CN106749688A

CN106749688A - A kind of production method of microcrystalline cellulose

Info

Publication number: CN106749688A
Application number: CN201611238112.6A
Authority: CN
Inventors: 张睿哲; 刘运思; 闵渝
Original assignee: Ying Sheng Bio Tech Ltd Guangzhou
Current assignee: Ying Sheng Bio Tech Ltd Guangzhou
Priority date: 2016-12-28
Filing date: 2016-12-28
Publication date: 2017-05-31

Abstract

The present invention provides a kind of production method of microcrystalline cellulose, and methods described is pre-processed using organic solvent or aqueous solutions of organic solvent to plant fiber material, obtains plant fiber material and pretreatment fluid by pre-processing；It is boiling solvent with organic solvent or aqueous solutions of organic solvent, and adds catalyst, boiling is carried out to pretreated plant fiber material, and separation of solid and liquid obtains cooking liquor and fiber；It is raw material with the fiber for obtaining, microcrystalline cellulose is prepared through bleaching, washing process, dried process and pulverization process.The production method of the microcrystalline cellulose that the present invention is provided, strong acid consumption is few, and cost of material is low, and production liquid waste processing is simple, and microcrystalline cellulose product purity is high, yield is high.

Description

A kind of production method of microcrystalline cellulose

Technical field

The invention belongs to natural plant constituents extraction field, it is related to a kind of production method of microcrystalline cellulose.

Background technology

Microcrystalline cellulose (Microcrystalline cellulose, MCC) is native cellulose through sour water solution to the limit The free flowable imperceptible corynebacterium or powdery porous shape particle of the degree of polymerization (LOOP), color are white or near white Color, odorless, tasteless, levelling off degree of polymerization (LODP) is 15~375；Do not have fibroid and mobility is extremely strong.Water insoluble, diluted acid, Organic solvent and grease, are partly dissolved in dilute alkaline soln, moisten and rise, and have in carboxy methylation, acetylation, esterification process higher Reactivity worth.Because with the special nature such as low degree and larger specific surface area, microcrystalline cellulose is widely used In medicine, food, cosmetics and light industry industry.

The physical and chemical indexes for evaluating microcrystalline cellulose property have a lot.Conventional mainly has crystallinity, the degree of polymerization, crystalline State, hygroscopicity value, the heat of wetting, granularity, than tabular value, mobility, gelling performance, reactivity worth etc..

In pharmaceuticals industry, microcrystalline cellulose is commonly used for adsorbent, suspending agent, diluent, disintegrant.Microcrystalline cellulose is wide It is general to be applied to pharmaceutical preparation, diluent and adhesive are mainly used as in oral tablet and capsule, cannot be only used for wet granulation Can also be used for dry method direct tablet compressing.Also certain lubrication and calving disaggregation, it is highly useful in tablet preparation.

CN 103864941A disclose a kind of preparation method of microcrystalline cellulose for toothpaste, and methods described is refined with 150kg Cotton or 100kg wood pulps are raw material, adopt 0.2~0.23mo1/L watery hydrochloric acid, 46~52kg hydrolysis, and 30% pair is added in hydrolytic process Oxygen water 50000mL is bleached, and is crushed through micronizer again and obtained after drying is just broken.With microcrystalline cellulose obtained in the present invention Water imbibition is high, and viscosity is low, and whiteness is good.But the raw material that the method is used is purified cotton or wood pulp, cost of material is high, and using big Amount hydrochloric acid, liquid waste processing is complicated, is unfavorable for industrialized production.

CN 105037564A disclose a kind of production method of microcrystalline cellulose, and methods described step is：1) pre-process： Purified cotton is crushed by opener, is then sieved, obtaining 95% can be passed through the cotton powder of 80 mesh sieves, standby；2) degrade：Claim 65-75 parts of cotton powder is taken, vacuum system is opened, cotton powder is pumped into the bipyramid vacuum rotary reactor of liner enamel by vacuum, opened Motor is opened, reactor is opened and rotated, then is pumped into hydrochloric acid solution, closes vacuum system, keep rotating 15-30min, stop reactor Rotate, open vacuum system, be evacuated to below -0.06Mpa, close vacuum；Begin to warm up, and rotatable reactor, it is warming up to 100 DEG C -110 DEG C, it is incubated 30min-50min；Then lead to cooling water to be lowered the temperature, steamed while opening vacuum and extracting unnecessary hydrochloric acid out Vapour, hydrochloric acid vapour is reclaimed by acid mist recycling can, then obtains microcrystalline cellulose by the universal method such as washing, drying, pulverize and sieve Plain finished product.The method is using purified cotton as raw material, and cost of material is high, although reduces the usage amount of hydrochloric acid, but still has useless Acid is produced, while the microcrystalline cellulose purity of production is relatively low.

Therefore, a kind of strong acid consumption of research is few, and cost of material is low, and production liquid waste processing is simple, and microcrystalline cellulose product The microcrystalline cellulose production method that purity is high, yield is high is particularly significant.

The content of the invention

High for prior art microcrystalline cellulose production technology cost of material, sour consumption is big, and liquid waste processing difficulty is big, crystallite The low problem of cellulose products purity, the invention provides a kind of production method of microcrystalline cellulose, strong acid consumption is few, raw material into This is low, and production liquid waste processing is simple, and microcrystalline cellulose product purity is high, yield is high.

It is that, up to this purpose, the present invention uses following technical scheme：

(1) plant fiber material is pre-processed using organic solvent, obtains the plant fiber material by pre-processing And pretreatment fluid；

(2) it is boiling solvent with aqueous solutions of organic solvent, and adds catalyst, it is fine to the pretreated plant of step (1) Dimension raw material carries out boiling, and separation of solid and liquid obtains cooking liquor and fiber；

(3) fiber for being obtained with step (2) through alternatively acid treatment and alternatively the first washing process, then is passed through as raw material Bleaching, the second washing process, dried process and pulverization process prepare microcrystalline cellulose.

It is following as currently preferred technical scheme, but not as the present invention provide technical scheme limitation, pass through Following technical scheme, can preferably reach and realize technical purpose of the invention and beneficial effect.

Used as currently preferred technical scheme, step (1) described organic solvent is benzene kind solvent, alcohols solvent, ketone In solvent or organic acid solvent any one or at least two composition, combination typical case but non-limiting examples Have：The combination of benzene kind solvent and alcohols solvent, the combination of benzene kind solvent and ketones solvent, benzene kind solvent and organic acid solvent Combination, the combination of alcohols solvent and ketones solvent, the combination of alcohols solvent and organic acid solvent, ketones solvent and organic acid The combination of solvent or the combination of alcohols solvent, benzene kind solvent and organic acid solvent etc..

Preferably, the benzene kind solvent be benzene, toluene, ethylbenzene, n-proplbenzene, isopropylbenzene, paraxylene, ortho-xylene, In dimethylbenzene or mesitylene any one or at least two combination, combination typical case but non-limiting examples have, benzene With the combination of the combination of the combination of the combination of toluene, benzene and ethylbenzene, toluene and ethylbenzene, toluene and paraxylene, n-proplbenzene and different The combination of the combination of propyl benzene, the combination of paraxylene and meta-xylene, ortho-xylene and paraxylene, toluene and mesitylene Combination or toluene, ortho-xylene and equal three basic combination etc..

Preferably, the alcohols solvent include for methyl alcohol, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, just oneself In alcohol, cyclohexanol, n-octyl alcohol, phenmethylol or benzyl carbinol any one or at least two combination, the combination is typical but non- Limitative examples have：The combination of the combination of methyl alcohol and ethanol, the combination of methyl alcohol and normal propyl alcohol, ethanol and n-butanol, n-hexyl alcohol and The combination of the combination of cyclohexanol, the combination of ethanol and phenmethylol, ethanol and n-octyl alcohol, phenmethylol and benzyl carbinol or methyl alcohol, ethanol With the combination of propyl alcohol etc..

Preferably, the organic acid solvent be formic acid, acetic acid, ethanedioic acid, propionic acid, malonic acid, n-butyric acie, isobutyric acid, In benzoic acid or phenylacetic acid any one or at least two combination, combination typical case but non-limiting examples have：Formic acid The combination of the combination of combination, acetic acid and ethanedioic acid with acetic acid, the combination of acetic acid and propionic acid, propionic acid and malonic acid, acetic acid and just The combination of the combination of butyric acid, the combination of acetic acid and isobutyric combination, formic acid and benzoic acid, acetic acid and phenylacetic acid, benzoic acid and Combination of phenylacetic acid or formic acid, acetic acid and benzoic acid etc..

