CN110484022A - A kind of production technology of the nanometer calcium carbonate of transparent membrane - Google Patents
A kind of production technology of the nanometer calcium carbonate of transparent membrane Download PDFInfo
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- CN110484022A CN110484022A CN201910845374.6A CN201910845374A CN110484022A CN 110484022 A CN110484022 A CN 110484022A CN 201910845374 A CN201910845374 A CN 201910845374A CN 110484022 A CN110484022 A CN 110484022A
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- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C1/022—Treatment with inorganic compounds
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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Abstract
The invention discloses a kind of production technologies of the nanometer calcium carbonate of transparent membrane, are related to technical field of land improvement, include the following steps: the temperature and concentration that adjust calcium hydroxide, and crystal control agent is added；It is passed through carbon dioxide gas again, when being carbonized to PH=7~8, stop carbonization, it is slowly added by mole 1:1 than the sodium sulphate of preparation and the aqueous solution of barium chloride, continue to stir 30min, until the surface of nanometer calcium carbonate forms coreshell type structure, carbonized carbonaceous slurrying liquid is further continued for PH≤7, it is coated for the first time using fatty acid salt inorganic agent, second using coupling agent and citrate plasticizer cladding, the nanometer calcium carbonate coated is starched and carries out filters pressing, drying and depolymerization, the primary particle size for preparing the nanometer calcium carbonate completed is 30~60nm, after surface treatment, it is between 0.5~1.0 μm that secondary laser particle size analyzer, which detects average grain diameter, with good processing performance, it is good with plastic resin substrate compatibility, for there is the good transparency when plastic film, dispersibility and intensity.
Description
Technical field
The present invention relates to technical field of land improvement, in particular to the life of a kind of nanometer calcium carbonate applied to transparent membrane
Production. art.
Background technique
For packing and the film of coating layer, mainly by polyvinyl chloride, polyethylene, polypropylene, polystyrene and
Other resins are made, and have been widely used for the fields such as food, medicine, chemical industry, agricultural, light industry, but due to resin by
Oil product is process, and high production cost, effect on environment is big, so it is generally necessary to filler, which is added, reduces cost, it is common
Filler are as follows: coarse whiting, light calcium, kaolin, quartz, barium sulfate, white carbon black, talcum powder etc..The addition of common filler can all influence
The transparency of film.For only nano barium sulfate, sodium sulphate etc. of transparent membrane, the water solubility of sodium sulphate is very good, in air
In be easy absorb moisture, cause the film-strength made poor, the transparency it is poor；Nano barium sulfate since it is than great, same weight
Master batch, the membrane area produced by boasting is small, high production cost.
Nanometer calcium carbonate is as a kind of novel filler, with particle size is small, large specific surface area, can increase plastic film
Intensity, have specific gravity small, the advantages such as manufacturing cost is low when accomplishing that partial size is very tiny, can be used for filling transparent master batch.But it receives
Rice calcium carbonate partial size hour, it is poor with the intermiscibility of plastics to be easy to reunite, and will affect its transparency, the nano-calcium carbonate of scale at present
The production of calcium is simultaneously immature, common nanometer calcium carbonate.
Summary of the invention
For disadvantages described above, the present invention provides a kind of production technology of nanometer calcium carbonate applied to transparent membrane, it is intended to
Solve the problems, such as that sandy soil soil improvement and difficulty of governance are big.
