CN102786600B - Production method for high-viscosity high-purity carboxymethylcellulose by using bamboo pulp as raw material - Google Patents
Production method for high-viscosity high-purity carboxymethylcellulose by using bamboo pulp as raw material Download PDFInfo
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- 239000001768 carboxy methyl cellulose Substances 0.000 title claims abstract description 48
- 235000017166 Bambusa arundinacea Nutrition 0.000 title claims abstract description 33
- 235000017491 Bambusa tulda Nutrition 0.000 title claims abstract description 33
- 241001330002 Bambuseae Species 0.000 title claims abstract description 33
- 235000015334 Phyllostachys viridis Nutrition 0.000 title claims abstract description 33
- 239000011425 bamboo Substances 0.000 title claims abstract description 33
- 239000002994 raw material Substances 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 229920002134 Carboxymethyl cellulose Polymers 0.000 title claims description 48
- 235000010948 carboxy methyl cellulose Nutrition 0.000 title claims description 45
- 239000008112 carboxymethyl-cellulose Substances 0.000 title claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 112
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000006266 etherification reaction Methods 0.000 claims abstract description 19
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 229920002678 cellulose Polymers 0.000 claims description 21
- 235000010980 cellulose Nutrition 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000001913 cellulose Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000005956 quaternization reaction Methods 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 32
- 239000012429 reaction media Substances 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000003960 organic solvent Substances 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 abstract 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 abstract 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 abstract 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 229940106681 chloroacetic acid Drugs 0.000 abstract 1
- 238000003825 pressing Methods 0.000 abstract 1
- 239000003513 alkali Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000002002 slurry Substances 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000835 fiber Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
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- 238000009897 hydrogen peroxide bleaching Methods 0.000 description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
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- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
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- 230000007062 hydrolysis Effects 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
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- 235000014102 seafood Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
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Abstract
The invention provides a production method for high-viscosity high-purity sodium carboxymethylcellulose by using bamboo pulp as a raw material. The production method comprises the following steps of: carrying out an alkalization reaction and an etherification reaction to 5 parts of bamboo pulp by weight (the same below), 100 parts of 90% of ethanol aquifer based on volume by volume concentration, 5 to 8 parts of 30% of sodium hydroxide aqueous solution based on mass by mass concentration, and 7 to 10 parts of chloroacetic acid at an industrial level; washing via ethanol; pressing and filtering; parching; and crushing to obtain the finished product. The production method provided by the method is the first one to produce high-viscosity high-purity sodium carboxymethylcellulose through raw material with a low content of alpha-cellulose and a low degree of polymerization, and according to the high-viscosity high-purity sodium carboxymethylcellulose, the viscosity is more than 5000 mPas, and the purity is less than or equal to 0.1% based on the mass fraction of the chloride Cl. The production method is rich in raw material resources with low cost, so that the cost of production is greatly reduced. The reaction medium is hydrous ethanol and the washing solvent is the hydrous ethanol as well, so that problem of blending various organic solvents for use can be avoided, and the complex process for respectively recovering is saved. The production method has few processes, is energy-saving, time-saving and labor-saving, and has low production cost.
Description
Technical field
The present invention relates to a kind of method that bamboo pulp is raw material production high-viscosity high-purity carboxymethyl cellulose (CMC).
