CN103897434A - Method for preparing special nano calcium carbonate for plastic master batch - Google Patents
Method for preparing special nano calcium carbonate for plastic master batch Download PDFInfo
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- CN103897434A CN103897434A CN201410157088.8A CN201410157088A CN103897434A CN 103897434 A CN103897434 A CN 103897434A CN 201410157088 A CN201410157088 A CN 201410157088A CN 103897434 A CN103897434 A CN 103897434A
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Abstract
The invention provides a method for preparing special nano calcium carbonate for a plastic master batch. According to the method, on the basis of calcium carbonate and characteristics thereof in application in plastics, internal indicators, such as crystal form, particle size, whiteness, pH value and the like, of nano-CaCO3 are controlled, meanwhile, the agglomeration and second-time surface coating of nano-CaCO3 particles caused by dry-activation modification are avoided by adopting wet activation, the dispersity of nano-CaCO3 is improved by one-time conventional coating, the oil absorption value of nano-CaCO3 is lowered by the one-time conventional coating, the compatibility of nano-CaCO3 with polyolefin plastics is improved by second-time coupling coating, and the processability and compatibility of nano-CaCO3 in the master batch are effectively improved, so that the prepared nano master batch has reinforced, toughened, high-dispersion and high-extrusion characteristics.
Description
Technical field
The present invention relates to plastics technology field, specifically the preparation method of nano-calcium carbonate for a kind of plastic master batch.
Background technology
Filling plastic modified master batch is the new industries of the fastest plastics of development in recent years, has become one of the integral part of Plastics Processing Industry and main interpolation material of plastics, and as the main stuffing CaCO of plastic modified master batch
3, its consumption, more than 80%, was used CaCO in the past
3be mainly heavy CaCO
3, fine particle calcium carbonate or be mixed with coarse whiting, the fine particle calcium carbonate of a small amount of Namigai, use pure Namigai seldom, reinforcement, toughness reinforcing performance are very low, have been mainly filling effects.Along with the functionalization of modified master batch, to raw materials of Ca CO
3requirement also more and more higher, and nanometer CaCO
3as a kind of functional filler, because it has that size of particles is little, specific surface area is large, surface atom is in height active state, there is very strong interfacial interaction with polymkeric substance, can carry out toughness reinforcing enhancing to polymkeric substance simultaneously, thereby make the plastics/nanometer CaCO taking plastics as matrix
3that composite master batch has is inorganic, the overall merit of polymer and nano material, but nanometer CaCO
3dispersion size in plastic master batch and dispersing uniformity performance and the homogeneity to filler parent granule has a great impact, and can directly affect processing and the reinforcement of plastic master batch.Therefore, preparation has the nanometer CaCO of high filling and good dispersity in polyolefin plastics
3become key.Adopt wet-process modified the making of new coupling agents to gather hydrocarbon masterbatch nanometer CaCO as mentioned in patent No. CN101260249B
3though, adopting wet method and new coupling agents modification, this patent does not clearly propose the performance index such as the crystal formation of nano-calcium carbonate, and several patents of wherein mentioning also exist defect in various degree; And for example in patent No. CN101456969B, adopt the composite modified functional nano calcium that makes of coarse whiting, fine particle calcium carbonate and Namigai, the mixture of its wet-process modified coarse whiting and fine particle calcium carbonate, Namigai is still dry method modification; And patent No. CN101987926B adopts control carbonization technique wet method to make rubber and plastic nano level active CaCO
3, weak point adopts conventional surfactants coated, with rubber and plastic organism consistency and capable of resisting high-temperature yellowing poor effect.
Summary of the invention
The object of the invention is in order to solve above-mentioned problems of the prior art and to improve the functional of plastic master batch, and the preparation method of a kind of plastic master batch nano-calcium carbonate is provided.