In order to solve the above technical problems, the technical scheme is that
A kind of production technology of the nanometer calcium carbonate of transparent membrane, includes the following steps:
1) it calcines: taking natural limestone to carry out high-temperature calcination, obtain calcium oxide；
2) it refines: taking calcium oxide screening decontamination obtained in step 1), adding after hot water digests and obtaining concentration is 6~12%
Calcium hydroxide suspension；
3) carbonization synthesis: calcium hydroxide suspension addition chemical additives obtained in step 2 are taken, then are transported to stirring
In carbonization reactor, while the CO that volumetric concentration is 25~35% is passed through into carbonization reactor2Gas, at 20~30 DEG C into
Row carbonization synthetic reaction, when the solution in carbonization reactor is carbonized to PH=7~8, stopping is passed through CO2Gas, be slowly added by
The aqueous solution of sodium sulphate and barium chloride that molar ratio 1:1 is prepared, continues 30~60min of stirring, until the surface of nanometer calcium carbonate
Coreshell type structure is formed, when being further continued for carbonization slurries to PH≤7, obtains nanometer calcium carbonate slurry；
4) modified: to take nanometer calcium carbonate slurry obtained in step 3), be heated after being warming up to 60~80 DEG C and keep the temperature, rouge is added
Fat hydrochlorate carries out the first subsurface cladding, adds coupling agent after stirring 30~60min and citrate carries out the second subsurface
Cladding, continues 30~60min of stirring, obtains modified slurry；
5) finished product: taking modified slurry obtained in step 4), is carried out filters pressing, washing, removes water soluble salt；It presses again
Filter, drying；Most nanometer calcium carbonate is obtained through crushing depolymerization afterwards.
Wherein, the digestion process of step 2 is to heat calcium oxide made from step 1) after shaft kiln vibration screening decontamination
Water carries out digestion reaction, and the temperature of hot water is that 50~70 DEG C, cement-water ratio 1:5~7 are stood old after the slagging-off of multistage spin vibration sieve
The change time >=for 24 hours, calcium hydroxide suspension then is made after multistage cyclone hydraulic separators.
Wherein, the chemical additives in step 3) are saccharide compound, and the additional amount of chemical additives is dry for calcium hydroxide
The 0.1~1.0% of base total amount.
Wherein, the concentration of the aqueous solution of sodium sulphate and barium chloride is 20~30% in step 3)；Additional amount is by generation sulfuric acid
The amount of barium accounts for the 3.0~8.0% of calcium carbonate dry weight total amount.
Wherein, the additional amount of fatty acid salt is the 1.5~3.0% of calcium carbonate butt total amount in step 4)；Fatty acid salt is
The soluble-salt of Long carbon chain fatty acid.
Wherein, coupling agent and citric acid ester plasticizer mass ratio are 2:1 in step 4), and additional amount is that calcium carbonate butt is total
The 1.5~3.0% of amount.
Wherein, coupling agent is phosphate coupling agent, and citrate is citric acid tri butyl ester or tributyl 2-acetylcitrate class
Environment-friendly plasticizer.
Wherein, during step 5) finished product, modified slurry obtained in step 4) is first subjected to diaphragm filters pressing, is obtained
To moisture content be 35~45% filter cake, clear water is then passed through in filter press, after being washed to filters pressing product, then with every
The drying of filter press membrane back-pressure water, makes filter cake moisture between 30~35%；It is dried, is most obtained into through broken depolymerization afterwards again
Product.
After above-mentioned technical proposal, the beneficial effects of the present invention are:
Since the production technology of the nanometer calcium carbonate of transparent membrane passes through the temperature and concentration of adjusting calcium hydroxide, and crystalline substance is added
Shape controlling agent；It is passed through carbon dioxide gas again, when carbonization to PH=7~8, stops carbonization, be slowly added by mole 1:1 a ratio preparation
Sodium sulphate and barium chloride aqueous solution, continue stir 30min, until nanometer calcium carbonate surface formed coreshell type structure, then
Continue carbonized carbonaceous slurrying liquid to PH≤7, is coated for the first time using fatty acid salt inorganic agent, reduce the oil suction of nanometer calcium carbonate
Value, second of compatibility using coupling agent and citrate plasticizer cladding raising nanometer calcium carbonate and plastics will coat
Nanometer calcium carbonate slurry carry out filters pressing, drying, depolymerization, prepare the nanometer calcium carbonate of completion primary particle size be 30~60nm, warp
After crossing surface treatment, it is to have good processing performance between 0.5~1.0 μm that secondary laser particle size analyzer, which detects average grain diameter,
It is good with plastic resin substrate compatibility, for having the good transparency, dispersibility and intensity when plastic film.
