CN1213722A - Process for bleaching of chemical paper pulps - Google Patents
Process for bleaching of chemical paper pulps Download PDFInfo
- Publication number
- CN1213722A CN1213722A CN98120727A CN98120727A CN1213722A CN 1213722 A CN1213722 A CN 1213722A CN 98120727 A CN98120727 A CN 98120727A CN 98120727 A CN98120727 A CN 98120727A CN 1213722 A CN1213722 A CN 1213722A
- Authority
- CN
- China
- Prior art keywords
- pulp
- bleaching
- chlorine dioxide
- paper pulp
- section
- 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.)
- Pending
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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
- 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
- D21C9/147—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications
-
- 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
- D21C9/1057—Multistage, with compounds cited in more than one sub-group D21C9/10, D21C9/12, D21C9/16
-
- 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
- D21C9/12—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds
- D21C9/14—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds with ClO2 or chlorites
-
- 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
- D21C9/16—Bleaching ; Apparatus therefor with per compounds
- D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Paper (AREA)
Abstract
The invention relates to a method for bleaching a chemical pulp containing at least one treating stage using chlorine dioxide after pulp boiled and optional prebleaching stage.
Description
The present invention relates to a kind of method for bleaching of chemical pulp.More particularly, theme of the present invention is: the method for bleaching that comprises the chemical pulp of a chlorine dioxide treatment section at least.
Chemical pulp or chemical pulp are to utilize one or more chemical agents, and by to ligno-cellulosic materials, particularly timber carries out boiling and the paper pulp that obtains.Therefore, in chemical pulp, be categorized into as follows:
Kraft pulp or sulfate pulp,
Sulfite pulp or bisulfites slurry,
Semi-chemical pulp or monosulfite pulp,
With the paper pulp after the solvent boiling,
As the paper pulp (A.18 " Ullmann chemistry engineering encyclopedia " Ullmann ' sEncyclopedia ofIndustrial Chemistry, rolls up 1991, the 568-569 pages or leaves by the 5th edition) that obtains by organic solvent method.
Wherein, can use all timber:
Needlebush, as various pines or fir,
Leaf wood, as birch, poplar, beech and eucalyptus.
Most chemical pulps that obtain by boiling all need stand several delignifications and/or bleaching processing section.
First section comprises by boiling and carries out complete delignification.Subsequently each section is the bleaching section.
By use gas phase chlorine, handle usually by chlorine dioxide or oxygen for first delignification stages.
The conventional processing section of using chlorine dioxide normally under normal pressure and acid pH, makes the reaction of paper pulp and aqueous solution of chlorine dioxide.In the incipient stage of this program, pH is between 2 and 3, and in the ending phase of this program, pH is between 4 and 5.
The operating condition that is different from conventional section use has formed many research topics.Therefore, US5,474,654 have disclosed a kind of method, in the method, and after boiling, the temperature of paper pulp between 40 and 90 ℃, the pH of acid medium stands to comprise chlorine dioxide between 1 and 6, the effect of oxygen and water vapour.
At US3,655, two sections bleachings have been disclosed in 505, according to this method, at first, make the paper pulp of 20-60% concentration stand to be diluted in inert gas such as air at 15-100 ℃, the effect of the gas phase chlorine dioxide in the water vapour, for the time 20 seconds to 60 minutes, then, wash and handle with hydrogen peroxide.
In addition, the method that is disclosed among the SE93 03037 comprises: at least one chlorine dioxide treatment section, described processing are at 90-100 ℃, carry out under the 0.1-10 bar pressure.As for the character of diluent gas or the pH value of medium, wherein without any indication.
