阅读说明：本技术 一种玻璃纤维废丝的回收方法 (Recovery method of glass fiber waste silk ) 是由 谭海军 陈磊 刘东升 韩晓锋 孙文平 黄晓林 于 2019-12-12 设计创作，主要内容包括：本发明涉及纤维生产技术领域,尤其涉及一种玻璃纤维废丝的回收方法。所述玻璃纤维废丝的回收方法包括以下步骤：A)高压水洗玻璃纤维废丝,高压水洗的水压为0.2～0.4MPa；B)将所述高压水洗后的玻璃纤维废丝进行湿法研磨,得到玻璃粉；C)将所述玻璃粉进行干燥,得到干燥的玻璃粉；D)将所述干燥的玻璃粉和有机溶剂在80～100℃、0.1～0.3MPa下搅拌混合；E)将所述搅拌混合后的玻璃粉进行干燥,得到处理完成的玻璃粉。采用本发明的玻璃纤维废丝的回收方法得到的玻璃粉具有极佳的性能,玻璃粉的COD值较低,玻璃成分中亚铁含量几乎无变化,池窑的氧化还原处于良好的控制,运转率处于较高的水平。(The invention relates to the technical field of fiber production, in particular to a method for recovering waste glass fiber. The recovery method of the glass fiber waste silk comprises the following steps: A) washing the glass fiber waste silk with high pressure water, wherein the water pressure of the high pressure water washing is 0.2-0.4 MPa; B) carrying out wet grinding on the high-pressure water washed glass fiber waste silk to obtain glass powder; C) drying the glass powder to obtain dried glass powder; D) stirring and mixing the dried glass powder and the organic solvent at 80-100 ℃ and 0.1-0.3 MPa; E) and drying the stirred and mixed glass powder to obtain the treated glass powder. The glass powder obtained by the recovery method of the waste glass fiber has excellent performance, the COD value of the glass powder is low, the content of the ferrous iron in the glass components is almost unchanged, the oxidation reduction of the tank furnace is well controlled, and the operation rate is at a high level.)

1. A method for recovering glass fiber waste silk comprises the following steps:

A) washing the glass fiber waste silk with high pressure water, wherein the water pressure of the high pressure water washing is 0.2-0.4 MPa;

B) carrying out wet grinding on the high-pressure water washed glass fiber waste silk to obtain glass powder;

C) drying the glass powder to obtain dried glass powder;

D) stirring and mixing the dried glass powder and the organic solvent at 80-100 ℃ and 0.1-0.3 MPa;

E) and drying the stirred and mixed glass powder to obtain the treated glass powder.

2. The recycling method according to claim 1, wherein the time of the high pressure water washing is 5 to 10 min.

3. The recovery method according to claim 1, wherein in step B), the particle size of the glass frit is not more than 60 mesh, and the residual content of 200 mesh is not more than 0.8 wt%.

4. The recycling method according to claim 1, wherein the step C), before the drying, further comprises: carrying out centrifugal dehydration on the glass powder;

the water content of the glass powder after centrifugal dehydration is 5-10%.

5. The recycling method according to claim 1, wherein in the step C), the drying temperature is 150 to 200 ℃, and the drying time is 30 to 45 min.

6. The recycling method according to claim 1, wherein in the step C), the water content of the dried glass frit is 0 to 3%.

7. The recycling method according to claim 1, wherein in the step D), the organic solvent comprises one or more of methanol, ethanol, ethyl acetate, butyl acetate, isopropanol and acetone.

8. The recycling method according to claim 1, wherein in the step D), the mass ratio of the dried glass frit to the organic solvent is 1: 10 to 20.

9. The recycling method according to claim 1, wherein in the step D), the stirring and mixing time is 30-60 min.

10. The recycling method according to claim 1, wherein in the step E), the drying temperature is 80-90 ℃, and the drying time is 15-35 min.

Technical Field

The invention relates to the technical field of fiber production, in particular to a method for recovering waste glass fiber.

Background

The glass fiber is an inorganic non-metallic material with excellent performance, and has a wide variety of types, strong heat resistance, good corrosion resistance and high mechanical strength. The wire is made from various mineral raw materials such as pyrophyllite, quartz sand, limestone, dolomite, borocalcite, boromagnesite, fluorite, sepiolite, kaoline spodumene and the like through the processes of high-temperature melting, wire drawing/impregnating compound coating, drying, degradation and the like, and the diameter of a monofilament is between several microns and twenty-several microns according to different products. Glass fibers are commonly used as reinforcing materials in composite materials, electrical and thermal insulation materials, circuit substrates, and other various fields of the national economy.

