WO2009138090A2

WO2009138090A2 - A process for the production of hydrolysed plant material

Info

Publication number: WO2009138090A2
Application number: PCT/DK2009/050110
Authority: WO
Inventors: Jens Østergaard JENSEN
Original assignee: Rådet For Agroindustri
Priority date: 2008-05-14
Filing date: 2009-05-14
Publication date: 2009-11-19
Also published as: WO2009138090A3

Abstract

The invention relates to a process for the production of hydrolyzed lignocellulosic materials. In particular the present invention relates to a process wherein the hydrolyzed lignocellulosic materials are further processed to bio fuels and/or animal or human food. The process involves providing and maintaining one or more reaction zones at sufficient time, temperature, pressure and wavelength of UV-light, for allowing the synthesis of a first product ozone and a second product atomic oxygen from oxygen in a reaction zone by subjecting humidified air to UV- light. Subsequently, the process involves synthesis of a third product hydroxide from water and the synthesis product ozone in a reaction zone by subjecting said ozone and water to UV-light, thereby obtaining a mixture comprising atomic oxygen and hydroxide. Finally, the process involves impregnating the plant material with said mixture.

Description

A PROCESS FOR THE PRODUCTION OF HYDROLYSED PLANT MATERIAL

TECHNICAL FIELD OF THE INVENTION

The present invention relates to a process for the production of hydrolyzed plant materials, also named lignocellulosic materials. In particular the present invention relates to a process wherein the hydrolyzed lignocellulosic materials are further processed to bio fuels and/or animal or human food.

BACKGROUND OF THE INVENTION

Globally, there is a lack of CO₂ neutral products for the manufacture of energy sources. In recent years, the lack of products has been solved by using agricultural products which previously have been used as foodstuffs and animal feed. This concerns in particular grains like maize, wheat, barley, rye, and triticale. Though these products are suited for the purpose, the current prices for these crops have increased the production price for these CO2 neutral products.

One way to avoid the problems of using foodstuff and animal feed, but still use CO2 neutral components, for the production of bio-fuels, is to use wood waste materials, straws, wood pulp, dry matter from organic fertilizers, and other waste products containing woody material. One problem concerning these products is their hardy structure, which makes them resistant towards microbiological and biological processes. These processes are necessary for the manufacture of liquid fuels (e.g. bio-ethanol) and gas fuels (e.g. bio-gas).

Woody plant material typically is composed of 40-55% cellulose, 24-40% hemicelluloses, and 18-28% lignin. Cellulose is a polymer of D-glucose with beta linkages between each of about 10,000 glucose units. Hemicellulose is a polymer of sugars, primarily D-xylose with other pentoses and some hexoses with beta linkages. Lignin, a complex random polyphenols, coats the bundles of cellulose fibers and binds them together to provide the wood with rigidity and resistance to breakdown. Cellulose, hemicelluloses and lignin make up 96-98% of the wood dry weight. Methods already exist for the opening of the hardy structures, e.g. pressure- cooking at 220⁰C with or without the addition of chemicals to improve the reactions such as NaOH, H₂SO₄, or SO₂. However, these methods are very expensive and in some instances environmentally hazardous.

WO03/042451 relates to a process for the production of activated fibres or particles having self-binding properties comprising the steps of treating fibres or particles of lignocellulose containing material by contacting them with an oxidant during a time sufficient for the formation of water soluble reaction products with binding properties and retaining at least a significant part of said water soluble reaction products with the treated fibres or particles.

US3212932 describes a hydrolysis process in which lignocellulose is treated with mineral acid and subjected to high pressure steam (100-700 p.s.i.g.).

US4529699 describes a process for obtaining ethanol by continuous acid hydrolysis of cellulosic material under high pressure and heat (160⁰C to 250⁰C).

Both US3212932 and US4529699 describe methods wherein an acid is used. One disadvantage of these systems is that you have to remove the surplus of acids subsequent to the described processes, this can be both time- and labour- consuming and is also environmentally hazardous.

