CN102787393B - 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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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 analytic method, device and part byproduct recovery technology in the preparation of crystal of zirconium oxide fiber, particularly the poly-zirconium legal system of acetylacetone,2,4-pentanedione, for the poly-acetyl acetone zirconium precursor body fiber pressure analytic method in 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 the heat insulation and composite reinforcing materials of a kind of more excellent advanced person.Because it has the special performances such as the minimum and excellent acid-alkali-corrosive-resisting of high fusing point (2715 ° of C), thermal conductivity factor minimum, high temperature steam pressure in oxide, so, all there is the application prospect of particular importance at the sophisticated technologies such as Aeronautics and Astronautics and industrial circle.
The applicant started the key technology of crystal of zirconium oxide fiber formation mechanism and preparation to carry out systematically exploratory development from 1998.Adopt sol-gel and poly-acetyl acetone zirconium precursor body spin processes systematically to solve the preparation key technology of high performance zirconium oxide continuous fiber and short cellucotton.The patent that the applicant is relevant comprises preparation method and the equipment of CN03112408.9 continuous zirconia fiber, the organic poly-zirconium precursor body spinning solution of CNL200410024264.7 get rid of a legal system for Zirconium oxide fibre cotton, CN200410085390.3 for the preparation of the preparation method of the sintering furnace of continuous zirconia fiber, CN200910013781.7 complete stable cubic phase zircite crystal fibre, CN200910255807.9 mono-zirconia mesoporous fiber and preparation method thereof etc.According to technique and environmental issue in existing patent working process, the inventor has carried out exploratory development energetically.Found that by crystal of zirconium oxide fiber formation mechanism study, the performance of crystal of zirconium oxide fiber depends primarily on the processes such as the parsing, nucleation, crystal grain arrangement of acetylacetone,2,4-pentanedione, the crystal of zirconium oxide fiber forming to crystal grain oriented from the poly-zirconium glass state precursor fibre of acetylacetone,2,4-pentanedione changes, effective resolving of part is the key link that forms crystal of zirconium oxide fiber.The effect that precursor fibre is resolved, directly has influence on the problem such as formation, nucleation rate and uniformity, the oriented of crystal grain of zirconia nucleus in operation process below.On fabricating technology route, main manifestations is the technological parameters such as precursor fibre analyzing efficiency, analysis mode, parsing time, atmosphere, pressure etc., also relates to and resolves the comprehensive utilization of reclaiming rear part.
According to prior art, the poly-zirconium legal system of acetylacetone,2,4-pentanedione for crystal of zirconium oxide fiber comprise the steps: preparation, the spinning solution of presoma preparation, get rid of silk, heat treatment etc.Wherein being prepared as of presoma adopts eight hydration zirconium oxychlorides as zirconium source, acetylacetone,2,4-pentanedione, as part, is dissolved in alcoholic solvent, then adds gradually a certain amount of precipitating agent, form the crystallization of the poly-zirconium precursor liquid solution of acetylacetone,2,4-pentanedione and precipitating agent salt, separate the concentrated poly-zirconium precursor body of acetylacetone,2,4-pentanedione that obtains; Poly-acetylacetone,2,4-pentanedione zirconium precursor body and stabilizing agent are dissolved in successively according to a certain percentage in methyl alcohol or ethanol and form golden transparent solution, and then reduced pressure concentration is until obtain the poly-zirconium spinning solution of acetylacetone,2,4-pentanedione that viscosity is 10 ~ 50Pas; Spinning solution is injected and gets rid of wire tray, under certain rotating speed, make to get rid of a liquid and throw away from the aperture high speed centrifugation that gets rid of wire tray, collect and obtain the poly-zirconium precursor body fiber of acetylacetone,2,4-pentanedione.The poly-zirconium precursor body fiber of acetylacetone,2,4-pentanedione obtaining is the linear chain shaped polymer being connected to form by zirconium, acetyl acetone ligands and hydroxyl, and wherein part acetylacetone,2,4-pentanedione occupies larger component, and relative weight is about 42%.So the aspects such as the formation to high-performance zirconia crystal fibre such as the analysis mode of acetylacetone,2,4-pentanedione, analyzing efficiency, recovery technology and production cost, environmental protection play very crucial effect.
