CN103261514A - Process for delignification and bleaching of paper pulp by using activated hydrogen peroxide - Google Patents
Process for delignification and bleaching of paper pulp by using activated hydrogen peroxide Download PDFInfo
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- CN103261514A CN103261514A CN2011800618263A CN201180061826A CN103261514A CN 103261514 A CN103261514 A CN 103261514A CN 2011800618263 A CN2011800618263 A CN 2011800618263A CN 201180061826 A CN201180061826 A CN 201180061826A CN 103261514 A CN103261514 A CN 103261514A
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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
- D21C9/16—Bleaching ; Apparatus therefor with per compounds
- D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
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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
- D21C3/00—Pulping cellulose-containing materials
- D21C3/003—Pulping cellulose-containing materials with organic compounds
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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
- D21C3/00—Pulping cellulose-containing materials
- D21C3/006—Pulping cellulose-containing materials with compounds not otherwise provided for
Abstract
The invention relates to a process for the delignification and bleaching of paper pulp, comprising at least one step of bringing the paper pulp into contact with hydrogen peroxide and a molybdenum-based complex of formula (I): in which R represents an unsaturated C5-C6 cycloalkyl group or an unsaturated C5-C6 heterocycloalkyl group, being substituted or unsubstituted, and Ar represents an aryl group, optionally having one or more substitution(s) on the aromatic ring(s) by one or more of the following groups: - linear or branched C1-C4 alkyl, - halogen, -NO2, -OH, -COOH.
Description
Invention field
The present invention relates to make for the hydrogen peroxide that uses activation the method for delignified pulp lignin and bleaching.
Technical background
The production of paper pulp uses timber as raw material.Timber particularly comprises cellulose fibre, and it is white and painted lignin in color.
Therefore, the preparation of paper means usually and makes this delignified pulp lignin (except delignification) and/or bleaching.For the production that remains paper with use required engineering properties, desirable is during this method damaged fiber element as few as possible.
For example, known use chlorine-containing compound (chlorine, chlorine dioxide, hypochlorite) is used for delignification and the bleaching of this paper pulp.Because the cost of these compounds and contain the generation of chlorine derivative in flowing out liquid seeks to reduce their use.
Also known use oxygen, ozone or hydrogen peroxide are as delignification and bleaching agent.Yet the use of these reagent positively is not gratifying.These reagent have inferior to the bleaching power of chlorinated products and/or specificity.Especially, these reagent can cause cellulosic degraded and higher content of lignin.High lignin content limits the whiteness of paper pulp and causes the flavescence of paper and too early wearing out.In addition, cellulosic depolymerization weakens this fiber and weakens the strength of paper of acquisition subsequently.
Make the hydrogen peroxide activation also cause cellulosic remarkable decomposition by high temperature.Therefore, catalytic activation technology for hydrogen peroxide has been proposed.
Especially, various transition metal of known use and/or be used for the activation of hydrogen peroxide based on the complex compound of transition metal.
For example, document WO03/080925 described based on use with copper-phenanthroline complex compound activation hydrogen peroxide for making association with pulp bleaching and delignified method.
Patent CA1129161 has described and has been used for making association with pulp bleaching and delignified method, and it uses the hydrogen peroxide by the metal ion activation that is selected from tungsten, molybdenum, chromium, osmium and selenium in acid medium.
Article
Catalysis and activation of oxygen and peroxide delignification of chemical pulps:a review,M. Suchy and D.S. Argyropoulos, April 2002, vol.1, No.2, Tappi Journal has looked back the various delignified researchs that improve paper pulp with oxygen or hydrogen peroxide that relate to.Document special event is used diperoxy molybdate complex compound in acid medium.
Article
Activation of alkaline peroxide delignification using a vanadium peroxo complex, M. Suchy and D.S. Argyropoulos, June 2000, vol.83, No.6, Tappi Journal relates to and used vanadyl complex in alkaline medium.
Yet, still be difficult to find in being reduced in paper pulp content of lignin and preserve between the cellulose gratifying compromise.
And, paper pulp under alkaline pH, implement usually by the bleaching of hydrogen peroxide and therefore need be in alkaline medium the activator of active hydrogen peroxide.In fact, as mentioned above, most art methods is used the hydrogen peroxide activator in acid medium.
