CN1312354C - Process for bleaching lignocellulose-containing non-wood pulp - Google Patents
Process for bleaching lignocellulose-containing non-wood pulp Download PDFInfo
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- CN1312354C CN1312354C CNB038072785A CN03807278A CN1312354C CN 1312354 C CN1312354 C CN 1312354C CN B038072785 A CNB038072785 A CN B038072785A CN 03807278 A CN03807278 A CN 03807278A CN 1312354 C CN1312354 C CN 1312354C
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- 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
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- 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
- D21C9/1042—Use of chelating agents
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- 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
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
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Abstract
The present invention refers to a process for bleaching lignocellulose-containing pulp comprising pulp obtainable from lignocellulose-containing materials selected from the group consisting of non-wood with a peroxide-containing compound, where the pulp prior to the bleaching is treated with chlorine dioxide, characterised in that the pulp after the treatment with chlorine dioxide is treated in a separate stage with a chelating agent at a pH up to about 2.9 and washed between the chlorine dioxide treatment and chelating agent treatment.
Description
The present invention relates to contain the method for the paper pulp of ligno-ccllulose with the compound bleaching that contains peroxide, described paper pulp comprises the paper pulp that can obtain from the lignocellulose-containing materials that is selected from non-wood material, wherein paper pulp is used chlorine dioxide treatment before bleaching, thereby the paper pulp after the chlorine dioxide treatment is handled under up to about 2.9 pH value with chelating agent in independent step, and washing between chlorine dioxide treatment and chelating agent processing.
Background technology
The present invention is intended to be derived from the bleaching of the paper pulp of non-wood material.In the area and/or the in plentiful supply area of non-wood material that obviously lack timber, for example India and China are not only economically feasiblely with non-wood material papermaking, also be used as the raw material of papermaking and making sheet to a great extent.If non-wood pulp is used for the product of brightness that need be to a certain degree, for example be used for papermaking, non-wood pulp has to bleach behind pulping process.In order to reduce the content of environment hazardous compound in the bleaching equipment waste liquid, should avoid some bleaching chemical, particularly adopt gaseous chlorine, albeit chlorine is special the selection and effective bleaching chemical.Other bleaching chemicals that can be used for substituting gaseous chlorine can be chlorine dioxide and contain the compound of peroxide for example.Therefore, an advantage of the invention is in mode cheaply, use eco-friendly bleaching chemical, promptly without gaseous chlorine, bleaching is derived from the paper pulp of non-wood pulp, and the non-wood pulp of the bleaching with high brightness and acceptable viscosity further is provided.
Chlorine dioxide and the compound that contains peroxide have been widely used in wanting to be used for the bleaching process of bleached hardwood and softwood pulp.The a large amount of different bleaching process of the bleaching wood pulp that is used to comprise chlorine dioxide stage and peroxide stage are disclosed.When bleaching is derived from the paper pulp of non-wood material, we find amazedly, comprising especially chlorine dioxide and containing in all countless operations of peroxide compound, providing special result on the paper pulp of non-wood material being derived from according to the specific method for bleaching of claims.Although the certain position of processing section of the present invention originally provides the result who improves on the paper pulp that is derived from non-wood pulp just, the bleaching process that the present invention proposes even more amazing is because the present invention is with particularly opposite about the general knowledge from the bleaching of the paper pulp of timber.According to general knowledge, when before the peroxide bleaching section, when in to the bleaching process of cork or hardwood, carrying out independently complexant processing, shown that the pH value between 5 to 7 provides desirable hardwood and the performance of softwood pulp, for example EP-A2-402335 in the complexant processing.In view of these facts, we find with having one's heart in one's mouth, and when the paper pulp of the non-wood material source of bleaching, the independently chelating agent that is arranged in before the peroxide stage is handled, and be starkly lower than 5 to 7 pH value best bleachability is provided.
And the non-wood pulp of bleaching is easy to make brightness to reset into minimum according to the present invention.Further advantages will be clear and definite below.
Another advantage is with only comprising three processing sections, and does not comprise and obtained the high brightness non-wood pulp by the low-cost method for bleaching of the compactness of washing section.Another advantage of bleaching process of the present invention is, dehydration behind the chelating agent processing section or washing section even can omit, and can significantly not destroy pulp property after the peroxide stage.
