CN106283854B - A kind of method of the fine coal gray surface precipitated crystal formula coating modification as papermaking filler - Google Patents
A kind of method of the fine coal gray surface precipitated crystal formula coating modification as papermaking filler Download PDFInfo
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- CN106283854B CN106283854B CN201610611872.0A CN201610611872A CN106283854B CN 106283854 B CN106283854 B CN 106283854B CN 201610611872 A CN201610611872 A CN 201610611872A CN 106283854 B CN106283854 B CN 106283854B
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- Prior art keywords
- flyash
- reaction
- precipitated crystal
- gas
- coating modification
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000003245 coal Substances 0.000 title claims abstract description 14
- 239000013078 crystal Substances 0.000 title claims abstract description 14
- 239000011248 coating agent Substances 0.000 title claims abstract description 12
- 238000000576 coating method Methods 0.000 title claims abstract description 12
- 239000000945 filler Substances 0.000 title claims abstract description 12
- 238000012986 modification Methods 0.000 title claims abstract description 9
- 230000004048 modification Effects 0.000 title claims abstract description 9
- 239000010881 fly ash Substances 0.000 claims abstract description 39
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 13
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 230000005587 bubbling Effects 0.000 claims abstract description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 5
- 238000005253 cladding Methods 0.000 claims description 3
- 238000005273 aeration Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000006194 liquid suspension Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000002910 solid waste Substances 0.000 abstract description 3
- 238000013459 approach Methods 0.000 abstract description 2
- 238000012856 packing Methods 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract 2
- 239000002243 precursor Substances 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000005070 sampling Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002956 ash Substances 0.000 description 2
- 239000010883 coal ash Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
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
-
- 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
Abstract
The invention discloses a kind of method of the fine coal gray surface precipitated crystal formula coating modification as papermaking filler.For this method using flyash as raw material, the particle by choosing certain particle size range is modified object, under normal temperature condition by its Ca（OH）2CO is passed through using bottom Bubbling method in solution2Gas realizes precipitated crystal formula coating modification.Modified result is shown, can form the calcium carbonate granule clad of even compact under certain condition on flyash precursor granule surface, and the whiteness of flyash improves, and substantially meets the needs of paper grade (stock) filler.The technology provides new approach for the high value added utilization of flyash solid waste, while provides a kind of new packing source for paper industry.
Description
Technical field
The invention belongs to the filler modified technical field of Pulp and Paper Engineering subject, and in particular to one kind is used as papermaking filler
Fine coal gray surface precipitated crystal formula coating modification method.
Background technology
Flyash is the maximum cities and towns solid waste discharge source in China as the accessory substance after power plant boiler coal combustion
One of.The stacking of flyash will directly or indirectly trigger a series of environmental problems such as air, soil, river, while cause pole
The big wasting of resources.For many years, domestic and foreign scholars are by the application technology as the second resource of a variety of technique study flyash, and are building
Build, road, sewage disposal, mineral extraction, material the many-side such as are filled with and made a breakthrough.But there is product in the utilization in these fields
A series of problems, such as yield is low, added value is not high, processing procedure cost is high.Because flyash has and paper industry filler height
The similar chemical composition of ridge soil and unique surface hole defect structure, are filled with available for papermaking.And unburnt carbon in fly ash grain,
The interference in the color development such as ferriferous oxide source, it is allowed to whiteness only 30%ISO or so, it is difficult to meet that high brightness papers are filled with（≧80%ISO）
It is required that therefore the application in papermaking filler field is restricted.
Gai Guosheng is it is proposed that a kind of first by flyash 40 ~ 100oUnder the conditions of C and Ca（OH）2Mixing, is being cooled to again afterwards
CO is used under normal temperature condition2Neutralized, fine coal under the conditions of high-temperature alkaline is mainly then utilized to slurries filtration and drying, the method
The change of the surface texture of ash is modified, the CO in later stage2Simply play neutralization excess amount of Ca（OH）2Complementary effect.Yu Xiaodong
Then disclose another flyash discoloration method：First the flyash of carbon content 0.1% ~ 1% is completely soaked into water and is heated to
Boiling, then passes to 200oC high temperature COs2Gas can improve whiteness to 70 ~ 81%ISO, the method after fully contacting 5 ~ 15min
Necessarily constrained in the application of brightening of high carbon content, and need to provide certain hot environment.The present inventor also once discloses one
The first high temperature carbon removal of kind bonds PCC by adhesive of starch again（Winnofil）Particle to fly ash grain surface method, this
Procedure is slightly aobvious complicated and needs to consume energy, therefore the present invention optimizes on its basis.
