CN110038554A - A kind of V that mica supports2O5-WO3/TiO2The preparation method of catalyst - Google Patents
A kind of V that mica supports2O5-WO3/TiO2The preparation method of catalyst Download PDFInfo
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- CN110038554A CN110038554A CN201910476166.3A CN201910476166A CN110038554A CN 110038554 A CN110038554 A CN 110038554A CN 201910476166 A CN201910476166 A CN 201910476166A CN 110038554 A CN110038554 A CN 110038554A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20723—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20776—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/30—Silica
Abstract
The invention discloses a kind of V that mica supports2O5‑WO3/TiO2The preparation method of catalyst, comprising the following steps: S1: micarex pre-treatment；S2: the aerosil preparation of micarex is adulterated；S3:TiO2/V2O5/WO3Precursor solution preparation；S4:TiO2/V2O5/WO3Support；S5: catalyst is dry；S6: catalyst roasting, the V that the strict control of the present invention mica supports2O5‑WO3/TiO2The preparation method of catalyst, the V supported by strict control mica2O5‑WO3/TiO2The preparation method parameter of catalyst, mica surface carry out hydrophobically modified with silane coupling agent, and surface hydrophobic enhancing, catalyst stability is higher, tests for the denitration of SCR method, and catalyst activity is higher, and catalyst can handle after be recycled, by TiO2/V2O5/WO3Mixture supports on the aerosil of doping micarex, and supported catalyst is made, which can be used for SCR method denitration experiment, has the characteristics that large specific surface area, stability are strong, activity is high.
Description
Technical field
The present invention relates to smoke gas treatment technical field, specially a kind of V that mica supports2O5-WO3/TiO2The system of catalyst
Preparation Method.
Background technique
Nitrogen oxides, including multiple compounds, such as nitrous oxide (N2O), nitric oxide (NO), nitrogen dioxide (NO2)、
Nitrogen trioxide (N2O3), dinitrogen tetroxide (N2O4) and dinitrogen pentoxide (N2O5) etc..In addition to nitrogen dioxide, other nitrogen oxidations
Object is extremely unstable, meets light, wet or thermal change into nitrogen dioxide and nitric oxide, nitric oxide becomes nitrogen dioxide again.Therefore, duty
What is contacted in industry environment is that several admixture of gas are frequently referred to the smoke of gunpowder (gas), predominantly nitric oxide and nitrogen dioxide, and with two
Based on nitrogen oxide.Nitrogen oxides all has different degrees of toxicity.
Nitrogen oxides is universally acknowledged one of atmosphere pollution, and nitrogen oxides can stimulate lung, makes one more difficult resistance sense
The respiratory disease emitted etc, the problematic personage of respiratory system such as asthmatics can influence compared with vulnerable to nitrogen dioxide.It is right
For children, it is impaired that nitrogen oxides is likely to result in lung's development.Research points out that sucking nitrogen oxides for a long time may result in lung
Cage structure changes, but still not can determine the amount of nitrogen oxides for leading to this consequence and sucking gas time.
Nitrogen oxides based on nitric oxide and nitrogen dioxide is the important original to form photochemical fog and acid rain
Cause, nitrogen oxides and hydrocarbon in vehicle exhaust react the toxic smog to be formed, referred to as light through ultraviolet light irradiation
Chemical fumes, photochemical fog have special odor, stimulate eyes, injure plant, and atmospheric visibility can be made to reduce, in addition,
The nitric acid generated is reacted with the water in air for nitrogen oxides and nitrous acid is the ingredient of acid rain, the main source of nitrogen oxides in atmosphere
The conversion of nitrogenous compound in the burning of fossil fuel and the burning of plant and agricultural land soil and animal excrements, with
NH3Selective catalytic reduction flue gas denitration technology (SCR) for reducing agent is to administer flue gas NOx to pollute most effective technology.
But existing catalyst has the problem of being easy poor inactivation, activity, higher cost, can not reusing, and is
This is it is proposed that a kind of V that mica supports2O5-WO3/TiO2The preparation method of catalyst.
Summary of the invention
The purpose of the present invention is to provide a kind of V that mica supports2O5-WO3/TiO2The preparation method of catalyst, mica
Surface carries out hydrophobically modified with silane coupling agent, and surface hydrophobic enhancing, catalyst stability is higher, real for the denitration of SCR method
Test, catalyst activity is higher, and catalyst can handle after be recycled, by TiO2/V2O5/WO3Mixture supports doping
On the aerosil of micarex, be made supported catalyst, the catalyst can be used for SCR method denitration experiment, have than
The feature that surface area is big, stability is strong, activity is high, to solve the problems mentioned in the above background technology.