The present invention is achieved through the following technical solutions:
The preparation method that plastic master batch is Nano calcium carbonate dedicated, comprises the steps:
1) calcining: get natural limestone and carry out high-temperature calcination in shaft kiln, obtain calcium oxide;
2) digestion: get the calcinate calcium oxide making in step 1) hot water digestion after decon, it is the Ca (OH) of 10-15% that the refining thin up of slagging-off becomes concentration
2suspension;
3) carbonization is synthetic: get step 2) in the Ca (OH) that makes
2suspension, adds sequestrant and chemical additives, after stirring 10-30min, pumps in supergravity reactor, passes into the CO that volumetric concentration is 25-35% in supergravity reactor simultaneously
2gas carries out carbonization building-up reactions at 20-30 DEG C, and when the solution carbonization in supergravity reactor is during to pH=6.5-6.6, stopped reaction, obtains nano-calcium carbonate slurry;
4) modification: get the nano-calcium carbonate slurry making in step 3), be heated be warming up to 50-80 DEG C after insulation, in insulating process when the anti-alkali of the pH of nano-calcium carbonate slurry value adds when constant in enough organic or inorganic polyprotonic acids and remaining a small amount of Ca (OH)
2, after stirring, then add one-time surface activation coating, continue to be incubated and to stir 1h, then add the secondary treatment agent being formed by super dispersed lubricant and chelating titanate coupling agent, continue to obtain modified slurry after stirring 30min;
5) make finished product: get the modified slurry making in step 4), carry out press filtration, dry, obtain product of the present invention finally by broken depolymerization.
Further, in the calcination process of step 1), natural limestone is calcined in shaft kiln with coke, and wherein the mass ratio of coke and natural limestone is 1:10-11, and calcining temperature is 950-1000 DEG C, the preferred 12h of calcination time.
Step 2) digestive process in, that the calcium oxide that step 1) is made carries out digestion reaction through shaft kiln vibration screening decon post-heating water, the temperature of hot water is 40-60 DEG C, cement-water ratio 1:4-6, after the slagging-off of straight line shaker one-level, still aging>=48h, then after wet cyclone, thin up is crossed 325 orders and is revolved and screen out slag, is finally made into the Ca that mass concentration is 10-15% (OH)
2suspension.
Sequestrant described in step 3) is special-purpose metal ionic complexing agent, is that 1:1 is formulated in mass ratio by ammonium citrate and oxyacetic acid, and the add-on of sequestrant is the 0.05-0.10% of calcium hydroxide butt total amount; Chemical additives described in step 3) is the one in hydrogen peroxide, sodium polyphosphate and water glass, and the add-on of chemical additives is the 0.3-1.5% of calcium hydroxide butt total amount.
Organic or inorganic polyprotonic acid described in step 4) be a kind of or arbitrary proportion in toxilic acid, propanedioic acid, tartrate, boric acid, phosphoric acid, sulfurous acid, sulfuric acid mix several, the add-on of organic or inorganic polyprotonic acid is the 1.0-3.0% of calcium carbonate butt total amount; One-time surface activation coating described in step 4) is stearic acid, and add-on is the 1.0-2.5% of calcium carbonate butt total amount; In secondary treatment agent described in step 4), the mass ratio of super dispersed lubricant and chelating titanate coupling agent is 1:2, and the add-on of secondary treatment agent is the 1.0-1.5% of calcium carbonate butt total amount.
Making in finished product process of step 5), first the modified slurry making in step 4) is carried out to press filtration, be the press filtration product of 30-35% thereby obtain moisture content, then press filtration product being carried out respectively to one-level is dried and secondary drying, one-level drying temperature is 70-100 DEG C, makes the water content of press filtration product be down to 8-10%, secondary drying temperature is 100-120 DEG C, the water content of press filtration product is down to below 0.3%, obtains product of the present invention finally by broken depolymerization.
The nanometer CaCO3 that the inventive method makes has the characteristic of high whiteness, high extrusion capacity, low pH value, low water content and low oil absorption ferric, itself and plastic matrix have good blending, make plastic master batch in derived product is used, have height and melt the excellent effect of finger, high reinforcement and high dispersive.
The inventive method is passed through technology controlling and process:
1) product whiteness: (1) vibration screening decon of calcium oxide; (2) digest the three-stage filtration decon in operation; (3) in carbonization process, add the special chelant of chelated mineral particle, it has extremely strong capturing ability and dispersion effect to metal ion, can within the scope of quite wide pH value, there is sequestering action with multiple polyvalent metal ions such as iron, magnesium, lead, zinc, chromium, form more stable water soluble complex, thereby filtering workshop section's removal metallic impurity.
2) by controlling temperature of reaction and adding brilliant control, make the nanometer CaCO generating
3spherical for 60-80nm, selects to control nanometer CaCO
3particle diameter be 60-80nm, be mainly from cost, in the performance of filled plastics and processing fluidity three aspects: considers basis and tests and choose, and control nanometer CaCO
3crystal formation is spherical, and two performances superpose to effective raising nanometer CaCO
3mobility, extrudability more excellent.
