CN102787393A - Method and device for pressure analysis of polyacetylacetonatozirconium precursor fiber during zirconia crystalline fiber preparation and ligand recovery technology - Google Patents
Method and device for pressure analysis of polyacetylacetonatozirconium precursor fiber during zirconia crystalline fiber preparation and ligand recovery technology Download PDFInfo
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- CN102787393A CN102787393A CN2012102789395A CN201210278939A CN102787393A CN 102787393 A CN102787393 A CN 102787393A CN 2012102789395 A CN2012102789395 A CN 2012102789395A CN 201210278939 A CN201210278939 A CN 201210278939A CN 102787393 A CN102787393 A CN 102787393A
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Abstract
The invention relates to a method and a device for the pressure analysis of polyacetylacetonatozirconium precursor fiber during zirconia crystalline fiber preparation and a ligand recovery technology. The polyacetylacetonatozirconium precursor fiber is put in a high-temperature vapour pressure device to be subjected to the analytical treatment for 30 minutes-4hours at 2-8 atmospheric pressure and 20DEGC-170DEG C, so the acetylacetone ligand of the precursor fiber is effectively analyzed and separated out; and furthermore, the vapour which is rich in ligand acetylacetone is fed into an exchange column which contains powder such as Mg(OH)2, Ca(OH)2, Ni(OH)2, Co(OH)2, ZnO or Fe2O3, so the corresponding ligand by-product salt forming reaction is carried out, accordingly, the quality of the zirconia crystalline fiber is greatly improved, and the acetylacetone salt by-product is recovered. According to the method, not only can the performance of the prepared zirconia fiber be greatly improved and the energy consumption cost be reduced, but also the by-product recovery can be increased, and the green environmental-friendly production of the zirconia fiber can be facilitated.
Description
Technical field
The present invention relates to pressure solutions analysis method, device and part byproduct recovery technology in the crystal of zirconium oxide fiber production; Particularly acetylacetone,2,4-pentanedione gathers the zirconium legal system and is equipped with and gathers acetyl acetone zirconium precursor body fiber pressure solutions analysis method in the crystal of zirconium oxide fiber, belongs to superhigh temperature insulating fibre material field.
Background technology
Other oxide fibres such as the same aluminium oxide of crystal of zirconium oxide fiber, quartz, mullite, alumina silicate are compared with non-oxidized substance fibers such as carbon, carborundum, boron nitride, are a kind of more excellent advanced heat insulation and composite reinforcing materials.Because it has high fusing point (2715 ° of C), minimum, the minimum and excellent special performances such as acid-alkali-corrosive-resisting of high temperature steam pressure of thermal conductivity factor in oxide; So, all have the application prospect of particular importance at sophisticated technologies such as Aeronautics and Astronautics and industrial circle.
The applicant began from 1998 the key technology of crystal of zirconium oxide fiber formation mechanism and preparation has been carried out systematically exploratory development.Adopt sol-gel and gathered the preparation key technology that acetyl acetone zirconium precursor body spin processes has systematically solved high-performance zirconia continuous fibers and short cellucotton.The patent that the applicant is correlated with comprises the preparation method and the equipment of CN03112408.9 continuous zirconia fiber, and CNL200410024264.7 is organic to be gathered zirconium precursor body spinning solution and get rid of a legal system and be equipped with preparation method, CN200910255807.9 one zirconia mesoporous fiber and preparation method thereof of sintering furnace that Zirconium oxide fibre cotton, CN200410085390.3 be used to prepare continuous zirconia fiber, CN200910013781.7 complete stable cubic phase zircite crystal fibre etc.According to technology and environmental issue in the existing patent working process, the inventor has carried out exploratory development energetically.Forming the mechanism result of study through the crystal of zirconium oxide fiber finds; The performance of crystal of zirconium oxide fiber depends primarily on processes such as the parsing, nucleation, crystal grain arrangement of acetylacetone,2,4-pentanedione; Gather zirconium glass attitude precursor fibre to the crystal of zirconium oxide fiber transformation of crystal grain oriented formation from acetylacetone,2,4-pentanedione, effective resolving of part is the key link that forms the crystal of zirconium oxide fiber.The effect that precursor fibre is resolved directly has influence on formation, nucleation rate and the uniformity of zirconia nucleus in the operation process of back, the problems such as oriented of crystal grain.On the fabricating technology route, mainly show as technological parameters such as precursor fibre analyzing efficiency, analysis mode, parsing time, atmosphere, pressure etc., also relate to and resolve the comprehensive utilization of reclaiming the back part.
