CN107129540B - The Green production method of hydroxypropyl methylcellulose - Google Patents
The Green production method of hydroxypropyl methylcellulose Download PDFInfo
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- CN107129540B CN107129540B CN201610122501.6A CN201610122501A CN107129540B CN 107129540 B CN107129540 B CN 107129540B CN 201610122501 A CN201610122501 A CN 201610122501A CN 107129540 B CN107129540 B CN 107129540B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/193—Mixed ethers, i.e. ethers with two or more different etherifying groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
- C08B1/08—Alkali cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
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Abstract
The present invention relates to the Green production methods of hydroxypropyl methylcellulose.The present invention uses toluene-isopropanol-water mixed system, purified cotton after crushed reacts production with propylene oxide, chloromethanes in the presence of alkali and obtains HPMC crude product, the HPMC crude product is mixed with toluene-isopropanol-water mixed system, it needs then to post-process HPMC crude product solvent recovery.The present invention drains into the mixed system after neutralization in precipitation kettle, while stirring plus top hot water, continuously stirs 10 minutes or more, then static 20 minutes or more, forms solid-liquid-gas three phase；Most liquid solvent is recycled from the discharge of pipes of precipitation kettle waist position；Remaining fraction liquid solvent and gaseous solvent are recycled through distillation approach again.The scheme directly distilled compared with prior art, the present invention reduces energy consumption significantly, and the purity of HPMC crude product is higher, also reduces the processing difficulty of later period HPMC.
Description
Technical field
The present invention relates to the production method of hydroxypropyl methylcellulose more particularly to the Green production methods of hydroxypropyl methylcellulose.
Background technique
The production of domestic HPMC largely uses toluene-isopropanol-water mixed system, and the purified cotton after crushed is in alkali
Effect is lower to react production with propylene oxide, chloromethanes；The mixed gas of toluene, isopropanol can be generated in production process；Chloromethane
The side reaction product of alkane, propylene oxide；Contain sodium chloride and sodium acetate in waste water.Currently, the production technology of country HPMC is basic
On be all: a step slurry process, rough processing step are as follows: (1), pretreatment: purified cotton is made to the purified cotton of 60-100 mesh
Powder；(2) it alkalizes: purified cotton powder being reacted in the dispersion of 8-10 times of mixed solvent with alkali, alkalinized celluloses are generated；
(3), be etherified: etherification reaction occurs for alkalinized celluloses and propylene oxide, chloromethanes, HPMC crude product is made, which is dispersed in molten
In agent system；(4), it neutralizes: after reaction, remaining alkali is neutralized with acid, the pH value of product is made to reach defined requirement；
(5), solvent recovery: the mixed system after neutralization is heated up, after the recovery by condensing, cooling down the mixed solvent of recovery system
Solvent repeated recycling utilize；(6), post-process: the mixture after precipitation passes through horizontal decanter centrifuge, and centrifuge separation is being passed through
It is granulated, is dry, mixing, packing as final products.This method side reaction degree is low, product yield is high；But in solvent recovery
Link has that evaporation recycling energy consumption is high.
Summary of the invention
The invention solves the above problems, to provide a kind of Green production method of hydroxypropyl methylcellulose.
Technical proposal that the invention solves the above-mentioned problems is as follows:
The Green production method of hydroxypropyl methylcellulose, comprising the following steps:
1) it, pre-processes: purified cotton being broken into about 1-3 centimetres of diameter of purified cotton block by opener, subsequently into powder
Broken machine, through high energy shear milling at the purified cotton powder of 60-100 mesh；
2), alkalize: smashed purified cotton powder in the dispersion of 8-10 times of toluene-isopropanol-water mixed solvent,
Alkalinization occurs with alkali, generates the alkali cellulose with reactivity；
3), be etherified: etherification reaction occurs for alkali cellulose and propylene oxide, chloromethanes, by reaction temperature, reaction time
Pass through the content control to oxidant in system environment with the control of formula to adjust the height of methoxyl group and hydroxypropyl degree of substitution
System and purified cotton raw materials selection come adjust product viscosity height；
4) it, neutralizes: after reaction, remaining alkali is neutralized with acid；
5), precipitation: the mixed system after neutralization is drained into precipitation kettle, and the reinforcing of precipitation kettle is opened when discharge starts
Stirring continuously stirs 10 minutes or more while stirring plus top hot water, then static 20 minutes or more, forms solid-liquid-gas three phase；
Most liquid solvent is recycled from the discharge of pipes of precipitation kettle waist position；Again by the liquid solvent of part and gaseous solvent through steaming
Evaporate approach recycling；
6), post-process: mixture after precipitation passes through horizontal decanter centrifuge, centrifuge separation, using granulation, drying,
Mixing, packaging become final products.