Therefore still exist exploitation to compare improved demand be used to the method that makes delignified pulp lignin and bleaching with the method for prior art, the consumption that it allows to obtain more effective delignification and/or reduces cellulosic decomposition and/or reduce compound (chlorine-containing compound especially).Also there is the demand that remains the method that effectively makes delignified pulp lignin and bleaching when the alkaline pH to having.
The present invention's summary
The present invention at first relates to be used to the method that makes delignified pulp lignin and bleaching, comprises the step that at least one makes this paper pulp contact with the molybdenum base complex of hydrogen peroxide and formula (I):
Wherein:
R represents unsaturated C5-C6 cycloalkyl or unsaturated C5-C6 Heterocyclylalkyl, and it is for that replace or unsubstituted; With
Ar represents aryl, randomly have one or more aromatic rings with one or more linearities or branching C1-C4 alkyl, halogen ,-NO2 ,-OH ,-one or more replacements of COOH group.
Preferably, R represents C5 loop chain dialkylene (cycloalkyldi é nyle) group or C6 aryl, perhaps cyclopentadienyl group preferably.
Preferably, Ar represents phenyl.
This term " undersaturated C5-C6 cycloalkyl " is interpreted as expression, in meaning of the present invention, unsaturated cyclic carbon back group, its by or be not substituted and it can comprise 5 or 6 carbon atoms.Can mention for example cyclopentadienyl group.
" replacement " group is interpreted as atom or the atomic group of this group of expression, and hydrogen substitutes with C1-C6 alkyl, hydroxyl or halogen especially especially.
" " be interpreted as expression, in meaning of the present invention, as top defined unsaturated cycloalkyl, described cycloalkyl system comprises at least one hetero atom to undersaturated Heterocyclylalkyl to this term, and hetero atom is selected from sulphur, oxygen, nitrogen and phosphorus, preferred nitrogen especially.As the unsaturated heterocycle alkyl, can mention, for example, and pyridine, it is replaced by one of above-mentioned group or is not substituted.
" aryl " is interpreted as expression, in meaning of the present invention, comprises that at least one satisfies the aromatic systems of the ring of this H ü ckel aromaticity rule, namely comprise 4n+2 Pi (Π) electronics (n is natural integer) that can move at whole ring this term.Described aryl can comprise and has 6 to 24 carbon atoms, 6 to 12 carbon atoms for example, and (many) of 6 to 10 carbon atoms rings especially more particularly comprise the ring of 6 carbon atoms.Each ring of described aryl can comprise hetero atom.Described aryl randomly is substituted, and for example replaces with one of above-mentioned group.For example, aryl can be phenyl, benzyl chloride base, nitrobenzyl or tolyl.
Opposite with all expectations, with the activator of the hydrogen peroxide of prior art relatively, the basic molybdenum complex of Shi Yonging is verified in the method according to the invention is effective especially, even also is this situation in alkaline medium.Be not constrained in this theory, the inventor with this specific validity ascribe to exist the molybdenum transition metal that closes with acetylene-aryl bond, this acetylene-aryl key guarantee catalyst it various oxidation state Mo (V) and Mo (VI) in stablize.
Unless otherwise mentioned, otherwise hereinafter all percentages will provide as value by weight.
According to a kind of embodiment, oxygen-peroxide-cyclopentadienyl group-ethynylbenzene-molybdenum (VI) that this molybdenum base complex is formula (II):
(II)
According to a kind of embodiment, during making paper pulp and hydrogen peroxide and step that the molybdenum base complex contacts, the pH of this paper pulp is adjusted to 7 to 12, and preferably 7 to 11 value is preferably undertaken by adding NaOH.Keeping of alkaline pH allows to make it to be in acting as under the optimal conditions for hydrogen peroxide.Therefore be particularly advantageous according to molybdenum base complex of the present invention, this is because it remains effectively, even is also like this during the matter use in alkalescence is situated between at it.
According to a kind of embodiment, the step that this paper pulp and hydrogen peroxide are contacted with the molybdenum base complex is at 10 ℃ to 120 ℃, preferably 20 ℃ to 100 ℃, more particularly implements under 30 ℃ to 80 ℃ the temperature.
