CN1075144C - Method for bleaching micro powdered plant powder - Google Patents
Method for bleaching micro powdered plant powder Download PDFInfo
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- CN1075144C CN1075144C CN96100617A CN96100617A CN1075144C CN 1075144 C CN1075144 C CN 1075144C CN 96100617 A CN96100617 A CN 96100617A CN 96100617 A CN96100617 A CN 96100617A CN 1075144 C CN1075144 C CN 1075144C
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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
- D21C9/16—Bleaching ; Apparatus therefor with per compounds
- D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/02—Material of vegetable origin
Abstract
Process for bleaching a vegetable material in the form of a micronised powder using H2O2 in the presence of a base, comprising (a) if necessary drying the micronised powder to a moisture content of less than 30 wt.%, pref. 4-15 wt.% w.r.t. total wt., and heating to a temp. ta of 20-100 degrees C, (b) impregnating the powder simultaneously or successively (in either order) with separate solns. A and B in which soln. A is an aq. H2O2 soln. contg. an alkaline agent, in relative amts. such that the two solns. are completely absorbed by the powder so that it remains in a free flowing solid powder state with a water content of 10-50 wt.% w.r.t. total wt., and the impregnated powder has a temp. tb of 40-100 degrees C, and (c) maintaining the impregnated powder at a temp. tc of 40-100 degrees C until at least 75% of the initial amt. of H2O2 has been consumed.
Description
The present invention relates to a kind of method of in the presence of alkali, using hydrogen peroxide bleaching micronised powder shape vegetable material.
EP 0433413 B1 discloses a kind of porous micro powdered plant raw material, and its remaining water capacity is less than 20%, preferably less than 15%:
-d
95Particle size is less than 200 microns (the described plant feed particles that means at least 95% (wt) is by having the sieve of 200 * 200 microns square sieve aperture),
-physics specific surface is less than 2m
2/ g,
-the water surface covers specific surface (water-covering specific surface) less than 2m
2/ g,
-density is less than 500kg/m
3, preferably be less than or equal to 300kg/m
3,
With other condition be this raw material be by less than 150 ℃, preferably be less than or equal to that grinding/micronizing obtains under 100 ℃ the temperature.
All plant origins all are applicable to and obtain this micro powdered plant raw material, particularly cork class such as fir, pine tree or dragon spruce, hardwood class such as birch, beech, birch carpinus turczaninowii or chestnut or the like.Because economic reasons basically, plant origin preferably comes from plant waste, particularly waste wood.Waste wood can be for example from lumbering, the roughing of timber or intermediate conversion industry, or from saw, plane or edge industry.Waste wood also can come from and use or the industry of conversion woodwork, particularly gently or heavily wooden packing.Waste wood also can derive from the factory that produces chemical pulp.
Plant origin also can come from the results cereal as (particularly) plant waste that maize cob produced.
This micro powdered plant raw material is handled through the traditional bleaching in paper industry field, and obtaining the whiteness (measuring according to French Standard Q 03039) between 60 and 90, it is the percentage of 100% test stone that described whiteness is expressed as with respect to whiteness value.
The plant material by the bleaching of the waste wood production that comes from Landes seashore pine tree of above-mentioned patent report has following feature:
-d
95＜150 microns,
-physics specific surface=0.65m
2/ g,
-the water surface covers specific surface=0.52m
2/ g,
-whiteness=70%.
This whiteness is hydrogen peroxide, 2% NaOH, 3% silicate and 0.25% DTPA (diethylene-triamine pentaacetic acid sodium) the bleaching gained with 4%.Therefore, this bleaching is to carry out with the single aqueous solution of diluted mixture thing that contains hydrogen peroxide, NaOH, silicate and DTPA, and comprises and wash plant material with water.
These plant materials of not bleaching or bleaching can be used for making paper pulp, paper, cardboard and non-woven fabric on the one hand, can be used for making plastics, composite, pigment, coating and structural material on the other hand.
In addition, EP 0419385 B1 discloses a kind of method for preparing bleaching and the dry plant paper pulp of crossing, and wherein bleaches with hydrogen peroxide, contacts moisture content in the evaporation paper pulp with paper pulp and carries out drying with the dry air circulation, and bleaching is carried out simultaneously with drying.This method utilization contains the single liquid lime chloride or the liquid of the product of hydrogen peroxide and the product that randomly contains such as alkaline reagent, complexing agent and stable peroxide hydrogen.This liquid mixes with plant paper pulp so that the initial consistency of gained mixture equals 10% at least, and preferably between about 20% and 35%, the denseness of paper pulp is the dry matter content of representing with respect to the percetage by weight of its gross weight.