Detailed description of the invention
Fig. 1 is the electron microscope picture of the nano-calcium carbonate calcium product in the embodiment of the present invention one；
Fig. 2 is the electron microscope picture of the nano-calcium carbonate calcium product in the embodiment of the present invention two；
Fig. 3 is the electron microscope picture of the nano-calcium carbonate calcium product in the embodiment of the present invention three；
Fig. 4 is the electron microscope picture of the nano-calcium carbonate calcium product in the embodiment of the present invention four.
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is further explained.In the following detailed description, only pass through explanation
Mode describes certain exemplary embodiments of the invention.Undoubtedly, those skilled in the art will recognize, In
In the case where without departing from the spirit and scope of the present invention, described embodiment can be repaired with a variety of different modes
Just.Therefore, attached drawing and description are regarded as illustrative in nature, and are not intended to limit the scope of the claims.
Embodiment one:
In the carbonization kettle of 50L, addition concentration be 74g/L(mass concentration) raw pulp 35L, be added chemical additives, crystal form control
The additional amount of preparation be calcium hydroxide butt total amount 1.0%, after be passed through volumetric concentration be 25~35% carbon dioxide gas, In
Carbonization synthetic reaction is carried out at 20~30 DEG C, opens cooling water, and control temperature is no more than 25 DEG C, when the solution carbonization in reactor
When to PH=7~8, it is slowly added into the aqueous solution of sodium sulphate and barium chloride, wherein the ratio of sodium sulphate and barium chloride presses mole 1:1
Than preparation (additional amount accounts for the 5.0% of calcium carbonate dry weight total amount by the amount for generating barium sulfate), after the completion of addition, continue to stir
30~60min was further continued for carbonization until the surface of nanometer calcium carbonate forms coreshell type structure, carbonization slurries to PH≤7, i.e.,
Obtain nanometer calcium carbonate slurry.Obtained nanometer calcium carbonate slurry is entered into 50L activation pot by pump, is activated, is added the
Covering: fatty acid salt inorganic agent (additional amount is the 3.0% of calcium carbonate butt total amount) stirs 30 minutes, coupling is added
Agent (additional amount is the 1.5% of calcium carbonate butt total amount), citric acid rouge plasticizer is added simultaneously with coupling agent, and (additional amount is carbonic acid
The 1.5% of calcium butt total amount), it stirs 15 minutes, by modified slurry obtained, carries out filters pressing, dry, most being crushed depolymerization afterwards is
Nano-calcium carbonate calcium product is obtained, powder is without obvious agglomeration after being crushed.It is carried out using national standard (GB/T19588~2004)
Detection, whiteness 96.9%, 22.4 gDOP/100g of oil factor, 32.5 m of specific surface area2/g。
Embodiment two:
In the carbonization kettle of 50L, addition concentration be 85g/L(mass concentration) raw pulp 35L, be added chemical additives, crystal form control
The additional amount of preparation be calcium hydroxide butt total amount 1.0%, after be passed through volumetric concentration be 25~35% carbon dioxide gas, into
Row carbonization synthetic reaction, is not turned on cooling water, when the solution in reactor is carbonized to PH=7~8, be slowly added into sodium sulphate and
The aqueous solution of barium chloride, wherein (additional amount is by the amount for generating barium sulfate by a mole 1:1 ratio preparation for the ratio of sodium sulphate and barium chloride
Account for the 4.0% of calcium carbonate dry weight total amount), after the completion of addition, continue 30~60min of stirring, until the surface of nanometer calcium carbonate
Coreshell type structure is formed, is further continued for carbonized carbonaceous slurrying liquid PH≤7 to get nanometer calcium carbonate slurry is arrived.The nano-calcium carbonate that will be obtained