In order limiting chlorinated secondary product to be entered in the environment, to have advised substituting the chlorination reaction agent with other oxidant.The article of C.L.Forber " replacement of chlorine and chlorine dioxide in the kraft pulp " " Chlorine andChlorine Dioxide Replacements in Kraft Pulp Bleaching:Emerging Technologiesor Laboratory Curiosities " (TAPPI Atlanta, Georgia 1993) point out, existing the some kinds of compounds with enough bleaching powers substitutes chlorine and carries out delignification, as if bleach and can't realize but substitute chlorine dioxide, fortune is because still demonstrate the efficient of chlorine dioxide without any reactant, selectivity and useful cost.
Although (AOX: amount absorbable organic halogen) reduces widely, yet fortune still is not enough to satisfy ecological requirement can to make organic chloride derivative in pulp mill's waste liquid with the alternative simply chlorine of chlorine dioxide in bleaching schedule.
The method for bleaching that the purpose of this invention is to provide a kind of chemical pulp, this method comprise at least one titanium dioxide oxygen processing section, and in the protection environment, the paper pulp that makes it to be bleached by force.
Realized this purpose by the method for bleaching of chemical pulp according to the present invention, according to described method, make paper pulp stand the program of some processing sections, described program comprises a section that wherein forms reactant mixture at least, in this section, paper pulp stands the processing of ClO 2 solution, it is characterized in that, depresses at oxygen to keep described reactant mixture.
Surprisingly, applicant's company finds, depresses at oxygen and operates the consumption that can not only reduce chlorine dioxide, and can also improve the whiteness of chemical pulp.
The treatment in accordance with the present invention section can be used in any section in the chemical pulp bleaching schedule.Preferably when EP (end of program), use.
Although this section insertion can be utilized in the conventional CEDED program of mol-chloric, usually preferably, use it in ECF (element-free chlorine) method for bleaching that chlorine wherein substituted fully by chlorine dioxide.
According to the present invention, between 1 and 10, preferably between 7 and 10, useful is between 7 and 9 to the pH value of reactant mixture usually.
Oxygen is pressed and can be changed in wide region; Usually oxygen is pressed in the 0.1-100 crust, preferably clings at 3-10.
Existing oxygen can be pure oxygen, or provides by air.
Reaction temperature is usually at 25-150 ℃, preferably at 40-90 ℃.
The processing time of chlorine dioxide was from 2 minutes to 5 hours.This time is preferably between 30 minutes and 2 hours.
The concentration of paper pulp is represented with respect to the percentage of paper pulp gross weight with dry matter weight.During with chlorine dioxide treatment, this concentration is usually between 1 and 30%, preferably between 5 and 15%.
With respect to the weight of dry in the paper pulp, the consumption of chlorine dioxide is generally 0.05 to 5% weight.With respect to the weight of dry in the paper pulp, its useful consumption is a 0.2-3% weight.Preferably use chlorine dioxide with the form of the aqueous solution, wherein concentration preferably 7 and 15g/l between.
Use the following examples will understand the present invention better.
In the following embodiments, D represents conventional chlorine dioxide treatment section, and E represents NaOH extracting section.Chlorine dioxide is to represent with respect to the percetage by weight of paper pulp dry matter weight.
Test portion
The concentration of aqueous solution of chlorine dioxide is 7g/l.
Whiteness is measured according to NF standard T12030.
Degree of polymerization DP measures according to Tappi standard 230om-89.
Total step
Paper pulp is added in stirring and the thermostatically controlled autoclave, and the volume of described autoclave is 1.5 liters, and the inside is coated with polytetrafluoroethylene (PTFE), then, closes this autoclave hermetically.When mixing, add low amounts of water,, and if necessary, regulate the pH of mixture with cushioning liquid (acetate (acetic), phosphate and borate) so that obtain desirable concentration.Then with the adjustment to 55 of reactant mixture ℃.Then add ClO 2 solution, and utilize oxygen or nitrogen that reactor is pressurizeed by airtight dropping funel.After reaction 30 minutes, stop heating.Make the autoclave degasification then, and from paper pulp, isolate bleaching liquid.Stay titanium dioxide chlorine dose in the bleaching liquid by the iodometry quantitative measurment then.At last, carrying out various measurements (whiteness, the degree of polymerization) before, with deionized water to the pulp washing several times.