Summary of the invention
For the problem of prior art, the invention provides method and the part byproduct recovery technology of in a kind of crystal of zirconium oxide fiber preparation, poly-acetyl acetone zirconium precursor body fiber being carried out to pressure parsing.
The present invention also provides the suitable devices of described analytic method.
The handled thing of pressure analytic method of the present invention is that prior art acetylacetone,2,4-pentanedione gathers zirconium legal system for the precursor fibre obtaining in crystal of zirconium oxide fiber process, and described precursor fibre forms by gathering acetyl acetone zirconium, and molecular formula is abbreviated as Zr (CH
3cOCH
2cOCH
3) (OH)
3, wherein the structure of poly-acetyl acetone zirconium is that a part Zr is connected with a part acetylacetone,2,4-pentanedione, and pass through-OH effect connects and forms double-stranded linear polymer molecular structure, and the relative amount of part acetylacetone,2,4-pentanedione is about 42wt%, ZrO
2relative amount be about 50wt%.So can be attended by the generation of a large amount of part acetylacetone,2,4-pentanediones when precursor fibre post processing obtains crystal of zirconium oxide fiber, the recycling of acetylacetone,2,4-pentanedione can less environmental pollution can be increased production again a kind of byproduct.
Gather zirconium legal system for crystal of zirconium oxide fiber by prior art acetylacetone,2,4-pentanedione, comprise preparation (containing zirconium organic polymer synthetic), the spinning solution of presoma preparation, get rid of silk, heat treatment, getting rid of after a step, before heat treatment step, adopt pressure analytic method of the present invention to process poly-acetyl acetone zirconium precursor body fiber.
Technical scheme of the present invention is as follows:
One, pressure analytic method
The method that poly-acetyl acetone zirconium precursor body fiber is carried out to pressure parsing, step is as follows:
(1) pressure vessel is preheated to 70 ~ 120 ° of C;
(2) poly-acetylacetone,2,4-pentanedione zirconium legal system is placed in to the pressure vessel of preheating for the poly-acetyl acetone zirconium precursor body fiber obtaining in crystal of zirconium oxide fiber process, after passing into atmosphere, pressure is controlled at 2 ~ 8 atmospheric pressure, heat temperature raising, making temperature is 120 ° of C ~ 170 ° C, carry out dissection process, processing time is 30min ~ 4h, and the part acetylacetone,2,4-pentanedione in precursor fibre is parsed;
(3) after dissection process finishes, the steam of discharge enrichment part acetylacetone,2,4-pentanedione makes the temperature in pressure vessel be down to 100 ° of C ~ 80 ° C, and fiber is continued to be positioned over container inner drying 30min ~ 2h, then takes out to carry out subsequent heat treatment and prepare crystal of zirconium oxide fiber; Subsequent heat treatment is by prior art;
(4) steam of the enrichment part acetylacetone,2,4-pentanedione of collection discharge, carries out post processing and reclaims acetylacetone,2,4-pentanedione accessory substance.
In step (2), passing into atmosphere 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 by Steam Heating, steam be organic steam, water vapour one of or combination.Organic steam refers to the volatile organic vapor such as ethanol, benzene.From security consideration, most preferably water vapour.
In step (2), calculate the resolution factor 54 ~ 83wt% of part acetylacetone,2,4-pentanedione in precursor fibre according to precursor fibre weight difference before and after dissection process.