Background technology
Industry manufactures carboxymethyl cellulose and mainly contains hydrophily method and solvent method.Solvent method utilizes inert organic solvents for reaction medium, overcomes hydrophily method and to conduct heat bad intrinsic disadvantage, and reaction homogeneity improves, and therefore good product quality has become the advanced technologies that current carboxymethyl cellulose is produced.Solvent method adopt inert organic solvents be reaction medium, by reaction medium consumption number be divided into kneading method and slurry process.Kneading method is few due to solvent load, fully with complete, cannot easily there is the uneven phenomenon of reaction to cellulosic infiltration and dispersion.Slurry process Mierocrystalline cellulose under the condition of high liquor ratio fully contacts with alkali lye or etherifying agent by agitator, carries out even mass transfer and heat transfer, realizes evenly alkalization and etherification reaction.Industrial conventional resourceful ethanol, Virahol are as reaction medium.Ethanol can with water and alkali lye miscible, Virahol can be miscible substantially not miscible with alkali lye with water.Take Virahol as reaction medium, often select the slurry process of high liquor ratio, upper and lower two liquid layers are then formed when mixing with alkali lye, Mierocrystalline cellulose is scattered in this system and under agitation contacts with two liquid phases fully, and fully contact with alkali lye or etherifying agent under the condition of high liquor ratio, carry out even mass transfer and heat transfer, realize evenly alkalization and etherification reaction, product performance improve.And ethanol is when being reaction medium, impels more greatly alkalinized celluloses that hydrolysis occurs due to ethanol polarity and affect etherification reaction, so liquor ratio is unsuitable excessive, often selecting kneading method.
It take cotton fibre as raw material that CN101220099B has announced, and adopts 70%-98% aqueous ethanolic solution to be reaction medium, mediates the method for legal system for high viscosity carboxymethyl cellulose.This method is for improving viscosity, and alkalinization carries out under protection of inert gas, adopts helium, argon gas etc. do not react with raw material and do not make the rare gas element that cellulosic degree of polymerization is degraded.The rare gas element such as helium, argon gas is very expensive, and industrial production cannot operate.CN101033256A has announced the organic solvents such as employing Virahol, ethanol, Virahol/ethanol, acetone, toluene, ethanol/toluene, iso-propanol/toluene, isopropylcarbinol, the organic solvent that its mass concentration is not less than 80% is reaction medium, and slurry process prepares the technology of high viscosity carboxymethyl cellulose.But in order to obtain high viscosity, the raw material of employing is the purified cotton that the polymerization degree is greater than 2400, alkalization, etherification reaction are carried out all under nitrogen protection, and etherifying agent Mono Chloro Acetic Acid is dissolved in the solution that organic solvent becomes 40%-60%.This method expensive starting materials, operation is loaded down with trivial details, thus substantially increases production cost, and in large-scale commercial production, nitrogen protection operability is not strong.CN102167749A has announced " preparing the method for high degree of substitution and high viscosity carboxymethyl cellulose with bagasse " patented technology of Guangxi University, be raw material with bagasse, through ball milling pretreatment, boil 1-2 hour with 0.5%-5% sulfuric acid, 1%-5% sodium hydroxide solution successively, clorox and the bleaching of hydrogen peroxide bleaching liquid, after drying as carboxymethylation raw material.Refined cellulose raw material is reaction medium with ethanol, and slurry process prepares carboxymethyl cellulose.But realize high viscosity by interpolation linking agent, two step alkali adding methods.This method complex procedures, bagasse is obtained fiber after physico-chemical process process, with acid, alkaline purification, need pollute environment when producing fiber, and linking agent is added in alkalinization, in etherification procedure, constantly add ethanolic soln containing sodium hydroxide to realize high viscosity.
Summary of the invention
For the above-mentioned deficiency of prior art, the technical problem to be solved in the present invention designs a kind of to be raw material with bamboo pulp, to adopt the method for slurry process production high viscosity, high purity carboxymethyl cellulose.
