EP0088456B1 - Procédé pour l'élimination continue d'acide silicique des liqueurs usées provenant de la préparation de cellulose - Google Patents

Procédé pour l'élimination continue d'acide silicique des liqueurs usées provenant de la préparation de cellulose Download PDF

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Publication number
EP0088456B1
EP0088456B1 EP83200178A EP83200178A EP0088456B1 EP 0088456 B1 EP0088456 B1 EP 0088456B1 EP 83200178 A EP83200178 A EP 83200178A EP 83200178 A EP83200178 A EP 83200178A EP 0088456 B1 EP0088456 B1 EP 0088456B1
Authority
EP
European Patent Office
Prior art keywords
silica
sludge
separator
liquor
lime
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.)
Expired
Application number
EP83200178A
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German (de)
English (en)
Other versions
EP0088456A1 (fr
Inventor
Jürgen Mülder
Pedro Gutmann
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.)
GEA Group AG
Original Assignee
Metallgesellschaft AG
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 Metallgesellschaft AG filed Critical Metallgesellschaft AG
Priority to AT83200178T priority Critical patent/ATE19416T1/de
Publication of EP0088456A1 publication Critical patent/EP0088456A1/fr
Application granted granted Critical
Publication of EP0088456B1 publication Critical patent/EP0088456B1/fr
Expired legal-status Critical Current

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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
    • D21C11/04—Regeneration of pulp liquors or effluent waste waters of alkali lye
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S210/00—Liquid purification or separation
    • Y10S210/928—Paper mill waste, e.g. white water, black liquor treated
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S423/00—Chemistry of inorganic compounds
    • Y10S423/03—Papermaking liquor

Definitions

  • the invention relates to a process for the continuous removal of silica from cellulose waste liquor (black liquor) obtained by alkaline digestion of annual plants such as bamboo, bagasse, reeds and straw, the waste liquor being brought into intensive contact with CO 2 -containing gas and silica precipitates that one precipitates from the waste liquor treated with C0 2 precipitated silica as silica sludge in a first separating device, and that a silicic acid phase is causticized in a stirred tank by adding lime or milk of lime, whereby a sludge is formed, which in a second separating device from the liquid phase is separated.
  • Such a method is known from DE-A-3003090, wherein partial de-silicification is carried out by treating the waste liquor with CO 2 -containing gas and precipitated silica is separated off.
  • the partially silicified waste liquor from the first separation device is passed into the stirred tank, in which the causticization takes place.
  • the invention has for its object to provide an environmentally friendly method, wherein the silicate-containing waste product should be easy to remove and, if necessary, usable.
  • this is done according to the invention in that the pulp waste liquor is pre-concentrated to a concentration of 8 to 30% by weight dry matter in an evaporation device before the treatment with CO 2 -containing gas, by containing the amount of CO 2 -containing Gases to 30 to 40 m 3 per m 3 of spent liquor measured that a decilified waste liquor and silica sludge are discharged from the first separating device, that the silica sludge is completely fed to the stirred tank for causticization, whereby one also dilutes with water and washes that one Caustify and wash the Na 2 O-SiO 2 -CaO ratio in the sludge that is formed in the stirred tank to the lowest melting temperature, that the decalcified waste liquor produced in the first separating device is passed into the evaporation device and that the separated in
  • Flue gas is preferred as the gas containing CO 2 . This has the advantage that it is cheap and occurs in your own process.
  • the CO 2 content here can be very low and, for example, less than 5% by volume.
  • the waste liquor to be treated is first advantageously preconcentrated to a concentration of 12 to 25% by weight of dry substance.
  • the preconcentrated waste liquor is preferably brought into contact with the CO 2 -containing gas in a jacket-heated reaction vessel by means of a pipe bend exhaust gas gas, with a particularly intensive mass exchange taking place.
  • the precipitate precipitated by the treatment with the gases containing CO 2 can be separated from the waste liquor by sedimentation or centrifugation.
  • the separated silica sludge is diluted with water in a ratio of 1: 4 to preferably 1: 1 and washed.
  • Quicklime or milk of lime is preferably added to the washing water in an amount sufficient to convert the soda content of the precipitate into sodium hydroxide solution.
  • Organic compounds contained in the precipitate are removed by burning them out and a melt is produced which leaves the incinerator. This is cooled in the air flow and can e.g. B. ground using a grinder with sieve to granules of desired grain size. The granulate can be disposed of in an environmentally friendly manner or reused.
  • the advantages achieved by the invention are, in particular, that a simple process which can be carried out continuously can be used to remove silicic acid to a residual content of 0.2 to 0.4 g / l from leaching liquor, which in the alkaline digestion of annual plants, such as bamboo, Bagasse, reeds, straw, can be obtained, remove.
  • leaching liquor which in the alkaline digestion of annual plants, such as bamboo, Bagasse, reeds, straw, can be obtained, remove.
  • By setting the melting point to a low melting point it can be melted down in conventional coal, gas or oil combustion boilers.
  • the process is very economical because, with the exception of small amounts of lime, e.g. B. in the form of quicklime or milk of lime, no foreign chemicals are required.
  • the flue gas generated in your own process is available for decilification.
  • the process works in an environmentally friendly way.
  • the invention is shown schematically in the drawing, for example, and is described in more detail below.
  • Fiber-free thin liquor with a minimum concentration of 8% dissolved dry substance is pumped from the evaporation device 2 to the reaction vessel 4 of the decilification system.
  • flue gas the temperature of which should be above the dew point to prevent moisture precipitation, is blown into the container 4, which is designed as a pipe bend fumigator, via a blower 10.
  • the action of the pipe elbow fumigator creates intensive contact between the lye and the flue gas.
  • the exhaust gases escape via a mechanical foam separator via the dome of the reactor 4.
  • the treated lye leaves the reactor at the desired pH via a siphon and arrives at a continuously operating device 12 for separating the precipitated substances (centrifuge or sedimentation funnel and centrifuge). After separating the precipitate from the alkali, the clear filtrate is conveyed to an intermediate container 13.
  • the separated silica sludge is pumped into a stirred tank 14. For sludge washing, this is additionally charged with water and quicklime or milk of lime from a corresponding metering device 15. The amount of lime corresponds approximately to 1.5 to 2 times the stoichiometric requirement, based on the soda (Na 2 CO 3 ) content of the sludge.
  • the sludge suspension is drawn off and centrifuged on a separator or decanter 17.
  • the clear filtrate is passed to a separate stacking tank 18, from where it is either added to the clarified black liquor in the intermediate container 13 through line 19 or is used for other purposes.
  • the dewatered, washed sludge is fed to a combustion 22 to remove the remaining organic components still contained therein.
  • a melting process brought about by combustion leads to an environmentally friendly, landfillable or processable waste product after the melt has cooled and granulated.
  • the lowest possible melting point in the combustion 22 is set.
  • Such burning and melting can e.g. B. take place in a coal, gas or oil-fired steam boiler, which is provided for this purpose with a combustion chamber, the bottom of which is designed as a melting bed with an extraction device for the melt.
  • the inorganic components of the sludge from the first centrifuge 12 contain a certain amount of soda (Na 2 C0 3 ).
  • soda milk - Ca (OH) 2 - is added via the metering device 15 to the wash water from line 16 in a 1.5 to 2-fold stoichiometric ratio to the amount of soda present, the causticizing process