To achieve the above object, the invention provides the following technical scheme: a kind of V that mica supports2O5-WO3/TiO2Catalysis
The preparation method of agent, comprising the following steps:
S1: micarex is crushed, is sieved by micarex pre-treatment, after impregnating half an hour with the concentrated sulfuric acid, with second alcohol and water
Alternately wash；
S2: the aerosil preparation of micarex is adulterated, TEOS and silane coupled is added in processed micarex
In the ethanol solution of agent phenyl triethoxysilane, HCl is added and is hydrolyzed 3 hours, then it is small to carry out condensation 24 by addition NAOH
When, ethanol evaporation obtains the aerosil of doping micarex；
S3:TiO2/V2O5/WO3Precursor solution preparation, takes a certain amount of ammonium metavanadate and ammonium tungstate, after being dissolved in water,
Acquired solution is slowly stirred to no solid and floccule presence at 60-70 DEG C, then adds nanoscale TiO2Particle,
It is sufficiently stirred at 60-70 DEG C, stands 5h at room temperature；
S4:TiO2/V2O5/WO3Support, in Xiang Shangshu solution addition be prepared doping micarex silica
Aeroge is sufficiently stirred under conditions of 60-70 DEG C, stands 6h at room temperature；
S5: catalyst is dry, and above-mentioned sample is evaporated in 75 DEG C of water-baths, dries 10h in 100 DEG C of thermostatic drying chambers；
S6: the sample of step S5 is calcined 5h in 450 DEG C of Muffle furnaces, obtains V by catalyst roasting2O5-/WO3/TiO2/
SiO2Catalyst is finally sieved into the particle of 50 mesh by catalyst.
Preferably, mica stone is crushed using TF-320 mica vertical fluted disc flour mill in the step S1, and discharge grain
Degree is 10mm, and the sieve diameter of sieving is 10mm.
Preferably, the concentration range of the concentrated sulfuric acid of the step S1 is 70-80%；The concentration of ethyl alcohol is 65-75%.
Preferably, evaporating temperature when ethanol evaporation operates in the step S2 is 75-80 DEG C.
Preferably, the total amount of ammonium metavanadate and ammonium tungstate is to adulterate the aerosil of micarex in the step S3
2-3 times of amount, nanoscale TiO2The amount of particle is the half of the total amount of ammonium metavanadate and ammonium tungstate or more.
Preferably, the revolving speed stirred in the step S4 is 180-300r/min.
Preferably, in the step S5 the dry thermostatic drying chamber of catalyst using electric heating constant-temperature blowing drying box,
Temperature regulating range: 0-300 DEG C.
Preferably, the screening strainer used in the step S6 is stainless steel filtering net structure.
Compared with prior art, the beneficial effects of the present invention are: the V that the strict control of the present invention mica supports2O5-WO3/
TiO2The preparation method of catalyst, the V supported by strict control mica2O5-WO3/TiO2The preparation method parameter of catalyst, cloud
Matrix face carries out hydrophobically modified with silane coupling agent, and surface hydrophobic enhancing, catalyst stability is higher, is used for the denitration of SCR method
Experiment, catalyst activity is higher, and catalyst can handle after be recycled, by TiO2/V2O5/WO3Mixture, which supports, to be mixed
On the aerosil of miscellaneous micarex, supported catalyst is made, which can be used for SCR method denitration experiment, have
The feature that large specific surface area, stability are strong, activity is high.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, not
For limiting the present invention.