Preferably, step (1) described aqueous solutions of organic solvent is the alcohols solvent aqueous solution, the ketones solvent aqueous solution or organic In acids solvent aqueous solution any one or at least two combination, combination typical case but non-limiting examples have：Alcohols is molten The combination of the agent aqueous solution and the ketones solvent aqueous solution, the combination of the ketones solvent aqueous solution and organic acid solvent aqueous solution, alcohols The combination or the alcohols solvent aqueous solution of solvent aqueous solution and organic acid solvent aqueous solution, the ketones solvent aqueous solution and organic acid Combination of solvent aqueous solution etc.；

Preferably, the concentration of step (1) described aqueous solutions of organic solvent is 20~100%, without 100%, such as 20%, 30%th, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 99% etc., it is not limited to cited numerical value, the number Other unrequited numerical value are equally applicable in the range of value, and more preferably 60~100%, without 100%.

Preferably, step (1) described organic solvent is mixed acid or acetic acid and the isobutyric mixing of acetic acid and n-butyric acie Acid.

Preferably, in the mixed acid of the acetic acid and n-butyric acie, counted by 100wt% of the quality of mixed acid, acetic acid contains It is 60~98% to measure, such as 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98%, it is not limited to institute Other unrequited numerical value are equally applicable in the numerical value enumerated, the number range, balance of n-butyric acie.

Preferably, in the acetic acid and isobutyric mixed acid, counted by 100wt% of the quality of mixed acid, acetic acid contains It is 60~98% to measure, such as 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98%, it is not limited to institute Other unrequited numerical value are equally applicable in the numerical value enumerated, the number range, balance of isobutyric acid.

Preferably, step (1) described aqueous solutions of organic solvent be acetic acid and n-butyric acie mixed acid aqueous solution or acetic acid and Isobutyric mixed acid aqueous solution；

Preferably, in the mixed acid aqueous solution of the acetic acid and n-butyric acie, the quality with mixed acid aqueous solution is as 100wt% Meter, the content of acetic acid is 60~98%, and the content of n-butyric acie is 1~40%, balance of water；The content of acetic acid can be 60%, 65%th, 70%, 75%, 80%, 85%, 90%, 95% or 98% etc., it is not limited to cited numerical value, the numerical value model Other unrequited numerical value are equally applicable in enclosing；The content of n-butyric acie can be 15%, 10%, 15%, 20%, 25%, 30%, 35% or 40% etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range.

Preferably, in the acetic acid and isobutyric mixed acid aqueous solution, the quality with mixed acid aqueous solution is as 100wt% Meter, the content of acetic acid is 60~98%, and isobutyric content is 1~40%, balance of water；The content of acetic acid can be 60%, 65%th, 70%, 75%, 80%, 85%, 90%, 95% or 98% etc., it is not limited to cited numerical value, the numerical value model Other unrequited numerical value are equally applicable in enclosing；Isobutyric content can be 15%, 10%, 15%, 20%, 25%, 30%, 35% or 40% etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range.

Plant fiber material is pre-processed using organic solvent, can effectively remove fat, fat in plant fiber material The impurity such as fat acid, resin, terpenes, pigment, the purity of the microcrystalline cellulose that raising is produced.Meanwhile, after organic solvent pretreatment, It is easily recycled, it is environment-friendly, and reduce production cost.

Used as currently preferred technical scheme, step (1) described plant fiber material is over dry plant fiber material.

Preferably, the consumption of step (1) described organic solvent is 1~30 times of over dry plant fiber material quality, such as 1 Again, 2 times, 3 times, 4 times, 5 times, 10 times, 15 times, 20 times, 25 times or 30 times etc., preferably 2~20 times.

Preferably, the method for step (1) described pretreatment for diafiltration, dipping, boiling or washing in any one or at least Two kinds of combination, the combination is typical but non-limiting examples have：Diafiltration and dipping, dipping and boiling, dipping and washing, boiling With washing or dipping, boiling and washing etc., more preferably impregnate.

Preferably, the pressure of step (1) described pretreatment is 0.5 × 10⁵~3 × 10⁵Pa, such as 0.5 × 10⁵Pa、1× 10⁵Pa、1.5×10⁵Pa、2×10⁵Pa、2.5×10⁵Pa or 3 × 10⁵Pa etc., it is not limited to cited numerical value, the number Other unrequited numerical value are equally applicable in the range of value, and more preferably 1 × 10⁵~2 × 10⁵Pa。

Preferably, the temperature of step (1) described pretreatment be 50~200 DEG C, such as 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 120 DEG C, 150 DEG C, 180 DEG C, 190 DEG C or 200 DEG C etc., it is not limited to cited number Other unrequited numerical value are equally applicable in value, the number range, more preferably 70~200 DEG C.

Preferably, the time of step (1) described pretreatment be 10~600min, such as 10min, 15min, 20min, 25min, 30min、60min、90min、120min、150min、180min、240min、300min、360min、420min、480min、 540min or 600min etc., it is not limited to other unrequited numerical value are equally fitted in cited numerical value, the number range With more preferably 30~300min.

As currently preferred technical scheme, pretreatment fluid described in step (1) is concentrated under reduced pressure, reclaimed organic Solvent.

Preferably, the pressure of the evaporation and concentration is 0.1 × 10⁵~1.0 × 10⁵Pa, such as 0.1 × 10⁵Pa、0.2× 10⁵Pa、0.3×10⁵Pa、0.4×10⁵Pa、0.5×10⁵Pa、0.6×10⁵Pa、0.7×10⁵Pa、0.8×10⁵Pa or 0.9 × 10⁵Pa etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range, further Preferably 0.1 × 10⁵~0.7 × 10⁵Pa, particularly preferably 0.1 × 10⁵Pa。

Preferably, the temperature of the evaporation and concentration be 30~150 DEG C, such as 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 80 DEG C, 100 DEG C, 120 DEG C, 130 DEG C, 140 DEG C or 150 DEG C etc., it is not limited to other are unrequited in cited numerical value, the number range Numerical value it is equally applicable, more preferably 50~100 DEG C, particularly preferably 70 DEG C.

As currently preferred technical scheme, plant fiber material described in step (1) be pulverization after by mesh number The plant fiber material that leaves after the screen cloth screening of >=30 mesh, such as 30 mesh, 40 mesh, 60 mesh, 80 mesh, 100 mesh, 200 mesh, 500 mesh, 600 mesh or 800 mesh etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range, It is preferred that woody plant fiber material or/and grass class plant fiber material.

Preferably, the woody plant fiber material include hardwood, cork or shrub in any one or at least Two kinds of combination, the combination is typical but non-limiting examples have：It is the combination of hardwood and cork, the combination of hardwood and shrub, soft The combination of wood and shrub or the combination of hardwood, cork and shrub etc..

Preferably, the grass class plant fiber material is including in bagasse, bamboo, straw, wheat straw, cornstalk or reed Any one or at least two combination, combination typical case but non-limiting examples have：The combination of bagasse and bamboo, straw Combination or bagasse, combination of straw and cornstalk of combination, cornstalk and reed with straw etc..

Used as currently preferred technical scheme, catalyst described in step (2) is inorganic acid and/or hydrogen peroxide.

Preferably, the quality of the catalyst is the 0.01~10% of the quality of over dry plant fiber material, such as 0.01%, 0.05%th, 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10% etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range, enter One step is preferably 2~10%.

Preferably, the inorganic acid be hydrochloric acid, nitric acid or sulfuric acid in any one or at least two combination, it is described Combination is typical but non-limiting examples have：The combination of the combination of hydrochloric acid and nitric acid, the combination of hydrochloric acid and sulfuric acid, sulfuric acid and hydrochloric acid or The combination of hydrochloric acid, nitric acid and sulfuric acid, more preferably hydrochloric acid.

Preferably, the gross mass of step (2) organic solvent or aqueous solutions of organic solvent is over dry plant fiber material 2~20 times of quality, such as 2 times, 3 times, 4 times, 5 times, 8 times, 10 times, 12 times, 15 times, 18 times, 19 times or 20 times, further Preferably 2~15 times.

Used as currently preferred technical scheme, step (2) described organic solvent is benzene kind solvent, alcohols solvent, ketone In solvent or organic acid solvent any one or at least two composition, combination typical case but non-limiting examples Have：The combination of benzene kind solvent and alcohols solvent, the combination of benzene kind solvent and ketones solvent, benzene kind solvent and organic acid solvent Combination, the combination of alcohols solvent and ketones solvent, the combination of alcohols solvent and organic acid solvent, ketones solvent and organic acid The combination of solvent or the combination of alcohols solvent, benzene kind solvent and organic acid solvent etc..

