阅读说明：本技术 由木质纤维素生物质生产纸浆的低能量生产方法 (Low energy production process for producing pulp from lignocellulosic biomass ) 是由 M·戴尔马 于 2018-12-13 设计创作，主要内容包括：本发明提供由木质纤维素生物质生产纸浆的低能量生产方法,所述方法包括以下逐次步骤：a)通过在仅由水和甲酸组成的混合物存在下,在环境温度和混合物在大气压下的回流温度之间的受控反应温度条件下,优选在80℃-110℃下,将至少一种固态木质纤维素原料置于大气压下,其中所述至少一种固体木质纤维素原料/液体混合物的重量比为1/1-1/15,并且持续一段确定的反应时间,以从木质纤维素生物质提取木质素和半纤维素；b)在大气压和所述反应温度下,将构成原纸浆的固体级分与有机相分离,所述有机相在溶液中至少含有起始甲酸和水的混合物、可溶单糖和聚合糖、木质素。(The present invention provides a low energy production process for producing pulp from lignocellulosic biomass, said process comprising the successive steps of: a) extracting lignin and hemicellulose from lignocellulosic biomass by subjecting at least one solid lignocellulosic feedstock to atmospheric pressure in the presence of a mixture consisting only of water and formic acid, under controlled reaction temperature conditions between ambient temperature and the reflux temperature of the mixture at atmospheric pressure, preferably at 80 ℃ to 110 ℃, wherein the weight ratio of the at least one solid lignocellulosic feedstock/liquid mixture is between 1/1 and 1/15, and for a determined reaction time; b) at atmospheric pressure and at the reaction temperature, the solid fraction constituting the raw pulp is separated from the organic phase containing in solution at least the mixture of starting formic acid and water, soluble monosaccharides and polymeric sugars, lignin.)

1. A low energy production process for producing pulp from lignocellulosic biomass, said process comprising the successive steps of:

a) extracting lignin and hemicellulose from lignocellulosic biomass by subjecting at least one solid lignocellulosic feedstock to atmospheric pressure in the presence of a mixture consisting only of water and formic acid, under controlled reaction temperature conditions between ambient temperature and the reflux temperature of the mixture at atmospheric pressure, preferably at 80 ℃ to 110 ℃, wherein the weight ratio of the at least one solid lignocellulosic feedstock/liquid mixture is between 1/1 and 1/15, and for a determined reaction time;

b) at atmospheric pressure and at the reaction temperature, the solid fraction constituting the raw pulp is separated from the organic phase containing in solution at least the mixture of starting formic acid and water, soluble monosaccharides and polymeric sugars, lignin.

2. The low energy pulp production process of claim 1, comprising the additional steps of:

c) washing the raw pulp.

3. Low energy pulp production process according to claim 2, wherein the raw pulp is washed successively in the following two steps:

-c1) at room temperature, using a solution consisting of water and formic acid, the concentration of formic acid in said solution being between 80% and 100%; and

-c2) with hot water at 40 ℃ to 60 ℃.

4. Low energy pulp production process according to claim 1, wherein the concentration of formic acid in the mixture is between 50% and 100%, preferably between 80% and 90%.

5. The low energy pulp production process of claim 1, wherein the at least one solid lignocellulosic feedstock/liquid mixture is in a weight ratio of from 1/4 to 1/6.

6. Low energy pulp production process according to claim 1, wherein the reaction temperature is equal to 85 ℃.

7. The low energy pulp production process of claim 1, wherein the organic phase comprises in solution at least a mixture of starting formic acid and water, soluble and polymeric monosaccharides and sugars derived from plant material, lignin and acetic acid.

8. Low energy pulp production process according to claim 1, wherein the b) separation step is a centrifugation step or a filtration step at atmospheric pressure and the reaction temperature.

9. Low energy pulp production process according to claim 3, wherein a centrifugation step is performed at ambient temperature between the first washing step c1) with a solution consisting of water and formic acid and the second washing step c2) with hot water.

10. Low energy pulp production method according to claim 3, wherein after the second washing step c2) with hot water a centrifugation step is performed.

11. Low energy pulp production method according to claim 1, wherein the determined reaction time is dependent on the measured or determined kappa number of the pulp.

