A fiber-reinforced carbon-sulfur double salt plate and a preparation method and application thereof

Abstract

The application discloses a kind of fiber reinforced carbon sulfur double salt plate and its preparation method and application, it is related to building material technical field, with green low-carbon type gardenia yellow waste liquid, beta-glucosidase fermentation liquor, calcium magnesium sulfate double salt cementing material, waste sulfuric acid, biological macromolecule and carbonate mineral as raw material, and incorporate short cut fiber and lay glass fiber mesh cloth, by roller forming, maintenance and drying obtain fiber reinforced carbon sulfur double salt plate;The fiber reinforced carbon sulfur double salt plate obtained by the application has low density, low water absorption, low wet swelling rate, high impact resistance and bending strength, and its comprehensive performance is better than fiber reinforced calcium silicate plate.

Description

Technical Field

[0001] This invention relates to the field of building materials technology, specifically to a fiber-reinforced carbon-sulfur composite salt board, its preparation method, and its application. Background Technology

[0002] Fiber-reinforced calcium silicate board is a composite board made of siliceous and calcareous materials under high temperature and pressure to form tobermorite crystals. It has high strength, low thermal conductivity and good fire resistance, and is widely used in interior partitions, ceilings, sound insulation, decoration and fire protection projects.

[0003] However, fiber-reinforced calcium silicate boards also have disadvantages, such as being hard and heavy, difficult to cut, producing a lot of dust, and requiring special tools and professional workers; having low impact and flexural strength, with edges and corners prone to cracking, requiring extra care when drilling holes; and deforming after absorbing water, mainly due to its high water absorption rate (20~50%) and moisture absorption and expansion characteristics.

[0004] Patent CN102924000A discloses a method for preparing asbestos-free calcium silicate boards using industrial waste. It uses waste cement paper bags, quartz tailings powder, carbide sludge and other wastes as raw materials for preparing asbestos-free calcium silicate boards, which is conducive to saving natural resources and reducing environmental pollution.

[0005] Patent CN111423189A discloses a calcium silicate board prepared from straw ash and its preparation method. The board is made by using modified straw ash, modified oil shale ash, hydrated lime, ordinary silicate cement, wood fiber and water, and is prepared by pretreatment, weighing, mixing, stirring and pressing, and high temperature and high pressure curing. By using a large amount of straw ash, the raw material cost of calcium silicate board can be greatly reduced, while realizing the resource utilization of straw ash. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide a fiber-reinforced carbon-sulfur complex salt board and its preparation method. The fiber-reinforced carbon-sulfur complex salt board has low density, low water absorption, low moisture expansion rate, high impact resistance and flexural strength, and its comprehensive performance is better than that of fiber-reinforced calcium silicate board.

[0007] The technical problem to be solved by this invention is achieved by the following technical solution:

[0008] One objective of this invention is to provide a method for preparing fiber-reinforced carbon-sulfur composite salt board, comprising the following steps:

[0009] S1. Mix the gardenia yellow waste liquid, β-glucosidase fermentation broth and water evenly, add waste sulfuric acid to adjust the pH to 4-5, heat and stir to obtain the enzymatic hydrolysis product of gardenia yellow waste liquid.

[0010] S2. Mix the enzymatic hydrolysis product of gardenia yellow waste liquid obtained in step S1 with calcium magnesium sulfate double salt binder, carbonate mineral powder and sugar retarder evenly, grind and obtain nanoparticle suspension.

[0011] S3. Add biomacromolecules and short-cut fibers to the nanoparticle suspension obtained in step S2, mix evenly, and obtain a slurry.

[0012] S4. Spread the slurry prepared in step S3 evenly on the template, lay a layer of glass fiber mesh on the upper and lower surfaces of the slurry, and form a slab through the roller pressing process.

[0013] S5. Curing the slab prepared in step S4 to obtain a hardened slab;

[0014] S6. The hardened slab prepared in step S5 is dried and cut to obtain fiber-reinforced carbon-sulfur complex salt board.

[0015] In step S1, the mass ratio of the gardenia yellow waste liquid, β-glucosidase fermentation broth, and water is 100 : (20~30) : (160~180); wherein the content of gardenia yellow waste liquid is 20~30 mg / mL, and the enzyme content of β-glucosidase fermentation broth is 600~800 U / g.

[0016] In step S1, the waste sulfuric acid is generated from industrial and chemical fields such as titanium dioxide production, steel pickling, petroleum refining, and dye manufacturing, and the sulfuric acid concentration is 60-70%.

[0017] In step S1, the heating and stirring temperature is 50±2℃, and the stirring time is 11±1h.