According to prior art, acetylacetone,2,4-pentanedione gather the zirconium legal system be equipped with preparation that the crystal of zirconium oxide fiber comprises the steps: presoma, spinning solution preparation, get rid of silk, heat treatment etc.Wherein being prepared as of presoma adopts eight hydration zirconium oxychlorides as the zirconium source; Acetylacetone,2,4-pentanedione is dissolved in the alcoholic solvent as part, adds a certain amount of precipitating agent then gradually; Form the crystallization that acetylacetone,2,4-pentanedione gathers zirconium precursor liquid solution and precipitating agent salt, separate the concentrated acetylacetone,2,4-pentanedione that obtains and gather the zirconium precursor body; Acetylacetone,2,4-pentanedione is gathered zirconium precursor body and stabilizing agent be dissolved in successively according to a certain percentage and form golden transparent solution in methyl alcohol or the ethanol, to concentrate until obtaining viscosity be that the acetylacetone,2,4-pentanedione of 10 ~ 50Pas gathers the zirconium spinning solution in decompression then; Spinning solution injected get rid of the silk dish, under certain rotating speed, make and get rid of a liquid and throw away, collect and obtain acetylacetone,2,4-pentanedione and gather zirconium precursor body fiber from an aperture high speed centrifugation that gets rid of the silk dish.It is the linear chain shaped polymer that is linked to each other and formed by zirconium, acetyl acetone ligands and hydroxyl that the acetylacetone,2,4-pentanedione that obtains gathers zirconium precursor body fiber, and wherein the part acetylacetone,2,4-pentanedione occupies bigger component, and relative weight is about 42%.So the analysis mode of acetylacetone,2,4-pentanedione, analyzing efficiency, recovery technology etc. play very crucial effect to aspects such as the formation of high-performance zirconia crystal fibre and production cost, environmental protection.
Summary of the invention
To prior art problems, the present invention provides in a kind of crystal of zirconium oxide fiber production and carries out method and the part byproduct recovery technology that pressure is resolved to gathering acetyl acetone zirconium precursor body fiber.
The present invention also provides the suitable devices of said analytic method.
The handled thing of pressure solutions analysis method of the present invention is that the prior art acetylacetone,2,4-pentanedione gathers the zirconium legal system and is equipped with the precursor fibre that obtains in the crystal of zirconium oxide fiber process, and said precursor fibre constitutes by gathering the acetyl acetone zirconium, and molecular formula is abbreviated as Zr (CH
3COCH
2COCH
3) (OH)
3, the structure of wherein gathering the acetyl acetone zirconium is that a part Zr links to each other with a part acetylacetone,2,4-pentanedione, connects through-OH effect and forms double-stranded linear polymer molecular structure, the relative amount of part acetylacetone,2,4-pentanedione is about 42wt%, ZrO
2Relative amount be about 50wt%.So when the precursor fibre post processing obtains the crystal of zirconium oxide fiber, can be attended by the generation of plurality of ligand acetylacetone,2,4-pentanedione, the recycling of acetylacetone,2,4-pentanedione can less environmental pollution can be increased production a kind of byproduct again.
Gather the zirconium legal system by the prior art acetylacetone,2,4-pentanedione and be equipped with the crystal of zirconium oxide fiber; Comprise preparation (contain zirconium organic polymer synthetic), the spinning solution of presoma preparation, get rid of silk, heat treatment; After getting rid of a step, before the heat treatment step, adopt pressure solutions analysis method of the present invention to handle and gather acetyl acetone zirconium precursor body fiber.
Technical scheme of the present invention is following:
One, pressure solutions analysis method
A kind of to gathering the method that acetyl acetone zirconium precursor body fiber carries out the pressure parsing, step is following:
(1) pressure vessel is preheated to 70 ~ 120 ° of C;
(2) acetylacetone,2,4-pentanedione being gathered the zirconium legal system is equipped with the acetyl acetone zirconium precursor body fiber that gathers that obtains in the crystal of zirconium oxide fiber process and places the pressure vessel of preheating; Pressure control is at 2 ~ 8 atmospheric pressure after feeding atmosphere; Heat temperature raising, making temperature is 120 ° of C ~ 170 ° C, carries out dissection process; Processing time is 30min ~ 4h, makes that the part acetylacetone,2,4-pentanedione in the precursor fibre parses;
(3) after dissection process finished, the steam of discharging enrichment part acetylacetone,2,4-pentanedione made the temperature in the pressure vessel reduce to 100 ° of C ~ 80 ° C, and fiber is continued to be positioned over container inner drying 30min ~ 2h, took out then to carry out subsequent heat treatment and prepare the crystal of zirconium oxide fiber; Subsequent heat treatment gets final product by prior art;
(4) steam of the enrichment part acetylacetone,2,4-pentanedione of collection discharging carries out post processing and reclaims the acetylacetone,2,4-pentanedione accessory substance.