12. The low energy pulp production process of claim 11, wherein the determined reaction time is stopped when the kappa number of the pulp reaches a stable value depending on the properties of the at least one lignocellulosic feedstock.

13. The low energy pulp production process according to claim 12, comprising the steps of:

periodically measuring or determining the kappa number of the pulp during the determined reaction time to identify the stability of the kappa number of the pulp.

14. Low energy pulp production method according to claim 13, wherein the step of periodically measuring or determining the kappa number of the pulp consists in measuring or determining the kappa number every ten minutes.

15. Low energy pulp production method according to any of the claims 12-14, wherein the determined reaction time is stopped when the kappa number of the pulp stabilizes after at least three consecutive measurements or determinations of the kappa number of the pulp.

Technical Field

The present invention relates to a low energy production process for producing pulp starting from lignocellulosic biomass.

Background

For example, when considering lignocellulosic residues in the production of logging and palm or palm trees, or in the production of large scale straw and cereal straw or in bagasse in the sugar industry, the lignocellulosic plant material used with the extraction/production process for producing cellulose/pulp can be used in large quantities.

In both cases, the process of the invention can be carried out using very abundant raw materials, which, to date, have found no useful industrial use and have not been able to produce energy under environmentally acceptable conditions, for example for "in situ" power generation.

For example, lignocellulosic plant material for extraction/production processes for producing cellulose/pulp can also be obtained in large quantities from wood.

In a manufacturing facility, wood chips or other plant fiber sources are converted into thick fiber boards, which, when the pulp and paper mills are not integrated, can be transported to the paper mill for further processing. Pulp can be manufactured using mechanical, semi-chemical or full-chemical processes (Kraft and sulfite processes). The finished product may be bleached or unbleached, depending on the customer requirements.

Wood and other plant materials used for pulping contain three main components (in addition to water): cellulose fibers (used in papermaking), lignin (a phenolic oligomer that binds cellulose fibers together), and hemicellulose (a shorter branched carbohydrate polymer). The purpose of pulping is to disrupt the overall structure of the fiber source, chopping the fiber source (stems or other plant parts) into constituent fibers.

Chemical pulping accomplishes this by degrading lignin and hemicellulose to water-soluble small molecules that can be washed off cellulose fibers without depolymerizing the cellulose fibers. The chemical and thermal treatments reduce the energy subsequently required for mechanical treatment and also reduce the amount of strength loss suffered by the fibers.

The main industrial chemical extraction process for producing pulp from lignocellulosic plant material is the "Kraft" process followed by the "sulfite process".

The Kraft process (also known as Kraft pulping or Kraft process) is a process for converting wood into wood pulp, which consists of almost pure cellulose fibers and which is the main constituent of paper. The Kraft process requires the use of hot water, sodium hydroxide (NaOH) and sodium sulfide (Na)₂S) (referred to as "white liquor") treats the wood chips, which breaks bonds connecting lignin, hemicellulose and cellulose. The Kraft process technology requires several steps, including mechanical and chemical steps.

In the so-called "cooking step", the chips are cooked in a pressurized vessel called a digester. Typically, delignification takes several hours at 170 ℃ to 176 ℃. Under these conditions, lignin and hemicellulose are degraded, producing fragments that are soluble in strongly alkaline liquids. The solid pulp (about 50 wt% of dry wood chips) was collected and washed. In this regard, the pulp is referred to as brown stock due to its color. The combined liquor, called "black liquor", contains lignin fragments, carbohydrates from the breakdown of hemicellulose, sodium carbonate, sodium sulfate and other inorganic salts.

Various by-products of the Kraft process, including hydrogen sulfide, methyl mercaptan, dimethyl sulfide, dimethyl disulfide and other volatile sulfur compounds, are responsible for the malodorous air emissions at the pulp mill using the Kraft process.

Thus, in some cases, the Kraft process releases odorous products and in some cases generates large amounts of liquid waste.

In addition, the Kraft process consumes a lot of energy, including energy consumed in additional steps of screening, washing and bleaching the pulp.