Plant paper pulp used in the method has been characterised in that the food with high fiber content.They are selected from the paper pulp of beet, citrus fruit, fruit, oil plant, cereal or vegetables, after the product of the value that usually strengthens them has extracted or isolated as sugar, fruit juice, pectin, oil, starch, flour or the cereal when suitable.The production of this beet paper pulp for example is described in document " Sucrerie Francaise[French Sugar Refinery] ", and Octo-ber 1985, among the 439-454.The dry of these paper pulp is not at the micro mist state of hundreds of micron.
Be used for the tradition bleaching of high yield paper pulp in the paper industry,, be difficult to the micro powdered plant raw material as recommending among the above-mentioned EP 0433413B1.
In fact, utilize this type bleaching, average consistency is generally 10 to 20%, and as many as 30% then with the acid neutralization, washes with water again under the few cases.These processing are to be used for removing excesses of basic reagent before the drying, thereby avoid irreversible color reduction to make the effect of bleaching invalid.
W.G.Strunk is at " Pulp and Paper Manufacture, PeroxideBleaching ", 3rd edition, and volume 2, and chapter XX has described this quasi-tradition bleaching of paper industry among the pages 238-251.
In this quasi-tradition method for bleaching, in alkaline medium in bleaching and subsequently the neutralization and washing process, must water that wood pulp is diluted to is quite rare.Because micronized particle has d
95Particle size is less than 300 microns fineness, makes to utilize to filter and/or these neutralizations and the washing operation of extruding micronized material become difficult and expensive.
In addition, the industrial technology method of filtering and/or pushing makes denseness not surpass 20 to 30%.Very big by the dry water yield of removing, cause the energy consumption height.
And wastewater volume is very big and be loaded with large amount of organic.The purified treatment cost was higher before these waste water caused discharging.
The objective of the invention is to find a kind of method that does not have the bleaching micro powdered plant raw material of above-mentioned traditional shortcoming of bleaching.
This purpose is realized by following method, promptly uses the method for hydrogen peroxide bleaching micro mist shape vegetable material in the presence of alkali, it is characterized in that:
A) randomly make this micronised powder be dried to 30% (wt) of water content, and then make its temperature t less than its gross weight
aBe 20 to 100 ℃,
B) simultaneously or one after the other flood this powder with two solution A of separating and B, A can be before B or is opposite, the consumption of A and B with respect to the amount of wanting impregnated powder is, on the one hand so that two solution absorbed by powder fully, thereby this powder remains on water content is the pressed powder state with respect to 10% to 50% (wt) of gross weight, makes the temperature T of powder on the other hand
bAt 40 to 100 ℃, A contains 50 to 500g H by every liter
2O
2Aqueous hydrogen peroxide solution form, B is made up of the alkaline aqueous solution that contains alkaline reagent,
C) make impregnated powder like this remain on temperature t
cBe 40 to 100 ℃ of following a period of times, be enough to make add at least 75% of amount of hydrogen peroxide and consumed.
The vegetable material of micronised powder form can come from those the identical sources with above-mentioned EP 0433413 B1.In addition, extracting sugar beet paper pulp afterwards also can be the source of micronised powder.
Micronised powder is interpreted as d
95Particle size is less than 300 μ m (micron), preferably less than the powder of 200 μ m.Vegetable material before the micronizing can advantageously be handled through complexing, with the decomposition of known metal catalytic hydrogen peroxide.Carry out this complexing with the complexing agent that is selected from DTPA (diethylene-triamine pentaacetic acid sodium), EDTA (ethylene diaminetetraacetic acid sodium), many (Alpha-hydroxy propylene) hydrochlorates and phosphonate and handle, wash (known) then with water.
Also the complexing preliminary treatment of micronised powder can be carried out, but washing and the extruding finished will be caused being difficult on the commercial scale.
In a) section, the water content of micronised powder is preferably the water content of the vegetable material that micronization causes.
The latter is with dried as far as possible but have the plant material of certain humidity to carry out, to reduce the danger of catching fire in the micronization process.Therefore, micronised powder reaches a) section temperature t
aInitial water content before is preferably between 4 and 15% (wt) (with respect to gross weight).
A) section temperature t
aBe preferably 20 to 40 ℃, that is grind in the preparation process and the temperature of the micronised powder that obtains during the screening EO.When the micro powdered plant material contains catalase, the temperature t of the 90-100 ℃ of order of magnitude
aMore favourable.This enzyme is by the Institute of Micro-biology's secretion that can grow on the broken vegetable material of fine powder.Heating can make this enzyme deactivation of decomposition of hydrogen peroxide.
At b) in the section, on the one hand with the water solution A dipping powder that contains hydrogen peroxide, on the other hand with the aqueous solution B dipping of the complexing agent of metal in stabilizing agent that contains alkaline reagent and optional hydrogen peroxide and/or the slaine.Although can before flooding, preferably be immersed in before the B dipping with A with A with the B dipping.
More preferably A and B impose on powder simultaneously.
