WO2019208844A1

WO2019208844A1 - Apparatus and method for chemically pretreating herbaceous biomass by using high-concentration organosolv

Info

Publication number: WO2019208844A1
Application number: PCT/KR2018/004762
Authority: WO
Inventors: 오경근; 류현진; 최원일; 김준석
Original assignee: 주식회사 슈가엔
Priority date: 2018-04-24
Filing date: 2018-04-24
Publication date: 2019-10-31

Abstract

The present invention relates to a biomass pretreatment apparatus using a high-concentration organosolv catalyst, and a method for treating biomass by using same, and to a treatment method used in the recovery and reuse of a catalyst to be used for carrying out chemical treatment, and minimizes the generation of by-products by reacting biomass by means of an organosolv catalyst, and induces the maximum recovery of a pretreated solid part and, simultaneously, uses, as a pretreatment catalyst, a high-concentration organosolv catalyst, having an extremely low water amount, for enabling a used solvent to be recovered and reused.

Description

Chemical pretreatment and method of herbal biomass using high concentration organosolve

The present invention relates to a chemical pretreatment apparatus and method, and more particularly, to a chemical pretreatment apparatus and method for herbal biomass using a high concentration organosolve.

Fibrous biomass, the most abundant renewable resource on earth, has long produced fuels and chemicals. Because fibrinous biomass is difficult to apply naturally to enzyme saccharification, pretreatment is an essential process to obtain sugar by enzymatic saccharification. Pretreatment of fibrin-based biomass is an effective method that mainly affects the reduction of enzyme glycosylation inhibitors such as lignin. The purpose of pretreatment is to reduce the crystallization of cellulose, increase hemicellulose degradation and widen the biomass reaction area for woody enzymes in which the enzyme contacts the hard structure of cellulose for maximum sugar recovery.

Republic of Korea Patent No. 10-0994594 introduces a method for chemical pretreatment of biomass using an acid solvent. This is effective for the biomass pretreatment process for sugar production, but a subsequent process for removing the toxicity of the solvent is essential for producing biofuels.

Republic of Korea Patent No. 10-1190647 introduced a technology for the pretreatment process using an acid or an alkaline solvent for the pretreatment process of the substrate for ethanol fermentation. This too lacks a subsequent process for the pretreatment solvent and a process for the reprocessing portion thereof.

Republic of Korea Patent No. 10-1392736 describes a wood-based biomass pretreatment process using nitric acid for the production of bioethanol, the neutralization process for the fermentation process is necessary before the bioethanol production process.

Since the above methods only perform a chemical treatment method to increase the sugar efficiency, an additional process for solvent treatment is required, and thus a cost increase effect occurs in the entire process.

Accordingly, there is a demand for a treatment apparatus and a method for reducing the cost of a subsequent solvent treatment process by performing a biomass pretreatment process using a pretreatment solvent that is easy to recover.

The present invention is to solve the above problems, an object of the present invention is to provide a treatment method for increasing the efficiency of the reuse of the solvent used in the biomass pretreatment by performing a chemical pretreatment.

The present invention, which achieves the object as described above, and performs the task for eliminating the conventional defects, after the fibrinated biomass is put into the biomass reactor, the solvent and / or catalyst of the predetermined mixing conditions from the catalyst supply device A first step of mixing; A second step of performing the mixture of the first step under predetermined reaction conditions; A third step of separating and / or recovering the solid phase component from the mixture of the second step and cooling the liquid component to a used catalyst storage tank; A fourth step of recovering the solvent and / or the catalyst by filtering and / or washing the liquid component separated from the used catalyst storage tank in a catalyst recovery and filtration apparatus; And a fifth step of recycling the recovered solvent and / or catalyst to the catalyst supply device.

In addition, the step of pulverizing the fibrin-based biomass before the first step may be included.

In addition, the step of drying before the fibrin-based biomass to the biomass reactor; may include.

In addition, the mixing conditions may be a condition in which the amount of water input in which the solid-liquid ratio of cellulose-based biomass input to water input is 1: 3 to 1:10.