3) carbodiimide solution is by the intensification accumulation of salt in the surface soil, then adds enough organic acids or inorganic multivariate acid, removes little a part of calcium hydroxide (≤2%) remaining in product, makes the nanometer CaCO generating
3pH remains between 8.0-9.0.Can in synthetic master batch process, destroy the organic long molecular chain of polyolefine because basicity is high, reduce final plastics pulling force and reinforcement.
4) adopt and be coated for twice, be coated for the first time as conventional surface treatment coating stearic acid, adopt for the second time with the chelating titanate coupling agent of the good super lubrication dispersing agent of organism blending and hydrolysis coatedly, make it have low oil number, high dispersity and the consistency good with organism.
Another super dispersed lubricant ties up on the basis of ethylene bis-fatty acid amides and carries out structure of modification; introduce polarity gene; also can claim anchoring group; this group has firmly associativity to filler-calcium carbonate particle; be difficult to resolve, backbone molecule is long-chain lipophilic group, has certain consistency with resin; can ensure that dispersion agent forms certain thickness protective layer in solid particles surface, the material of main part in master batch can be evenly dispersed in vector resin.Like this, when being surrounded by while disperseing the solid particulate of group to interact because of Van der Waals force, mutually flick because the spatial obstacle between adsorption layer makes particle, thereby make to realize the stable dispersion of solid particulate in resin.Tradition dispersion agent is that unregulated polymer is as low molecular weight polyethylene, oxidation low molecular weight polyethylene or titanate coupling agent etc., the adsorption group of low molecular weight polyethylene or oxidation low molecular weight polyethylene is irregularly distributed on main polymer chain, easily forms the bridge formation flocculation between solid particulate.Hyper-dispersant be have rule multipolymer its structure be anchoring group in central BAB type segmented copolymer, its anchoring group the same side in dispersant molecule chain, can not the different solid particles surface of absorption, thereby has avoided the flocculation of building bridge.Can only improve and resin compatible and make coating with this class coupling agent of titanic acid ester, there is no lubrication, can not improve melt index.And the length of super dispersed lubricant body portion subchain is compared with resin much shorter, its internal cohesive energy is lower, and the inside and outside oilness of itself tool, is low melting point dispersion agent, and what therefore use this auxiliary agent can increase substantially melt index in master batch processing.Both combinations, can improve the over-all properties in plastic master batch.
By above control, make the nanometer CaCO generating
3becoming particle diameter is the equally distributed spherical calcium carbonate of 60-80nm, and has high whiteness, low oil absorption ferric, low pH value and the consistency with organic polyolefin plastics, and has ensured the high dispersive of the finished product, high extrudability and high reinforcement.
The nanometer CaCO that the inventive method makes after testing
3parameter is as follows:
With the nanometer CaCO described in the inventive method
3the standby detection of polyolefin plastics master batch of making: the performance comparison (employing Intelligent electronic tensil testing machine) for drawn wire product:
Sample 1:90 part PPT30S adds that 10 parts adopt ordinary calcium carbonate to make the prepared product of masterbatch.
Sample 2: adopt the prepared nanometer masterbatch of nano-calcium carbonate of gained of the present invention, dose again 8 parts of prepared products of this nanometer masterbatch on sample 1 is filled a prescription constant basis.
Nanometer CaCO prepared by traditional method
3almost disperse without molten finger, difficulty for derived product, and the nanometer CaCO that present method makes
3in derived product is used, can not change its molten finger, and other performance is also greatly improved.
The characteristic that the present invention applies according to calcium carbonate and in plastics, adopts and controls nanometer CaCO
3the inherent index such as crystal formation, size of particles, whiteness, pH value, adopt wet-process activation (to avoid dry activation modification to cause nanometer CaCO simultaneously
3particle aggregation), and secondary instrument bread covers, the once conventional coated nanometer CaCO that improves
3dispersiveness, reduce oil-absorption(number), the coated nanometer CaCO that improves of secondary coupling
3with the consistency of polyolefins plastics, effectively improve nanometer CaCO
3processibility and consistency in master batch uses, the nanometer master batch that makes to make has the characteristic that enhancings, toughness reinforcing, high dispersive and height are extruded.