Preferably by sprayed solution A and sprayed solution B dipping powder.Thereby A and B thin dripped and only met with particles of powder or approaching.This makes might use the solution A of high-strength hydrogen peroxide and the solution B of high concentration basic reagent and/or stabilizing agent and/or complexing agent.In fact, it is unsettled having the A of identical active component content and B to mix the single solution C that obtains in advance, and hydrogen peroxide decomposes and stabilizing agent particularly sodium metasilicate precipitation form gel.
The volume ratio of solution B/A is preferably 0.5 to 2, is more preferably to equal about 1.
The H that is used to flood
2O
2The weight of amount (calculate with pure state, thereby be expressed as 100%) gained powder when a) section finishes be 1 to 10% (wt).
This amount depends on the bleachability of plant material.Usually, for micronizing timber, 2 to 6% amount is enough to obtain high degree of bleaching.Select the H of solution A
2O
2Concentration, so that solution A and B absorb by micronised powder fully, and this powder still keeps the outward appearance and the characteristic of powder.Every liter of H that contains 100 to 350g (representing) of preferred use with pure state
2O
2Solution A, promptly every volume contains 10 to 35% (wt) H
2O
2Solution A.
Because the heat generation of the reaction that they produced and the danger of catching fire under normal pressure, working concentration is more difficult greater than 35% solution A.Carry out b) and c) section and at inert atmosphere, particularly drying can partly be controlled these danger under blanket of nitrogen.
B) temperature t of powder in the section dipping process
bMore favourable between 60 and 90 ℃.
This temperature is obtained by the reactor that heating contains powder, and the exothermicity of reaction is resultant when perhaps being contacted with B with solution A by powder.B) period duration be 5 minutes to 2 hours more favourable, be preferably 10 to 30 minutes.The alkaline reagent of solution B is selected from NaOH, KOH, Na
2CO
3, K
2CO
3, sodium metasilicate, DTPA or other any pH of solution B that can make be more favourable greater than 7 reactant.With respect to the amount of the used alkaline reagent of wanting impregnated powder weight according to used H
2O
2The amount and the character of plant material change.Select this amount so that c) final pH of powder was 6.5 to 8.5 when section finished.
When using NaOH, the amount of NaOH is that 0.5 to 5% (wt) is more suitable with respect to the weight of wanting impregnated plant powder.
Institute's water consumption is so that the active component of this solution is dissolved fully in the selection formation solution B.The total amount of solution A and B is the function calculation of powder water content when a) section finishes preferably, so that at b) after the section dipping, water content reaches 30 to 40% (wt) with respect to the powder gross weight.
The stabilizing agent of hydrogen peroxide is selected from sodium metasilicate, magnesium salts, disodium hydrogen phosphate, sodium polyphosphate, sodium pyrophosphate and phosphonate.The preferred sodium metasilicate that uses, more preferably using density is 1.33 sodium silicate aqueous solution.The amount of stabilizing agent is for respect to (representing with dry state) b) want in the section 1 to 10% (wt) of impregnated powder weight more favourable.This amount is preferably 4 to 8%.Complexing agent is selected from the salt and the phosphonate of DTPA (diethylene-triamine pentaacetic acid sodium), EDTA (ethylene diaminetetraacetic acid sodium), many (Alpha-hydroxy acrylic acid).
Because cost and effectiveness, preferred complexing agent are 40% DTPA solution.
The consumption of 40%DTPA is more favourable with respect to 0.1 to 1% (wt) of plant material weight before the dipping.
Advantageously, solution B also contains fluorescent whitening agent to improve the shading value of final white.Fluorescent whitening agent can be selected from those that use always in the paper industry.
The amount that adds fluorescent whitening agent is for respect to the b that represents with dry state) 0.01 to 0.5% (wt) of the powder weight of section reaction feed be more favourable.
At the c that is called execution phase (latency stage)) section in, finish bleaching.During this section, impregnated micro powdered plant powder is in temperature t
cFollowing stirring and duration d
cTemperature t
cBe preferably 60 ℃ to 90 ℃.
Duration d
cThe character and the temperature t that depend on plant material
cUsually, this duration is 5 to 120 minutes, is preferably 15 to 60 fens.
Some application requirements product of the micronised powder of bleaching is dried as far as possible.In the case, c) carry out drying again after the section.Carry out this drying by conventional art used in timber and the vegetable material industry, and consideration is burnt in oxidizing atmosphere and/or the catastrophe risk of blast.For avoiding this danger, can very carry out this drying under the atmosphere of dilution at inert gas atmosphere or oxygen.
If sodium metasilicate is present in the solution B, because it needn't be from a) washing out the section, it is present in the final powder as fire retardant.
Preferably to be dried to water content be 5 to 20% (wt) with respect to its gross weight to the gained powder when c) section finished.
