CN105544289B - A kind of wastewaters with modified calcium sulfate whiskers and its application - Google Patents
A kind of wastewaters with modified calcium sulfate whiskers and its application Download PDFInfo
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- CN105544289B CN105544289B CN201510884652.0A CN201510884652A CN105544289B CN 105544289 B CN105544289 B CN 105544289B CN 201510884652 A CN201510884652 A CN 201510884652A CN 105544289 B CN105544289 B CN 105544289B
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- Prior art keywords
- calcium sulfate
- wastewaters
- whiskers
- starch
- modified calcium
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Classifications
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- 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
The invention belongs to papermaking filler technical fields, more particularly to a kind of wastewaters with modified calcium sulfate whiskers and its application, this wastewaters with modified calcium sulfate whiskers is that the starch crosslinking agent shell for accounting for crystal quality percentage 1 8% is uniformly coated by calcium sulfate crystal whiskers crystal and its outer layer, and the ratio of starch and crosslinking agent is 1 in starch crosslinking agent shell:0.05‑0.12.Customary filler has coarse whiting (natural CaCO in paper industry at present3Grinding agent), fine particle calcium carbonate (synthesis technology), all kinds of silica grade calcium sulphate crystals and other inorganic fillers, and calcium sulfate is trade waste, if can calcium sulfate replace calcium carbonate, social benefit will be considerably increased.And calcium sulfate crystal whiskers reach certain size and will reunite, and the size requirement of commercial paper filler is not achieved, and this wastewaters with modified calcium sulfate whiskers will not reunite, filler size and filler and paper fibre repercussion effect are taken into account, substitute of this wastewaters with modified calcium sulfate whiskers as calcium carbonate, does not reduce paper performance.
Description
Technical field
The invention belongs to papermaking filler technical field, more particularly to a kind of wastewaters with modified calcium sulfate whiskers and its application.
Background technology
In pulping and papermaking process, generally using packed art, customary filler has coarse whiting (natural CaCO3Grinding agent), fine particle calcium carbonate
(synthesis technology), all kinds of silica grade calcium sulphate crystals and other inorganic fillers.Calcium sulfate crystal whiskers are that a kind of new have
The very inorganic material of high combination property, both different from plant fiber, also different from conventional filler such as calcium carbonate, talcum powder etc..It
It is the tencel shape material between plant fiber and conventional filler, there are some particularity not available for conventional filler
Matter, such as good dimensional stability, heat resistance, chemical resistance, anti-flammability and electrical insulating property, these properties are that plant fiber can not
Analogy；It is also that conventional filler calcium carbonate etc. can not compare to enhance properties, these properties such as high brightness, high bulk, the high grade of transparency
Intend.
The use of various types of filler, there are two the indexs of Primary Reference：
1. shape, size.
2. " affine " effect of filler particles and paper fiber.
In terms of geomery, research direction is mostly submicron order nano-sized filler at present.Due to paper fiber macroscopic view ruler
Very little close, the gap that the filler of submicron-scale is possible between paper fiber is retained, in addition the ionic bond between fiber, hydrogen
Key and other intermolecular effects.Increase " retention " in its paper-making process, and the filler of nano-scale, it has been reported that, it
Even be not only present in fiber gap, even more enter space in plant cell, play filler effect, by plant cell wall into
For their skeleton.So as to achieve the effect that increase retention.
It is that they must dimensionally distinguish " Asia first in the premise that this various sizes of filler particles of two classes works
Micron ", the requirement of " nanometer " grade.Even if during " sub-micron " and " nanometer " size filler particle is prepared, due to preparing work
The reason for skill and filler material properties itself, inevitably cause aggregation and the changes in distribution of Particle surface charge, one
Directly as a result, be exactly prepared particle generation " reunion ", in use, agglomerated particle is bigger than the size before reunion
Several or even tens orders of magnitude, cause to drop under the action of above-mentioned filler.Therefore, the surface of the filler particles prepared with
Paper fibre interaction process is most important.Macroscopically, " retention " of filler particles can be greatly improved, to reach paper
Every effect of filler.
For the weakness of the prior art, the present invention provides a kind of wastewaters with modified calcium sulfate whiskers, it is contemplated that filler size and filler
With taking into account for paper fibre repercussion effect, filler can be substantially improved for amount of filling and paper in paper-making process by coming into operation
Physical property.