Embodiment
Embodiment 1
The preparation method that plastic master batch is Nano calcium carbonate dedicated, comprises the steps:
1) calcining: get natural limestone and carry out high-temperature calcination in shaft kiln, obtain calcium oxide;
2) digestion: get the calcinate calcium oxide making in step 1) hot water digestion after decon, it is 13% Ca (OH) that the refining thin up of slagging-off becomes concentration
2suspension;
3) carbonization is synthetic: get step 2) in the Ca (OH) that makes
2suspension, adds sequestrant and chemical additives, and stir after 10min and pump in supergravity reactor, be 30% CO to passing into volumetric concentration in supergravity reactor simultaneously
2gas carries out carbonization building-up reactions at 30 DEG C, and when the solution carbonization in supergravity reactor is during to pH=6.53, stopped reaction, obtains nano-calcium carbonate slurry;
4) modification: get the nano-calcium carbonate slurry making in step 3), be heated be warming up to 80 DEG C after insulation, in insulating process when the anti-alkali of the pH of nano-calcium carbonate slurry value adds when constant in enough organic or inorganic polyprotonic acids and remaining a small amount of Ca (OH)
2, after stirring, then add one-time surface activation coating, continue to be incubated and to stir 1h, then add the secondary treatment agent being formed by super dispersed lubricant and chelating titanate coupling agent, continue to obtain modified slurry after stirring 30min;
5) make finished product: get the modified slurry making in step 4), carry out press filtration, dry, obtain product of the present invention finally by broken depolymerization.
When concrete enforcement, in the calcination process of step 1), natural limestone is calcined in shaft kiln with coke, and wherein the mass ratio of coke and natural limestone is 1:10, and calcining temperature is 1000 DEG C, the preferred 12h of calcination time.
Step 2) digestive process in, that the calcium oxide that step 1) is made carries out digestion reaction through shaft kiln vibration screening decon post-heating water, the temperature of hot water is 50 DEG C, cement-water ratio 1:4, after the slagging-off of straight line shaker one-level, still aging>=48h, then after wet cyclone, thin up is crossed 325 orders and is revolved and screen out slag, is finally made into mass concentration and is 13% Ca (OH)
2suspension.
Sequestrant described in step 3) is special-purpose metal ionic complexing agent, is that 1:1 is formulated in mass ratio by ammonium citrate and oxyacetic acid, and the add-on of sequestrant is 0.10% of calcium hydroxide butt total amount; Chemical additives described in step 3) is hydrogen peroxide, and the add-on of chemical additives is 0.3% of calcium hydroxide butt total amount.
Organic or inorganic polyprotonic acid described in step 4) is toxilic acid, and the add-on of organic or inorganic polyprotonic acid is 1.5% of calcium carbonate butt total amount; One-time surface activation coating described in step 4) is stearic acid, and add-on is 2.0% of calcium carbonate butt total amount; In secondary treatment agent described in step 4), the mass ratio of super dispersed lubricant and chelating titanate coupling agent is 1:2, and the add-on of secondary treatment agent is 1.2% of calcium carbonate butt total amount.
Making in finished product process of step 5), first the modified slurry making in step 4) is carried out to press filtration, thereby obtain moisture content and be 35% press filtration product, then press filtration product being carried out respectively to one-level is dried and secondary drying, one-level drying temperature is 70 DEG C, makes the water content of press filtration product be down to 8%, secondary drying temperature is 120 DEG C, the water content of press filtration product is down to below 0.3%, obtains product of the present invention finally by broken depolymerization.
Embodiment 2
The preparation method that plastic master batch is Nano calcium carbonate dedicated, comprises the steps:
1) calcining: get natural limestone and carry out high-temperature calcination in shaft kiln, obtain calcium oxide;
2) digestion: get the calcinate calcium oxide making in step 1) hot water digestion after decon, it is 15% Ca (OH) that the refining thin up of slagging-off becomes concentration
2suspension;
3) carbonization is synthetic: get step 2) in the Ca (OH) that makes
2suspension, adds sequestrant and chemical additives, and stir after 25min and pump in supergravity reactor, be 33% CO to passing into volumetric concentration in supergravity reactor simultaneously
2gas carries out carbonization building-up reactions at 27 DEG C, and when the solution carbonization in supergravity reactor is during to pH=6.6, stopped reaction, obtains nano-calcium carbonate slurry;
4) modification: get the nano-calcium carbonate slurry making in step 3), be heated be warming up to 60 DEG C after insulation, in insulating process when the anti-alkali of the pH of nano-calcium carbonate slurry value adds when constant in enough organic or inorganic polyprotonic acids and remaining a small amount of Ca (OH)
2, after stirring, then add one-time surface activation coating, continue to be incubated and to stir 1h, then add the secondary treatment agent being formed by super dispersed lubricant and chelating titanate coupling agent, continue to obtain modified slurry after stirring 30min;
5) make finished product: get the modified slurry making in step 4), carry out press filtration, dry, obtain product of the present invention finally by broken depolymerization.