Preferably, step (2) described aqueous solutions of organic solvent is the alcohols solvent aqueous solution, the ketones solvent aqueous solution or organic In acids solvent aqueous solution any one or at least two combination, combination typical case but non-limiting examples have：Alcohols is molten The combination of the agent aqueous solution and the ketones solvent aqueous solution, the combination of the ketones solvent aqueous solution and organic acid solvent aqueous solution, alcohols The combination or the alcohols solvent aqueous solution of solvent aqueous solution and organic acid solvent aqueous solution, the ketones solvent aqueous solution and organic acid Combination of solvent aqueous solution etc..

Preferably, the concentration of step (2) described aqueous solutions of organic solvent is 20~100%, without 100%, such as 20%, 30%th, 40%, 50%, 60%, 70%, 80%, 90%, 95% or 99% etc., it is not limited to cited numerical value, the number Other unrequited numerical value are equally applicable in the range of value, and more preferably 60~100%, without 100%.

Preferably, polyacrylic acid is added in step (2) described digestion process as digesting assistant.

Preferably, the addition of the polyacrylic acid accounts for organic solvent or aqueous solutions of organic solvent and polyacrylic acid gross mass 0.1~10%, such as 0.1%, 0.2%, 0.5%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10% etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range, it is further excellent Elect 1~5% as.

Preferably, aqueous solutions of organic solvent described in step (2) is the mixed acid aqueous solution of acetic acid and n-butyric acie, mixed at this Close in aqueous acid, counted by 100wt% of the quality of aqueous solutions of organic acids, the content of acetic acid is 60~98%, n-butyric acie contains It is 1~40% to measure, balance of water；The content of acetic acid can be 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% Or 98% etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range；N-butyric acie Content can be 15%, 10%, 15%, 20%, 25%, 30%, 35% or 40% etc., it is not limited to cited number Other unrequited numerical value are equally applicable in value, the number range.

Preferably, aqueous solutions of organic solvent described in step (2) is the mixed acid aqueous solution of acetic acid and n-butyric acie, works as boiling When process adds polyacrylic acid as digesting assistant, counted by 100wt% of the quality sum of aqueous solutions of organic acids and polyacrylic acid, The content of acetic acid is 68~97%, and n-butyric acie content is 1~30%, and the content of polyacrylic acid is 1~5%, balance of water.

Wherein the content of acetic acid can be 68%, 70%, 72%, 75%, 78%, 80%, 82%, 85%, 88%, 90%th, 92%, 95% or 97% etc.；The content of n-butyric acie can be 1%, 2%, 5%, 8%, 10%, 15%, 20%, 25% Or 30% etc.；The content of polyacrylic acid can be 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5% etc., It is not limited to other unrequited numerical value are equally applicable in cited numerical value, each number range of the above.

Preferably, aqueous solutions of organic solvent described in step (2) is acetic acid and isobutyric mixed acid aqueous solution, is mixed at this Close in aqueous acid, counted by 100wt% of the quality of aqueous solutions of organic acids, the content of acetic acid is 60~98%, isobutyric to contain It is 1~40% to measure, balance of water；The content of acetic acid can be 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% Or 98% etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range；Isobutyric acid Content can be 15%, 10%, 15%, 20%, 25%, 30%, 35% or 40% etc., it is not limited to cited number Other unrequited numerical value are equally applicable in value, the number range.

Preferably, aqueous solutions of organic solvent described in step (2) is acetic acid and isobutyric mixed acid aqueous solution, works as boiling When process adds polyacrylic acid as digesting assistant, counted by 100wt% of the quality sum of aqueous solutions of organic acids and polyacrylic acid, The content of acetic acid is 68~97%, and isobutyl acid content is 1~30%, and the content of polyacrylic acid is 1~5%, balance of water.

Wherein the content of acetic acid can be 68%, 70%, 72%, 75%, 78%, 80%, 82%, 85%, 88%, 90%th, 92%, 95% or 97% etc.；Isobutyric content can be 1%, 2%, 5%, 8%, 10%, 15%, 20%, 25% Or 30% etc.；The content of polyacrylic acid can be 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5% etc., It is not limited to other unrequited numerical value are equally applicable in cited numerical value, each number range of the above.

Preferably, the temperature of step (2) described boiling be 70~200 DEG C, such as 70 DEG C, 75 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 120 DEG C, 150 DEG C, 180 DEG C, 190 DEG C or 200 DEG C etc., it is not limited to cited numerical value, in the number range, other are not The numerical value enumerated is equally applicable, preferably 90~150 DEG C.

Preferably, the time of step (2) described boiling be 10~600min, such as 10min, 15min, 20min, 25min, 30min、60min、90min、120min、150min、180min、240min、300min、360min、420min、480min、 540min or 600min etc., it is not limited to other unrequited numerical value are equally fitted in cited numerical value, the number range With more preferably 50~300min.

Preferably, the pressure of step (2) described boiling is 0.5 × 10⁵~3 × 10⁵Pa, such as 0.5 × 10⁵Pa、1× 10⁵Pa、1.5×10⁵Pa、2×10⁵Pa、2.5×10⁵Pa or 3 × 10⁵Pa etc., it is not limited to cited numerical value, the number Other unrequited numerical value are equally applicable in the range of value, and more preferably 1 × 10⁵~2 × 10⁵Pa。

As currently preferred technical scheme, step (2) described solid-liquid separating method is filtering, sedimentation, evaporation or from In the heart any one or at least two combination, combination typical case but non-limiting examples have：The combination of filtering and sedimentation, Combination of combination or filtering, centrifugation and sedimentation of combination, filtering and evaporation of filtering and centrifugation etc., more preferably filters.

Preferably, organic acid elution is used to the fiber obtained in step (2), is washed with water and washs, collect the organic acid The cleaning solution that washing and the water washing are produced.

Preferably, the organic acid that organic acid elution is used is formic acid, acetic acid, ethanedioic acid, propionic acid, malonic acid, positive fourth In acid, isobutyric acid, benzoic acid or phenylacetic acid any one or at least two combination, the combination is typical but non-limiting reality Example has：The combination of the combination of formic acid and acetic acid, the combination of acetic acid and ethanedioic acid, acetic acid and propionic acid, the combination of propionic acid and malonic acid, The combination of the combination of acetic acid and n-butyric acie, the combination of acetic acid and isobutyric combination, formic acid and benzoic acid, acetic acid and phenylacetic acid, Combination of benzoic acid and phenylacetic acid or formic acid, acetic acid and benzoic acid etc..

Preferably, the organic acid quality of the washing and the quality of water independently are over dry plant fiber material quality 0.5~20 times, such as 0.5 times, 0.8 times, 1 times, 2 times, 5 times, 8 times, 10 times, 15 times or 20 times, it is not limited to listed Other unrequited numerical value are equally applicable in the numerical value of act, the number range, and washing times independently are 1~20 time, and such as 1 It is secondary, 2 times, 5 times, 8 times, 10 times, 15 times or 20 inferior, it is not limited to other are not in cited numerical value, the number range The numerical value enumerated is equally applicable.

Used as currently preferred technical scheme, acid includes hydrochloric acid, sulfuric acid, nitric acid, phosphorus in step (3) described acid treatment In acid, hypochlorous acid, permanganic acid, molybdic acid, formic acid, acetic acid, ethanedioic acid, propionic acid, malonic acid, butyric acid or succinic acid any one or extremely Few two kinds combination, the combination is typical but non-limiting examples have：The combination of hydrochloric acid and sulfuric acid, the combination of hydrochloric acid and nitric acid, Combination, the combination of potassium permanganate and molybdic acid, the first of the combination of sulfuric acid and nitric acid, the combination of phosphoric acid and hydrochloric acid, hypochlorous acid and sulfuric acid Acid and the combination of the combination of acetic acid, the combination of ethanedioic acid and acetic acid, propionic acid and malonic acid, the combination of butyric acid and succinic acid or salt Combination of acid, nitric acid and sulfuric acid etc., more preferably hydrochloric acid.

Preferably, step (3) it is described acid concentration be 0.5~20wt%, such as 0.5wt%, 0.8wt%, 1wt%, 2wt%, 5wt%, 8wt%, 10wt%, 12wt%, 15wt%, 18wt% or 20wt% etc., it is not limited to cited Other unrequited numerical value are equally applicable in numerical value, the number range.

Preferably, the consumption of step (3) acid is 1~30 times of over dry plant fiber material gross mass, such as 1 times, 2 Again, 5 times, 8 times, 10 times, 12 times, 15 times, 18 times, 20 times, 22 times, 25 times, 28 times or 30 times etc., it is not limited to cited Numerical value, other unrequited numerical value are equally applicable in the number range.

Preferably, the temperature of step (3) described acid treatment be 30~150 DEG C, such as 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C, 50 DEG C, 60 DEG C, 80 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C or 150 DEG C etc., it is not limited to cited numerical value, should Other unrequited numerical value are equally applicable in number range.

