阅读说明：本技术 一种杨木化学机械法制浆的木片预处理工艺及其应用 (Wood chip pretreatment process for chemi-mechanical pulping of poplar and application thereof ) 是由 吉兴香 田中建 郭玉倩 杨桂花 陈嘉川 张革仓 陈洪国 胡长青 于 2020-10-22 设计创作，主要内容包括：本发明提供一种杨木化学机械法制浆的木片预处理工艺及其应用,其特征在于：采用耐热木聚糖酶预处理,酶用量为5-30 U/g,酶处理温度为60-90℃。液比1:3.5-4.5,保温30-90min。用于杨木化学机械法制浆,将预处理后的杨木片进行碱浸渍,再将碱浸渍后的杨木片进行过氧化氢漂白；经磨浆,磨浆后的纤维质均长度为1.10mm以上,卷曲指数为5.25-5.30%。采用本发明预处理方法制备的杨木纸浆的撕裂指数为3.72-3.75mN·m~2/g,抗张强度为3.75-3.78kN/m,白度为70.28-70.32%ISO。(The invention provides a wood chip pretreatment process for poplar chemi-mechanical pulping and application thereof, which is characterized in that: heat-resistant xylanase is adopted for pretreatment, the enzyme dosage is 5-30U/g, and the enzyme treatment temperature is 60-90 ℃. The liquid ratio is 1:3.5-4.5, and the temperature is kept for 30-90 min. The method is used for pulping poplar by a chemico-mechanical method, and comprises the steps of performing alkali impregnation on pretreated poplar slices, and performing hydrogen peroxide bleaching on the poplar slices subjected to the alkali impregnation; grinding to obtain pulp with average fiber length of 1.10mm or moreAbove, the curl index is 5.25-5.30%. The tearing index of the poplar pulp prepared by adopting the pretreatment method is 3.72-3.75 mN.m 2 (iv) g, a tensile strength of 3.75-3.78kN/m, a whiteness of 70.28-70.32% ISO.)

1. A wood chip pretreatment process for poplar chemi-mechanical pulping is characterized by comprising the following steps: heat-resistant xylanase is adopted for pretreatment, the enzyme dosage is 5-30U/g, and the enzyme treatment temperature is 60-90 ℃.

2. The wood chip pretreatment process for poplar chemi-mechanical pulping according to claim 1, wherein the wood chip pretreatment process comprises the following steps: the heat-resistant xylanase is pretreated with a liquid ratio of 1:3.5-4.5, and the temperature is kept for 30-90 min.

3. The wood chip pretreatment process for poplar chemi-mechanical pulping according to claim 1, wherein the wood chip pretreatment process comprises the following steps: the heat-resistant xylanase is pretreated, wherein the enzyme treatment temperature is 60-90 ℃, and the enzyme dosage is 5-30U/g.

4. The use of the wood chip pretreatment process for poplar chemi-mechanical pulping according to claim 1, wherein the wood chip pretreatment process comprises the following steps: the method is used for pulping poplar by a chemico-mechanical method, and comprises the steps of performing alkali impregnation on pretreated poplar slices, and performing hydrogen peroxide bleaching on the poplar slices subjected to the alkali impregnation; grinding to obtain pulp with average fiber length of 1.11 mm and crimp index of 5.29%.

5. The use of the wood chip pretreatment process for poplar chemi-mechanical pulping according to claim 4, wherein the wood chip pretreatment process comprises the following steps: the alkali impregnation: the alkali liquor is adopted, the content of sodium hydroxide is 5-7%, the dipping temperature is 85-95 ℃, and the heat preservation is carried out for 30-90 min.

6. The use of the wood chip pretreatment process for poplar chemi-mechanical pulping according to claim 4, wherein the wood chip pretreatment process comprises the following steps: the hydrogen peroxide bleaching: the adopted bleaching solution comprises the following components in percentage by mass: hydrogen peroxide 5.8-6.2% and Na₂SiO₃2.8-3.2%、 MgSO₄0.4-0.6 percent of EDTA, 0.48-0.52 percent of EDTA, bleaching temperature of 85-95 ℃ and heat preservation time of 30-90 min.