The content of the invention
The purpose of the present invention, the shortcomings that being to overcome the said goods and deficiency, change calcium sulfate crystal whiskers surface state
Into calcium sulfate crystal whiskers is made not reunite, substantially improve filler for amount of filling and the physical property of paper in paper-making process.
The purpose of the present invention can be achieved through the following technical solutions：
The wastewaters with modified calcium sulfate whiskers is that the starch for accounting for crystal quality percentage 1-8% is uniformly coated by crystal and its outer layer
Crosslinking agent shell forms；The mass ratio of starch and crosslinking agent is 1 in the starch crosslinking agent shell:0.05-0.12.
Preferably, the one kind or its mixture of crosslinking agent in sodium tripolyphosphate or calgon；
Preferably, starch is common corn starch or tapioca；
Preferably, wastewaters with modified calcium sulfate whiskers is prepared by its following step：
(1) starch and water are configured to the slurry that mass percent is 4-9%, stir evenly down, be warming up to 70-100 DEG C
Gelatinization, when constant temperature 1.5-2.5 is small, obtains starch size, is subsequently cooled to 45-60 DEG C；
(2) 4%-6% cross-linking agent solutions are made in crosslinking agent, and it is interior when 0.2-0.5 is small, at the uniform velocity instill the starch slurry
In material, when isothermal reaction 1-5 is small after, pH value is modulated to 11 with alkaline PH conditioning agents, obtains crosslinked starch solution；
(3) the crosslinked starch solution for preparing calcium sulfate crystal whiskers and step (2), spray-dried device spray drying treatment
Afterwards, that is, wastewaters with modified calcium sulfate whiskers is made；
It is furthermore preferred that in step (2), alkaline PH conditioning agents are sodium carbonate, one kind of sodium acid carbonate, sodium hydroxide solution or
It is a variety of.
It is furthermore preferred that in step (2), the alkalescence PH conditioning agents are 30% sodium carbonate liquor.
It is furthermore preferred that in the spray dryer spray drying treatment mode of step (3), 50-80 DEG C of mixing temperature is kept,
Calcium sulfate crystal whiskers and during the crosslinked starch solution reaction 2-5 small.
It is furthermore preferred that the crosslinked starch solution is injected using peristaltic pump.
A kind of application of wastewaters with modified calcium sulfate whiskers in pulping and paper-making field.
The beneficial effects of the invention are as follows：
1st, this wastewaters with modified calcium sulfate whiskers will not reunite, and taken into account filler size and imitated with filler and paper fibre interaction
Fruit.
2nd, this wastewaters with modified calcium sulfate whiskers is used to improve amount of filling and the physical property of paper in paper-making process.
3rd, since calcium sulfate is trade waste, substitute of this wastewaters with modified calcium sulfate whiskers as calcium carbonate does not reduce
Paper performance considerably increases social benefit.
Description of the drawings
Fig. 1 be according to an embodiment of the invention in 1 in wastewaters with modified calcium sulfate whiskers obtained C1s every layer of XPS spectrum figure.
Fig. 2 is the Ca2p of wastewaters with modified calcium sulfate whiskers obtained in 1 according to an embodiment of the invention3/2And Ca2p1/2Every layer
XPS spectrum figure.
Specific embodiment
With reference to embodiment, the invention will be further described：
1st, three embodiment wastewaters with modified calcium sulfate whiskers are made：
Embodiment 1：
11 μm of length, the calcium sulfate crystal whiskers that 1.1 μm of diameter are raw material A.
To with there is a thermometer, blender, Dropping feeder, in the glass reactor of the reflux condenser of nitrogen ingress pipe plus
Enter 85g deionized waters, 5g cornstarch.Under stiring, 80 DEG C of gelatinizations are warming up to, when keeping temperature 2.5 small.Be cooled to 50 DEG C
The 0.5 interior dropwise addition 10ml of sodium hexametaphosphate solution containing 0.5g when small, when keeping 50 DEG C 5 small, reaction was completed.With 30% sodium carbonate
Solution adjusting is pH=11, and B is made.
Proportioning：
A：50 (mass fractions)
B：50 (mass fractions)
A adds in spray dryer cavity and opens airflow apparatus, heats up simultaneously, until temperature reaches 50 DEG C in reaction kettle.It starts
Peristaltic pump injects liquid；Temperature and blowing speeds are kept, when noticing that observation powder cladding phenomenon 5 is small, discharges, filters, it is dry, it obtains
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 to CS-CSWs-0.5
6 layers of etching, and obtain C1s, Ca2p3/2And Ca2p1/2Spectrogram.