Above advantage obtains by the method for bleaching that proposes according to claims.More particularly, the present invention is intended to contain with the reagent bleaching that contains peroxide the method for the paper pulp of ligno-ccllulose, described paper pulp comprises the paper pulp that can obtain from the material of the lignocellulose-containing that is selected from non-wood material, wherein paper pulp is used chlorine dioxide treatment before bleaching, thereby the paper pulp after the chlorine dioxide treatment is handled in the highest about 2.9 pH value at Duan Zhongyong chelating agent independently, and between chlorine dioxide treatment and chelating agent are handled, washed.
Summary of the invention
The inventive method is used for effectively bleaching the paper pulp that contains ligno-ccllulose that comprises the paper pulp that can obtain from the lignocellulose-containing materials that is selected from non-wood material.Non-wood material is often referred to the annual plant material such as crops and crop residues.Word " non-wood " is the common definition in the technology of the present invention field, comprises in theory removing the material with wood feature, for example the material of all lignocellulose-containings beyond cork and the hardwood.The material that belongs in term " non-wood " scope is for example interior hide fiber, cereal hair, grass, leaf fibre.The example of grass is bamboo, cereal, bar, north African cogongrass, papyrus, reed (reed rod grass); Various straw from wheat, rye, oat, rice etc.; Sugarcane and bagasse are only mentioned small part.The kind of interior hide fiber is for example flax (seed flax), hemp, jute, mestha, ramine, bast fiber and their mixture, and cotton, cotton linter, kapok and their mixture are suitable cereal batt material.At last, aloe, sisal and abaca are the examples that belongs to leaf fibre class material.The present invention preferably is applied to be selected from reed and straw, and suitable is the material that is selected from the lignocellulose-containing of reed and straw.Non-wood and a wood difference relatively are the silica and the ash of high level in fact to be arranged in non-wood.Like this, non-wood pulp can differentiate with wood pulp aspect dioxide-containing silica.Therefore, this method for bleaching can suitably be applied to comprise and contain the dried fiber of 500ppm Si/ at least, the dried fiber of 800ppm Si/ at least preferably, the dried fiber of 1200ppm Si/ at least more preferably is most preferably at least on the lignocellulose-containing paper pulp of the paper pulp of the dried fiber of 1500ppm Si/.The dioxide-containing silica of non-wood material is measured by XRF analysis.
According to a preferred embodiment of the present invention, the paper pulp that is used for this method contains the non-wood pulp of at least 75% weight, and suitable is at least 85% weight.Preferably described paper pulp is basically by constituting from the paper pulp that non-wood material obtains.
Non-wood pulp suitably obtains by the applied chemistry pulping process.The non-wood slurrying of chemistry relates at the boiling method such as sulfate, sulphite, soda or organosolv method, or these methods use such as the improving one's methods of the nonessential additive of anthraquinone, for example the paper pulp of boiling in sodium anthraquinone (AQ) pulping process.Preferably, the non-wood pulp of lignocellulose-containing is by the preparation of alkali pulp-making method.The chemical pulp that can obtain from the lignocellulose-containing materials that is selected from non-wood material can then carry out one or more oxygen processing sections behind pulping process.
The inventive method can be applicable to initial card uncle number, and promptly after the boiling but the uncle of the card before oxygen delignification number, from about 5 to the most about 40 scope, suitable is from 8 to 30, preferably the non-wood pulp of from 8 to 18 chemical steaming.Alleged card uncle is several to measure according to the SCAN-C1:77 standard method.
The chlorine dioxide that adds non-wood pulp can prepare according to routine techniques.The bleached pulp productivity ratio of the bleaching equipment of design bleaching non-wood pulp significantly is lower than the conventional bleaching equipment of the timber of similar hardwood of bleaching and cork usually.Along with the productivity ratio reduction of bleaching equipment, the cost of bleached pulp per ton just increases usually.Therefore, for economically feasible non-wood material method for bleaching is provided, used bleaching chemical should preferably prepare with least cost.Therefore the chlorine dioxide that is applied to the inventive method preferably passes through to adopt the productivity ratio of chlorine dioxide at about 0.1 ton of ClO
2/ sky is to the highest about 12 tons of ClO
2Chlorine dioxide equipment in the/day scope prepares.This chlorine dioxide production equipment can be made up of one or several production unit.The pH value of useful the is chlorine dioxide of producing should be preferably lower than 2, promptly is lower than in the conventional method.The example of this appropriate method is SVP Pure
TMOr its modification.