SUMMARY OF THE INVENTION

One object of the invention may be to provide a process to prepare lignocellulotic materials for fermentations processes without having a large volume of hazardous waste material (e.g. acids or bases) subsequent to the impregnation process.

This object may be obtained by one aspect of the invention, said aspect relating to a process for the production of hydrolyzed plant material, said process comprising the steps of a) Providing and maintaining one or more reaction zones at sufficient time, temperature, pressure and wavelength of UV-light, for allowing b) the synthesis of a first product ozone and a second product atomic oxygen from oxygen in a reaction zone by subjecting humidified air to UV-light, and c) the synthesis of a third product hydroxide from water and the synthesis product ozone, according to step b), in a reaction zone by subjecting said ozone and water to UV-light, thereby obtaining a mixture comprising atomic oxygen and hydroxide and d) impregnating the plant material with said mixture.

This object may be also obtained by another aspect of the invention, said aspect relating to a process for the production of hydrolyzed plant material, said process comprising the steps of a) providing and maintaining one or more reaction zones at sufficient time, temperature, pressure and wavelength of UV-light, for allowing b) the synthesis of a first product, ozone, and a second product, atomic oxygen, from oxygen in a reaction zone by subjecting humidified air to

UV-light, and c) the synthesis of a third product, hydroxide, from hydrogen peroxide in a reaction zone being subjected to compression-relaxation, d) obtaining a mixture comprising atomic oxygen and hydroxide, and e) impregnating the plant material with said mixture.

It is to be understood that the teaching of the present invention also incorporates reaction products, by-products, degradation products and intermediates of the process for generating hydroxide (OH^").

Alternatively to or additionally to atomic oxygen O, superoxide (O₂ ^") such as but not limited to O₃, O₃ ^", O₂, O₂ ^", HO₂, HO₂ ^", HO₄, OH, HO₃, and O₂ ^2" may be applied in the process according to the invention.

Thus, the invention applies in general to intermediate products resulting from ozone. Furthermore, it is also to be understood that the teaching of the invention includes radicals generated by the process or generated from by-products, degradation products and intermediates of the process. These products may arise both before, during and after impregnation is performed, whether the impregnation is in a gaseous form or in an aqueous solution.

One of the advantages of the process according to the one aspect of the invention may be that OH^" and O are very strong oxidants. Another advantage of the process according to the one aspect of the invention may be that OH^" and O produced in this way are cheaper than e.g. chemically synthesized NaOH. An even further advantage of the process according to the one aspect of the invention may be that the environmental considerations following the process is much easier to overcome, since additional OH^" and O are short lived and will therefore be transformed into H₂O.

The amount of steam should theoretically be 1.125 times higher than the amount of ozone (O3). Surprisingly, experiments have shown that the amount of steam should be above 1.125 times higher than the amount of ozone (O3).

The described process prepares plant material for several purposes e.g. for the production of bio-fuel and animal food and/or human food. Therefore, in one embodiment of the invention, the invention relates to a process, wherein the plant material is used in fermentation processes to biomass fuel, ethanol and bio gas, and animal food and/or human food.

In a possible embodiment concerning animal food and/or human food, the invention relates to a process wherein plant material is used for ruminants and non-ruminants. In yet another embodiment the invention relates to a process, wherein the processed plant material is used as paper pulp.

The process can be performed using different temperatures, different pressures, and OH^" and O can be generated using different wavelengths of light.

Furthermore, the time each step is performed is important. Most likely, the optimal combination depends on the type of plant material which is being used. Therefore, in another embodiment according to the one aspect of the invention, the invention relates to a process for the production of hydrolyzed plant material, wherein the temperature in step b) is 0⁰C to 100⁰C, such as 0⁰C to 80⁰C, such as 5°C to 50⁰C, or such as 10⁰C to 30⁰C.