According to a kind of embodiment, the step that this paper pulp and hydrogen peroxide are contacted with the molybdenum base complex continues 1 minute to 4 hours, preferably 30 minutes to 3 hours time.
According to a kind of embodiment, during making this paper pulp and hydrogen peroxide and step that the molybdenum base complex contacts, the denseness of this paper pulp is the dry pulp of 1% to 40% weight, and the dry pulp of 5% to 30% weight preferably is with respect to the gross weight of this non-dry pulp.
" " be interpreted as expression as the concentration of defined paper pulp in the standard ISO 4119 in June, 1996: this is the ratio of moisture free weight with the weight of this unfiltered sample of its material that can filter from the sample of the paper pulp of form of suspension to denseness to this term, and this test is implemented according to described international standard.The concentration of paper pulp is here represented with percentage by weight.
Therefore " drying " paper pulp is interpreted as that expression comes the moisture free weight of the material of the sample of the form of suspension of definition in above-mentioned standard ISO 4119 freely, and it is measured after according to the filtration of described standard and drying.
According to a kind of embodiment, the initial content of the hydrogen peroxide during making this paper pulp and hydrogen peroxide and step that the molybdenum base complex contacts is less than or equal to 10% weight of dry pulp, 4% weight that preferably is less than or equal to dry pulp more particularly is 0.1% to 2% weight of dry pulp.
According to a kind of embodiment, the content of molybdenum base complex is 0.001% to 1% weight of dry pulp during making this paper pulp and step that hydrogen peroxide contacts, preferably 0.01% of dry pulp to 0.2% weight, preferably 0.01% of dry pulp to 0.1% weight.
According to a kind of embodiment, this method comprises:
The aqueous solution of-the precursor by the molybdenum base complex and the prepared in reaction molybdenum base complex of aqueous hydrogen peroxide adds the aqueous solution of molybdenum base complex then in the paper pulp; Perhaps
-be incorporated as the precursor of the molybdenum base complex of solid form or aqueous solution form to paper pulp.
The precursor of described molybdenum base complex is preferably formula CpMo (CO)
3The complex compound of (C ≡ CPh), wherein Cp representative ring pentadienyl and Ph represent phenyl.It is three carbonyls-cyclopentadienyl group-ethynylbenzene-molybdenum (VI) preferably.
Second kind of modification of this embodiment be advantageously: the molybdenum base complex in paper pulp by forming in position with the hydroperoxidation that has existed.Therefore do not need to add hydrogen peroxide.
The invention still further relates to for the preparation of with the method for pulp treatment, comprising:
The first step of-boiling timber is preferably carried out when NaOH and vulcanized sodium exist, in order to obtain paper pulp;
-randomly, use oxygen to make the preliminary step of delignified pulp lignin and bleaching;
-make delignified pulp lignin and bleaching according to aforesaid method of the present invention;
-randomly, by the alkali extraction and/or by the processing of use ozone and/or by the processing of use peracetic acid and/or by contacting the additional step that makes delignified pulp lignin and bleaching with hydrogen peroxide and/or chlorine-containing compound (as chlorine dioxide).
The additional step of this delignification and bleaching can indifference be located at one or more what is called " preparation " with delignification the method according to this invention and blanching step before or after.According to this additional step of the application choice of hope.
The invention still further relates to the method for the preparation of paper, comprise according to preceding method preparation and pulp treatment, make page and drying then.
Be understood that significantly paper pulp prepared according to the methods of the invention can not have above-mentioned molybdenum base complex and/or its precursor of any trace, this especially since washing, dilution operation and other especially purpose be the method for removing impurity.
The present invention allows to overcome the shortcoming of prior art.More particularly be provided for making the method for delignified pulp lignin and bleaching, the consumption that it allows to obtain more effective delignification and/or reduces cellulosic decomposition and/or reduce compound.The present invention remains the method that effectively makes delignified pulp lignin and bleaching when also being provided at alkaline pH, compare with the method for prior art.
This is by means of use formula (I), and more particularly the hydrogen peroxide of the molybdenum base complex of formula (II) activation is finished.
According to some specific embodiments, the present invention also demonstrates one or more following favorable characteristics preferably.
