CN101962808A - High-efficiency and energy-saving potassium titanate whisker preparation method - Google Patents
High-efficiency and energy-saving potassium titanate whisker preparation method Download PDFInfo
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Abstract
The invention discloses a high-efficiency and energy-saving potassium titanate whisker preparation method, which comprises: firstly, mixing and grinding a titanium raw material and a potassium raw material, and preheating; and secondly, calcining, crushing, absorbing and desorbing moisture, converting potassium ions, forming and obtaining pure white potassium titanate whiskers. In the invention, potassium dititanate is crushed by a machine, the moisture absorption and desorption speed is improved, and the production efficiency is improved considerably; through heat recycling, the energy consumption is reduced greatly; heat generated in a high-temperature area is used in a preheating kiln and a constant-temperature moisture absorption and desorption kiln, the structural integrity of the crystals and the utilization rate of raw materials are improved, and the high-efficiency and energy-saving preparation of potassium titanate whisker is realized; and a quantitative injection mode is used to realize the quantitative digestion conversion of the potassium ions, so the effective control of different whiskers is realized and the obtained whisker products have complete crystal structure and contain white crystals with flaky, lamellar or needle-like shapes. The product can be widely used in fields of thermal insulation, reinforcement, corrosion prevention, toughening and the like.
Description
Technical field
The invention belongs to the materials chemistry field, be specifically related to a kind of preparation method of energy-efficient potassium titanate crystal whisker.
Background technology
The potassium titanate series crystal whisker is a class new function material, has very excellent mechanical property and physicals: high strength, high-modulus, abrasion performance, high temperature resistant, heat insulation, high electric insulating quality and excellent properties of infrared reflection.Especially the micro-filling of this whisker and strengthen the property good especially, available its developed various novel high-caliber lightweights, strong, the attrition resistant reinforced plastics matrix material of height ratio, have splendid physical and mechanical properties and chemical property, had one of functional materials of exploitation value by 21st century.
Potassium titanate crystal whisker has good mechanics and physicals, and have very high electrical insulating property, heat-resisting, heat-proof quality and an excellent infrared wavelength zone emitting performance, the coefficient of expansion and plastics are suitable, and the composite reinforced plastics consistency is good, show good wear resistance and oilness.Therefore, obtained using widely in fields such as engineering plastics, friction materials, heat insulation, insulating material.Can replace asbestos to be applied to brake facing, disc type liner and the clutch facing of automobile as potassium titanate crystal whisker.Potassium titanate crystal whisker to infrared reflection power height, can be used as the paper grade (stock) white pigment because its hidden power is strong, can be used as coating raw material preparation infrared reflecting paint and heat-resisting thermal insulating coating, is used for coatings such as building materials, machinery.Potassium titanate crystal whisker at high temperature thermal conductivity is low, and is very superior as lagging material.The refractory brick made from crystal whisker of hexa potassium titanate is under 1200 ℃ high temperature, and no abnormal phenomenon generation in a year is used in circulation heating continuously.The potassium titanate crystal whisker alkali resistance is good, can do alkaline electrolysis and use with barrier film, fuel cell barrier film and battery sorting device.In addition, because potassium titanate crystal whisker self good hydrophilic property after the employing surface treatment agent is handled, also has good lipophilicity, can make various filtering materials and use.The filter membrane made from potassium titanate crystal whisker enhanced macromolecular material is thin and fine and close, infiltration is forced down, strong with solution avidity, this class film has improved wetting ability, physical strength and the thermotolerance of film when having kept the original excellent properties of organic membrane, be used for the occasion that industries such as health care, food need often be carried out high-temperature steam sterilization.Potassium titanate has good chemical stability, as the very active K of chemical property in six potassium titanates
+By tunnel-shaped TiO
6The octahedra coating, thus greatly reduce K
+Chemically reactive, make potassium titanate to exist at diluted acid, highly basic and high temperatures.The potassium titanate crystal whisker stable performance, but generally to use through after the surface treatment, compare with other clays that use in the chemical process industry, potassium titanate crystal whisker has that specific surface area is big, absorption and the strong characteristics of decolorizing ability, is ideal trace metal ion separation and concentration material.