Preferably, the pressure of step (3) described acid treatment is 1 × 10⁵~2 × 10⁵Pa, such as 1 × 10⁵Pa、1.1× 10⁵Pa、1.2×10⁵Pa、1.3×10⁵Pa、1.4×10⁵Pa、1.5×10⁵Pa、1.6×10⁵Pa、1.7×10⁵Pa、1.8× 10⁵Pa、1.9×10⁵Pa or 2 × 10⁵Pa etc., it is not limited to other are unrequited in cited numerical value, the number range Numerical value is equally applicable.

Preferably, step (3) the acid treatment time be 10~600min, such as 10min, 20min, 30min, 50min, 80min, 100min, 150min, 200min, 250min, 300min, 400min, 500min or 600min etc., it is not limited to Other unrequited numerical value are equally applicable in cited numerical value, the number range.

Preferably, the consumption of step (3) the first washing process reclaimed water is the 0.5~50 of over dry plant fiber material Times, such as 0.5 times, 0.8 times, 1 times, 1.5 times, 2 times, 3 times, 5 times, 8 times, 10 times, 15 times, 20 times, 30 times, 40 times, 42 times, 45 Again, 48 times or 50 times etc., it is not limited to other unrequited numerical value are equally fitted in cited numerical value, the number range With.

When step (2) organic solvent or aqueous solutions of organic solvent are organic acid or aqueous solutions of organic acids, can not Carry out the acid treatment described in step (3) and the first washing process.

As currently preferred technical scheme, step (3) described bleaching include dioxygen water process, oxygen treatments applied, Alkali process, ozone treatment, any one that chlorine dioxide treatment and hypochlorite are processed or at least two combination, the combination Typical but non-limiting examples have：The combination of dioxygen water process and oxygen treatments applied, the combination of dioxygen water process and alkali process, dioxygen The combination for the treatment of of the combination, chlorine dioxide treatment and hypochlorite of water process and ozone treatment, oxygen treatments applied and ozone treatment Combination or dioxygen water process, oxygen treatments applied and hypochlorite combination etc., preferably dioxygen water process, oxygen treatments applied and ozone The combination for the treatment of.

Preferably, in the alkali process alkali include NaOH, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium acid carbonate, One kind or at least two combination in potassium carbonate or saleratus, the combination is typical but non-limiting examples have：Hydroxide The combination of the combination of sodium and potassium hydroxide, the combination of NaOH and potassium hydroxide, potassium hydroxide and calcium hydroxide, sodium carbonate and Combination, the combination or NaOH of sodium acid carbonate and saleratus, combination of potassium hydroxide and calcium hydroxide of sodium acid carbonate etc..

Preferably, hypochlorite includes sodium hypochlorite and/or calcium hypochlorite in the hypochlorite treatment.

Preferably, the consumption of step (3) the second washing process reclaimed water is 0.5~50 times of bone dry fiber quality amount, Such as 0.5 times, 1 times, 2 times, 5 times, 8 times, 10 times, 15 times, 20 times, 25 times, 30 times, 35 times, 40 times, 45 times or 50 times, but simultaneously It is not limited only to other unrequited numerical value in cited numerical value, the number range equally applicable, more preferably 2~30 Times.

Boiling is carried out to fiber using organic solvent, the lignin in raw material is on the one hand eliminated, on the other hand can be same When degraded cellulose, the degree of polymerization of cellulose is met the product requirement of microcrystalline cellulose, it is to avoid the step of next step acid treatment Suddenly, the use of strong acid is reduced, while reducing the generation of acid waste water.

Preferably, the method for step (3) described dried process includes spray drying, vacuum drying, heat drying, naturally dry In dry or forced air drying any one or at least two combination, combination typical case but non-limiting examples have：Spray drying The combination of combination, heat drying and forced air drying with vacuum drying combination, heat drying and natural drying, spray drying and Combination or spray drying, vacuum drying and combination of heat drying of heat drying etc., are more preferably spray-dried, heat The combination of any one or two kinds in drying.

Preferably, the time of the dried process is 3~40 hours, such as 3 hours, 5 hours, 10 hours, 15 hours, it is 20 small When, 25 hours, 30 hours, 35 hours or 40 hours etc., it is not limited to other are not in cited numerical value, the number range The numerical value enumerated is equally applicable.

Preferably, the method for step (3) described pulverization process includes that extruding is crushed, shearing crushes, grinds or clash into In crushing any one or at least two combination, combination typical case but non-limiting examples have：Extruding is crushed and shearing powder Broken combination, grind and clash into combination, shearing that the combination crushed, extruding crush and grind and crush and clash into and crush Combination or extruding is crushed, shearing is crushed and the combination that grinds etc., preferably extruding is crushed or ground；

Preferably, the granularity of the microcrystalline cellulose that the pulverization process is obtained be 2~200 μm, such as 2 μm, 5 μm, 10 μm, 20 μm, 30 μm, 50 μm, 80 μm, 100 μm, 120 μm, 150 μm, 180 μm or 200 μm etc., it is not limited to cited numerical value, Other unrequited numerical value are equally applicable in the number range.

As currently preferred technical scheme, the described method comprises the following steps：

1) organic solvent of 1~30 times of over dry plant fiber material is used, in pressure 0.5 × 10⁵~3 × 10⁵Pa, temperature At for 50~200 DEG C, 10~600min is pre-processed to plant fiber material；To the pretreatment fluid that is obtained after pretreatment 0.1 × 10⁵~1.0 × 10⁵At a temperature of the pressure of Pa and 30~150 DEG C, it is concentrated under reduced pressure and reclaims organic solvent；

(2) it is water-soluble as 2~20 times of the quality of over dry plant fiber material of organic solvent or organic solvent with gross mass Liquid used as digestant, make by 0.1~10% polyacrylic acid of organic solvent or aqueous solutions of organic solvent and polyacrylic acid gross mass Be additive, the quality of over dry plant fiber material 0.01~10% catalyst, 0.5 × 10⁵~3 × 10⁵The pressure of Pa And 10~600min of boiling at a temperature of 70~200 DEG C, filtering, obtain cooking liquor and fiber；To the fiber that obtains using for Organic acid elution of 0.5~20 times of over dry plant fiber material quality 1~20 time, then with being over dry plant fiber material quality 0.5~20 times of water washing 1~20 time；

(3) fiber after the washing obtained with step (2) is as raw material, through acid treatment, the first washing process, bleaching, Second washing process, dried process and pulverization process prepare microcrystalline cellulose.

Compared with prior art, the present invention at least has the advantages that：

(1) present invention is pre-processed with organic solvent to plant fiber material, effectively eliminates the grey matter in raw material, and By acid cooking, the lignin in fiber is eliminated, therefore the application can be raw material preparation with woody or grass class plant Microcrystalline cellulose, compared to traditional microcrystalline cellulose preparation method, it is possible to decrease the cost more than 50% of raw material.

(2) present invention not remove only lignin impurity during acid cooking, while making fiber degradation to microcrystalline cellulose The degree of polymerization needed for element production, reduces the consumption of strong acid in production process, while reducing the yield of waste liquid in production.

(3) the microcrystalline cellulose yield that the inventive method production is obtained reaches as high as 96.5% 85% or so, and yield exists 85% or so, 92.2% is reached as high as, better than the purity and yield of prior art.

Brief description of the drawings

Fig. 1 is a kind of microcrystalline cellulose production method flow chart that the present invention is provided.

The present invention is described in more detail below.But following examples is only simple example of the invention, not generation Table or limitation the scope of the present invention, protection scope of the present invention are defined by claims.

Specific embodiment

For the present invention is better described, technical scheme is readily appreciated, below to the present invention further specifically It is bright.But following embodiments is only simple example of the invention, the scope of the present invention is not represented or limits, this Invention protection domain is defined by claims.

Specific embodiment of the invention part provide a kind of production method of microcrystalline cellulose, methods described as shown in figure 1, The described method comprises the following steps：

Embodiment 1

A kind of production method of microcrystalline cellulose, the described method comprises the following steps：

(1) benzene-alcohol mixture of 10 times of over dry plant fiber material is used, wherein benzene and the volume ratio of ethanol is 2:1, In pressure 1 × 10⁵Pa, temperature is at 80 DEG C, the 50g bagasse (moisture 12%) that 60 mesh screen-apertures are more than to particle diameter is pre- Treatment 50min；To the pretreatment fluid that is obtained after pretreatment 0.8 × 10⁵At a temperature of the pressure of Pa and 70 DEG C, it is concentrated under reduced pressure Reclaim benzene-alcohol mixture；

(2) using gross mass as 12 times of the quality of over dry plant fiber material acetic acid aqueous solution (concentration 95wt%) as Digestant, the quality of over dry plant fiber material 4% hydrochloric acid as catalyst, 1 × 10⁵The pressure of Pa and 100 DEG C At a temperature of boiling 180min, filtering, obtain cooking liquor；

(3) bleaching is carried out using hydrogen peroxide to the fiber that step (2) is obtained, over dry plant fiber material is used afterwards 50 times of water washing process is carried out to bleached fiber, then the fiber after washing is vacuum dried, finally using grinding Milling is broken to be crushed to required granularity by fiber, and microcrystalline cellulose is obtained.