In another embodiment or the same embodiment according to the one aspect of the invention, the invention relates to a process for the production of hydrolyzed plant material, wherein the pressure in step b) is 0-200 bar, such as 0-100 bar, such as 0-50 bar, such as 0-20 bar, such as 0-10 bar, such as 0-5 bar, is 0-2 bar, or such as 1-2 bar.

In another embodiment or the same embodiment according to the one aspect of the invention, the invention relates to a process for the production of hydrolyzed plant material, wherein the wavelength of light in step b) is 1000-2300 A, such as 1500-2300 A, such as 1500-2100 A, such as 1700-2000 A, such as 1800-1900 A, such as 1849 A.

In another embodiment or the same embodiment according to the one aspect of the invention, the invention relates to a process, wherein the temperature in step c) is 0⁰C to 100⁰C, such as 0⁰C to 80⁰C, such as 5°C to 50⁰C, or such as 10⁰C to 30⁰C.

In a another embodiment or the same embodiment according to the one aspect of the invention, the invention relates to a process, wherein the pressure in step c) is 0-200 bar, such as 0-100 bar, such as 0-50 bar, such as 0-20 bar, such as 0-10 bar, such as 0-5 bar, is 0-2 bar, such as 2 bar, such as 1 bar, or such as 0 bar.

In a another embodiment or the same embodiment according to the one aspect of the invention, the invention relates to a process, wherein the wavelength of light in step c) is 2000-4000 A, such as 2000-3000 A, such as 2200-2800 A, such as 2400-2600 A, or such as 2540 A.

Another important parameter is the amount of OH^" and O compared to the amount and type of plant material, these parameters can be controlled using equipment controlling e.g. the redox potential. In a third embodiment of the invention the amount of OH- is 0.43 g per 10 g dried plant material.

Impregnating the plant material with the synthesized OH^" and O can be performed in several ways.

One way is to perform the impregnation in an aqueous solution. Therefore, in yet another embodiment of the invention, the invention relates to a process for the production of hydrolyzed plant material, wherein the impregnation is performed in an aqueous solution.

Alternatively, the impregnation is performed in air by blowing it through the plant material. Therefore in yet another embodiment of the invention, the invention relates to a process for the production of hydrolyzed plant material, wherein the impregnation is performed by blowing O and OH^" through the material as a gas.

It could also be an advantage to steam the plant material subsequent to the impregnation. In this way the material is further prepared for subsequent fermentation processes. Thus, in yet another embodiment of the invention, the invention relates to a process for the production of hydrolyzed plant material, wherein the plant material is steamed subsequently to the impregnation steps.

During the steaming process time, temperature and pressure are important parameters where optimal parameters depend on the type of plant material.

Thus, in yet another embodiment of the invention, the invention relates to a process for the production of hydrolyzed plant material, wherein the plant material is steamed subsequently to the impregnation steps at a temperature of 100-500⁰C, such as 100-300⁰C, such as 100-200⁰C, such as 100-150⁰C, or such as 100-120⁰C and wherein the pressure during steaming is 0-200 bar, such as 0- 100 bar, such as 0-50 bar, such as 0-20 bar, such as 0-10 bar, such as 0-5 bar, is 0-2 bar, or such as 1-2 bar, and wherein, the time of steaming is 5-240 min, such as 5-120 min, such as 5-6 min, such as 5-30 min, such as 15-30 min. In the present context, one advantage of steaming the plant material is that steam is relatively more reactive towards further processing of the material than water as a liquid, derived from water or from an aqueous solution.

Another way to prepare the plant material for subsequent fermentation processes could be by cracking open the plant material by one or more frost bursts. The concept is that the physical internal structures of the bio-mass are cracked opened by the frost burst. This would be a very cheap way to prepare plant materials for subsequent fermentation processes. Furthermore, the freeze-thaw steps could be repeated one ore more times to further increase the opening of the structures. Thus, in a second aspect of the invention, the invention relates to

A process for the production of degraded plant material by one or more frost bursts, said method comprising the steps of a) providing and maintaining one or more reaction zones at sufficient time and temperature, and b) soaking said plant material in an aqueous solution c) incubating said plant material below 0⁰C, thereby inducing a frost burst d) transfer said plant material to temperatures above 0⁰C e) optionally, repeating step a) to d).

