CN103755816B - A kind of preparation method of sodium carboxymethylcellulose - Google Patents
A kind of preparation method of sodium carboxymethylcellulose Download PDFInfo
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- CN103755816B CN103755816B CN201310711906.XA CN201310711906A CN103755816B CN 103755816 B CN103755816 B CN 103755816B CN 201310711906 A CN201310711906 A CN 201310711906A CN 103755816 B CN103755816 B CN 103755816B
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Abstract
The invention provides a kind of preparation method of sodium carboxymethylcellulose. It is to prepare sodium carboxymethylcellulose by the semidry method process of organic solvent-free, taking wood pulp or paper pulp as raw material, comprising: quaternization: by raw material taking water as medium and NaOH carry out quaternization and obtain alkali cellulose; Etherification reaction: alkali cellulose and chloroacetic acid are carried out to etherification reaction and obtain sodium carboxymethylcellulose crude product; Neutralization and washing: sodium carboxymethylcellulose crude product is neutralized in the aqueous solution of alcohol, and wash in alcohol; Dry processing: the solid matter obtaining is dried, pulverized, sieves after processing obtains sodium carboxymethylcellulose. The inventive method raw material sources are extensive, can be taking secondary stocks as raw material, and in preparation process, taking a small amount of water in sodium hydroxide solution as reaction medium, without organic solvent, preparation cost is low, and properties of product are controlled. The whole preparation flow of the inventive method can complete in pulverizer, has realized the efficient utilization of equipment.
Description
Technical field
The present invention relates to a kind of preparation method of sodium carboxymethylcellulose, particularly taking wood pulp or secondary stock as raw material,Prepare the method for the sodium carboxymethylcellulose of different viscosities and substitution value by semidry method, belong to natural polymer chemical modification neckTerritory.
Background technology
Sodium carboxymethylcellulose (Sodiumcarboxymethylcellulose, Na-CMC) is with cellulose substancesFor raw material, the product obtaining after carboxymethylation reaction modification, is referred to as CMC traditionally. Fig. 1 is shown in by its molecular formula schematic diagram. CMCBe one of most important cellulose ether, after it is water-soluble, can form the colloidal solution with certain viscosity, have thickening, bonding,The effects such as film forming, moisture maintenance, colloid protection, emulsification and suspension, are widely used in oil drilling, dyeing textile, papermaking, potteryThe fields such as porcelain, building, food processing and daily-use chemical industry. Development cost is cheap, the carboxymethyl cellulose technology of high-efficiency high-quality,Not only development and the light industry of support China, heavy industry and chemical industry are significant, Ye Shi China cellulose ether industryThe requirement of development, has wide market prospects.
The common preparation technology of CMC can be divided into hydrophily method and the large class of solvent method two.
Hydrophily method is taking water as reaction medium, and cellulosic material forms suspension and basifier and etherifying agent and sends out in reactorRaw reaction. Its advantage is that equipment is simple, cost is low, but because cellulosic material can gelatinization form micelle, reaction in large water gagingReagent is difficult to deeply extremely cellulosic crystalline region, causes reaction abundant not, and the carboxy methylation product substitution value of gained is low, salt contentGreatly, moisture content is high, and product water solution is compared with strong basicity, and heat resistance and salt tolerance are poor, is low-and-medium-grade products.
Solvent method technique is taking inert organic solvents as medium, saved ripe after the intrinsic caustic dip of hydrophily method, squeezing, alkalizationThe operations such as change, alkalization and etherificate are all carried out in kneader, with short production cycle. The uniformity of product, dissolubility, the aqueous solution thoroughlyLightness is all better, belongs to the carboxy methylation product of medium-to-high grade time. Therefore produce CMC mainly with solvent method both at home and abroad at present. But organicThe cost of solvent is higher, generally need in the technological process of solvent method, increase solvent recovering system. In addition, have in a large number owing to usingMachine solvent, also requires to take a series of measure at secure context, and what guarantee was produced carries out smoothly.
Two kinds of traditional handicrafts all have certain limitation. Along with the develop rapidly of national economy, the day of economic globalization pacesFast increasingly, the cellulose ether production industry of China faces huge challenge. Under this background, be produced in the urgent need to researching and developing oneThis is lower, and technique is simple, convenient operation, and the good new method of products obtained therefrom performance is prepared CMC.
