passed in countercurrent (see FIG. 3).
  • the CO2-saturated bicarbonate solution is lifted up into the stripping stage by the low pressure and the further stripping reduces the sulfide content to values less than lg / 1.
  • the H2S stripping is carried out in bubble tray columns. The required number of steps of more than 15 trays per stripping step results in low equipment costs.
  • the highly concentrated H2S gas from the stripping stages is fed to the H2S muffle 13 after separation of the water vapor in the condenser 17. In this the combustion takes place automatically and the waste heat released can be used for further overheating of the only slightly overheated saturated steam generated in the lye combustion boiler 1.
  • sodium sulfite is produced in the sulfitization 16 with bicarbonate from the H2S stripping 11 and the CO2 is obtained in a concentrated form.
  • That portion of the bicarbonate after the H2S stripping 11 which is not required in the sulfitization 16 is fed to the decarbonation 12 after heating to 115 ° C.
  • the CO 2 vapor mixture is fed to the H2S stripping 11.
  • sodium sulfite and sodium carbonate are actively available in the product in a concentration of up to 2.7 mol Na '/ l for pulping.
  • the bicarbonate can be crystallized and the mother liquor returned to the melt dissolving container and the crystals dissolved in the sulfitization a higher concentration of lye can be achieved.
  • the disadvantage is a higher energy requirement and a higher cooling water requirement for cooling the crystallization stage.
  • FIG. 2 shows a partial circuit diagram of the H2S stripping 11, the CO2 being brought into solution and reacting with increasing pressure and higher temperature in several hydraulic compressors 18, 19, 20, 21, the reinforcement with CO2 being added between the stripping stages a total pressure greater than one bar is carried out.
  • CaO or Ca (0H) 2 is blown into the combustion chamber of the caustic combustion boiler, so that additional gypsum is produced, which is undissolved as sludge in the second washing stage 5, while the Na2S04 solution of the burning waste liquor is added.

Landscapes

  • Treating Waste Gases (AREA)
  • Paper (AREA)

Abstract

Pour récupérer les composés de soufre de sodium selon un procédé de fabrication de cellulose à base de sodium, comme par exemple le procédé alcalin au sulfite sous apport d'anthraquinone et de méthanol ou le procédé basique, éventuellement acide, au sulfite de sodium, la lessive résiduaire est brûlée dans une chaudière de combustion (1) avec extraction sous forme liquide des scories, les gaz brûlés sont soumis à un procédé d'épuration à plusieurs stades successifs avec une récupération sous forme sèche des cendres volantes, et les composés sulfureux gazeux sont également séparés dans un procédé de lavage à plusieurs stades successifs. Les constituants solubles dans l'eau des cendres volantes sont acheminés jusqu'à la lessive résiduaire à brûler, ce qui augmente le volume de soufre récupéré dans les scories. Les scories sont dissoutes dans l'eau et les composés sodium dissous convertis en bicarbonate de sodium et en H2S par une opération de carbonisation à plusieurs stades successifs, avec une partie des gaz brûlés et épurés. Le H2S est brûlé et est converti en sulfite de sodium, de manière à obtenir la lessive désirée pour la dissolution de la cellulose, à partir du sulfite de sodium et du carbonate de sodium.
EP94912988A 1993-04-05 1994-03-31 Procede de conversion du sulfate de sodium Expired - Lifetime EP0693145B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AT682/93 1993-04-05
AT0068293A AT398992B (de) 1993-04-05 1993-04-05 Verfahren zur umwandlung von natriumsulfat
PCT/AT1994/000038 WO1994023124A1 (fr) 1993-04-05 1994-03-31 Procede de conversion du sulfate de sodium

Publications (2)

Publication Number Publication Date
EP0693145A1 true EP0693145A1 (fr) 1996-01-24
EP0693145B1 EP0693145B1 (fr) 1997-09-17

Family

ID=3497044

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94912988A Expired - Lifetime EP0693145B1 (fr) 1993-04-05 1994-03-31 Procede de conversion du sulfate de sodium

Country Status (8)

Country Link
US (1) US5759345A (fr)
EP (1) EP0693145B1 (fr)
AT (1) AT398992B (fr)
AU (1) AU6532294A (fr)
CA (1) CA2160008C (fr)
DE (1) DE59404103D1 (fr)
FI (1) FI954695A0 (fr)
WO (1) WO1994023124A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007036380A1 (de) * 2007-07-31 2009-02-05 Voith Patent Gmbh Verfahren und Anlage zur Aufbereitung der Ablauge eines Sulfitverfahrens
FI125337B (fi) * 2010-10-18 2015-08-31 Andritz Oy Menetelmä ja järjestely epäpuhtauksien erottamiseksi nesteistä tai höyryistä
CN102874769B (zh) * 2012-10-09 2014-07-02 广西大学 碱熔物中硫化钠的氧化转化方法及装置
CN109233884A (zh) * 2018-10-17 2019-01-18 四川锐源能环科技有限公司 一种液态危险废物处理***
US10888818B2 (en) * 2019-01-15 2021-01-12 Honeywell International Inc. Integrated mercaptan extraction and/or sweetening processes combined with thermal oxidation and flue gas treatment
CN111717897A (zh) * 2019-03-19 2020-09-29 萍乡市华星环保工程技术有限公司 一种采用硫泡沫制酸的方法
CN115401054B (zh) * 2022-09-16 2023-04-07 贵州中蓝环保科技有限公司 一种无害化处理电解锰渣的方法
CN115716078A (zh) * 2022-10-17 2023-02-28 北京中科国润环保科技有限公司 二氧化碳资源化利用的方法和***

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3366535A (en) * 1966-07-11 1968-01-30 William T Neiman Process for regenerating waste liquor for reuse in kraft pulping operation
US3826710A (en) * 1972-04-21 1974-07-30 Owens Illinois Inc Carbonation system for recovery of sodium base pulping liquor
US4148684A (en) * 1976-11-08 1979-04-10 Mei Systems Inc. Methods for recovery and recycling of chemicals from sodium sulfite and sodium bisulfite pulping operations
AT351359B (de) * 1977-06-08 1979-07-25 Erco Envirotech Ltd Verfahren zur entfernung des natriumchlorids bei der herstellung von zellstoff
SE448173B (sv) * 1985-06-03 1987-01-26 Croon Inventor Ab Forfarande for utvinning av kemikalier fran cellulosaavlut genom pyrolys
SE456254B (sv) * 1987-02-12 1988-09-19 Korsnes Ab Sett att rena gronlut i sulfatmassafabrikers kemikalieatervinning
AT398440B (de) * 1991-10-25 1994-12-27 Waagner Biro Ag Verfahren zur rückgewinnung der chemikalien der kochlauge
JP3447112B2 (ja) * 1994-05-23 2003-09-16 アルインコ株式会社 作業台の伸縮脚

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9423124A1 *

Also Published As

Publication number Publication date
US5759345A (en) 1998-06-02
CA2160008A1 (fr) 1994-10-13
FI954695A (fi) 1995-10-03
DE59404103D1 (de) 1997-10-23
AT398992B (de) 1995-02-27
CA2160008C (fr) 2001-06-12
WO1994023124A1 (fr) 1994-10-13
FI954695A0 (fi) 1995-10-03
EP0693145B1 (fr) 1997-09-17
AU6532294A (en) 1994-10-24
ATA68293A (de) 1994-07-15

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