Embodiment 1
A kind of V that mica supports2O5-WO3/TiO2The preparation method of catalyst, comprising the following steps:
S1: micarex is crushed, is sieved by micarex pre-treatment, after impregnating half an hour with the concentrated sulfuric acid, with second alcohol and water
Alternately wash；
S2: the aerosil preparation of micarex is adulterated, TEOS and silane coupled is added in processed micarex
In the ethanol solution of agent phenyl triethoxysilane, HCl is added and is hydrolyzed 3 hours, then it is small to carry out condensation 24 by addition NAOH
When, ethanol evaporation obtains the aerosil of doping micarex；
S3:TiO2/V2O5/WO3Precursor solution preparation, takes a certain amount of ammonium metavanadate and ammonium tungstate, after being dissolved in water,
Acquired solution is slowly stirred to no solid and floccule presence at 60 DEG C, then adds nanoscale TiO2Particle, at 60 DEG C
Under be sufficiently stirred, stand 5h at room temperature；
S4:TiO2/V2O5/WO3Support, in Xiang Shangshu solution addition be prepared doping micarex silica
Aeroge is sufficiently stirred under conditions of 60 DEG C, stands 6h at room temperature；
S5: catalyst is dry, and above-mentioned sample is evaporated in 75 DEG C of water-baths, dries 10h in 100 DEG C of thermostatic drying chambers；
S6: the sample of step S5 is calcined 5h in 450 DEG C of Muffle furnaces, obtains V by catalyst roasting2O5-/WO3/TiO2/
SiO2Catalyst is finally sieved into the particle of 50 mesh by catalyst.
Mica stone is crushed using TF-320 mica vertical fluted disc flour mill in the step S1, and discharging-material size is
10mm, the sieve diameter of sieving are 10mm, and the concentration range of the concentrated sulfuric acid of the step S1 is 70%；The concentration of ethyl alcohol is
Evaporating temperature when ethanol evaporation operates in 65%, the step S2 is 75 DEG C, ammonium metavanadate and ammonium tungstate in the step S3
Total amount be adulterate micarex aerosil 2 times of amount, nanoscale TiO2The amount of particle is ammonium metavanadate and tungsten
More than the half of the total amount of sour ammonium, the revolving speed stirred in the step S4 is 180r/min, catalyst in the step S5
Dry thermostatic drying chamber is using electric heating constant-temperature blowing drying box, temperature regulating range: 0-300 DEG C, in the step S6
The screening strainer used is stainless steel filtering net structure.
Embodiment 2
A kind of V that mica supports2O5-WO3/TiO2The preparation method of catalyst, comprising the following steps:
S1: micarex is crushed, is sieved by micarex pre-treatment, after impregnating half an hour with the concentrated sulfuric acid, with second alcohol and water
Alternately wash；
S2: the aerosil preparation of micarex is adulterated, TEOS and silane coupled is added in processed micarex
In the ethanol solution of agent phenyl triethoxysilane, HCl is added and is hydrolyzed 3 hours, then it is small to carry out condensation 24 by addition NAOH
When, ethanol evaporation obtains the aerosil of doping micarex；
S3:TiO2/V2O5/WO3Precursor solution preparation, takes a certain amount of ammonium metavanadate and ammonium tungstate, after being dissolved in water,
Acquired solution is slowly stirred to no solid and floccule presence at 65 DEG C, then adds nanoscale TiO2Particle, at 65 DEG C
Under be sufficiently stirred, stand 5h at room temperature；
S4:TiO2/V2O5/WO3Support, in Xiang Shangshu solution addition be prepared doping micarex silica
Aeroge is sufficiently stirred under conditions of 65 DEG C, stands 6h at room temperature；
S5: catalyst is dry, and above-mentioned sample is evaporated in 75 DEG C of water-baths, dries 10h in 100 DEG C of thermostatic drying chambers；
S6: the sample of step S5 is calcined 5h in 450 DEG C of Muffle furnaces, obtains V by catalyst roasting2O5-/WO3/TiO2/
SiO2Catalyst is finally sieved into the particle of 50 mesh by catalyst.
Mica stone is crushed using TF-320 mica vertical fluted disc flour mill in the step S1, and discharging-material size is
10mm, the sieve diameter of sieving are 10mm, and the concentration range of the concentrated sulfuric acid of the step S1 is 75%；The concentration of ethyl alcohol is
Evaporating temperature when ethanol evaporation operates in 70%, the step S2 is 77.5 DEG C, ammonium metavanadate and wolframic acid in the step S3
The total amount of ammonium is to adulterate 2.5 times of amount of the aerosil of micarex, nanoscale TiO2The amount of particle is ammonium metavanadate
More than the half of the total amount of ammonium tungstate, the revolving speed stirred in the step S4 is 190r/min, is urged in the step S5
The dry thermostatic drying chamber of agent is using electric heating constant-temperature blowing drying box, temperature regulating range: 0-300 DEG C, the step
The screening strainer used in S6 is stainless steel filtering net structure.