The denseness of paper pulp is not crucial in the chlorine dioxide treatment section, can be about 1-40% weight, preferably 3-30% weight), more preferably about 5-15% weight.PH value in the chlorine dioxide stage is can be obviously different, but generally in the 1.5-5 scope, that suitable is 2-3.Paper pulp is used chlorine dioxide treatment 3 minutes-2 hours usually in 20-90 ℃ of temperature range.In order to obtain the fully paper pulp of bleaching, suitable chlorine dioxide addition is equivalent to 0.05-0.6, preferably 0.1-0.5, the more preferably card of the 0.2-0.4 uncle factor.Card uncle's factor is that the card uncle number of the active chlorine content (%) of the dry pulp paper pulp that entered the bleaching section removes.
After the chlorine dioxide treatment section non-wood pulp is washed.Used term " washing " relates to the waste liquid of replacing fully more or less in the pulp suspension in this method, to reduce the method for the trace metal ion content that dissolves in for example described suspension.Washing methods will bring the increase of pulp density, for example by drawing or squeezing.Washing methods also can cause pulp density to reduce, and for example dilutes by cleaning solution.Washing also can cause wherein, and pulp density replaces method and the operation that increases and reduce.
The pH value of washing section should suitably be selected, and makes to add extra additional chemicals such as acid or alkali compounds in subsequently chelating agent is handled.As mentioned above, chlorine dioxide stage is carried out under acid or acid ph value.Two sections it is desirable to chlorine dioxide stage and chelating agent section and can add any additional chemicals and carry out, because all can be carried out under similar pH value scope.Therefore, another advantage of the present invention be the additional chemicals that need to add seldom carry out in suitable pH value scope because chlorine dioxide treatment and chelating agent are handled.
After the carrying out washing treatment, handle non-wood pulp at Duan Zhongyong chelating agent independently.According to the present invention as seen, not only specific pH value scope is very important for the effect of this method, and chelating agent add the implantation site for realizing that excellent bleaching results is also very important.By after chlorine dioxide stage, washing non-wood pulp, then at Duan Zhongyong chelating agent independently in the most about 2.9 pH value pulp treatment, not necessarily carry out washing section subsequently, non-wood pulp suspension becomes and is suitable for then bleaching with the compound that contains peroxide.Suitable chelating agent is an organic compounds containing nitrogen, mainly is nitrogenous polybasic carboxylic acid, nitrogenous polyphosphonic acid and nitrogenous polyalcohol.Preferably nitrogenous polybasic carboxylic acid is diethylene-triamine pentaacetic acid (DTPA), ethylenediamine tetra-acetic acid (EDTA) or nitrilotriacetic acid(NTA) (NTA).EDTA is preferably nitrogenous polybasic carboxylic acid.Other compounds also can be used as chelating agent, polybasic carboxylic acid for example, and suitable is oxalic acid, citric acid or tartaric acid, or the phosphonic acids of similar diethylenetriamines penta methylene phosphonic acid.In addition, such as also can be used as chelating agent with the organic acid that forms during the chlorine-free bleaching agent pulp treatment particularly.
Handling suitable with chelating agent is at about 1.5-2.9, and preferably about 2-is about 2.9, carries out in the pH value scope of most preferably about 2.5-about 2.9.
Can influence bleaching efficiency with the temperature in the chelating agent processing.About 120 ℃ at about 20-of suitable temperatures during chelating agent is handled, about 100 ℃ of preferably about 40-is in the about 90 ℃ of scopes of most preferably about 55-.
The addition of chelating agent depends on the kind and the content of inorganic compound in the particularly pending non-wood pulp.Addition also is subjected to the chelating agent type, and such as the influence of the treatment conditions of temperature, the time of staying and pH value.The suitable addition of chelating agent is calculated as the about 10kg of the about 0.1-of paper pulp per ton with 100% chelating agent.Preferably addition is calculated as paper pulp 0.3-5kg per ton with 100% chelating agent, even more suitably is dry pulp 0.5-2.5kg per ton.
Pulp density during chelating agent is handled can be about 60% weight of about 1-, and suitable is 2.0-40% weight, 3.0-25% weight preferably, and only is 5.0-15% weight.
The chelating agent processing time was generally about 1 minute-Yue 2 hours, preferably 20 minutes-1 hour.
The chelating agent section is preferably carried out under the situation that does not have chlorine dioxide basically, because most of basically chlorine dioxide is by the washing section flush away.
If special adding acid can be adopted the acid that obtains easily in the pulp mill in chelating agent is handled.The example of appropriate acid is such as the inorganic acid of sulfuric acid, nitric acid, hydrochloric acid or sour from the remnants of chlorine dioxide reaction device, can independently add or add with form of mixtures.
