A kind of parameter adjustment for eliminating different lignocellulosic material pretreatment efficiency variances
Method
[technical field]
It is that a kind of to eliminate different lignocellulosics former the present invention relates to biorefinery of lignocellulose and field of biological energy source
The parameter regulation means of material pretreatment efficiency variance.
[background technique]
Currently, the preprocess method of lignocellulosic material most mainstream includes that dilute acid pretreatment and steam blasting pre-process,
It is especially maximally efficient with dilute sulfuric acid pretreatment and the pretreatment of acid catalysis steam blasting.Its principle is to utilize the acidity under high temperature and pressure
Environment hydrolyzed hemicellulose, and then the structure of ligno-cellulosic materials is destroyed, improve the conversion of cellulose in subsequent enzymolysis process
Rate.Three key factors for influencing dilute acid pretreatment intensity are sour dosage, residence time and pretreatment temperature respectively.However, wooden
Matter cellulosic material is mostly agriculture and forestry organic waste material, these materials can mix a large amount of alkaline ash content object in growth, collection, storage process
Matter, these alkaline matters are measured with different acid in meeting in preprocessing process, cause pretreating effect different with raw material and exist
Significant difference has seriously affected the applicability of biorefinery technology.And for these different batches, different cultivars or from not
With the raw material in the place of production, according to the conditions such as temperature, reaction time and sour dosage optimize experiment need to take a substantial amount of time and
Energy, this becomes a challenge for restricting lignocellulosic preprocessing process industrial applications.
For dry method dilute acid pretreatment, since preprocessing process solid content is high (50% or more), and without free acid solution
In the presence of the build-up effect of ash content is particularly acute, very big for preprocessing process stability influence.Therefore, the present invention is in wooden fibre
Before tieing up plain high solids content low-kappa number, by measurement raw material acid neutralization capacity adjustment acid dosage, can not change it is pre-
Treatment process reaction temperature and in the case where the residence time simply and effectively determines that different batches ligno-cellulosic materials diluted acid is pre-
Sour dosage needed for treatment process obtains stable pre-processing intensity, and solving lignocellulosic material dilute acid pretreatment process can
The problem of poor repeatability, reaches more stable index to subsequent enzymatic saccharification and fermentation procedure and is of great significance, to wood
Matter cellulose is that the biorefinery industry of raw material has apparent impetus.
[summary of the invention]
The present invention is based on lignocellulosic dilute acid pretreatment processes, it is therefore intended that simple and fast to carry out to pretreatment parameter
Difference existing for different lignocellulosic material pretreatment efficiency is eliminated in adjustment.This method can quickly determine dilute acid pretreatment
Acid dosage required for process saves a large amount of manpower and material resources needed for conventional pretreatment parameter determines experiment, effectively avoids
The excessive bring acid solution waste of sour dosage and mortifier lead to the problem of it is more, while can to avoid sour dosage it is insufficient caused by it is pre-
Handle the weaker problem of intensity;Material has similar inhibitor contents after pretreatment, helps to improve subsequent detoxification and bacterial strain
The stability of fermentation process;Pretreated material has similar cellulose hydrolyzation transformation efficiency, is provided simultaneously with similar
Hemicellulose removal rate and pentose conversion ratio, help to obtain concentration relatively stable liquid glucose or are that platform ferments with sugar
Biological-based chemicals.
To achieve the above object, the technical solution adopted by the present invention are as follows:
(1) lignocellulosic material is slightly cut, except sandstone and crushing;(2) material that step (1) obtains is configured to suspend
Slurry is titrated to specific pH value using dilute sulfuric acid, is calculated according to the sulfuric acid dosage based on unit dry solid pretreated
The sulfuric acid dosage of Cheng Suoxu, and carry out dry method dilute acid pretreatment;(3) material carries out enzyme water after the pretreatment for obtaining step (2)
The subsequent biological processing process such as solution or simultaneous saccharification and fermentation.Compared with prior art, the present invention has the advantage that with effect such as
Under:
This method is simple and fast efficiently, can effectively avoid difference on the basis of without the experiment of a large amount of optimal conditions
Growth collects, pre-processes stabilised efficiency caused by the acid neutralization capacity for the ligno-cellulosic raw materials that banking system obtains difference
Property difference problem;Material has similar inhibitor contents after pretreatment, helps to improve subsequent detoxification and strain fermentation process
Stability;Pretreated material has similar cellulose hydrolyzation transformation efficiency, is provided simultaneously with similar hemicellulose
Removal rate and xylose yield, the biology base chemistry for helping to obtain the relatively stable liquid glucose of concentration or being fermented with sugar for platform
Product.