7. The use of the wood chip pretreatment process for poplar chemi-mechanical pulping according to claim 4, wherein the wood chip pretreatment process comprises the following steps: the grinding process comprises the following steps: the first section is a coarse grinding area, the disc grinding gap is 0.48-0.52 mm, wood chips are extruded and defibered into fibers, and the needed pulping energy consumption is large; the second section is a refining zone, and the disc grinding gap is 0.15-22 mm.

8. The use of the wood chip pretreatment process for poplar chemi-mechanical pulping according to claim 4, wherein the wood chip pretreatment process comprises the following steps: performing latent pulp screening on the fibers after the pulp grinding, and making paper pulp to obtain paper pulp; the tear index of the pulp is 3.72-3.75 mN.m²(iv) g, a tensile strength of 3.75-3.78kN/m, a whiteness of 70.28-70.32% ISO.

Technical Field

The invention relates to a wood chip pretreatment process for poplar chemi-mechanical pulping and application thereof, belonging to the technical field of papermaking.

Background

In the pulping process of the chemi-mechanical method, the section directly determining the physical strength and optical properties of the pulp is the alkali impregnation section. In order to more effectively improve the efficiency of the alkaline impregnation stage, the wood chips are usually pretreated to remove part of hemicellulose and lignin under the premise of protecting carbohydrate as much as possible, and the porosity and the specific surface area of the wood chips are increased to improve the contact area between subsequent alkali liquor and the wood chips. Therefore, the selection of a suitable pretreatment method is critical to the reaction efficiency of the alkaline impregnation stage.

At present, the application of mature pretreatment technologies mainly comprises chemical methods, such as dilute acid treatment, alkali treatment, organic solvent method, ionic liquid and the like, and mainly softens wood chips and destroys the crystalline structure of the wood chips through the swelling effect of chemicals. The physical method is to increase the contact area mainly by destroying the morphological structure of the raw material. The biological method adopts microorganisms to treat poplar wood, breaks a connection barrier between hemicellulose and lignin, and improves the porosity of wood chips.

A wood chip pretreatment process with better wood chip softening effect is explored, and the method has great significance for subsequent chemical mechanical pulping of poplar.

The prior art has the following technical defects: the specific surface area and the porosity of the pretreated wood chips are low, the pretreated wood chips are ground into pulp, the fiber length is short, and the quality of the prepared poplar pulp is poor.

Disclosure of Invention

Aiming at the technical problems, the invention provides a wood chip pretreatment process for poplar chemico-mechanical pulping and application thereof, and achieves the following aims: the specific surface area and the porosity of the pretreated wood chips are improved; the pretreated wood chips are ground into pulp, the fiber length after grinding is improved, the crimping index is improved, and the quality of the prepared poplar pulp is further improved.

The technical scheme is as follows:

a wood chip pretreatment process for poplar chemi-mechanical pulping is characterized by comprising the following steps: heat-resistant xylanase is adopted for pretreatment, the enzyme dosage is 5-30U/g, and the enzyme treatment temperature is 60-90 ℃.

The heat-resistant xylanase is pretreated with a liquid ratio of 1:3.5-4.5, and the temperature is kept for 30-90 min.

The heat-resistant xylanase is pretreated, wherein the enzyme treatment temperature is 60-90 ℃, and the enzyme dosage is 5-30U/g.

The application of the wood chip pretreatment process for the chemi-mechanical pulping of poplar is characterized in that: the method is used for pulping poplar by a chemico-mechanical method, and comprises the steps of performing alkali impregnation on pretreated poplar slices, and performing hydrogen peroxide bleaching on the poplar slices subjected to the alkali impregnation; grinding to obtain pulp with average fiber length of 1.11 mm and crimp index of 5.29%.

The alkali impregnation: the alkali liquor is adopted, the content of sodium hydroxide is 5-7%, the dipping temperature is 85-95 ℃, and the heat preservation is carried out for 30-90 min.

The hydrogen peroxide bleaching: the adopted bleaching solution comprises the following components in percentage by mass: hydrogen peroxide 5.8-6.2% and Na₂SiO₃2.8-3.2%、 MgSO₄0.4-0.6 percent of EDTA, 0.48-0.52 percent of EDTA, bleaching temperature of 88-92 ℃ and heat preservation time of 30-90 min.