In addition, the reaction temperature in the biomass reactor may be 150 ~ 200 ℃, the reaction pressure may be 350 ~ 400 psi.

In addition, the biomass reactor may further include a pressure maintaining device for maintaining a suitable pressure for the reaction.

A catalyst recovery and filtration device may also be included for recovering and reusing used solvents and / or catalysts.

In addition, the catalyst used in the biomass reactor may be reusable without washing.

As described above, the present invention may be a biomass high concentration catalyst pretreatment apparatus for pretreating the cellulose-based biomass using the biomass high concentration catalyst pretreatment method.

According to the present invention, by carrying out the pretreatment process using a high concentration of the organosolve, it is possible to improve the production efficiency by reusing the solvent with the pretreatment effect, and to reduce the process cost by not following a subsequent process for the treated pretreatment solvent Can be.

In addition, the hydrolyzate (carbohydrate) produced in the present invention has the advantage that can be applied directly to the fermentation process without the need for the neutralization process or washing process with most glucose and xylose can reduce the process cost.

1 is a view schematically showing a biomass high concentration catalyst pretreatment apparatus according to an embodiment of the present invention.

Figure 2 is a result table of the biomass sugar recovery rate and glycation rate according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail with reference to embodiments and drawings.

The present invention relates to a pretreatment process and method using a high concentration organosolve catalyst to partially remove ligrin and the like from the cellulose-based biomass and swell its structure, and to change the cellulose-based biomass into a form suitable for sugar production. The aim is to reduce process costs and environmental pollution by facilitating the reuse of used catalysts.

1 is a view schematically showing a biomass high concentration organosolve catalyst pretreatment apparatus 100 according to an embodiment of the present invention. As shown, to clearly describe the present invention, when the part not related to the description is omitted and a part "includes" a certain element, it does not exclude other elements unless specifically stated otherwise. It means that it may further include other components.

The biomass high concentration organosolve catalyst pretreatment device 100 includes a catalyst supply device 10 for supplying a high concentration catalyst, a biomass reaction device 20 for reacting biomass with a catalyst, and a catalyst storage tank using the used catalyst. ) And a catalyst recovery and filtration device 33. The present invention can recover the catalyst used in the pretreatment reaction and the reaction to give a structural change of the fibrin-based biomass by supplying the organosolve catalyst to the reactor can be reused. Pretreatment refers to a process of swelling the inhibitor or structure of a subsequent process of biomass to obtain biofuel through a saccharification process and a fermentation process from the biomass to increase efficiency.

A first step of adding the fibrous biomass to the biomass reaction apparatus and then adding a solvent and / or a catalyst having a predetermined mixing condition from the catalyst supply device to mix the fibrinous biomass; A second step of performing the mixture of the first step under predetermined reaction conditions; A third step of separating and / or recovering the solid phase component from the mixture of the second step and cooling the liquid component to a used catalyst storage tank; A fourth step of recovering the solvent and / or the catalyst by filtering and / or washing the liquid component separated from the used catalyst storage tank in a catalyst recovery and filtration apparatus; And a fifth step of recycling the recovered solvent and / or catalyst to the catalyst supply device.

The catalyst supply device may be composed of a solvent storage tank, a catalyst storage tank, and a mixed storage tank. The solvent and catalyst are selectively supplied or uniformly mixed and then supplied to improve the biomass pretreatment reaction characteristics.

It is also obvious that valves, pumps, pressure gauges, thermometers, and the like for the supply of solvents and / or catalysts can of course be selected.

It may be a solvent and / or a catalyst of the predetermined mixing conditions introduced.

The solvent may be a solvent of 80 to 99.9 parts by weight based on 10 to 50 parts by weight of the fibrin-based biomass. Preferably it may be 95 to 99.7 parts by weight of solvent, more preferably 99.5 parts by weight of solvent.

The solvent may be an organosolve. The organosolve may be a high concentration solvent of 99.5 wt%. If the above conditions are exceeded, the yield of the second generation biomass is lowered.

The organosolve may be preferably primary alcohol, secondary alcohol or tertiary alcohol.

