CN105544289A - Modified calcium sulfate whisker and application thereof - Google Patents
Modified calcium sulfate whisker and application thereof Download PDFInfo
- Publication number
- CN105544289A CN105544289A CN201510884652.0A CN201510884652A CN105544289A CN 105544289 A CN105544289 A CN 105544289A CN 201510884652 A CN201510884652 A CN 201510884652A CN 105544289 A CN105544289 A CN 105544289A
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- CN
- China
- Prior art keywords
- calcium sulfate
- starch
- wastewaters
- modified calcium
- whiskers
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Classifications
-
- 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
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/025—Calcium sulfates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paper (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Belonging to the technical field of papermaking filler, the invention in particular relates to a modified calcium sulfate whisker and application thereof. The modified calcium sulfate whisker comprises calcium sulfate whisker crystal and an outer uniformly coated starch cross-linking agent shell accounting for 1-8% of the mass of the crystal, and in the starch cross-linking agent shell, the starch and the cross-linking agent are in a proportion of 1:0.05-0.12. Currently, the frequently used fillers in the papermaking industry are heavy calcium carbonate (natural CaCO3 grinding agent), light calcium carbonate (synthesis process), various silicon dioxide grade calcium sulfate crystals and other inorganic fillers, and calcium sulfate is industrial waste, if calcium sulfate can replace calcium carbonate, the social benefits can be greatly increased. And the calcium sulfate whisker can agglomerate after reaching certain size and therefore cannot meet the size requirements of industrial papermaking filler, while the modified calcium sulfate whisker does not agglomerate, thereby giving consideration to the filler size and the interaction effect of the filler and paper fiber. The modified calcium sulfate whisker provided by the invention does not reduce the paper performance as a calcium carbonate substitute.
Description
Technical field
The invention belongs to papermaking filler technical field, particularly a kind of wastewaters with modified calcium sulfate whiskers and application thereof.
Background technology
In papermaking, generally adopt packed art, customary filler has coarse whiting (natural CaCO
3grinding agent), fine particle calcium carbonate (synthesis technique), all kinds of silica level calcium sulphate crystal and other inorganic filler.Calcium sulfate crystal whiskers is a kind of novel inorganic material with very high combination property, is both different from string, and is also different from conventional filler as calcium carbonate, talcum powder etc.It is the tencel shape material between string and conventional filler, there is some special nature not available for conventional filler, as good DIMENSIONAL STABILITY, heat resistance, chemical resistance, anti-flammability and electrical insulating property, these character are that string is incomparable; Strengthen the character such as high brightness, high bulk, the high grade of transparency, these character are also that conventional filler calcium carbonate etc. is incomparable.
The use of various types of filler, the index of Primary Reference has two:
1. shape, size.
2. " affine " of filler particles and paper fiber acts on.
In geomery, current research direction mostly is submicron order nano-sized filler.Due to close on paper fiber macro-size, the gap of filler likely between paper fiber of submicron-scale is retained, and adds the ionic bond between fiber, hydrogen bond and other intermolecular effect.Increase " retention " in its paper-making process, and the filler of nano-scale, have report, they are even not only present in fiber gap, enter space in plant cell especially, play filler effect, are become their skeleton by plant cell wall.Thus reach the effect increasing retention.
In the prerequisite that the filler particles of this two classes different size works, be that they must be distinguished " sub-micron " first dimensionally, the requirement of " nanometer " level.Even if in preparation " sub-micron " and " nanometer " size filler particle process, due to the reason of preparation technology and the material properties of filler own, inevitably cause gathering and the changes in distribution of Particle surface charge, a direct result, be exactly that the particle prepared produces " reunion ", in use, agglomerated particle is larger several than the size before reunion, even tens orders of magnitude, cause the effect of above-mentioned filler to decline.Therefore, surface and the paper fibre interaction process of the filler particles prepared are most important.Macroscopically, greatly can improve " retention " of filler particles, to reach every effect of filler.
For the weakness of prior art, the invention provides a kind of wastewaters with modified calcium sulfate whiskers, consider taking into account of filler size and filler and paper fibre repercussion effect, come into operation and greatly can improve the physical property of filler for amount of filling in paper-making process and paper.
Summary of the invention
Object of the present invention, is the shortcoming and defect overcoming the said goods, improves calcium sulfate crystal whiskers surface state, and calcium sulfate crystal whiskers can not be reunited, and greatly improves the physical property of filler for amount of filling in paper-making process and paper.
Object of the present invention can be achieved through the following technical solutions:
Described wastewaters with modified calcium sulfate whiskers by crystal and its skin evenly the coated starch crosslinking agent shell accounting for crystal mass percentage 1-8% form; In described starch crosslinking agent shell, the mass ratio of starch and crosslinking agent is 1:0.05-0.12.