Chelating agent can wash non-wood pulp after handling.Yet if omitted carrying out washing treatment after chelating agent is handled, bleaching efficiency can not be subjected to very big influence.Therefore, according to preferred implementation of the present invention, behind chelating agent processing section independently and before, there is not washing section with the compound treatment that contains peroxide.
Detersive efficiency can relatively provide by the liquid amount mutually that exists in the liquid removed and the preceding pulp suspension of washing.Total detersive efficiency calculates with the efficient sum in each washing section.Like this, behind processing section, the dehydration of pulp suspension is from the pulp thickness of for example 10-25%, and then to be diluted with water to the detersive efficiency that 10% pulp thickness obtains be 66.7%.Behind washing section subsequently, wherein paper pulp further is diluted to 3%, is dewatered to 25% then, and total detersive efficiency is 96.9%.Particularly the detersive efficiency in the washing section after chelating agent is handled can be low to moderate approximately 25%, and can significantly not destroy pulp property.Suitable detersive efficiency scope is about 25-100%, more preferably about 25-75%.
Chelating agent is handled the back then with the bleaching non-wood pulp that contains peroxide compound, the described compound that contains peroxide can be the inorganic peroxide compound such as hydrogen peroxide or peroxidating one sulfuric acid (permonosulphuric acid), or the inorganic peroxide compound of similar aliphatic peracid and aromatics peracid and their salt.Suitable organic peroxide is peracetic acid and performic acid.The compound that preferably contains peroxide is the mixture of hydrogen peroxide or hydrogen peroxide and peracetic acid, is commonly referred to equilibrium peracetic acid.It most preferably is hydrogen peroxide.If adopt equilibrium peracetic acid, its pH value should preferably remain on for example acid range of 3-6.5 and the alkaline range of for example 8-12 respectively in peroxide stage.By changing change pH values, the bleaching of peracetic acid and hydrogen peroxide and delignification effectiveness all are utilized effectively.When adopting hydrogen peroxide, the pH value of pulp suspension should suitably be higher than 7, preferably in the pH value scope of about 7-about 13.More preferably be that the pH value is in the 8-12 scope.Most preferably pH value scope is 9.5-11.5.The hydrogen peroxide bleaching temperature is about 130 ℃ of about 30-, preferably 50-100 ℃, more preferably 50-90 ℃.The hydrogen peroxide treatment time can be about 3-960 minute, and suitable is 10-360 minute, preferably 60-240 minute.Hydrogen peroxide treatment is carried out under normal pressure usually, yet the hydrogen peroxide bleaching section can be pressurizeed, particularly when oxygen uses with hydrogen peroxide.Suitable pressure is the about 7bar of 1.5-, preferably 2-5.5bar.Pulp thickness is generally 1-70% weight, and suitable is 3-59% weight, most preferably 9-30% weight.The hydrogen peroxide addition depends on pending non-wood pulp type and peroxide bleaching condition, and the brightness of expectation.The addition of hydrogen peroxide is calculated with 100% hydrogen peroxide and is generally the about 60kg of the about 1-of dry pulp per ton.Higher limit is not crucial, only proposes for economic reasons.Suitable amount of hydrogen peroxide is at dry pulp 6-50kg per ton, dry pulp 13-40kg scope preferably per ton.The hydrogen peroxide bleaching section can add other bleaching agents such as oxygen.
Method for bleaching of the present invention can carry out an optional position in bleaching process, for example carries out immediately after such as the pulping process of chemical steaming method, or carries out after initial oxygen delignification is handled, and described oxygen is handled and comprised one or more sections suitably.Handle if the non-wood pulp after the chemical pulping is carried out oxygen delignification, the suitable card uncle number of paper pulp is lower than 20 after the oxygen delignification, is preferably lower than 10.
Non-wood pulp can further be bleached in one or more bleaching sections after with the compound treatment that contains peroxide, although can obtain the non-wood pulp (being higher than 85%ISO) of high brightness after the peroxide compound processing with the oxygen enhancing.Preferably, the bleaching agents that use with the one or more bleaching sections after the compound treatment that contains peroxide are selected from the essentially no chlorine bleach such as chlorine dioxide, inorganic peroxide with similar for example hydrogen peroxide, peroxidating one sulfuric acid, or organic peracid, normally aliphatic peracid, aromatics peracid or their salt contain peroxide bleaches.Organic peracid commonly used is peracetic acid and performic acid.Ozone and sodium dithionite also are the examples of available bleaching agent.
According to a preferred embodiment of the present invention, paper pulp is by the method bleaching without gas chlorine.
