CN109232774A - A kind of method that dissolving pulp pre-processes hemicellulose isolation and purification in workshop section's pre-hydrolyzed solution - Google Patents
A kind of method that dissolving pulp pre-processes hemicellulose isolation and purification in workshop section's pre-hydrolyzed solution Download PDFInfo
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- CN109232774A CN109232774A CN201811160812.7A CN201811160812A CN109232774A CN 109232774 A CN109232774 A CN 109232774A CN 201811160812 A CN201811160812 A CN 201811160812A CN 109232774 A CN109232774 A CN 109232774A
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- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
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Abstract
The present invention relates to the methods of hemicellulose isolation and purification in a kind of dissolving pulp pretreatment workshop section's pre-hydrolyzed solution, belong to pulping and paper-making field.The method of the invention includes the following steps: to be first 100-400 by wood chip and 150-175 DEG C of water heat preservation to the P factor, and cooling, centrifugation obtains supernatant I, then is concentrated, and centrifugation obtains supernatant II；Being acidified to pH value to supernatant II using acid is 1.5-2.5, and centrifugation obtains supernatant III；Supernatant III and non-ionic high polymer are mixed, centrifugation obtains supernatant IV；First being alkalized supernatant IV to pH value using alkali is 6-10, and centrifugation obtains supernatant V, then supernatant V and ethyl alcohol are mixed, and stands, and collects precipitating, dry, obtains hemicellulose.The hemicellulose that the method for the invention has many advantages, such as is with high purity, easy to operate, at low cost, environmentally friendly.
Description
Technical field
The present invention relates to the methods of hemicellulose isolation and purification in a kind of dissolving pulp pretreatment workshop section's pre-hydrolyzed solution, belong to
Pulping and paper-making field.
Background technique
In the production process of dissolving pulp, carrying out pretreatment to plant fiber material is widely applied method.It is specific real
It applies and usually carries out hydrolyzing certainly for plant fiber material under the conditions of certain temperature, dissolve out a large amount of hemicelluloses and part is wooden
Element, in favor of subsequent chemistry boiling.In this course pre-hydrolyzed solution usually mixed with black liquor as waste liquid send alkali recovery furnace into
Row burning, the method added value for processing of burning is lower, causes the waste of biomass resource.Advocating environmental protection, resource-effective the present
It, needs to explore the effective use to pre-hydrolyzed solution.
For the degree that pretreatment carries out, generally characterized using the P factor, the P factor be six the seventies of last century by
Brash et al. is proposed, similar to the concept of the boiling H factor, to be one by two combined factors of prehydrolysis temperature and time
Variable, Sixta etc. further illustrate the concept of the P factor, and on the basis based on carbohydrate glycosidic bond fracture activation energy
On give the calculation formula of the P factor, for instructing the formulation of pre-hydrolysis technique condition, the P factor is higher to indicate pretreated journey
It spends deeper.
If heating rate is constant, it can be calculated according to Simpson's expansion, and total P factor is temperature rise period and heat preservation rank
The sum of the P factor of section.The calculating of the P factor such as following formula:
Wherein: T0Initial temperature, K；The temperature of T- any time, K；T- is by T0It is warming up to the required time of T, h.
As the hemicellulose in the carry out pre-hydrolyzed solution of pre-hydrolysis process can gradate as formic acid, acetic acid, furfural etc.
Product.
Summary of the invention
The present invention by being concentrated, being acidified to pre-hydrolyzed solution, non-ionic high polymer flocculation treatment and alkalization, separation, purifying
Hemicellulose in pre-hydrolyzed solution, solves the above problem.
The present invention provides the method for hemicellulose isolation and purification in a kind of dissolving pulp pretreatment workshop section's pre-hydrolyzed solution, institutes
The method of stating includes the following steps: to be first 100-400 by wood chip and 150-175 DEG C of water heat preservation to the P factor, and cooling, centrifugation obtains
Clear liquid I, then be concentrated, centrifugation obtains supernatant II；Being acidified to pH value to supernatant II using acid is 1.5-2.5, and centrifugation obtains
Clear liquid III；Supernatant III and non-ionic high polymer are mixed, centrifugation obtains supernatant IV；First alkalized using alkali to supernatant IV
It is 6-10 to pH value, centrifugation obtains supernatant V, then supernatant V and ethyl alcohol are mixed, and stands, and collects precipitating, and it is dry, it obtains
Hemicellulose.