Feeding atmosphere in the step (2) is one of water vapour, volatile organic vapor or combination; Wherein organic steam preferred alcohol or benzene etc.
The heat temperature raising of step (2) is to use Steam Heating, steam be organic steam, water vapour one of or combination.Organic steam is meant volatile organic vapors such as ethanol, benzene.From security consideration, water vapour most preferably.
In the step (2), calculate the resolution factor 54 ~ 83wt% of part acetylacetone,2,4-pentanedione in the precursor fibre according to precursor fibre weight difference before and after the dissection process.
Preferably, in the step (2), feed atmosphere after Pressure control at 8 atmospheric pressure, heat temperature raising, making temperature is 170 ° of C, carries out dissection process, the processing time is 30min ~ 4h.This moment, the resolution factor of part acetylacetone,2,4-pentanedione was higher.But consider the cost of pressure, temperature, under comparatively gentle condition, in the preferred step (2), Pressure control is at 2 ~ 4 atmospheric pressure after the feeding atmosphere, and temperature is 120 ~ 145 ° of C dissection process, and the processing time is 1 ~ 2h.
Two, the device of pressure parsing
According to the present invention; A kind of being used for carried out the device that pressure is resolved to precursor fibre; Comprise inner bag and interlayer, be provided with the net grid support that multilayer is used to put precursor fibre in the inner bag, the inner bag peripheral hardware is useful on and feeds steam-heated interlayer; The top of this device is provided with atmosphere and feeds mouth, and the bottom is provided with the steam outlet of enrichment part acetylacetone,2,4-pentanedione.Structure is as shown in Figure 1.
Said net grid support places on the stent support baffle plate on the inner bag inwall.
Preferably, liner material adopts stainless steel or enamel or glass.Wherein the stainless steel model is 304,316 or high target more; It is high temperature resistant, acid-alkali-corrosive-resisting that liner material requires, can bear elevated pressures.
Preferably, to get material be 304,316 or the stainless steel of higher model for support material and net grid support.Can bear 2 ~ 8 atmospheric pressures, 120 ° of C ~ 170 ° C of withstand temperature.
This device inner bag has outside interlayer, before handling precursor fibre, can make the preheating of device inner bag through jacket steam, avoids steam to run into the lower precursor fibre of temperature and is cooled to drop, destroys fiber; In the inner bag is the net grid support of sandwich construction.
Bottom at the pressure solutions analysis apparatus is provided with steam outlet, can the steam that contains acetylacetone,2,4-pentanedione that discharge in the resolving be discharged through this steam outlet.
The steam of the enrichment part acetylacetone,2,4-pentanedione of getting rid of is transported to the by-product postprocessing working procedures that reclaims acetylacetone,2,4-pentanedione through pipeline, inserts and reclaims in the exchange column, carries out the formation reaction of acetylacetone,2,4-pentanedione by-product salt.
Three, the recovery of part acetylacetone,2,4-pentanedione
A kind of recovery method of part acetylacetone,2,4-pentanedione comprises the steam that utilizes the enrichment part acetylacetone,2,4-pentanedione of collecting in the above-mentioned pressure solutions analysis method of the present invention, and step is following:
[1] metal oxide powder or hydroxide powder are filled in the exchange column, described metal oxide is ZnO or Fe
2O
3, said hydroxide is Mg (OH)
2, Ca (OH)
2, Ni (OH)
2Or Co (OH)
2
[2] steam with the enrichment part acetylacetone,2,4-pentanedione of collecting feeds in the exchange column of step [1], and fully reaction generates and obtains corresponding acetylacetonate and little acetic acid salt; Wherein, acetate comes from the acetic acid that the part acetylacetone,2,4-pentanedione is decomposed to form in the steam condition lower part;
[3] through after the step [2], steam cooled forms liquid state and the acetate that generates is dissolved as liquid, flows out from the exchange column lower liquid outlet; Then; With the solid that generates in the exchange column at normal temperatures with ethanol or washed with methanol; The acetylacetonate of generation is fully dissolved, get rid of, make acetylacetonate and the metal oxide or the hydroxide of complete reaction do not separate from liquid outlet; The solution of then liquid outlet being got rid of that contains acetylacetonate reduces pressure under 30 ° of C ~ 40 ° C and concentrates, and obtains the crystallization of acetylacetonate.