Solving the problems of the technologies described above adopted technical scheme is:
This take bamboo pulp as the high-viscosity high-purity carboxymethyl cellulose production method of raw material, carries out as follows:
(1) get the raw materials ready: with alpha-cellulose content be 87%-89%, the polymerization degree is that the bamboo pulp of 800-950 makes cellulosic material, natural moisture content 8%-12%, from paper mill produce bamboo pulp want to buy obtain or with chemistry, physics, biology mode self-produced in obtain;
(2) carry out fully and uniformly disperseing to bamboo pulp: the bamboo pulp of acquisition is ground into powdery, add bamboo pulp powder 5 weight part in a kettle., add aqueous ethanol 100 weight part that volume ratio is 85%-95% again, stir 10-20 minute, make Mierocrystalline cellulose in a solvent dispersed;
(3) cellulosic alkalization: add 5-8 weight part NaOH in step (2) stirs the abundant cellulosic material disperseed, NaOH being mixed with quality than concentration is the aqueous solution of 30%, in normal pressure and 20-30 DEG C, stir 1h, carry out quaternization, make alkalinized celluloses;
(4) etherificate of alkalinized celluloses: add the technical grade Mono Chloro Acetic Acid 7-10 weight part as etherifying agent in whole alkalinized celluloses that step (3) is made, etherification reaction 2 hours under normal pressure and 50-80 DEG C of condition, be cooled to room temperature, be that 80% aqueous acetic acid is neutralized to neutrality by volume ratio, suction filtration, obtained faint yellow etherate;
(5) the making of carboxymethyl cellulose: the etherate that step (4) is obtained is carried out conventional washing, press filtration, adopt volume ratio be 80% aqueous ethanol washing 3-4 time, be washing with alcohol 1-2 time of 95% again by volume ratio, dry, pulverizing, finally makes the carboxymethyl cellulose product of white or pale yellow powder shape.
Described step (2) middle volume ratio is 90% aqueous ethanol, add-on is 150 weight parts, in step (3), the add-on of NaOH is 7 weight parts, in step (4), chloroacetic add-on is 9 weight parts, obtained carboxymethyl cellulose product viscosity > 5000mPas after measured, in muriate massfraction≤0.1% of Cl.
The invention has the beneficial effects as follows:
Employing alpha-cellulose content 87%-89%, alpha-cellulose are the bamboo pulp of 800-950 is cellulosic material, with the larger aqueous ethanol of polarity for reaction medium, need not method be mediated but obtain viscosity > 5000mPas with slurry process, in the carboxymethyl cellulose of muriate massfraction≤0.1% of Cl.With compared with prior art, with the polymerization degree and the much lower raw material of alpha-cellulose content, adopt and be contrary to routine and the technique against convention, unexpectedly can prepare high viscosity like this, high-purity C MC, create unforeseeable technique effect really.Cellulosic material abundance of the present invention, inexpensive, production cost significantly reduces; Reaction medium adopts aqueous ethanol, and cleaning solvent also uses aqueous ethanol, therefore avoids reaction solvent different with cleaning solvent, numerous and diverse operation that need reclaim respectively, energy-conservation, save time, economize labor, and production cost is low.
Embodiment
The present invention is described in further detail below in conjunction with embodiment:
Now eight embodiments of each raw material and weight value thereof that participate in reaction are listed in the table below:
Embodiment 1 (see the corresponding raw material of embodiment in table 1 and weight part): add bamboo pulp powder 5 weight part (lower same) in reactor, adding 100 parts of volume ratios is the aqueous ethanol of 90%, stir 10-20 minute, add 7 parts of NaOH, NaOH being mixed with quality than concentration is the aqueous solution of 30%, 1h is stirred in normal pressure and 20-30 DEG C, generate alkalinized celluloses, add Mono Chloro Acetic Acid 9 parts again, control temperature of reaction 60 DEG C, etherification reaction 2 hours, be cooled to room temperature, neutrality is neutralized to the aqueous acetic acid that volume ratio is 80%, suction filtration, obtained yellow etherate, through the washing of routine, press filtration, washing volume ratio is 80% washing with alcohol 4 times, use 95% washing with alcohol 1 time again, pulverize after drying, just obtained white fiber sprills, be this high-viscosity high-purity carboxymethyl cellulose, through testing oneself, viscosity is 4764mPas, in muriate massfraction≤0.1% of Cl.