The present invention will further specify by following examples, yet not constitute limitation of the scope of the invention.The percentage of explaining among specification, claims and the embodiment and part refer to percentage by weight and weight portion respectively, except as otherwise noted.PH value when the pH value that provides among specification, claims and the embodiment refers to each processing section end, unless otherwise indicated.The addition of chlorine dioxide is by calculated as active chlorine.In addition, 100%Mg on all hydrogen peroxide sections add with dry pulp
2+Be calculated as the magnesium sulfate of 300ppm, dry pulp per ton adds the 30kg hydrogen peroxide, unless otherwise indicated.
In following examples, the card of paper pulp uncle number, viscosity and brightness are measured according to SCAN standard method C1:77R, C15-16:62 and C11-75:R respectively.The hydrogen peroxide consumption amount is measured by the iodometry of sodium thiosulfate.
The brightness of restoring is being measured on the paper of following heat treatment after 16 hours with 120 ℃.The content of magnesium and manganese is to the paper pulp that enters last P stage ICP commercial measurement in the paper pulp.The content of silica XRF commercial measurement in the paper pulp.
Embodiment 1
To block that uncle's number is 10.2, brightness is that 35.1%ISO, dioxide-containing silica are that 2000ppm and viscosity are 1171dm
3The sodium anthraquinone of the non-oxygen delignification of/kg (AQ) reed pulp in all tests with chlorine dioxide (D) bleaching, handle and with hydrogen peroxide (P) bleaching, so that explanation is handled the importance of reed pulp, the independently location of chela the present agent processing section and the pH value during the chelating agent section at Duan Zhongyong chelating agent independently with EDTA (Q).Reed pulp in test 1 earlier under 60 ℃ of temperature with dry pulp per ton 30kg chlorine dioxide treatment, 30 minutes time of staying, pulp thickness 10% weight, pH value are 2.1.Use EDTA pulp treatment (Q section) then.The addition of EDTA is that dry pulp 2kg per ton, pH value are 2.8,6 ℃ of temperature, 30 minutes time of staying, pulp thickness 10% weight.Then use hydrogen peroxide bleaching paper pulp (P section), pH value 10.5,240 minutes time of staying, 90 ℃ of temperature, pulp thickness 10% weight.The hydrogen peroxide addition is dry pulp 30kg per ton.In order to contrast, be 6.8 (tests 2) with the final pH value in the EDTA processing, other experimental condition is identical with test 1.In addition, hydrogen peroxide bleaching (test 3) is preceding further using, and reed pulp elder generation handles with 5.9 pH value with EDTA, then bleaches with 2.0 pH value with chlorine dioxide.Except EDTA with pH value level in the chlorine dioxide stage is slightly different, its condition is identical with three processing sections in the test 1.Handle reed pulp at last in two sections operations, wherein paper pulp is handled with dry pulp 30kg chlorine dioxide per ton and dry pulp 2kg EDTA per ton earlier, then with 30kg hydrogen peroxide treatment per ton (test 4).In conjunction with the EDTA/ chlorine dioxide stage in the pH value be 3.0.30 minutes processing times, 60 ℃ of temperature, pulp thickness 10% weight.Condition during the hydrogen peroxide section is identical with test 1.Behind each processing section in above-mentioned all tests, spend deionised water paper pulp, obtain 96.9% detersive efficiency according to standard method.All pH values are measured and are all carried out at the processing section end, i.e. the final pH value.
Table I, reed pulp
| Test | Pulp property after the hydrogen peroxide section | |||||
| Brightness (%ISO) | Viscosity (dm 3/kg) | Card uncle number | The Mg/Mn mol ratio | Residual hydrogen peroxide (kg/t) | The brightness (%ISO) of restoring | |
| 1：D-Q(pH 2.8)-P | 86.5 | 959 | Be lower than 1.0 | 18 | 5.6 | 82.6 |
| 2：D-Q(pH 6.8)-P | 83.8 | 879 | Be lower than 1.0 | 68 | 3.0 | - |
| 3：Q-D-P | 81.7 | 867 | 1.1 | 19 | 0 | - |
| 4：(DQ)(pH 3.0)-P | 77.4 | 870 | 1.1 | 16 | 0 | 74.5 |
Obvious from Table I, lower pH value in the Q section, promptly the highest by 2.9 (test 1), higher pH value (test 2) comparison with 6.8 has significantly improved brightness and viscosity.In addition, by test 1 and test comparison shows that the position of Q section is very important in operation between 3, and from test 1 with test 4 relatively as seen, the Q section is independently section.