[Detailed description of the invention]
Fig. 1 difference content of ashes (3.26%, 4.33%, 4.63%, 5.30%, 6.65%) corn stover is neutralized according to acid
The pretreatment condition and the evaluation of pretreated enzymatic hydrolysis that ability determines;
The pretreatment condition that Fig. 2 difference content of ashes (5.87%, 10.04%) wheat stalk is determined according to acid neutralization capacity
And pretreated enzymatic hydrolysis evaluation;
Fig. 3 difference content of ashes (8.06%, 11.68%) straw is according to the determining pretreatment condition of acid neutralization capacity and in advance
Enzymatic hydrolysis evaluation that treated;
[specific embodiment]
A kind of parameter regulation means for eliminating different lignocellulosic material pretreatment efficiency variances of the present invention presented below
Specific embodiment.
Embodiment 1
Air-dried corn stover is slightly cut into 0.1-10cm long, and removes the stone gravel of bulky grain, it is straight without dedusting
It connects and is crushed to the sieve that particle size passes through internal diameter 1cm with beater grinder, raw material content of ashes is 6.65% at this time, sour dosage
Adjustment is not titrated, takes 2.00% (w/w) sulfuric acid/g dry solid, the acid being made into using corn stover and according to the acid dosage
Liquid pre-processes 5min under conditions of 175 DEG C, 0.8MPa with the solid-to-liquid ratio of 2:1;Pretreated material xylan content 9.01
± 0.30%, acetic acid content 10.56 ± 0.24mg/g DM, 0.82 ± 0.02mg/g of furfural content DM.To the batch pre-treatment
Corn stover carries out enzymatic hydrolysis test afterwards, and operating condition is solid content 2.5% (mass ratio), and cellulase dosage 20FPU/g is dry
Solid, 50 DEG C, enzymolysis time 72 hours in the water bath with thermostatic control of 150rpm, cellulose conversion ratio is up to 64.82 ± 2.00%.
Embodiment 2
Air-dried corn stover is slightly cut into 0.1-10cm long, and removes the stone gravel of bulky grain, it is straight without dedusting
It connects and is crushed to the sieve that particle size passes through internal diameter 1cm with beater grinder, raw material content of ashes is 6.65% at this time, and 2g is done
When solid is mixed with 100g deionized water, pH value at this time is 6.81, is titrated when using 4% (w/w) sulfuric acid solution to it
To pH be 2.30 when, required acid solution 1.62g, by calculate know sulfuric acid dosage required for dilute acid pretreatment process be 3.24%
(w/w) sulfuric acid/g dry solid, using corn stover with according to the acid solution that the acid dosage is made into the solid-to-liquid ratio of 2:1, in 175 DEG C,
5min is pre-processed under conditions of 0.8MPa;Pretreated material xylan content 3.09 ± 0.22%, acetic acid content 18.25 ±
0.20mg/g DM, 3.09 ± 0.02mg/g of furfural content DM.Enzymatic hydrolysis test is carried out to corn stover after the batch pre-treatment, is grasped
Making condition is solid content 2.5% (mass ratio), cellulase dosage 20FPU/g dry solid, 50 DEG C, the water bath with thermostatic control of 150rpm
Middle enzymolysis time 72 hours, cellulose conversion ratio is up to 93.29 ± 1.17%.
Embodiment 3
Air-dried corn stover is slightly cut into 0.1-10cm long, and removes the stone gravel of bulky grain, with mass ratio 10:1
The ratio of (water: stalk) is added water and cleans stalk, is squeezed after having cleaned, solid is placed in 105 DEG C of baking ovens and dries, after drying
It is crushed to the sieve that particle size passes through internal diameter 1cm with beater grinder, raw material content of ashes is 5.30% at this time, and 2g is solid
When body is mixed with 100g deionized water, pH value at this time is 6.74, is titrated to when using 4% (w/w) sulfuric acid solution to it
When pH is 2.30, required acid solution 1.195g knows that sulfuric acid dosage required for dilute acid pretreatment process is 2.39% (w/ by calculating
W) sulfuric acid/g dry solid, using corn stover with according to the acid solution that the acid dosage is made into the solid-to-liquid ratio of 2:1, in 175 DEG C,
5min is pre-processed under conditions of 0.8MPa;Pretreated material xylan content 3.18 ± 0.03%, acetic acid content 19.90 ±
0.53mg/g DM, 3.42 ± 0.03mg/g of furfural content DM.Enzymatic hydrolysis test is carried out to corn stover after the batch pre-treatment, is grasped
Making condition is solid content 2.5% (mass ratio), cellulase dosage 20FPU/g dry solid, 50 DEG C, the water bath with thermostatic control of 150rpm
Middle enzymolysis time 72 hours, cellulose conversion ratio is up to 90.82 ± 1.96%.