-comparing with using independent hydrogen peroxide, the present invention allows to obtain outstanding delignification's effect and causes cellulose fibre suitable or that reduce to decompose.
-comparing with using hydrogen peroxide according to the catalytic activation of prior art (for example use with the phenanthroline of copper complexing or use ammonium molybdate), the present invention allows still less the decomposition of cellulose fiber and obtains more effective delignification to act on (perhaps consuming still less hydrogen peroxide).
-to compare with the activator that only is the hydrogen peroxide of active prior art in acid medium, formula (I) or molybdenum base complex (II) remain effectively and therefore prove delignification and the bleaching that is particularly suitable for paper pulp in alkaline medium.
The molybdenum base complex of-Shi (II) allows especially effectively delignification's effect.
The explanation of embodiment of the present invention
The present invention is described and does not mean that restriction in the specification now below in more detail.
Comprise the step of boiling timber according to the preparation of paper pulp of the present invention, preferably when NaOH and vulcanized sodium exist, in order to obtain paper pulp (chemical pulp).
At 80 ℃ to 200 ℃, for example under 170 ℃ temperature, this boiling step can be implemented during 8 to 12 hours.
So the paper pulp that obtains carries out delignification and bleaching, perhaps only by using according to the present invention with the hydrogen peroxide of molybdenum base complex activation, perhaps before or after the processing that relates to the molybdenum base complex, by also using one or more additional treatments.
This additional treatments can be to use the processing of hydrogen peroxide (activate or do not activate with described molybdenum base complex), use oxygen processing, use ozone processing, use chlorine-containing compound, the processing of chlorine dioxide or use the processing of any other bleaching agent (peracetic acid etc.) especially.These processing can also be the conventional steps (extraction, washing, chelation etc.) of any known method for bleaching.
No matter when, compare with the processing of prior art, for in result suitable aspect delignification and the bleaching or that improve, allow to cause duration or the reagent consumption (for example using chlorine dioxide and/or peracetic acid) that reduces these additional treatments by means of the use of the processing of the hydrogen peroxide by the activation of molybdenum base complex.
Should be noted in the discussion above that use can implement only once or repeat to implement (for example twice) by the treatment step of the hydrogen peroxide of molybdenum base complex activation.
Relate between the continuous treatment step molybdenum base complex and/or additional at two, can suppress and wash this paper pulp.When all processing steps was finished, (presse-pate) carried out drying at the paper pulp press, and perhaps it is sent in the paper machine.
Molybdenum base complex used according to the invention has formula (I).Preferred molybdenum base complex is those of formula (II) in the present invention.It is complex compound oxygen-peroxide-cyclopentadienyl group-ethynylbenzene-molybdenum (VI).
Oxygen-peroxide-cyclopentadienyl group-ethynylbenzene-molybdenum (VI) complex compound has been described in the following document "
Selective oxidation of aromatic primary alcohols to aldehydes using molybdenum acetylide oxo-peroxo complex as catalyst", Ankush V. Biradar, Mohan K. Dongare, Shubhangi B. Umbarkar, Tetrahedron Letters, 50 (2009), 2885-2888.Yet it does not namely have instruction not have hint this complex compound to be applied to delignification and the bleaching of paper pulp yet.
Use means adding hydrogen peroxide and molybdenum base complex or its precursor in paper pulp by the treatment step of the hydrogen peroxide of molybdenum base complex activation.This contact procedure can be implemented according to different modification.
Can prepare the aqueous solution of molybdenum base complex especially by the precursor that in aqueous hydrogen peroxide solution, adds described complex compound in advance, add this solution to paper pulp then.
Can also add the molybdenum base complex on the one hand and add hydrogen peroxide on the other hand to paper pulp respectively.The molybdenum base complex can mix with aqueous solution form especially.
Can also add the precursor of one side molybdenum base complex and add hydrogen peroxide on the other hand to paper pulp respectively, make the molybdenum base complex in this paper pulp, form in position.The precursor of molybdenum base complex can be mixed with solid form or with aqueous solution form especially.
Described precursor for example is CpMo (CO)
3(C ≡ CPh) complex compound, wherein Cp representative ring pentadienyl and Ph represent phenyl.It is three carbonyls-cyclopentadienyl group-ethynylbenzene-molybdenum (VI) preferably.It is contemplated that other precursor, as long as they allow to form described molybdenum complex in this paper pulp.