Landscapes

  • Removal Of Specific Substances (AREA)
  • Paper (AREA)
  • Silicon Compounds (AREA)
  • Processing Of Solid Wastes (AREA)
  • Treatment Of Sludge (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Treating Waste Gases (AREA)

Claims (4)

1. Procédé d'élimination en continu de l'acide silicique de la liqueur de préparation de la cellulose (liqueur noire), obtenu par attaque alcaline de plantes annuelles, comme le bambou, la bagasse, le roseau et la paille qui consiste à mettre la liqueur résiduaire en contact intense avec du gaz contenant du CO2, et à précipiter l'acide silicique, à séparer dans un premier dispositif de séparation en forme de boue d'acide silicique l'acide silicique précipité de la liqueur traitée par le C02, à causti- fier dans un récipient de brassage, une phase contenant de l'acide silicique par addition de chaux ou de lait de chaux, en formant une boue que l'on sépare de la phase liquide dans un second dispositif de séparation, caractérisé en ce qu'il consiste à concentrer au préalable la liqueur résiduaire de préparation de cellulose, avant le traitement par du gaz contenant du C02, dans un dispositif d'évaporation, à une concentration de 8 à 30% en poids de substance sèche, à ajuster la quantité du gaz contenant du C02 entre 30 et 40 m3 par m3 de la liqueur résiduaire traversée, à évacuer du premier dispositif de séparation une liqueur résiduaire désilicée, et de la boue d'acide silicique, à envoyer la boue d'acide silicique entièrement au récipient de brassage pour la caustification, en diluant également par de l'eau et en lavant, à régler, lors de la caustification et du lavage dans le récipient de brassage le rapport Na20-SiO2-CaO de la boue qui se forme à la température de fusion la plus basse, à envoyer au dispositif d'évaporation la liqueur résiduaire désilicée se produisant dans le premier dispositif de séparation, et à brûler la boue séparée dans le second dispositif de séparation en créant une masse fondue qui est refroidie.
2. Procédé suivant la revendication 1, caractérisé en ce qu'il consiste à ajouter au récipient de brassage de l'eau de lavage, ainsi que pour la caustification, de la chaux vive ou du lait de chaux, en une quantité telle que le carbonate de sodium restant (Na2C03) dans la boue est transformé en lessive de soude.
3. Procédé suivant la revendication 1 ou 2, caractérisé en ce qu'il consiste à envoyer au dispositif d'évaporation la phase liquide obtenue dans le second dispositif de séparation, en même temps que la liqueur désilicée provenant du premier dispositif de séparation.
4. Procédé suivant la revendication 1, ou l'une des suivantes, caractérisé en ce qu'il consiste à refroidir et à granuler la masse fondue.
EP83200178A 1982-03-06 1983-02-03 Procédé pour l'élimination continue d'acide silicique des liqueurs usées provenant de la préparation de cellulose Expired EP0088456B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83200178T ATE19416T1 (de) 1982-03-06 1983-02-03 Verfahren zur kontinuierlichen entfernung von kieselsaeure aus zellstoffablaugen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19823208200 DE3208200A1 (de) 1982-03-06 1982-03-06 Verfahren zur kontinuierlichen entfernung von kieselsaeure aus zellstoffablaugen
DE3208200 1982-03-06