Shown in all the other embodiment 2-8 all see the above table by the aqueous ethanol concentration of raw material corresponding in upper table and weight value, etherification temperature and reaction medium, preparation method is with embodiment 1.Obtained product is through testing oneself, and viscosity and purity respectively have different.Above-mentioned eight embodiments are preferred with embodiment 1.
According to document announcement, bamboo tankage are isolated bamboo cellulose for the preparation of carboxymethyl cellulose through alkaline boiling, hypochlorous acid and hydrogen peroxide bleaching by deep seafood etc., carboxymethyl cellulose 2% solution viscosity 780mPas obtained under its optimal conditions.Wood chip pulverizing, water boil, alkaline boiling, hypochlorous acid and hydrogen peroxide bleaching are isolated wood cellulose for the preparation of carboxymethyl cellulose by Xia Shipeng, carboxymethyl cellulose 2% solution viscosity 600mPas obtained under its optimal conditions.
Introducing the applicant below take bamboo pulp as the particular case that carboxymethyl cellulose prepared by raw material:
This experiment is with the bamboo pulp of Sichuan Yongfeng Paper-making Joint-Stock Co., Ltd. (alpha-cellulose content 88%, alpha-cellulose suddenly right 900) for raw material, and the contrived experiment of according to the form below, optimizes carboxymethyl cellulose (CMC) processing condition to seek.
Experimental design
5g bamboo pulp powder is claimed to put into reaction flask at the bottom of three mouthfuls of gardens, add 100ml volume ratio be 90% aqueous ethanol be reaction medium, abundant stirring 10 minutes, add 5 respectively, 6,7,8g NaOH, NaOH is respectively mixed with the aqueous solution of 30% concentration, the add-on different by NaOH tetra-times is tested as a comparison, all quaternizations 1 hour at normal pressure and 25 DEG C, then adds 9g Mono Chloro Acetic Acid etherification reaction 2 hours at normal pressure and 60 DEG C.Be cooled to room temperature, be that 80% acetic acid is neutralized to neutrality by volume ratio, suction filtration, be 80% washing with alcohol 4 times by volume ratio, again with concentration be the washing with alcohol of 95% once, at 50 DEG C, be dried to constant weight after suction filtration, just obtained white powder product, adopt viscometer (HAAKEViscotester 6 plus type) to measure the viscosity (seeing the following form) of the 2%CMC aqueous solution.
From upper table, different NaOH add-ons, has a significant effect to the viscosity of product.Add NaOH 5g to alkalize, 2% solution viscosity of CMC is minimum, only has 44mPas, and when NaOH add-on is 7g, the viscosity of 2% aqueous solution of CMC is maximum, reaches 4764mPas, and during NaOH add-on 8g, the viscosity of 2% aqueous solution of CMC reduces.Alkali number is lower, and Mierocrystalline cellulose all can not be converted to alkalinized celluloses, and the too low fiber degree of swelling that also causes of alkali number is low simultaneously, and alkalinized celluloses generates difficulty, and etherification reaction carries out also not thorough, and product viscosity is low.Appropriate free alkali can promote that alkali is to cellulosic infiltration, makes product viscosity reach maximum value.If but alkali quality is excessive, soda cellulose meeting severely degrade, rapid right reduction, viscosity degradation, and when free alkali number is excessive, also exacerbate the chloroacetic hydrolytic side reactions of etherifying agent, etherifying agent utilization ratio reduces, the acid amount increase of neutralization.
When NaOH is 7g, 2% solution viscosity of CMC is the highest, and employing NaOH is 7g, and NaOH concentration is respectively 20%, 30%, 40%, 50%, other conditions are constant, prepare carboxymethyl cellulose, inquire into alkali concn to the impact of product viscosity, its viscosity measurements sees the following form.
When NaOH quality is than concentration 20%, its product viscosity is minimum, only has 129mPas, and when NaOH quality is than concentration 30%, its product viscosity is the highest, reaches 4764mPas.Along with alkali concn raises, viscosity decreases.