As a preferred embodiment of the above technical solution, in step 5), reinforcing stirring, the reinforcing stirring are carried out by stirring structure
It is level-one blade to be added on the agitating shaft of precipitation kettle, and upper and lower blade is connected to the frame knot to be formed using connecting rod
Structure.
As a preferred embodiment of the above technical solution, in step 5), the additional amount of hot water is 0.6~1.0 times of solvent volume.
As a preferred embodiment of the above technical solution, in step 5), liquid solvent imports after the discharge of the pipeline of precipitation kettle waist position
Into bypass channel tank, and after through static layering, water is discharged.
As a preferred embodiment of the above technical solution, in step 5), after hot water is added, to prevent temperature lower than 100 DEG C.
As a preferred embodiment of the above technical solution, in step 5), before solvent discharge, pneumatic operated valve need to be first opened, then open on visor
Square ball valve.
As a preferred embodiment of the above technical solution, in step 5), when solvent discharge, Yao Xiankai solvent tube valve, with a small portion
Point solvent recoil delivery pipe and pneumatic operated valve, it is appropriate it is static once.
As a preferred embodiment of the above technical solution, in step 5), when solvent discharge, start solvent pump, then a little open solvent
Pipe ball valve observes the situation of recycling design in visor, solvent clear, then gradually opens big solvent pipe ball valve, increases solvent
Recycle speed.
As a preferred embodiment of the above technical solution, in step 5), when solvent discharge is completed, solvent pump is shut down, then with a small amount of height
Position slot solvent suitably recoils solvent discharge pipe and pneumatic operated valve, is then shut off each valve.
As a preferred embodiment of the above technical solution, in step 5), when solvent discharge, if solvent is opaque, containing a large amount of materials,
And continuously, then it must terminate solvent discharge in time, closing valve and stop solvent pump, it is then appropriate with a small amount of head tank solvent
Recoil, then appropriate static a period of time, then discharge.
The invention has the following advantages:
1, the present invention after completion of the reaction, is first heating water, and stirs simultaneously, using precipitating, makes solvent and reactant point
From, then by be located at precipitation kettle waist position pipe most liquid solvent is discharged, remaining fraction solvent then passes through
Conventional distillation approach recycling；The scheme directly distilled compared with prior art, reduces energy consumption significantly；
2, the reactant recycled using method of the invention takes part in separation process because heating water, so that of the invention
The material HPMC that method is produced compared with prior art, the purity of crude product is higher, reduces the processing difficulty of later period HPMC；
3, the present invention, due to increasing hot water, after solvent recovery, is needed water by dividing water in solvent recovery
Groove tank is separated, to obtain reusable solvent, the recovery utilization rate of solvent has reached 90% or more；
4, solvent reclaiming rate of the invention is high, and in solvent recovery, a large amount of hot water has been used greatly to dilute
The concentration of reaction product and solvent, therefore in final waste discharge, the content of COD is very low, has reached environmental protection standard, can be straight
Run in and puts.
Specific embodiment
Present embodiment is only explanation of the invention, is not limitation of the present invention.Those skilled in the art
Any change for being made after having read specification of the invention of member, as long as within the scope of the claims, it all will be by
The protection of Patent Law.
Embodiment one
1, the pretreatment of cellulosic material
Purified cotton is broken into about 1-3 centimetres of diameter of purified cotton block by opener, subsequently into pulverizer, through high speed
Shearing is ground into the purified cotton powder of 60-100 mesh.
Existing HPMC production technology is all by cellulosic material --- purified cotton, by shredding, crushing, cyclonic separation,
Several steps such as bag-type dusting packaging complete the preprocessing process of cellulosic material.
The primary pollution source of this technical process is dust pollution, and the main source of dust is the cellulose that crushing process generates
Molecule causes the dust pollution of air.
The dust of entire pretreating process process opened packet and crush two steps generates less.Shredding step is by hand
The sheet purified cotton that work opens after wrapping is placed on opener, is torn into the loose fritter of 1-3cm.The step is due to charging
It is generally unlimited so being easier to generate dust, and the equipment of different manufacturers, the leakproofness of feeding device is variant, adds
The difference of upper worker operation, the degree and quantity for generating dust also have biggish difference.