Calcium slurry enters 50L activation pot by pump, is activated, addition first time covering: fatty acid salt inorganic agent additional amount is
The 2.5% of calcium carbonate butt total amount stirs 30 minutes, coupling agent (additional amount is the 1.0% of calcium carbonate butt total amount) is added, with idol
Citric acid rouge plasticizer (additional amount is the 1.5% of calcium carbonate butt total amount) is added in connection agent simultaneously, stirs 15 minutes, will be obtained
Modified slurry carries out filters pressing, dry, is most crushed depolymerization afterwards and obtains nanometer calcium carbonate product, and powder is without obvious group after being crushed
Poly- phenomenon.It is detected using national standard (GB/T19588~2004), whiteness 96.5%, 23.5 gDOP/ of oil factor
100g, 31.3 m of specific surface area2/g。
Embodiment three:
In the carbonization kettle of 50L, addition concentration be 100g/L(mass concentration) raw pulp 35L, be added chemical additives, crystal form control
The additional amount of preparation be calcium hydroxide butt total amount 0.8%, after be passed through volumetric concentration be 25~35% carbon dioxide gas, In
Carbonization synthetic reaction is carried out at 20~30 DEG C, is opened cooling water temperature and is no more than 25 DEG C, when the solution in reactor is carbonized to PH
When=7~8, it is slowly added into the aqueous solution of sodium sulphate and barium chloride, wherein the ratio of sodium sulphate and barium chloride is matched by a mole 1:1 ratio
System (additional amount by generate barium sulfate amount account for the 5.0% of calcium carbonate dry weight total amount), after the completion of addition, continue stirring 30~
60min is further continued for carbonized carbonaceous slurrying liquid PH≤7 until the surface of nanometer calcium carbonate formation coreshell type structure to get nano-sized carbon is arrived
Sour calcium slurry.Obtained nanometer calcium carbonate slurry is entered into 50L activation pot by pump, is activated, first time covering is added:
Fatty acid salt inorganic agent additional amount is the 3.0% of calcium carbonate butt total amount, is stirred 30 minutes, and coupling agent is added, and (additional amount is carbon
The 1.0% of sour calcium butt total amount), citric acid rouge plasticizer is added simultaneously with coupling agent, and (additional amount is calcium carbonate butt total amount
1.0%) it, stirs 15 minutes, by modified slurry obtained, carries out filters pressing, it is dry, most nano-calcium carbonate is obtained through crushing depolymerization afterwards
Calcium product, powder is without obvious agglomeration after being crushed.It is detected using national standard (GB/T19588~2004), whiteness
96.8%, 22.3 gDOP/100g of oil factor, 29.2 m of specific surface area2/g。
Example IV:
In the carbonization kettle of 50L, addition concentration be 110g/L(mass concentration) raw pulp 35L, be added chemical additives, crystal form control
The additional amount of preparation be calcium hydroxide butt total amount 1.0%, after be passed through volumetric concentration be 25~35% carbon dioxide gas, In
Carry out carbonization synthetic reaction at 20~30 DEG C, open cooling water, when the solution in reactor is carbonized to PH=7~8, slowly plus
Enter the aqueous solution of sodium sulphate and barium chloride, wherein (additional amount is by generation by a mole 1:1 ratio preparation for the ratio of sodium sulphate and barium chloride
The amount of barium sulfate accounts for the 3.0% of calcium carbonate dry weight total amount), after the completion of addition, continue 30~60min of stirring, until nano-sized carbon
The surface of sour calcium forms coreshell type structure, is further continued for carbonized carbonaceous slurrying liquid PH≤7 to get nanometer calcium carbonate slurry is arrived.It will obtain
Nanometer calcium carbonate slurry by pump enter 50L activation pot, activated, be added first time covering: fatty acid salt processing
Agent additional amount is the 2.5% of calcium carbonate butt total amount, is stirred 30 minutes, and coupling agent is added, and (additional amount is calcium carbonate butt total amount