The present invention is preferably that the weight ratio of the wood chip and water is 1:3-8.
The present invention is preferably that the percent by volume of the concentration is 30-90%.
The present invention is preferably that the acid is the concentrated sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or acetic acid.
The present invention is preferably that the non-ionic high polymer is polyethylene glycol oxide or polyethylene glycol.
The present invention is preferably that the alkali is sodium hydroxide, potassium hydroxide, calcium hydroxide or barium hydroxide.
The present invention is preferably that the volume ratio of the supernatant V and ethyl alcohol is 1:4-10.
It is 0.5-2h that the present invention, which is preferably the time of the standing,.
The invention has the following beneficial effects:
The hemicellulose that the method for the invention has many advantages, such as is with high purity, easy to operate, at low cost, environmentally friendly.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
The source area of following Acacias is Vietnam, moisture 6%.
Embodiment 1
The preparation of pre-hydrolyzed solution:
106.4g Acacia wood chip (the Acacia wood chip for being equivalent to 100g over dry) is taken, is carried out by 1:4 liquor ratio and tap water
Prehydrolysis is warming up to 170 DEG C, and different soaking times is arranged, and to obtain the pre-hydrolyzed solution of the expected P factor, the P factor is respectively
100,130,160,200,250,300,500,700,900 and 1100, cooling after heat preservation, supernatant liquor is collected in centrifugation,
The ingredient of Acacia pre-hydrolyzed solution see the table below 1.
The ingredient of 1 Acacia pre-hydrolyzed solution of table
| The P factor | 100 | 130 | 160 | 200 | 250 | 300 | 500 | 700 | 900 | 1100 |
| pH | 3.57 | 3.23 | 3.18 | 3.15 | 3.13 | 3.11 | 3.07 | 3.07 | 3.05 | 3.03 |
| Solid content/% | 0.62 | 1.38 | 1.52 | 1.64 | 1.77 | 2.38 | 2.62 | 2.81 | 3.01 | 3.33 |
| Ash content/% | 0.027 | 0.036 | 0.032 | 0.035 | 0.043 | 0.046 | 0.051 | 0.053 | 0.050 | 0.058 |
| Content of lignin g/L | 2.41 | 2.80 | 3.13 | 3.65 | 3.82 | 4.00 | 4.19 | 4.35 | 5.28 | 5.44 |
| Xylose Content g/L | 1.11 | 4.34 | 6.17 | 9.22 | 10.80 | 12.29 | 14.31 | 18.31 | 18.50 | 17.07 |
Embodiment 2
Determine the optimal P factor condition of prehydrolysis:
Each 100mL of pre-hydrolyzed solution for taking the different P factors is mixed by 1:6 volume ratio with ethyl alcohol, stands 1h, collects precipitating, is done
Dry, the quality and purity of hemicellulose precipitating see the table below 2.
The quality and purity of 2 hemicellulose of table precipitating
| The P factor | 100 | 130 | 160 | 200 | 250 | 300 | 500 | 700 | 900 | 1100 |
| Quality g/L | 1.42 | 2.45 | 2.86 | 2.94 | 2.31 | 2.10 | 0.50 | 0.37 | 0.26 | 0.21 |
| Purity % | 65.5 | 70.1 | 69.9 | 71.2 | 66.6 | 70.0 | 53.9 | 29.0 | — | — |
It is obtained by table 2, the P factor 200 is optimal prehydrolysis condition.
Embodiment 3
Determine the optimal volume ratio of pre-hydrolyzed solution and ethyl alcohol:
Taking the P factor is 200 pre-hydrolyzed solution 100mL, presses 1:4,1:6,1:8,1:10 and 1:12 volume ratio and ethyl alcohol respectively
Mixing stands 1h, collects precipitating, dry, and the quality and purity of hemicellulose precipitating see the table below 3.