Preferably, in step (2), pass into atmosphere after pressure be controlled at 8 atmospheric pressure, heat temperature raising, making temperature is 170 ° of C, carries out dissection process, the processing time is 30min ~ 4h.Now the resolution factor of part acetylacetone,2,4-pentanedione is higher.But consider the cost of pressure, temperature, under comparatively gentle condition, in preferred step (2), pass into atmosphere after pressure be controlled at 2 ~ 4 atmospheric pressure, temperature is 120 ~ 145 ° of C dissection process, the processing time is 1 ~ 2h.
Two, the device that pressure is resolved
According to the present invention, a kind of for precursor fibre being carried out to the device of pressure parsing, comprise inner bag and interlayer, in inner bag, be provided with multilayer for putting the net grid support of precursor fibre, inner bag peripheral hardware is useful on and passes into steam-heated interlayer, the top of this device is provided with atmosphere and passes into mouth, and bottom is provided with the steam outlet of enrichment part acetylacetone,2,4-pentanedione.Structure as shown in Figure 1.
Described net grid support is placed on the stent support baffle plate on inner bag inwall.
Preferably, liner material adopts stainless steel or enamel or glass.Wherein 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 obtain 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, with outside interlayer, can make the preheating of device inner bag by jacket steam before processing precursor fibre, avoided steam to run into the precursor fibre that temperature is lower and was cooled to drop, destroyed fiber; In inner bag, it is the net grid support of sandwich construction.
Bottom at pressure resolver is provided with steam outlet, the steam that contains acetylacetone,2,4-pentanedione discharging can be discharged by this steam outlet in resolving.
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 by pipeline, access is reclaimed in 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 recovery method for part acetylacetone,2,4-pentanedione, comprises the steam that utilizes the enrichment part acetylacetone,2,4-pentanedione of collecting in the above-mentioned pressure analytic method of the present invention, and step is as follows:
[1] metal oxide powder or hydroxide powder are filled in exchange column, described metal oxide is ZnO or Fe
2o
3, described hydroxide is Mg (OH)
2, Ca (OH)
2, Ni (OH)
2or Co (OH)
2;
[2] steam of the enrichment part acetylacetone,2,4-pentanedione of collection is passed in the exchange column of step [1], fully reaction, generates and obtains corresponding acetylacetonate and a small amount of acetate; Wherein, acetate comes from part acetylacetone,2,4-pentanedione at the raw acetic acid being decomposed to form of steam condition bottom distribution;
[3], after step [2], the cooling formation of steam is liquid and the acetate of generation is dissolved as to liquid, flows out from exchange column lower liquid outlet; Then, by the solid generating in exchange column at normal temperatures by ethanol or washed with methanol, the acetylacetonate generating is fully dissolved, get rid of from liquid outlet, make acetylacetonate and metal oxide or the hydroxide of complete reaction do not separate, then the solution that contains acetylacetonate reduced pressure concentration under 30 ° of C ~ 40 ° C of liquid outlet being got rid of, obtains the crystallization of acetylacetonate.
Preferably, the exchange column in step [1], diameter 10-100cm, long 1-10m, compactedness 60 ~ 90%.
Preferably, to pass into the flow of exchange column be 5Kg/h-20Kg/h to the steam in step [2].
Preferably, exchange column is to adopt stainless steel material cylinder.
Preferably, the exchange column of industrial employing, inside can be tower plate structure layer by layer, and each joint adopts flange to connect, and structure is as shown in Figure 4; Exchange column top has steam to enter control valve (11), controls steam flow rate, exchange column cylinder (13) inner filling material (14) by flowmeter (12), and liquid outlet and control valve (16) are arranged at exchange column bottom.
Excellent results of the present invention:
The present invention relates to the standby key technology of producing in crystal of zirconium oxide fiber of the poly-zirconium legal system of acetylacetone,2,4-pentanedione, about adopting pressure analytic method at the poly-zirconium precursor body fiber of acetylacetone,2,4-pentanedione in crystal of zirconium oxide fiber transition process, make acetyl acetone ligands effectively be resolved, separate, thereby realize that crystal of zirconium oxide fiber quality increases substantially, optimization and acetylacetonate byproduct reclaim.The present invention both can improve performance, the reduction energy consumption cost of prepared Zirconium oxide fibre, also can increase byproduct and reclaim, contributes to realize crystal of zirconium oxide fiber environmental protection production.