Embodiment 2
In the present embodiment,, original intensity 42.5%ISO, viscosity 1013dm several 11.6 according to the operation of describing among the embodiment 1 (test 1,2 and 4) bleaching initial card uncle
3The soda AQ wheat straw paper pulp of the non-oxygen delignification of/kg and dioxide-containing silica 10000ppm.Therefore, all the condition with embodiment 1 stage casing is identical for the condition of processing section in the test, and the pH value that different is in some section is slightly different as shown in Table II, and wheat straw paper pulp is handled with dry pulp 20kg chlorine dioxide per ton (D section) in all tests.The pH value is about 10 in the P section in all tests.After above-mentioned every section, spend deionised water paper pulp according to standard technology, obtaining detersive efficiency is 96.9%.
Table II, wheat straw paper pulp
| Test | Pulp property after the hydrogen peroxide section | ||||
| Brightness (%ISO) | Viscosity (dm 3/kg) | The Mg/Mn mol ratio | Residual hydrogen peroxide (kg/t) | Card uncle number | |
| 1：D(pH 2.1)-Q(pH 2.7)-P | 84.0 | 1044 | 106 | 19.2 | 2.2 |
| 3：Q(pH 6.1)-D(pH 3.5)-P | 82.6 | 950 | 116 | 11.0 | 2.3 |
| 4：(DQ)(pH 6.1)-P | 80.8 | 912 | 140 | 4.4 | 2.8 |
The Table II explanation, if bleach (test 1) according to the present invention, wheat paper pulp is that a kind of performance of straw pulp just obtains improving.
Embodiment 3
In order to contrast, will block that uncle's number is 16.3, brightness is 35.3, viscosity is 1106dm
3The sulphate softwood pulp ClO 2 bleaching of the oxygen delignification of/kg in independently Duan Zhongyong EDTA bleaching, is used hydrogen peroxide bleaching then at last.Described softwood pulp is at first used the chlorine dioxide of dry pulp 25kg per ton, handles 30 minutes under pH 2.1 and 60 ℃ of temperature.Pulp thickness is 10% weight.PH value in the EDTA processing section is respectively 2.8 (tests 1) and 6.1 (tests 2).The addition of EDTA is dry pulp 2kg per ton, 30 minutes time of staying, 60 ℃ of temperature, pulp thickness 10% weight.Described paper pulp at last with the test 1 of embodiment 1 under the identical condition, with dry pulp 30kg hydrogen peroxide bleaching per ton.After above-mentioned every section, spend deionised water paper pulp according to standard technology, obtaining detersive efficiency is 96.9%.
Table III, softwood pulp
| Test | Pulp property after the hydrogen peroxide section | ||||
| Brightness (%ISO) | Viscosity (dm 3/kg) | The Mg/Mn mol ratio | Card uncle number | Residual hydrogen peroxide (kg/t) | |
| 1：D-Q(pH 2.8)-P | 84.8 | 847 | 30 | 2.3 | 7.2 |
| 2：D-Q(pH 6.1)-P | 85.9 | 853 | 452 | 2.2 | 12.1 |
As shown in Table III, when the bleaching wood pulp, during softwood pulp,, be 6.1 for example if pH value be 5-7 in the independently Q section before the peroxide treatment section herein, just can obtain the pulp property of the best.It is shocking, if with identical compound with identical sequential processes non-wood pulp, if the pH value in the Q section is up to 2.9, pulp property just be improved significantly (seeing Table I).
Embodiment 4
The soda AQ wheat straw paper pulp of used identical non-oxygen delignification among another batch and the embodiment 2 is bleached according to the present invention.In the pH value is before 2.8 (Q sections), 60 ℃ of temperature, dry pulp per ton add 2kg EDTA, handle 30 minutes EDTA processing section, earlier with dry pulp 20kg chlorine dioxide per ton (D section), with pH 2.2 and 60 ℃ of following bleached pulps 30 minutes.After chelating agent is handled, dry pulp per ton 30kg hydrogen peroxide,, temperature 90 ℃ following bleached pulps about 10 240 minutes in the pH value.Pulp thickness during D section, Q section and the P section is respectively 10%.Paper pulp after the D section spends deionised water according to standard technology, and obtaining detersive efficiency is 96.9%.Yet the detersive efficiency after chelating agent is handled is different as shown in Table IV.Treatment conditions in each section are corresponding with the condition in embodiment 1 test 1.