In view of potassium titanate series crystal whisker wide applications, existing more both at home and abroad at present preparation research report about the potassium titanate series crystal whisker.Gier etc. have synthesized crystal whisker of hexa potassium titanate under 600～700 ℃, 500～4000atm, the corrodibility of strongly basic medium is to the requirement height of equipment, dangerous big (USPatent 2833620 for T.E.Gier, P.L.Salzberg) under high top pressure operation and the high temperature.People such as Toshitaka are raw material with the hydrated titanium dioxide, under 390 ℃, 150～200atm, adopt Metal Zn as dewatering agent prepared crystal whisker of hexa potassium titanate (Toshitaka, et al., J.Cryst.Growth, 1979,46:331-338).Chinese invention patent 200810055803.1 discloses a kind of quick method for preparing lamellate potassium titanate, belongs to the nano material preparation technical field.Getting potassium titanium molar ratio is 1: 2 the potassium stearate and the reactant of butyl (tetra) titanate, butyl (tetra) titanate is added in the potassium stearate of molten state, mixes, calcining preparation then, this method has been simplified reaction process, has been shortened the reaction times, has guaranteed the purity of product, but the industrialization difficulty is very big.Patent 03116985.6 is a raw material with titanium compound and potassium compound, raw material is the crystalline compound that contains titanium, the crystalline compound of this titanium is Detitanium-ore-type hydrolyzed titanium dioxide or Detitanium-ore-type metatitanic acid, prepare spherical reaction precursor body by spraying drying or rotary flashing drying process, this spherical reaction precursor body is the coacervate that crystalline compound and the potassium compound by titanium forms; Pack into the reaction precursor body in the crucible or be pre-formed as blank sintering; Separate with deionized water and to knit whisker; By filtering, wash, drying finally makes crystal whisker of hexa potassium titanate again.Patent 200710190552.3 is with K
2CO
3With metatitanic acid be raw material, with K
2CO
3Mix with metatitanic acid, wherein K
2CO
3With TiO in the metatitanic acid
3 2-Mol ratio be 1: 2～5, simultaneously according to mol ratio K
2CO
3: K
2SO
4Be that 1: 0.01～2 ratio adds vitriolate of tartar, dry, levigate; Mixture 900 ℃～1150 ℃ calcinings, after burned material is cooled off in air, is dipped in and boils 5～8h in the deionized water, filter, washing, oven dry obtains potassium titanate crystal whisker.This invention has that reaction is easy to control, cost is low and advantage such as simple flow, emits contaminate environment but have a large amount of carbon dioxides in the reaction process.Chinese invention patent 200710064631.X discloses a kind of potassium titanate crystal whisker or potassium titanate particulate preparation method based on disintegration effect, this method is to utilize disintegration effect and series-parallel connection effect and synthetic potassium titanate crystal whisker, the synthetic of described whisker is raw material with common titanium source compound and potassium source compound, in calcining furnace, through high-temperature calcination, directly synthetic the or diffusion disintegration of disintegration and series-parallel connection such as synthesize at one-step synthesis nano level or micron-sized crystal whisker of hexa potassium titanate.It is the method for raw material clean production of titanium dioxide and crystal whisker of hexa potassium titanate that Chinese invention patent 200610007297.X relates to ilmenite or titanium slag.This method comprises that ilmenite or titanium slag react in inferior fused salt KOH liquid phase medium, the weight ratio of KOH and ilmenite or titanium slag is 4: 1～8: 1; Reaction obtains containing the reaction product mixture of alkali lye, titanate and rich scum; Obtain the titanium dioxide or the crystal whisker of hexa potassium titanate product of purifying after the hydrolysis of titanate reaction product or acidolysis, calcining, the removal of impurities.The deficiency of this method is difficult to obtain high-purity product.Chinese invention patent 200610132373.X is a raw material with titanium dioxide and salt of wormwood, comprises batching/batch mixing, granulation, calcining, pulverizing/four steps of separation.The feature of the six potassium titanate crystalline materials that this method synthesizes is that crystal habit is that no several styloid is crossed as structure of ethnic group, and each crystal is approximated to ellipse or polygonal cylinder, and straight, end and the surface is slick and sly, even thickness along its length, but uneven in length.After pulverizing, separating, the finished product become based on styloid, and the particulate state crystal is the single crystal material of assisting.Chinese invention patent 200710037251.7 provides a kind of synthesis preparation method that adopts slow cooling sintering crystallization process to produce potassium titanate series crystal whisker and titanium dioxide crystal whisker.This patent earlier with titaniferous materials, contain potassium raw material and solubility promoter and mix and place vessels crucible, put into kiln 600～1300 ℃ of sintering that heat up gradually; The sintered molten body slowly cools off with kiln temperature, and reaction becomes ingot shape object; Taking-up is placed in the drying room of 50～300 ℃ of humidity 50～100%, temperature carries out 2～10 days natural decomposition, makes it become complete uniform raphioid fiber shape; Take out and place in 80～102 ℃ of hydrothermal reaction devices, regulate the control reacting solution pH value and the method in reaction times, obtain the variable conversion typing thing of two or four or six or eight potassium titanate crystal whiskers or titanium dioxide crystal whisker, washing, dehydration by up time; Take out dry; Place vessels crucible, put into kiln and be warming up to 600～1300 ℃ of high temperature sinterings gradually, obtaining length is 50～100 microns, and diameter is the finished product of the fixed conversion typing thing of 5～10 microns two or four or six or eight potassium titanate crystal whiskers or titanium dioxide crystal whisker.The two potassium titanate crystalline solid blocks that this technology obtains first sintering, place under certain humidity and the temperature condition, under the situation that no mechanical external force is intervened, disperse to separate voluntarily to knit, only a step process just needs the time more than 2 days, the time that the whole production complete process then needs is longer, and production efficiency is low, is unfavorable for save energy.Chinese invention patent 200610022304.3 relates to a kind of crystal whisker of hexa potassium titanate and with the method for Hydrothermal Preparation, crystal whisker of hexa potassium titanate (K
2Ti
6O
13) diameter between 200～500nm, be about 20 μ m～30 μ m; This method is a raw material with titanium compound and potassium compound, and raw material is amounted to into K
2O and TiO
2, press K
2O: TiO
2=20: 1～2: 1 molar ratio ingredient, through reaction, solid-liquid separation, washing, ultra-sonic dispersion, processing steps such as drying make crystal whisker of hexa potassium titanate.Chinese invention patent 200410102439.1 relates to a kind of preparation method of Nano lines of potassium titanate, comprises the steps: that (1) mix the potassium hydroxide aqueous solution of titanium-containing compound with weight percent concentration 20-80% in container; (2) with microwave as heating source, reflux 30 minutes-15 hours; (3) will reacting afterwards, mixed solution cooling-sedimentation, washing of precipitate to pH value are 6-8, separation; (4) above-mentioned reaction products therefrom is carried out high-temperature calcination.Described titanium-containing compound is metatitanic acid or Detitanium-ore-type, rutile-type, brookite type titanium dioxide or titanic acid ester, and titanium-containing compound and potassium hydroxide mol ratio are 1: 4～1: 80.Described microwave oven frequency is 300MHz-300GHz, and reaction system is for opening wide system.Calcining temperature is 400～1100 ℃, and calcination time is 10 minutes-5 hours.Chinese invention patent 200410054039.8 relates to a kind of production potassium titanate crystal whisker series product method, this method comprises two potassium titanate crystal whiskers molten potassium ion that goes in the aqueous solution, step is: titanium source and potassium source are placed 900～1300 ℃ of tunnel furnace by 1: 1.9～2.5 weighing mixings, stopped 60～120 minutes, and became molten mass; Molten mass is poured the metal blade into and is made minitype particle; Minitype particle and pure water are put reactor in 1: 5～30 ratios, heat 60～98 ℃, add 5～25% diluted acids, stir to become suspension in 90～200 minutes; Solid-liquid suspension is separated into amorphous hydrate and sloughs surface water being lower than under 100 ℃; It is put 500～800 ℃ of tunnel furnace, sintering 100～240 minutes; Use the pure water washing material; Material is sloughed surface water earlier, 200～300 ℃ down dry, get final product the potassium titanate crystal whisker series product.Chinese invention patent 200510040921.1 relates to the preparation method of the potassium titanate whisker of a kind of high porosity, high-flexural strength, anti-alkali corrosion, low deformation rate, high liquid holdup.Chinese invention patent 02136082.0 provides a kind of synthetic method of new potassium titanate crystal whisker.Titanium dioxide TiO
2: potassium oxide K
2The O mol ratio is 2.5～3.5: 1, the add-on of boron compound is 1～5% of a titanium dioxide weight, behind the above-mentioned raw materials mixing, the alkaline-resisting container of packing into, be warming up to 800 ℃, be warming up to 900～1200 ℃ with 1 ℃/minute, stopped 1～4 hour, take out after slowly being cooled to 800 ℃, obtain the potassium tetratitanate whisker beam; The potassium tetratitanate whisker beam is disperseed in cold water, promptly obtain the potassium tetratitanate whisker.Potassium tetratitanate whisker mechanical stirring 1～4 hour in 80～100 ℃ of hot water, with the potassium ion that comes out with leaching in 5～15% the dilute sulphuric acid, promptly obtain the crystal whisker of hexa potassium titanate amorphous hydrate, this hydrate stopped in 800～1200 ℃ temperature 2～6 hours again, finish the crystallization conversion, in hot water (80～100 ℃), clean the soluble potassium compound again,, promptly obtain the finished product crystal whisker of hexa potassium titanate at the temperature drying more than 200 ℃.On average long 10～50 μ m of crystal whisker of hexa potassium titanate, whisker, mean diameter is less than 0.5 μ m.Chinese invention patent 200710044770.6 discloses a kind of manufacture method of crystal whisker of hexa potassium titanate.This method adopts melting quench method technology to synthesize, earlier with titaniferous materials, contain the potassium raw material and fusing assistant is mixed, enter and carry out sintering in the elevated temperature vessel, take out after the fusion, quenching on special-purpose chilled equipment, generate the uniform fine powder of particle diameter less than 1mm, enter into the hydrothermal reaction device again, method with the control solution acidity is controlled the potassium ion stripping quantity, after reaction is finished, after filtration, 20～40 ℃ of deionized water repetitive scrubbings, tensio-active agents soak, and directly carries out sintering after the filtration, can obtain finished product.Chinese invention patent 01134183.1, disclose a kind of method of producing crystal whisker of hexa potassium titanate, this method comprises steps such as mixing, sintering, quenching, dispersion treatment, separation, washing, drying, high temperature crystallization sintering, secondary dispersion treatment, redrying processing and screening.