Bamboo pulp powder 5g, adds NaOH 7g, NaOH is mixed with the aqueous solution of 30% concentration, then add respectively Mono Chloro Acetic Acid 7,8,9,10g, prepare carboxymethyl cellulose, its viscosity measurements is as following table.
Reasonable adjustment NaOH and Mono Chloro Acetic Acid mol ratio, be conducive to improving product viscosity, theoretically, NaOH and chloroacetic mol ratio are 2.Sichuan Yongfeng Paper-making Joint-Stock Co., Ltd.'s bamboo pulp is CMC prepared by raw material, NaOH and chloroacetic mol ratio when being 1.83, and 2% solution viscosity of CMC is the highest, reaches 4764mPas.
Etherification reaction temperature is also the principal element affecting CMC viscosity, therefore be 7g at NaOH, NaOH is mixed with the aqueous solution of 30% concentration, Mono Chloro Acetic Acid is under 9g condition, etherification reaction is carried out respectively under 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C conditions, obtained carboxymethyl cellulose, its viscosity measurements sees the following form.
During etherification reaction temperature 60 DEG C, 2% solution viscosity of CMC is the highest, reaches 4768mPas.Etherification reaction phase temperature is high, etherification reaction excessive velocities, the local reaction on top layer can be caused, fiber surface is made to generate CMC gel coat, and hinder etherifying agent to fully diffusion, infiltration and the reaction further of soda cellulose, thus cause carboxymethyl evenly to replace, application indexes and performance not ideal enough.Temperature is too low, and initial reaction stage then easily generates crystalline sodium chloroacetate, intersperses among soda cellulose outside, and etherifying agent efficiency and reaction homogeneity are all affected.
5g bamboo pulp powder at the highest experiment condition of this experimental design medium viscosity and preferred version, volume ratio be 90% aqueous ethanol 100ml be reaction medium, NaOH 7g, NaOH is mixed with the aqueous solution of 30% concentration, quaternization 1 hour at normal pressure and 25 DEG C, add 9g Mono Chloro Acetic Acid, etherification reaction 2 hours at normal pressure and 60 DEG C.Under this optimization experiment condition, through testing oneself, viscosity is 4764mPas, in muriate massfraction≤0.1% of Cl.
For verifying the viscosity of CMC product and the stability of purity and reliability produced at above-mentioned preferred version, carry out again six tests, under Optimizing Technical, with above-mentioned Sichuan Yongfeng Paper-making Joint-Stock Co., Ltd. bamboo pulp for raw material, prepare carboxymethyl cellulose (CMC).Claim 5, 10, 20, 50, 80, 400g bamboo pulp powder puts into reactor at the bottom of three mouthfuls of gardens, adds the aqueous ethanol 100 that volume ratio is 90% respectively, 200, 400, 1000, 1600, 5000ml, as reaction medium, fully stirs 10 minutes, adds 7 respectively, 14, 28, 70, 112, the NaOH of 560g, is respectively mixed with the aqueous solution of 30% concentration by NaOH, quaternization 1 hour at normal pressure and 25 DEG C, then adds 9 respectively, 18, 36, 90, 144, 720g Mono Chloro Acetic Acid, at normal pressure and 60 DEG C, etherification reaction 2 hours, is cooled to room temperature, being that 80% acetic acid is neutralized to neutrality, suction filtration by volume ratio, is that 80% aqueous ethanolic solution washs 4 times by volume ratio, wash once with the aqueous ethanolic solution that volume ratio is 95% again, dry at 50 DEG C after suction filtration, pulverize, just obtained white powder product, adopts the viscosity of viscometer (HAAKE Vi scotester 6plus type) the Determination of The Proper Motions 2%CMC aqueous solution, is respectively 4764, 4691, 4723, 4771, 4698, 4787mPas, concrete test design and measurement result see the following form:
Experimental design
This experiment adopt alpha-cellulose content 87%-89%, the rapid right 800-950 of alpha-cellulose and water ratio be 10% bamboo pulp be cellulosic material, take volume ratio as the aqueous ethanol of 90% be reaction medium, adopt slurry process, prepare carboxymethyl cellulose at ambient pressure.Product detects through company limited of quality of chemical products test house of Zhejiang Province: 2% solution viscosity is 5625mPas, in muriate massfraction≤0.1% of Cl, meets the index of correlation requirement of foodstuff additive Xylo-Mucine GB 1904-2005.