[0018] In step S2, the mass ratio of the enzymatic hydrolysis product of gardenia yellow waste liquid, calcium magnesium sulfate double salt binder, carbonate mineral powder and sugar retarder is 60 : (180~200) : (80~100) : (1~2).

[0019] In step S2, the grinding speed is 14000~18000 rpm and the grinding time is 8~12 min.

[0020] In step S2, the calcium magnesium sulfate double salt binder is prepared by the method disclosed in patent CN109809722A.

[0021] In step S2, the carbonate mineral is one or more of calcium carbonate, magnesium carbonate, calcium magnesium carbonate, barium carbonate, and lead carbonate.

[0022] In step S2, the sugar retarder includes, but is not limited to, one or more of glucose, galactose, fructose, and straw mixed sugars.

[0023] In step S3, the mass ratio of the nanoparticle suspension, biomacromolecules and chopped fibers is 1000 : (50~60) : (8~12).

[0024] In step S3, the biomacromolecules include, but are not limited to, one or more of proteins, collagen, gelatin and chitosan.

[0025] In step S3, the chopped fiber is one or more of the following polymer chopped fibers: polypropylene fiber, polyvinyl alcohol fiber, polylactic acid fiber, polyester fiber, etc.

[0026] In step S3, the length of the chopped fiber is 6~12mm and the diameter is 1.3~6.0dtex.

[0027] In step S4, the unit area mass of the glass fiber mesh is 60~300g / m². 2 .

[0028] In step S5, the curing temperature is 20~30℃, the humidity is 90~95%RH, the carbon dioxide concentration is 15±2%, and the time is 168±2h.

[0029] In step S6, the drying temperature is 45~50℃, the humidity is 20~30%RH, and the time is 24±1h.

[0030] The second objective of this invention is to provide a fiber-reinforced carbon-sulfur complex salt board obtained by the aforementioned method for preparing the fiber-reinforced carbon-sulfur complex salt board.

[0031] A third objective of this invention is to provide the application of the fiber-reinforced carbon-sulfur composite salt board in building materials.

[0032] The reaction equation for preparing carbon-sulfur complex hardened bodies using calcium-magnesium sulfate double salt binder and carbonate minerals is as follows:

[0033] CaMg(SO4)2+ MgO + Aa(CO3) b + H2O→Ca x Mg y Az(OH) l (CO3) m (SO4) n H2O

[0034] The beneficial effects of this invention are as follows: Calcium magnesium sulfate double salt binder is a green, low-carbon cementitious material. After reacting with carbonate minerals and water, the resulting carbon-sulfur double salt solidified body exhibits excellent physical and mechanical properties. Furthermore, the genipin, the main product of the enzymatic hydrolysis of gardenia yellow waste liquid, reacts with biomacromolecules to form nanoscale biomacromolecules, which, together with nanoscale carbon-sulfur double salt crystals, form a nanoscale biomimetic composite structure, improving the toughness, tensile strength, flexural strength, and hydrophobicity of the entire solidified body. Compared to fiber-reinforced calcium silicate boards with tobermorite as the core component, the prominent features of the carbon-sulfur double salt hardened body described in this invention are rapid setting, high strength, and good water resistance. The prepared boards have lower water absorption and hygroscopic expansion, and higher flexural strength, thus improving the board's performance. Compared to the surface hydrophobic film of fiber-reinforced calcium silicate boards, this invention achieves full-section hydrophobicity of the board. The incorporation of high-molecular-weight chopped fibers and the surface coating with glass fiber mesh further enhance the mechanical properties of the board. Using a carbon dioxide atmosphere for wet curing can further improve the water repellency and strength of carbon-sulfur composite salt plates. Attached Figure Description

[0035] Figure 1 This is a cross-sectional SEM image of the fiber-reinforced carbon-sulfur complex salt plate prepared in Example 1 of the present invention;

[0036] Figure 2 This is a cross-sectional SEM image of the fiber-reinforced carbon-sulfur complex salt plate prepared in Comparative Example 4 of this invention. Detailed Implementation

[0037] To make the technical means, creative features, objectives and effects of this invention easier to understand, the invention will be further described below with reference to specific embodiments and illustrations.