Embodiment 4
Air-dried corn stover is slightly cut into 0.1-10cm long, and removes the stone gravel of bulky grain, with mass ratio 30:1
The ratio of (water: stalk) is added water and cleans stalk, is squeezed after having cleaned, solid is placed in 105 DEG C of baking ovens and dries, after drying
It is crushed to the sieve that particle size passes through internal diameter 1cm with beater grinder, raw material content of ashes is 4.63% at this time, and 2g is solid
When body is mixed with 100g deionized water, pH value at this time is 6.63, is titrated to when using 4% (w/w) sulfuric acid solution to it
When pH is 2.30, required acid solution 1.175g knows that sulfuric acid dosage required for dilute acid pretreatment process is 2.35% (w/ by calculating
W) sulfuric acid/g dry solid, using corn stover with according to the acid solution that the acid dosage is made into the solid-to-liquid ratio of 2:1, in 175 DEG C,
5min is pre-processed under conditions of 0.8MPa;Pretreated material xylan content 3.05 ± 0.15%, acetic acid content 19.43 ±
0.08mg/g DM, 3.16 ± 0.13mg/g of furfural content DM.Enzymatic hydrolysis test is carried out to corn stover after the batch pre-treatment, is grasped
Making condition is solid content 2.5% (mass ratio), cellulase dosage 20FPU/g dry solid, 50 DEG C, the water bath with thermostatic control of 150rpm
Middle enzymolysis time 72 hours, cellulose conversion ratio is up to 92.33 ± 4.07%.
Embodiment 5
Air-dried corn stover is slightly cut into 0.1-10cm long, and removes the stone gravel of bulky grain, with mass ratio 50:1
The ratio of (water: stalk) is added water and cleans stalk, is squeezed after having cleaned, solid is placed in 105 DEG C of baking ovens and dries, after drying
It is crushed to the sieve that particle size passes through internal diameter 1cm with beater grinder, raw material content of ashes is 4.33% at this time, and 2g is solid
When body is mixed with 100g deionized water, pH value at this time is 6.31, is titrated to when using 4% (w/w) sulfuric acid solution to it
When pH is 2.30, required acid solution 1.15g knows that sulfuric acid dosage required for dilute acid pretreatment process is 2.30% (w/ by calculating
W) sulfuric acid/g dry solid, using corn stover with according to the acid solution that the acid dosage is made into the solid-to-liquid ratio of 2:1, in 175 DEG C,
5min is pre-processed under conditions of 0.8MPa;Pretreated material xylan content 3.29 ± 0.09%, acetic acid content 16.85 ±
0.78mg/g DM, 2.92 ± 0.01mg/g of furfural content DM.Enzymatic hydrolysis test is carried out to corn stover after the batch pre-treatment, is grasped
Making condition is solid content 2.5% (mass ratio), cellulase dosage 20FPU/g dry solid, 50 DEG C, the water bath with thermostatic control of 150rpm
Middle enzymolysis time 72 hours, cellulose conversion ratio is up to 90.25 ± 0.63%.
Embodiment 6
Air-dried corn stover is slightly cut into 0.1-10cm long, and removes the stone gravel of bulky grain, with mass ratio 100:1
The ratio of (water: stalk) is added water and cleans stalk, is squeezed after having cleaned, solid is placed in 105 DEG C of baking ovens and dries, after drying
It is crushed to the sieve that particle size passes through internal diameter 1cm with beater grinder, raw material content of ashes is 3.26% at this time, and 2g is solid
When body is mixed with 100g deionized water, pH value at this time is 6.16, is titrated to when using 4% (w/w) sulfuric acid solution to it
When pH is 2.30, required acid solution 1g knows that sulfuric acid dosage required for dilute acid pretreatment process is 2.00% (w/w) sulphur by calculating
Acid/g dry solid, using corn stover with according to the acid solution that the acid dosage is made into the solid-to-liquid ratio of 2:1, in 175 DEG C, 0.8MPa
Under the conditions of pre-process 5min;Pretreated material xylan remnants 3.62 ± 0.05%, 17.88 ± 1.33mg/g of acetic acid content
DM, 1.89 ± 0.15mg/g of furfural content DM.Enzymatic hydrolysis test is carried out to corn stover after the batch pre-treatment, operating condition is
Solid content 2.5% (mass ratio), cellulase dosage 20FPU/g dry solid, 50 DEG C, when digesting in the water bath with thermostatic control of 150rpm
Between 72 hours, cellulose conversion ratio is up to 93.88 ± 4.08%.