Preferably, crosslinking agent is selected from one in sodium phosphate trimer or calgon or its mixture;
Preferably, starch is common corn starch or tapioca;
Preferably, wastewaters with modified calcium sulfate whiskers is by following its step preparation:
(1) starch and water are mixed with the slip that mass percent is 4-9%, stir down, be warming up to 70-100 DEG C of gelatinization, constant temperature 1.5-2.5 hour, obtains starch size, is then cooled to 45-60 DEG C;
(2) crosslinking agent is obtained 4%-6% cross-linking agent solution, and in 0.2-0.5 hour, at the uniform velocity instill in described starch size, after isothermal reaction 1-5 hour, with alkaline PH conditioning agent, pH value is modulated to 11, obtains crosslinked starch solution;
(3) by crosslinked starch solution prepared by calcium sulfate crystal whiskers and step (2), after spray-dried device spray drying treatment, i.e. obtained wastewaters with modified calcium sulfate whiskers;
Preferred, in step (2), alkaline PH conditioning agent be sodium carbonate, sodium bicarbonate, sodium hydroxide solution one or more.
Preferred, in step (2), described alkaline PH conditioning agent is 30% sodium carbonate liquor.
Preferred, in the spray dryer spray drying treatment mode of step (3), keep the mixing temperature of 50-80 DEG C, described calcium sulfate crystal whiskers and described crosslinked starch solution reaction 2-5 hour.
Preferred, described crosslinked starch solution uses peristaltic pump to inject.
The application of a kind of wastewaters with modified calcium sulfate whiskers in pulping and paper-making field.
The invention has the beneficial effects as follows:
1, this wastewaters with modified calcium sulfate whiskers can not be reunited, and has taken into account filler size and filler and paper fibre repercussion effect.
2, this wastewaters with modified calcium sulfate whiskers is used for the physical property improving amount of filling and paper in paper-making process.
3, because calcium sulfate is trade waste, this wastewaters with modified calcium sulfate whiskers, as the substitute of calcium carbonate, does not reduce paper performance, considerably increases social benefit.
Accompanying drawing explanation
Fig. 1 is every layer of XPS spectrum figure according to C1s in wastewaters with modified calcium sulfate whiskers obtained in embodiments of the invention 1.
Fig. 2 is the Ca2p according to wastewaters with modified calcium sulfate whiskers obtained in embodiments of the invention 1
3/2and Ca2p
1/2every layer of XPS spectrum figure.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described:
1, obtained three embodiment wastewaters with modified calcium sulfate whiskers:
Embodiment 1:
Length 11 μm, the calcium sulfate crystal whiskers that diameter is 1.1 μm is raw material A.
To with there being thermometer, agitator, Dropping feeder, adds 85g deionized water in the glass reactor of the reflux condenser of nitrogen ingress pipe, 5g cornstarch.Under agitation, be warming up to 80 DEG C of gelatinizations, keep temperature 2.5 hours.Be cooled to 50 DEG C to drip containing 0.5g sodium hexametaphosphate solution 10ml in 0.5 hour, keeps 50 DEG C 5 hours, terminate to react.Regulating with 30% aqueous sodium carbonate is pH=11, obtained B.
Proportioning:
A:50 (mass fraction)
B:50 (mass fraction)
A adds spray dryer cavity and opens airflow apparatus, heats up simultaneously, and to reactor, temperature reaches 50 DEG C.Start peristaltic pump and inject liquid; Keep temperature and blowing speeds, note observing the coated phenomenon of powder 5 hours, discharging, filter, dry, obtain required wastewaters with modified calcium sulfate whiskers.
Fig. 1 is every layer of XPS spectrum figure of C1s in gained wastewaters with modified calcium sulfate whiskers.In this experiment, with XPS, 6 layers are etched to CS-CSWs-0.5, and obtain C1s, Ca2p
3/2and Ca2p
1/2spectrogram.
Fig. 2 is the Ca2p of obtained wastewaters with modified calcium sulfate whiskers
3/2and Ca2p
1/2every layer of XPS spectrum figure as shown in the figure, C1s (≈ 288.3eV) can belong to calcium carboxylates in the combination of etching of first layer and the second layer.The hydroxy-acid group existed in starch, define calcium carboxylates .C1s with calcium ion and (≈ 286.3eV) C-O key in starch molecule can be belonged in the combination of etching first to fourth layer, which illustrate the surface that starch is bonded in crystal whisker of gypsum preferably. along with the increase of etching depth, innermost layer is pure crystal whisker of gypsum, so be etched to after the 4th layer, only occurred C1s at 282.8eV place in conjunction with energy.Ca2p
3/2and Ca2p
1/2the XPS spectrum figure of the 5th and layer 6 substantially overlap, illustrate from layer 5, modified crystal whiskers sample is pure crystal whisker of gypsum.Calculating etching depth is by front four layers of calculating.