The quality and purity of 3 hemicellulose of table precipitating
| Volume ratio | 1:4 | 1:6 | 1:8 | 1:10 | 1:12 |
| Quality g/L | 1.66 | 2.94 | 3.43 | 3.61 | 3.66 |
| Purity % | 72.6 | 71.2 | 70.7 | 69.6 | 74.6 |
It is obtained by table 3, as the hemicellulose quality that the increase of volume ratio is collected into is gradually increased, but increase tendency gradually subtracts
It is slow, and the hemicellulose purity being collected into is without significant change, volume ratio 1:8,1:10 and 1:12 ratio, in view of economic situation
Under, pre-hydrolyzed solution and ethyl alcohol volume ratio 1:8 are optimal volume ratio.
Embodiment 4
Determine optimal concentration volume score:
Taking the P factor is 200 pre-hydrolyzed solution 100mL, and concentration volume score is respectively 10%, 30%, 50%, 70% and
90%, centrifugation obtains supernatant, mixes supernatant with ethyl alcohol by 1:8 volume ratio, stands 1h, collects precipitating, dry, hemicellulose
The quality and purity of element precipitating see the table below 4.
The quality and purity of 4 hemicellulose of table precipitating
| Fractional volume is concentrated | 10% | 30% | 50% | 70% | 90% |
| Quality g/L | 3.70 | 4.78 | 5.45 | 5.90 | 6.11 |
| Purity % | 69.1 | 72.3 | 69.2 | 72.8 | 71.4 |
It is obtained by table 4, the hemicellulose precipitating quality being collected into the increase of concentration volume score is gradually increased, and is collected
The hemicellulose precipitating purity arrived is without significant change, but the unit dose of ethyl alcohol is being reduced, therefore 90% is optimal concentration volume
Score.
Embodiment 5
Determine optimal acidification:
The use of the concentrated sulfuric acid is 200 to the P factor, 90% pre-hydrolyzed solution is concentrated is acidified, be acidified to 3.0 respectively, 2.5,
2.0 and 1.5, centrifugation obtains supernatant, mixes supernatant with ethyl alcohol by 1:8 volume ratio, stands 1h, and it is heavy to collect hemicellulose
It forms sediment, dry, the quality and purity of hemicellulose precipitating see the table below 5.
The quality and purity of 5 hemicellulose of table precipitating
| pH | 3 | 2.5 | 2 | 1.5 |
| Quality g/L | 6.06 | 5.95 | 5.43 | 5.37 |
| Purity % | 75.2 | 76.0 | 79.2 | 79.4 |
It is obtained by table 5, the hemicellulose for being declined with the hemicellulose quality that the reduction of pH value is collected into, but being collected into
Purity is being gradually increased, and wherein the absolute magnitude of saccharic composition has no significant change, therefore pH value 2.0 is optimal acidic environment.
Embodiment 6
Non-ionic high polymer flocculation treatment:
To the P factor be 200, concentration 90%, be acidified to be added in the pre-hydrolyzed solution that pH value is 2 mass fraction be 5% it is poly-
Ethylene oxide solution makes the mass concentration 200mg/L in pre-hydrolyzed solution, stirs 10min, centrifugation, by supernatant liquor and ethyl alcohol
With volume ratio 1:8 mixing, 1h is stood, collects hemicellulose precipitating, dry, through detecting, every liter of pre-hydrolyzed solution collects 5.26g half
Cellulose, hemicellulose purity is up to 87%.
Embodiment 7
Determine optimal alkalization:
The sodium hydroxide solution for the use of mass fraction being 50% is respectively 200 to the P factor, concentration 90%, is acidified to pH value
Alkalize for the 2, pre-hydrolyzed solution after 200mg/L polyethylene glycol oxide flocculation treatment, alkalized respectively to 4.0,6.0,8.0,
10.0 and 12.0, centrifugation obtains supernatant, mixes supernatant with ethyl alcohol by 1:8 volume ratio, stands 1h, and it is heavy to collect hemicellulose
It forms sediment, dry, the quality and purity of hemicellulose precipitating see the table below 6.
The quality and purity of 6 hemicellulose of table precipitating
| pH | 4 | 6 | 8 | 10 | 12 |
| Quality g/L | 7.44 | 9.87 | 9.94 | 10.35 | 12.74 |
| Purity % | 78.2 | 76.4 | 75.8 | 73.1 | 69.9 |
| Ash content % | 8.0 | 9.1 | 9.0 | 9.3 | 20.1 |
It is obtained by table 6, the half fiber that the hemicellulose precipitating quality being collected into the increase of pH value is gradually increased, but is collected into
Dimension element precipitating purity is gradually decreased, and the yield and purity of hemicellulose precipitating are comprehensively considered, and pH value 8 is optimal alkaline ring
Border.