Sum up existing aforesaid method, mainly can be divided into sintering process, scorification, flux method and slow cooling sintering process etc., these methods adopt indirect method to prepare potassium titanate crystal whisker mostly, promptly earlier make two potassium titanates or potassium tetratitanate whisker by sintering process, then through acid or water treatment, obtain amorphous amorphous phase material, obtain potassium titanate crystal whisker by double sintering again.In these methods, product is six potassium titanates mostly, can not be by different potassium titanate crystal whisker products of forming such as technical process precise control acquisitions two, four, six, eight.Preparation condition harshness, the energy consumption height that has in the existing method, productive rate is low, environmental pollution is serious or product purity not high (product is not the pure white crystal, but has the product of yellow phase), does not possess the industrial production possibility; The method that has need add solubility promoter, not only solubility promoter price height, and separation costs costliness.And the technology that some is being produced, the waste heat that calcining kiln and typing kiln produce is not fully used, and has wasted the energy.In addition, some production technique adopt nature to separate the mode of knitting, and production efficiency is too low.Therefore, explore a kind of energy-efficient novel preparation method, have important practical significance.
Summary of the invention
The objective of the invention is to deficiency, a kind of energy-efficient potassium titanate series crystal whisker preparation method is provided at existing preparation method.This method adopts recovery of heat to utilize design concept again, and the waste heat that calcining kiln and typing kiln high temperature are produced is used for the preheating of precursor and moisture absorption to be separated and knit, and has effectively improved rate of energy.This method is separated in two potassium titanate moisture absorptions has increased mechanical crushing process before knitting, and has greatly shortened the production time, is can finish in 8～24 hours needing more than 2 days moisture absorption to separate to knit time decreased at least, has improved production efficiency.Because the adding of preheating procedure makes the starting material reaction more abundant, system is mixed more even, makes the crystalline structure of final product more complete, and final product is sheet, stratiform or needle-like crystal.In potassium ion stripping step, the present invention adopts acid cut amount injection method, has accurately controlled the quantity of potassium ion stripping, has accurately controlled the component of final potassium titanate crystal whisker, realizes potassium titanate crystal whisker product artificially controlled of different componentss such as two, four, six, eight.
The present invention realizes by following steps:
1) be that mechanical mill was even to system, obtains the needed presoma of preparation whisker after 1: 1～6 ratio took by weighing with titanium source and potassium source in titanium potassium atom mol ratio;
2) above-mentioned presoma is placed crucible, then crucible is placed pre-heating kiln preheating, it is more even that system is disperseed, and reacts more abundant, to improve the crystalline structure integrity degree of utilization ratio of raw materials and whisker;
3) presoma after the preheating is put into continuous rotary kiln, change insulation processing in the insulation kiln behind the high temperature sintering again over to;
4) product after will calcining is put into fixed temperature and humidity moisture absorption hydrolysis kiln and is carried out the moisture absorption hydrolysis treatment after machine is pulverized, and obtains two potassium titanates;
5) two potassium titanates that step 4) is obtained carry out neutralizing treatment by quantitative pickler, finish the quantitative stripping of potassium ion, and filter, and can obtain different potassium titanate crystal whiskers;
6) potassium titanate crystal whisker that step 5) is obtained carries out the high-temperature shaping processing through the typing kiln, can obtain target potassium titanate crystal whisker product.
The titanium source of being adopted is any one in titanium dioxide or the metatitanic acid; The potassium source is any one in salt of wormwood, potassium oxide or the potassium hydroxide.
Presoma needs to carry out abundant preheating before calcining, to reach the purpose of the crystalline structure integrity degree that improves original utilization ratio and whisker.The temperature of pre-heating kiln is 35～500 ℃, and be 0.1～5 hour warm up time; The temperature of calcining kiln is 800～1300 ℃, and calcination time is 0.5～5 hour; The temperature of typing kiln is 500～1000 ℃, and shaping time is 0.5～5 hour.