Research thinks that starch molecule Zhong – NH2 group can form chelate with metal ion.Ca2p
3/2combination can increase to some extent at 1 ~ 4 layer, the Ca in starch molecule and solution can be regarded as
2+caused by formation chelate.XPS analysis proves that starch adsorption is on the surface of crystal whisker of gypsum, forms coated protective layer, and its solubility is in aqueous reduced.And the coated thickness of known starch is 12.9nm.
Embodiment 2
Length 8.5 μm, the calcium sulfate crystal whiskers that diameter is 1.3 μm is raw material A.
Preparation has thermometer, agitator, Dropping feeder, and the glass of the reflux condenser of nitrogen ingress pipe is answered in device and added 170g water, 8g cornstarch.Under agitation, be warming up to 85 DEG C of gelatinizations, keep temperature 2 hours.Be cooled to 50 DEG C to drip containing 0.35g tripolyphosphate sodium water solution 10ml in 0.3 hour, keeps 50 DEG C 3 hours, terminate to react.Regulating with 30% aqueous sodium carbonate is pH=11, obtained B.
Proportioning:
A:50 (mass fraction)
B:45 (mass fraction)
A adds spray dryer 1 cavity and opens airflow apparatus, and heat up, to reactor, temperature reaches 55 DEG C simultaneously.Start peristaltic pump and inject liquid; Keep temperature and blowing speeds, note observing the coated phenomenon of powder 4 hours, discharging, filter, dry, obtain required wastewaters with modified calcium sulfate whiskers.
Embodiment 3
Length 5.3 μm, the calcium sulfate crystal whiskers that diameter is 0.75 μm is raw material A.
To with there being thermometer, agitator, Dropping feeder, the glass of the reflux condenser of nitrogen ingress pipe is answered in device and is added 170g water, 8.5g cornstarch.Under agitation, be warming up to 85 DEG C of gelatinizations, keep temperature 1.5 hours.Be cooled to 55 DEG C in 0.2 hour drip containing 0.3g sodium phosphate trimer, 0.2g calgon mixed aqueous solution 10ml, keeps 55 DEG C 1 hour, terminate react.Regulating with 30% aqueous sodium carbonate is pH=10.5, obtained B.
Proportioning:
A:50 (mass fraction)
B:35 (mass fraction)
A adds spray dryer 1 cavity and opens airflow apparatus, and heat up, to reactor, temperature reaches 65 DEG C simultaneously.Start peristaltic pump and inject liquid; Keep temperature and blowing speeds, note observing the coated phenomenon of powder 2 hours, discharging, filter, dry, obtain required wastewaters with modified calcium sulfate whiskers.
Test result:
1, tested by calcium sulfate crystal whiskers obtained in above-mentioned three embodiments, concrete data are as shown in table 1 below:
Table 1
| Length (average μm) | Draw ratio | Coated productive rate (%) | Domain size distribution D50 | |
| Embodiment 1 | 11 | 10:1 | 99.8 | 11.7 |
| Embodiment 2 | 8.5 | 20:3 | 100 | 9.0 |
| Embodiment 3 | 5.3 | 7:1 | 100 | 6.2 |
2, the wastewaters with modified calcium sulfate whiskers that above-mentioned three embodiments obtain is used for copy paper filler by after following copy paper technique, then tests handsheet pattern index:
Manufacture paper with pulp quantitative 100g/m
2
Technique:
Blank: slurry 80g/m
2(100% fiber)+AKD403 (10kg/t paper)+PCC (20g/m
2)+CPAM (200ppm) (dry/dry)
Whisker: slurry 80g/m
2(80% fiber+20% whisker)+AKD403 (10kg/t paper)+PCC (20g/m
2)+CPAM (200ppm) (dry/dry)
By above-mentioned technique, take slurry, add whisker successively, AKD, PCC, CPAM stir, take off the slurry prepared, by the semi-automatic sheet forming apparatus handsheet of 73-62, after the squeezing of 73-50 standard page squeezer, natural air drying, the index such as 1minCobb value, opacity, tensile strength, percentage elongation, folding strength.
Table 2 handsheet pattern index (temperature/humidity 20 DEG C/45%)
As can be seen from the table, the calcium sulfate crystal whiskers of modification, when part instead of calcium carbonate, does not reduce paper performance.
The above is preferred embodiment of the present invention, but the present invention should not be confined to the content disclosed in this embodiment.The equivalence completed under not departing from spirit disclosed in this invention so every or amendment, all fall into the scope of protection of the invention.