Claims (8)
1. a kind of method of hemicellulose isolation and purification in dissolving pulp pretreatment workshop section's pre-hydrolyzed solution, it is characterised in that: described
Method includes the following steps:
It is first 100-400 by wood chip and 150-175 DEG C of water heat preservation to the P factor, cooling, centrifugation obtains supernatant I, then is concentrated, from
Gains in depth of comprehension are to supernatant II；
Being acidified to pH value to supernatant II using acid is 1.5-2.5, and centrifugation obtains supernatant III；
Supernatant III and non-ionic high polymer are mixed, centrifugation obtains supernatant IV；
First being alkalized supernatant IV to pH value using alkali is 6-10, and centrifugation obtains supernatant V, then supernatant V is mixed with ethyl alcohol
It is even, it stands, collects precipitating, it is dry, obtain hemicellulose.
2. the method that dissolving pulp pre-processes hemicellulose isolation and purification in workshop section's pre-hydrolyzed solution according to claim 1,
Be characterized in that: the weight ratio of the wood chip and water is 1:3-8.
3. the method that dissolving pulp pre-processes hemicellulose isolation and purification in workshop section's pre-hydrolyzed solution according to claim 2,
Be characterized in that: the percent by volume of the concentration is 30-90%.
4. the method that dissolving pulp pre-processes hemicellulose isolation and purification in workshop section's pre-hydrolyzed solution according to claim 3,
Be characterized in that: the acid is the concentrated sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or acetic acid.
5. the method that dissolving pulp pre-processes hemicellulose isolation and purification in workshop section's pre-hydrolyzed solution according to claim 4,
Be characterized in that: the non-ionic high polymer is polyethylene glycol oxide or polyethylene glycol.
6. the method that dissolving pulp pre-processes hemicellulose isolation and purification in workshop section's pre-hydrolyzed solution according to claim 5,
Be characterized in that: the alkali is sodium hydroxide, potassium hydroxide, calcium hydroxide or barium hydroxide.
7. the method that dissolving pulp pre-processes hemicellulose isolation and purification in workshop section's pre-hydrolyzed solution according to claim 6,
Be characterized in that: the volume ratio of the supernatant V and ethyl alcohol is 1:4-10.
8. the method that dissolving pulp pre-processes hemicellulose isolation and purification in workshop section's pre-hydrolyzed solution according to claim 7,
Be characterized in that: the time of the standing is 0.5-2h.
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Cited By (3)
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| CN110256608A (en) * | 2019-06-24 | 2019-09-20 | 齐鲁工业大学 | The method that horseradish peroxidase processing removes lignin in plant fiber pre-hydrolyzed solution |
| CN110295510A (en) * | 2019-06-27 | 2019-10-01 | 大连工业大学 | A method of lignin crude product and liquid glucose are prepared using pulping and paper-making waste liquid |
| CN114008264A (en) * | 2019-06-26 | 2022-02-01 | 维美德公司 | Method for extracting hemicellulose from lignocellulose material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256608A (en) * | 2019-06-24 | 2019-09-20 | 齐鲁工业大学 | The method that horseradish peroxidase processing removes lignin in plant fiber pre-hydrolyzed solution |
| CN110256608B (en) * | 2019-06-24 | 2021-04-20 | 齐鲁工业大学 | Method for removing lignin in plant fiber prehydrolysis liquid by horse radish peroxidase treatment |
| CN114008264A (en) * | 2019-06-26 | 2022-02-01 | 维美德公司 | Method for extracting hemicellulose from lignocellulose material |
| CN114008264B (en) * | 2019-06-26 | 2022-09-13 | 维美德公司 | Method for extracting hemicellulose from lignocellulose material |
| CN110295510A (en) * | 2019-06-27 | 2019-10-01 | 大连工业大学 | A method of lignin crude product and liquid glucose are prepared using pulping and paper-making waste liquid |
| CN110295510B (en) * | 2019-06-27 | 2021-10-01 | 大连工业大学 | Method for preparing lignin crude product and sugar solution by using pulping and papermaking waste liquor |
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