The grinding process comprises the following steps: the first section is a coarse grinding area, the disc grinding gap is 0.48-0.52 mm, wood chips are extruded and defibered into fibers, and the needed pulping energy consumption is large; the second section is a refining zone, and the disc grinding gap is 0.15-22 mm.

Performing latent pulp screening on the fibers after the pulp grinding, and making paper pulp to obtain paper pulp; the tear index of the pulp is 3.72-3.75 mN.m²(iv) g, a tensile strength of 3.75-3.78kN/m, a whiteness of 70.28-70.32% ISO.

Has the advantages that:

(1) the specific surface area of the wood chips pretreated by the method reaches 11.20m²More than g, the porosity of the wood chip is more than 19.50 percent;

(2) the wood chips pretreated by the method are ground into pulp, the average length of the fiber after the pulp is ground into pulp is more than 1.10mm, and the curl index is 5.25-5.30%.

(3) The tearing index of the poplar pulp prepared by adopting the pretreatment method is 3.72-3.75 mN.m²(iv) g, a tensile strength of 3.75-3.78kN/m, a whiteness of 70.28-70.32% ISO.

Drawings

FIG. 1 is a graph showing the removal rate of hemicellulose and acid-soluble lignin of wood chips pretreated by hot water at different temperatures;

FIG. 2 is a graph showing the comparative removal rate of cellulose and acid-insoluble lignin from wood chips pretreated with hot water at different temperatures;

FIG. 3 is a graph showing the removal rate of hemicellulose, cellulose, acid-soluble lignin and acid-insoluble lignin from wood chips at different enzyme treatment temperatures;

FIG. 4 is a graph showing the removal rate of hemicellulose, cellulose, acid-soluble lignin and acid-insoluble lignin of a wood chip after different enzyme dosages;

FIG. 5 is a graph comparing the specific surface area and porosity of wood chips pretreated with hot water at different temperatures;

FIG. 6 is a graph showing the removal rate of hemicellulose, cellulose, acid-soluble lignin and acid-insoluble lignin from a wood chip pretreated with heat-resistant xylanase at different enzyme treatment temperatures;

FIG. 7 is a graph comparing the specific surface area and porosity of wood chips pretreated with thermostable xylanase at different enzyme dosages.

Detailed Description

Example 1 Wood chip Pre-treatment Process for Populus Wood pulping by chemical mechanical Process

1. Raw material preparation

Poplar chips (supplied by Shandong Chengning paper group GmbH) were manually screened for acceptable size, air dried and stored for future use.

Equipment: a plant sample crusher (FZ 102, Yongguangming medical instruments, Inc. of Beijing), a mercury intrusion instrument (PoreMaster 60GT, Congta instruments, USA), a Hitachi scanning electron microscope (Regulus 8220, Hitachi high and new technology Co., Ltd.), an ion chromatography 5000+ (ICS-5000 +, Thermo-Fisher, USA), a micro CT (SkyScan 2211, Bruker), a nuclear magnetic resonance spectrometer (Bruker AVANCEIIIHD500, Bruker technologies, Inc.); ultraviolet spectrophotometer (Agilent 8454, Agilent technologies, Inc.); fourier transform infrared spectrometer (Bruker Vertex70, Bruker technologies, Inc.).

2. Hot water pretreatment

Taking 250 g of air-dried qualified wood chips, adding 1.5L of deionized water, and performing high-temperature hot water pretreatment in a high-pressure reaction kettle at the treatment temperature of 80 ℃ for 60 min. After the reaction is finished, filtering and separating, reserving the pretreatment solution, and airing and storing a solid part.

The solid fraction is used for subsequent chemi-mechanical pulping.

Enzyme treatment temperature single factor analysis experiment:

the pretreatment of wood chips was carried out according to the method of example 1, and the following experimental groups were carried out while changing only the treatment temperature of the hot water pretreatment step;

experimental group 1: the treatment temperature is 90 ℃;

experimental group 2: the treatment temperature is 100 ℃;

experimental group 3: the treatment temperature is 110 ℃;

experimental group 4: the treatment temperature is 120 ℃;

experimental group 5: the treatment temperature is 130 ℃;

experimental group 6: the treatment temperature is 140 ℃;

experimental group 7: the treatment temperature is 150 ℃;

experimental group 8: the treatment temperature is 160 ℃;

experimental group 9: the treatment temperature is 170 ℃;

experimental group 10: the treatment temperature was 180 ℃.