The present invention is except keeping the advantage of prior art, before processing, middle High Temperature Gas first precursor fibre is carried out in pressure resolver to dissection process, precursor fibre is fully resolved at short notice, and atmosphere amount and processing time can make heat-treated under medium temperature time greatly reduce, and reduce production costs; And the part of resolving is present in pressure atmosphere with the form of organic molecule, be more conducive to directly reclaim and prepare byproduct, can meet environment protection requirement.Part is fully resolved and can further be put forward the high fibre strength of crystal of zirconium oxide, speed production efficiency, shortening production cycle, reduction energy consumption and effectively reclaim part byproduct.
The present invention has improved the removal efficiency of solvent and part greatly, not only improved target product crystal of zirconium oxide fiber quality, accelerated production efficiency, reduced energy consumption, and be more conducive to effective recovery of part byproduct.Thereby, adopt method of the present invention to carry out pressure parsing to precursor fibre and there is the excellent results such as product quality is higher, production efficiency is faster, production cost is lower, pollution-free, environmental protection for preparing crystal of zirconium oxide fiber, be applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is pressure resolver structural representation of the present invention.Wherein, 1, shell, 2, inner bag, 3, interlayer, 4, atmosphere entrance, 5, steam outlet, 6, flow control valve, 7, net grid support, 8, stent support baffle plate.
Fig. 2 is the gas chromatogram that contains enrichment acetylacetone,2,4-pentanedione water vapour of collecting in embodiment 2.Abscissa is time (min).
Fig. 3 is part acetylacetone,2,4-pentanedione resolution factor under different pressures in embodiment 7 (temperature), time conditions.
Fig. 4 is the exchange column structural representation of acetylacetone,2,4-pentanedione reaction in embodiment 3.Wherein, 11, steam enters control valve, 12, flowmeter, 13, exchange column cylinder, 14, stuffing, 15, post internal partition, 16, liquid outlet control valve, 17, adpting flange.
Fig. 5 is the crystal of zirconium oxide fiber photo that the poly-acetyl acetone zirconium precursor body fiber of embodiment 17 obtains after excess pressure parsing, heat treatment.
Fig. 6 is the stereoscan photograph of the crystal of zirconium oxide fiber that obtains after excess pressure parsing, heat treatment of the poly-acetyl acetone zirconium precursor body fiber of embodiment 17.
The specific embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention will be further described, but be not limited to this.
Embodiment 1:
A kind of pressure resolver, comprise inner bag 2 and interlayer 3, in inner bag 2, be provided for putting the multi-layer net support 7 of precursor fibre 9, inner bag 2 peripheral hardwares are useful on and pass into steam-heated interlayer 3, the top of device is provided with atmosphere and passes into 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 is placed on the stent support baffle plate 8 on inner bag 2 inwalls.
Inner bag material adopts 304 stainless steels, can bear 2 ~ 8 atmospheric pressures, 120 ° of C ~ 170 ° C of withstand temperature.Net grid support material adopts 316 stainless steels.Stent support baffle plate adopts 304 stainless steels.
Embodiment 2:
A method of in the preparation of crystal of zirconium oxide fiber, poly-acetyl acetone zirconium precursor body fiber being carried out to pressure parsing, the pressure resolver of employing embodiment 1, step is as follows:
(1) water vapour is passed in interlayer 3, inner bag is preheated to 70 ° of C;
(2) poly-acetylacetone,2,4-pentanedione zirconium legal system is placed on the multi-layer net support in inner bag for the precursor fibre 9 obtaining in crystal of zirconium oxide fiber process, pass into mouth 4 by atmosphere and pass into water vapour atmosphere in inner bag 2, pressure is controlled at 2 atmospheric pressure, by the steam heat temperature raising in interlayer, making the temperature in 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 precursor fibre according to weight difference before and after processing parses;
(3) after dissection process finishes, the steam outlet 5 of device for opening bottom, the steam of discharge enrichment part acetylacetone,2,4-pentanedione makes the temperature in inner bag be down to 100 ° of C, and fiber continues to be positioned over 2h in inner bag, and the fiber of drying is taken out; Carry out subsequent heat treatment step by prior art.