[0038] The following examples and comparative examples illustrate the sources of raw materials:

[0039] Gardenia yellow waste liquid was purchased from Guangxi Shanyun Biochemical Technology Co., Ltd., with a gardenoside content of 30 mg / mL; β-glucosidase fermentation broth was purchased from Wuxi Lianhe Hengzhou Chemical Co., Ltd., with an enzyme content of 800 U / g; waste sulfuric acid was purchased from Anhui Fengyuan Biotechnology Co., Ltd., with a sulfuric acid concentration of 60%; calcium magnesium sulfate double salt binder was prepared by the method provided in Example 1 of the specification of patent CN109809722A; calcium carbonate and magnesium carbonate were chemically pure; straw mixed sugar and galactose were purchased from Anhui Fengyuan Biotechnology Co., Ltd.; gelatin and chitosan were purchased from Anhui Fengyuan Biotechnology Co., Ltd.; polyvinyl alcohol chopped fiber and polyester chopped fiber were purchased from Anhui Xinyuan Biotechnology Co., Ltd.; glass fiber mesh was purchased from Qinhuangdao Guangyu Glass Fiber Products Co., Ltd.

[0040] Example 1

[0041] S1. Mix gardenia yellow waste liquid, β-glucosidase fermentation broth and water in a mass ratio of 100:30:160, add waste sulfuric acid to adjust the pH to 5, stir at 50℃ for 12h to obtain gardenia yellow waste liquid enzymatic hydrolysis product.

[0042] S2. The enzymatic hydrolysis product of gardenia yellow waste liquid obtained in step S1 is mixed with calcium magnesium sulfate double salt binder, calcium carbonate and straw mixed sugar in a mass ratio of 60:180:100:1, and ground at 18000 rpm for 12 min to obtain a nanoparticle suspension.

[0043] S3. Add chitosan and polyester chopped fibers to the nanoparticle suspension obtained in step S2 in a mass ratio of 1000:50:12, mix evenly, and obtain a slurry.

[0044] S4. First, lay a layer of fiberglass mesh on a PVC template with a length of 2480mm, a width of 1250mm, and a thickness of 8mm. Pour the slurry onto the fiberglass mesh and use a roller press to flatten it to a thickness of 8mm. Then, lay another layer of fiberglass mesh on top of the slurry to form a slab.

[0045] S5. The slab is solidified and hardened for 168 hours under the conditions of 20℃, 90%RH and 15% carbon dioxide concentration, and then demolded to obtain the hardened slab.

[0046] S6. The hardened slab is dried at 50°C and 30%RH for 24 hours to obtain fiber-reinforced carbon-sulfur composite salt board.

[0047] Example 2

[0048] Fiber-reinforced carbon-sulfur complex salt boards were prepared according to the method in Example 1, except that the mass ratio of gardenia yellow waste liquid, β-glucosidase fermentation broth and water in step S1 was adjusted to 100:20:180.

[0049] Example 3

[0050] Fiber-reinforced carbon-sulfur double salt board was prepared according to the method of Example 1, except that the mass ratio of gardenia yellow waste liquid enzymatic hydrolysis product to calcium magnesium sulfate double salt binder, calcium carbonate and straw mixed sugar in step S2 was adjusted to 60:200:80:2.

[0051] Example 4

[0052] Fiber-reinforced carbon-sulfur complex salt plates were prepared according to the method in Example 1, except that the mass ratio of nanoparticle suspension to chitosan and polyester chopped fibers in step S3 was adjusted to 1000:60:8.

[0053] Example 5

[0054] Fiber-reinforced carbon-sulfur complex salt boards were prepared according to the method of Example 1, except that calcium carbonate was replaced with magnesium carbonate in step S2.

[0055] Example 6

[0056] Fiber-reinforced carbon-sulfur complex salt boards were prepared according to the method of Example 1, except that the straw mixed sugar in step S2 was replaced with galactose.

[0057] Example 7

[0058] Fiber-reinforced carbon-sulfur complex salt plates were prepared according to the method in Example 1, except that chitosan was replaced with gelatin in step S3.

[0059] Example 8

[0060] Fiber-reinforced carbon-sulfur complex salt board was prepared according to the method of Example 1, except that the polyester chopped fibers in step S3 were replaced with polyvinyl alcohol chopped fibers.

[0061] Comparative Example 1

[0062] Fiber-reinforced carbon-sulfur complex salt boards were prepared according to the method in Example 1, except that calcium carbonate was not added in step S2.

[0063] Comparative Example 2

[0064] Fiber-reinforced carbon-sulfur complex salt board was prepared according to the method of Example 1, except that polyester chopped fibers were not added in step S3.

[0065] Comparative Example 3

[0066] Fiber-reinforced carbon-sulfur complex salt board was prepared according to the method of Example 1, except that straw mixed sugar was not added in step S2.