1.5%), be added simultaneously with coupling agent citric acid rouge plasticizer the 1.5% of calcium carbonate butt total amount (additional amount be), stirring 15
Minute, by modified slurry obtained, filters pressing is carried out, it is dry, it is most crushed depolymerization afterwards and obtains nanometer calcium carbonate product, after being crushed
Powder slightly has agglomeration.It is detected using national standard (GB/T19588~2004), whiteness 96.5%, oil factor 23.6
GDOP/100g, 27.8 m of specific surface area2/g。
The common nanometer calcium carbonate of existing market sale being surface-treated using resin acid acid and its ester, is marked using country
Quasi- (GB/T19588~2004) are detected, whiteness 96.1,24.5 gDOP/100g of oil factor, 28.3 m of specific surface area2/
g.Now by the performance of the common nano-calcium carbonate calcium product of the nanometer calcium carbonate produced of embodiment one to five and existing market into
Row comparison, such as the following table 1:
Table 1
| Project | Embodiment one | Embodiment two | Embodiment three | Example IV | Common product |
| Whiteness (%) | 96.9 | 96.5 | 96.8 | 96.5 | 96.1 |
| Oil factor (gDOP/100g) | 22.4 | 23.5 | 22.3 | 23.6 | 24.5 |
| Specific surface area (m2/ g) | 32.5 | 31.3 | 29.2 | 27.8 | 28.3 |
One to four product of above embodiments and common product are applied in the experimental formula of PE product, together with not filled PE
Product carries out performance comparison:
(1), it by the mass fraction proportion such as formula of the following table 2, is added in high-speed mixer, is mixed, when stirring reaches 110
It discharges at~125 DEG C.
2 powder application of table is in the test recipe of PE
| Project | Deal | Remarks |
| PE | 78 | High pressure polyethylene LDPE blown film grade |
| PE wax | 1 | 105 DEG C of polyethylene wax softening point |
| Aluminate coupling agent | 1 | DL411 type distearyl acyl-oxygen isopropyl Aluminate |
| Hydroxy silicon oil | 0.5 | End group is the linear polydimethylsiloxane- of hydroxyl |
| Toughener | 1 | Ethylene-propylene diene copolymer EPDM4770 |
| Heat stabilizer | 1 | Organotin |
| Paraffin wax lubricants | 2.5 | 50~65 DEG C of fusing point |
| Powder | 0~15 | Product, common product and the not filled blank sample of embodiment one to four |
(2) kneaded material, is added in double screw extruder, and extrusion temperature is 135~150 DEG C；After being granulated, squeezing
Film is cast on casting apparatus out, then drawn obtains oriented film, the mechanical property and light transmission of test gained cast film
Performance, light transmission are measured by GB/2410~2008 " transparent plastic light transmittance and haze test method ", as shown in table 3.
The performance test of the powder filled PE of table 3 compares
| Project | Application examples 1 | Application examples 2 | Application examples 3 | Application examples 4 | Application examples 5 | Application examples 6 |
| Powder | One product of embodiment | Two product of embodiment | Three product of embodiment | Example IV product | Common product | Powder is not added in blank |
| Longitudinal tensile strength/MPa | 15.6 | 15.3 | 14.6 | 15.3 | 12.3 | 10.3 |
| Mould is to tensile strength/MPa | 8.8 | 8.3 | 7.8 | 7.5 | 6.5 | 4.6 |
| Longitudinal tensile strain rate/% | 285 | 290 | 300 | 290 | 265 | 345 |
| Cross direction elongation/% | 445 | 460 | 435 | 430 | 405 | 480 |
| Light transmittance | 92.1 | 91.7 | 91.6 | 91.4 | 87.9 | 93.5 |
There is good intensity with respect to application examples 5 by use above example 1, application examples 2, application examples 3,4 gained filler of application examples and is stretched
Long rate, and the transparency is high；Filling intensity increase is not added in comparison application examples 6, so this product is for plastic film industry with good
Good intensity and elongation, and the transparency is high.
The present invention is not limited to above-mentioned specific embodiment, those skilled in the art from the above idea,
Without creative labor, the various transformation made are within the scope of the present invention.