Preferably, the exchange column in the step [1], diameter 10-100cm, long 1-10m, compactedness 60 ~ 90%.
Preferably, the flow of the feeding of the steam in the step [2] exchange column is 5Kg/h-20Kg/h.
Preferably, exchange column is to adopt the stainless steel material cylinder.
Preferably, the exchange column that adopts in the industry, inside can be tower plate structure layer by layer, and each joint adopts flange to connect, and structure is as shown in Figure 4; The exchange column top has steam to get into control valve (11), and through flowmeter (12) control steam flow rate, exchange column cylinder (13) inner filling material (14), liquid outlet and control valve (16) are arranged at the exchange column bottom.
Excellent results of the present invention:
The present invention relates to acetylacetone,2,4-pentanedione gathers the zirconium legal system and produces a key technology in the crystal of zirconium oxide fiber fully; Be in crystal of zirconium oxide fiber transition process, to adopt the pressure solutions analysis method about gather zirconium precursor body fiber at acetylacetone,2,4-pentanedione; Make acetyl acetone ligands resolved effectively, separate, thereby realize that the crystal of zirconium oxide fiber quality increases substantially, optimization and acetylacetonate byproduct reclaim.The present invention both can improve the performance of prepared Zirconium oxide fibre, the cost that cuts down the consumption of energy, and also can increase byproduct and reclaim, helps to realize crystal of zirconium oxide fiber environmental protection production.
The present invention is except the advantage that keeps prior art;, middle High Temperature Gas earlier precursor fibre is carried out dissection process in the pressure solutions analysis apparatus before handling; Precursor fibre is fully resolved at short notice, and atmosphere amount and processing time when temperature is handled in can making significantly reduce, and reduce production costs; And the part of resolving is present in the pressure atmosphere with the form of organic molecule, more helps directly reclaiming the preparation byproduct, can satisfy environment protection requirement.Part is fully resolved and can further be put forward the high fibre strength of crystal of zirconium oxide, speed production efficient, shortens the production cycle, cuts down the consumption of energy and effectively reclaim the part byproduct.
The present invention has improved the removal efficient of solvent and part greatly, has not only improved target product crystal of zirconium oxide quality of fiber, has accelerated production efficiency, has reduced energy consumption, and more helped effective recovery of part byproduct.Thereby, adopt method of the present invention that precursor fibre is carried out pressure and resolve and to have for preparation crystal of zirconium oxide fiber that product quality is higher, production efficiency is faster, excellent results such as production cost is lower, pollution-free, environmental protection, be applicable to suitability for industrialized production.
Description of drawings
Fig. 1 is a pressure solutions analysis apparatus structural representation of the present invention.Wherein, 1, shell, 2, inner bag, 3, interlayer, 4, the atmosphere inlet, 5, steam outlet, 6, flow control valve, 7, net grid support, 8, stent support baffle plate.
Fig. 2 is the gas chromatogram of collecting among the embodiment 2 that contains enrichment acetylacetone,2,4-pentanedione water vapour.Abscissa is time (min).
Fig. 3 is a part acetylacetone,2,4-pentanedione resolution factor under different pressures among the embodiment 7 (temperature), the time conditions.
Fig. 4 is the exchange column structural representation of acetylacetone,2,4-pentanedione reaction among the embodiment 3.Wherein, 11, steam gets into control valve, 12, flowmeter, 13, exchange column cylinder, 14, stuffing, 15, the post internal partition, 16, the liquid outlet control valve, 17, adpting flange.
Fig. 5 is that embodiment 17 gathers the crystal of zirconium oxide fiber photo that obtains after the parsing of acetyl acetone zirconium precursor body fiber process pressure, the heat treatment.
Fig. 6 is the stereoscan photograph that embodiment 17 gathers the crystal of zirconium oxide fiber that obtains after the parsing of acetyl acetone zirconium precursor body fiber process pressure, the heat treatment.
The specific embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is further specified, but be not limited thereto.