The content of the invention
Based on deficiency and one-sidedness existing for above method, the present invention proposes a kind of novel powdered coal gray surface precipitated crystal formula
Coating modification method.In order to which the raw materials technology and scheme by low cost under normal temperature condition realize that whiteness performance is obviously improved,
The original grain structure of coal ash is not destroyed simultaneously.
The present invention program is as follows.
A kind of method of the fine coal gray surface precipitated crystal formula coating modification as papermaking filler, including following methods：
（1）Raw material is chosen：Tong Guo Oscillating shake flyash powder particle that screening takes particle diameter in 30 ~ 55 μ ms as surface
Modified raw material；
（2）Crystallization cladding：By the flyash and Ca of selection under normal temperature（OH）2The mixing suspension of solution, uniformly after mixing,
Under agitation, CO is passed through with Bubbling method from the bottom of reaction vessel2Precipitated crystal reaction occurs for gas, after reaction, stops
It is passed through CO2Gas and stirring terminating reaction；
（3）Thicken standby：Concentration adjustment is carried out to reacted mixed liquor with clear water, it is standby as papermaking filler afterwards.
In the above method, using under normal temperature（10~30℃）Carburizing reagent realize the precipitation of calcium carbonate knot of fine coal gray surface
Brilliant coating modification, the physical-chemical reaction under any other preprocess method or hot conditions is not used.
In the above method, institute's flyash and Ca（OH）2Solute Ca in solution（OH）2Mass ratio be 0.1 ~ 3.0；It is described
Mass percent concentration of the flyash in mixing suspension is 20% ~ 50%.
In the above method, used coating modification reaction medium is Ca（OH）2Solution, and it is passed through CO2In fine coal gray surface
Precipitated crystal is produced, is added without other any chemicals in addition.
In the above method, using the gas dispersion apparatus installed in reaction container bottom continuous bubbling, the gas disperses
Device is the aeration board of single air inlet mouth of pipe.
In the above method, the stir speed (S.S.) control range is 100 ~ 600rpm, CO2Flow control is in 0.1 ~ 1.5L/
Min, reaction time are 10 ~ 60min.
In the above method, the compound liquid suspension of flyash-calcium carbonate that is obtained after the completion of reaction is used after directly adjusting concentration
It is filled with paper, mass percent concentration is 1% ~ 30% after adjustment.
Compared with prior art, advantage of the invention is that：
（1）Raw material（Flyash, Ca（OH）2And CO2）It is convenient to obtain, and cost is relatively low, and in normal temperature 10 ~ 30oUnder the conditions of C i.e.
It can react, suitable for varying environment；
（2）The precipitated crystal formula cladding under temperate condition is directly carried out in fine coal gray surface, crystal shape is sheet, needle-like
Or column, 0.5 ~ 3 μm of particle diameter（As shown in Figure 3）, grain structure unexcellent to flyash impacts；
（3）Can be by the whiteness performance of the regulation and control final products of reaction condition, whiteness 65 ~ 86%ISO of modification scope can
To meet that what different whiteness required paper is filled with needs.
（4）It is 1% ~ 30% feeding paper machine stock mixing system that concentration is directly adjusted after wet-process modified, without being added after drying,
Effectively reduce energy consumption.
（5）The technology provides approach for the high value added utilization of flyash solid waste, while is provided for paper industry
A kind of new packing source.
Brief description of the drawings
Fig. 1 is fine coal gray surface precipitated crystal formula coating modification reaction unit schematic diagram；
Fig. 2 is surface fly ash grain SEM patterns before modified；
Fig. 3 is the modified fly ash grain SEM patterns in surface.