Claims (8)
1. a kind of production technology of the nanometer calcium carbonate of transparent membrane, which comprises the steps of:
1) it calcines: taking natural limestone to carry out high-temperature calcination, obtain calcium oxide；
2) it refines: taking calcium oxide screening decontamination obtained in step 1), adding after hot water digests and obtaining concentration is 6~12%
Calcium hydroxide suspension；
3) carbonization synthesis: calcium hydroxide suspension addition chemical additives obtained in step 2 are taken, then are transported to stirring
In carbonization reactor, while the CO that volumetric concentration is 25~35% is passed through into carbonization reactor2Gas, at 20~30 DEG C into
Row carbonization synthetic reaction, when the solution in carbonization reactor is carbonized to PH=7~8, stopping is passed through CO2Gas, be slowly added by
The aqueous solution of sodium sulphate and barium chloride that molar ratio 1:1 is prepared, continues 30~60min of stirring, until the surface of nanometer calcium carbonate
Coreshell type structure is formed, when being further continued for carbonization slurries to PH≤7, obtains nanometer calcium carbonate slurry；
4) modified: to take nanometer calcium carbonate slurry obtained in step 3), be heated after being warming up to 60~80 DEG C and keep the temperature, rouge is added
Fat hydrochlorate carries out the first subsurface cladding, adds coupling agent after stirring 30~60min and citrate carries out the second subsurface
Cladding, continues 30~60min of stirring, obtains modified slurry；
5) finished product: taking modified slurry obtained in step 4), is carried out filters pressing, washing, removes water soluble salt；It presses again
Filter, drying；Most nanometer calcium carbonate is obtained through crushing depolymerization afterwards.
2. a kind of production technology of the nanometer calcium carbonate of transparent membrane as described in claim 1, which is characterized in that step 2
Digestion process be calcium oxide made from step 1) is heated after shaft kiln vibration screening decontamination water carry out digestion reaction, hot water
Temperature be that 50~70 DEG C, cement-water ratio 1:5~7 still aging time >=for 24 hours, are then passed through after the slagging-off of multistage spin vibration sieve
Calcium hydroxide suspension is made after multistage cyclone hydraulic separators.
3. a kind of production technology of the nanometer calcium carbonate of transparent membrane as described in claim 1, which is characterized in that step 3)
Described in chemical additives be saccharide compound, the additional amounts of chemical additives be calcium hydroxide butt total amount 0.1~
1.0%。
4. a kind of production technology of the nanometer calcium carbonate of transparent membrane as described in claim 1, it is characterised in that: step
3) concentration of the aqueous solution of sodium sulphate described in and barium chloride is 20~30%；Additional amount accounts for calcium carbonate by the amount for generating barium sulfate
The 3.0~8.0% of dry weight total amount.
5. a kind of production technology of the nanometer calcium carbonate of transparent membrane as described in claim 1, which is characterized in that step 4)
Described in fatty acid salt additional amount be calcium carbonate butt total amount 1.5~3.0%；The fatty acid salt is Long carbon chain fat
The soluble-salt of acid.
6. a kind of production technology of the nanometer calcium carbonate of transparent membrane as described in claim 1, which is characterized in that step 4)
Described in coupling agent and the citric acid ester plasticizer mass ratio be 2:1, additional amount be calcium carbonate butt total amount 1.5~
3.0%。
7. a kind of production technology of the nanometer calcium carbonate of transparent membrane as claimed in claim 6, which is characterized in that the idol
Connection agent is phosphate coupling agent, and the citrate is citric acid tri butyl ester or tributyl 2-acetylcitrate class environment-friendly plasticizer.
8. a kind of production technology of the nanometer calcium carbonate of transparent membrane as described in claim 1, which is characterized in that step 5)
During finished product, modified slurry obtained in step 4) is first subjected to diaphragm filters pressing, obtaining moisture content is 35~45%
Filter cake, clear water is then passed through in filter press, after being washed to filters pressing product, then with diaphragm filter press back-pressure water dry up,
Make filter cake moisture between 30~35%；It is dried again, most obtains finished product through broken depolymerization afterwards.
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