When concrete enforcement, in the calcination process of step 1), natural limestone is calcined in shaft kiln with coke, and wherein the mass ratio of coke and natural limestone is 1:11, and calcining temperature is 980 DEG C, the preferred 12h of calcination time.
Step 2) digestive process in, that the calcium oxide that step 1) is made carries out digestion reaction through shaft kiln vibration screening decon post-heating water, the temperature of hot water is 40 DEG C, cement-water ratio 1:5.5, after the slagging-off of straight line shaker one-level, still aging>=48h, then after wet cyclone, thin up is crossed 325 orders and is revolved and screen out slag, is finally made into mass concentration and is 15% Ca (OH)
2suspension.
Sequestrant described in step 3) is special-purpose metal ionic complexing agent, is that 1:1 is formulated in mass ratio by ammonium citrate and oxyacetic acid, and the add-on of sequestrant is 0.08% of calcium hydroxide butt total amount; Chemical additives described in step 3) is sodium polyphosphate, and the add-on of chemical additives is 0.8% of calcium hydroxide butt total amount.
Organic or inorganic polyprotonic acid described in step 4) is phosphoric acid, and the add-on of organic or inorganic polyprotonic acid is 3% of calcium carbonate butt total amount; One-time surface activation coating described in step 4) is stearic acid, and add-on is 1.5% of calcium carbonate butt total amount; In secondary treatment agent described in step 4), the mass ratio of super dispersed lubricant and chelating titanate coupling agent is 1:2, and the add-on of secondary treatment agent is 1% of calcium carbonate butt total amount.
Making in finished product process of step 5), first the modified slurry making in step 4) is carried out to press filtration, thereby obtain moisture content and be 32% press filtration product, then press filtration product being carried out respectively to one-level is dried and secondary drying, one-level drying temperature is 90 DEG C, makes the water content of press filtration product be down to 9.5%, secondary drying temperature is 105 DEG C, the water content of press filtration product is down to below 0.3%, obtains product of the present invention finally by broken depolymerization.
Embodiment 3
The preparation method that plastic master batch is Nano calcium carbonate dedicated, comprises the steps:
1) calcining: get natural limestone and carry out high-temperature calcination in shaft kiln, obtain calcium oxide;
2) digestion: get the calcinate calcium oxide making in step 1) hot water digestion after decon, it is 10% Ca (OH) that the refining thin up of slagging-off becomes concentration
2suspension;
3) carbonization is synthetic: get step 2) in the Ca (OH) that makes
2suspension, adds sequestrant and chemical additives, and stir after 30min and pump in supergravity reactor, be 25% CO to passing into volumetric concentration in supergravity reactor simultaneously
2gas carries out carbonization building-up reactions at 20 DEG C, and when the solution carbonization in supergravity reactor is during to pH=6.5, stopped reaction, obtains nano-calcium carbonate slurry;
4) modification: get the nano-calcium carbonate slurry making in step 3), be heated be warming up to 50 DEG C after insulation, in insulating process when the anti-alkali of the pH of nano-calcium carbonate slurry value adds when constant in enough organic or inorganic polyprotonic acids and remaining a small amount of Ca (OH)
2, after stirring, then add one-time surface activation coating, continue to be incubated and to stir 1h, then add the secondary treatment agent being formed by super dispersed lubricant and chelating titanate coupling agent, continue to obtain modified slurry after stirring 30min;
5) make finished product: get the modified slurry making in step 4), carry out press filtration, dry, obtain product of the present invention finally by broken depolymerization.
When concrete enforcement, in the calcination process of step 1), natural limestone is calcined in shaft kiln with coke, and wherein the mass ratio of coke and natural limestone is 1:11, and calcining temperature is 960 DEG C, the preferred 12h of calcination time.