The "organic solvent" process has also been proposed in industrial papermaking processes. The organosolv process is a pulping technique that uses an organosolv to dissolve lignin and hemicellulose. In the context of pulping and papermaking, as well as biorefinery, the subsequent conversion of cellulose to fuel ethanol has been considered. The method is an environment-friendly alternative method for Kraft pulping.

The organic solvent process has several advantages over other common processes, such as Kraft or sulfite pulping. In particular, the ability to obtain relatively high quality lignin adds value to the process stream (which otherwise would be considered waste). The solvent of the organic solvent process is readily recovered by distillation, thereby reducing water pollution and eliminating the odors typically associated with Kraft pulping.

Organic solvent process pulping involves contacting a lignocellulosic feedstock with an aqueous organic solvent at a temperature of, for example, 140 ℃ to 220 ℃. The solvent used includes acetone, methanol, ethanol, butanol, ethylene glycol, formic acid and acetic acid. The concentration of the solvent in the water is 40-80%. Higher boiling solvents have the advantage of lower process pressures. This is weighed against the more difficult solvent to recover by distillation.

For pulp production, pulping with aqueous ethanol can result in lignin-free pulp yields of 4-4.5% higher than Kraft pulp. For pulp properties, the commonly used solvents acetone and ethanol have been examined. Pulping wheat straw with a 40% mixture of acetone or ethanol and water requires 60 minutes at 180 ℃ to make the pulp have acceptable properties.

For process considerations, such as lowering the vapor pressure and lowering the pH, organic solvents are almost always used as a mixture with water in order to also dissolve the hemicellulose.

Various organic solvent processes (Alcell process, CIMV process, chempois process, etc.) have been proposed, all of which require a large amount of energy, since the reaction/cooking temperature is always higher than 100 ℃ and/or since it is necessary to ensure a high reaction pressure. They also have to be subjected to solvent recycling.

There is therefore a global need for a method and a way of treating lignocellulosic biomass, in particular waste from agricultural production and forestry, which makes it possible to produce high-quality pulp and then high-quality paper, requiring as low energy as possible.

Disclosure of Invention

The present invention provides a low energy production process for producing pulp from lignocellulosic biomass, said process comprising the successive steps of:

a) extracting lignin and hemicellulose from lignocellulosic biomass by subjecting at least one solid lignocellulosic feedstock to atmospheric pressure in the presence of a mixture consisting only of water and formic acid, under controlled reaction temperature conditions between ambient temperature and the reflux temperature of the mixture at atmospheric pressure, preferably at 80 ℃ to 110 ℃, wherein the weight ratio of the at least one solid lignocellulosic feedstock/liquid mixture is between 1/1 and 1/15, and for a determined reaction time (also referred to as the digestion period);

b) separating the solid fraction constituting the raw pulp from an organic phase containing in solution at least a mixture of starting formic acid and water, soluble monosaccharides and polymeric sugars, lignin, at atmospheric pressure and at said reaction temperature; and

according to other aspects of the method:

-it comprises a further step consisting in c) washing said raw pulp;

-the raw pulp is washed successively in the following two steps:

-c1) at room temperature, using a solution consisting of water and formic acid, the concentration of formic acid in said solution being between 80% and 100%; and

-c2) with hot water at 40 ℃ -60 ℃;

-the concentration of formic acid in the mixture is between 50% and 100%, preferably between 80% and 90%;

-the weight ratio of the at least one solid lignocellulosic feedstock/liquid mixture is from 1/4 to 1/6;

-the reaction temperature is equal to 85 ℃;

-said organic phase comprises in solution at least a mixture of starting formic acid and water, soluble mono-and polymeric sugars derived from plant material, lignin and acetic acid;

-said b) separation step is a centrifugation step or a filtration step at atmospheric pressure and at said reaction temperature;

-performing a centrifugation step at ambient temperature between said first washing step c1) with a solution consisting of water and formic acid and said second washing step c2) with hot water;

-performing a centrifugation step after said second washing step c2) with hot water;

-said determined reaction time is dependent on the measured or determined kappa number of the pulp;

-stopping the determined reaction time when the kappa number of the pulp reaches a stable value depending on the properties of the at least one lignocellulosic feedstock;

-the method comprises the steps consisting in periodically measuring or determining the kappa number of the pulp during the determined reaction time, in order to identify the stability of the kappa number of the pulp;

-said step of periodically measuring or determining the kappa number of the pulp consists in measuring or determining the kappa number every ten minutes;

-stopping said determined reaction time when the kappa number of the pulp stabilizes after at least three consecutive measurements or determinations of the kappa number of the pulp.