Embodiment 3
A kind of V that mica supports2O5-WO3/TiO2The preparation method of catalyst, comprising the following steps:
S1: micarex is crushed, is sieved by micarex pre-treatment, after impregnating half an hour with the concentrated sulfuric acid, with second alcohol and water
Alternately wash；
S2: the aerosil preparation of micarex is adulterated, TEOS and silane coupled is added in processed micarex
In the ethanol solution of agent phenyl triethoxysilane, HCl is added and is hydrolyzed 3 hours, then it is small to carry out condensation 24 by addition NAOH
When, ethanol evaporation obtains the aerosil of doping micarex；
S3:TiO2/V2O5/WO3Precursor solution preparation, takes a certain amount of ammonium metavanadate and ammonium tungstate, after being dissolved in water,
Acquired solution is slowly stirred to no solid and floccule presence at 70 DEG C, then adds nanoscale TiO2Particle, at 70 DEG C
Under be sufficiently stirred, stand 5h at room temperature；
S4:TiO2/V2O5/WO3Support, in Xiang Shangshu solution addition be prepared doping micarex silica
Aeroge is sufficiently stirred under conditions of 70 DEG C, stands 6h at room temperature；
S5: catalyst is dry, and above-mentioned sample is evaporated in 75 DEG C of water-baths, dries 10h in 100 DEG C of thermostatic drying chambers；
S6: the sample of step S5 is calcined 5h in 450 DEG C of Muffle furnaces, obtains V by catalyst roasting2O5-/WO3/TiO2/
SiO2Catalyst is finally sieved into the particle of 50 mesh by catalyst.
Mica stone is crushed using TF-320 mica vertical fluted disc flour mill in the step S1, and discharging-material size is
10mm, the sieve diameter of sieving are 10mm, and the concentration range of the concentrated sulfuric acid of the step S1 is 80%；The concentration of ethyl alcohol is
Evaporating temperature when ethanol evaporation operates in 75%, the step S2 is 80 DEG C, ammonium metavanadate and ammonium tungstate in the step S3
Total amount be adulterate micarex aerosil 3 times of amount, nanoscale TiO2The amount of particle is ammonium metavanadate and tungsten
More than the half of the total amount of sour ammonium, the revolving speed stirred in the step S4 is 300r/min, catalyst in the step S5
Dry thermostatic drying chamber is using electric heating constant-temperature blowing drying box, temperature regulating range: 0-300 DEG C, in the step S6
The screening strainer used is stainless steel filtering net structure.
A kind of V that mica supports of the present invention2O5-WO3/TiO2In the preparation method of catalyst, TiO2/V2O5/WO3Predecessor
Solution preparation and TiO2/V2O5/WO3The technological parameter data such as the following table 1 supported:
| Parameter | Temperature (DEG C) | Time (h) |
| TiO2/V2O5/WO3Precursor solution preparation | 60-70℃ | 5 |
| TiO2/V2O5/WO3Support | 60-70℃ | 6 |
In summary: the V that the strict control of the present invention mica supports2O5-WO3/TiO2The preparation method of catalyst, passes through
The V that strict control mica supports2O5-WO3/TiO2The preparation method parameter of catalyst, mica surface are dredged with silane coupling agent
Water is modified, and surface hydrophobic enhancing, catalyst stability is higher, tests for the denitration of SCR method, and catalyst activity is higher, and
Catalyst is recycled after can handle, by TiO2/V2O5/WO3Mixture supports the aerosil of doping micarex
On, supported catalyst is made, which can be used for SCR method denitration experiment, have large specific surface area, stability strong, active
High feature.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (8)
1. a kind of V that mica supports2O5-WO3/TiO2The preparation method of catalyst, it is characterised in that: the following steps are included:
S1: micarex is crushed, is sieved by micarex pre-treatment, after impregnating half an hour with the concentrated sulfuric acid, is replaced with second alcohol and water
Washing；
S2: the aerosil preparation of micarex is adulterated, TEOS and silane coupling agent benzene is added in processed micarex
In the ethanol solution of ethyl triethoxy silicane alkane, HCl is added and is hydrolyzed 3 hours, NAOH is then added and carries out condensation 24 hours, steams
Hair ethyl alcohol obtains the aerosil of doping micarex；
S3:TiO2/V2O5/WO3Precursor solution preparation, takes a certain amount of ammonium metavanadate and ammonium tungstate, after being dissolved in water, by institute
It obtains solution to be slowly stirred at 60-70 DEG C to no solid and floccule presence, then adds nanoscale TiO2Particle, in 60-70
It is sufficiently stirred at DEG C, stands 5h at room temperature；
S4:TiO2/V2O5/WO3Support, in Xiang Shangshu solution addition be prepared doping micarex silica airsetting
Glue is sufficiently stirred under conditions of 60-70 DEG C, stands 6h at room temperature；
S5: catalyst is dry, and above-mentioned sample is evaporated in 75 DEG C of water-baths, dries 10h in 100 DEG C of thermostatic drying chambers；
S6: the sample of step S5 is calcined 5h in 450 DEG C of Muffle furnaces, obtains V by catalyst roasting2O5-/WO3/TiO2/SiO2It urges
Catalyst is finally sieved into the particle of 50 mesh by agent.