[0067] Comparative Example 4

[0068] Fiber-reinforced carbon-sulfur complex salt plates were prepared according to the method in Example 1, except that chitosan was not added in step S3.

[0069] Comparative Example 5

[0070] Fiber-reinforced carbon-sulfur complex salt boards were prepared according to the method of Example 1, except that step S1 was not performed, and the enzymatic hydrolysis product of gardenia yellow waste liquid in step S2 was replaced with water.

[0071] Comparative Example 6

[0072] Fiber-reinforced carbon-sulfur complex salt board was prepared according to the method of Example 1, except that the curing conditions in step S5 were replaced with air curing for 168 hours.

[0073] The performance of fiber-reinforced carbon-sulfur composite salt boards prepared in Examples 1-8 and Comparative Examples 1-6 was tested according to standard JC / T 564.1-2018, and the results are shown in Table 1.

[0074] Table 1 Performance test results of fiber-reinforced carbon-sulfur composite salt board

[0075] <![CDATA[Apparent density (kg / m 3 )]]> Flexural strength (saturated strength) (MPa) Water absorption rate (%) Moisture expansion rate (%) Example 1 1140 21 18 0.13 Example 2 1150 18 22 0.15 Example 3 1190 24 21 0.17 Example 4 1130 23 16 0.11 Example 5 1120 21 18 0.13 Example 6 1140 21 18 0.13 Example 7 1140 20 18 0.13 Example 8 1140 23 18 0.13 Comparative Example 1 870 13 35 0.32 Comparative Example 2 1140 16 18 0.13 Comparative Example 3 1140 19 18 0.13 Comparative Example 4 1130 19 26 0.28 Comparative Example 5 1130 20 27 0.30 Comparative Example 6 1080 20 26 0.27

[0076] As can be seen from Table 1:

[0077] The fiber-reinforced carbon-sulfur composite salt boards prepared in Examples 1-8 have high flexural strength and low water absorption and swelling rate, which indicates that the fiber-reinforced carbon-sulfur composite salt boards of the present invention have high strength and good water resistance.

[0078] As can be seen from Examples 1 and 2, the lower the amount of β-glucosidase fermentation broth, the lower the flexural strength (saturated strength) of the fiber-reinforced carbon-sulfur complex salt board, and the greater the mass water absorption rate and wet swelling rate.

[0079] As can be seen from Examples 1 and 3, the higher the content of calcium magnesium sulfate double salt binder in step S2, the greater the flexural strength (saturated strength), mass water absorption rate and wet expansion rate of the fiber-reinforced carbon-sulfur double salt board.

[0080] As can be seen from Examples 1 and 4, the higher the chitosan content in step S3, the greater the flexural strength (saturated strength) of the fiber-reinforced carbon-sulfur complex salt board, and the smaller the mass water absorption rate and wet swelling rate.

[0081] As can be seen from Examples 1 and 5, when calcium carbonate is replaced with magnesium carbonate in step S2, the various properties of the fiber-reinforced carbon-sulfur complex salt board remain basically unchanged.

[0082] As can be seen from Examples 1 and 6, when the straw mixed sugar is replaced with galactose in step S2, the various properties of the fiber-reinforced carbon-sulfur complex salt board remain basically unchanged.

[0083] As can be seen from Examples 1 and 7, when chitosan is replaced with gelatin in step S3, the various properties of the fiber-reinforced carbon-sulfur complex salt board remain basically unchanged.

[0084] As can be seen from Examples 1 and 8, when polyester chopped fibers are replaced with polyvinyl alcohol chopped fibers in step S3, the flexural strength (water saturation strength) of the fiber-reinforced carbon-sulfur composite salt board is higher.

[0085] As can be seen from Example 1 and Comparative Example 1, when calcium carbonate is not added in step S2, the mass water absorption rate and wet swelling rate of the fiber-reinforced carbon-sulfur complex salt board are significantly increased, while the apparent density and flexural strength (saturated strength) are lower.

[0086] As can be seen from Example 1 and Comparative Example 2, when polyester chopped fibers are not added in step S3, the flexural strength (water saturation strength) of the fiber-reinforced carbon-sulfur composite salt board is significantly reduced.

[0087] As can be seen from Example 1 and Comparative Example 3, when straw mixed sugar is not added in step S2, the flexural strength (water-saturated strength) of the fiber-reinforced carbon-sulfur complex salt board is lower.

[0088] As can be seen from Example 1 and Comparative Example 4, when chitosan is not added in step S3, the mass water absorption rate and wet swelling rate of the fiber-reinforced carbon-sulfur complex salt board are significantly increased, and the flexural strength (saturated strength) is lower.