Through detection, the wood chip pretreatment is carried out at the treatment temperature of 80-180 ℃ in the example 1 and the experimental groups 1-10, and after the hot water pretreatment at different temperatures, the removal rate of hemicellulose and acid soluble lignin of the wood chips is shown in the attached figure 1; after the pretreatment of hot water at different temperatures, the removal rates of cellulose and acid-insoluble lignin of the wood chips are shown in figure 2; after the pretreatment of hot water at different temperatures, the specific surface area and porosity of the wood chips are shown in figure 5; analyzing the attached figure 1, it is found that the removal rate of hemicellulose and acid soluble lignin gradually increases with the increase of the pretreatment temperature. At 150 ℃, the rate of hemicellulose removal was 21.53%, while at 170 ℃ the rate of hemicellulose removal was 39.86%, which is nearly doubled over the data at 150 ℃. Analysis of FIG. 2 reveals that the removal rates of cellulose and acid-insoluble lignin show an increasing trend with increasing pretreatment temperature. The cellulose removal rate is increased along with the increase of the pretreatment temperature, but the change of the removal rate is not obvious; the removal rate of the acid-insoluble lignin basically shows an ascending trend along with the increase of the temperature, but the change of the removal rate is not obvious. Analysis of figure 5 shows that the specific surface area of the treated wood chips increases with the temperature of the hot water pretreatment. The increase in specific surface area is slow at lower temperature treatment, but is more pronounced at pretreatment temperatures above 130 ℃. The porosity between the wood chips increases and then decreases along with the temperature rise, wherein the maximum porosity between the wood chips is 15.12 percent when the hot water pretreatment temperature is 150 ℃.

When the pretreatment temperature is higher than 150 ℃, the porosity decreases with increasing temperature.

Example 2 Wood chip pretreatment Process for chemi-mechanical pulping of Populus

1. Raw material preparation

Same as in example 1.

2. Heat resistant xylanase pretreatment

Taking 150 g of wood chips for enzyme treatment, keeping the temperature at 60 ℃, keeping the enzyme dosage at 20U/g and the liquor ratio at 1:4 for 60 min. And (4) inactivating the raw material after enzyme treatment for storage.

And preparing for subsequent chemical mechanical pulping.

The enzyme is heat-resistant xylanase which is obtained from Longket company, the enzyme activity is detected by adopting the national standard ((GB/T23874) -2009)), and the detected enzyme activity is 255785U/mL.

Enzyme treatment temperature single factor analysis experiment:

the pretreatment of wood chips was carried out according to the method of example 2, and the following experimental groups were carried out while changing only the enzyme treatment temperature of the heat-resistant xylanase pretreatment step;

experimental group 1: the enzyme treatment temperature is 70 ℃;

experimental group 2: the enzyme treatment temperature is 80 ℃;

experimental group 3: the enzyme treatment temperature is 90 ℃;

experimental group 4: the enzyme treatment temperature was 100 ℃.

The pretreatment of wood chips was carried out according to the method of example 2, changing the enzyme treatment temperature of the heat-resistant xylanase pretreatment step to 90 ℃ and changing the enzyme dosage to each of the following experimental groups;

experimental group 5: the enzyme dosage is 5U/g;

experimental group 6: the enzyme dosage is 10U/g;

experimental group 7: the enzyme dosage is 15U/g;

experimental group 8: the dosage of the enzyme is 25U/g;

experimental group 9: the enzyme dosage was 30U/g.