The high concentration solvent may be primary alcohol. Preferably ethanol.

The catalyst may be 0.1 parts by weight to 10 parts by weight of the catalyst. Preferably it may be 0.2 to 8 parts by weight of catalyst, more preferably 0.5 to 5 parts by weight of catalyst. The catalyst may be 0.1 to 2 wt%. If the above conditions are exceeded, the yield of second generation biomass is lowered.

The catalyst may be an acid solution, preferably sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, acetic acid, formic acid, any one or a mixture of two or more thereof.

Second generation biomass introduced into the reactor may be 10 to 90 parts by weight, preferably 20 to 80 parts by weight.

The solids ratio of second generation biomass to solvent and / or catalyst introduced into the reactor may be 0.5 to 10 days.

If the input amount of the second generation biomass is out of the effective yield recovery rate is lowered.

The reaction conditions may be reaction temperature 140 ~ 200 ℃, reaction pressure 200 to 500 psi, and reaction time 5 ~ 100 minutes, preferably reaction temperature 150 ~ 180 ℃, reaction pressure 250 ~ 450 psi, and reaction time 5 ~ 80 minutes, more preferably, the reaction temperature may be 160 ~ 180 ℃, the reaction pressure 350 to 400 psi, and the reaction time 30 to 50 minutes. Outside the above conditions, the yield is lowered and side reactions may be generated.

In the reactor, a high concentration organosolve catalyst is supplied to the reactor using the pump 11 at a constant speed in the catalyst supply device 10 to react for a predetermined time at a predetermined temperature in the biomass reactor 20. In Examples, the reaction temperature is preferably 150 to 200 ° C, and the reaction time is preferably 20 to 60 minutes. At this time, in order to raise the reactor to a constant temperature, a temperature supply device such as an oven may be added to the reactor.

In the reactor, the high concentration organosolve catalyst may react with the biomass while flowing at a constant speed in the biomass reactor 20, and the finished catalyst may be stored in the used catalyst storage tank 30. At this time, the storage tank may comprise a cooling device to recover the high temperature catalyst in the liquid phase.

When the reaction is carried out in the reactor, the reaction pressure is preferably 350 ~ 400 psi. At this time, it may include a device for giving a back pressure (back pressure) to reach the internal pressure. At this time, when the pressure is increased to 400 psi or more by the high concentration organosolve in the high temperature reactor, the internal pressure of the reactor may be adjusted by opening and closing the pressure control tank valve 22 connected to the reactor pressure control tank 21.

After the reaction is completed in the reactor, the catalyst stored in the catalyst storage tank 30 to be used first closes the catalyst reservoir shutoff valve 31 while maintaining the pressure in the biomass reactor 20, and then the reservoir discharge control valve 32. You can open) to recover.

At this time, in order to recover the residual catalyst remaining in the biomass reactor 20, the catalyst supply shutoff valve 12 is closed and the used catalyst reservoir shutoff valve 31 and the reservoir discharge control valve 32 are opened. It is preferable to recover the residual catalyst by using.

After the final reaction, the pretreated biomass of the biomass reactor 20 is recovered. At this time, the recovered biomass may be used in subsequent processes such as enzyme glycosylation immediately or after drying without undergoing a washing process.

The catalyst recovered after the reaction in the reactor can be reused in the catalyst feeder 10 via the catalyst recovery and filtration device 33. In this case, the filtration process may include all of the various processes previously used.

Biomass high concentration organosolve catalyst pretreatment method according to an embodiment of the present invention (S100) is a high concentration catalyst supply step (S10) for supplying a catalyst to react with the biomass, pretreatment of the biomass and the catalyst in the biomass reactor Reaction step (S20) and catalyst recovery and resupply step (S30) for recovering and reusing the used catalyst. The present invention can have the effect of not only chemically treating the biomass with the catalyst but also recovering and reusing the used catalyst.

Hereinafter, the configuration of the present invention and its effects through the following examples will be described in more detail. However, this embodiment is intended to illustrate the present invention in more detail, and the scope of the present invention is not limited to these examples.