Using the operating condition (denseness of paper pulp, time, temperature etc.) of the treatment step of hydrogen peroxide and molybdenum base complex or its precursor is those that specify above.
The amount of the lignin in paper pulp can be passed through Kappa number, measures according to the standard ISO 302 in July, 1987.
Cellulosic better or relatively poor preservation can characterize by the degree of polymerization in paper pulp.This uses by the viscosity measurement value of capillary viscometer method (Tappi method of testing T 230 om-08) measurement paper pulp and calculates.
As top explanation ground, the denseness of this paper pulp is corresponding to the pulp density as definition in the standard ISO 4119 in June, 1996.It is measured according to this standard.
The ratio of residual hydrogen peroxide can be measured by the iodometric titration test when this is finished dealing with.This method can be implemented with following manner:
When this processing finished, this paper pulp filtered according to this standard ISO 4119.With sulfuric acid solution (300 the gram/l) and liquor kalii iodide (100 g/l) join in this filtrate.KI release molecular iodine by hydrogen peroxide oxidation enters in this filtrate.So the molecular iodine that discharges is then by adding hypo solution (24.8 gNa continuously to filtrate
2S
2O
3.5H
2O/l) carry out titration.
If when this processing finishes, residual hydrogen dioxide, this expression can prolong this and handle to improve delignification and bleaching, maybe can reduce the priming dose of hydrogen peroxide.
Embodiment
Following examples can illustrate the present invention and not limit it.
The comparison of the bleaching of the present invention and use prior art
As the raw material that are used for following test, use Northern Europe cork chemical pulp of supplying with the form of oxygen delignification with in advance.This paper pulp demonstrates 11.3 Kappa number and 1540 the degree of polymerization at first.
Amount with the denseness that is enough to reach 10% weight dry pulp joins water in the paper pulp, with respect to the weight of non-dry pulp.
Three seed ginsengs is several measures according to said method for these.
Test 1: handle according to this molybdenum base complex of usefulness of the present invention
This pulp sample that will comprise the 20g dry pulp is incorporated in the plastic bag.
(as the percentage by weight with respect to the gross weight of dry pulp) below adding to this sample successively:
-0.4g (2 weight %) NaOH,
Three carbonyls-cyclopentadienyl group-ethynylbenzene-molybdenum (VI) of-0.01g (0.05 weight %),
-0.4g (2 weight %) H
2O
2
This molybdenum base complex, oxygen-peroxide-cyclopentadienyl group-ethynylbenzene-molybdenum (VI) forms in this paper pulp in position.It is present in wherein with the content of 0.044% weight, with respect to the gross weight of this dry pulp, thinks that the conversion that is incorporated into the precursor in the sample is completely.
Seal this sack and manually knead so that the mixture homogenising by heat bonding.It is immersed in the water-bath of 50 ℃ of temperature 3 hours.The paper pulp filtering that reclaims this sack and make acquisition by B ü chner filter (according to the standard ISO 4119 in June, 1996) so that filtrate separate with the fiber cake.
Below the measurement:
The pH of-filtrate
-measure the ratio of residual hydrogen peroxide in filtrate by above-mentioned iodometric titration method of testing
The Kappa number of-fiber cake,
The degree of polymerization of-fiber cake.
Test 1bis: according to the prepared beforehand of the solution of molybdenum base complex of the present invention
Preparation comprises 0.4g H in 50ml water
2O
2The aqueous solution.0.01 gram joined this solution for the precursor three carbonyls-cyclopentadienyl group-ethynylbenzene-molybdenum (VI) of solid form.Stirred this mixture 1 to 2 minute, and dissolved until precursor.
So obtain molybdenum base complex, the solution of oxygen-peroxide-cyclopentadienyl group-ethynylbenzene-molybdenum (VI).
Implement and the identical flow process that is used for embodiment 1, the paper pulp initial sample that comprises the 20g dry pulp is handled with following material (as the percentage by weight with respect to the dry pulp gross weight):
-0.4 the gram (2% weight) NaOH and
-so prepare the solution of molybdenum base complex.
