WO2004042140A1 - クラフトパルプの製造方法 - Google Patents
クラフトパルプの製造方法 Download PDFInfo
- Publication number
- WO2004042140A1 WO2004042140A1 PCT/JP2003/011606 JP0311606W WO2004042140A1 WO 2004042140 A1 WO2004042140 A1 WO 2004042140A1 JP 0311606 W JP0311606 W JP 0311606W WO 2004042140 A1 WO2004042140 A1 WO 2004042140A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pulp
- liquor
- sodium
- caustic soda
- recovered
- 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
- D21C11/06—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
- D21C11/04—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
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/1026—Other features in bleaching processes
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/40—Production or processing of lime, e.g. limestone regeneration of lime in pulp and sugar mills
Definitions
- the present invention relates to a method for producing kraft pulp.
- the basic method of producing kraft pulp is caustic soda and sodium sulfide.
- A a pulp washing step of washing the obtained pulp and separating and collecting a black liquor containing sodium carbonate and soda sulfate converted from the cooking liquor (B), treating the pulp with a bleaching agent in the presence of an alkali
- a black liquor combustion step (E) in which soda and sodium carbonate are collected from the flue gas by a dust collector, and a green liquor, which is a water solution of the smelt collected in the combustion step, is treated with quick lime.
- the chemical recovery is closed and the chemical recovery rate is further increased.
- sodium carbonate and sodium sulfate have been collected from the collected ash collected by the dust collector from the combustion exhaust gas in the combustion process (E).
- the above-mentioned publication discloses a potassium ion adsorption / removal step using a Na type strongly acidic ion exchange resin, a polyvalent metal ion adsorption / removal step using a chelate resin, and a chloride ion separation step using an amphoteric ion exchange resin.
- the methods of regenerating the Na-type strongly acidic ion exchange resin and the chelate resin that require chemical regeneration include, for example, a method in which an acid (eg, aqueous hydrochloric acid) is passed and then a solution of sodium hydroxide or saline is passed.
- a method is described in which an aqueous solution of caustic soda is passed after passing an acid (for example, aqueous hydrochloric acid).
- FIG. 1 is a process chart of an example of the method for producing kraft pulp of the present invention.
- FIG. 2 is an outflow curve obtained in the power stream ion removal step of Example 1. Disclosure of the invention
- the present inventors have earnestly studied and obtained the following findings. That is, in the bleaching process of treating pulp with a bleaching agent in the presence of alkali, high-purity caustic soda is used as an alkali.
- a method of passing an aqueous solution of caustic soda is used as a method for regenerating the sodium-type cation exchange resin, a sodium hydroxide wastewater containing a large amount of potassium ions is produced as a by-product.
- a caustic soda effluent can be used in the above-mentioned bleaching process as well as high-purity caustic soda.
- the present invention has been completed based on the above-mentioned findings, and has selected a method of using an aqueous solution of sodium hydroxide as a method of regenerating a sodium-type cation exchange resin. This is the invention that was used.
- the gist of the present invention is a digestion step (A) in which raw chips are treated with a cooking liquor containing caustic soda and sodium sulfide as a main component and converted into pulp, the obtained pulp is washed and converted from the cooking liquor.
- a black liquor concentration step (D) in which the collected black liquor is concentrated, the concentrated black liquor is burned to reduce sodium sulfate to sodium sulfide, and further contains sodium sulfate and soda carbonate from a flue gas by a dust collector.
- causticizing process (F) In the process for producing kraft pulp, the white liquor recovered in the causticizing process (F) is circulated to the digestion process (A). Collected ash A potassium ion removal step (G) for adsorbing and removing the potassium ion by passing the aqueous solution of water through a packed bed of a sodium-type cation exchange resin; and a cation exchange resin used in the potassium ion removal step (G).
- a regeneration step (H) using an aqueous solution of caustic soda is provided, and a fraction rich in sodium sulfate and sodium carbonate recovered from the potassium ion removal step (G) is circulated to the black liquor concentration step (D).
- a method for producing a kraft pulp characterized in that the caustic soda effluent recovered in the regeneration step (H) is reused in the bleaching step (C).
- the method for producing kraft pulp of the present invention is basically the same as a conventionally known method, and includes a cooking step (A), a pulp washing step (B), a pulp bleaching step (C), and a black liquor concentration step (D ), Black liquor combustion step (E) and causticizing step (F). These steps are performed according to known conditions.
- raw chips are treated in a digester with a cooking liquor containing caustic soda and sodium sulfide as a main component, and converted into pulp.
- the processing of raw material chips is performed under high temperature and high pressure.
- the temperature is 150-160 ° C and the pressure is 8.5-9.5 KgZcn ⁇ G.