Detailed Description

All biomasses contain varying percentages of cellulose, hemicellulose and lignin, as well as inorganic components as a source of ash. Cellulose is a linear polymer comprising anhydroglucopyranose linked by ether linkages. Hemicellulose is an amorphous polysaccharide containing branched sugar units and different sugar types. Lignin is the most complex constituent and is the polymer structure of phenyl propane units.

The most prominent component of biomass is lignocellulose, which is composed of the non-starch fiber fraction of plant material. Cellulose or pulp, hemicellulose and lignin are the three main components of lignocellulosic biomass.

First embodiment

One example of extracting raw pulp from a biomass lignocellulosic feedstock (LRM) using a mixture of water and formic acid (HCOOH) at low temperature and atmospheric pressure according to the present invention is as follows.

The first step consists in preparing a mixture or solution of formic acid in water using a ratio of 85% by weight of formic acid and 15% by weight of water, i.e. a concentration of formic acid equal to 85%.

In the second step, a 30 g dry sample of lignocellulosic feedstock (LRM) and 270 g liquid mixture of formic acid in water were introduced into a 500 ml glass reactor.

For example, the mass ratio (ratio by weight) of the solid/liquid ratio (i.e. mixture of lignocellulosic feedstock/acid and water) is equal to 1/9.

To increase the contact surface between the liquid and the solid, the lignocellulosic feedstock sample may be comminuted.

The mixture of acid/water solution and biomass lignocellulosic feedstock sample was heated at a temperature of 80 ℃ to 90 ℃ at ambient atmospheric pressure and using an oil bath.

Therefore, the mixture was stirred to a uniform temperature using a mechanical stirrer with an Inox anchor.

The temperature was stabilized at 85 ℃ using a thermometer.

At this stable temperature, the reaction was started and maintained for 4 hours.

This extraction step is a very low energy consuming step because it works at low temperatures below 110 ℃.

At the end of the reaction for this period of time, the contents of the reactor were cooled to ambient temperature and contained a solid fraction and a liquid fraction.

The contents of the reactor are then filtered to separate the raw solid cellulose or raw paper pulp from the liquid phase or fraction (first organic liquid).

The separated cellulose has been washed with formic acid and then pressed and filtered to remove another part of the liquid phase or fraction in liquid form (second organic liquid).

The first and second organic liquids are then mixed together to obtain the main organic liquid.

The primary liquid fraction is further concentrated under vacuum, preferably heated at a pressure of 100mbar at 40 ℃ to 50 ℃.

The concentrated phase is maintained until the dry matter content is about 50 wt.% to 60 wt.%.

At this stage, all part of the formic acid contained in the first organic liquid is recovered and separated to obtain an intermediate liquid fraction.

It appears that some other organic acids, such as acetic acid (CH), may be formed or produced in very small amounts starting from a mixture of formic acid and water in the extraction step₃CO₂H)。

To separate or "extract" the lignin from the hemicellulose fraction in the intermediate liquid fraction, warm water has been added to the intermediate liquid fraction to reach a liquid/solid mass ratio equal to 4/1, for example.

To enhance the separation of lignin from the hemicellulose fraction, a high performance rotor/stator disperser is used at a rotational speed of more than 15000 revolutions per minute only during a dispersing time of e.g. 2-3 minutes.

At the end of this dispersion step, it has been treated with a filtration step or a centrifugation step to separate the lignin from the hemicellulose fraction and obtain a residual liquid fraction.

The separated lignin is then washed with warm water until a filtrate of neutral pH is obtained.

Then, the lignin was comminuted and dried until a dry matter of 94% by weight was reached, the drying temperature being not more than 40 ℃.

Second embodiment

A second example of raw pulp extraction from biomass lignocellulosic feedstock (LRM) using a mixture of water and formic acid (HCOOH) at low temperature and atmospheric pressure according to the invention is as follows.