The waste heat that the high-temperature calcination kiln is produced will be separated for pre-heating kiln, typing kiln and moisture absorption by pipeline transmission and knit kiln, and the high-temperature vapor that the high-temperature calcination kiln is produced will send moisture absorption hydrolysis kiln to by pipeline, realize the recycling of heat energy; Two potassium titanates are separated in moisture absorption and are knitted in the kiln moisture absorption to separate the time of knitting be 2～24 hours, and humidity is 70～100%, and temperature is 100～400 ℃; Two potassium titanates after high temperature burns and to separate must carry out machine to be pulverized, and then carries out moisture absorption and separate and knit; Potassium ion transforms the acid of being adopted can be sulfuric acid, any one in nitric acid or the hydrochloric acid; The stripping of titanium ion transforms and adopts quantitative pickling to realize accurate control in two potassium titanates, and the flow velocity and the time of acid must adopt under meter accurately to control.
Beneficial effect
Advantage of the present invention is as follows:
1. the present invention adopts presoma to carry out abundant preheating before calcining, has improved the integrity of utilization ratio of raw materials and product crystalline structure greatly;
2. the present invention adopts the pickling mode of quantitative injection to regulate the stripping quantity of potassium ion, can adjust the composition of potassium titanate crystal whisker product very exactly;
3. moisture absorption of the present invention is separated weaving process and is adopted first machine to pulverize fixed temperature and humidity to separate the mode of knitting, shortened moisture absorption greatly and separated the time of knitting again, and production efficiency significantly improves;
4. the product that technology of the present invention obtains is the pure white crystal, and purity will be higher than the product that has yellow phase of other prepared.And the product that the present invention makes has sheet, stratiform or needle-like pattern, crystalline structure is more complete, its thermal conductivity is 0.1657w/mk, (Jing Xiaoming is etc., Southwest University for Nationalities journal to be better than the product of close prepared, 2008,34 (3), 539-544), its thermal and insulating performance is better than the potassium titanate crystal whisker product of traditional technology preparation;
5. technology of the present invention is separated for pre-heating kiln and moisture absorption at the waste heat of calcining kiln and the generation of typing kiln by pipeline transmission and is knitted kiln, improved rate of energy, reduced production cost, meet the Sustainable development requirement.
Description of drawings
Fig. 1 is the sem photograph that utilizes the potassium titanate crystal whisker that the present invention prepares; Fig. 2 is the sem photograph that utilizes the potassium titanate crystal whisker that the present invention prepares; Fig. 3 is the sem photograph that utilizes the potassium titanate crystal whisker that the present invention prepares; Fig. 4 is the X-ray powder diffraction figure that utilizes the potassium titanate crystal whisker that the present invention prepares.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment 1
After titanium source titanium dioxide and potassium source 1: 1 in molar ratio ratio of potassium oxide taken by weighing, mechanical mill was even to system, obtains the needed presoma of preparation whisker; Above-mentioned presoma is placed 35 ℃ in crucible, and be 5 hours warm up time; Presoma after the preheating is put into continuous rotary calciner calcine, temperature is 800 ℃, and calcination time is 5 hours; After the high-temperature calcination, machine is pulverized, and putting into humidity is 100%, and temperature is that 100 ℃ moisture absorption is separated and knitted in the kiln moisture absorption and separate and knit 24 hours, obtains two potassium titanates; This two potassium titanate carries out neutralizing treatment by quantitative pickler, finishes the Quantitative yield of potassium ion, and filters, and can obtain the different potassium titanate crystal whiskers of forming; The potassium titanate crystal whisker that obtains carries out high-temperature shaping through the typing kiln to be handled, and the temperature of typing kiln is 500 ℃, and shaping time is 5 hours.Can obtain the acicular crystal whisker of hexa potassium titanate product of pure white.The length of this potassium titanate crystal whisker is 40-50 μ m, and width is 12-15 μ m.
Embodiment 2
After titanium source metatitanic acid and potassium source potassium hydroxide taken by weighing in 1: 6 the ratio of mol ratio of titanium potassium atom, mechanical mill was even to system, obtains the needed presoma of preparation whisker; Above-mentioned presoma is placed 500 ℃ in crucible, and be 0.1 hour warm up time; Presoma after the preheating is put into continuous rotary calciner calcine, temperature is 1300 ℃, and calcination time is 0.5 hour; After the high-temperature calcination, machine is pulverized, and moisture absorption is separated and knitted, and it is 2 hours that the time of knitting is separated in moisture absorption, and humidity is 70%, and temperature is 400 ℃.Product after the calcining after machine is pulverized, is put into fixed temperature and humidity moisture absorption hydrolysis kiln and carried out the moisture absorption hydrolysis treatment, obtain two potassium titanates; This two potassium titanate carries out neutralizing treatment by quantitative pickler, finishes the Quantitative yield of potassium ion, and filtering drying, can obtain different potassium titanate crystal whiskers; The potassium titanate crystal whisker that obtains carries out high-temperature shaping through the typing kiln to be handled, and the temperature of typing kiln is 1000 ℃, and shaping time is 0.5 hour.Can obtain pure white potassium tetratitanate stratiform crystal whisker products.The length of this potassium titanate crystal whisker is 90-100 μ m, and width is 30-40 μ m.