In one embodiment of the invention, and according to another aspect of the invention, the invention relates to a process, wherein said degraded plant material is used in fermentation processes to biomass full, ethanol, biogas, or for animal food and/or human food.

It is also likely that a combination of frost bursts and oxidants, e.g. OH^" and O, gives an additional effect, thereby achieving an even better result. Thus, in a third aspect of the invention, the invention relates to a process for the production of degraded plant material by one or more frost bursts, wherein said process is performed preliminary to said process for the production of hydrolyzed plant material. Since the process of inducing frost bursts depends on both temperature and time these parameters are important to optimize. Furthermore, the optimal parameters are likely to differ depending on the type of used plant material.

Thus, in another embodiment of the invention, the invention relates to a process for the production of degraded plant material by frost bursts, wherein said temperatures below 0⁰C is -1°C to -273°C, such as -1°C to -100⁰C, such as -1°C to -80⁰C, such as -1°C to -50⁰C, or such as -1°C to -25°C.

according to the other aspect of the invention, the invention relates to a process, wherein said incubation time below 0⁰C is 5 minutes to 24 hours, such as 5 minutes to 16 hours, such as 5 minutes to 8 hours, such as 5 minutes to 4 hours, such as 15 minutes to 2 hours, or such as 30 minutes to 1 hour.

DEFINITIONS

Lignocellulosic material is defined as originating from the not limiting list of hardwood, softwood, recycled paper, wood waste materials, straws, wood pulp, dry matter from organic fertilizers, grass, and other waste products containing woody material, etc.

Hydrolysis is defined as a chemical reaction or process in which a chemical compound is broken down by reaction with water. It is to be understood that the teaching of the invention also incorporates that hydrolysis can be initiated by ozone and derivatives of ozone such as but not limited to O3, O3^", O2, O₂ ^", HO2, HO₂ ^", HO₄, OH, HO₃, H₂O₂, O₂ ^2", or OH^".

BRIEF DESCRIPTION OF THE FIGURES

The invention will hereafter be described with reference to the drawings, where

Fig. 1 is a flowchart for processing of lignocellulosic material using OH^" and O in a gas phase for impregnation,

Fig. 2 is a flowchart for processing of lignocellulotic material from spruce using OH^" and O in a water phase for impregnation, Fig. 3 is a flowchart for processing of lignocellulosic material using frost bursts, Fig. 4 is a flowchart for processing of lignocellulosic material using a combination of frost bursts and OH^" and O in a gas phase for impregnation, and Fig. 5 is a flowchart for processing of lignocellulotic material using a combination of frost bursts and OH^" and O in a water phase for impregnation.

DETAILED DESCRIPTION OF AN EMBODIMENT OF THE INVENTION

Fig. 1 is a flowchart for the processing of a plant material, being referred to as a lignocellulotic material, using OH^" and O in a gas phase for impregnation.

In step 101 the lignocellolosic material is prepared for the processing, this could be by e.g. grinding. In step 102 the material is steeped in e.g. water, and subsequently excess aqueous solution is removed through step 112.

In step Ili a compressor provides the necessary pressure for conversion of O₂ to O₃ (ozone) and atomic oxygen O catalysed by UV-radiation in a first reaction chamber 110 and the necessary pressure for the transfer into a second reaction chamber 108, wherein O₃ reacts with H₂O to form OH^", catalysed by UV-radiation.

Step 111 may in the alternative involve a compression-relaxation cycle. Initially, the lignocellolosic material may be subjected to hydrogen peroxide, and during the alternative step 111, involving compression-relaxation, hydroxide is formed.