All parts are as follows in figure：
Agitator 1, reaction vessel 2, mixing suspension（Ca（OH）2+ flyash）3、
Gas dispersion apparatus 4, CO2Gas tank 5, gas flow control valve 6.
Embodiment
Experimental provision as shown in Figure 1, gas dispersion apparatus 4 are in the bottom of reaction vessel 2, react and disperse in the gas
Carried out in the mixing suspension 3 of the top of device 4.The gas dispersion apparatus 4 and extraneous CO2Gas tank 5 is connected by tracheae, is used for
CO needed for reaction is provided2, and gas flow rate is adjusted by the gas flow control valve 6 on tracheae.The rotor of agitator 1 simultaneously
In mixing suspension 3 in reaction vessel, for being stirred for course of reaction, by controlling its rotation speed regulating and controlling stirring speed
Rate.
Embodiment 1
25oAccording to M under the conditions of CFlyash：MCalcium hydroxide（Solute）=1.0 mass ratio is equipped with flyash（40 μm of average grain diameter）And Ca
（OH）2Mixing suspension, and the mass concentration of flyash in mixed liquor is adjusted to 30%.Then under 400rpm stir speed (S.S.)s
CO is passed through with 0.4L/min flow velocitys2Gas, after 50min, stopping is passed through CO2Gas and stirring terminating reaction, are measured by sampling its whiteness
For 73%ISO, it is filled with after being diluted to 1% mass percent concentration with clear water for copy paper.
Embodiment 2
25oAccording to M under the conditions of CFlyash：MCalcium hydroxide（Solute）=1.6 mass ratio is equipped with flyash（40 μm or so of average grain diameter）
And Ca（OH）2Mixing suspension, and the mass concentration of flyash in mixed liquor is adjusted to 40%.Then speed is stirred in 400rpm
CO is passed through with 0.1L/min flow velocitys under rate2Gas, after 30min, stopping is passed through CO2Gas and stirring terminating reaction, are measured by sampling it
Whiteness is 78%ISO, is filled with after being diluted to 5% mass percent concentration with clear water for copy paper.
Embodiment 3
25oAccording to M under the conditions of CFlyash：MCalcium hydroxide（Solute）=0.185 mass ratio is equipped with flyash（40 μm of left sides of average grain diameter
It is right）And Ca（OH）2Mixing suspension, and the mass concentration of flyash in mixed liquor is adjusted to 25%.Then stirred in 300rpm
CO is passed through with 0.1L/min flow velocitys under speed2Gas, after 30min, stopping is passed through CO2Gas and stirring terminating reaction, are measured by sampling
Its whiteness is 86%ISO, is filled with after being diluted to 10% mass percent concentration with clear water for copy paper.
Surface fly ash grain SEM patterns before modified are illustrated in figure 2, Fig. 3 is then the modified fly ash grain SEM in surface
Pattern.It can clearly be seen that the calcium carbonate that set a large amount of particle diameters in fly ash grain surface are far smaller than original coal ash particle is brilliant
Body, and uniformly arrangement is presented, certain covering effect is played, and grain structure is kept substantially, effectively complete to improve fine coal
Surface coating for the purpose of the whiteness of ash.
The above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not to the present invention
Embodiment restriction.For those of ordinary skill in the field, can also make on the basis of the above description
Other various forms of changes or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all the present invention
All any modification, equivalent and improvement made within spirit and principle etc., should be included in the protection of the claims in the present invention
Within the scope of.