Embodiment 1-9
The use softwood pulp is listed in the embodiment 1-9 in the table 1, described softwood pulp has carried out sulphate cook (the Kappa number KN=24.1 after the boiling that prolongs in advance, DP=1530, whiteness 29,1%) and carried out the pre-bleaching of DEDE program, and the degree of polymerization of this paper pulp is 1370, and the ISO whiteness is 69.9%.
The operating condition of the one D section of carrying out under normal pressure is as follows:
Pulp density=10%
The temperature of reactant mixture=55 ℃
The pH=2.5 of reactant mixture
Chlorine dioxide consumption=2%
Processing time=1 hour
With first section identical condition under carry out the 2nd D section of pre-bleaching, different is that the consumption of chlorine dioxide is reduced to 1%.
When this D section finishes, paper pulp is dehydrated, carry out the E section then.The operating condition of E section is as follows:
Pulp density=10%
The temperature of reactant mixture=70 ℃
NaOH consumption=2%
Normal pressure
Processing time=1 hour.
In embodiment 1-9, operation is in the presence of 0.5% chlorine dioxide, utilizes the paper pulp of 10% concentration to carry out.
Embodiment 1-3 carries out under normal pressure.
Embodiment 10-13
The use softwood pulp is listed in the embodiment 10-13 in the table 1, described softwood pulp has carried out boiling (Kappa number KN=24.1 after the boiling) that prolongs and the pre-bleaching that has carried out the DE program in advance, and the degree of polymerization of this paper pulp is 1420, and the ISO whiteness is 43.1%, and card uncle valency is 5.7.First period two steps of the program of using among the operating condition of pre-bleaching and the embodiment 1-9 are identical.
Under the described existence that operates in 1% (embodiment 10 and 12) and 1.6% (embodiment 11 and 13) chlorine dioxide, utilize the paper pulp (embodiment 10-13) of 10% concentration to carry out.
Table 1
| Embodiment | Pressure (crust) | The character of gas | ????pH | ％ClO 2Consume | Whiteness (%ISO) |
| ????1 | ????1 | Air | ????4.5 | ????83.5 | ????82.1 |
| ????2 | ????1 | Air | ????7 | ????71.0 | ????82.1 |
| ????3 | ????1 | Air | ????9 | ????54.0 | ????81.6 |
| ????4 | ????5 | Oxygen | ????4.5 | ????82.0 | ????82.6 |
| ????5 | ????5 | Oxygen | ????7 | ????73.5 | ????83.3 |
| ????6 | ????5 | Oxygen | ????9 | ????59.0 | ????83.0 |
| ????7 | ????5 | Nitrogen | ????4.5 | ????85.0 | ????82.6 |
| ????8 | ????5 | Nitrogen | ????7 | ????70.0 | ????82.9 |
| ????9 | ????5 | Nitrogen | ????9 | ????59.0 | ????81.4 |
| ????10 | ????1 | Air | ????3 | ????99.7 | ????65.9 |
| ????11 | ????1 | Air | ????3 | ????99.8 | ????65.5 |
| ????12 | ????3 | Oxygen | ????3 | ????99.4 | ????66.8 |
| ????13 | ????3 | Oxygen | ????3 | ????98.6 | ????68.0 |
Claims (7)
1. the method for bleaching of a chemical pulp, according to this method, paper pulp stands the program of some processing sections, described program comprises a section that wherein forms reactant mixture at least, and in this section, paper pulp stands the processing of chlorine dioxide, it is characterized in that, depress this reactant mixture of maintenance at oxygen.
2. according to the method for claim 1, it is characterized in that the pH of mixture is between 1 and 10.
3. according to the method for claim 2, it is characterized in that pH is between 7 and 10.
4. according to the method for one of claim 1-3, it is characterized in that oxygen is pressed between 3 and 10 crust.