(1) Through detection, after wood chips are pretreated at the enzyme treatment temperature of 70-100 ℃ in the example 2 and the experimental groups 1-4, and the heat-resistant xylanase pretreatment at different enzyme treatment temperatures, the removal rates of hemicellulose, cellulose, acid-soluble lignin and acid-insoluble lignin of the wood chips are shown in the attached figure 3; after the heat-resistant xylanase pretreatment at different enzyme treatment temperatures, the specific surface area and porosity of the wood chips are shown in figure 6; analysis of FIG. 3 shows that the hemicellulose removal effect is obvious with the increase of the enzyme treatment temperature, and the removal rate of other components has a small change range. Wherein the enzyme treatment temperature is 90 deg.C, halfThe highest cellulose removal rate is 43.35%; while the removal rates of cellulose, acid-soluble lignin and acid-insoluble lignin have smaller change ranges. When the enzyme treatment temperature is 90 ℃, the removal rates of hemicellulose and acid-soluble lignin are maximum values, and the content of cellulose in the biomass raw material corresponding to the treatment conditions is highest, so that the temperature of 90 ℃ is the optimal temperature for heat-resistant xylanase treatment; analysis of FIG. 6 shows that the specific surface area of the treated wood chips increases with the increase of the enzyme reaction temperature, wherein the specific surface area is higher and is 11.28 m at the enzyme treatment temperature of 90 DEG C²(ii) in terms of/g. The porosity of the wood chips after the enzyme treatment increases with increasing temperature. Wherein, when the temperature of the enzyme treatment is 90 ℃, the specific surface area and the porosity of the wood chip are both high, and the porosity of the wood chip is 19.56%.

(2) Through detection, after wood chips are respectively pretreated under the condition that the enzyme dosage of example 2 and experimental groups 5-9 is 5-30U/g, and heat-resistant xylanase with different enzyme dosages is adopted for pretreatment, the removal rates of hemicellulose, cellulose, acid-soluble lignin and acid-insoluble lignin of the wood chips are shown in the attached figure 4; after pretreatment with heat-resistant xylanase with different enzyme dosages, the specific surface area and porosity of the wood chip are shown in figure 7; analyzing figure 4, the change range of the hemicellulose removal rate is the largest along with the increase of the enzyme dosage, and the change of the acid-soluble lignin removal rate is the next, while the change of the cellulose and acid-insoluble lignin removal rates is smaller. With the increase of the enzyme dosage, the hemicellulose removal rate firstly shows an ascending trend and then declines, wherein when the enzyme dosage is 20U/g, the hemicellulose removal efficiency is highest, the enzyme dosage continues to increase, and the hemicellulose removal rate is reduced on the contrary. Analysis of FIG. 7 shows that the specific surface area and porosity of the treated wood chips increase and decrease with increasing enzyme dosage, wherein the specific surface area and porosity of the wood chips are the highest values at 20U/g, indicating that the treatment conditions at 90 ℃ and 20U/g are most suitable for the action of the thermostable xylanase.

Example 3 application of a Wood chip Pre-treatment Process for Populus Wood chemi-mechanical pulping

1. Raw material preparation

Poplar chips (supplied by Shandong Chengning paper group GmbH) were manually screened for acceptable size, air dried and stored for future use.

The chemical composition of the poplar chips is shown in the following table:

equipment: a plant sample crusher (FZ 102, Yongguangming medical instruments, Inc. of Beijing), a mercury intrusion instrument (PoreMaster 60GT, Congta instruments, USA), a Hitachi scanning electron microscope (Regulus 8220, Hitachi high and new technology Co., Ltd.), an ion chromatography 5000+ (ICS-5000 +, Thermo-Fisher, USA), a micro CT (SkyScan 2211, Bruker), a nuclear magnetic resonance spectrometer (Bruker AVANCEIIIHD500, Bruker technologies, Inc.); ultraviolet spectrophotometer (Agilent 8454, Agilent technologies, Inc.); fourier transform infrared spectrometer (Bruker Vertex70, Bruker technologies, Inc.).

2. Heat resistant xylanase pretreatment

Taking poplar chips for enzyme treatment, wherein the enzyme treatment temperature is 90 ℃, the enzyme dosage is 20U/g, the liquid ratio is 1:4, and the temperature is kept for 60 min. And inactivating the raw material after enzyme treatment for later pulping by a chemical mechanical method.

The enzyme is heat-resistant xylanase which is obtained from Longket company, the enzyme activity is detected by adopting the national standard ((GB/T23874) -2009)), and the detected enzyme activity is 255785U/mL.

The pretreated wood chips have a specific surface area of 11.28 m²The porosity of the wood chip is 19.56 percent, and the removal rate of hemicellulose is 43.35 percent.