Embodiment 1:
A kind of pressure solutions analysis apparatus; Comprise inner bag 2 and interlayer 3; Be provided for putting the multi-layer net support 7 of precursor fibre 9 in the inner bag 2; Inner bag 2 peripheral hardwares are useful on and feed steam-heated interlayer 3, and the top of device is provided with atmosphere and feeds mouth 4, and the steam outlet 5 of enrichment part acetylacetone,2,4-pentanedione is arranged at the bottom of device.Net grid support 7 places on the stent support baffle plate 8 on inner bag 2 inwalls.
The inner bag material adopts 304 stainless steels, can bear 2 ~ 8 atmospheric pressures, 120 ° of C ~ 170 ° C of withstand temperature.The net grid support material adopts 316 stainless steels.The stent support baffle plate adopts 304 stainless steels.
Embodiment 2:
Carry out the method that pressure is resolved to gathering acetyl acetone zirconium precursor body fiber in a kind of crystal of zirconium oxide fiber production, adopt the pressure solutions analysis apparatus of embodiment 1, step is following:
(1) water vapour is fed in the interlayer 3, inner bag is preheated to 70 ° of C;
(2) acetylacetone,2,4-pentanedione being gathered the zirconium legal system is equipped with the precursor fibre 9 that obtains in the crystal of zirconium oxide fiber process and is placed on the multi-layer net support in the inner bag; Feed mouth 4 through atmosphere and in inner bag 2, feed water vapour atmosphere, Pressure control is at 2 atmospheric pressure, through the steam heat temperature raising in the interlayer; Making the temperature in the inner bag is 120 ° of C; Carry out dissection process, the processing time is 30min, and the 54wt% that calculates part acetylacetone,2,4-pentanedione in the precursor fibre according to weight difference before and after handling parses;
(3) after the dissection process end, the steam outlet 5 of device for opening bottom, the steam of discharging enrichment part acetylacetone,2,4-pentanedione makes the temperature in the inner bag reduce to 100 ° of C, and fiber continues to be positioned over 2h in the inner bag, and the fiber of drying is taken out; Carry out the subsequent heat treatment step by prior art.
(4) vapor enrichment of the part acetylacetone,2,4-pentanedione of collection discharging is used to carry out post processing and reclaims accessory substance.
Embodiment 3:
A kind of part acetylacetone,2,4-pentanedione recoverying and utilizing method, step is following:
[1] with 3.0Kg stuffing 14Mg (OH)
2Powder is filled in the exchange column 13, and the length of exchange column is 2m, and diameter is 50cm, and compactedness is 60%;
The steam of the enrichment part acetylacetone,2,4-pentanedione of [2] embodiment 2 being collected feeds in the exchange column of step [1], and 12 controls are about 5Kg/h to steam flow with flowmeter through control valve 11, react to be 6h, obtain magnesium acetate and magnesium acetylacetonate;
[3] will pass through step [2] back steam cooled and form liquid state, the magnesium acetate of generation is dissolved in this liquid, and the outlet of being furnished with control valve 16 from the bottom is flowed out; Solid in the exchange column is adopted alcohol flushing at normal temperatures; The magnesium acetylacetonate of generation is fully dissolved; Magnesium acetylacetonate is separated with the magnesium hydroxide of complete reaction not, and the solution that will contain magnesium acetylacetonate then reduces pressure under 30 ° of C ~ 40 ° C and concentrates the crystallization that obtains magnesium acetylacetonate.
Embodiment 4:
Of embodiment 1, different is that inner bag and net grid support material are 316 stainless steels, more corrosion-resistant than 304 stainless steels, longer service life.
Embodiment 5:
Of embodiment 1, different is that the inner bag material is an enamel, than stainless steel acid and alkali-resistance more, precursor fibre is not polluted.
Embodiment 6:
Of embodiment 2, different is with inner bag preheating temperature to 120 ° C.
Embodiment 7:
Step such as embodiment 2 are said, and different is that atmosphere pressures is respectively 2,2.5,3,4,5,6,8 atmospheric pressure, and each self-corresponding temperature is 120 ° of C, 125 ° of C, 135 ° of C, 146 ° of C, 152 ° of C, 159 ° of C, 170 ° of C;
Processing time is 30min, 1h, 2h, 4h, and it is as shown in Figure 3 that the part acetylacetone,2,4-pentanedione is resolved effect.
Embodiment 8:
Of embodiment 2, different is to change water vapour atmosphere into alcohol vapour atmosphere, resolution factor 51wt%.