In the production and manufacturing process of glass fiber, a lot of waste glass fiber yarns are generated in the processes of drawing, annealing and the like, cannot be decomposed through biodegradation and combustion, can only be treated through a conventional landfill mode, and has high recovery cost. In order to save cost, the conventional solution is to process the waste glass fiber into glass powder in a certain way, and the glass powder is reused as a raw material and added into a tank furnace for blending.

In the methods for recycling waste glass fiber proposed in patent CN 106583420 a and patent CN 108975680 a, the organic impregnating compound coated on the waste glass fiber cannot be removed, and the treated organic impregnating compound is added into a tank furnace as a raw material, although the production cost can be reduced, because of the type and content of different impregnating compounds on the waste glass fiber, the content of COD (chemical oxygen demand) in the waste glass powder (formed by grinding waste glass fiber) is high, the stability is very poor, the control of S/C ratio in the whole formula is affected, and the adjustment of redox atmosphere in the tank furnace is not facilitated, the fluctuation of ferrous iron in the glass liquid is large, the thermal conductivity of the glass liquid is unstable, and the wire drawing operation is deteriorated, and the full cylinder rate of wire drawing is affected.

Disclosure of Invention

In view of the above, the technical problem to be solved by the present invention is to provide a method for recovering waste glass fiber, in which the glass powder obtained by the method for recovering waste glass fiber has excellent performance, the COD value of the glass powder is low, the content of ferrous iron in the glass component is almost unchanged, the redox of the tank furnace is well controlled, and the operation rate is at a high level.

The invention provides a method for recovering waste glass fiber, which comprises the following steps:

A) washing the glass fiber waste silk with high pressure water, wherein the water pressure of the high pressure water washing is 0.2-0.4 MPa;

B) carrying out wet grinding on the high-pressure water washed glass fiber waste silk to obtain glass powder;

C) drying the glass powder to obtain dried glass powder;

D) stirring and mixing the dried glass powder and the organic solvent at 80-100 ℃ and 0.1-0.3 MPa;

E) and drying the stirred and mixed glass powder to obtain the treated glass powder.

Preferably, the time of the high-pressure water washing is 5-10 min.

Preferably, in the step B), the particle size of the glass powder is less than or equal to 60 meshes, and the residual content of 200-mesh sieve is less than or equal to 0.8 wt%.

Preferably, step C) further comprises, before the drying: carrying out centrifugal dehydration on the glass powder;

the water content of the glass powder after centrifugal dehydration is 5-10%.

Preferably, in the step C), the drying temperature is 150-200 ℃, and the drying time is 30-45 min.

Preferably, in the step C), the water content of the dried glass powder is 0-3%.

Preferably, in step D), the organic solvent includes one or more of methanol, ethanol, ethyl acetate, butyl acetate, isopropanol and acetone.

Preferably, in the step D), the mass ratio of the dried glass powder to the organic solvent is 1: 10 to 20.

Preferably, in the step D), the stirring and mixing time is 30-60 min.

Preferably, in the step E), the drying temperature is 80-90 ℃, and the drying time is 15-35 min.

The invention provides a method for recovering waste glass fiber, which comprises the following steps: A) washing the glass fiber waste silk with high pressure water, wherein the water pressure of the high pressure water washing is 0.2-0.4 MPa; B) carrying out wet grinding on the high-pressure water washed glass fiber waste silk to obtain glass powder; C) drying the glass powder to obtain dried glass powder; D) stirring and mixing the dried glass powder and the organic solvent at 80-100 ℃ and 0.1-0.3 MPa; E) and drying the stirred and mixed glass powder to obtain the treated glass powder. The glass powder obtained by the recovery method of the waste glass fiber has excellent performance, the COD value of the glass powder is low, the content of the ferrous iron in the glass components is almost unchanged, the oxidation reduction of the tank furnace is well controlled, and the operation rate is at a high level.

Experimental results show that the glass fiber yarn powder obtained by the recovery method provided by the invention has excellent performance, the chemical oxygen demand COD of the glass fiber yarn powder is less than 70ppm, and the glass fiber yarn powder is basically equal to high-calcination-degree calcination-type mineral raw materials, such as light calcined powder and calcined dolomite; the raw materials are added into a tank furnace, the ferrous content in the glass components is basically unchanged, and the oxidation reduction of the tank furnace is well controlled; the operation running rate is higher than 96%, and the operation running rate is at a higher level.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention provides a method for recovering waste glass fiber, which comprises the following steps:

A) washing the glass fiber waste silk with high pressure water, wherein the water pressure of the high pressure water washing is 0.2-0.4 MPa;

B) carrying out wet grinding on the high-pressure water washed glass fiber waste silk to obtain glass powder;

C) drying the glass powder to obtain dried glass powder;

D) stirring and mixing the dried glass powder and the organic solvent at 80-100 ℃ and 0.1-0.3 MPa;

E) and drying the stirred and mixed glass powder to obtain the treated glass powder.

