Flame-retardant biomass filler as well as preparation method and application thereof

Abstract

The invention discloses a flame-retardant biomass filler as well as a preparation method and application thereof, and belongs to the technical field of biomass fillers, the flame-retardant biomass filler comprises the following components in parts by weight: 10-30 parts of biomass, 10-40 parts of a composite flame retardant and 10-30 parts of a dispersing agent; the composite flame retardant is at least two of adenosine triphosphate, phosphoric acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, borax, sodium tripolyphosphate, pentaerythritol, hydroxypropyl-beta-cyclodextrin, boric acid, ammonium polyphosphate, ammonium sulfate, diammonium hydrogen phosphate and amidinourea phosphate. The biomass capable of replacing flour and the common flame retardant are used as raw materials, a physical blending method is adopted, the environment-friendly biomass filler is prepared, the additional value of agriculture and forestry processing residues is increased, the production cost of the biomass filler is reduced, development of the flame-retardant filler industry is promoted, and the biomass filler has important economic benefits and social benefits.

Description

Technical Field

[0001] The present invention relates to the technical field of biomass fillers, and specifically to a flame-retardant biomass filler, a preparation method thereof, and an application thereof. Background Art

[0002] With the rapid economic development and population growth, the global demand for energy is increasing continuously. However, traditional fossil energy resources such as coal, oil, and natural gas are limited and non-renewable, and the problem of energy shortage is becoming increasingly prominent. Finding alternative renewable energy has become an urgent task. As a rich biomass energy resource, agricultural and forestry processing residues have great development potential.

[0003] In China, the agriculture and forestry industries have developed rapidly, and a huge amount of agricultural and forestry residues are generated every year. However, only a small part of them is effectively utilized, and most of them are burned, landfilled, or discarded at will, which not only wastes valuable resources but also occupies a large amount of land space.

[0004] Soybean meal powder, tea seed meal powder, cottonseed meal powder, palm kernel meal powder, sweet potato powder, Jatropha curcas meal powder, rubber seed meal powder, etc. are all residues after oil extraction or food processing, containing certain amounts of components such as cellulose, hemicellulose, and lignin. Adding them to wood adhesives can be used as fillers to increase the solid content of the adhesives and reduce production costs. At present, relevant literature on bio-based compound fillers has been published, for example: 1. Patent application CN202210013097.4 discloses a modified oil-tea fruit shell powder, a preparation method thereof, an oil-tea fruit shell powder filler, and an application thereof. This technology belongs to the field of wood adhesive additives. In this invention, the preparation process of the modified oil-tea fruit shell powder is as follows: First, mix oil-tea fruit shell powder, NaOH solution, and polypropylene and react to obtain a reaction solution. Then, adjust the pH value of the reaction solution, centrifuge to obtain a first precipitate, and dry it to obtain pre-modified oil-tea fruit shell powder. Next, soak the pre-modified oil-tea fruit shell powder in boric acid solution to form an acidic oil-tea fruit shell powder solution. After that, adjust the pH value of the acidic oil-tea fruit shell powder solution again, centrifuge to obtain a second precipitate, and dry it to finally obtain the modified oil-tea fruit shell powder. When this modified oil-tea fruit shell powder is used in combination with coconut shell activated carbon, it can be used as a filler for wood-based panels, significantly improving the bonding strength and flame-retardant performance of wood-based panels while reducing the formaldehyde release amount.

[0005] 2. Patent Application CN202410214391.0 discloses a biomass-based composite filler for adhesives, its preparation method, an adhesive, and its application in plywood. The biomass-based filler includes at least one of corncob, walnut shell, bamboo sawdust, and straw powder, and is used after pretreatment to expose surface hydrophilic groups. The gelatinizing agent includes at least one of soluble starch, carboxymethyl starch, xanthan gum, guar gum, and konjac gum. This invention can achieve the reuse of inexpensive and renewable biomass-based fillers and improve the initial viscosity of adhesives. However, this filler needs to go through steps such as acid treatment, heat treatment, grinding, sieving, washing, filtering, and drying before it can be used, and the process is relatively complex.