[0089] As can be seen from Example 1 and Comparative Example 5, when step S1 is not performed and the enzymatic hydrolysis product of gardenia yellow waste liquid in step S2 is replaced with water, the mass water absorption rate and wet swelling rate of fiber reinforced carbon-sulfur complex salt board are significantly increased, and the flexural strength (saturated strength) is lower.

[0090] As can be seen from Example 1 and Comparative Example 6, when the curing conditions in step S5 are replaced with air condensation and hardening, the fiber-reinforced carbon-sulfur composite salt board has a higher water absorption rate and wet expansion rate, and a lower flexural strength (saturated strength). This indicates that a suitable CO2 concentration during the curing process can improve the quality of the fiber-reinforced carbon-sulfur composite salt board.

[0091] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a fiber-reinforced carbon-sulfur complex salt board, characterized in that, Includes the following steps: S1. Mix the gardenia yellow waste liquid, β-glucosidase fermentation broth and water evenly, add waste sulfuric acid to adjust the pH to 4-5, heat and stir to obtain the enzymatic hydrolysis product of gardenia yellow waste liquid. S2. Mix the enzymatic hydrolysis product of gardenia yellow waste liquid obtained in step S1 with calcium magnesium sulfate double salt binder, carbonate mineral powder and sugar retarder evenly, grind and obtain nanoparticle suspension. S3. Add biomacromolecules and short-cut fibers to the nanoparticle suspension obtained in step S2, mix evenly, and obtain a slurry. S4. Spread the slurry prepared in step S3 evenly on the template, lay a layer of glass fiber mesh on the upper and lower surfaces of the slurry, and form a slab through the roller pressing process. S5. Curing the slab prepared in step S4 to obtain a hardened slab; S6. The hardened slab prepared in step S5 is dried and cut to obtain fiber-reinforced carbon-sulfur complex salt board.

2. The preparation method according to claim 1, characterized in that: In step S1, the mass ratio of the gardenia yellow waste liquid, β-glucosidase fermentation broth, and water is 100 : (20~30) : (160~180); wherein the content of gardenia yellow waste liquid is 20~30 mg / mL, and the enzyme content of β-glucosidase fermentation broth is 600~800 U / g; Preferably, the waste sulfuric acid is generated from titanium dioxide production, steel pickling, petroleum refining, and dye manufacturing, wherein the sulfuric acid concentration is 60-70%. Preferably, the heating and stirring temperature is 50±2℃ and the stirring time is 11±1h.

3. The preparation method according to claim 1, characterized in that: In step S2, the mass ratio of the enzymatic hydrolysis product of gardenia yellow waste liquid, calcium magnesium sulfate double salt binder, carbonate mineral powder and sugar retarder is 60 : (180~200) : (80~100) : (1~2); Preferably, the grinding speed is 14,000~18,000 rpm and the grinding time is 8~12 min; Preferably, the carbonate mineral is one or more selected from calcium carbonate, magnesium carbonate, calcium magnesium carbonate, barium carbonate, and lead carbonate; Preferably, the sugar retarder is one or more of glucose, galactose, fructose, and straw mixed sugars.

4. The preparation method according to claim 1, characterized in that: In step S2, the calcium magnesium sulfate double salt binder is prepared by the method disclosed in patent CN109809722A.

5. The preparation method according to claim 1, characterized in that: In step S3, the mass ratio of the nanoparticle suspension, biomacromolecules, and chopped fibers is 1000 : (50~60) : (8~12); Preferably, the biomacromolecule is one or more selected from protein, collagen, gelatin, and chitosan; Preferably, the chopped fibers are one or more selected from polypropylene fibers, polyvinyl alcohol fibers, polylactic acid fibers, and polyester fibers; Preferably, the chopped fibers have a length of 6-12 mm and a diameter of 1.3-6.0 dtex.

6. The preparation method according to claim 1, characterized in that: In step S4, the unit area mass of the glass fiber mesh is 60~300g / m². 2 .

7. The preparation method according to claim 1, characterized in that: In step S5, the curing temperature is 20~30℃, the humidity is 90~95%RH, the carbon dioxide concentration is 15±2%, and the time is 168±2h.

8. The preparation method according to claim 1, characterized in that: In step S6, the drying temperature is 45~50℃, the humidity is 20~30%RH, and the time is 24±1h.

9. Fiber-reinforced carbon-sulfur complex salt board obtained by the preparation method according to any one of claims 1 to 8.

10. The application of the fiber-reinforced carbon-sulfur composite salt board according to claim 9 in building materials.

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