Claims (1)
- A kind of 1. method of the fine coal gray surface precipitated crystal formula coating modification as papermaking filler, it is characterised in that including with Lower step：（1）Raw material is chosen：Tong Guo Oscillating shake the original that screening takes particle diameter to be modified in 30 ~ 55 μm of flyash powder particle as surface Material；（2）Crystallization cladding：By the flyash and Ca of selection under normal temperature（OH）2The mixing suspension of solution, uniformly after mixing, stirring Under the conditions of mixing, CO is passed through with Bubbling method from the bottom of reaction vessel2Precipitated crystal reaction occurs for gas, after reaction, stops being passed through CO2Gas and stirring terminating reaction；（3）Thicken standby：Concentration adjustment is carried out to reacted mixed liquor with clear water, it is standby as papermaking filler afterwards；The flyash and Ca（OH）2Solute Ca in solution（OH）2Mass ratio be 0.1 ~ 3.0；The flyash is mixing Mass percent concentration in suspension is 20% ~ 50%；Using the gas dispersion apparatus installed in reaction container bottom continuous bubbling, the gas dispersion apparatus is single air inlet mouth of pipe Aeration board；Stir speed (S.S.) control range is 100 ~ 600rpm, CO2For flow control in 0.1 ~ 1.5L/min, the reaction time is 10 ~ 60min；The compound liquid suspension of flyash-calcium carbonate obtained after the completion of reaction is filled with after directly adjusting concentration for paper, adjustment Mass percent concentration is 1% ~ 30% afterwards.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610611872.0A CN106283854B (en) | 2016-07-30 | 2016-07-30 | A kind of method of the fine coal gray surface precipitated crystal formula coating modification as papermaking filler |
| PCT/CN2016/110208 WO2018023918A1 (en) | 2016-07-30 | 2016-12-15 | Method using crystal deposition coating for modifying surface of fly ash for manufacturing paper filler |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610611872.0A CN106283854B (en) | 2016-07-30 | 2016-07-30 | A kind of method of the fine coal gray surface precipitated crystal formula coating modification as papermaking filler |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106283854A CN106283854A (en) | 2017-01-04 |
| CN106283854B true CN106283854B (en) | 2018-03-13 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610611872.0A Active CN106283854B (en) | 2016-07-30 | 2016-07-30 | A kind of method of the fine coal gray surface precipitated crystal formula coating modification as papermaking filler |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN106283854B (en) |
| WO (1) | WO2018023918A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109608911A (en) * | 2018-11-23 | 2019-04-12 | 华南理工大学 | A kind of fly ash base carbonization modification compounded mix preparation method being filled with for paper |
| CN113605139A (en) * | 2021-08-13 | 2021-11-05 | 江苏硕茂苏彩新材料有限公司 | Papermaking filler additive and preparation method thereof |
| CN114477825B (en) * | 2022-03-01 | 2022-09-23 | 徐州无废城市技术研究院有限公司 | Method for improving quality of circulating fluidized bed coal ash and reducing emission by combining mineralization of carbon dioxide, modified coal ash and application of modified coal ash |
| CN115012244A (en) * | 2022-04-27 | 2022-09-06 | 六盘水师范学院 | Filler paper and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594185A (en) * | 2004-07-07 | 2005-03-16 | 清华大学 | Fly ash brightening method |
| CN1648051A (en) * | 2004-11-30 | 2005-08-03 | 上海耀华纳米科技有限公司 | Method for preparing crystal nucleus prefabricated nano calcium carbonate and special equipment |
| CN102532955A (en) * | 2012-01-09 | 2012-07-04 | 淮南市蓝彩环保科技有限公司 | Method for preparing nano calcium carbonate coated fly ash ultrafine powder |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI126239B (en) * | 2013-12-31 | 2016-08-31 | Hannu Kuopanportti | Equipment for granulation of liquid bag |
-
2016
- 2016-07-30 CN CN201610611872.0A patent/CN106283854B/en active Active
- 2016-12-15 WO PCT/CN2016/110208 patent/WO2018023918A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594185A (en) * | 2004-07-07 | 2005-03-16 | 清华大学 | Fly ash brightening method |
| CN1648051A (en) * | 2004-11-30 | 2005-08-03 | 上海耀华纳米科技有限公司 | Method for preparing crystal nucleus prefabricated nano calcium carbonate and special equipment |
| CN102532955A (en) * | 2012-01-09 | 2012-07-04 | 淮南市蓝彩环保科技有限公司 | Method for preparing nano calcium carbonate coated fly ash ultrafine powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106283854A (en) | 2017-01-04 |
| WO2018023918A1 (en) | 2018-02-08 |
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