[0006] 3. Patent Application CN201711369836.9 discloses a method for producing a biomass filler for wood-based panels from ultrafine activated eucalyptus bark. This invention uses eucalyptus bark as raw material, and through cyclic processing and utilization, replaces flour as the active filler for wood processing adhesives, turning waste into treasure. Eucalyptus bark needs to go through steps such as raw material crushing, microbial treatment, infiltration treatment, extrusion dehydration, drying, impurity removal, impact crushing, and functional modification before use.

[0007] 4. Patent Application CN201410542290.2 discloses a lignin-based filler, its preparation method, and application. This invention hydrolyzes agricultural and forestry biomass residues to obtain agricultural and forestry biomass residue powder; purifies industrial alkali lignin to obtain purified industrial alkali lignin powder; mixes the agricultural and forestry biomass residue powder and the industrial alkali lignin powder to prepare the lignin-based filler. This filler is mainly used as an additive for urea-formaldehyde resin adhesives.

[0008] Among the above disclosed documents, the preparation methods of Patent Applications CN202410214391.0 and CN201711369836.9 are relatively cumbersome, thus increasing production costs. Patent Application CN202210013097.4 mentions that bio-based fillers can improve the flame retardancy of wood-based panels, but does not mention relevant flame retardancy indicators.

[0009] In order to endow biomass fillers with flame retardant functions, it is particularly important to develop a flame retardant biomass filler. Summary of the Invention

[0010] The purpose of the present invention is to provide a flame retardant biomass filler to solve the problems raised in the above background technology.

[0011] To achieve the above purpose, the embodiments of the present invention provide the following technical solutions: A flame-retardant biomass filler, which comprises the following components in parts by weight: 10-30 parts of biomass, 10-40 parts of a composite flame retardant, and 10-30 parts of a dispersant; the composite flame retardant is at least two of adenosine triphosphate, phosphoric acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, borax, sodium tripolyphosphate, pentaerythritol, hydroxypropyl-β-cyclodextrin, boric acid, ammonium polyphosphate, ammonium sulfate, diammonium hydrogen phosphate, and guanylurea phosphate.

[0012] Preferably, the flame-retardant biomass filler comprises the following components in parts by weight: 15-25 parts of biomass, 20-30 parts of a composite flame retardant, and 15-25 parts of a dispersant.

[0013] Preferably, the biomass is agricultural and forestry processing residues, specifically at least one of soybean meal powder, tea seed meal powder, cottonseed meal powder, palm kernel meal powder, sweet potato powder, Jatropha curcas meal powder, and rubber seed meal powder.

[0014] Preferably, the dispersant is at least one of sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, triethylhexyl phosphate, sodium dodecyl sulfate, methyl pentanol, cellulose derivatives, polyacrylamide, melamine, and fatty acid polyethylene glycol ester.

[0015] Preferably, the mass ratio of the composite flame retardant to the dispersant is 0.9:2.1-2.1:0.9.

[0016] Another object of the present invention is to provide a preparation method of the above-mentioned flame-retardant biomass filler, which comprises the following steps: Crush the biomass to more than 120 meshes; Crush the composite flame retardant to more than 120 meshes; Crush the dispersant to more than 120 meshes; Mix the crushed biomass, composite flame retardant, and dispersant evenly to obtain the flame-retardant biomass filler.

[0017] Another object of the present invention is to provide an application of the above-mentioned flame-retardant biomass filler in the preparation of flame-retardant wood-based panels, and the performance indicators meet the requirements of Class II plywood specified in the national standard GBT 9846-2015 (gluing strength ≥ 0.7 MPa), and the flame-retardant index (oxygen index) exceeds 42%, meeting the B1 level (oxygen index OI ≥ 32%) specified in GB / T 8624-2012.