The purity of the microcrystalline cellulose for preparing is 83%, and yield is 83.7%.

Embodiment 2

(1) benzene-alcohol mixture of 15 times of over dry plant fiber material is used, wherein benzene and the volume ratio of ethanol is 0.2: 1, in pressure 1.5 × 10⁵Pa, temperature be 70 DEG C at, to particle diameter more than 60 mesh screen-apertures 50g bagasse (moistures 12%) 120min is pre-processed；To the pretreatment fluid that is obtained after pretreatment 0.8 × 10⁵At a temperature of the pressure of Pa and 70 DEG C, It is concentrated under reduced pressure to reclaim benzene-alcohol mixture；

(2) with gross mass as 15 times of the quality of over dry plant fiber material of acetic acid and n-butyric acie mixing aqueous acid As digestant, counted by 100wt% of the quality of aqueous solutions of organic acids, wherein acetic acid content is 65%, n-butyric acie content is 24%, aqueous solutions of organic acids and polyacrylic acid gross mass 1% polyacrylic acid as additive, over dry plant fiber material The hydrochloric acid of the 3% of quality as catalyst, 1.5 × 10⁵Boiling 240min at a temperature of the pressure of Pa and 120 DEG C, filtering, Obtain cooking liquor；

(3) bleaching is carried out using NaOH to the fiber that step (2) is obtained, it is former using over dry string afterwards The water of 0.5 times of material carries out washing process to bleached fiber, then the fiber after washing is sprayed, finally using extruding Fiber is crushed to required granularity by crushing, and microcrystalline cellulose is obtained.

The purity of the microcrystalline cellulose for preparing is 86.3%, and yield is 84.2%.

Embodiment 3

(1) benzene-alcohol mixture of 20 times of over dry plant fiber material is used, wherein benzene and the volume ratio of ethanol is 5:1, In pressure 2 × 10⁵Pa, temperature is at 90 DEG C, the 50g bagasse (moisture 12%) that 60 mesh screen-apertures are more than to particle diameter is pre- Treatment 180min；To the pretreatment fluid that is obtained after pretreatment 0.8 × 10⁵At a temperature of the pressure of Pa and 70 DEG C, depressurize dense Retract and receive benzene-alcohol mixture；

(2) with gross mass as 20 times of the quality of over dry plant fiber material of acetic acid and isobutyric acid mixing aqueous acid As digestant, counted by 100wt% of the quality of aqueous solutions of organic acids, wherein acetic acid content is 70%, isobutyl acid content is 15%, aqueous solutions of organic acids and polyacrylic acid gross mass 5% polyacrylic acid as additive, over dry plant fiber material The hydrochloric acid of the 5% of quality as catalyst, 2 × 10⁵Boiling 300min at a temperature of the pressure of Pa and 150 DEG C, filtering, obtains To cooking liquor；

(3) bleaching is carried out respectively using hydrogen peroxide and NaOH to the fiber that step (2) is obtained, afterwards using exhausted The water of 25 times of dry plant fiber material carries out washing process to bleached fiber, then the fiber after washing is carried out vacuum do Dry, finally use grinds and for fiber to be crushed to required granularity, and microcrystalline cellulose is obtained.

The purity of the microcrystalline cellulose for preparing is 89.7%, and yield is 85.0%.

Embodiment 4

(1) acetic acid aqueous solution of 25 times of over dry plant fiber material is used, the wherein concentration of acetic acid is 95wt%, in pressure 1×10⁵Pa, temperature is at 100 DEG C, the 100g straws that 60 mesh screen-apertures are more than to particle diameter pre-process 240min；To pretreatment The pretreatment fluid for obtaining afterwards is 0.7 × 10⁵At a temperature of the pressure of Pa and 100 DEG C, it is concentrated under reduced pressure and reclaims acetic acid solution；

(2) using gross mass as 10 times of the quality of over dry plant fiber material acetic acid aqueous solution (concentration 70wt%) as The polyacrylic acid of the 0.5% of digestant, aqueous solutions of organic acids and polyacrylic acid gross mass is used as additive, and over dry string is former The sulfuric acid of the 0.5% of the quality of material as catalyst, 1 × 10⁵Boiling 360min at a temperature of the pressure of Pa and 100 DEG C, Filtering, obtains cooking liquor；

(3) bleaching is carried out using ozone and oxygen to the fiber that step (2) is obtained, over dry string is used afterwards The water of 20 times of raw material carries out washing process to bleached fiber, then the fiber after washing is thermally dried, and finally adopts Crushed with shearing and fiber is crushed to required granularity, microcrystalline cellulose is obtained.

The purity of the microcrystalline cellulose for preparing is 90.3%, and yield is 87.8%.

Embodiment 5

(1) acetic acid aqueous solution of 30 times of over dry plant fiber material is used, the wherein concentration of acetic acid is 10wt%, in pressure 1×10⁵Pa, temperature is at 100 DEG C, the 100g straws that 60 mesh screen-apertures are more than to particle diameter pre-process 300min；To pretreatment The pretreatment fluid for obtaining afterwards is 0.7 × 10⁵At a temperature of the pressure of Pa and 100 DEG C, it is concentrated under reduced pressure and reclaims acetic acid solution；

(2) with gross mass as 5 times of the quality of over dry plant fiber material of acetic acid and n-butyric acie mixing aqueous acid As digestant, counted by 100wt% of the quality of aqueous solutions of organic acids, wherein acetic acid content is 80%, n-butyric acie content is 14.9%, aqueous solutions of organic acids and polyacrylic acid gross mass 0.1% polyacrylic acid as additive, over dry string is former The nitric acid of the 0.1% of the quality of material as catalyst, 1 × 10⁵Boiling 420min at a temperature of the pressure of Pa and 100 DEG C, Filtering, obtains cooking liquor；

(3) bleaching is carried out using ozone and hydrogen peroxide to the fiber that step (2) is obtained, it is fine using over dry plant afterwards The water of 30 times of dimension raw material carries out washing process to bleached fiber, then the fiber after washing is spontaneously dried, finally Fiber is crushed to required granularity using clashing into crush, microcrystalline cellulose is obtained.

The purity of the microcrystalline cellulose for preparing is 87.3%, and yield is 86.0%.

Embodiment 6

(1) acetone of 10 times of over dry plant fiber material is used, in pressure 1 × 10⁵Pa, temperature be 50 DEG C at, to particle diameter 100g cornstalks more than 60 mesh screen-apertures pre-process 30min；To the pretreatment fluid that is obtained after pretreatment 0.9 × 10⁵Pa Pressure and 40 DEG C at a temperature of, be concentrated under reduced pressure reclaim acetone；

(2) using gross mass as 15 times of the quality of over dry plant fiber material acetic acid aqueous solution (concentration 30wt%) as The polyacrylic acid of the 5% of digestant, aqueous solutions of organic acids and polyacrylic acid gross mass is used as additive, over dry plant fiber material Quality 5% hydrochloric acid as catalyst, 1 × 10⁵Boiling 480min at a temperature of the pressure of Pa and 70 DEG C, filtering, Obtain cooking liquor；

(3) bleaching is carried out using sodium hypochlorite to the fiber that step (2) is obtained, it is former using over dry string afterwards The water of 40 times of material carries out washing process to bleached fiber, then the fiber after washing is vacuum dried and is heated dry It is dry, finally use extruding to crush and grind and fiber is crushed to required granularity, microcrystalline cellulose is obtained.

The purity of the microcrystalline cellulose for preparing is 83.5%, and yield is 85.2%.