Thus, in the alternative, in step Ili a compressor provides the necessary pressure for conversion of O₂ to O₃ (ozone) and atomic oxygen O catalysed by UV-radiation in a first reaction chamber 110 and the necessary pressure for the transfer into a second reaction chamber 108, wherein hydrogen peroxide is present and where compression-relaxation takes place to form OH^".

As the lignocellolosic material relaxes, it decompresses and absorb the mixture containing hydroxide. The compression-relaxation may be the step of impregnation or may be part of an impregnation. After the lignocellolosic material has absorbed the mixture including the hydroxide, the material can be removed from the mixture and placed in a storage vessel for subsequent use. In a first reactor 103 the synthesized atomic oxygen O, hydroxide and surplus reagents are blown through the material under sufficient pressure to hydrolyze the material. The material is transferred to a second reactor 104, where the material is steamed (steam supplier, 109) for a sufficient time, using a sufficient pressure and temperature. In step 105 and step 106 the material is washed and subsequently dried on a filter in step 107. Step 113 and step 114 are exits for surplus reagents.

Fig. 2 shows a flowchart for the processing of lignocellulosic material from spruce using OH^" and O in an aqueous solution.

In step 201 the lignocellolosic material is prepared for the processing, this could be by e.g. grinding. In step 202 the material is steeped in e.g. water, and subsequently excess aqueous solution is removed through step 212.

A compressor in step 211 provides the necessary pressure for conversion of O₂ to O₃ (ozone) and atomic oxygen O catalysed by UV-radiation in a first reaction chamber 210 and for the transfer into a second reaction chamber 208, wherein O₃ reacts with H₂O to form OH^", catalysed by UV-radiation.

In a third reactor reactor 215 the material is suspended in an aqueous solution e.g. H₂O and subsequently the synthesized O, OH^" and surplus reagents are blown into the suspension under sufficient pressure to hydrolyze the material. In step 216 the fluid can be removed e.g. through a filter, to preserve all the non- dissolved material.

The material is transferred to a second reactor, step 204, where the material is steamed (steam supplier, 209) for a sufficient time, using a sufficient pressure and temperature. In step 205 and step 206 the material is washed and subsequently dried on a filter in step 207. Step 213 and step 214 are exits for surplus reagents.

Fig. 3 shows a flowchart for the processing of lignocellulotic material using frost bursts. In step 301 the lignocellolotic material is prepared for the processing, this could be by e.g. grinding. In step 302 the material is steeped in e.g. water, and subsequently excess aqueous solution is removed through step 312.

In step 317 the material is positioned in a cooling chamber. In step 318 the material is thawed again. In step 305 and step 306 the material is washed and subsequently dried on a filter in step 307.

Fig. 4 shows a flowchart for the processing of lignocellulosic material using a combination of frost bursts and OH^" and O in a gas phase for impregnation.

In step 401 the lignocellolosic material is prepared for the processing, this could be by e.g. grinding. In step 402 the material is steeped in e.g. water, and subsequently excess aqueous solution is removed through step 412.

In step 417 the material is positioned in a cooling chamber. In step 418 the material is thawed again. A compressor in step 411 provides the necessary pressure for conversion of O₂ to O₃ (ozone) and atomic oxygen O catalysed by UV-radiation in a first reaction chamber 410 and for the transfer into a second reaction chamber 408, wherein O₃ reacts with H₂O to form OH^", catalysed by UV- radiation.

In a first reactor 403 the synthesized atomic oxygen O, OH^" and surplus reagents are blown through the material under sufficient pressure to hydrolyze the material. The material is transferred to a second reactor 404, where the material is steamed (steam supplier, 409) for a sufficient time, using a sufficient pressure and temperature. In step 405 and step 406 the material is washed and subsequently dried on a filter in step 407. Step 413 and step 414 are exits for surplus reagents.

Fig. 5 shows a flowchart for the processing of lignocellulosic material using a combination of frost bursts and impregnation with OH^" and O in water. In step 501 the lignocellulosic material is prepared for the processing, this could be by e.g. grinding. In step 502 the material is steeped in e.g. water, and subsequently excess aqueous solution is removed through step 512.