Except that top description, following embodiment can understand the present invention more fully.
Embodiment
This method can be intermittently or continuation mode carry out.
1) intermittently bleaching
The micro powdered plant powder adding is preheated in about 40 ℃ powder blenders, then on the one hand with 35%H
2O
2Solution and on the other hand alkaline solution being sprayed in the powder simultaneously.
35%H
2O
2The volume ratio of solution and alkaline solution is about 1.
The temperature t of powder
bRise to 80 ℃.After adding solution, under 70 ℃ powder temperature, stir 30 again and mix, discharge powder then to 60 minutes, randomly dry, in the container of packing into then.
Above-mentioned blender can be:
-the cone blender that stirs by the screw rod of band scraper,
-hurricane band blender,
-concrete mixer,
-have by air-flow or mechanical agitation fluidisation the bed blender.
The blender material therefor must be applicable to and use H
2O
2And anti-H
2O
2, for example be selected from stainless steel, glassed steel, scribble the steel or the plastics of anticorrosive paint.
2) continuous bleaching
Preferred this embodiment of the industrial production of high yield, it can control the exothermicity of bleaching action better.
The micro powdered plant raw material is added in the continuous mixing device continuously by metering screw, injects H in the blender on the one hand continuously
2O
2Solution injects alkaline solution on the other hand continuously.
The time of staying in blender is about 1 to 5 second, also can go up to 1 to 3 minute scope.
In the outlet of continuous mixing device, micronised powder is detained jar by one continuously, and the holdup time therein is enough to consume (thereby disappearance) at least 75% H that adds
2O
2
Best bleaching temperature t
bIt is 70 to 80 ℃.This temperature preferably by with H
2O
2The exothermicity of oxidation reaction obtain.
The maximum temperature t that is reached
bDepend on and add H
2O
2Amount, reactant mix the water content of back plant material, initial temperature and the solution A of injecting mixer and the temperature of B of plant material.
If the exothermicity of bleaching action is not enough to reach best bleaching temperature, no matter be because the H that uses
2O
2Measure little, still since the water content of the plant material of being bleached less than but near 20%, all will be before adding reactant or the heating plant material.In the case, heating must evenly and not cause hot-spot.Preferred mode of heating is at blender and/or is detained circulating hot water, perhaps injected steam in blender in the jar chuck on every side.
Heating alkaline solution B also is a kind of traditional approach of introducing heat in reactant mixture.Preferably make the temperature of alkaline solution B rise to 40 to 90 ℃.
The preheating that the micro powdered plant raw material joins before the continuous mixing device can be in the head tank of metering screw or metering screw, by steam in jection or in the chuck around the head tank of metering screw and/or screw rod circulating hot water carry out.
Can be used for providing device to be selected from solution A and B continuous impregnating micro powdered plant powder:
-hurricane band powder blenders,
-various types of rotation dispersing and mixing machines: contain the trunnion axis of being with scraper or contain the rotating disk of paper pulp homogenate type,
-turbomixer,
-have by air-flow or mechanical agitation fluidisation the bed blender,
-have a cylinder of the interior spiral shell hoop of cement kiln type.
Can be used for providing with the device of a holdup time and be selected from solution A and B dipping micro powdered plant raw material:
The Archimedes spiral type screw rod of-high yield,
-cone blender,
-cement kiln shape cylinder.
Should notice that dipping (b section) and the holdup time (c section) can carry out in same device.
In following examples, use following micronizing timber:
I-micronizing pine/spruce wood
Whiteness=49%ISO
pH＝5.1
Water content=5.6% (wt) is with respect to gross weight (w/wt)
II-micronizing seashore pine
Whiteness=50%ISO
pH＝4.4
Water content=10.7%w/wt
III-micronizing spruce wood
Whiteness=51%ISO
pH＝6.2
Water content=6.1%w/wt
IV-micronizing beech wood
Whiteness=41%ISO
pH＝5.7
Water content=7%w/wt
The d of these micronizing timber
95Particle size is less than 150 μ m, from Societe Par-isienne des Sciures[Paris Sawdusts Company].
Whiteness records according to the whiteness of using " ISO Brightness " standard to measure paper with the Hun-terlab spectrophotometer under the wavelength of 457nm in the paper industry.
Experimental arrangement
A) device therefor:
Capacity is 1 liter a jacket type glass reactor, by circulating hot water in chuck heating, its be furnished with central authorities fast propeller and two at a slow speed scraper be used to stir its content.
Solution A (35%H
2O
2) with the pumping of H.P.L.C. type high-pressure pump, then with the nozzle ejection that is positioned at above the reactor.
The device that is used to spray alkaline solution B is the same with said apparatus.