Embodiment 7

(1) toluene of 1 times of over dry plant fiber material is used, in pressure 3 × 10⁵Pa, temperature be 80 DEG C at, it is big to particle diameter 420min is pre-processed in the 100g hardwood of 60 mesh screen-apertures；To the pretreatment fluid that is obtained after pretreatment 0.8 × 10⁵The pressure of Pa At a temperature of power and 80 DEG C, it is concentrated under reduced pressure and reclaims toluene；

(2) with gross mass as 15 times of the quality of over dry plant fiber material of acetic acid and n-butyric acie mixing aqueous acid As digestant, counted by 100wt% of the quality of aqueous solutions of organic acids, wherein acetic acid content is 85%, n-butyric acie content is 5%, aqueous solutions of organic acids and polyacrylic acid gross mass 5% polyacrylic acid as additive, over dry plant fiber material The sulfuric acid of the 5% of quality as catalyst, 0.5 × 10⁵Boiling 540min at a temperature of the pressure of Pa and 90 DEG C, filtering, Obtain cooking liquor；

(3) the fiber use quality obtained to step (2) is the hydrochloric acid of the 0.5wt% of 30 times of over dry plant fiber material, At 150 DEG C and 2 × 10⁵Acid treatment 600min is carried out under Pa, afterwards using the water of 0.5 times of over dry plant fiber material to acid at Fiber after reason carries out the first washing process, and reusing hydrogen peroxide, sodium hypochlorite carries out bleaching, and over dry plant is used afterwards The water of 25 times of fibrous raw material carries out the second washing process to bleached fiber, then the fiber after washing is carried out vacuum do Dry, finally use grinds and for fiber to be ground to required granularity, and microcrystalline cellulose is obtained.

The purity of the microcrystalline cellulose for preparing is 87.8%, and yield is 88.0%.

Embodiment 8

(1) normal propyl alcohol of 10 times of over dry plant fiber material is used, in pressure 0.5 × 10⁵Pa, temperature be 80 DEG C at, it is right 100g cork pretreatment 600min of the particle diameter more than 60 mesh screen-apertures；To the pretreatment fluid that is obtained after pretreatment 0.1 × 10⁵At a temperature of the pressure of Pa and 60 DEG C, it is concentrated under reduced pressure and reclaims normal propyl alcohol；

(2) with gross mass as 10 times of the quality of over dry plant fiber material of acetic acid and isobutyric acid mixing aqueous acid As digestant, counted by 100wt% of the quality of aqueous solutions of organic acids, wherein acetic acid content is 80%, isobutyl acid content is 14%, aqueous solutions of organic acids and polyacrylic acid gross mass 1% polyacrylic acid as additive, over dry plant fiber material The hydrochloric acid of the 1% of quality as catalyst, 3 × 10⁵Boiling 540min at a temperature of the pressure of Pa and 200 DEG C, filtering, obtains To cooking liquor；

(3) the fiber use quality obtained to step (2) is the hydrochloric acid of the 20wt% of 1 times of over dry plant fiber material, 30 DEG C and 1 × 10⁵Acid treatment 10min is carried out under Pa, afterwards using the water of 50 times of over dry plant fiber material to acid treatment after Fiber carry out the first washing process, reuse NaOH, hydrogen peroxide and sodium hypochlorite carries out bleaching respectively, makes afterwards The second washing process is carried out to bleached fiber with 25 times of over dry plant fiber material of water, then the fiber after washing is entered Capable vacuum drying, finally use grinds and for fiber to be ground to required granularity, and microcrystalline cellulose is obtained.

The purity of the microcrystalline cellulose for preparing is 90.3%, and yield is 88.0%.

Embodiment 9

(1) ethanol water (concentration of alcohol 95%) of 10 times of over dry plant fiber material is used, in pressure 1 × 10⁵Pa, Temperature is at 80 DEG C, the 100g corks that 60 mesh screen-apertures are more than to particle diameter pre-process 300min；It is pre- to what is obtained after pretreatment Treatment fluid is 0.1 × 10⁵At a temperature of the pressure of Pa and 60 DEG C, it is concentrated under reduced pressure and reclaims ethanol；

(2) with gross mass as 10 times of the quality of over dry plant fiber material of acetic acid and n-butyric acie mixing aqueous acid As digestant, counted by 100wt% of the quality of aqueous solutions of organic acids, wherein acetic acid content is 97%, n-butyric acie content is 2%, aqueous solutions of organic acids and polyacrylic acid gross mass 1% polyacrylic acid as additive, over dry plant fiber material The hydrochloric acid of the 1% of quality as catalyst, 1 × 10⁵Boiling 240min at a temperature of the pressure of Pa and 80 DEG C, filtering, obtains To cooking liquor；

(3) the fiber use quality obtained to step (2) is the hydrochloric acid of the 10wt% of 10 times of over dry plant fiber material, 60 DEG C and 1.5 × 10⁵Acid treatment 240min is carried out under Pa, afterwards using the water of 20 times of over dry plant fiber material to acid treatment Fiber afterwards carries out the first washing process, and reusing NaOH, hydrogen peroxide and oxygen carries out bleaching, and over dry is used afterwards The water of 25 times of plant fiber material carries out the second washing process to bleached fiber, then carries out vacuum to the fiber after washing Drying, finally use grinds and for fiber to be ground to required granularity, and microcrystalline cellulose is obtained.

The purity of the microcrystalline cellulose for preparing is 93.5%, and yield is 91.3%.

Embodiment 10

(2) with gross mass as 10 times of the quality of over dry plant fiber material of acetic acid and isobutyric acid mixing aqueous acid As digestant, counted by 100wt% of the quality of aqueous solutions of organic acids, wherein acetic acid content is 97%, isobutyl acid content is 2%, aqueous solutions of organic acids and polyacrylic acid gross mass 1% polyacrylic acid as additive, over dry plant fiber material The hydrochloric acid of the 3% of quality as catalyst, 1 × 10⁵Boiling 540min at a temperature of the pressure of Pa and 80 DEG C, filtering, obtains To cooking liquor；

(3) the fiber use quality obtained to step (2) is the hydrochloric acid of the 15wt% of 20 times of over dry plant fiber material, 90 DEG C and 1.8 × 10⁵Acid treatment 120min is carried out under Pa, afterwards using the water of 50 times of over dry plant fiber material to acid treatment Fiber afterwards carries out the first washing process, and reusing NaOH, hydrogen peroxide and ozone carries out bleaching, and over dry is used afterwards The water of 30 times of plant fiber material carries out the second washing process to bleached fiber, then carries out vacuum to the fiber after washing Drying, finally use grinds and for fiber to be ground to required granularity, and microcrystalline cellulose is obtained.

The purity of the microcrystalline cellulose for preparing is 96.5%, and yield is 92.2%.

Embodiment 11

(2) it is 15 times of the quality of over dry plant fiber material of ethanol as digestant, ethanol and poly- third using gross mass The polyacrylic acid of the 5% of olefin(e) acid gross mass as additive, the quality of over dry plant fiber material 5% sulfuric acid as catalysis Agent, 0.5 × 10⁵Boiling 540min at a temperature of the pressure of Pa and 90 DEG C, filtering, obtains cooking liquor；

(3) the fiber use quality obtained to step (2) is the hydrochloric acid of the 0.5wt% of 30 times of over dry plant fiber material, At 150 DEG C and 2 × 10⁵Acid treatment 600min is carried out under Pa, afterwards using the water of 0.5 times of over dry plant fiber material to acid at Fiber after reason carries out the first washing process, and reusing hydrogen peroxide carries out bleaching, and over dry plant fiber material is used afterwards 25 times of water the second washing process is carried out to bleached fiber, then the fiber after washing is vacuum dried, finally adopt Fiber is ground to required granularity with grinding, microcrystalline cellulose is obtained.

The purity of the microcrystalline cellulose for preparing is 86.3%, and yield is 87.1%.

Embodiment 12

(2) it is 10 times of the quality of over dry plant fiber material of acetone as digestant, acetone and poly- third using gross mass The polyacrylic acid of the 1% of olefin(e) acid gross mass as additive, the quality of over dry plant fiber material 1% hydrochloric acid as catalysis Agent, 3 × 10⁵Boiling 540min at a temperature of the pressure of Pa and 200 DEG C, filtering, obtains cooking liquor；

(3) the fiber use quality obtained to step (2) is the hydrochloric acid of the 20wt% of 1 times of over dry plant fiber material, 30 DEG C and 1 × 10⁵Acid treatment 10min is carried out under Pa, afterwards using the water of 50 times of over dry plant fiber material to acid treatment after Fiber carry out the first washing process, reuse hydrogen peroxide and sodium hypochlorite carries out bleaching respectively, is planted using over dry afterwards The water of 25 times of fibres raw material carries out washing process to bleached fiber, then the fiber after washing is vacuum dried, Finally use to grind and fiber is ground to required granularity, microcrystalline cellulose is obtained.

The purity of the microcrystalline cellulose for preparing is 82.2%, and yield is 85.6%.

