WO2023147247A1 - Production de panneau de fibres de paille de riz à l'aide de lignine à partir d'une paille de riz dépolymérisée par voie catalytique - Google Patents

Production de panneau de fibres de paille de riz à l'aide de lignine à partir d'une paille de riz dépolymérisée par voie catalytique Download PDF

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Publication number
WO2023147247A1
WO2023147247A1 PCT/US2023/060900 US2023060900W WO2023147247A1 WO 2023147247 A1 WO2023147247 A1 WO 2023147247A1 US 2023060900 W US2023060900 W US 2023060900W WO 2023147247 A1 WO2023147247 A1 WO 2023147247A1
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WIPO (PCT)
Prior art keywords
fiber
mixture
resin
formaldehyde
package
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PCT/US2023/060900
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English (en)
Inventor
James CARUTHERS
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Purdue Research Foundation
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Publication of WO2023147247A1 publication Critical patent/WO2023147247A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/04—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N1/00—Pretreatment of moulding material
    • B27N1/003—Pretreatment of moulding material for reducing formaldehyde gas emission

Definitions

  • Rice is one of the staple crops. Rice is grown over a large part of Asia, South America, and North America. In 2017, one-hundred and seventy-eight million hundredweight (CWT) of rice was produced in the US, and California has 70% of the USA medium grain rice production!. Once the crop is harvested using mechanical combines, it leaves behind significant lengths of straw, that have traditionally been used as fuel (usually for direct burning with deleterious environmental effects), livestock feed, as a substrate for growing mushrooms or for production of biochar for improving soil conditions, and the like.
  • Rice straw fiber is composed of 20% lignin, with 32% cellulose, 28% hemicellulose, 11% ash, and 9% of other materials, where the lignin is the natural binder, the cellulose is the reinforcing fiber and hemi-cellulose is a filler that provides minimal mechanical strength.
  • Methods that have been used to obtain lignin from rice fiber include ultrasound- assisted alkaline extraction ⁇ steam explosion and biological treatments; hydrothermal extractions; solvent extraction using bio-ionic liquid (with cholinium (choline chloride) as the cation and amino acids as the anions). While useful, these methods tend to suffer from inefficiency and the requirement of potentially hazardous chemistry.
  • Methods that have been proposed using rice fiber in composite boards with binder systems from the chemical industry include rice straw fiber board with modified surface using NaOH and modified soy protein isolate adhesivess; medium and high density rice fiber boards with methylene diphenyl diisocyanate (MDI) adhesives*; fiber board using rice straw and urea formaldehyde resin.
  • MDI methylene diphenyl diisocyanate
  • these methods tend to suffer from inefficient use of production energy and the need for unnecessarily complex and potentially hazardous chemistry.
  • the composition of current laminating resins is typically a phenol-formaldehyde mixture.
  • the objective is to produce a composite board where both the binder and the reinforcing fibers are made from rice straw, which is an agricultural waste product.
  • Two results are detailed herein: (1) the method for catalytically degrading rice straw to obtain a product stream of cellulose that are relatively clean of lignin and a material that includes depolymerized lignin and other products such as waxes, sugars and hemicellulose and (2) formulation of a binder system using the depolymerized along with appropriate curing agents that can be used with a mixture of the clean cellulose fibers and additional rice fibers to produce composite boards with desirable physical properties.
  • One attractive feature of this approach is to produce a formaldehyde free composite board.
  • Steps include:
  • A-Stage Cure The depolymerized lignin with curing agents was heated to partially advance the cure in to control the viscosity of the resin mixture.
  • Resin Extension The main component of the laminating resin in a traditional phenol-formaldehyde resin is extended by the addition of depolymerized lignin resin from the A-stage cure.
  • Kraft Paper Saturation The resin mixture is brushed onto the kraft paper using a small paint brush so that the paper is fully saturated with minimal bleed though of resin through the paper. The kraft paper is not dripping wet, but tacky to the touch, where the resin should not be pooled.
  • B-Stage Cure The resin impregnated kraft paper is now subjected to a partial cure of the resin.
  • the impregnated paper is heated in an oven at 130 °C for 1 minute on a first side of the laminate, turned over and then heated for an additional 1.5 minutes on the opposite side.
  • the B-stage cure stiffens the kraft paper as well as removes solvent which thereby reduces the flow of the resin.
  • Layup Procedure The impregnated kraft paper that has been partially cured in the B-Stage cure is laid up as follows: 1) topcoat, 2) decor paper, and 3) impregnated kraft paper that has been B-Staged cured.
  • the three-component laminate is placed between two metal plates, where the plate next to the topcoat layer is often a texture plate that is a stainless-steel plate textured with a wood grain or pattern.
  • This assembly in now ready to be placed in the hot press. Press Process.
  • the laminate assembly is now placed in the hot press where it undergoes a two-step cure procedure.
  • One commonly selected laminate size is 8.5 in. by 11 in. or 21.6 cm. by 28 cm.
  • 1283 psi pressure is applied as the press is heated from 68°C to 115°C, where the overall process takes 13.5 minutes.
  • the temperature ramp from 68°C to 115°C is typically timed to last about 7 minutes, and the temperature ramp is more typically a linear time/temperature relationship.
  • the laminate assembly is held (soaked) at 115°C for the remainder of the 13.5 minutes.
  • the laminate is then removed from the press and cooled, such as between two aluminum plates that act as heat sinks. Samples are cooled until they can be handled by hand without heat gloves.
  • Step 8 After completion of Step 8 the cured laminate is removed from the press and its physical properties are evaluated.
  • the present novel technology relates to a process for extracting and/or depolymerizing lignin as well as fibrous material from rice straw for use in the production of composite boards.
  • a reaction mixture was prepared, consisting of 15 g of rice straw fibers in 300 ml of methanol with 1.5 g of nickel on activated carbon catalyst.