2. the V that a kind of mica according to claim 1 supports2O5-WO3/TiO2The preparation method of catalyst, feature exist
In: mica stone is crushed using TF-320 mica vertical fluted disc flour mill, discharging-material size 10mm, sieving in the step S1
Sieve diameter be 10mm.
3. the V that a kind of mica according to claim 1 supports2O5-WO3/TiO2The preparation method of catalyst, feature exist
In: the concentration range of the concentrated sulfuric acid of the step S1 is 70-80%；The concentration of ethyl alcohol is 65-75%.
4. the V that a kind of mica according to claim 1 supports2O5-WO3/TiO2The preparation method of catalyst, feature exist
In: evaporating temperature when ethanol evaporation operates in the step S2 is 75-80 DEG C.
5. the V that a kind of mica according to claim 1 supports2O5-WO3/TiO2The preparation method of catalyst, feature exist
In: the total amount of ammonium metavanadate and ammonium tungstate is to adulterate 2-3 times of amount of the aerosil of micarex in the step S3,
Nanoscale TiO2The amount of particle is the half of the total amount of ammonium metavanadate and ammonium tungstate or more.
6. the V that a kind of mica according to claim 1 supports2O5-WO3/TiO2The preparation method of catalyst, feature exist
In: the revolving speed stirred in the step S4 is 180-300r/min.
7. the V that a kind of mica according to claim 1 supports2O5-WO3/TiO2The preparation method of catalyst, feature exist
In: the dry thermostatic drying chamber of catalyst is using electric heating constant-temperature blowing drying box in the step S5, temperature regulating range:
0-300℃。
8. the V that a kind of mica according to claim 1 supports2O5-WO3/TiO2The preparation method of catalyst, feature exist
In: the screening strainer used in the step S6 is stainless steel filtering net structure.
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| CN114592246A (en) * | 2021-12-27 | 2022-06-07 | 浙江恒逸高新材料有限公司 | Preparation process of three-dimensional crimped hollow polyester staple fiber |
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| CN110404553A (en) * | 2019-08-05 | 2019-11-05 | 无锡威孚环保催化剂有限公司 | Low temperature SCR denitration catalyst and preparation method thereof with water resistant resistance to SO_2 |
| CN110586080A (en) * | 2019-10-12 | 2019-12-20 | 安徽工业大学 | Preparation method of hydrophobic biomass charcoal low-temperature SCR catalyst |
| CN111013566A (en) * | 2019-12-31 | 2020-04-17 | 弘大科技（北京）股份公司 | Novel rare earth modified aerogel denitration flue gas catalyst and preparation method thereof |
| CN111013566B (en) * | 2019-12-31 | 2023-01-06 | 弘大科技（北京）股份公司 | Novel rare earth modified aerogel denitration flue gas catalyst and preparation method thereof |
| CN113351172A (en) * | 2021-07-22 | 2021-09-07 | 安徽元琛环保科技股份有限公司 | Preparation method of denitration synergistic CO2 adsorption material and prepared adsorption material |
| CN113351172B (en) * | 2021-07-22 | 2023-01-06 | 安徽元琛环保科技股份有限公司 | Preparation method of denitration and CO2 adsorption material and prepared adsorption material |
| CN114592246A (en) * | 2021-12-27 | 2022-06-07 | 浙江恒逸高新材料有限公司 | Preparation process of three-dimensional crimped hollow polyester staple fiber |
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