In step 517 the material is positioned in a cooling chamber. In step 518 the material is thawed again. A compressor in step 411 provides the necessary pressure for conversion of O₂ to O3 (ozone) and atomic oxygen O catalysed by UV-radiation in a first reaction chamber 510 and for the transfer into a second reaction chamber 508, wherein O₃ reacts with H₂O to form OH^", catalysed by L)V- radiation.

In a third reactor 515 the material is suspended in an aqueous solution e.g. H₂O and subsequently the synthesized O, OH^" and surplus reagents are blown into the suspension under sufficient pressure to hydrolyze the material. In step 516 the fluid can be removed e.g. through a filter, to preserve all the non-dissolved material.

The material is transferred to a second reactor 504, where the material is steamed (steam supplier, 509) for a sufficient time, using a sufficient pressure and temperature. In step 505 and step 506 the material is washed and subsequently dried on a filter in step 507. Step 513 and step 514 are exits for surplus reagents.

It should be noted that embodiments and features described in the context of one of the aspects of the present invention also apply to the other aspects of the invention. All patent and non-patent references cited in the present application, are hereby incorporated by reference in their entirety.

The invention will be described in further detail in the following non-limiting examples: EXAMPLES

In all examples the success rate is determined using the following equations:

Materials are positioned at 105⁰C for 2 hours. The weight of the material before and after drying is determined. The dry matter content is abbreviated T. S.

(vtm / vwm) *100 = T.S. % where vtm: Weight of material after drying. vwm: Weight of wet material before drying. T.S. %: Percentage of dry matter in the material.

The amount of lignocellulose in dried spruce: Ash 4%

Hemicellulose 26% Lignin 29% Cellulose 41%

The amount of lignocellulose in dried straws:

Ash 11%

Hemicellulose 29%

Lignin 23%

Cellulose 37%

Since the temperature by steaming at 120⁰C no loss of dry matter to the air is expected. Dry matter is expected to be transferred into the water phase.

Principle of determining the amount of dry matter dissolved in to the water phase: 1. The bio mass T.S. is dried in a drying chamber

2. The weight is determined

3. The described processes are performed

4. The solid fraction is filtered away and T.S. is dried in a drying chamber

5. The weight of the solid fraction is determined. Scale for water-solubility: Ash > Hemicellulose > Lignin > Cellulose

Equations to determine the amount of dissolved dry matter in the water.

vtmi - vtmu = vtm

((vtmi - vtmu) :vtmi) *100 = dissolved dry matter in the fluid (%).

vtmi: Weight of dry matter going in to the process, vtmu: Weight of dry matter coming out of the process. vtm: Amount of dissolved dry matter.

Example 1

Method for synthesis of air comprising OH- and O₂ ^" used in example 2-3 and 5-6.

1. Air comprising a relatively high humidity is pressed in a reaction chamber at bar

2. UV-radiation of 1849A catalyzes the reaction: 5O₂ + energy => 2O3 + 2O₂ ^"

3. in the same or another reaction chamber L)V radiation of 254θA catalyzes the reaction O3 + H₂O => 6OH^" from product of step 2.

4. O₂ ^" and OH^" are present in the same reactive mixture of air.

Example 2 - See also Fig. 1

Impregnation of sawdust from spruce using OH^" and O2^" in a gas phase.

1. Sawdust (particle size 3-7 mm) is dried for 2 hours at 105⁰C.

2. 10 g of dried material is steeped (10 g to 200 ml water) for 2 hours, of which 15 minutes are under steering.

3. The material is put on a sieve (pore size 0.5 mm) for 30 minutes to remove excess of water.

4. Air comprising OH^" and O2^" is blown through the material at two bar for 30 min. The reaction takes place in reactor 1. 5. The material is steamed at 120⁰C and 2 bar for 30 min.