Embodiment 3
After titanium source titanium dioxide and potassium source 1: 4 in molar ratio ratio of salt of wormwood taken by weighing, mechanical mill was even to system, obtains the needed presoma of preparation whisker; Above-mentioned presoma is placed 300 ℃ in crucible, and be 3 hours warm up time; Presoma after the preheating is put into continuous rotary calciner calcine, temperature is 800 ℃, and calcination time is 5 hours; After the high-temperature calcination, machine is pulverized behind the high temperature sintering, and moisture absorption is separated and knitted, and it is 4 hours that the time of knitting is separated in moisture absorption, and humidity is 90%, and temperature is 300 ℃.Product after the calcining after machine is pulverized, is put into fixed temperature and humidity moisture absorption hydrolysis kiln and carried out the moisture absorption hydrolysis treatment, obtain two potassium titanates; This two potassium titanate carries out neutralizing treatment by quantitative pickler, finishes the Quantitative yield of potassium ion, and filtering drying, can obtain different potassium titanate crystal whiskers; The potassium titanate crystal whisker that obtains carries out high-temperature shaping through the typing kiln to be handled, and the temperature of typing kiln is 600 ℃, and shaping time is 4 hours.Can obtain pure white eight potassium titanate crystal whisker products.The length of this potassium titanate crystal whisker is 60-80 μ m, and width is 10-15 μ m.
Embodiment 4
After titanium source titanium dioxide and potassium source 1: 3 in molar ratio ratio of potassium oxide taken by weighing, mechanical mill was even to system, obtains the needed presoma of preparation whisker; Above-mentioned presoma is placed 200 ℃ in crucible, and be 4 hours warm up time; Presoma after the preheating is put into continuous rotary calciner calcine, temperature is 1200 ℃, and calcination time is 3 hours; After the high-temperature calcination, machine is pulverized behind the high temperature sintering, and moisture absorption is separated and knitted, and it is 3 hours that the time of knitting is separated in moisture absorption, and humidity is 80%, and temperature is 400 ℃.Product after the calcining after machine is pulverized, is put into fixed temperature and humidity moisture absorption hydrolysis kiln and carried out the moisture absorption hydrolysis treatment, obtain two potassium titanates; This two potassium titanate carries out neutralizing treatment by quantitative pickler, finishes the Quantitative yield of potassium ion, and filtering drying, can obtain different potassium titanate crystal whiskers; The potassium titanate crystal whisker that obtains carries out high-temperature shaping through the typing kiln to be handled, and the temperature of typing kiln is 800 ℃, and shaping time is 2 hours.Can obtain pure white eight potassium titanate crystal whisker products.The length of this potassium titanate crystal whisker is 45-60 μ m, and width is 8-12 μ m.
Claims (11)
1. the preparation method of an energy-efficient potassium titanate series crystal whisker is characterized in that concrete steps are as follows:
1) be that mechanical mill was even to system, obtains the needed presoma of preparation whisker after 1: 0.5～6 ratio took by weighing with titanium source and potassium source in titanium potassium atom mol ratio;
2) above-mentioned presoma is placed crucible, then crucible is placed pre-heating kiln preheating, it is more even that system is disperseed, and reacts more abundant, to improve the crystalline structure integrity degree of utilization ratio of raw materials and whisker;
3) presoma after the preheating is put into continuous rotary calciner, high-temperature calcination;
4) product after will calcining is after machine is pulverized, and puts into the fixed temperature and humidity moisture absorption and separates and knit kiln and carry out moisture absorption and separate and knit processing, obtains two potassium titanates;
5) two potassium titanates that step 4) is obtained carry out neutralizing treatment by quantitative pickler, and the quantitative stripping of finishing potassium ion transforms, and filters, and can obtain the potassium titanate crystal whisker of different components;
6) potassium titanate crystal whisker that step 5) is obtained carries out the high-temperature shaping processing through the typing kiln, can obtain target potassium titanate crystal whisker product.
2. a kind of preparation method who produces potassium titanate crystal whisker according to claim 1 is characterized in that the titanium source of being adopted is any one in titanium dioxide or the metatitanic acid; The potassium source is any one in salt of wormwood, potassium oxide or the potassium hydroxide.