Embodiment 13

(2) it is 10 times of the quality of over dry plant fiber material of toluene as digestant, over dry plant fibre using gross mass Tie up raw material quality 1% hydrochloric acid as catalyst, 1 × 10⁵Boiling 240min at a temperature of the pressure of Pa and 80 DEG C, Filtering, obtains cooking liquor；

(3) the fiber use quality obtained to step (2) is the hydrochloric acid of the 10wt% of 10 times of over dry plant fiber material, 60 DEG C and 1.5 × 10⁵Acid treatment 240min is carried out under Pa, afterwards using the water of 20 times of over dry plant fiber material to acid treatment Fiber afterwards carries out the first washing process, and reuse hydrogen peroxide and calcium hypochlorite carries out bleaching respectively, and over dry is used afterwards The water of 25 times of plant fiber material carries out washing process to bleached fiber, then the fiber after washing is carried out vacuum do Dry, finally use grinds and for fiber to be ground to required granularity, and microcrystalline cellulose is obtained.

The purity of the microcrystalline cellulose for preparing is 85.6%, and yield is 83.1%.

Embodiment 14

(2) with gross mass as 10 times of the quality of over dry plant fiber material of isopropanol and the mixed solvent of cyclopentanedione (volume ratio 1:1) as digestant, isopropanol and cyclopentanedione mixed solvent and polyacrylic acid gross mass 1% polyacrylic acid As additive, the quality of over dry plant fiber material 1% hydrochloric acid as catalyst, 1 × 10⁵The pressure of Pa and 80 Boiling 540min at a temperature of DEG C, filtering, obtains cooking liquor；

(3) the fiber use quality obtained to step (2) is the hydrochloric acid of the 15wt% of 20 times of over dry plant fiber material, 90 DEG C and 1.8 × 10⁵Acid treatment 120min is carried out under Pa, afterwards using the water of 50 times of over dry plant fiber material to acid treatment Fiber afterwards carries out the first washing process, and reuse hydrogen peroxide and ozone carries out bleaching respectively, and over dry plant is used afterwards The water of 30 times of fibrous raw material carries out washing process to bleached fiber, then the fiber after washing is vacuum dried, most Use to grind afterwards and fiber is ground to required granularity, microcrystalline cellulose is obtained.

The purity of the microcrystalline cellulose for preparing is 91.3%, and yield is 88.4%.

Embodiment 15

A kind of production method of microcrystalline cellulose, except 15 times with gross mass as the quality of over dry plant fiber material Ethanol water (concentration 95%) as digestant outside, other conditions are identical with embodiment 11.

The purity of the microcrystalline cellulose for preparing is 84.4%, and yield is 83.1%.

Embodiment 16

A kind of production method of microcrystalline cellulose, except 10 times with gross mass as the quality of over dry plant fiber material Aqueous acetone solution (concentration 20%) as digestant outside, other conditions are identical with embodiment 12.

The purity of the microcrystalline cellulose for preparing is 86.2%, and yield is 83.3%..

Comparative example 1

A kind of production method of microcrystalline cellulose, methods described except not include step (1) described pre-treatment step, other Condition is same as Example 3.

The purity of the microcrystalline cellulose for preparing is 65.7%, and yield is 71.2%.

Comparative example 2

A kind of production method of microcrystalline cellulose, methods described is molten using the sodium carbonate of 25wt% concentration except step (1) Liquid is replaced outside benzene-ethanol, and other are same as Example 3.

The purity of the microcrystalline cellulose for preparing is 73.1%, and yield is 74.7%.

Comparative example 3

A kind of production method of microcrystalline cellulose, methods described is molten using the sodium carbonate of 50wt% concentration except step (1) Liquid is replaced outside benzene-ethanol, and other are same as Example 3.

The purity of the microcrystalline cellulose for preparing is 75.3%, and yield is 76.0%.

Comparative example 4

A kind of production method of microcrystalline cellulose, methods described is except step (1) is using the sodium carbonate liquor of 1wt% concentration Replace outside benzene-ethanol, other are same as Example 3.

The purity of the microcrystalline cellulose for preparing is 68.5%, and yield is 74.1%.

Obtained by being can be seen that without organic solvent pretreatment by embodiment 1 and comparative example 1-4 without cellulose Purity it is low, and the side of the purity of microcrystalline cellulose obtained through sodium carbonate liquor pretreatment production and organic solvent pretreatment Method is compared, and the purity of the microcrystalline cellulose that production is obtained is also low.As can be seen that using herein described compared with comparative example 5 The microcrystalline cellulose purity and yield that method production is obtained are above prior art, and the usage amount of prior art hydrochloric acid will be much More than method described herein.

Applicant states that the present invention illustrates detailed construction feature of the invention by above-described embodiment, but the present invention is simultaneously Above-mentioned detailed construction feature is not limited to, that is, does not mean that the present invention has to rely on above-mentioned detailed construction feature and could implement.Institute Category those skilled in the art it will be clearly understood that any improvement in the present invention, to the equivalence replacement of part selected by the present invention And increase, the selection of concrete mode of accessory etc., within the scope of all falling within protection scope of the present invention and disclosing.

The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this A little simple variants belong to protection scope of the present invention.

It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy is no longer separately illustrated.

Additionally, can also be combined between a variety of implementation methods of the invention, as long as it is without prejudice to originally The thought of invention, it should equally be considered as content disclosed in this invention.

Claims

1. a kind of production method of microcrystalline cellulose, it is characterised in that the described method comprises the following steps：

(1) plant fiber material is pre-processed using organic solvent or aqueous solutions of organic solvent, is obtained by pretreatment Plant fiber material and pretreatment fluid；

(2) it is boiling solvent with organic solvent or aqueous solutions of organic solvent, and adds catalyst, it is pretreated to step (1) Plant fiber material carries out boiling, and separation of solid and liquid obtains cooking liquor and fiber；

(3) fiber for being obtained with step (2) as raw material, through alternatively acid treatment and alternatively the first washing process, then through bleaching Treatment, the second washing process, dried process and pulverization process prepare microcrystalline cellulose.

2. method according to claim 1, it is characterised in that step (1) described organic solvent is molten benzene kind solvent, alcohols In agent, ketones solvent or organic acid solvent any one or at least two composition；

Preferably, the benzene kind solvent is benzene, toluene, ethylbenzene, n-proplbenzene, isopropylbenzene, paraxylene, ortho-xylene, a diformazan In benzene or mesitylene any one or at least two combination；

Preferably, the alcohols solvent includes methyl alcohol, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, n-hexyl alcohol, hexamethylene In alcohol, n-octyl alcohol, phenmethylol or benzyl carbinol any one or at least two combination；

Preferably, the ketones solvent is including in acetone, butanone, two butanone, pentanedione, cyclopentanedione, cyclohexanone or acetophenone Any one or at least two combination；

Preferably, the organic acid solvent is formic acid, acetic acid, ethanedioic acid, propionic acid, malonic acid, n-butyric acie, isobutyric acid, benzene first Acid or phenylacetic acid in any one or at least two combination；

Preferably, step (1) described aqueous solutions of organic solvent is the alcohols solvent aqueous solution, the ketones solvent aqueous solution or organic acid In solvent aqueous solution any one or at least two combination；

Preferably, the concentration of step (1) described aqueous solutions of organic solvent is 20~100%, without 100%, more preferably 60~100%, without 100%；

Preferably, step (1) described organic solvent is the mixed acid or acetic acid and isobutyric mixed acid of acetic acid and n-butyric acie；

Preferably, in the mixed acid of the acetic acid and n-butyric acie, counted by 100wt% of the quality of mixed acid, the content of acetic acid is 60~98%, balance of n-butyric acie；

Preferably, in the acetic acid and isobutyric mixed acid, counted by 100wt% of the quality of mixed acid, the content of acetic acid is 60~98%, balance of isobutyric acid；

Preferably, step (1) described aqueous solutions of organic solvent is the mixed acid aqueous solution or acetic acid and isobutyl of acetic acid and n-butyric acie The mixed acid aqueous solution of acid；

Preferably, in the mixed acid aqueous solution of the acetic acid and n-butyric acie, counted by 100wt% of the quality of mixed acid aqueous solution, The content of acetic acid is 60~98%, and the content of n-butyric acie is 1~40%, balance of water；

Preferably, in the acetic acid and isobutyric mixed acid or mixed acid aqueous solution, the quality with mixed acid aqueous solution is 100wt% is counted, and the content of acetic acid is 60~98%, and isobutyric content is 1~40%, balance of water.

3. method according to claim 1 or claim 2, it is characterised in that step (1) described plant fiber material is fine over dry plant Dimension raw material；

Preferably, the consumption of step (1) organic solvent is 1~30 times of over dry plant fiber material quality, preferably 2~20 Times；

Preferably, the method for step (1) described pretreatment for diafiltration, dipping, boiling or washing in any one or at least two Combination, more preferably impregnate；

Preferably, the pressure of step (1) described pretreatment is 0.5 × 10⁵~3 × 10⁵Pa, more preferably 1 × 10⁵~2 × 10⁵Pa；

Preferably, the temperature of step (1) described pretreatment is 50~200 DEG C, more preferably 70~200 DEG C；

Preferably, the time of step (1) described pretreatment is 10~600min, more preferably 30~300min.