6. The material is washed under stirring for 3x 15 minutes in 600 ml water (6⁰C).

7. The material is placed on a filter and washed in running cold water.

8. The material is pressed.

9. The material is dried for 2 hours at 105⁰C. 10. The weight of the material is determined. A success rate, following the equation to determine the amount of dissolved dry matter in the water, of 38% has been achieved.

Example 3 - See also Fig. 2

Impregnation of sawdust from spruce using OH^" and O₂ ^" in water.

1. Sawdust (particle size 3-7 mm) is dried for 2 hours at 105⁰C.

2. 10 g of dried material is steeped (10 g to 200 ml water) for 2 hours, of which 15 minutes are under steering. 3. The material is put on a sieve (pore size 0.5 mm) for 30 min.

4. The material is incubated in water under stirring (10 g material for 1 L water), and air comprising OH^" and O2^" is blown into the suspension for 30 min. The reaction takes place in reactor 3.

5. The fluid is removed from the material by using a filter. 6. The material is steamed at 120⁰C and 2 bar for 30 min. The reaction takes place in reaction chamber 2.

7. The material is washed under stirring for 3x 15 minutes in 600 ml water (6⁰C).

8. The material is placed on a filter and washed in running cold water. 9. The material is pressed.

10. The material is dried for 2 hours at 105⁰C.

11. The weight of the material is determined.

A success rate, following the equation to determine the amount of dissolved dry matter in the water, of 43% has been achieved.

Example 4 - See also Fig. 3

Opening of sawdust from spruce using frost bursts. 1. Sawdust (particle size 3-7 mm) is dried for 2 hours at 105⁰C. 2. 10 g of dried material is steeped (10 g to 200 ml water) for 2 hours, of which 15 minutes are under steering.

3. The material is put on a sieve (pore size 0.5 mm) for 30 min.

4. The material is placed at -21.5°C for 1 hour.

5. The material is thawed. 6. The material is washed under stirring for 3x 15 minutes in 600 ml water (6°C).

7. The material is placed on a filter and washed in running cold water.

8. The material is pressed. 9. The material is dried for 2 hours at 105⁰C. 10. The weight of the material is determined.

A success rate, following the equation to determine the amount of dissolved dry matter in the water, of 31% has been achieved.

Example 5 - See also Fig. 4

Opening of sawdust from spruce using frost bursts and impregnation with air comprising OH^" and O₂ ^". The process is performed combining example 4 with 2.

Example 6 - See also Fig. 5

Opening of sawdust from spruce using frost bursts and impregnation with OH^" and O2^" in water. The process is performed combining example 4 with 3.

Claims

2. A process for the production of hydrolyzed plant material, said process comprising the steps of a) providing and maintaining one or more reaction zones at sufficient time, temperature, pressure and wavelength of UV-light, for allowing b) the synthesis of a first product, ozone, and a second product, atomic oxygen, from oxygen in a reaction zone by subjecting humidified air to UV-light, and c) the synthesis of a third product, hydroxide, from water and the synthesis product, ozone, according to step b) in a reaction zone by d) subjecting said ozone and water to UV-light, thereby obtaining a mixture comprising atomic oxygen and hydroxide, and e) impregnating the plant material with said mixture.

3. A process for the production of hydrolyzed plant material, said process comprising the steps of a) providing and maintaining one or more reaction zones at sufficient time, temperature, pressure and wavelength of UV-light, for allowing b) the synthesis of a first product, ozone, and a second product, atomic oxygen, from oxygen in a reaction zone by subjecting humidified air to UV-light, and c) the synthesis of a third product, hydroxide, from hydrogen peroxide in a reaction zone being subjected to compression-relaxation, d) obtaining a mixture comprising atomic oxygen and hydroxide, and e) impregnating the plant material with said mixture.

4. A process according to claim 1 or claim 2, wherein said plant material is used in fermentation processes to biomass fuel, ethanol and bio gas, and for the production of animal food and/or human food.

5. A process according to claims 1 and 2, wherein the temperature in step b) is 0⁰C to 100⁰C, such as 0⁰C to 80⁰C, such as 5°C to 50⁰C, or such as 10⁰C to 30⁰C.