Publications (2)

Publication Number Publication Date
EP0088456A1 EP0088456A1 (fr) 1983-09-14
EP0088456B1 true EP0088456B1 (fr) 1986-04-23

Family

ID=6157565

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83200178A Expired EP0088456B1 (fr) 1982-03-06 1983-02-03 Procédé pour l'élimination continue d'acide silicique des liqueurs usées provenant de la préparation de cellulose

Country Status (6)

Country Link
US (1) US4504356A (fr)
EP (1) EP0088456B1 (fr)
JP (1) JPS58166983A (fr)
AT (1) ATE19416T1 (fr)
DE (2) DE3208200A1 (fr)
EG (1) EG15935A (fr)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6241390A (ja) * 1985-08-09 1987-02-23 株式会社荏原製作所 黒液濃縮方法および装置
AT393284B (de) * 1989-12-01 1991-09-25 Waagner Biro Ag Verfahren zur entkieselung der ablauge
AT401070B (de) * 1993-12-23 1996-06-25 Austrian Energy & Environment Verfahren zur gewinnung grobkörniger reiner kieselsäure
US5965027A (en) 1996-11-26 1999-10-12 Microbar Incorporated Process for removing silica from wastewater
US5871648A (en) * 1996-11-26 1999-02-16 Environmental Chemistries, Inc. Wastewater treatment process and apparatus for high flow impurity removal
US6428705B1 (en) 1996-11-26 2002-08-06 Microbar Incorporated Process and apparatus for high flow and low pressure impurity removal
US5900220A (en) * 1997-01-16 1999-05-04 Microbar Incorporated Soda ash processing method
US6398964B1 (en) 1999-08-19 2002-06-04 Koch Microelectronic Service Company, Inc. Process for treating aqueous waste containing copper and copper CMP particles
US6338803B1 (en) 1999-08-30 2002-01-15 Koch Microelectronic Service Co., Inc. Process for treating waste water containing hydrofluoric acid and mixed acid etchant waste
EP1094047A1 (fr) * 1999-10-22 2001-04-25 Technische Universiteit Delft Crystallisation de materiau a partir de solutions aqueuses
US6203705B1 (en) 1999-10-22 2001-03-20 Koch Microelectronic Service Company, Inc. Process for treating waste water containing copper
WO2005024125A1 (fr) * 2003-09-08 2005-03-17 Alberta Research Council Inc. Desilicification chimio-mecanique de matieres vegetales non ligneuses
US20060225852A1 (en) * 2005-04-11 2006-10-12 Jan Pekarovic Process for removing silica from cellulosic material
CN103693650B (zh) * 2013-12-25 2015-11-18 中盈长江国际新能源投资有限公司 利用生物质电厂稻壳灰和烟道气生产纳米二氧化硅和纳米碳酸钙的方法
CN113443737B (zh) * 2021-05-18 2022-05-13 中国环境科学研究院 一种制备改性草浆造纸白泥的工艺及脱硫生产石膏的工艺

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1231638A (fr) * 1957-01-15 1960-09-30 Pechiney Procédé de traitement des minerais d'aluminium
JPS5381705A (en) * 1976-12-24 1978-07-19 Hokusan Kk Regenerative treatment of waste liquor generated from pulping process oxidizing nonnwood plant by oxygen
JPS55103387A (en) * 1979-02-05 1980-08-07 Mitsubishi Heavy Ind Ltd Silica removal from pulp digesting liqur
US4331507A (en) * 1979-12-10 1982-05-25 Dorr-Oliver Incorporated Desilication in alkaline pulp processes
DE3003090A1 (de) * 1980-01-29 1981-08-13 Debendra Kumar Ph.D. Athinä Misra Verfahren zur entkieselung alkalischer ablaugen

Also Published As

Publication number Publication date
DE3208200A1 (de) 1983-09-08
US4504356A (en) 1985-03-12
JPH0225674B2 (fr) 1990-06-05
DE3363132D1 (en) 1986-05-28
EG15935A (en) 1988-03-30
EP0088456A1 (fr) 1983-09-14
JPS58166983A (ja) 1983-10-03
ATE19416T1 (de) 1986-05-15

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