Embodiment 9:
Of embodiment 2, different is the mixed atmosphere that water vapour atmosphere is changed into percent by volume 5% water vapour and 95% alcohol vapour, can the part acetylacetone,2,4-pentanedione be resolved resolution factor 52wt%.
Embodiment 10:
Of embodiment 3, the length of different is exchange column is 3m, and diameter is 20cm, and compactedness is 80%, and the reaction time is 4h;
Embodiment 11:
Of embodiment 3, the length of different is exchange column is 5m, and diameter is 10cm; Compactedness is 90%, and the reaction time is 2h, increases the length of exchange column and the haptoreaction time that compactedness can prolong steam and filler; Make reaction more abundant, improve the efficient that reaction is reclaimed;
Embodiment 12:
Of embodiment 3, different is with Mg (OH)
2Powder is changed to Ni (OH)
2Powder, fully the crystallization that obtains the acetylacetone,2,4-pentanedione nickel salt is separated in the reaction back.
Embodiment 13:
Of embodiment 3, different is with Mg (OH)
2Powder is adjusted into Ca (OH)
2Powder, fully the crystallization that obtains the acetylacetone,2,4-pentanedione calcium salt is separated in the reaction back.
Embodiment 14:
Of embodiment 3, different is with Mg (OH)
2Powder is adjusted into Co (OH)
2Powder, fully the crystallization that obtains the acetylacetone,2,4-pentanedione cobalt salt is separated in the reaction back.
Embodiment 15:
Of embodiment 3, different is with Mg (OH)
2Powder is adjusted into ZnO powder, and fully the crystallization that obtains the acetylacetone,2,4-pentanedione zinc salt is separated in the reaction back.
Embodiment 16:
Of embodiment 3, different is with Mg (OH)
2Powder is adjusted into Fe
2O
3Powder, fully the crystallization that obtains acetylacetone iron salt is separated in the reaction back.
Embodiment 17: the application of the inventive method
A kind of crystal of zirconium oxide fiber preparation method, of embodiment among the CN200910013781.7 1, different is, and to get rid of a liquid be 27 ° of C in temperature; Relative humidity 20%; Centrifuge speed is 15000r/min, and getting rid of a hole linear velocity is 30m/s, gets rid of under the condition that an aperture is 0.2mm; Spinning solution is thrown away at a high speed from getting rid of a hole, obtain to gather acetyl acetone zirconium fiber (containing the zirconium organic polymer fiber).
The acetyl acetone zirconium fiber that gathers of above-mentioned acquisition is placed in the pressure solutions analysis apparatus, carry out pressure by the method for the embodiment of the invention 2 and resolve, different is that the pressure analysis condition is: carry out the pressure dissection process under 2.2 atmospheric pressure, 134 ° of C, the time is 4h; The acetylacetone,2,4-pentanedione resolution factor is 66%.
The acetyl acetone zirconium fiber that gathers of dissection process is placed in the quartzy sintering furnace of program control heat treatment; In the presence of steam; Heating rate with 1 ° of C/min is warming up to 600 ° of C, this stage steam feeding amount be among the CN200910013781.7 embodiment 1 1/3 ~ 1/5, significantly reduced energy consumption; Heating rate with 3 ° of C/min is warming up to 1600 ° of C again, and insulation 1h, can obtain high-purity, the full grown crystal of zirconium oxide fiber of crystal grain.As shown in Figure 5, pure white translucent, the fluffy accumulation of the crystal of zirconium oxide fiber of acquisition, fibre diameter 1-10 μ m; Fiber crystal grain is arranged fine and close, even, tiny (stereoscan photograph such as Fig. 6), fibre strength 500 ~ 1100MPa, and performance such as high temperature resistant is good.
Claims (10)
1. one kind is carried out the method that pressure is resolved to gathering acetyl acetone zirconium precursor body fiber, may further comprise the steps:
(1) pressure vessel is preheated to 70 ~ 120 ° of C;
(2) acetylacetone,2,4-pentanedione being gathered the zirconium legal system is equipped with the acetyl acetone zirconium precursor body fiber that gathers that obtains in the crystal of zirconium oxide fiber process and places the pressure vessel of preheating; Pressure control is at 2 ~ 8 atmospheric pressure after feeding atmosphere; Heat temperature raising, making temperature is 120 ° of C ~ 170 ° C, carries out dissection process; Processing time is 30min ~ 4h, makes that the part acetylacetone,2,4-pentanedione in the precursor fibre parses;
(3) after dissection process finished, the steam of discharging enrichment part acetylacetone,2,4-pentanedione made the temperature in the pressure vessel reduce to 100 ° of C ~ 80 ° C, and fiber is continued to be positioned over container inner drying 30min ~ 2h, took out then to carry out subsequent heat treatment and prepare the crystal of zirconium oxide fiber; Subsequent heat treatment gets final product by prior art;
(4) steam of the enrichment part acetylacetone,2,4-pentanedione of collection discharging carries out post processing and reclaims the acetylacetone,2,4-pentanedione accessory substance.