Fig. 2 is the Ca2p of wastewaters with modified calcium sulfate whiskers obtained3/2And Ca2p1/2Every layer of XPS spectrum figure as shown in the figure, C1s exists
The combination energy (≈ 288.3eV) of etching of first layer and the second layer belongs to calcium carboxylates.Carboxylic acid group present in starch, with calcium ion
Form calcium carboxylates .C1s first to fourth layer of etching combination can (≈ 286.3eV) belong to C-O keys in starch molecule, this
Illustrate that starch is preferably bonded in the surface of crystal whisker of gypsum with the increase of etching depth, innermost layer is pure crystal whisker of gypsum, institute
After being etched to the 4th layer, only there is combination energy of the C1s at 282.8eV.Ca2p3/2And Ca2p1/2The the 5th and the 6th
The XPS spectrum figure of layer essentially coincides, and illustrates since layer 5, and modified crystal whiskers sample is pure crystal whisker of gypsum.Calculating etching depth is
By first four layers calculating.
Research thinks that-NH2 the groups in starch molecule can form chelate with metal ion.Ca2p3/2Combination can be
1~4 layer increased, and can be regarded as starch molecule and the Ca in solution2+It is formed caused by chelate.XPS analysis prove to form sediment
Powder adsorbs the solubility reduction on the surface of crystal whisker of gypsum, formation cladding protective layer, making it in aqueous solution.And understand starch
Cladding thickness be 12.9nm.
Embodiment 2
8.5 μm of length, the calcium sulfate crystal whiskers that 1.3 μm of diameter are raw material A.
Preparation has thermometer, and blender, Dropping feeder, the glass of the reflux condenser of nitrogen ingress pipe, which is answered in device, to be added in
170g water, 8g cornstarch.Under stiring, 85 DEG C of gelatinizations are warming up to, when keeping temperature 2 small.Be cooled to 50 DEG C it is interior when 0.3 is small
The sodium water solution 10ml of tripolyphosphate containing 0.35g is added dropwise, when keeping 50 DEG C 3 small, reaction was completed.It is adjusted with 30% aqueous sodium carbonate
It is pH=11, B is made.
Proportioning：
A：50 (mass fractions)
B：45 (mass fractions)
A adds in 1 cavity of spray dryer and opens airflow apparatus, heats up simultaneously, until temperature reaches 55 DEG C in reaction kettle.It starts
Peristaltic pump injects liquid；Temperature and blowing speeds are kept, when noticing that observation powder cladding phenomenon 4 is small, discharges, filters, it is dry, it obtains
Required wastewaters with modified calcium sulfate whiskers.
Embodiment 3
5.3 μm of length, the calcium sulfate crystal whiskers that 0.75 μm of diameter are raw material A.
To with there is thermometer, blender, Dropping feeder, the glass of the reflux condenser of nitrogen ingress pipe, which is answered in device, to be added in
170g water, 8.5g cornstarch.Under stiring, 85 DEG C of gelatinizations are warming up to, when keeping temperature 1.5 small.It is cooled to 55 DEG C small 0.2
When interior dropwise addition sodium tripolyphosphate containing 0.3g, the mixed aqueous solution 10ml of 0.2g calgons, when keeping 55 DEG C 1 small, terminate anti-
It should.It is pH=10.5 with the adjusting of 30% aqueous sodium carbonate, B is made.
Proportioning：
A：50 (mass fractions)
B：35 (mass fractions)
A adds in 1 cavity of spray dryer and opens airflow apparatus, heats up simultaneously, until temperature reaches 65 DEG C in reaction kettle.It starts
Peristaltic pump injects liquid；Temperature and blowing speeds are kept, when noticing that observation powder cladding phenomenon 2 is small, discharges, filters, it is dry, it obtains
Required wastewaters with modified calcium sulfate whiskers.