The first step consists in preparing a mixture or solution of formic acid in water using a ratio of 85% by weight of formic acid and 15% by weight of water, i.e. a concentration of formic acid equal to 85%.

In the second step, a quantity of a dry sample of the lignocellulosic feedstock (LRM) and a quantity of a liquid mixture of formic acid in water are introduced into a glass reactor.

For example, the mass ratio (ratio by weight) of the solid/liquid ratio (i.e., lignocellulosic feedstock/mixture of acid and water) is from 1/4 to 1/6 to minimize contact between the acid mixture and the biomass sample.

To increase the contact surface between the liquid and the solid, the lignocellulosic feedstock sample may be comminuted.

The mixture of acid/water solution and biomass lignocellulosic feedstock sample was heated at a temperature of 80 ℃ to 90 ℃ at ambient atmospheric pressure and using an oil bath.

Therefore, the mixture was stirred to a uniform temperature using a mechanical stirrer with an Inox anchor.

The temperature was stabilized at 85 ℃ using a thermometer.

At this stable temperature, the reaction was started and maintained for 2-4 hours.

A sample of the fibril cellulose (raw pulp) is subjected to kappa index analysis periodically, for example using TAPPI standard method T236 om-99.

For example, kappa index analysis is performed at least every 30 minutes after the first two hours of reaction.

Kappa index analysis may be performed every 10 minutes after the first two hours of reaction.

The reaction, the so-called cooking period, is stopped when the kappa number reaches a constant value, i.e. when its value stabilizes.

At this stage, the contents are treated to separate the fibril cellulose (solid phase or solid fraction) from the so-called first organic liquid (liquid phase or liquid fraction).

The separation is obtained by filtration or centrifugation.

Thereafter, the separated fibril is washed with a solution consisting of water and formic acid, the concentration of formic acid in the solution being 85% to 99%.

Thereafter, the washed cellulose is treated by pressing and filtration, or preferably by centrifugation, to remove residual second organic liquid.

Furthermore, the cellulose obtained can be washed in a further step using only water at a temperature of 40 ℃ to 60 ℃.

After this additional washing step with "hot" water, the cellulose or pulp may be centrifuged again.

After washing, the pH of the pulp is near neutral.

The previously obtained first and second organic liquids are mixed together in a single main organic liquid.

The main organic liquid is then concentrated under vacuum. The medium has been heated at a temperature below 50 ℃ under a pressure of 100 mBar. The concentration step is maintained until an organic pulp is obtained, which pulp has a dry matter content of about 50-60 wt.%.

To separate or "extract" lignin from the hemicellulose fraction in the intermediate liquid fraction, warm water has been added to the intermediate liquid fraction to achieve a liquid/solid mass ratio equal to, for example, at least about 2/1.

To enhance the separation of lignin from the hemicellulose fraction, a high performance rotor/stator disperser is used at a rotational speed of more than 15000 revolutions per minute only during a dispersing time of e.g. 2-3 minutes.

At the end of this dispersion step, it has been treated with a filtration step to separate the lignin from the hemicellulose fraction and obtain a residual liquid fraction.

The separated lignin is then washed with warm water until a filtrate of neutral pH is obtained.

Then, the lignin is comminuted and dried until a dry matter of 90 wt.% (preferably 95 wt.%) is reached, the drying temperature being not more than 40 ℃.

After the rectification step has reached the preferred 85% concentration, the re-concentrated formic acid/water previously obtained can be reused for another biomass extraction or for washing of the fibril cellulose or base pulp.

According to this second example, the following corresponding values were obtained depending on the nature of the value of the raw material.

This extraction step is very energy intensive because it operates at low temperatures below 100 ℃.

For example, for one ton (1T) of dry pulp, the average energy consumption of a plant using the process according to the invention is about 2MWh (+/-20%) compared to the average energy consumption of a non-integrated plant using the Kraft process (5-6 MWh).

The process according to the invention can be industrially implemented using batch techniques for the extraction step, which also comprise stirring the contents of each batch.

This is advantageous compared to diffusion techniques which imply long and energy consuming extraction times.