Table IV, bleaching process D-Q-P
| Test | Detersive efficiency * (％) | Brightness (%ISO) | Card uncle number | Residual hydrogen peroxide (kg/t) | Viscosity (dm 3/kg) |
| 1 | 29 | 84.7 | 2.2 | 11.9 | 966 |
| 2 | 65 | 85.1 | 2.0 | 14.2 | 989 |
| 3 | 97 | 85.3 | 1.9 | 18.4 | 1004 |
*How many cumulative volumes detersive efficiency refers to have replaced by deionized water in the dilution of P section and chemicals from the filtrate of Q section.
As shown in Table IV, low-down detersive efficiency (test 1) does not have the brightness of paper pulp after the remarkable destroying hydrogen peroxide section.
Embodiment 5
The soda AQ wheat straw paper pulp of the used identical non-oxygen delignification of another batch and embodiment 4 is used for present embodiment, and the bleaching according to the present invention.Paper pulp carries out chlorine dioxide treatment earlier, then is the EDTA processing section, then under 110 ℃ of temperature, with the hydrogen peroxide bleaching paper pulp 150 minutes (PO section) of oxygen enhancing.In the PO section, dry pulp per ton is used the 40kg hydrogen peroxide, and oxygen pressure is 0.5MPa.The D section is identical with embodiment 4 with treatment conditions in the Q section.PH value after the PO section is about 10.The test 1 in, paper pulp after D section and PO section, yet after the Q section, do not wash.In test 2, paper pulp washs after D section, PO section and Q section.Washing section carries out according to standard technology, and the gained detersive efficiency is 96.9%.
Table V, step D-Q-PO
| Test | Brightness (%ISO) | Card uncle number | The brightness (%ISO) of restoring | Viscosity (dm 3/kg) |
| 1:D-Q (pH 2.8)-(not washing)-PO | 87 | 1.3 | 81.1 | 841 |
| 2：D-Q(pH 2.8)-PO | 88 | 1.2 | 81.1 | 911 |
As shown in Table V, non-wood pulp can be by only just bleaching high brightness with three processing sections.The not final brightness of apparent damage of washing after the Q section.
Claims (11)
1, a kind of usefulness contains the method for paper pulp of the compound bleaching lignocellulose-containing of peroxy, described paper pulp obtains from the material of the lignocellulose-containing that is selected from non-wood material, wherein paper pulp is used chlorine dioxide treatment before bleaching, it is characterized in that: with the paper pulp after the chlorine dioxide treatment independently the section in, under the highest 2.9 pH, handle with chelating agent, and washing between chlorine dioxide treatment and chelating agent processing.
2, according to the method for claim 1, it is characterized in that: the paper pulp of lignocellulose-containing comprises and contains the paper pulp of 500ppm silica at least.
3, according to the method for claim 1, it is characterized in that: paper pulp obtains from the material of the lignocellulose-containing that is selected from wheat and reed and their mixture.
4, according to the method for claim 1, it is characterized in that: the compound that contains peroxy is a hydrogen peroxide.
5, according to the method for claim 1, it is characterized in that: the pH value during chelating agent is handled is 1.5 to 2.5.
6, according to the method for claim 1, it is characterized in that: chelating agent is selected from organic compounds containing nitrogen.
7, according to the method for claim 1, it is characterized in that: paper pulp is being handled the back washing with chelating agent.
8, according to the method for claim 1, it is characterized in that: in one or more sections, further bleach the brightness of 85%ISO at least with the paper pulp after the compound bleaching that contains peroxy.
9, according to the method for claim 1, it is characterized in that: paper pulp is without the gas chlorine bleach.
10, according to the method for claim 1, it is characterized in that: the material of lignocellulose-containing is by the chemical method boiling.