B) general embodiment:
The micro powdered plant raw material that 50g is selected from raw material I, II, III and IV is packed in the reactor.Sprayed into solution A and solution B then simultaneously 15 minutes.Keep 30 to 60 minutes time of implementation of stirring, to finish bleaching, then raw material is discharged from reactor, being dried to content of residual water in 90 ℃ aeration cabinet is about 5% (wt) with respect to (representing with dry state) powder weight.
Measure the H of whiteness, pH and consumption then
2O
2
Under embodiment 1 to 14 and their the results are shown among Table I and the II.
The amount of hydrogen peroxide and NaOH is represented with respect to the percentage of the weight of dry state micro powdered plant raw material with the weight of net product.
The amount of DTPA is represented with respect to the percentage of dry state micro powdered plant raw material weight with the weight that is purchased solution (about 40%).
The amount of sodium metasilicate equals the weight of 1.33 sodium silicate aqueous solution and represents with respect to the percentage of dry state plant material weight with density.
In some test, with the DTPA preliminary treatment be 10% in denseness, temperature is to carry out with 0.5% DTP for 90 ℃ times, the duration is 15 minutes.After this processing finishes, filter the micro powdered plant raw material, the initial water content shown in washing with water, being dried to again.
Embodiment 15
Step is identical with embodiment 3, is another micronizing spruce wood of 5 as 44.7%ISO, denseness 94% and initial pH but use initial whiteness.
Following material is sprayed into 50g simultaneously to be preheated on this timber of 70 ℃:
-11.4g 35％H
2O
2(8％)，
The solution B of-16.9g contains 1.5g NaOH, 8% sodium metasilicate, 0.5%DTPA and 0.3% liquid " BLANCOPHOR P " fluorescent whitening agent by Bayer production, and each solution is all represented with weight.
After 70 ℃ of 45 minutes following execution cycles, pH is 6.9, H
2O
2Consumption is 84.3%.
Whiteness is 62.5%ISO.
Get with Huntelab spectrophotometer measurement color according to CIE standard D65/10:
L
*＝87.49 a
*＝-1.01 b
*＝8.77
Table I
| A) preparatory phase of micronised powder is a) before for impregnation stage | While impregnation stage b) | ||||||||
| Embodiment | The character of micronizing timber | Use the DTPA preliminary treatment | Preheating ℃ | H 2O 2 ％ | NaOH ％ | Silicate % | DTPA ％ | t b ℃ | Dipping back water content % |
| 1 2 3 | I | Whether | 70 70 70 | 5 5 8 | 2.5 1.5 1.5 | 4 4 8 | 0 0 0.5 | 70 70 70 | 28 28 38 |
| 4 5 6 | II | Whether deny | 70 70 70 | 5 8 8 | 2 2.5 2.5 | 4 8 8 | 0 0.5 0.5 | 70 70 70 | 31 42 42 |
Table I (continuing)
| 7 8 9 10 11 12 | III | Whether deny | 60 90 60 70 60 60 | 8 8 8 8 8 8 | 2.5 2.5 1.8 1.8 2.5 1.8 | 8 8 8 8 8 8 | 0.5 0.5 0.5 0.5 0 0.5 | 60 60 60 70 60 60 | 50 50 50 50 50 50 |
| 13 14 | IV | Whether | 70 70 | 5 8 | 1.5 2.5 | 4 8 | 0 0.5 | 70 70 | 27 39 |
Table II
| The execution cycle stage c) | The result | ||||
| Embodiment | t c℃ | C) duration of section divide or hour | H 2O 2Consume % | Final pH | Whiteness %ISO |
| 1 2 3 | 70 70 70 | 30 minutes 30 minutes 45 minutes | 100 95.5 92.3 | 10.3 8 7 | 61 68 68 |
| 4 5 6 | 70 70 70 | 45 minutes 20 minutes 45 minutes | 88 77.4 84.7 | 7.6 8.1 7.8 | 72 74 75 |
| 7 8 9 10 11 12 | 60 60 60 60 60 60 | 16 hours 5 hours 18 hours 20 hours 18 hours 6 hours | 100 98.6 92.2 89 99.5 93 | 9.5 9.8 7.1 6.4 9.8 8 | 63 67 72 73 67 73 |
| 13 14 | 70 70 | 15 minutes 45 minutes | 84.1 98.5 | 6 7 | 68 64.5 |
Embodiment 16-bench-scale testing No.1
7kg micronizing timber III is packed in the stainless copper cement mixer, and this blender has been preheated to 40 ℃, and working volume is 40l (volume that can be stirred in obliquity).
Sprayed into following material simultaneously 15 minutes with two metering piston pumps
-on the one hand, the hydrogen peroxide of 1.6kg 35%,
-on the other hand, 2.37kg equals the alkaline solution that 1.33 sodium silicate aqueous solution, 35g 40%DTPA and 1.65kg water are formed by 126g NaOH, 560g density.
In the spraying process, temperature t
bReach 78 ℃, the final water content of impregnated micronizing timber is 40%.