Embodiment 7
Air-dried wheat stalk is slightly cut into 0.1-10cm long, and removes the stone gravel of bulky grain, it is straight without dedusting
It connects and is crushed to the sieve that particle size passes through internal diameter 1cm with beater grinder, raw material content of ashes is 10.04% at this time, and acid is used
Amount is not titrated adjustment, takes 2.00% (w/w) sulfuric acid/g dry solid, is made into using wheat stalk and according to the acid dosage
Acid solution pre-processes 5min under conditions of 175 DEG C, 0.8MPa with the solid-to-liquid ratio of 2:1;Pretreated material xylan content
7.72 ± 0.29%, acetic acid content 3.80 ± 0.03mg/g DM, 1.04 ± 0.02mg/g of furfural content DM.The batch is located in advance
Wheat stalk carries out enzymatic hydrolysis test after reason, and operating condition is solid content 2.5% (mass ratio), cellulase dosage 20FPU/g
Dry solid, 50 DEG C, enzymolysis time 72 hours in the water bath with thermostatic control of 150rpm, cellulose conversion ratio is up to 68.55 ± 2.65%.
Embodiment 8
Air-dried wheat stalk is slightly cut into 0.1-10cm long, and removes the stone gravel of bulky grain, it is straight without dedusting
It connects and is crushed to the sieve that particle size passes through internal diameter 1cm with beater grinder, raw material content of ashes is 10.04% at this time, by 2g
When dry solid is mixed with 100g deionized water, pH value at this time is 6.76, is dripped when using 4% (w/w) sulfuric acid solution to it
When being calmly 2.34 to pH, required acid solution 1.67g knows that sulfuric acid dosage required for dilute acid pretreatment process is 3.34% by calculating
(w/w) sulfuric acid/g dry solid, using wheat stalk with according to the acid solution that the acid dosage is made into the solid-to-liquid ratio of 2:1, in 175 DEG C,
5min is pre-processed under conditions of 0.8MPa;Pretreated material xylan content 2.88 ± 0.19%, acetic acid content 12.00 ±
0.09mg/g DM, 2.53 ± 0.09mg/g of furfural content DM.Enzymatic hydrolysis test is carried out to wheat stalk after the batch pre-treatment, is grasped
Making condition is solid content 2.5% (mass ratio), cellulase dosage 20FPU/g dry solid, 50 DEG C, the water bath with thermostatic control of 150rpm
Middle enzymolysis time 72 hours, cellulose conversion ratio is up to 94.52 ± 0.89%.
Embodiment 9
Air-dried wheat stalk is slightly cut into 0.1-10cm long, and removes the stone gravel of bulky grain, with mass ratio 100:1
The ratio of (water: stalk) is added water and cleans stalk, is squeezed after having cleaned, solid is placed in 105 DEG C of baking ovens and dries, after drying
It is crushed to the sieve that particle size passes through internal diameter 1cm with beater grinder, raw material content of ashes is 5.87% at this time, and 2g is solid
When body is mixed with 100g deionized water, pH value at this time is 6.68, is titrated to when using 4% (w/w) sulfuric acid solution to it
When pH is 2.34, required acid solution 1g knows that sulfuric acid dosage required for dilute acid pretreatment process is 2.00% (w/w) sulphur by calculating
Acid/g dry solid, using wheat stalk with according to the acid solution that the acid dosage is made into the solid-to-liquid ratio of 2:1, in 175 DEG C, 0.8MPa
Under the conditions of pre-process 5min;Pretreated material xylan remnants 3.32 ± 0.45%, 11.55 ± 0.12mg/g of acetic acid content
DM, 1.74 ± 0.01mg/g of furfural content DM.Enzymatic hydrolysis test is carried out to wheat stalk after the batch pre-treatment, operating condition is
Solid content 2.5% (mass ratio), cellulase dosage 20FPU/g dry solid, 50 DEG C, when digesting in the water bath with thermostatic control of 150rpm
Between 72 hours, cellulose conversion ratio is up to 92.15 ± 1.22%.