3. a kind of preparation method who produces potassium titanate crystal whisker according to claim 1 is characterized in that presoma needs to carry out abundant preheating before calcining, to reach the purpose of the crystalline structure integrity degree that improves utilization ratio of raw materials and whisker.The temperature of pre-heating kiln is 35～500 ℃, and be 0.1～5 hour warm up time;
4. a kind of preparation method who produces potassium titanate crystal whisker according to claim 1, it is characterized in that, high-temperature calcination kiln and the typing waste heat that kiln produced will be separated for pre-heating kiln and moisture absorption by pipeline transmission and knit kiln, the high-temperature vapor that the high-temperature calcination kiln is produced will send moisture absorption to by pipeline and separate and knit kiln, realize the recycling of heat energy;
5. a kind of preparation method who produces potassium titanate crystal whisker according to claim 1 is characterized in that, two potassium titanates are separated in moisture absorption and knitted in the kiln moisture absorption to separate the time of knitting be 2～24 hours, and humidity is 70～100%, and temperature is 35～400 ℃;
6. a kind of preparation method who produces potassium titanate crystal whisker according to claim 1 is characterized in that, two potassium titanates after the high-temperature calcination carry out machine to be pulverized, and then carries out moisture absorption and separate and knit;
7. a kind of preparation method who produces potassium titanate crystal whisker according to claim 1 is characterized in that the acid that the potassium ion Quantitative yield is adopted can be sulfuric acid, any one in nitric acid or the hydrochloric acid;
8. a kind of preparation method who produces potassium titanate crystal whisker according to claim 1 is characterized in that the temperature of calcining kiln is 800～1300 ℃, and calcination time is 0.5～5 hour;
9. a kind of preparation method who produces potassium titanate crystal whisker according to claim 1 is characterized in that, the conversion of titanium ion adopts quantitative injection pickling to realize accurate control in two potassium titanates, and the flow velocity of acid and flow adopt under meter accurately to control;
10. a kind of preparation method who produces potassium titanate crystal whisker according to claim 1 is characterized in that, the temperature of typing kiln is 500～1000 ℃, and shaping time is 0.5～5 hour.
11. a kind of preparation method who produces potassium titanate crystal whisker according to claim 1, it is characterized in that, the potassium titanate series crystal whisker product of present method preparation is the pure white crystal, have sheet, stratiform or needle-like pattern, its crystalline structure is more complete, and thermal and insulating performance is better than the potassium titanate crystal whisker product of traditional method preparation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102024835A CN101962808B (en) | 2010-06-17 | 2010-06-17 | High-efficiency and energy-saving potassium titanate whisker preparation method |
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| CN2010102024835A CN101962808B (en) | 2010-06-17 | 2010-06-17 | High-efficiency and energy-saving potassium titanate whisker preparation method |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102259910A (en) * | 2011-06-16 | 2011-11-30 | 申偲伯 | Method for producing potassium titanate in large scale by utilizing ore-grade titanium-containing compound |
| CN102839413A (en) * | 2012-09-18 | 2012-12-26 | 武汉理工大学 | Method for preparing ultrathin layered K2Ti4O9 crystal whiskers |
| CN102851738A (en) * | 2012-09-18 | 2013-01-02 | 武汉理工大学 | Preparation method of ultramicro columnar K2Ti6O13 whiskers |
| CN102925981A (en) * | 2012-11-28 | 2013-02-13 | 北京科技大学 | Method for preparing potassium hexatitanate nano whisker from titanium-containing electric furnace molten slag |
| CN105033506A (en) * | 2015-08-24 | 2015-11-11 | 句容亿格纳米材料厂 | Potassium titanate welding rod additive and preparation method thereof |
| CN106367810A (en) * | 2016-09-18 | 2017-02-01 | 唐山晶须复合材料制造有限公司 | Method for synthesizing potassium magnesium titanate lamellar crystals from lamellar raw material |
| CN106637408A (en) * | 2016-12-23 | 2017-05-10 | 张家港大塚化学有限公司 | Preparation method of acicular short fiber composite potassium hexatitanate crystal whisker |
| CN107381628A (en) * | 2017-08-25 | 2017-11-24 | 陕西科技大学 | A kind of platy particles of layered potassium titanate containing zinc and its hydrothermal preparing process |