3. Alkali and hydrogen peroxide treatment

Performing alkali impregnation on the pretreated poplar chips, and performing hydrogen peroxide bleaching on the poplar chips subjected to alkali impregnation;

the treatment conditions of the alkali impregnation are as follows: adopting alkali liquor with sodium hydroxide content of 6%, soaking at 90 deg.C, and keeping the temperature for 60 min; the treatment conditions for hydrogen peroxide bleaching are as follows: the adopted bleaching solution comprises the following components in percentage by mass: 6% of hydrogen peroxide and Na₂SiO₃3%、 MgSO₄0.5 percent of EDTA, bleaching temperature of 90 ℃ and heat preservation time of 60 min.

The percentages are mass percentages.

4. Grinding pulp

The chemically treated wood chip is ground by using a KPK high-concentration continuous disc grinder and adjusting the gap of the grinding discs. The first section is a coarse grinding area, the disc grinding gap is 0.5 mm, wood chips are extruded and defibered into fibers, and the needed grinding energy consumption is large; the second stage is a fine grinding zone, the disc grinding gap is 0.2 mm, and the fiber is finely processed.

The average length of the fiber after grinding is 1.11 mm, and the crimp index is 5.29%.

5. Latency-eliminating screen pulp

The latent condition is as follows: the concentration of the slurry is 2 percent, the latency elimination temperature is 80 ℃, and the temperature is kept for 30 min. And screening the pulp subjected to latency elimination through a pulp screening machine with screen gaps of 0.2 mm to obtain good pulp and screen slag.

6. Paper pulp making machine

And (3) preparing the obtained fine pulp into 10-15% of concentration, putting the fine pulp into a PFI pulping machine, and adjusting the pulping revolution and the grinding disc distance, wherein the set pulping degree is 40-degree SR.

The prepared paper pulp has better strength performance and whiteness, and the tearing index of the paper pulp is 3.73 mN.m²G, tensile strength of 3.77 kN/m, whiteness of 70.3% ISO.

The method for measuring the effect of the pretreated wood chips comprises the following steps:

1. the method for measuring the content of the components of the pretreated wood chips comprises the following steps:

and determining the contents of cellulose, hemicellulose and lignin in the pretreated wood chips by adopting an NREL method. Firstly, wood chips are crushed into wood powder of 40-60 meshes, water extraction and alcohol extraction are carried out on the wood powder, the extracted wood powder is washed and dried by deionized water, 0.3 g of wood powder is taken and transferred into a digestion tube, and 3 mL of H with the concentration of 72 percent is added₂SO₄And keeping the temperature at 30 ℃ for 1 h, transferring the concentrated acid hydrolysate into a digestion bottle, diluting the acid concentration to 4%, and keeping the temperature at 121 ℃ for 1 h. Filtering acidolysis solution, oven drying the obtained insoluble solid at 105 deg.C, determining acid-insoluble lignin content, and filteringAnd (4) diluting by a proper multiple, determining the sugar content in the solution by adopting ion chromatography, and calculating the contents of cellulose and hemicellulose according to the conversion of the sugar recovery rate.

2. Method for measuring specific surface area and pore size distribution of pretreated wood chips

The treated wood chips were cut into cubes with dimensions of less than 2mm x 2mm, dried under vacuum at 45 ℃ for 24h and analyzed using a mercury porosimeter (Geminiv 2380). The measurement conditions were as follows: the mercury density was 13.5 g/cm³Contact angle of 140 DEG, surface tension of 480 erg/cm³Data was analyzed using the software PoreMaster.

3. Method for extracting and analyzing lignin

Drying the pretreated wood chips in a vacuum drying oven, crushing by using a plant pulverizer, freeze-drying 40-60-mesh powder, further removing water in the powder, performing ball milling for 4 hours, performing propanol extraction in a Soxhlet extractor, hydrolyzing the wood powder by using neutral cellulase, removing cellulose and hemicellulose in the wood powder at the temperature of 45 ℃ in a shaking table for 48 hours, and washing by using hydrochloric acid with the pH value of 2 to obtain crude lignin. Extracting crude lignin in dioxane aqueous solution (85: 15, V/V), concentrating the extracted lignin in a rotary evaporator, and dripping into hydrochloric acid solution with pH of 2 for precipitation and separation to obtain lignin sample. The extracted lignin samples were analyzed using an ALPHA infrared spectrometer, nuclear magnetic resonance spectrometer (AVANCE II 400).

Unless otherwise specified, the proportions in the present invention are mass proportions, and the percentages are mass percentages.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.