Impregnated powder was stirred 45 minutes under 70 ℃ of temperature again.
Obtain the micronizing timber that 10.5kg bleached, its pH be 9.1 and contain 0.7% the residue H
2O
2(use pure H
2O
2Weight is represented with respect to the percentage of dry state micronizing timber weight).Whiteness is 62.7%ISO (dry sample).
Storage is after 5 hours down at 70 ℃, and pH equals 7, residue H
2O
2Amount be 0.18%, whiteness is 63%ISO (dry sample).
Embodiment 17-bench-scale testing No.2
This embodiment is identical with embodiment 16, but the amount of NaOH is lower: replace 126g (promptly replacing 1.8% with respect to dried timber with 1.6%) with 105g.
The maximum temperature that is reached during two solution while spraying is 70 ℃.After 70 ℃ were stirred 45 fens down, pH was 8.5, residue H
2O
2Amount be 1.25%, whiteness is 62.3%ISO.
After 70 ℃ were handled 5 hours down, pH was 6.1, residue H
2O
2Amount be 0.5%, whiteness is 63%ISO.
Embodiment 18,19 and 20.Bench-scale testing No.3,4 and 5 uses other micro powdered plant raw material.
Use following micronizing raw material.
V-powder shape corn bran
Whiteness=32%ISO
pH＝5
Water content=8%
VI-powder shape sunflower shell
Whiteness=26%ISO
pH＝6.5
Water content=7.6%
VII-powder shape beet paper pulp
Whiteness=30.5%ISO
pH＝6
Water content=4%
The d of these micronised powder
95Particle size is 180 μ m.
Micro powdered plant raw material V or VI or VII are packed in 100 liters of stainless steel S-helical mixing-driers (trade name GUEDU), by the chuck heating of circulating hot water, this charging of preheating then.
On the one hand with 35%H
2O
2Solution sprays into alkaline solution in the blender on the other hand simultaneously.Allow reaction to take place to consume, under vacuum, carry out drying then until at least 75% hydrogen peroxide charging.
The results are shown among Table III and the IV of embodiment 18 to 20 and they.
Table III
| Stage a) | Impregnation stage b) | |||||||
| Embodiment | The micronizing raw material properties | The weight (kg) that adds the raw material of reaction | Preheating ℃ | H 2O 2Solution kg | NaOH solution kg | Temperature t b ℃ | Duration minute | Final water content % |
| 18 19 20 | V VI VII | 20 16.2 18.75 | 72 80 70 | 6.165 (30％H 2O 2) charging=10% 3.0 (35%H 2O 2) charging=7% 5.14 (35%H 2O 2) charging=10% | 2.77 (10%NaOH) charging=1.5% 3.0 (10%NaOH) chargings=2% 3.6 (10%NaOH) charging=2% | 90 91 95 | 15 32 36 | 36 30 30 |
Table IV
| The time of implementation stage c) | The result | ||||
| Embodiment | Temperature ℃ | The duration branch | Final pH | Residue H 2O 2％ | ISO whiteness % |
| 18 19 20 | 90 90 70 | 15 65 60 | 6 5.6 5.4 | 0.18 0.21 1.5 | 46 54 50 |
Claims (31)
1, in the presence of alkali, use the method for hydrogen peroxide bleaching micronised powder shape plant material, it is characterized in that:
A) randomly make this micronised powder be dried to 30% (wt) of water content, make its temperature t then less than its gross weight
aBe 20 to 100 ℃,
B) simultaneously or one after the other flood this powder with two kinds of solution A of separating and B, A can be before B or is opposite, A and B are such with respect to the consumption of the amount of wanting impregnated powder, so that two solution are absorbed by powder fully on the one hand, be pressed powder state thereby remain on water content, make the temperature t of powder on the other hand with respect to 10% to 50% (wt) of gross weight
bAt 40 to 100 ℃, A contains 50 to 500g H by every liter
2O
2Aqueous hydrogen peroxide solution form, B is made up of the alkaline aqueous solution that contains alkaline reagent,
A) make impregnated powder like this remain on temperature t
oBe 40 to 100 ℃ of following a period of times, be enough to make add at least 75% of amount of hydrogen peroxide and consumed.
2,, it is characterized in that described micronised powder is rising to a) section temperature t according to the method for claim 1
aWater content before is between 4 and 15% (wt) with respect to its gross weight.
3, according to the method for claim 1, the volume ratio that it is characterized in that described solution B/A is in 0.5 to 2 scope.
4, according to the method for claim 2, the volume ratio that it is characterized in that described solution B/A is in 0.5 to 2 scope.
5,, it is characterized in that described solution B contains stabilizer of hydrogen peroxide according to the method for claim 1.
6,, it is characterized in that described solution B contains stabilizer of hydrogen peroxide according to the method for claim 2.