(4) vapor enrichment of the part acetylacetone,2,4-pentanedione of collection discharge, reclaims accessory substance for carrying out post processing.
Embodiment 3:
A kind of part acetylacetone,2,4-pentanedione recoverying and utilizing method, step is as follows:
[1] by 3.0Kg stuffing 14Mg (OH)
2powder is filled in 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 passes in the exchange column of step [1], and steam flow is controlled and is about 5Kg/h by control valve 11 and flowmeter 12, reacts for 6h, obtains magnesium acetate and magnesium acetylacetonate;
[3] will be after step [2] the cooling formation of steam liquid, the magnesium acetate of generation is dissolved in this liquid, the outlet of being furnished with control valve 16 from bottom is flowed out; Solid in exchange column is adopted to alcohol flushing at normal temperatures, the magnesium acetylacetonate generating is fully dissolved, magnesium acetylacetonate is separated with the magnesium hydroxide of complete reaction not, then the solution that contains magnesium acetylacetonate reduced pressure concentration under 30 ° of C ~ 40 ° C is obtained to the crystallization of magnesium acetylacetonate.
Embodiment 4:
As described in Example 1, difference 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:
As described in Example 1, difference is that inner bag material is enamel, than more acid and alkali-resistance of stainless steel, precursor fibre is not polluted.
Embodiment 6:
As described in Example 2, difference is by inner bag preheating temperature to 120 ° C.
Embodiment 7:
As described in Example 2, difference is that atmosphere pressures is respectively 2,2.5,3,4,5,6,8 atmospheric pressure to step, 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 part acetylacetone,2,4-pentanedione is resolved effect as shown in Figure 3.
Embodiment 8:
As described in Example 2, difference is to change water vapour atmosphere into alcohol vapour atmosphere, resolution factor 51wt%.
Embodiment 9:
As described in Example 2, difference is the mixed atmosphere that water vapour atmosphere is changed into percent by volume 5% water vapour and 95% alcohol vapour, part acetylacetone,2,4-pentanedione can be resolved resolution factor 52wt%.
Embodiment 10:
As described in Example 3, difference is that the length of exchange column is 3m, and diameter is 20cm, and compactedness is 80%, and the reaction time is 4h;
Embodiment 11:
As described in Example 3, difference is that the length of exchange column is 5m, and diameter is 10cm, compactedness is 90%, and the reaction time is 2h, and the length of increase exchange column and compactedness can extend the haptoreaction time of steam and filler, make reaction more abundant, improve the efficiency that reaction is reclaimed;
Embodiment 12:
As described in Example 3, difference is by Mg (OH)
2powder is changed to Ni (OH)
2powder, fully separates the crystallization that obtains acetylacetone,2,4-pentanedione nickel salt after reaction.
Embodiment 13:
As described in Example 3, difference is by Mg (OH)
2powder is adjusted into Ca (OH)
2powder, fully separates the crystallization that obtains acetylacetone,2,4-pentanedione calcium salt after reaction.
Embodiment 14:
As described in Example 3, difference is by Mg (OH)
2powder is adjusted into Co (OH)
2powder, fully separates the crystallization that obtains acetylacetone,2,4-pentanedione cobalt salt after reaction.
Embodiment 15:
As described in Example 3, difference is by Mg (OH)
2powder is adjusted into ZnO powder, fully after reaction, separates the crystallization that obtains acetylacetone,2,4-pentanedione zinc salt.