2, alkalization, etherificate, solvent recovery, washing process
This process is the main stage of reaction and the main generation link of pollution sources of HPMC production.
Technical process is as follows:
Smashed purified cotton powder is in the dispersion of 8-10 times of mixed solvent and alkalinization occurs for alkali, generates tool
There is the alkali cellulose of reactivity.
Etherificate: etherification reaction occurs for alkali cellulose and propylene oxide, chloromethanes, by reaction temperature, the reaction time and
The control of formula is controlled to adjust the height of methoxyl group and hydroxypropyl degree of substitution by the content to oxidant in system environment,
With purified cotton raw materials selection come adjust product viscosity height.
It neutralizes: after reaction, remaining alkali is neutralized with acid.
Precipitation: the mixed system after neutralization is drained into precipitation kettle, and the reinforcing that precipitation kettle is opened when discharge starts is stirred
It mixes, while stirring plus top hot water, continuously stirs 10 minutes or more, then static 20 minutes or more, form solid-liquid-gas three phase；It will
Most liquid solvent is recycled from the discharge of pipes of precipitation kettle waist position；Again by the liquid solvent of part and gaseous solvent through distilling
Approach recycling.
In whole process, solvent recovery is emphasis.Organic solvent is not only the valuable means of production, and deals with improperly just
It can cause environmental pollution, pollute water and soil and air.
In the prior art, recycling organic solvent is using direct distillation, and processing energy consumption in this way is higher.
In the present invention, water after completion of the reaction, is first being heated, and stir simultaneously, using precipitating, is making solvent and reactant point
From, then by be located at precipitation kettle waist position pipe most liquid solvent is discharged, remaining fraction solvent then passes through
Conventional distillation approach recycling；The scheme directly distilled compared with prior art, reduces energy consumption significantly.
The material balance of process is as follows: solvent balance: to feed intake, 7000 kilograms of solvents are calculated
Chloromethanes balance: to feed intake, 600 kilograms of chloromethanes are calculated
Propylene oxide balance: to feed intake, 180 kg ethylene propane are calculated
3, the post-processing of HPMC
Post-processing: the mixture after precipitation passes through horizontal decanter centrifuge, and centrifuge separation using granulation, drying, mixes
It closes, packaging becomes final products.
HPMC aftertreatment technology has been mature on the whole now, so also gradually having obtained manufacturing enterprise in terms of environment influence
Attention, while the control of dust also creates new economic benefit to enterprise.
Claims (7)
1. the Green production method of hydroxypropyl methylcellulose, comprising the following steps:
1), pre-process: it is 1-3 centimetres of purified cotton block that purified cotton, which is broken into diameter, by opener, subsequently into pulverizer,
Through high energy shear milling at the purified cotton powder of 60-100 mesh；
2), alkalize: smashed purified cotton powder is in the dispersion of 8-10 times of toluene-isopropanol-water mixed solvent and alkali
Alkalinization occurs, generates the alkali cellulose with reactivity；
3), be etherified: etherification reaction occurs for alkali cellulose and propylene oxide, chloromethanes；
4) it, neutralizes: after reaction, remaining alkali is neutralized with acid；
5), precipitation: the mixed system after neutralization is drained into precipitation kettle, and the reinforcing that precipitation kettle is opened when discharge starts is stirred
It mixes, while stirring plus top hot water, the additional amount of hot water are 0.6~1.0 times of solvent volume, it continuously stirs 10 minutes or more,
Then static 20 minutes or more, solid-liquid-gas three phase is formed；
Carry out reinforcing stirring by stirring structure, the reinforcing stirring be level-one blade is added on the agitating shaft of precipitation kettle, and
Upper and lower blade is connected into the frame structure to be formed using connecting rod；
Most liquid solvent is recycled from the discharge of pipes of precipitation kettle waist position, liquid solvent is arranged from the pipeline of precipitation kettle waist position
After out, imported into bypass channel tank, and after through static layering, water is discharged；
The liquid solvent of part and gaseous solvent are recycled through distillation approach again；
6), post-process: mixture after precipitation passes through horizontal decanter centrifuge, centrifuge separation, using granulation, drying, mixing,
Packaging becomes final products.
2. the Green production method of hydroxypropyl methylcellulose according to claim 1, it is characterised in that: in step 5), hot water
After addition, to prevent temperature lower than 100 DEG C.