Step 2) digestive process in, that the calcium oxide that step 1) is made carries out digestion reaction through shaft kiln vibration screening decon post-heating water, the temperature of hot water is 55 DEG C, cement-water ratio 1:6, after the slagging-off of straight line shaker one-level, still aging>=48h, then after wet cyclone, thin up is crossed 325 orders and is revolved and screen out slag, is finally made into mass concentration and is 10% Ca (OH)
2suspension.
Sequestrant described in step 3) is special-purpose metal ionic complexing agent, is that 1:1 is formulated in mass ratio by ammonium citrate and oxyacetic acid, and the add-on of sequestrant is 0.09% of calcium hydroxide butt total amount; Chemical additives described in step 3) is water glass, and the add-on of chemical additives is 1.5% of calcium hydroxide butt total amount.
Organic or inorganic polyprotonic acid described in step 4) is tartrate, and the add-on of organic or inorganic polyprotonic acid is 2% of calcium carbonate butt total amount; One-time surface activation coating described in step 4) is stearic acid, and add-on is 2.5% of calcium carbonate butt total amount; In secondary treatment agent described in step 4), the mass ratio of super dispersed lubricant and chelating titanate coupling agent is 1:2, and the add-on of secondary treatment agent is 1.5% of calcium carbonate butt total amount.
Making in finished product process of step 5), first the modified slurry making in step 4) is carried out to press filtration, thereby obtain moisture content and be 30% press filtration product, then press filtration product being carried out respectively to one-level is dried and secondary drying, one-level drying temperature is 100 DEG C, makes the water content of press filtration product be down to 8.5%, secondary drying temperature is 100 DEG C, the water content of press filtration product is down to below 0.3%, obtains product of the present invention finally by broken depolymerization.
Embodiment 4
The preparation method that plastic master batch is Nano calcium carbonate dedicated, comprises the steps:
1) calcining: get natural limestone and carry out high-temperature calcination in shaft kiln, obtain calcium oxide;
2) digestion: get the calcinate calcium oxide making in step 1) hot water digestion after decon, it is 11% Ca (OH) that the refining thin up of slagging-off becomes concentration
2suspension;
3) carbonization is synthetic: get step 2) in the Ca (OH) that makes
2suspension, adds sequestrant and chemical additives, and stir after 15min and pump in supergravity reactor, be 35% CO to passing into volumetric concentration in supergravity reactor simultaneously
2gas carries out carbonization building-up reactions at 23 DEG C, and when the solution carbonization in supergravity reactor is during to pH=6.55, stopped reaction, obtains nano-calcium carbonate slurry;
4) modification: get the nano-calcium carbonate slurry making in step 3), be heated be warming up to 70 DEG C after insulation, in insulating process when the anti-alkali of the pH of nano-calcium carbonate slurry value adds when constant in enough organic or inorganic polyprotonic acids and remaining a small amount of Ca (OH)
2, after stirring, then add one-time surface activation coating, continue to be incubated and to stir 1h, then add the secondary treatment agent being formed by super dispersed lubricant and chelating titanate coupling agent, continue to obtain modified slurry after stirring 30min;
5) make finished product: get the modified slurry making in step 4), carry out press filtration, dry, obtain product of the present invention finally by broken depolymerization.
When concrete enforcement, in the calcination process of step 1), natural limestone is calcined in shaft kiln with coke, and wherein the mass ratio of coke and natural limestone is 1:10, and calcining temperature is 950 DEG C, the preferred 12h of calcination time.
Step 2) digestive process in, that the calcium oxide that step 1) is made carries out digestion reaction through shaft kiln vibration screening decon post-heating water, the temperature of hot water is 60 DEG C, cement-water ratio 1:5, after the slagging-off of straight line shaker one-level, still aging>=48h, then after wet cyclone, thin up is crossed 325 orders and is revolved and screen out slag, is finally made into mass concentration and is 10% Ca (OH)
2suspension.
Sequestrant described in step 3) is special-purpose metal ionic complexing agent, is that 1:1 is formulated in mass ratio by ammonium citrate and oxyacetic acid, and the add-on of sequestrant is 0.06% of calcium hydroxide butt total amount; Chemical additives described in step 3) is sodium polyphosphate, and the add-on of chemical additives is 1.0% of calcium hydroxide butt total amount.