EXAMPLE

The biomass-filled biomass reactor 20 transfers 99.5% of ethanol, which is a high concentration organosolve of the catalyst feeder 10, to the pump 11 so that the biomass is sufficiently wetted. Then, the temperature of the reactor was maintained at 170 ℃, the internal pressure of 350 psi in a state in which all the valves are closed.

The catalyst supply blocking valve 12 is opened and the catalyst is transferred to the biomass reactor 20 at a constant speed and reacted with the biomass for 40 minutes. At this time, the catalyst reacted with the biomass was collected in the catalyst storage tank 30 used together with materials such as lignin dissolved in the catalyst in the biomass.

As the reaction proceeds, the internal pressure is maintained between 350 and 400 psi. At this time, when the internal pressure exceeds 400 psi by using the pressure control tank valve 22 to lower the pressure to maintain the appropriate pressure.

After the final reaction, the pretreated biomass of the biomass reactor 20 is recovered. At this time, the recovered biomass was used in a subsequent process. In addition, the catalyst collected in the catalyst storage tank 30 to be used is recovered to remove the insoluble solids through the filtration process 33 and then supplied to the catalyst supply device 10 to reuse the catalyst while the biomass biomass reactor Transfer to (20) was repeated the process. The results of total initial, 1 ^st reuse, 2 ^nd reuse, and 3 ^rd reuse are shown in FIG. 2 as final results after the experiment.

As shown in FIG. 2, since the high concentration organosolve catalyst was found to have no significant degradation of pretreatment performance even after repeated reuse, the utility value of the reuse of the high concentration organosolve catalyst was excellent.

100: biomass high concentration catalyst pretreatment device

10: catalyst feeder

11: catalyst feed pump

12: catalyst feed shutoff valve

20 biomass reactor

21: reactor pressure regulation tank

22: pressure regulating tank valve

30: used catalyst storage tank

31: use catalyst reservoir shutoff valve

32: reservoir discharge control valve

33: catalyst recovery and filtration apparatus

S100: Biomass high concentration catalyst treatment method

S10: high concentration catalyst supply step

S20: biomass reaction step

S30: catalyst recovery and resupply step

Claims

A first step of adding the fibrous biomass to the biomass reaction apparatus and then adding a solvent and / or a catalyst having a predetermined mixing condition from the catalyst supply device to mix the fibrinous biomass;

A second step of performing the mixture of the first step under predetermined reaction conditions;

A third step of separating and / or recovering the solid phase component from the mixture of the second step and cooling the liquid component to a used catalyst storage tank;

A fourth step of recovering the solvent and / or the catalyst by filtering and / or washing the liquid component separated from the used catalyst storage tank in a catalyst recovery and filtration apparatus; And

And a fifth step of recycling the recovered solvent and / or catalyst to the catalyst supply device.
The method according to claim 1,

Biomass high concentration catalyst pretreatment method comprising the step of pulverizing the cellulose-based biomass before the first step
The method according to claim 1 or 2,

And drying the fibrin-based biomass before inputting the biomass reactor to the biomass reactor.
The method according to claim 1,

The mixing condition is a biomass high-concentration catalyst pretreatment method, characterized in that the water input amount of the cellulose-based biomass input to the water input amount is very small 1: 1: 1 to 1:10.
The method according to claim 1,

The reaction temperature in the biomass reactor is 150 ~ 200 ℃, the reaction pressure is biomass high concentration catalyst pretreatment method, characterized in that 350 ~ 400 psi.
The method according to claim 5,

The biomass high concentration catalyst pretreatment method further comprises a pressure maintaining device for maintaining a suitable pressure for the biomass reactor reaction.
The method according to claim 1,

And a catalyst recovery and filtration apparatus for recovering and reusing the used solvent and / or catalyst.
The method according to claim 1,

The catalyst used in the biomass reactor is a biomass high concentration catalyst pretreatment method, characterized in that can be reused without washing.
The method according to any one of claims 1 to 8,

A biomass high concentration catalyst pretreatment apparatus for pretreating the fibrin-based biomass by the biomass high concentration catalyst pretreatment method.