Claims (8)
1. a wastewaters with modified calcium sulfate whiskers, is characterized in that: described wastewaters with modified calcium sulfate whiskers by calcium sulfate crystal whiskers crystal and its skin evenly the coated starch crosslinking agent shell accounting for crystal mass percentage 1-8% form; In described starch crosslinking agent shell, the mass ratio of starch and crosslinking agent is 1:0.05-0.12.
2. wastewaters with modified calcium sulfate whiskers according to claim 1, is characterized in that: described starch is common corn starch or tapioca.
3. wastewaters with modified calcium sulfate whiskers according to claim 1, is characterized in that: described wastewaters with modified calcium sulfate whiskers be by the preparation of following its step:
(1) starch gelatinization: described starch and water are mixed with the slip that mass percent is 4-9%, stir down, be warming up to 70-100 DEG C of gelatinization, constant temperature 1.5-2.5 hour, obtains starch size, is then cooled to 45-60 DEG C;
(2) described crosslinking agent is obtained 4%-6% cross-linking agent solution, and in 0.2-0.5 hour, at the uniform velocity instill in described starch size, after isothermal reaction 1-5 hour, with alkaline PH conditioning agent, pH value is modulated to 11, obtains crosslinked starch solution;
(3) by crosslinked starch solution prepared by described calcium sulfate crystal whiskers and step (2), after spray-dried device spray drying treatment, i.e. obtained wastewaters with modified calcium sulfate whiskers.
4. wastewaters with modified calcium sulfate whiskers according to claim 3, is characterized in that: in described step (2), described alkaline PH conditioning agent be sodium carbonate, sodium bicarbonate, sodium hydroxide solution one or more.
5. wastewaters with modified calcium sulfate whiskers according to claim 3, is characterized in that: in described step (2), and described alkaline PH conditioning agent is 30% sodium carbonate liquor.
6. wastewaters with modified calcium sulfate whiskers according to claim 3, it is characterized in that: in the spray dryer spray drying treatment mode of described step (3), keep the mixing temperature of 50-80 DEG C, described calcium sulfate crystal whiskers and described crosslinked starch solution reaction 2-5 hour.
7. wastewaters with modified calcium sulfate whiskers according to claim 6, is characterized in that: described crosslinked starch solution uses peristaltic pump to inject.
8. the application of wastewaters with modified calcium sulfate whiskers in pulping and paper-making field.
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|---|---|---|---|
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|---|---|---|---|
| CN201510884652.0A CN105544289B (en) | 2015-12-04 | 2015-12-04 | A kind of wastewaters with modified calcium sulfate whiskers and its application |
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| CN105544289A true CN105544289A (en) | 2016-05-04 |
| CN105544289B CN105544289B (en) | 2018-05-22 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106497142A (en) * | 2016-11-01 | 2017-03-15 | 四川理工学院 | A kind of method of modifying of calcium sulfate crystal whiskers paper making raw material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102852031A (en) * | 2012-09-07 | 2013-01-02 | 长沙理工大学 | Modified calcium sulfate crystal whisker papermaking filler, preparation method and applications thereof |
| CN103790068A (en) * | 2014-02-18 | 2014-05-14 | 福建农林大学 | Method for preparing capsule type papermaking filler by spray drying of starch |
| CN103788848A (en) * | 2014-02-20 | 2014-05-14 | 铜陵祥云消防科技有限责任公司 | Calcium sulfate whisker added fireproof coating material |
| US20150158997A1 (en) * | 2013-12-06 | 2015-06-11 | Georgia-Pacific Gypsum Llc | Gypsum composite modifiers |
-
2015
- 2015-12-04 CN CN201510884652.0A patent/CN105544289B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102852031A (en) * | 2012-09-07 | 2013-01-02 | 长沙理工大学 | Modified calcium sulfate crystal whisker papermaking filler, preparation method and applications thereof |
| US20150158997A1 (en) * | 2013-12-06 | 2015-06-11 | Georgia-Pacific Gypsum Llc | Gypsum composite modifiers |
| CN103790068A (en) * | 2014-02-18 | 2014-05-14 | 福建农林大学 | Method for preparing capsule type papermaking filler by spray drying of starch |
| CN103788848A (en) * | 2014-02-20 | 2014-05-14 | 铜陵祥云消防科技有限责任公司 | Calcium sulfate whisker added fireproof coating material |
Non-Patent Citations (1)
| Title |
|---|
| 张迎等: ""SHMP改性硫酸钙晶须纸张加填研究"", 《中国造纸》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106497142A (en) * | 2016-11-01 | 2017-03-15 | 四川理工学院 | A kind of method of modifying of calcium sulfate crystal whiskers paper making raw material |
| CN106497142B (en) * | 2016-11-01 | 2018-04-06 | 四川理工学院 | A kind of method of modifying of calcium sulfate crystal whiskers paper making raw material |
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| Publication number | Publication date |
|---|---|
| CN105544289B (en) | 2018-05-22 |
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