Organic or inorganic polyprotonic acid described in step 4) is propanedioic acid and the tartrate that arbitrary proportion mixes, and the add-on of organic or inorganic polyprotonic acid is 1.3% of calcium carbonate butt total amount; One-time surface activation coating described in step 4) is stearic acid, and add-on is 1% of calcium carbonate butt total amount; In secondary treatment agent described in step 4), the mass ratio of super dispersed lubricant and chelating titanate coupling agent is 1:2, and the add-on of secondary treatment agent is 1.1% of calcium carbonate butt total amount.
Making in finished product process of step 5), first the modified slurry making in step 4) is carried out to press filtration, thereby obtain moisture content and be 34% press filtration product, then press filtration product being carried out respectively to one-level is dried and secondary drying, one-level drying temperature is 80 DEG C, makes the water content of press filtration product be down to 9%, secondary drying temperature is 110 DEG C, the water content of press filtration product is down to below 0.3%, obtains product of the present invention finally by broken depolymerization.
Embodiment 5
The preparation method that plastic master batch is Nano calcium carbonate dedicated, comprises the steps:
1) calcining: get natural limestone and carry out high-temperature calcination in shaft kiln, obtain calcium oxide;
2) digestion: get the calcinate calcium oxide making in step 1) hot water digestion after decon, it is 12% Ca (OH) that the refining thin up of slagging-off becomes concentration
2suspension;
3) carbonization is synthetic: get step 2) in the Ca (OH) that makes
2suspension, adds sequestrant and chemical additives, and stir after 20min and pump in supergravity reactor, be 27% CO to passing into volumetric concentration in supergravity reactor simultaneously
2gas carries out carbonization building-up reactions at 25 DEG C, and when the solution carbonization in supergravity reactor is during to pH=6.57, stopped reaction, obtains nano-calcium carbonate slurry;
4) modification: get the nano-calcium carbonate slurry making in step 3), be heated be warming up to 50 DEG C after insulation, in insulating process when the anti-alkali of the pH of nano-calcium carbonate slurry value adds when constant in enough organic or inorganic polyprotonic acids and remaining a small amount of Ca (OH)
2, after stirring, then add one-time surface activation coating, continue to be incubated and to stir 1h, then add the secondary treatment agent being formed by super dispersed lubricant and chelating titanate coupling agent, continue to obtain modified slurry after stirring 30min;
5) make finished product: get the modified slurry making in step 4), carry out press filtration, dry, obtain product of the present invention finally by broken depolymerization.
When concrete enforcement, in the calcination process of step 1), natural limestone is calcined in shaft kiln with coke, and wherein the mass ratio of coke and natural limestone is 1:10, and calcining temperature is 990 DEG C, the preferred 12h of calcination time.
Step 2) digestive process in, that the calcium oxide that step 1) is made carries out digestion reaction through shaft kiln vibration screening decon post-heating water, the temperature of hot water is 45 DEG C, cement-water ratio 1:4.5, after the slagging-off of straight line shaker one-level, still aging>=48h, then after wet cyclone, thin up is crossed 325 orders and is revolved and screen out slag, is finally made into mass concentration and is 10% Ca (OH)
2suspension.
Sequestrant described in step 3) is special-purpose metal ionic complexing agent, is that 1:1 is formulated in mass ratio by ammonium citrate and oxyacetic acid, and the add-on of sequestrant is 0.05% of calcium hydroxide butt total amount; Chemical additives described in step 3) is hydrogen peroxide, and the add-on of chemical additives is 1.2% of calcium hydroxide butt total amount.
Organic or inorganic polyprotonic acid described in step 4) is boric acid, sulfurous acid, the sulfuric acid that arbitrary proportion mixes, and the add-on of organic or inorganic polyprotonic acid is 1.0% of calcium carbonate butt total amount; One-time surface activation coating described in step 4) is stearic acid, and add-on is 2% of calcium carbonate butt total amount; In secondary treatment agent described in step 4), the mass ratio of super dispersed lubricant and chelating titanate coupling agent is 1:2, and the add-on of secondary treatment agent is 1.4% of calcium carbonate butt total amount.
Making in finished product process of step 5), first the modified slurry making in step 4) is carried out to press filtration, thereby obtain moisture content and be 31% press filtration product, then press filtration product being carried out respectively to one-level is dried and secondary drying, one-level drying temperature is 85 DEG C, makes the water content of press filtration product be down to 10%, secondary drying temperature is 115 DEG C, the water content of press filtration product is down to below 0.3%, obtains product of the present invention finally by broken depolymerization.