This experimental result, when Determination of The Proper Motions viscosity, with the tap water configuration 2%CMC aqueous solution, under room temperature (28-30 DEG C), adopts HAAKE Viscotester 6 plus type digital display viscometer determining viscosity.Record the determination data of viscosity lower than company limited of quality of chemical products test house of Zhejiang Province of legal detection unit voluntarily, may be the viscometer difference owing to using or mensuration temperature of not controlling well, especially the water intermediate ion concentration difference that the configuration 2%CMC aqueous solution is used causes, and the result that should measure with legal detection unit be as the criterion.
The ethanol that the present invention adopts polarity larger is as reaction medium, and the concentration of ethanol is when 90%, another anti-convention uses slurry process, what select is that alpha-cellulose content and the polymerization degree do cellulosic material far below the bamboo pulp of purified cotton, prepare carboxymethyl cellulose, unexpectedly can prepare viscosity > 5000mPas, in the high viscosity of muriate massfraction≤0.1% of Cl, highly purified carboxymethyl cellulose, produce unforeseeable technique effect.This series of result running counter to convention and routine, its Related Mechanism, needs to be inquired into further.
Claims (2)
1. bamboo pulp is a high-viscosity high-purity carboxymethyl cellulose production method for raw material, it is characterized in that carrying out as follows:
(1) get the raw materials ready: with alpha-cellulose content be 87%-89%, the polymerization degree is that the bamboo pulp of 800-950 makes cellulosic material, natural moisture content 8%-12%, from paper mill produce bamboo pulp want to buy obtain or with chemistry, physics, biology mode self-produced in obtain;
(2) carry out fully and uniformly disperseing to bamboo pulp: the bamboo pulp of acquisition is ground into powdery, adding bamboo pulp powder 5 weight part in a kettle., adding volume ratio is again that aqueous ethanol 100 weight part of 85%-95% makes solvent, stir 10-20 minute, make Mierocrystalline cellulose in a solvent dispersed;
(3) cellulosic alkalization: add 5-8 weight part NaOH in step (2) stirs the abundant cellulosic material disperseed, NaOH being mixed with quality than concentration is the aqueous solution of 30%, in normal pressure and 20-30 DEG C, stir 1h, carry out quaternization, make alkalinized celluloses;
(4) etherificate of alkalinized celluloses: add the technical grade Mono Chloro Acetic Acid 7-10 weight part as etherifying agent in whole alkalinized celluloses that step (3) is made, etherification reaction 2 hours under normal pressure and 50-80 DEG C of condition, be cooled to room temperature, be that 80% aqueous acetic acid is neutralized to neutrality by volume ratio, suction filtration, obtained faint yellow etherate;
(5) the making of carboxymethyl cellulose: the etherate that step (4) is obtained is carried out conventional washing, press filtration, adopt volume ratio be 80% aqueous ethanol washing 3-4 time, be washing with alcohol 1-2 time of 95% again by volume ratio, dry, pulverizing, finally makes the carboxymethyl cellulose product of white or pale yellow powder shape.
2. bamboo pulp as claimed in claim 1 is the high-viscosity high-purity carboxymethyl cellulose production method of raw material, it is characterized in that described step (2) middle volume ratio is that 90% aqueous ethanol makes solvent, in step (3), the add-on of NaOH is 7 weight parts, in step (4), chloroacetic add-on is 9 weight parts, obtained carboxymethyl cellulose product viscosity > 5000mPas after measured, in muriate massfraction≤0.1% of Cl.
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