7,, it is characterized in that described solution B contains stabilizer of hydrogen peroxide according to the method for claim 3.
8,, it is characterized in that described stabilizing agent is a sodium metasilicate according to the method for claim 5.
9,, it is characterized in that described stabilizing agent is a sodium metasilicate according to the method for claim 6.
10,, it is characterized in that described stabilizing agent is a sodium metasilicate according to the method for claim 7.
11, method according to Claim 8, the content that it is characterized in that described sodium metasilicate is with respect to the b that represents with dry state) to want impregnated powder weight in the section be 1 to 10% (wt).
12, according to the method for claim 9, the content that it is characterized in that described sodium metasilicate is with respect to the b that represents with dry state) to want impregnated powder weight in the section be 1 to 10% (wt).
13, according to the method for claim 10, the content that it is characterized in that described sodium metasilicate is with respect to the b that represents with dry state) to want impregnated powder weight in the section be 1 to 10% (wt).
14,, it is characterized in that described solution B also contains the complexing or the chelating agent of the metal of the slaine that known catalyzing hydrogen peroxide is decomposed according to the method for one of claim 1 to 13.
15,, it is characterized in that powder for drying to the water content that obtains when a) section finishes is 5 to 20% (wt) with respect to its gross weight according to the method for one of claim 1 to 13.
16,, it is characterized in that powder for drying to the water content that obtains when a) section finishes is 5 to 20% (wt) with respect to its gross weight according to the method for claim 14.
17,, it is characterized in that a) temperature t of section according to the method for one of claim 1 to 13
aIt is 20 to 40 ℃.
18,, it is characterized in that a) temperature t of section according to the method for claim 15
aIt is 20 to 40 ℃.
19, according to the method for one of claim 1 to 13, it is characterized in that b) section temperature t
bIt is 60 to 90 ℃.
20, according to the method for claim 17, it is characterized in that b) section temperature t
bIt is 60 to 90 ℃.
21,, it is characterized in that a) temperature t of section according to the method for one of claim 1 to 13
oIt is 60 to 90 ℃.
22,, it is characterized in that a) temperature t of section according to the method for claim 19
oIt is 60 to 90 ℃.
23, according to the method for one of claim 1 to 13, it is characterized in that, in stage b), by spraying into solution A and spraying into solution B dipping powder.
24, according to the method for claim 21, it is characterized in that, in stage b), by spraying into solution A and spraying into solution B dipping powder.
According to the method for one of claim 1 to 13, it is characterized in that 25, in stage b), the amount of flooding used hydrogen peroxide is 1 to 10% weight of gained powder weight when a) section finishes, the amount of hydrogen peroxide is the pure state meter.
According to the method for claim 23, it is characterized in that 26, in stage b), the amount of flooding used hydrogen peroxide is 1 to 10% weight of gained powder weight when a) section finishes, the amount of hydrogen peroxide is the pure state meter.
27,, it is characterized in that described solution B also contains fluorescent whitening agent according to the method for one of claim 1 to 13.
28,, it is characterized in that described solution B also contains fluorescent whitening agent according to the method for claim 25.
29, according to the method for claim 1, it is characterized in that: described micronised powder is rising to a) section temperature t
aWater content before is between 4 and 15% (wt) with respect to its gross weight, and the volume ratio of described solution B/A is in 0.5 to 2 scope, and described solution B contains stabilizer of hydrogen peroxide.
30, according to the method for claim 1, it is characterized in that: described micronised powder is rising to a) section temperature t
aWater content before is between 4 and 15% (wt) with respect to its gross weight, and the volume ratio of described solution B/A is in 0.5 to 2 scope, and described solution B contains stabilizer of hydrogen peroxide, and described stabilizing agent is a sodium metasilicate.