In the recovery method provided by the invention, the glass fiber waste silk is washed by high-pressure water. The source of the waste glass fiber is not particularly limited, and in some embodiments, the waste glass fiber is selected from waste glass fiber generated during a drawing operation or a degradation process.

In the invention, the water pressure of the high-pressure water washing is 0.2-0.4 MPa. In certain embodiments of the invention, the water pressure of the high pressure water wash is 0.3MPa, 0.2MPa, or 0.4 MPa. In some embodiments of the present invention, the high-pressure water washing time is 5-10 min. In certain embodiments, the time for the high pressure water wash is 8min, 6min, or 10 min. In certain embodiments of the invention, the high pressure water wash is performed by repeatedly tumbling the fiberglass waste. The high-pressure water washing can remove conventional inorganic impurities, metal impurities and stains on the waste glass fibers.

And after the high-pressure water washing is finished, carrying out wet grinding on the glass fiber waste silk subjected to the high-pressure water washing to obtain glass powder.

In the embodiment of the invention, after the high-pressure water washing is finished, the wet grinding is directly carried out without any treatment.

In certain embodiments of the present invention, the wet milling is selected from one or more of ball milling, vertical milling, and laser milling. In certain embodiments of the present invention, the glass frit has a particle size of 60 mesh or less and a 200 mesh residue of 0.8 wt% or less.

And after the glass powder is obtained, drying the glass powder to obtain the dried glass powder.

In certain embodiments of the present invention, the glass frit further comprises, before drying: and carrying out centrifugal dehydration on the glass powder. In certain embodiments of the present invention, the water content of the centrifugally dewatered glass frits is 5% to 10%. In certain embodiments, the water content of the centrifugally dewatered glass frits is 8%.

In certain embodiments of the present invention, the method for drying the glass frit is selected from one or more of hot air circulation drying, microwave drying and infrared drying. In some embodiments of the invention, the drying temperature of the glass powder is 150-200 ℃, and the drying time is 30-45 min. In certain embodiments, the glass frit is dried at a temperature of 180 ℃, 160 ℃, or 200 ℃ for a time of 40min, 30min, or 45 min. In some embodiments of the present invention, the water content of the dried glass frit is 0 to 3%. In certain embodiments, the water content of the dried glass frit is 1.7%, 2.3%, or 1.8%.

And after obtaining the dried glass powder, stirring and mixing the dried glass powder and the organic solvent at 80-100 ℃ and 0.1-0.3 MPa.

In certain embodiments of the present invention, the organic solvent comprises one or more of methanol, ethanol, ethyl acetate, butyl acetate, isopropanol, and acetone.

In certain embodiments of the present invention, the mass ratio of the dried glass frit to the organic solvent is 1: 10 to 20. In certain embodiments, the mass ratio of the dried glass frit to the organic solvent is 1: 15. 1: 10 or 1: 20.

in certain embodiments of the invention, the temperature of the agitation mixing is 90 ℃, 80 ℃, or 95 ℃. In certain embodiments of the invention, the pressure of the agitation mixing is 0.2MPa, 0.1MPa, or 0.3 MPa. In some embodiments of the present invention, the rotation speed of the stirring and mixing is 100 to 150 rpm. In certain embodiments of the invention, the rotational speed of the agitation mixing is 125rpm, 100rpm, or 150 rpm. In some embodiments of the present invention, the time for stirring and mixing is 30-60 min. In certain embodiments, the time of the stirring and mixing is 45min, 30min, or 60 min. In certain embodiments of the invention, the agitated mixing is performed in an organic reaction vessel. The dried glass powder and the organic solvent are stirred and mixed, so that the impregnating compound on the glass powder is dissolved in an organic solvent system, and the organic desorption of the glass powder is realized.

And after the stirring and mixing are finished, drying the glass powder after stirring and mixing to obtain the glass powder after treatment.

In certain embodiments of the present invention, the drying is selected from one of heated air circulation drying, microwave drying, and infrared drying. In some embodiments of the invention, the drying temperature is 80-90 ℃, and the drying time is 15-35 min. In certain embodiments, the temperature of the drying is 85 ℃, 80 ℃ or 90 ℃, and the time of the drying is 25min, 15min or 35 min.

The source of the above-mentioned raw materials is not particularly limited in the present invention, and may be generally commercially available.