- the pulp obtained above is washed, and a black liquor (a washing liquor containing the pulp digestion liquor) containing sodium carbonate and sodium sulfate converted from the digestion liquor is separated and recovered. I do.
- the black liquor contains organic substances in the chip together with chemical components.
- the solid content in the black liquor is usually 15 to 25% by weight.
- the pulp is treated with a bleach in the presence of an alkali.
- treatment with various chemicals is performed as follows. For example, (1) chlorine or chlorine dioxide bleaching ⁇ alkali extraction-hypochlorite bleaching ⁇ chlorine dioxide bleaching, (2) chlorine or chlorine dioxide bleaching-extraction of hypochlorite ⁇ bleaching of hypochlorite ⁇ alkaline bleaching Extraction ⁇ chlorine dioxide bleaching, etc., and some of these methods are omitted.
- the alkali extraction stage completes the digestion, oxygen bleaching, chlorination and subsequent lignin removal steps. Da is mainly used.
- E p hydrogen peroxide
- EH hypochlorite
- E op oxygen is also used in combination
- ECF chlorine-free and hypochlorite-free chlorine-free bleaching
- the black liquor discharged from the pulp washing step (B) with a solids concentration of 15 to 25% by weight is concentrated in an evaporator until the black liquor becomes flammable. I do. Normally, it is concentrated until the solid concentration becomes about 70 to 80% by weight.
- the concentrated black liquor is burned to reduce sodium sulfate to sulfurated soda. That is, black liquor is injected into the furnace of the boiler, and a mountain called a char at about 100 ° C. is formed at the furnace bottom and burned. Then, the smelt (chemical component) that has been melted at a temperature of about 800 ° C at the furnace bottom is recovered. Furthermore, in the black liquor combustion process (E), the collected ash containing sodium sulfate and sodium carbonate is collected from the flue gas by a dust collector arranged in the flue of the boiler.
- green liquor which is a water solution of the smelt recovered in the combustion step
- quick lime the sodium carbonate in the green liquor is converted to caustic soda to obtain a white liquor.
- Quicklime is converted to lime sludge.
- a step of removing sludge from a milk liquid (emulsion) containing lime sludge to clarify white liquor and burning the separated lime sludge in a kiln And then return it to quicklime again.
- the white liquor converted in the causticizing step (F) is used as a cooking liquor in the cooking step (A).
- the aqueous solution of the collected ash collected from the flue gas in the black liquor combustion step (E) by a dust collector is converted to a sodium-type cation exchange resin. Pass through a packed bed to adsorb and remove potassium ions
- a potassium ion removal step (G) and a regeneration step (H) of the cation exchange resin used in the potassium ion removal step (G) using an aqueous solution of caustic soda are provided.
- hot water is used for dissolving the collected ash in water in consideration of the solubility of the collected ash in the case of a dry electric dust collector.
- the ash recovery liquid obtained from the attached wet scrubber can be used. Usually, 3 to 10 times the weight of the collected ash is used.
- sodium-type cation exchange resin for example, "Diaion (registered trademark) UBK550" manufactured by Mitsubishi Chemical Corporation) is suitable.
- An ordinary ion exchange column is used to form a packed bed of the cation exchange resin.
- the hourly space velocity (SV) is usually 1 to 10 hr- 1 and the temperature is usually 20 to 80 ° C. The continuation of such flow causes the leakage of potassium ions to start. At this point, the liquid supply is stopped.
- the adsorbed potassium ions are desorbed by passing an aqueous solution of caustic soda.
- the potassium ion removal process (G) supply of the collected ash water solution is stopped due to leakage of potassium ions. Since the collected ash water solution is stored in the ion exchange tower, it is washed with water to replace it with water. Subsequently, an aqueous solution of caustic soda is supplied for regeneration of the cation exchange resin. At this time, the concentration of the aqueous solution of caustic soda used is usually 2 to 20%.
- the space velocity during regeneration is usually 1 to 1 hr- 1 and the temperature is usually 20 to 80 ° C.
- potassium ions are desorbed from the cation exchange resin, and regeneration to the sodium form is performed. By repeating the above operation, potassium ions can be continuously removed from the collected ash aqueous solution.
- the fraction (potassium removal liquid) rich in sodium sulfate and sodium carbonate recovered from the potassium ion removal step (G) is circulated to the black liquor concentration step (D).
- valuable components sodium carbonate and sodium sulfate
- the caustic soda effluent recovered in the regeneration step (H) is reused in the bleaching step (C). That is, it is supplied to the extraction stage in the bleaching process (C).
- one or both of a step of adsorbing and removing polyvalent metal ions with a chelate resin and a step of separating chloride ions with an amphoteric ion exchange resin may be provided as necessary.