2. as claimed in claim 1 to gathering the method that acetyl acetone zirconium precursor body fiber carries out the pressure parsing, it is characterized in that feeding atmosphere in the step (2) is water vapour, ethanol or benzene.
3. as claimed in claim 1 to gathering the method that acetyl acetone zirconium precursor body fiber carries out the pressure parsing, the heat temperature raising that it is characterized in that step (2) is to use Steam Heating, preferred water steam.
4. as claimed in claim 1ly carry out the method that pressure is resolved, it is characterized in that in the step (2) gathering acetyl acetone zirconium precursor body fiber, feed atmosphere after Pressure control at 8 atmospheric pressure; Heat temperature raising; Making temperature is 170 ° of C, carries out dissection process, and the processing time is 30min ~ 4h.
5. as claimed in claim 1ly carry out the method that pressure is resolved, it is characterized in that in the step (2) gathering acetyl acetone zirconium precursor body fiber, feed atmosphere after Pressure control at 2 ~ 4 atmospheric pressure, temperature is 120 ~ 145 ° of C dissection process, the processing time is 1 ~ 2h.
6. a method that is used for claim 1 is carried out the device that pressure is resolved to precursor fibre; It is characterized in that comprising inner bag and interlayer; Be provided with the net grid support that multilayer is used to put precursor fibre in the inner bag; The inner bag peripheral hardware is useful on and feeds steam-heated interlayer, and the top of this device is provided with atmosphere and feeds mouth, and the bottom is provided with the steam outlet of enrichment part acetylacetone,2,4-pentanedione.
7. the device that precursor fibre is carried out the pressure parsing as claimed in claim 6 is characterized in that said net grid support places on the stent support baffle plate on the inner bag inwall.
8. a part acetylacetone,2,4-pentanedione recovery method comprises the steam that utilizes the enrichment part acetylacetone,2,4-pentanedione of collecting in the described pressure solutions analysis method of claim 1, and step is following:
[1] metal oxide powder or hydroxide powder are filled in the exchange column; Described metal oxide is ZnO or Fe
2O
3, said hydroxide is Mg (OH)
2, Ca (OH)
2, Ni (OH)
2Or Co (OH)
2
[2] steam with the enrichment part acetylacetone,2,4-pentanedione of collecting quantitatively feeds in the exchange column of step [1], and fully reaction generates and obtains corresponding acetylacetonate and acetate; Wherein, acetate comes from the acetic acid that the part acetylacetone,2,4-pentanedione is decomposed to form in the steam condition lower part;
[3] form liquid state through step [2] back steam cooled, the acetate of generation is dissolved in this liquid, flows out from the exchange column lower liquid outlet; With the solid that generates in the exchange column at normal temperatures with ethanol or washed with methanol; The acetylacetonate of generation is fully dissolved; Get rid of from liquid outlet; Acetylacetonate is separated, the solution of then liquid outlet being got rid of that the contains acetylacetonate concentrated crystallization that obtains acetylacetonate of under 30 ° of C ~ 40 ° C, reducing pressure with the not metal oxide or the hydroxide of complete reaction.
9. part acetylacetone,2,4-pentanedione recovery method as claimed in claim 8 is characterized in that, the exchange column in the step [1], and the footpath is 10-100cm, long 1-10m, compactedness 60 ~ 90%.