[0018] The flame-retardant biomass filler provided by the present invention uses biomass that can replace flour and common flame retardants as raw materials. The raw materials are easily obtainable and can be directly and uniformly blended with adhesives. By using a physical blending method, the preparation process is simple. The biomass used is all derived from agricultural and forestry products and is pure biomass, which is beneficial to reducing the wood industry's dependence on fossil resources, increasing the added value of agricultural and forestry processing residues, reducing the production cost of biomass fillers, and promoting the development of the flame-retardant filler industry. It provides a flame-retardant, low-cost, green and environmentally friendly filler for wood-based panel products, especially plywood, which can improve the market competitiveness of biomass fillers and promote the development of the biomass filler industry and the wood industry, and has important economic and social benefits. In addition, the present invention uses a composite flame retardant that coexists well with adhesives, which greatly improves the flame retardant performance without affecting the bonding performance, and the performance is stable. Detailed implementation manners

[0019] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0020] Example 1: This example provides a flame-retardant biomass filler, and its preparation method includes the following steps: S1. Select sweet potato starch as the biomass and crush the biomass with a crusher to more than 120 mesh. S2. Select an equal mass ratio mixture of 2-acrylamido-2-methyl-1-propanesulfonic acid and guanylurea phosphate as the composite flame retardant, and crush the composite flame retardant with a crusher to more than 120 mesh. S3. Select sodium tripolyphosphate as the dispersant and crush the dispersant with a crusher to more than 120 mesh. S4. Mix 20 kg of the crushed biomass, 25.2 kg of the composite flame retardant, and 10.8 kg of the dispersant evenly with a mixer (the mass ratio of the composite flame retardant to the dispersant is 2.1:0.9), and then obtain the flame-retardant biomass filler after batch packaging.

[0021] After testing, the performance indicators of the flame-retardant biomass filler are as follows: the limiting oxygen index is 44.75%; the strength of the plywood prepared from the flame-retardant biomass filler after soaking in water at 63 ± 3 °C for 3 h is 1.22 MPa; when the flame-retardant biomass filler is used to produce flame-retardant wood-based panels, the performance indicators of the flame-retardant wood-based panels meet the requirements of Class II plywood specified in the national standard GB / T 9846.3-2004 (gluing strength ≥ 0.7 MPa), and the flame-retardant index (oxygen index) meets the requirements of Class B1 (oxygen index OI ≥ 32%) specified in GB / T 8624-2012.

[0022] Example 2: This example provides a flame-retardant biomass filler, and its preparation method includes the following steps: S1. Select sweet potato starch as the biomass and crush the biomass with a crusher to more than 120 mesh. S2. Select an equal mass ratio mixture of 2-acrylamido-2-methyl-1-propanesulfonic acid and guanylurea phosphate as the composite flame retardant, and crush the composite flame retardant with a crusher to more than 120 mesh. S3. Select sodium tripolyphosphate as the dispersant and crush the dispersant with a crusher to more than 120 mesh. S4. Mix 20 kg of the crushed biomass, 18 kg of the composite flame retardant, and 18 kg of the dispersant evenly with a mixer (the mass ratio of the composite flame retardant to the dispersant is 2.1:2.1), and then obtain the flame-retardant biomass filler after batch packaging.

[0023] After testing, the performance indicators of the flame-retardant biomass filler are as follows: the limiting oxygen index is 44.45%; the strength of the plywood prepared from the flame-retardant biomass filler after soaking in water at 63 ± 3 °C for 3 h is 1.82 MPa.

[0024] Example 3: This example provides a flame-retardant biomass filler, and its preparation method includes the following steps: S1. Select sweet potato starch as the biomass and crush the biomass with a crusher to more than 120 mesh. S2. Select an equal mass ratio mixture of 2-acrylamido-2-methyl-1-propanesulfonic acid and guanylurea phosphate as the composite flame retardant, and crush the composite flame retardant with a crusher to more than 120 mesh. S3. Select sodium tripolyphosphate as the dispersant and crush the dispersant with a crusher to more than 120 mesh. S4. Mix 20 kg of the crushed biomass, 10.8 kg of the composite flame retardant, and 25.2 kg of the dispersant evenly with a mixer, and then obtain the flame-retardant biomass filler after batch packaging.