| CN107381626A (en) * | 2017-08-25 | 2017-11-24 | 陕西科技大学 | A kind of iron content layered potassium titanate platy particles and its hydrothermal preparing process |
| CN107381627A (en) * | 2017-08-25 | 2017-11-24 | 陕西科技大学 | A kind of cupric layered potassium titanate platy particles and its hydrothermal preparing process |
| CN107555488A (en) * | 2017-08-25 | 2018-01-09 | 陕西科技大学 | A kind of cobalt containing layer shape potassium titanate platy particles and its hydrothermal preparing process |
| CN114394617A (en) * | 2016-12-13 | 2022-04-26 | 大塚化学株式会社 | Potassium titanate powder, method for producing same, friction control material, resin composition, friction material, and friction member |
| CN114790116A (en) * | 2022-04-21 | 2022-07-26 | 湖北顺富医疗器械科技有限公司 | Ceramic reinforced composite false tooth and manufacturing method thereof |
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Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102259910A (en) * | 2011-06-16 | 2011-11-30 | 申偲伯 | Method for producing potassium titanate in large scale by utilizing ore-grade titanium-containing compound |
| CN102259910B (en) * | 2011-06-16 | 2014-03-12 | 申偲伯 | Method for producing potassium titanate in large scale by utilizing ore-grade titanium-containing compound |
| CN102839413A (en) * | 2012-09-18 | 2012-12-26 | 武汉理工大学 | Method for preparing ultrathin layered K2Ti4O9 crystal whiskers |
| CN102851738A (en) * | 2012-09-18 | 2013-01-02 | 武汉理工大学 | Preparation method of ultramicro columnar K2Ti6O13 whiskers |
| CN102839413B (en) * | 2012-09-18 | 2015-04-08 | 武汉理工大学 | Method for preparing ultrathin layered K2Ti4O9 crystal whiskers |
| CN102851738B (en) * | 2012-09-18 | 2015-04-08 | 武汉理工大学 | Preparation method of ultramicro columnar K2Ti6O13 whiskers |
| CN102925981A (en) * | 2012-11-28 | 2013-02-13 | 北京科技大学 | Method for preparing potassium hexatitanate nano whisker from titanium-containing electric furnace molten slag |
| CN102925981B (en) * | 2012-11-28 | 2014-12-10 | 北京科技大学 | Method for preparing potassium hexatitanate nano whisker from titanium-containing electric furnace molten slag |
| CN105033506A (en) * | 2015-08-24 | 2015-11-11 | 句容亿格纳米材料厂 | Potassium titanate welding rod additive and preparation method thereof |
| CN106367810B (en) * | 2016-09-18 | 2018-09-04 | 唐山晶须复合材料制造有限公司 | The synthetic method of magnesium titanate platelet is synthesized by sheet-shaped material |
| CN106367810A (en) * | 2016-09-18 | 2017-02-01 | 唐山晶须复合材料制造有限公司 | Method for synthesizing potassium magnesium titanate lamellar crystals from lamellar raw material |
| CN114394617B (en) * | 2016-12-13 | 2023-08-15 | 大塚化学株式会社 | Potassium titanate powder and method for producing same, friction control material, resin composition, friction material, and friction member |
| CN114394617A (en) * | 2016-12-13 | 2022-04-26 | 大塚化学株式会社 | Potassium titanate powder, method for producing same, friction control material, resin composition, friction material, and friction member |
| CN106637408A (en) * | 2016-12-23 | 2017-05-10 | 张家港大塚化学有限公司 | Preparation method of acicular short fiber composite potassium hexatitanate crystal whisker |
| CN107381627A (en) * | 2017-08-25 | 2017-11-24 | 陕西科技大学 | A kind of cupric layered potassium titanate platy particles and its hydrothermal preparing process |
| CN107555488A (en) * | 2017-08-25 | 2018-01-09 | 陕西科技大学 | A kind of cobalt containing layer shape potassium titanate platy particles and its hydrothermal preparing process |
| CN107381626B (en) * | 2017-08-25 | 2019-06-14 | 陕西科技大学 | A kind of iron content layered potassium titanate platy particles and its hydrothermal preparing process |
| CN107555488B (en) * | 2017-08-25 | 2019-06-14 | 陕西科技大学 | A kind of cobalt containing layer shape potassium titanate platy particles and its hydrothermal preparing process |
| CN107381628B (en) * | 2017-08-25 | 2019-06-14 | 陕西科技大学 | One kind platy particles of layered potassium titanate containing zinc and its hydrothermal preparing process |
| CN107381626A (en) * | 2017-08-25 | 2017-11-24 | 陕西科技大学 | A kind of iron content layered potassium titanate platy particles and its hydrothermal preparing process |
| CN107381628A (en) * | 2017-08-25 | 2017-11-24 | 陕西科技大学 | A kind of platy particles of layered potassium titanate containing zinc and its hydrothermal preparing process |
| CN114790116A (en) * | 2022-04-21 | 2022-07-26 | 湖北顺富医疗器械科技有限公司 | Ceramic reinforced composite false tooth and manufacturing method thereof |
| CN114790116B (en) * | 2022-04-21 | 2023-12-01 | 程舜 | Ceramic reinforced composite false tooth and manufacturing method thereof |
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