- the order of the respective steps is preferably a polyvalent metal ion adsorption and removal step—a chloride ion separation step—a potassium ion removal step (G).
- the present invention is implemented as described above. Examples of the characteristic parts of the present invention, namely, the potassium ion removal step (G), the regeneration step (H), and the bleaching step (C) are shown below. It is not limited to the example.
- Cation exchange resin Mitsubishi Chemical's “Diaion UBK 550” trademark
- the solution was passed at a rate of 2 hr- 1 to adsorb potassium ions.
- Whiteness An index of the whiteness of pulp and paper, measured as Hunter whiteness with a digital center whiteness meter manufactured by Toyo Seiki Co., Ltd. (Compliant standard: JISP 81)
- Kappa monovalent One of the indicators of the degree of pulping and delignification of pulp, expressed as the number of m 1 of 1 Z 10 N permanganate power lime solution consumed by 1 g of dry pulp ( Compliant standard: TAP PIT 236).
- Viscosity an index of the average degree of polymerization of cellulose, from which the deterioration due to Palpig or bleaching can be relatively known (Standard: TAP PIT2
- ⁇ whiteness represents the difference in eight-degree whiteness before and after fading. It was measured with a digital hunter whiteness meter manufactured by Toyo Seiki Co., Ltd.
- PC value One of the methods of indicating fading, which was determined from the whiteness before and after the heat aging test at 105 ° C by the following formula.
- K and K0 are the light absorption coefficients after and before fading, respectively.
- S and S O are the light scattering coefficients before and after fading and before fading, respectively.
- Test Example 3 1.11 71.8 2.8 Average 1.14 72.0 2.8 Test Example 4 1.30 71.5 2.9 Test Example 5 1.19 72.2 2.8
- Test Example 6 1.37 72.0 2.8 Average 1.29 71.9 2.8
- the ratio of pulp alkali addition required for adjusting the outlet pH of the alkali extraction stage to 11 is 1.29% on average in the case of the current alkali extraction treatment (Comparative Example 1), while using recycled wastewater
- the result was 1.14% and the alkali addition rate was low. That is, the Al force in the present invention It was confirmed that the pulp quality and bleachability were not inferior to the conventional method by adopting the re-extraction method.
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Paper (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003268636A AU2003268636A1 (en) | 2002-11-05 | 2003-09-11 | Process for producing kraft pulp |
US10/533,460 US7553394B2 (en) | 2002-11-05 | 2003-09-11 | Method for removing potassium from ash produced in a kraft pulping process recovery boiler using a Na-type cation exchange organic resin |
BRPI0315901-9A BR0315901B1 (pt) | 2002-11-05 | 2003-09-11 | processo para produção de polpa kraft. |
EP03748523A EP1566480B1 (en) | 2002-11-05 | 2003-09-11 | Process for producing kraft pulp |
CA002504303A CA2504303C (en) | 2002-11-05 | 2003-09-11 | Process for producing kraft pulp |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002/320651 | 2002-11-05 | ||
JP2002320651A JP3811674B2 (ja) | 2002-11-05 | 2002-11-05 | クラフトパルプの製造方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004042140A1 true WO2004042140A1 (ja) | 2004-05-21 |
Family
ID=32310351
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2003/011606 WO2004042140A1 (ja) | 2002-11-05 | 2003-09-11 | クラフトパルプの製造方法 |
Country Status (8)
Country | Link |
---|---|
US (1) | US7553394B2 (ja) |
EP (1) | EP1566480B1 (ja) |
JP (1) | JP3811674B2 (ja) |
CN (1) | CN1288298C (ja) |
AU (1) | AU2003268636A1 (ja) |
BR (1) | BR0315901B1 (ja) |
CA (1) | CA2504303C (ja) |
WO (1) | WO2004042140A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006029478A3 (en) * | 2004-09-17 | 2008-02-21 | Orica Australia Pty Ltd | Effluent treatment process |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2025807A1 (en) * | 2007-07-25 | 2009-02-18 | Rinheat OY | Method to recover chemicals in mechanical pulping |