3. the Green production method of hydroxypropyl methylcellulose according to claim 1, it is characterised in that: in step 5), solvent
Before discharge, pneumatic operated valve need to be first opened, then opens ball valve above visor.
4. the Green production method of hydroxypropyl methylcellulose according to claim 1, it is characterised in that: in step 5), solvent
When discharge, Yao Xiankai solvent tube valve is recoiled delivery pipe and pneumatic operated valve with sub-fraction solvent, it is appropriate it is static once.
5. the Green production method of hydroxypropyl methylcellulose according to claim 1, it is characterised in that: in step 5), solvent
When discharge, starts solvent pump, then a little opening solvent pipe ball valve, observe the situation of recycling design in visor, solvent clear
, then big solvent pipe ball valve is gradually opened, solvent recovery speed is increased.
6. the Green production method of hydroxypropyl methylcellulose according to claim 1, it is characterised in that: in step 5), solvent
When discharge is completed, solvent pump is shut down, then suitably recoiled solvent discharge pipe and pneumatic operated valve with a small amount of head tank solvent, be then shut off respectively
Valve.
7. the Green production method of hydroxypropyl methylcellulose according to claim 1, it is characterised in that: in step 5), solvent
When discharge, if solvent is opaque, containing a large amount of materials, and continuously, then must terminate solvent discharge in time, closing valve and
Stop solvent pump, then suitably recoiled with a small amount of head tank solvent, then appropriate static a period of time, then discharges.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610122501.6A CN107129540B (en) | 2016-03-04 | 2016-03-04 | The Green production method of hydroxypropyl methylcellulose |
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| CN201610122501.6A CN107129540B (en) | 2016-03-04 | 2016-03-04 | The Green production method of hydroxypropyl methylcellulose |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108129575A (en) * | 2017-12-13 | 2018-06-08 | 浙江中维药业股份有限公司 | A kind of preparation method of low viscosity pharmaceutic adjuvant plant capsule hydroxypropyl methylcellulose |
| CN109337116A (en) * | 2018-11-22 | 2019-02-15 | 北方天普化工有限公司 | A kind of hydroxypropyl methyl cellulose method for recovering solvents |
| CN117229425B (en) * | 2023-10-16 | 2024-03-22 | 河北双牛建材纤维素有限公司 | Method for preparing high-purity hydroxypropyl methyl cellulose |
| CN118108863A (en) * | 2024-04-29 | 2024-05-31 | 山东光大赛路新材料科技有限公司 | Low-viscosity hydroxypropyl methyl cellulose and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260158A (en) * | 2008-04-14 | 2008-09-10 | 浙江中维药业有限公司 | Method for preparing hydroxypropylmethylcellulose |
| CN102603899A (en) * | 2012-02-24 | 2012-07-25 | 邸勇 | Process for producing low-substituted hydroxypropyl cellulose |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260158A (en) * | 2008-04-14 | 2008-09-10 | 浙江中维药业有限公司 | Method for preparing hydroxypropylmethylcellulose |
| CN102603899A (en) * | 2012-02-24 | 2012-07-25 | 邸勇 | Process for producing low-substituted hydroxypropyl cellulose |
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Address after: 313000 No. 88, Zhongde Road, Linghu Town, Nanxun District, Huzhou City, Zhejiang Province (self declaration) Patentee after: Meixinjia Zhongwei Pharmaceutical Co.,Ltd. Address before: 313000 No.366 Zijing Road, Huzhou Economic and Technological Development Zone, Huzhou City, Zhejiang Province Patentee before: ZHEJIANG JOINWAY PHARMACEUTICAL CO.,LTD. |
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Denomination of invention: Green production method of hydroxypropyl methylcellulose Effective date of registration: 20220223 Granted publication date: 20191101 Pledgee: Huzhou Wuxing Rural Commercial Bank Co.,Ltd. Pledgor: Meixinjia Zhongwei Pharmaceutical Co.,Ltd. Registration number: Y2022980001769 |
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Address after: 313000 No. 366, Zijing Road, Longxi Street, South Taihu New District, Huzhou, Zhejiang Patentee after: Meixinjia Zhongwei Pharmaceutical Co.,Ltd. Address before: 313000 No. 88, Zhongde Road, Linghu Town, Nanxun District, Huzhou City, Zhejiang Province (self declaration) Patentee before: Meixinjia Zhongwei Pharmaceutical Co.,Ltd. |