4. according to claim 1-3 any one methods describeds, it is characterised in that pretreatment fluid described in step (1) is subtracted Pressure concentration, reclaims organic solvent；

Preferably, the pressure of the evaporation and concentration is 0.1 × 10⁵~1.0 × 10⁵Pa, more preferably 0.1 × 10⁵~0.7 ×10⁵Pa, particularly preferably 0.1 × 10⁵Pa；

Preferably, the temperature of the evaporation and concentration is 30~150 DEG C, more preferably 50~100 DEG C, particularly preferably 70 ℃。

5. according to claim 1-4 any one methods describeds, it is characterised in that plant fiber material described in step (1) is powder By the plant fiber material that leaves after the screen cloth screening of mesh number >=30 mesh after fragmentation, preferably woody plant fiber material or/ With grass class plant fiber material；

Preferably, the woody plant fiber material includes any one in hardwood, cork or shrub or at least two Combination；

Preferably, the grass class plant fiber material is including any in bagasse, bamboo, straw, wheat straw, cornstalk or reed It is a kind of or at least two combination.

6. according to claim 1-5 any one methods describeds, it is characterised in that catalyst described in step (2) be inorganic acid and/ Or hydrogen peroxide；

Preferably, the quality of the catalyst is the 0.01~10% of the quality of over dry plant fiber material, more preferably 2 ~10%；

Preferably, the inorganic acid be hydrochloric acid, nitric acid or sulfuric acid in any one or at least two combination, further it is excellent Elect hydrochloric acid as；

Preferably, the gross mass of step (2) organic solvent or aqueous solutions of organic solvent is the matter of over dry plant fiber material 2~20 times, more preferably 2~15 times of amount；

Preferably, step (2) described organic solvent is in benzene kind solvent, alcohols solvent, ketones solvent or organic acid solvent Any one or at least two composition；

Preferably, the aqueous solutions of organic solvent is the alcohols solvent aqueous solution, the ketones solvent aqueous solution or organic acid aqueous solvent In solution any one or at least two combination；

Preferably, the concentration of the aqueous solutions of organic solvent is 20~100%, without 100%, more preferably 60~ 100%, without 100%；

Preferably, polyacrylic acid is also added as digesting assistant in step (2) described digestion process；

Preferably, the addition of the polyacrylic acid accounts for organic solvent or aqueous solutions of organic solvent and polyacrylic acid gross mass 0.1~10%, more preferably 1~5%；

Preferably, aqueous solutions of organic solvent described in step (2) is the mixed acid aqueous solution of acetic acid and n-butyric acie, in the mixed acid In the aqueous solution, counted by 100wt% of the quality of aqueous solutions of organic acids, the content of acetic acid is 60~98%, the content of n-butyric acie is 1 ~40%, balance of water；

Preferably, aqueous solutions of organic solvent described in step (2) is the mixed acid aqueous solution of acetic acid and n-butyric acie, works as digestion process When addition polyacrylic acid is as digesting assistant, counted by 100wt% of the quality sum of aqueous solutions of organic acids and polyacrylic acid, acetic acid Content be 68~97%, n-butyric acie content is 1~30%, and the content of polyacrylic acid is 1~5%, balance of water；

Preferably, aqueous solutions of organic solvent described in step (2) is acetic acid and isobutyric mixed acid aqueous solution, in the mixed acid In the aqueous solution, counted by 100wt% of the quality of aqueous solutions of organic acids, the content of acetic acid is 60~98%, and isobutyric content is 1 ~40%, balance of water；

Preferably, aqueous solutions of organic solvent described in step (2) is acetic acid and isobutyric mixed acid aqueous solution, works as digestion process When addition polyacrylic acid is as digesting assistant, counted by 100wt% of the quality sum of aqueous solutions of organic acids and polyacrylic acid, acetic acid Content be 68~97%, isobutyl acid content is 1~30%, and the content of polyacrylic acid is 1~5%, balance of water；

Preferably, the temperature of step (2) described boiling is 70~200 DEG C, preferably 90~150 DEG C；

Preferably, the time of step (2) described boiling is 10~600min, more preferably 50~300min；

Preferably, the pressure of step (2) described boiling is 0.5 × 10⁵~3 × 10⁵Pa, more preferably 1 × 10⁵~2 × 10⁵Pa。

7. according to claim 1-6 any one methods describeds, it is characterised in that step (2) described solid-liquid separating method for filtering, Sedimentation, evaporation or centrifugation in any one or at least two combination, more preferably filter；

Preferably, carry out organic acid elution and water washing successively to the fiber obtained in step (2) carries out step (3) again, collects The cleaning solution that organic acid elution and the water washing are produced；

Preferably, the organic acid that organic acid elution is used is formic acid, acetic acid, ethanedioic acid, propionic acid, malonic acid, n-butyric acie, different In butyric acid, benzoic acid or phenylacetic acid any one or at least two combination；

Preferably, the organic acid quality of the washing and the quality of water independently are over dry plant fiber material quality 0.5~20 times, washing times independently are 1~20 time.

8. according to claim 1-7 any one methods describeds, it is characterised in that in step (3) described acid treatment acid include hydrochloric acid, In sulfuric acid, nitric acid, phosphoric acid, hypochlorous acid, permanganic acid, molybdic acid, formic acid, acetic acid, ethanedioic acid, propionic acid, malonic acid, butyric acid or succinic acid Any one or at least two combination, more preferably hydrochloric acid；

Preferably, the concentration of the acid is 0.5~20wt%；

Preferably, the consumption of the acid is 1~30 times of over dry plant fiber material gross mass；

Preferably, the temperature of step (3) described acid treatment is 30~150 DEG C；

Preferably, the pressure of step (3) described acid treatment is 1 × 10⁵~2 × 10⁵Pa；

Preferably, the time of step (3) described acid treatment is 10~600min；

Preferably, the consumption of step (3) the first washing process reclaimed water is 0.5~50 times of bone dry fiber element raw material.

9. according to claim 1-8 any one methods describeds, it is characterised in that step (3) described bleaching includes hydrogen peroxide Treatment, oxygen treatments applied, alkali process, ozone treatment, chlorine dioxide treatment and hypochlorite treatment any one or at least two Combination, preferably dioxygen water process, oxygen treatments applied and ozone treatment combination；

Preferably, alkali includes NaOH, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium acid carbonate, carbonic acid in the alkali process One kind or at least two combination in potassium or saleratus；

Preferably, hypochlorite includes sodium hypochlorite and/or calcium hypochlorite in the hypochlorite treatment；

Preferably, the consumption of step (3) the second washing process reclaimed water is the 0.5~50 of over dry plant fiber material quality Times, more preferably 2~30 times；

Preferably, the method for step (3) described dried process include spray drying, vacuum drying, heat drying, natural drying or In forced air drying any one or at least two combination, more preferably spray drying, in heat drying any one or Two kinds of combination；

Preferably, the time of the dried process is 3~40 hours；

Preferably, the method for step (3) described pulverization process includes that extruding is crushed, shearing crushes, grinds or clash into crushing In any one or at least two combination, preferably extruding crush or grind；

Preferably, the granularity of the microcrystalline cellulose that the pulverization process is obtained is 2~200 μm.

10. the preparation method according to claim any one of 1-9, it is characterised in that the described method comprises the following steps：

(1) organic solvent of 1~30 times of over dry plant fiber material is used, in pressure 0.5 × 10⁵~3 × 10⁵Pa, temperature is 50 At~200 DEG C, 10~600min is pre-processed to plant fiber material；To the pretreatment fluid that is obtained after pretreatment 0.1 × 10⁵~ 1.0×10⁵At a temperature of the pressure of Pa and 30~150 DEG C, it is concentrated under reduced pressure and reclaims organic solvent；

(2) make by 2~20 times of the quality of over dry plant fiber material of organic solvent or aqueous solutions of organic solvent of gross mass It is digestant, addition accounts for the polyacrylic acid of the 0.1~10% of organic solvent or aqueous solutions of organic solvent and polyacrylic acid gross mass As additive, the 0.01~10% of the quality of over dry plant fiber material catalyst is added, 0.5 × 10⁵~3 × 10⁵Pa Pressure and 70~200 DEG C at a temperature of 10~600min of boiling, filtering, obtain cooking liquor and fiber；To the fiber for obtaining Using organic acid elution 1~20 time of 0.5~20 times for over dry plant fiber material quality, then with being former over dry string The water washing of 0.5~20 times of material quality 1~20 time；

(3) fiber after the washing obtained with step (2) is as raw material, through acid treatment, the first washing process, bleaching, washing Treatment, dried process and pulverization process prepare microcrystalline cellulose.