[0025] After testing, the performance indicators of the flame-retardant biomass filler are as follows: the limiting oxygen index is 42.05%; the strength of the plywood prepared from the flame-retardant biomass filler after soaking in water at 63 ± 3 °C for 3 h is 1.32 MPa.

[0026] Example 4: This example provides a flame-retardant biomass filler, and its preparation method includes the following steps: S1. Select a mixture of tea seed meal and cottonseed meal in equal mass ratio as the biomass, and crush the biomass with a crusher to more than 120 mesh; S2. Select a mixture of adenosine triphosphate, phosphoric acid and borax in equal mass ratio as the composite flame retardant, and crush the composite flame retardant with a crusher to more than 120 mesh; S3. Select a mixture of sodium hexametaphosphate and sodium pyrophosphate in equal mass ratio as the dispersant, and crush the dispersant with a crusher to more than 120 mesh; S4. Mix 10 kg of the crushed biomass, 10 kg of the composite flame retardant and 10 kg of the dispersant evenly with a mixer, and then pack them in batches to obtain the flame-retardant biomass filler.

[0027] Example 5: This example provides a flame-retardant biomass filler, and its preparation method includes the following steps: S1. Select palm kernel meal as the biomass, and crush the biomass with a crusher to more than 120 mesh; S2. Select a mixture of sodium tripolyphosphate, pentaerythritol and hydroxypropyl-β-cyclodextrin in equal mass ratio as the composite flame retardant, and crush the composite flame retardant with a crusher to more than 120 mesh; S3. Select a mixture of triethylhexyl phosphate, sodium dodecyl sulfate and methyl pentanol in equal mass ratio as the dispersant, and crush the dispersant with a crusher to more than 120 mesh; S4. Mix 30 kg of the crushed biomass, 40 kg of the composite flame retardant and 30 kg of the dispersant evenly with a mixer, and then pack them in batches to obtain the flame-retardant biomass filler.

[0028] Example 6: This example provides a flame-retardant biomass filler, and its preparation method includes the following steps: S1. Select a mixture of soybean meal, jatrophacurcas meal and rubber seed meal in equal mass ratio as the biomass, and crush the biomass with a crusher to more than 120 mesh; S2. Select a mixture of boric acid and ammonium polyphosphate in equal mass ratio as the composite flame retardant, and crush the composite flame retardant with a crusher to more than 120 mesh; S3. Select a cellulose derivative as the dispersant, and crush the dispersant with a crusher to more than 120 mesh; S4. Mix 15 kg of crushed biomass, 20 kg of composite flame retardant, and 15 kg of dispersant evenly using a blender. After batch packaging, the flame-retardant biomass filler can be obtained.

[0029] Example 7: This example provides a flame-retardant biomass filler, and its preparation method includes the following steps: S1. Select Jatropha curcas meal as the biomass and crush the biomass to more than 120 meshes using a pulverizer. S2. Select a mixture of ammonium sulfate and diammonium hydrogen phosphate with an equal mass ratio as the composite flame retardant and crush the composite flame retardant to more than 120 meshes using a pulverizer. S3. Select a mixture of polyacrylamide, melamine, and fatty acid polyethylene glycol ester with an equal mass ratio as the dispersant and crush the dispersant to more than 120 meshes using a pulverizer. S4. Mix 25 kg of crushed biomass, 30 kg of composite flame retardant, and 25 kg of dispersant evenly using a blender. After batch packaging, the flame-retardant biomass filler can be obtained.