Test 2 (contrast tests): use the processing of hydrogen peroxide separately
Implement and the identical flow process that is used for embodiment 1, the paper pulp initial sample that comprises the 20g dry pulp is handled with following material (as the percentage by weight with respect to the dry pulp gross weight):
-0.4 the gram (2% weight) NaOH and
The H of-0.4 gram (2% weight)
2O
2
Test 3 (contrast tests): with the processing of this copper-phenanthroline complex compound
Implement and the identical flow process that is used for embodiment 1, the paper pulp initial sample that comprises the 20g dry pulp is handled with following material (as the percentage by weight with respect to the dry pulp gross weight):
The NaOH of-0.4 gram (2% weight),
The H of-0.4 gram (2% weight)
2O
2And
Copper-phenanthroline the complex compound of the document WO 03/080925 of-0.01 gram (0.05% weight), copper (phenanthroline)
2
Test 4 (contrast tests): with the processing of permolybdic acid ammonium
Implement and the identical flow process that is used for embodiment 1, the paper pulp initial sample that comprises the 20g dry pulp is handled with following material (as the percentage by weight with respect to the dry pulp gross weight):
-0.4 the gram (2% weight) NaOH and
The H of-0.4 gram (2% weight)
2O
2And
Formula (the NH of-0.01 gram (0.05% weight)
4)
6Mo
7O
24.4H
2The ammonium molybdate of O.
The results are shown in the following table of bleaching.
* the ratio of residual hydrogen peroxide provides as percentage by weight, with respect to the gross weight that is incorporated into the hydrogen peroxide in the pulp sample at first.
These results show:
The use of-ammonium molybdate (test 4), though its representative saving aspect industrial cost does not more bring improvement with using copper-phenanthroline (test 3): its more bad ground delignification also makes the cellulose decomposition simultaneously.The individualism of this evidence transition metal molybdenum in activator is not enough to improve the performance of bleaching;
-according to molybdenum base complex of the present invention (test 1):
Permission activates hydrogen peroxide (Kappa number is lower than the Kappa number of test 2) in delignification,
Preserve cellulose (degree of polymerization that approaches with initial value and be higher than test 3 and 4 significantly),
The decomposition of restriction hydrogen peroxide (ratio of residual hydrogen peroxide is higher than test 3 and 4 significantly),
The paper pulp of handling according to the inventive method that obtains when test 1 finishes is subsequently:
-be sent to paper machine directly to carry out drying and to make page; Perhaps
-be sent to the paper pulp press to carry out drying and to be made as the page form in advance, put in the ball, to transfer to factory for the preparation of paper to stand with post processing there.
Claims (14)
1. make the method for delignified pulp lignin and bleaching, comprise the step that at least one makes this paper pulp contact with the molybdenum base complex of hydrogen peroxide and formula (I):
(I)
Wherein:
R represents unsaturated C5-C6 cycloalkyl or unsaturated C5-C6 Heterocyclylalkyl, and it is for that replace or unsubstituted; With
Ar represents aryl, randomly have one or more aromatic rings with one or more linearities or branching C1-C4 alkyl, halogen ,-NO2 ,-OH or-one or more replacements of COOH group.
2. according to the process of claim 1 wherein that R represents C5 loop chain dialkylene or C6 aryl, preferably cyclopentadienyl group.
3. according to the method for claim 1 or 2, wherein Ar represents phenyl.
4. according to each method of claim 1-3, wherein the molybdenum base complex is oxygen-peroxide-cyclopentadienyl group-ethynylbenzene-molybdenum (VI) of formula (II):
(II)
。
5. according to each method of claim 1-4, wherein during making paper pulp and hydrogen peroxide and step that the molybdenum base complex contacts, the pH of this paper pulp is adjusted to 7 to 12, preferably 7 to 11 value is preferably undertaken by adding NaOH.
6. according to each method of claim 1-5, the step that this paper pulp and hydrogen peroxide are contacted with the molybdenum base complex is at 10 ℃ to 120 ℃, preferably 20 ℃ to 100 ℃, more particularly implements under 30 ℃ to 80 ℃ the temperature.
7. according to each method of claim 1-6, the step that this paper pulp and hydrogen peroxide are contacted with the molybdenum base complex continues 1 minute to 4 hours, preferably 30 minutes to 3 hours time.