  • the activated nickel catalyst was prepared by incipient wetness impregnation of nickel nitrate hexahydrate solution (2.76 gram salt in 8 mL de-ionized water), on 5 grams of 100 mesh screened activated carbon. This mixture was oven air dried for 24 hours, followed by oven drying at 120oC, and finally treated in 50 standard cubic centimeters flow of nitrogen in a tube furnace, for two hours, with heat ramp of 1 hour.
  • the resulting catalyst sample was cooled in the continuous nitrogen flow to room temperature and stored in glass vials prior to use.
  • the reaction mixture was a fiber slurry that consisted of fibrous chunks settled at the bottom of the slurry.
  • the reaction mixture described above was added at room temperature to a 600 ml stainless steel reactor.
  • the reaction mass was heated over 60 mins to 200°C where the reaction generated a pressure of 40 bar.
  • This reaction was sub-critical, where the critical point for methanol is 239°C at a pressure of 80 bar.
  • the reaction was allowed to proceed for 6 hours.
  • the reaction mass at the end of the reaction had the appearance of dark red slurry, and the viscosity of liquid products was similar to that of methanol, with chunks of fibers settled at the bottom of the reactor, and few lighter chunks floating on liquid surface.
  • the resulting products from the reaction were filtered using a funnel, separating fibrous residue and catalyst from the liquid products. Fibers were air dried and stored in desiccator, whereas the liquid product was stored in rubber stoppered conical flask. . Excess methanol was removed from liquid product, using a rotary evaporator under vacuum, resulting in viscosity of products similar to honey, along with waxy precipitates sticking to the wall of glass vial.
  • reaction scheme described above was repeated 15-20 times to produce several batches of products. On the average 3 g of depolymerized products were obtained per 15 grams of straw fibers charged into the reactor (although this mixture including some quantity of methanol), where 15 g of rice straw contains 2.9 grams of lignin. Qualitative and quantitative analysis of the reaction products in underway, using gas chromatography - mass spectrometry and gas chromatography - flame ionization detection.
  • Materials used in the rice straw fiberboard including a combination of depolymerized rice lignin reactor product, urea, ethylene urea, glyoxal, glutaraldehyde, Polycup, maleic anhydride, succinic anhydride, potassium hydroxide, and a paraffin wax.
  • POLYCUP is a registered trademark of Solenis Technologies, LP, a Delaware Limited Partnership, 3 Beaver Valley Road, Suite 500, Wilmington, DELAWARE, 19803, reg. no. 0863338. Solvents in the process consist of water and methanol. The various components of the resin and associated costs are given in Table 1 for No. 106 resin formulation.
  • the solids content of the liquid phase i.e.
  • the composite boards were made with 11 wt% of the resin package given in Table 1.
  • the 89% of fibers was composed of 1/3 from the fibers used to produce the rice resin and 2/3 from new rice fibers.
  • the total cost of materials is:
  • the total material cost to the board manufacturer using the instant rice resin system is approximately 50% of that of the PMDI formaldehyde free alternative.
  • there is considerable room for optimization such as, for example, reduction of succinic anhydride, better cost on production of rice resin, efficiencies of scale, and the like.
  • the process of first making rice straw fiberboard may be envisioned to begins with making a Resin Cure Package (RCP) and then a Wax + Surface Modification Package (WSMP).
  • RCP Resin Cure Package
  • WSMP Wax + Surface Modification Package
  • Resin Cure Package Solid urea pellets and/or ethylene urea powders are added to a capable vessel.
  • the depolymerized rice lignin product is mixed with methanol solvent to reach 60% “solids” content and this mixture is then added to the vessel and subsequently both glyoxal and glutaraldehyde crosslinkers are added.
  • additional methanol is used to adjust the viscosity of this mixture so as to yield a sprayable mixture, where the amount of methanol added is typically 2-3 ml per ml of the lignin, glyoxal and glutaraldehyde solution.
  • the resulting mixture is subsequently heated in an oven at 85°C for about five minutes.
  • an aqueous solution of maleic anhydride is added to the mixture, followed by the Polycup crosslinking agent.
  • potassium hydroxide is added to bring pH to the neutral condition that is desired for optimal reaction of the Polycup.
  • Wax + Surface Modification Package The WPSMP is made in a separate vial. First 0.1 g of succinic anhydride is dissolved in 0.3 ml of a 1:5 by mass water-methanol mixture with slight heating to facilitate the dissolution of the succinic. Paraffin based wax is then added to this mixture. This mixture already is at or near the proper viscosity for spraying.
  • the first step is to determine the required amount of fiber for the desired density and size of board.
  • the WPSMP is sprayed on the fibers; the wetted fibers are mixed; and the mixture is dried in an oven, for example at 75oC for ten minutes.
  • the optimal moisture content approximately 10 to 12 wt % as may be determined by touch
  • the RCP is sprayed on these fibers; and, the fiber with resin mixture is further agitated to ensure uniform coating of the fibers with the RCP.
  • This RCP-fiber pre-composite is then dried in the oven, for example at 85oC for two minutes, to remove some additional moisture content so that the pre-composite have appropriate tack (i.e. the ability for fibers and resin to form the appropriate shape for the mold).
  • Ideal conditions for pressing are 10-12% moisture content.
  • a formaldehyde-free fiber-based composite board can be produced as described above, wherein the board includes a fiber portion with a weight percentage of 80-95% and a resin portion with a weight percentage of 5-20%.
  • the resin portion further includes a resin cure package and a wax-based surface modification package.
  • the resin cure package defines a mixture of a catalytically depolymerized product of a fiber-based lignin, wherein the catalytically depolymerized product includes at least one compound selected from the group consisting of:
  • the wax-based surface modification package includes at least one wax material with a formula of CnH2n+2, wherein n is between 15 and 40.
  • the fiber is typically a rice-straw- based fiber.
  • the mixture of the resin cure package typically also includes at least one dialdehyde with a formula of OHCfCHsJnCHO, wherein n is between 0 and 6.
  • the mixture of the resin cure package typically incudes an anhydride, and that anhydride is typically maleic anhydride.
  • the mixture of the resin cure package may also include a polyamideepichlorohydrin as a crosslinking agent.
  • the mixture of the resin cure package typically has a pH value of 6.5-7.5.