[0030] Example 8: This example provides a flame-retardant biomass filler, and its preparation method includes the following steps: S1. Select palm kernel meal as the biomass and crush the biomass to more than 120 meshes using a pulverizer. S2. Select a mixture of adenosine triphosphate, diammonium hydrogen phosphate, and guanylurea phosphate with an equal mass ratio as the composite flame retardant and crush the composite flame retardant to more than 120 meshes using a pulverizer. S3. Select a mixture of triethylhexyl phosphate, methyl pentanol, and fatty acid polyethylene glycol ester with an equal mass ratio as the dispersant and crush the dispersant to more than 120 meshes using a pulverizer. S4. Mix 20 kg of crushed biomass, 25 kg of composite flame retardant, and 20 kg of dispersant evenly using a blender. After batch packaging, the flame-retardant biomass filler can be obtained.

[0031] Comparative Example 1: This comparative example provides a biomass filler, and the difference from Example 1 is that no composite flame retardant and dispersant are added, and other conditions remain unchanged.

[0032] After testing, the performance indexes of the biomass filler prepared in this comparative example are: the limiting oxygen index is 30.75%; the strength after soaking the plywood prepared from this biomass filler in water at 63 ± 3 °C for 3 h is 1.77 MPa.

[0033] In summary, the embodiments of the present invention adopt the above technical solutions and have the following beneficial effects: (1) The biomass used in the embodiments of the present invention is all derived from agricultural and forestry products and is pure biomass. The raw materials used have a wide source, simple preparation, and convenient operation, reducing the production cost of the adhesive.

[0034] (2) The embodiments of the invention adopt a physical blending method of biomass and common flame retardants, without any pretreatment in the early stage, and can be directly used in combination with the adhesive, with a simple preparation process.

[0035] (3) The embodiments of the invention adopt a composite flame retardant that coexists well with the adhesive. The performance indicators of the plywood meet the requirements of various plywood specified in the national standard GBT 9846-2015 (depending on the adhesive used in the factory). The flame retardant index (oxygen index) exceeds 42%, meeting the B1 level (oxygen index OI≥32%) specified in GB / T 8624-2012.

[0036] Taking the ideal embodiments based on the present invention as inspiration, through the above description, relevant staff can completely make various changes and modifications without departing from the technical idea of the present invention. The technical scope of the present invention is not limited to the content in the specification.

Claims

1. A flame retardant biomass filler, characterized in that: The invention comprises the following components in parts by weight: 10-30 parts of biomass, 10-40 parts of composite flame retardant and 10-30 parts of dispersant; the composite flame retardant is at least two of adenosine triphosphate, phosphoric acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, borax, sodium tripolyphosphate, pentaerythritol, hydroxypropyl-β-cyclodextrin, boric acid, ammonium polyphosphate, ammonium sulfate, diammonium hydrogen phosphate and guanyl urea phosphate.

2. The flame retardant biomass filler according to claim 1, characterized in that: The invention comprises the following components in parts by weight: 15-25 parts of biomass, 20-30 parts of composite flame retardant and 15-25 parts of dispersant.

3. The flame retardant biomass filler according to claim 1 or 2, characterized in that: The biomass is agricultural and forestry processing residues, specifically at least one of soybean meal, tea meal, cotton seed meal, palm kernel meal, sweet potato meal, tung seed meal and rubber seed meal.

4. The flame retardant biomass filler according to claim 1 or 2, characterized in that: The dispersant is at least one of sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, triethylhexyl phosphoric acid, sodium lauryl sulfate, methyl amyl alcohol, cellulose derivatives, polyacrylamide, melamine and fatty acid polyethylene glycol ester.

5. The flame retardant biomass filler according to claim 1, characterized in that: The mass ratio of the composite flame retardant to the dispersant is 0.9:2.1-2.1:0.

9.

6. A method for preparing the flame retardant biomass filler according to any one of claims 1 to 5, characterized in that: The following steps are involved: Grind the biomass to above 120 mesh; The composite flame retardant is crushed to a size of 120 mesh or more; Crush the dispersant to more than 120 mesh; The crushed biomass, the composite flame retardant and the dispersant are uniformly mixed to obtain the flame retardant biomass filler.

7. Use of the flame-retardant biomass filler according to any one of claims 1 to 5 in the preparation of flame-retardant artificial boards.