Embodiment 16:
As described in Example 3, difference is by Mg (OH)
2powder is adjusted into Fe
2o
3powder, fully separates the crystallization that obtains acetylacetone iron salt after reaction.
Embodiment 17: the application of the inventive method
A kind of preparation method of crystal of zirconium oxide fiber, as described in embodiment in CN200910013781.7 1, difference is that 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 poly-acetyl acetone zirconium fiber (containing zirconium organic polymer fiber).
The poly-acetyl acetone zirconium fiber of above-mentioned acquisition is placed in pressure resolver, carries out pressure parsing by the method for the embodiment of the present invention 2, difference is that pressure analysis condition is: under 2.2 atmospheric pressure, 134 ° of C, carry out pressure dissection process, the time is 4h; Acetylacetone,2,4-pentanedione resolution factor is 66%.
The poly-acetyl acetone zirconium fiber of dissection process is placed in program control heat treatment quartz sintering furnace, under steam exists, be warming up to 600 ° of C with the heating rate of 1 ° of C/min, this stage steam intake be in CN200910013781.7 embodiment 1 1/3 ~ 1/5, greatly reduced energy consumption; Be warming up to 1600 ° of C with the heating rate of 3 ° of C/min again, and be incubated 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 is as Fig. 6), fibre strength 500 ~ 1100MPa, and the performance such as high temperature resistant is good.
Claims (1)
1. a method of poly-acetyl acetone zirconium precursor body fiber being carried out to pressure parsing, comprises the following steps:
(1) pressure vessel is preheated to 70 ~ 120 ℃;
(2) poly-acetylacetone,2,4-pentanedione zirconium legal system is placed in to the pressure vessel of preheating for the poly-acetyl acetone zirconium precursor body fiber obtaining in crystal of zirconium oxide fiber process, after passing into atmosphere, pressure is controlled at 2 ~ 8 atmospheric pressure, heat temperature raising, making temperature is 120 ℃ ~ 170 ℃, carry out dissection process, processing time is 30min ~ 4h, and the part acetylacetone,2,4-pentanedione in precursor fibre is parsed;
(3) after dissection process finishes, the steam of discharge enrichment part acetylacetone,2,4-pentanedione makes the temperature in pressure vessel be down to 100 ℃ ~ 80 ℃, and fiber is continued to be positioned over container inner drying 30min ~ 2h, then takes out to carry out subsequent heat treatment and prepare crystal of zirconium oxide fiber; Subsequent heat treatment is by prior art;
(4) steam of the enrichment part acetylacetone,2,4-pentanedione of collection discharge, carries out post processing and reclaims acetylacetone,2,4-pentanedione accessory substance.
2
.the method that poly-acetyl acetone zirconium precursor body fiber is carried out to pressure parsing as claimed in claim 1, is characterized in that in step (2), passing into atmosphere is water vapour, ethanol or benzene.
3
.the method that poly-acetyl acetone zirconium precursor body fiber is carried out to pressure parsing as claimed in claim 1, is characterized in that the heat temperature raising of step (2) is to use Steam Heating.
4
.the method that poly-acetyl acetone zirconium precursor body fiber is carried out to pressure parsing as claimed in claim 3, is characterized in that described steam is water vapour.
5
.the method that poly-acetyl acetone zirconium precursor body fiber is carried out to pressure parsing as claimed in claim 1, is characterized in that in step (2), pass into atmosphere after pressure be controlled at 8 atmospheric pressure, heat temperature raising, making temperature is 170 ℃, carries out dissection process, and the processing time is 30min ~ 4h.
6
.the method that poly-acetyl acetone zirconium precursor body fiber is carried out to pressure parsing as claimed in claim 1, is characterized in that in step (2), pass into atmosphere after pressure be controlled at 2 ~ 4 atmospheric pressure, temperature is 120 ~ 145 ℃ of dissection process, the processing time is 1 ~ 2h.