JP5127760B2 (ja) * | 2009-03-30 | 2013-01-23 | 三井造船株式会社 | 発酵残渣を用いた飼料の製造方法 |
FI126767B (en) * | 2012-11-16 | 2017-05-15 | Andritz Oy | Method for extracting the ash from a recovery boiler |
WO2015010179A1 (en) * | 2013-07-25 | 2015-01-29 | Noram Engineering And Constructors Ltd. | Method of reducing chloride and potassium ion concentrations in a pulp mill chemical recovery system |
CN103469696B (zh) * | 2013-09-26 | 2016-02-03 | 句容市植保植检站 | 一种牛皮纸及其制造方法 |
CN106731627B (zh) * | 2015-11-20 | 2019-09-20 | 金光纸业(中国)投资有限公司 | 烟气脱硫并将脱硫副产物循环利用的系统 |
CN106192539A (zh) * | 2016-08-26 | 2016-12-07 | 江苏理文造纸有限公司 | 一种牛皮箱板纸的制作工艺 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS52140702A (en) | 1976-05-20 | 1977-11-24 | Babcock Hitachi Kk | Removing method of sodium chloride at black-water collection boiler |
JPH05171586A (ja) | 1991-12-24 | 1993-07-09 | Oji Paper Co Ltd | クラフトパルプ蒸解廃液の脱塩方法 |
US5628874A (en) | 1992-08-24 | 1997-05-13 | Eka Nobel Ab | Reduction of chloride in pulping chemical recovery systems |
US5922171A (en) | 1997-01-24 | 1999-07-13 | Eco-Tec Limited | Method and apparatus for removing sodium chloride from pulping chemicals using an amphoteric ion-exchange resin |
US5980717A (en) | 1997-01-03 | 1999-11-09 | Eka Chemical Ab | Recovery process in a pulp mill |
JP2002138382A (ja) | 2000-10-31 | 2002-05-14 | Nippon Rensui Co Ltd | 蒸解薬品回収工程の捕集灰の処理方法 |
JP2002146691A (ja) | 2000-11-06 | 2002-05-22 | Nippon Rensui Co Ltd | 蒸解薬品回収工程の捕集灰の処理方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5616280A (en) * | 1993-08-25 | 1997-04-01 | Burlington Chemical Co., Inc. | Bleaching composition |
-
2002
- 2002-11-05 JP JP2002320651A patent/JP3811674B2/ja not_active Expired - Lifetime
-
2003
- 2003-09-11 US US10/533,460 patent/US7553394B2/en active Active
- 2003-09-11 AU AU2003268636A patent/AU2003268636A1/en not_active Abandoned
- 2003-09-11 CA CA002504303A patent/CA2504303C/en not_active Expired - Lifetime
- 2003-09-11 WO PCT/JP2003/011606 patent/WO2004042140A1/ja active Application Filing
- 2003-09-11 EP EP03748523A patent/EP1566480B1/en not_active Expired - Lifetime
- 2003-09-11 CN CNB038246899A patent/CN1288298C/zh not_active Expired - Lifetime
- 2003-09-11 BR BRPI0315901-9A patent/BR0315901B1/pt active IP Right Grant
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS52140702A (en) | 1976-05-20 | 1977-11-24 | Babcock Hitachi Kk | Removing method of sodium chloride at black-water collection boiler |
JPH05171586A (ja) | 1991-12-24 | 1993-07-09 | Oji Paper Co Ltd | クラフトパルプ蒸解廃液の脱塩方法 |
US5628874A (en) | 1992-08-24 | 1997-05-13 | Eka Nobel Ab | Reduction of chloride in pulping chemical recovery systems |
US5980717A (en) | 1997-01-03 | 1999-11-09 | Eka Chemical Ab | Recovery process in a pulp mill |
US5922171A (en) | 1997-01-24 | 1999-07-13 | Eco-Tec Limited | Method and apparatus for removing sodium chloride from pulping chemicals using an amphoteric ion-exchange resin |
JP2002138382A (ja) | 2000-10-31 | 2002-05-14 | Nippon Rensui Co Ltd | 蒸解薬品回収工程の捕集灰の処理方法 |
JP2002146691A (ja) | 2000-11-06 | 2002-05-22 | Nippon Rensui Co Ltd | 蒸解薬品回収工程の捕集灰の処理方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1566480A4 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006029478A3 (en) * | 2004-09-17 | 2008-02-21 | Orica Australia Pty Ltd | Effluent treatment process |
Also Published As
Publication number | Publication date |
---|---|
EP1566480A4 (en) | 2007-10-03 |
CN1288298C (zh) | 2006-12-06 |
CN1694987A (zh) | 2005-11-09 |
JP2004156154A (ja) | 2004-06-03 |
EP1566480B1 (en) | 2010-01-06 |
EP1566480A1 (en) | 2005-08-24 |
BR0315901A (pt) | 2005-09-20 |
JP3811674B2 (ja) | 2006-08-23 |
AU2003268636A8 (en) | 2004-06-07 |
US20060219375A1 (en) | 2006-10-05 |
CA2504303A1 (en) | 2004-05-21 |
CA2504303C (en) | 2009-10-06 |
US7553394B2 (en) | 2009-06-30 |
BR0315901B1 (pt) | 2012-10-30 |
AU2003268636A1 (en) | 2004-06-07 |
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