11, according to the method for claim 1, it is characterized in that: paper pulp prepares with alkaline method.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE02009819 | 2002-03-28 | ||
| SE0200981A SE0200981D0 (en) | 2002-03-28 | 2002-03-28 | Process for bleaching lignocellulose-containing non-wood pulp |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1643209A CN1643209A (en) | 2005-07-20 |
| CN1312354C true CN1312354C (en) | 2007-04-25 |
Family
ID=20287449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038072785A Expired - Fee Related CN1312354C (en) | 2002-03-28 | 2003-03-27 | Process for bleaching lignocellulose-containing non-wood pulp |
Country Status (5)
| Country | Link |
|---|---|
| CN (1) | CN1312354C (en) |
| AU (1) | AU2003216028B2 (en) |
| CO (1) | CO5611215A2 (en) |
| SE (1) | SE0200981D0 (en) |
| WO (1) | WO2003083208A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050051288A1 (en) * | 2003-09-09 | 2005-03-10 | Caifang Yin | Extended retention and medium consistency pulp treatment |
| FI123102B (en) * | 2006-03-31 | 2012-11-15 | Laennen Tutkimus Western Res Inc Oy | Chemical pulp bleaching process |
| FI122626B (en) * | 2006-03-31 | 2012-04-30 | Laennen Tutkimus Western Res Inc Oy | Chemical pulp bleaching process |
| JP4967451B2 (en) | 2006-05-17 | 2012-07-04 | 三菱瓦斯化学株式会社 | Method for producing bleached pulp |
| CN101451313B (en) * | 2007-12-05 | 2012-01-25 | 山东福荫造纸环保科技有限公司 | Method for preparing bleached chemical pulp by using grass type plants as raw materials |
| CN101451312B (en) * | 2007-12-05 | 2012-05-02 | 山东福荫造纸环保科技有限公司 | Method for preparing bleached chemical pulp by using grass type plants as raw materials |
| CN101812812B (en) * | 2009-02-25 | 2012-08-08 | 山东福荫造纸环保科技有限公司 | Elemental chlorine free bleaching method for plant fiber stuff |
| CN104179056A (en) * | 2013-05-23 | 2014-12-03 | 中国制浆造纸研究院 | Wheat straw pulp elemental-chlorine-free bleaching wastewater recycling method |
| CN104928964B (en) * | 2014-03-18 | 2017-02-15 | 中国科学院大连化学物理研究所 | Method for reducing generation of dioxins in non-wood pulp papermaking chlorine bleaching process |
| KR101806632B1 (en) * | 2015-12-04 | 2018-01-11 | 현대자동차주식회사 | Wet paper friction material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0622491A2 (en) * | 1993-04-20 | 1994-11-02 | Eka Nobel Ab | Method for bleaching lignocellulose-containing pulp |
| CN1157644A (en) * | 1994-08-31 | 1997-08-20 | 瑞典商顺智公司 | Pulp bleaching |
| WO1998021400A1 (en) * | 1996-11-08 | 1998-05-22 | Sunds Defibrator Industries Ab | Prebleaching of paperpulp before a peroxide bleaching stage |
| US6258208B1 (en) * | 1994-04-05 | 2001-07-10 | Mo Och Domsjo Aktiebolag | Method for complex treatment of pulp in conjunction with a chlorine dioxide stage |
| US6302997B1 (en) * | 1999-08-30 | 2001-10-16 | North Carolina State University | Process for producing a pulp suitable for papermaking from nonwood fibrous materials |
-
2002
- 2002-03-28 SE SE0200981A patent/SE0200981D0/en unknown
-
2003
- 2003-03-27 CN CNB038072785A patent/CN1312354C/en not_active Expired - Fee Related
- 2003-03-27 WO PCT/SE2003/000512 patent/WO2003083208A1/en not_active Application Discontinuation
- 2003-03-27 AU AU2003216028A patent/AU2003216028B2/en not_active Ceased
-
2004
- 2004-10-25 CO CO04106973A patent/CO5611215A2/en active IP Right Grant
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0622491A2 (en) * | 1993-04-20 | 1994-11-02 | Eka Nobel Ab | Method for bleaching lignocellulose-containing pulp |
| US6258208B1 (en) * | 1994-04-05 | 2001-07-10 | Mo Och Domsjo Aktiebolag | Method for complex treatment of pulp in conjunction with a chlorine dioxide stage |
| CN1157644A (en) * | 1994-08-31 | 1997-08-20 | 瑞典商顺智公司 | Pulp bleaching |
| WO1998021400A1 (en) * | 1996-11-08 | 1998-05-22 | Sunds Defibrator Industries Ab | Prebleaching of paperpulp before a peroxide bleaching stage |
| US6302997B1 (en) * | 1999-08-30 | 2001-10-16 | North Carolina State University | Process for producing a pulp suitable for papermaking from nonwood fibrous materials |
Also Published As
| Publication number | Publication date |
|---|---|
| SE0200981D0 (en) | 2002-03-28 |
| CO5611215A2 (en) | 2006-02-28 |
| WO2003083208A1 (en) | 2003-10-09 |
| CN1643209A (en) | 2005-07-20 |
| AU2003216028A1 (en) | 2003-10-13 |
| AU2003216028B2 (en) | 2006-03-16 |
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