Abstract

Un panneau composite à base de fibres sans formaldéhyde peut être produit comme décrit ci-dessus, le panneau comprenant une partie fibres présentant un pourcentage en poids compris entre 80 à 95 % et une partie résine présentant un pourcentage en poids compris entre 5 et 20 %. La partie résine comprend en outre un ensemble de durcissement de résine et un ensemble de modification de surface à base de cire. L'ensemble de durcissement de résine définit un mélange d'un produit dépolymérisé par voie catalytique d'une lignine à base de fibres. Le mélange de l'ensemble de durcissement de résine comprend généralement, également, au moins un dialdéhyde de formule OHC(CH2)nCHO, n étant compris entre 0 et 6. Le mélange de l'ensemble de durcissement de résine comprend typiquement un anhydride, et cet anhydride est typiquement de l'anhydride maléique. Le mélange de l'ensemble de durcissement de résine peut également comprendre une polyamide-épichlorhydrine en tant qu'agent de réticulation. Le mélange de l'ensemble de durcissement de résine a typiquement une valeur de pH comprise entre 6,5 et 7,5.
PCT/US2023/060900 2022-01-31 2023-01-19 Production de panneau de fibres de paille de riz à l'aide de lignine à partir d'une paille de riz dépolymérisée par voie catalytique WO2023147247A1 (fr)

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US202263304719P 2022-01-31 2022-01-31
US63/304,719 2022-01-31

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006102543A2 (fr) * 2005-03-24 2006-09-28 Xyleco, Inc. Materiaux fibreux et composites associes
US20130287993A1 (en) * 2012-04-27 2013-10-31 Georgia-Pacific Chemicals Llc Composite products made with binder compositions that include tannins and multifunctional aldehydes
US20140121307A1 (en) * 2012-10-30 2014-05-01 Cyclewood Solutions, Inc. Blending lignin with thermoplastics and a coupling agent or compatibilizer
US20180209070A1 (en) * 2015-07-17 2018-07-26 Changwon National University Industry Academy Cooperation Corps Flame retardant composite fiber and preparation method therefor
US20200061571A1 (en) * 2008-04-30 2020-02-27 Xyleco, Inc. Processing biomass and petroleum containing materials
US20200248047A1 (en) * 2019-01-31 2020-08-06 Eastman Chemical Company Processes for making low volatile tackifier compositions

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006102543A2 (fr) * 2005-03-24 2006-09-28 Xyleco, Inc. Materiaux fibreux et composites associes
US20200061571A1 (en) * 2008-04-30 2020-02-27 Xyleco, Inc. Processing biomass and petroleum containing materials
US20130287993A1 (en) * 2012-04-27 2013-10-31 Georgia-Pacific Chemicals Llc Composite products made with binder compositions that include tannins and multifunctional aldehydes
US20140121307A1 (en) * 2012-10-30 2014-05-01 Cyclewood Solutions, Inc. Blending lignin with thermoplastics and a coupling agent or compatibilizer
US20180209070A1 (en) * 2015-07-17 2018-07-26 Changwon National University Industry Academy Cooperation Corps Flame retardant composite fiber and preparation method therefor
US20200248047A1 (en) * 2019-01-31 2020-08-06 Eastman Chemical Company Processes for making low volatile tackifier compositions

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