Test result：
1st, calcium sulfate crystal whiskers obtained in above three embodiment are tested, specific data are as shown in table 1 below：
Table 1
| Length (average μm) | Draw ratio | Coat yield (%) | Particle diameter 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 |
2nd, wastewaters with modified calcium sulfate whiskers made from above three embodiment is passed through into following copy paper technique for copy paper filler
Afterwards, handsheet pattern index is then tested：
Manufacture paper with pulp quantitative 100g/m2
Technique：
Blank：Starch 80g/m2(100% fiber)+AKD403 (10kg/t paper)+PCC (20g/m2)+CPAM (200ppm) (dry/
It is dry)
Whisker：Starch 80g/m2(+20% whisker of 80% fiber)+AKD403 (10kg/t paper)+PCC (20g/m2)+CPAM
(200ppm) (dry/dry)
By above-mentioned technique, slurry is weighed, whisker, AKD, PCC, CPAM stirring is sequentially added, removes the slurry prepared, use
The semi-automatic sheet forming apparatus handsheets of 73-62, after being squeezed with 73-50 standard pages squeezer, natural air drying, 1minCobb values, no
The indexs such as transparency, tensile strength, elongation, folding strength.
2 handsheet pattern index of table (temperature/humidity 20 DEG C/45%)
As can be seen from the table, for modified calcium sulfate crystal whiskers in the case where part is instead of calcium carbonate, there is no reduce paper
Extensional energy.
The above is presently preferred embodiments of the present invention, but the present invention should not be limited to disclosed in the embodiment
Content.So every do not depart from the lower equivalent or modification completed of spirit disclosed in this invention, the model that the present invention protects is both fallen within
It encloses.
Claims (7)
1. a kind of wastewaters with modified calcium sulfate whiskers, it is characterised in that：The wastewaters with modified calcium sulfate whiskers is by calcium sulfate crystal whiskers crystal and its
Outer layer uniformly coats the starch crosslinking agent shell composition for accounting for crystal quality percentage 1-8%；It forms sediment in the starch crosslinking agent shell
The mass ratio of powder and crosslinking agent is 1:0.05-0.12；The crosslinking agent in sodium tripolyphosphate or calgon one
Kind or its mixture；
The wastewaters with modified calcium sulfate whiskers is prepared by its following step：
(1) starch gelatinization：The starch and water are configured to the slurry that mass percent is 4-9%, stirs evenly down, is warming up to
70-100 DEG C of gelatinization, when constant temperature 1.5-2.5 is small, obtains starch size, is subsequently cooled to 45-60 DEG C；
(2) 4%-6% cross-linking agent solutions are made in the crosslinking agent, and it is interior when 0.2-0.5 is small, at the uniform velocity instill the starch slurry
In material, when isothermal reaction 1-5 is small after, with alkaline pH adjusting agent by pH values modulate to 11, obtain crosslinked starch solution；
(3) the crosslinked starch solution for preparing the calcium sulfate crystal whiskers and step (2), spray-dried device spray drying treatment
Afterwards, that is, wastewaters with modified calcium sulfate whiskers is made.
2. wastewaters with modified calcium sulfate whiskers according to claim 1, it is characterised in that：The starch is common corn starch or wood
Sweet potato starch.
3. wastewaters with modified calcium sulfate whiskers according to claim 1, it is characterised in that：In the step (2), the alkaline pH
Conditioning agent is sodium carbonate, sodium acid carbonate, the one or more of sodium hydroxide solution.
4. wastewaters with modified calcium sulfate whiskers according to claim 1, it is characterised in that：In the step (2), the alkaline pH
Conditioning agent is 30% sodium carbonate liquor.
5. wastewaters with modified calcium sulfate whiskers according to claim 1, it is characterised in that：The spray dryer spray of the step (3)
In mist drying process mode, 50-80 DEG C of mixing temperature, the calcium sulfate crystal whiskers and the crosslinked starch solution reaction 2- are kept
5 it is small when.
6. wastewaters with modified calcium sulfate whiskers according to claim 5, it is characterised in that：The crosslinked starch solution uses peristaltic pump
Injection.
7. the wastewaters with modified calcium sulfate whiskers that according to claim 1-6 prepared by any preparation method is in pulping and paper-making field
In application.
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| Application Number | Priority Date | Filing Date | Title |
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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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| 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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| CN105544289B true CN105544289B (en) | 2018-05-22 |
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| 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 |
Citations (3)
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015085139A1 (en) * | 2013-12-06 | 2015-06-11 | Georgia-Pacific Gypsum Llc | Gypsum composite modifiers |
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2015
- 2015-12-04 CN CN201510884652.0A patent/CN105544289B/en active Active
Patent Citations (3)
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| "SHMP改性硫酸钙晶须纸张加填研究";张迎等;《中国造纸》;20130831;第32卷(第8期);第23页—27页 * |
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