Claims (6)
1. the Nano calcium carbonate dedicated preparation method of plastic master batch, is characterized in that, comprises the steps:
1) calcining: get natural limestone and carry out high-temperature calcination in shaft kiln, obtain calcium oxide;
2) digestion: get the calcinate calcium oxide making in step 1) hot water digestion after decon, it is the Ca (OH) of 10-15% that the refining thin up of slagging-off becomes concentration
2suspension;
3) carbonization is synthetic: get step 2) in the Ca (OH) that makes
2suspension, adds sequestrant and chemical additives, after stirring 10-30min, pumps in supergravity reactor, passes into the CO that volumetric concentration is 25-35% in supergravity reactor simultaneously
2gas carries out carbonization building-up reactions at 20-30 DEG C, and when the solution carbonization in supergravity reactor is during to pH=6.5-6.6, stopped reaction, obtains nano-calcium carbonate slurry;
4) modification: get the nano-calcium carbonate slurry making in step 3), be heated be warming up to 50-80 DEG C after insulation, in insulating process when the anti-alkali of the pH of nano-calcium carbonate slurry value adds when constant in enough organic or inorganic polyprotonic acids and remaining a small amount of Ca (OH)
2, after stirring, then add one-time surface activation coating, continue to be incubated and to stir 1h, then add the secondary treatment agent being formed by super dispersed lubricant and chelating titanate coupling agent, continue to obtain modified slurry after stirring 30min;
5) make finished product: get the modified slurry making in step 4), carry out press filtration, dry, obtain product of the present invention finally by broken depolymerization.
2. the Nano calcium carbonate dedicated preparation method of a kind of plastic master batch according to claim 1, it is characterized in that: in the calcination process of step 1), natural limestone is calcined in shaft kiln with coke, wherein the mass ratio of coke and natural limestone is 1:10-11, calcining temperature is 950-1000 DEG C, the preferred 12h of calcination time.
3. the Nano calcium carbonate dedicated preparation method of a kind of plastic master batch according to claim 1, it is characterized in that: step 2) digestive process in, that the calcium oxide that step 1) is made carries out digestion reaction through shaft kiln vibration screening decon post-heating water, the temperature of hot water is 40-60 DEG C, cement-water ratio 1:4-6, after the slagging-off of straight line shaker one-level, still aging>=48h, then after wet cyclone, thin up is crossed 325 orders and is revolved and screen out slag, is finally made into the Ca that mass concentration is 10-15% (OH)
2suspension.
4. the Nano calcium carbonate dedicated preparation method of a kind of plastic master batch according to claim 1, it is characterized in that: the sequestrant described in step 3) is special-purpose metal ionic complexing agent, be that 1:1 is formulated in mass ratio by ammonium citrate and oxyacetic acid, the add-on of sequestrant is the 0.05-0.10% of calcium hydroxide butt total amount; Chemical additives described in step 3) is the one in hydrogen peroxide, sodium polyphosphate and water glass, and the add-on of chemical additives is the 0.3-1.5% of calcium hydroxide butt total amount.
5. the Nano calcium carbonate dedicated preparation method of a kind of plastic master batch according to claim 1, it is characterized in that: the organic or inorganic polyprotonic acid described in step 4) be a kind of or arbitrary proportion in toxilic acid, propanedioic acid, tartrate, boric acid, phosphoric acid, sulfurous acid, sulfuric acid mix several, the add-on of organic or inorganic polyprotonic acid is the 1.0-3.0% of calcium carbonate butt total amount; One-time surface activation coating described in step 4) is stearic acid, and add-on is the 1.0-2.5% of calcium carbonate butt total amount; In secondary treatment agent described in step 4), the mass ratio of super dispersed lubricant and chelating titanate coupling agent is 1:2, and the add-on of secondary treatment agent is the 1.0-1.5% of calcium carbonate butt total amount.
6. the Nano calcium carbonate dedicated preparation method of a kind of plastic master batch according to claim 1, it is characterized in that: the making in finished product process of step 5), first the modified slurry making in step 4) is carried out to press filtration, be the press filtration product of 30-35% thereby obtain moisture content, then press filtration product being carried out respectively to one-level is dried and secondary drying, one-level drying temperature is 70-100 DEG C, make the water content of press filtration product be down to 8-10%, secondary drying temperature is 100-120 DEG C, the water content of press filtration product is down to below 0.3%, obtain product of the present invention finally by broken depolymerization.
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