5. according to the method for one of claim 1-4, it is characterized in that, with respect to the paper pulp dry matter weight, the consumption of chlorine dioxide from 0.05 to 5% weight.
6. according to the method for one of claim 1-5, it is characterized in that the temperature of reactant mixture is between 40 and 90 ℃.
7. according to the method for one of claim 1-6, it is characterized in that the concentration of paper pulp is between 5 and 15%.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9712367A FR2769327B1 (en) | 1997-10-03 | 1997-10-03 | PROCESS FOR BLEACHING CHEMICAL PAPER PULP |
| FR9712367 | 1997-10-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1213722A true CN1213722A (en) | 1999-04-14 |
Family
ID=9511814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98120727A Pending CN1213722A (en) | 1997-10-03 | 1998-09-25 | Process for bleaching of chemical paper pulps |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0906987A1 (en) |
| JP (1) | JPH11152693A (en) |
| KR (1) | KR19990036671A (en) |
| CN (1) | CN1213722A (en) |
| AU (1) | AU8787798A (en) |
| BR (1) | BR9803865A (en) |
| CA (1) | CA2246569A1 (en) |
| FR (1) | FR2769327B1 (en) |
| ID (1) | ID21153A (en) |
| MA (1) | MA24659A1 (en) |
| NO (1) | NO984593L (en) |
| ZA (1) | ZA988300B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101105011B (en) * | 2004-01-17 | 2010-05-12 | 梅秀泉 | Oxygen delignification and bleaching integration paste preparing method and device for realizing the same method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2706673A (en) * | 1951-10-19 | 1955-04-19 | Elmer R Burling | Method of bleaching with chlorine dioxide |
| DK0651832T3 (en) * | 1991-08-23 | 1998-05-11 | Olin Corp | Method for gas phase delignification of wood fiber pulp |
| WO1996015317A1 (en) * | 1994-11-10 | 1996-05-23 | Olin Corporation | Process for gas phase chlorine dioxide delignification |
-
1997
- 1997-10-03 FR FR9712367A patent/FR2769327B1/en not_active Expired - Fee Related
-
1998
- 1998-09-03 EP EP98402178A patent/EP0906987A1/en not_active Withdrawn
- 1998-09-10 ZA ZA988300A patent/ZA988300B/en unknown
- 1998-09-24 KR KR1019980039686A patent/KR19990036671A/en not_active Application Discontinuation
- 1998-09-25 CN CN98120727A patent/CN1213722A/en active Pending
- 1998-09-29 MA MA25275A patent/MA24659A1/en unknown
- 1998-10-01 JP JP10279873A patent/JPH11152693A/en active Pending
- 1998-10-01 NO NO984593A patent/NO984593L/en not_active Application Discontinuation
- 1998-10-02 AU AU87877/98A patent/AU8787798A/en not_active Abandoned
- 1998-10-02 CA CA002246569A patent/CA2246569A1/en not_active Abandoned
- 1998-10-02 BR BR9803865-6A patent/BR9803865A/en unknown
- 1998-10-02 ID IDP981319A patent/ID21153A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101105011B (en) * | 2004-01-17 | 2010-05-12 | 梅秀泉 | Oxygen delignification and bleaching integration paste preparing method and device for realizing the same method |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2769327B1 (en) | 1999-11-05 |
| EP0906987A1 (en) | 1999-04-07 |
| ZA988300B (en) | 1999-03-11 |
| MA24659A1 (en) | 1999-04-01 |
| JPH11152693A (en) | 1999-06-08 |
| BR9803865A (en) | 1999-12-07 |
| FR2769327A1 (en) | 1999-04-09 |
| NO984593L (en) | 1999-04-06 |
| ID21153A (en) | 1999-04-29 |
| KR19990036671A (en) | 1999-05-25 |
| AU8787798A (en) | 1999-04-22 |
| CA2246569A1 (en) | 1999-04-03 |
| NO984593D0 (en) | 1998-10-01 |
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