10. part acetylacetone,2,4-pentanedione recovery method as claimed in claim 8 is characterized in that, the flow that the steam in the step [2] feeds exchange column is 5Kg/h-20Kg/h, and the reaction time is 2-6h.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310492286.5A CN103614809B (en) | 2012-08-07 | 2012-08-07 | The pressure resolver of poly-acetyl acetone zirconium precursor body fiber in zirconia crystal fiber preparation |
| CN201210278939.5A CN102787393B (en) | 2012-08-07 | 2012-08-07 | Method and device for pressure analysis of polyacetylacetonatozirconium precursor fiber during zirconia crystalline fiber preparation and ligand recovery technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210278939.5A CN102787393B (en) | 2012-08-07 | 2012-08-07 | Method and device for pressure analysis of polyacetylacetonatozirconium precursor fiber during zirconia crystalline fiber preparation and ligand recovery technology |
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Cited By (7)
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| CN103556303A (en) * | 2013-10-19 | 2014-02-05 | 山东大学 | Preparation method of tin oxide fiber precursor and tin oxide crystal fibers |
| CN103993388A (en) * | 2014-05-30 | 2014-08-20 | 山东大学 | High-temperature pressure resolution technology for preparing high-performance zirconia crystal fiber |
| CN103993366A (en) * | 2014-05-30 | 2014-08-20 | 山东大学 | Method for preparing polyvinyl acetate zirconium oxygen precursor sol spinning solution and zirconia crystal fiber based on basic zirconium carbonate-methyl alcohol system |
| CN103993387A (en) * | 2014-05-30 | 2014-08-20 | 山东大学 | Method for preparing ultrahigh-temperature-resistant kilometric continuous zirconia crystal fiber |
| CN103993365A (en) * | 2014-05-30 | 2014-08-20 | 山东大学 | Method for preparing high-stability polyvinyl acetate zirconium oxide sol and high-quality zirconium oxide crystal fibers by adoption of zirconium oxychloride |
| CN103993389A (en) * | 2014-05-30 | 2014-08-20 | 山东大学 | Method for preparing continuous zirconia crystal fiber through zirconium acetate oxide-methanol system |
| CN106929927A (en) * | 2015-12-30 | 2017-07-07 | 山东大学 | The preparation method of poly- acetyl acetone zirconium precursor body colloidal sol spinning solution and sub-micron zirconium oxide crystal fibre |
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| CN103556303A (en) * | 2013-10-19 | 2014-02-05 | 山东大学 | Preparation method of tin oxide fiber precursor and tin oxide crystal fibers |
| CN103556303B (en) * | 2013-10-19 | 2015-06-10 | 山东大学 | Preparation method of tin oxide fiber precursor and tin oxide crystal fibers |
| CN103993388A (en) * | 2014-05-30 | 2014-08-20 | 山东大学 | High-temperature pressure resolution technology for preparing high-performance zirconia crystal fiber |
| CN103993366A (en) * | 2014-05-30 | 2014-08-20 | 山东大学 | Method for preparing polyvinyl acetate zirconium oxygen precursor sol spinning solution and zirconia crystal fiber based on basic zirconium carbonate-methyl alcohol system |
| CN103993387A (en) * | 2014-05-30 | 2014-08-20 | 山东大学 | Method for preparing ultrahigh-temperature-resistant kilometric continuous zirconia crystal fiber |
| CN103993365A (en) * | 2014-05-30 | 2014-08-20 | 山东大学 | Method for preparing high-stability polyvinyl acetate zirconium oxide sol and high-quality zirconium oxide crystal fibers by adoption of zirconium oxychloride |
| CN103993389A (en) * | 2014-05-30 | 2014-08-20 | 山东大学 | Method for preparing continuous zirconia crystal fiber through zirconium acetate oxide-methanol system |
| CN103993389B (en) * | 2014-05-30 | 2015-11-04 | 山东大学 | A kind of zirconium oxyacetate-methanol system prepares the method for continuous oxidation zirconium crystal fibre |
| CN103993387B (en) * | 2014-05-30 | 2016-08-17 | 山东大学 | A kind of preparation method of the superhigh temperature resistant continuous zirconia crystal fiber of km level |
| CN103993366B (en) * | 2014-05-30 | 2016-08-24 | 山东大学 | Zirconium oxycarbonate-methanol system prepares the method for zirconia crystal fiber |
| CN103993365B (en) * | 2014-05-30 | 2016-08-24 | 山东大学 | Use the method that zirconium oxychloride prepares zirconia crystal fiber |
| CN106929927A (en) * | 2015-12-30 | 2017-07-07 | 山东大学 | The preparation method of poly- acetyl acetone zirconium precursor body colloidal sol spinning solution and sub-micron zirconium oxide crystal fibre |
Also Published As
| Publication number | Publication date |
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| CN102787393B (en) | 2014-05-21 |
| CN103614809A (en) | 2014-03-05 |
| CN103614809B (en) | 2015-07-29 |
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