In the examples of the present invention, the chemical oxygen demand COD test (evaluation of reducing substance content) of the treated glass frits was as follows:

under the strong acid condition, reducing substances (organic and inorganic) in the glass powder react with a certain amount of potassium dichromate standard solution, the reaction is carried out by heating, boiling and refluxing, excessive potassium dichromate takes resorufin as an indicator, ammonium ferrous sulfate standard solution is used for back dripping, and the amount of the reducing substances in the sample is calculated according to the consumption of the ammonium ferrous sulfate. Specifically, the method comprises the following steps:

accurately weighing 2.000g of sample in a 500mL triangular flask, and adding 0.100g of HgSO₄Plus 40mLH₂SO₄The solution (sulfuric acid mixed with equal volume of deionized water) was accurately pipetted 10mLK₂Cr₂O₇Adding 30ml of LAg into the standard solution₂SO₄-H₂SO₄Shaking, installing a condenser tube, boiling on an electric furnace, keeping slightly boiling for 2h, washing the inner wall and the plug of the tube with distilled water after cooling, cooling to room temperature, adding water to make the volume of the tube 200-250 mL, adding 4 drops of ferron indicator, and using (NH)₄)₂Fe(SO₄)₂The standard solution was titrated from yellow through blue-green to reddish-brown to the end point.

The chemical oxygen demand COD of the sample is represented by C and calculated according to the formula (1):

C＝750.8(10-aV)/m (1)；

in formula (1):

c-chemical oxygen demand, mg/kg (ppm);

a-10/titration of blank consumption (NH)₄)₂Fe(SO₄)₂Amount of (mL);

v is the volume (mL) of the ammonium ferrous sulfate standard titration solution consumed in the sample measurement;

m-mass (g) of the sample.

Note 1: potassium dichromate standard solution K₂Cr₂O₇0.2500mol/L；

Note 2: (NH)₄)₂Fe(SO₄)₂0.2mol/L。

In the examples of the invention, the ferrous oxide test in glass (evaluation of the redox atmosphere of the tank furnace) is as follows:

titrating by using a potassium dichromate standard solution, wherein the reaction formula is as follows:

6Fe²⁺+Cr₂O₇ ^2-+14H⁺＝6Fe³⁺+2Cr³⁺+7H₂O

grinding a glass sample to about 200 meshes by using an agate mortar; 0.3000 +/-0.0030 g of glass powder sample is weighed, and 15mL of H is added₂SO₄Adding 10mL of concentrated hydrofluoric acid into the solution (sulfuric acid is mixed with deionized water with the same volume), uniformly stirring, standing for 10min, adding 2 drops of 0.1% sodium diphenylaminesulfonate indicator, titrating by using 0.005mol/L potassium dichromate solution, and obtaining the end point when the solution is changed from colorless to mauve. The FeO content is calculated according to the formula (2).

FeO％＝MV×0.07185×100/G (2)；

In formula (2):

m is the concentration (mol/L) of the potassium dichromate standard solution;

v-volume of potassium dichromate solution consumed for titration (mL);

g, weighing the mass (G) of the glass powder to be measured.

The invention provides a method for recovering waste glass fiber, which comprises the following steps: A) washing the glass fiber waste silk with high pressure water, wherein the water pressure of the high pressure water washing is 0.2-0.4 MPa; B) carrying out wet grinding on the high-pressure water washed glass fiber waste silk to obtain glass powder; C) drying the glass powder to obtain dried glass powder; D) stirring and mixing the dried glass powder and the organic solvent at 80-100 ℃ and 0.1-0.3 MPa; E) and drying the stirred and mixed glass powder to obtain the treated glass powder. The glass powder obtained by the recovery method of the waste glass fiber has excellent performance, the COD value of the glass powder is lower, the content of the ferrous iron in the glass components is almost unchanged, the oxidation reduction of the tank furnace is well controlled, and the operation rate is at a higher level

When the glass powder treated by the method is used as a raw material, the S/C ratio of the whole raw material is not influenced, the balance of the redox atmosphere of the tank furnace can be well maintained, and the stability of wire drawing operation is ensured.

The glass fiber yarn contains less organic impregnating compound, so that the organic solvent for treating the glass fiber yarn at high temperature and high pressure can be repeatedly used, and the treatment cost is greatly saved.

In addition, the treatment mode of high temperature and high pressure ensures that the organic impregnating compound in the glass fiber yarn powder can be dissolved in an organic solvent system in a very short time, thereby greatly improving the treatment efficiency of the glass powder.

Experimental results show that the glass fiber yarn powder obtained by the recovery method provided by the invention has excellent performance, the chemical oxygen demand COD of the glass fiber yarn powder is less than 70ppm, and the glass fiber yarn powder is basically equal to high-calcination-degree calcination-type mineral raw materials, such as light calcined powder and calcined dolomite; the raw materials are added into a tank furnace, the ferrous content in the glass components is basically unchanged, and the oxidation reduction of the tank furnace is well controlled; the operation running rate is higher than 96%, and the operation running rate is at a higher level.

In order to further illustrate the present invention, the following will describe the method for recycling waste glass fiber in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.

The starting materials used in the following examples are all generally commercially available.