8. according to each method of claim 1-7, wherein during making this paper pulp and hydrogen peroxide and step that the molybdenum base complex contacts, the denseness of this paper pulp is the dry pulp of 1% to 40% weight, and the dry pulp of 5% to 30% weight preferably is with respect to the gross weight of this non-dry pulp.
9. according to each method of claim 1-8, wherein the initial content of the hydrogen peroxide during making this paper pulp and hydrogen peroxide and step that the molybdenum base complex contacts is less than or equal to 10% weight of dry pulp, 4% weight that preferably is less than or equal to dry pulp more particularly is 0.1% to 2% weight of dry pulp.
10. according to each method of claim 1-9, wherein the content of molybdenum base complex is 0.001% to 1% weight of dry pulp, preferably 0.01% of dry pulp to 0.2% weight during making this paper pulp and step that hydrogen peroxide contacts.
11. according to each method of claim 1-10, wherein this method comprises:
The aqueous solution of-the precursor by the molybdenum base complex and the prepared in reaction molybdenum base complex of aqueous hydrogen peroxide adds the aqueous solution of molybdenum base complex then in the paper pulp; Perhaps
-add the precursor of molybdenum base complex to paper pulp.
12. according to each method of claim 1-11, it comprises adding in the paper pulp to have formula CpMo (CO)
3The precursor of the molybdenum base complex of (C ≡ CPh), wherein Cp representative ring pentadienyl and Ph represent phenyl, it is three carbonyls-cyclopentadienyl group-ethynylbenzene-molybdenum (VI) preferably.
13. for the preparation of with the method for pulp treatment, comprising:
The first step of-boiling timber is preferably carried out when NaOH and vulcanized sodium exist, to obtain paper pulp;
-randomly, use oxygen to make the preliminary step of delignified pulp lignin and bleaching;
-make delignified pulp lignin and bleaching according to the method as one of claim 1-12;
-randomly, by alkali extract and/or processing by using ozone and/or the processing by using peracetic acid and/or by with hydrogen peroxide and/or chlorine-containing compound, as chlorine dioxide, contact makes the additional step of delignified pulp lignin and bleaching.
14. for the preparation of the method for paper, comprise method preparation and pulp treatment according to claim 13, make page and drying then.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1061174 | 2010-12-23 | ||
| FR1061174A FR2969668B1 (en) | 2010-12-23 | 2010-12-23 | METHOD FOR DELIGNIFYING AND WHITENING PAPER PULP USING ACTIVE HYDROGEN PEROXIDE |
| PCT/FR2011/053150 WO2012085476A1 (en) | 2010-12-23 | 2011-12-22 | Process for delignification and bleaching of paper pulp using activated hydrogen peroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103261514A true CN103261514A (en) | 2013-08-21 |
| CN103261514B CN103261514B (en) | 2015-11-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180061826.3A Expired - Fee Related CN103261514B (en) | 2010-12-23 | 2011-12-22 | For the method using the hydrogen peroxide of activation to make delignified pulp lignin and bleaching |
Country Status (6)
| Country | Link |
|---|---|
| CN (1) | CN103261514B (en) |
| BR (1) | BR112013012374A2 (en) |
| CL (1) | CL2013001800A1 (en) |
| FR (1) | FR2969668B1 (en) |
| RU (1) | RU2529974C1 (en) |
| WO (1) | WO2012085476A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105723028A (en) * | 2013-11-06 | 2016-06-29 | 赢创德固赛有限公司 | Method for delignifying and bleaching pulp |
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| SU787518A1 (en) * | 1979-02-05 | 1980-12-15 | Белорусский технологический институт им.С.М.Кирова | Method of producing pulp |
| US4661205A (en) * | 1981-08-28 | 1987-04-28 | Scott Paper Company | Method of bleaching lignocellulosic material with peroxide catalyzed with a salt of a metal |
| WO1995026438A1 (en) * | 1994-03-28 | 1995-10-05 | The United States Of America, Represented By The Secretary, Dept. Of Agriculture | Polyoxometalate delignification and bleaching |