6. A process according to any of claims 1 to 4, wherein the pressure in step b) is 0-200 bar, such as 0-100 bar, such as 0-50 bar, such as 0-20 bar, such as 0- 10 bar, such as 0-5 bar, is 0-2 bar, or such as 1-2 bar.

7. A process according to any of claims 1 to 5, wherein the wavelength of light in step b) is 1000-2300 A, such as 1500-2300 A, such as 1500-2100 A, such as 1700-2000 A, such as 1800-1900 A, such as 1849 A.

8. A process according to any of claims 1 to 6, wherein the temperature in step c) is 0⁰C to 100⁰C, such as 0⁰C to 80⁰C, such as 5°C to 50⁰C, or such as 10⁰C to 30⁰C.

9. A process according to any of claims 1 to 7, wherein the pressure in step c) is 0-200 bar, such as 0-100 bar, such as 0-50 bar, such as 0-20 bar, such as 0-

10 bar, such as 0-5 bar, is 0-2 bar, such as 2 bar, such as 1 bar, or such as 0 bar.

10. A process according to any of claims 1 to 8, wherein the wavelength of light i in step c) is 2000-4000 A, such as 2000-3000 A, such as 2200-2800 A, such as

2400-2600 A, or such as 2540 A.

11. A process according to any of claim 1-9, said process comprising an initial step, preferably a step initial to step a), said initial step comprising i) soaking said plant material in an aqueous solution ii) incubating said plant material below 0⁰C, thereby inducing a frost burst iii) transfer said plant material to temperatures above 0⁰C iiii) optionally, repeating step i) to iii)

12. A process according to any of claims 1 to 10, wherein said impregnation in step d) is performed by blowing said OH^" and O through said plant material as a gas.

13. A process according to any of claims 1 to 10, wherein said impregnation in step d) is performed by blowing said OH^" and O through said plant material in an aqueous solution.

14. A process according to claim 11 or 12, wherein said impregnation is followed by a step, wherein said plant material is steamed.

15. A process according to claim 13, wherein the plant material is steamed subsequently to the impregnation steps at a temperature of 100-500⁰C, such as 100-300⁰C, such as 100-200⁰C, such as 100-150⁰C, or such as 100- 120⁰C.

16. A process according to claim 13 or 14, wherein the pressure during steaming is 0-200 bar, such as 0-100 bar, such as 0-50 bar, such as 0-20 bar, such as 0-10 bar, such as 0-5 bar, is 0-2 bar, or such as 1-2 bar.

17. A process according to any of claims 13-15, wherein, the time of steaming is 5-240 min, such as 5-120 min, such as 5-6 min, such as 5-30 min, such as 15-30 min.

18. A process for the production of degraded plant material by one or more frost bursts, said method comprising the steps of a) Providing and maintaining one or more reaction zones at sufficient time and temperature, and b) soaking said plant material in an aqueous solution c) incubating said plant material below 0⁰C, thereby inducing a frost burst d) transfer said plant material to temperatures above 0⁰C e) optionally, repeating step a) to d)

19. A process according to claim 17, wherein said hydrolyzed plant material is used in fermentation processes to biomass full, ethanol, biogas, or for the production of animal food and/or human food and/or human food.

20. A process according to claim 17 or 18, wherein said process is performed preliminary to any of claims 1-14.

21. A process according to any of claims 17-19, wherein said temperatures below 0⁰C is -1°C to -273°C, such as -1°C to -100⁰C, , such as -1°C to -80⁰C, such as -1°C to -50⁰C, or such as -1°C to -25°C.

22. A process according to any of claims 17-20, wherein said incubation time below 0⁰C is 5 minutes to 24 hours, such as 5 minutes to 16 hours, such as 5 minutes to 8 hours, such as 5 minutes to 4 hours, such as 15 minutes to 2 hours, or such as 30 minutes to 1 hour.