Embodiment 10
Air-dried straw is slightly cut into 0.1-10cm long, and removes the stone gravel of bulky grain, is directly used without dedusting
Beater grinder is crushed to the sieve that particle size passes through internal diameter 1cm, and raw material content of ashes is 11.68% at this time, and sour dosage is not
Adjustment is titrated, 2.00% (w/w) sulfuric acid/g dry solid is taken, the acid solution being made into using straw and according to the acid dosage is with 2:
1 solid-to-liquid ratio pre-processes 5min under conditions of 175 DEG C, 0.8MPa;Pretreated material xylan content 7.26 ±
0.16%, acetic acid content 4.85 ± 0.44mg/g DM, 0.92 ± 0.03mg/g of furfural content DM.To rice after the batch pre-treatment
Grass carries out enzymatic hydrolysis test, and operating condition is solid content 2.5% (mass ratio), cellulase dosage 20FPU/g dry solid, and 50
DEG C, enzymolysis time 72 hours in the water bath with thermostatic control of 150rpm, cellulose conversion ratio is up to 61.28 ± 1.48%.
Embodiment 11
Air-dried straw is slightly cut into 0.1-10cm long, and removes the stone gravel of bulky grain, is directly used without dedusting
Beater grinder is crushed to the sieve that particle size passes through internal diameter 1cm, and raw material content of ashes is 11.68% at this time, and 2g is solid
When body is mixed with 100g deionized water, pH value at this time is 6.15, is titrated to when using 4% (w/w) sulfuric acid solution to it
When pH is 2.25, required acid solution 1.57g knows that sulfuric acid dosage required for dilute acid pretreatment process is 3.14% (w/ by calculating
W) sulfuric acid/g dry solid, using straw with according to the acid solution that the acid dosage is made into the solid-to-liquid ratio of 2:1, in 175 DEG C, 0.8MPa
Under the conditions of pre-process 5min;Pretreated material xylan content 3.41 ± 0.14%, 11.14 ± 0.52mg/g of acetic acid content
DM, 2.75 ± 0.06mg/g of furfural content DM.Enzymatic hydrolysis test is carried out to straw after the batch pre-treatment, operating condition is solid
Content 2.5% (mass ratio), cellulase dosage 20FPU/g dry solid, 50 DEG C, enzymolysis time 72 in the water bath with thermostatic control of 150rpm
Hour, cellulose conversion ratio is up to 90.32 ± 2.11%.
Embodiment 12
Air-dried straw is slightly cut into 0.1-10cm long, and removes the stone gravel of bulky grain, with mass ratio 100:1 (water:
Stalk) ratio be added water clean straw, squeezed after clean, solid is placed in 105 DEG C of baking ovens and dries, after drying with hammer into shape
Formula pulverizer is crushed to particle size by the sieve of internal diameter 1cm, and raw material content of ashes is 8.06% at this time, by 2g dry solid with
When 100g deionized water mixes, pH value at this time is 6.01, is when using 4% (w/w) sulfuric acid solution to carry out being titrated to pH to it
When 2.25, required acid solution 1g knows that sulfuric acid dosage required for dilute acid pretreatment process is 2.00% (w/w) sulfuric acid/g by calculating
Dry solid, it is pre- under conditions of 175 DEG C, 0.8MPa using straw and according to the acid solution that the acid dosage is made into the solid-to-liquid ratio of 2:1
Handle 5min;Pretreated material xylan remnants 3.78 ± 0.44%, acetic acid content 9.69 ± 0.23mg/g DM, furfural
2.18 ± 0.08mg/g of content DM.Enzymatic hydrolysis test is carried out to straw after the batch pre-treatment, operating condition is solid content
2.5% (mass ratio), cellulase dosage 20FPU/g dry solid, 50 DEG C, enzymolysis time 72 is small in the water bath with thermostatic control of 150rpm
When, cellulose conversion ratio is up to 92.15 ± 1.22%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, without departing from the inventive concept of the premise, can also make several improvements and modifications, these improvements and modifications also should be regarded as
In protection scope of the present invention.