| WO1996037654A1 (en) * | 1995-05-22 | 1996-11-28 | Mo Och Domsjö Aktiebolag | Bleaching of cellulose pulp in one and the same stage with a complexing agent, a molybdenum containing substance and an oxidative bleaching agent |
| US5824189A (en) * | 1992-08-28 | 1998-10-20 | The United States Of America As Represented By The Secretary Of Agriculture | Oxidative delignification of wood pulp or fibers using transition metal-substituted polyoxometalates |
| WO1999063149A1 (en) * | 1998-06-02 | 1999-12-09 | The United States Of America, Represented By The Secretary Of Agriculture | Method for selectively delignifying lignocellulosic materials |
| US6048437A (en) * | 1995-09-22 | 2000-04-11 | Mitsubishi Gas Chemical Company, Inc. | Process for bleaching chemical pulp with chlorine dioxide, peroxide and Na2 M0 O4 as reaction catalyt |
| CN101611062A (en) * | 2007-02-14 | 2009-12-23 | 阿克马法国公司 | The method that carbohydrate is functionalized |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2206654C1 (en) * | 2002-02-04 | 2003-06-20 | Сибирский государственный технологический университет | Cellulose production process |
-
2010
- 2010-12-23 FR FR1061174A patent/FR2969668B1/en not_active Expired - Fee Related
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2011
- 2011-12-22 BR BR112013012374A patent/BR112013012374A2/en active Search and Examination
- 2011-12-22 CN CN201180061826.3A patent/CN103261514B/en not_active Expired - Fee Related
- 2011-12-22 RU RU2013134239/12A patent/RU2529974C1/en not_active IP Right Cessation
- 2011-12-22 WO PCT/FR2011/053150 patent/WO2012085476A1/en active Application Filing
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2013
- 2013-06-19 CL CL2013001800A patent/CL2013001800A1/en unknown
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|---|---|---|---|---|
| SU787518A1 (en) * | 1979-02-05 | 1980-12-15 | Белорусский технологический институт им.С.М.Кирова | Method of producing pulp |
| US4661205A (en) * | 1981-08-28 | 1987-04-28 | Scott Paper Company | Method of bleaching lignocellulosic material with peroxide catalyzed with a salt of a metal |
| US5824189A (en) * | 1992-08-28 | 1998-10-20 | The United States Of America As Represented By The Secretary Of Agriculture | Oxidative delignification of wood pulp or fibers using transition metal-substituted polyoxometalates |
| WO1995026438A1 (en) * | 1994-03-28 | 1995-10-05 | The United States Of America, Represented By The Secretary, Dept. Of Agriculture | Polyoxometalate delignification and bleaching |
| WO1996037654A1 (en) * | 1995-05-22 | 1996-11-28 | Mo Och Domsjö Aktiebolag | Bleaching of cellulose pulp in one and the same stage with a complexing agent, a molybdenum containing substance and an oxidative bleaching agent |
| US6048437A (en) * | 1995-09-22 | 2000-04-11 | Mitsubishi Gas Chemical Company, Inc. | Process for bleaching chemical pulp with chlorine dioxide, peroxide and Na2 M0 O4 as reaction catalyt |
| WO1999063149A1 (en) * | 1998-06-02 | 1999-12-09 | The United States Of America, Represented By The Secretary Of Agriculture | Method for selectively delignifying lignocellulosic materials |
| CN101611062A (en) * | 2007-02-14 | 2009-12-23 | 阿克马法国公司 | The method that carbohydrate is functionalized |
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| ANKUSH V.BIRADAR,MOHAN K.DONGARE,SHUBHANGI B. UMBARKAR: "Selective oxidation of aromatic primary alcohols to aldehydes using molybdenum acetylide oxo-peroxo complex as catalyst", 《TETRAHEDRON LETTERS》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105723028A (en) * | 2013-11-06 | 2016-06-29 | 赢创德固赛有限公司 | Method for delignifying and bleaching pulp |
Also Published As
| Publication number | Publication date |
|---|---|
| CL2013001800A1 (en) | 2013-12-06 |
| CN103261514B (en) | 2015-11-25 |
| WO2012085476A1 (en) | 2012-06-28 |
| BR112013012374A2 (en) | 2016-08-30 |
| FR2969668B1 (en) | 2013-01-04 |
| RU2529974C1 (en) | 2014-10-10 |
| FR2969668A1 (en) | 2012-06-29 |
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