7
.a kind of part acetylacetone,2,4-pentanedione recovery method, comprises the steam of the enrichment part acetylacetone,2,4-pentanedione of collecting in the pressure analytic method utilizing described in claim 1, and step is as follows:
[1] metal oxide powder or hydroxide powder are filled in exchange column; Described metal oxide is ZnO or Fe
2o
3, described hydroxide is Mg (OH)
2, Ca (OH)
2, Ni (OH)
2or Co (OH)
2;
[2] steam of the enrichment part acetylacetone,2,4-pentanedione of collection is quantitatively passed in the exchange column of step [1], fully reaction, generates and obtains corresponding acetylacetonate and acetate; Wherein, acetate comes from part acetylacetone,2,4-pentanedione at the raw acetic acid being decomposed to form of steam condition bottom distribution;
[3] after step [2], the cooling formation of steam is liquid, and the acetate of generation is dissolved in this liquid, flows out from exchange column lower liquid outlet; By the solid generating in exchange column at normal temperatures by ethanol or washed with methanol, the acetylacetonate generating is fully dissolved, get rid of from liquid outlet, acetylacetonate is separated with not metal oxide or the hydroxide of complete reaction, and the solution that contains acetylacetonate reduced pressure concentration under 30oC ~ 40oC of then liquid outlet being got rid of obtains the crystallization of acetylacetonate.
8
.part acetylacetone,2,4-pentanedione recovery method as claimed in claim 7, is characterized in that, the exchange column in step [1], and diameter is 10-100cm, long 1-10m, compactedness 60 ~ 90%.
9
.part acetylacetone,2,4-pentanedione recovery method as claimed in claim 7, is characterized in that, the flow that the steam in step [2] passes into exchange column is 5 kg/h-20kg/h, and the reaction time is 2-6h.
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| 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 |
| 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 |
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|---|---|---|---|
| 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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| CN201310492286.5A Expired - Fee Related 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 Expired - Fee Related 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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| CN103556303B (en) * | 2013-10-19 | 2015-06-10 | 山东大学 | Preparation method of tin oxide fiber precursor and tin oxide crystal fibers |
| 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 |
| CN103993388B (en) * | 2014-05-30 | 2016-05-04 | 山东大学 | A kind of high temperature pressure analytic technique for the preparation of high-performance zirconia crystal fibre |
| CN103993365B (en) * | 2014-05-30 | 2016-08-24 | 山东大学 | Use the method that zirconium oxychloride prepares zirconia crystal fiber |
| 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 |
| CN106929927B (en) * | 2015-12-30 | 2020-03-24 | 山东大学 | Preparation method of polyacetylacetonatozirconium precursor sol spinning solution and submicron zirconia crystal fiber |
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| KR910006396B1 (en) * | 1988-12-14 | 1991-08-21 | 포항종합제철 주식회사 | Manufacturing method of stabilized zirconia staple fiber |
| CN1206397C (en) * | 2003-06-10 | 2005-06-15 | 山东大学 | Method and equipment of preparing high performance zirconium oxide continuous fiber |
| CN1234927C (en) * | 2004-06-11 | 2006-01-04 | 山东大学 | Zirconium oxide fabrics prepared from organic polyzirconium fore spinning solution by silk process |
| US7507844B2 (en) * | 2005-05-09 | 2009-03-24 | Sd Lizenzverwertungsgesellschaft Mbh & Co. Kg | Nanometer scale restructuring of alumina carrier surface and catalysts for the production of alkene oxides |
| CN100417620C (en) * | 2005-11-03 | 2008-09-10 | 山东大学 | Process for preparing zirconium oxide ceramic continuous fibre |
| CN101172856B (en) * | 2007-11-27 | 2010-11-10 | 中国建筑材料科学研究总院 | Method for producing zirconium oxide fibre and the produced zirconium oxide fibre |
| CN101498063B (en) * | 2009-01-14 | 2011-11-23 | 山东大学 | Preparation of complete stable cubic phase zircite crystal fibre |
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