31, according to the method for claim 1, it is characterized in that: described micronised powder is rising to a) section temperature t
aWater content before is between 4 and 15% (wt) with respect to its gross weight, the volume ratio of described solution B/A is in 0.5 to 2 scope, described solution B contains stabilizer of hydrogen peroxide, described stabilizing agent is a sodium metasilicate, and the content of described sodium metasilicate is with respect to the b that represents with dry state) to want impregnated powder weight in the section be 1 to 10% (wt).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9500093 | 1995-01-06 | ||
| FR9500093A FR2729096A1 (en) | 1995-01-06 | 1995-01-06 | PROCESS FOR WHITENING MICRONIZED VEGETABLE POWDER |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1136493A CN1136493A (en) | 1996-11-27 |
| CN1075144C true CN1075144C (en) | 2001-11-21 |
Family
ID=9474901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96100617A Expired - Fee Related CN1075144C (en) | 1995-01-06 | 1996-01-05 | Method for bleaching micro powdered plant powder |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0722010A1 (en) |
| JP (1) | JPH08232184A (en) |
| CN (1) | CN1075144C (en) |
| CA (1) | CA2166242C (en) |
| CZ (1) | CZ284990B6 (en) |
| FI (1) | FI960065A (en) |
| FR (1) | FR2729096A1 (en) |
| NO (1) | NO960023L (en) |
| PL (1) | PL181230B1 (en) |
| SK (1) | SK1196A3 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2747125B1 (en) * | 1996-04-05 | 1999-07-16 | Generale Sucriere Sa | PROCESS FOR THE VALORIZATION OF BEET PULPES TO OBTAIN PRODUCTS WITH HIGH ADDED VALUE |
| GB201304939D0 (en) * | 2013-03-18 | 2013-05-01 | Cellucomp Ltd | Process for Preparing Cellulose-Containing Particles from Plant Material |
| CN103978533B (en) * | 2014-06-09 | 2016-04-06 | 山东轻工职业学院 | A kind of bleaching process of raffia |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5094866A (en) * | 1989-06-05 | 1992-03-10 | Atochem | Bleaching of vegetable pulps |
| DE4111574A1 (en) * | 1991-04-10 | 1992-10-15 | Haindl Papier Gmbh | Oxidative bleaching of pulp, esp. for paper mfr. - using depot alkali besides soluble alkali and pref. hydrogen peroxide to increase whiteness |
| JPH0614744A (en) * | 1991-03-15 | 1994-01-25 | Elf Atochem Sa | Method of bleaching vegetable material by drying medium |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2199376A (en) * | 1939-09-29 | 1940-04-30 | Du Pont | Bleaching of ground wood pulp |
| FR2648488B1 (en) * | 1989-06-15 | 1991-09-13 | Gomez Daniel | POROUS, MICRONIZED, LOW DENSE PLANT LOAD, CONTROLLED SIZE AND LOW SPECIFIC PHYSICAL AND HYDRAULIC SURFACES; PREPARATION AND USE PROCESS |
| FR2651965B1 (en) * | 1989-09-21 | 1991-12-06 | Atochem | PROCESS FOR THE MANUFACTURE OF BLEACHED VEGETABLE PULPES. |
| US5069919A (en) * | 1990-08-08 | 1991-12-03 | Fmc Corporation | Process for bleaching/sanitizing food fiber |
| US5332474A (en) * | 1993-01-19 | 1994-07-26 | Maxham John V | Conversion of pulp and paper mill waste solids to a papermaking filler product |
-
1995
- 1995-01-06 FR FR9500093A patent/FR2729096A1/en active Granted
- 1995-12-07 EP EP95402756A patent/EP0722010A1/en not_active Ceased
- 1995-12-28 CA CA002166242A patent/CA2166242C/en not_active Expired - Fee Related
-
1996
- 1996-01-03 SK SK11-96A patent/SK1196A3/en unknown
- 1996-01-04 NO NO960023A patent/NO960023L/en not_active Application Discontinuation
- 1996-01-04 PL PL96312152A patent/PL181230B1/en unknown
- 1996-01-05 CN CN96100617A patent/CN1075144C/en not_active Expired - Fee Related
- 1996-01-05 FI FI960065A patent/FI960065A/en unknown
- 1996-01-05 JP JP8000217A patent/JPH08232184A/en active Pending
- 1996-01-08 CZ CZ9662A patent/CZ284990B6/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5094866A (en) * | 1989-06-05 | 1992-03-10 | Atochem | Bleaching of vegetable pulps |
| JPH0614744A (en) * | 1991-03-15 | 1994-01-25 | Elf Atochem Sa | Method of bleaching vegetable material by drying medium |
| DE4111574A1 (en) * | 1991-04-10 | 1992-10-15 | Haindl Papier Gmbh | Oxidative bleaching of pulp, esp. for paper mfr. - using depot alkali besides soluble alkali and pref. hydrogen peroxide to increase whiteness |
Also Published As
| Publication number | Publication date |
|---|---|
| NO960023L (en) | 1996-07-08 |
| CZ6296A3 (en) | 1996-07-17 |
| JPH08232184A (en) | 1996-09-10 |
| FR2729096B1 (en) | 1997-02-07 |
| NO960023D0 (en) | 1996-01-04 |
| CA2166242C (en) | 2000-03-21 |
| CA2166242A1 (en) | 1996-07-07 |
| CZ284990B6 (en) | 1999-04-14 |
| PL181230B1 (en) | 2001-06-29 |
| SK1196A3 (en) | 1996-08-07 |
| CN1136493A (en) | 1996-11-27 |
| PL312152A1 (en) | 1996-07-08 |
| FI960065A0 (en) | 1996-01-05 |
| EP0722010A1 (en) | 1996-07-17 |
| FR2729096A1 (en) | 1996-07-12 |
| FI960065A (en) | 1996-07-07 |
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