From raw material aspect, the traditional raw material that CMC prepares in China be mainly by short velveteen through boiling, pickling, wash, floatIn vain, the cellulose that rolls, obtain after the preprocessing process such as oven dry, be called purified cotton. The impurity content of purified cotton is lower, after refiningAlpha-cellulose content exceedes 95% (mass fraction). But in recent years, raw material supply growing tension, cost of material is higher, causesThe production cost of CMC is higher, therefore, except preparation method's innovation, is also necessary to seek cheap novel celluloseResource replaces purified cotton to prepare CMC.
By literature search, there are some both at home and abroad about replacing purified cotton to prepare sodium carboxymethylcellulose by non-cotton fiber resourceResearch and report:
A. patent CN1272346C discloses one taking straw as raw material, and by solvent method, (reaction medium is alcohol-waterMixed liquor) prepare the method for sodium carboxymethylcellulose. This method is easier, but as previously mentioned, organic owing to having usedSolvent, has increased preparation cost to a certain extent. Last with after the refining CMC of concentrated hydrochloric acid solution washing, not in this patentProduct is washed, neutralized, and the insoluble H-CMC generating while making hydrochloric acid solution washing is not reduced into soluble Na-CMC,Affect to a great extent the quality of product. This patent only provides the application effect of products obtained therefrom in copper concentrate flotation in additionReally, with regular domestic and international professional standard, the performance of product is not evaluated.
B. it is wooden that patent CN101230547B discloses a kind of stalk with bagasse, corn, Chinese sorghum, straw or wheat straw etc.Cellulosic material is prepared the method for sodium carboxymethylcellulose. The method first infiltrates with the mixed solution of NaOH and hydrogen peroxideRaw material, the cellulose of then purifying out under microwave, then taking low-carbon (LC) alcohol-water solution as medium, exist and have at hydrogen peroxideUnder the condition of microwave, make CMC through alkalization and etherification reaction. This method need be carried out purification processes to raw material, and technique is more complicated;And must under microwave, react, be difficult to realize heavy industrialization.
C. patent CN101830989B discloses one taking potato starchy residue as raw material, 70% ethanol-water solutionFor reaction medium, the method by solvent legal system for carboxymethyl cellulose. The aqueous solution of the method products obtained therefrom has higherViscosity, but the shortcoming of this method is to purify (comprising the steps such as acidolysis, soda boiling, bleaching, oven dry) to raw material in advance, techniqueFlow process is more complicated. The substitution value of this method products obtained therefrom is lower in addition, does not exceed 0.6.
D. patent CN101857639B discloses and has a kind ofly produced the residue of biological butanol with maize straw and prepare carboxymethylThe method of sodium cellulosate. This method adopts solvent method, using ethanolic solution as reaction medium. For used former in this patentMaterial---produce the residue of biological butanol with maize straw, must first extract lignin with alkali, then float with hydrogen peroxideIn vain, use running water washed twice, more just can be prepared reaction after drying, drying. This makes preparation process comparatively loaded down with trivial details.Another one shortcoming is that obviously, this method must coordinate biological butanol preparation technology just can obtain sufficient raw material, and it is hadCertain limitation.
E. patent CN102167749B discloses and a kind of has prepared high degree of substitution and high viscosity carboxymethyl cellulose with bagasseThe method of sodium. This method is first carried out ball milling pretreatment to bagasse, then through peracid boil, soda boiling, washing, bleaching, drying and other steps obtainTo refining bagasse cellulose, then taking ethanol water as medium, by solvent legal system for CMC. This patent is in order to improve productProduct viscosity, has also added sodium trimetaphosphate as crosslinking agent. CN103159861A discloses a kind of taking bagasse pulpboard as formerMaterial, taking ethanol as reaction medium, the method by solvent legal system for sodium carboxymethylcellulose. This method is complete in whole preparation processPortion is used nitrogen protection, and must be through continuous stripping step.
F.CN1490336A discloses a kind of taking bamboo fibre as raw material, the process system of being combined with solvent method by hydrophily methodThe method of standby ultra low viscosity carboxymethyl cellulose sodium. This method is first carried out quaternization with hydrophily method, then taking ethanolic solution as anti-Answer medium, carry out etherification reaction by solvent method, and by hydrogen peroxide, or sodium peroxide, or one in Peracetic acid is comeReduce the viscosity of product. This method has reduced production cost to a certain extent, has saved the consumption of organic solvent, but preparation costStill higher, and because alkalization process has adopted the poor hydrophily method of reaction uniformity coefficient, the performance of final products has been subject toImpact to a certain degree. CN102786600A discloses the method for preparing sodium carboxymethylcellulose taking bamboo pulp as raw material. ShouldMethod adopts ethanol as reaction medium, and the liquid-solid mass ratio of reaction is up to 20:1, and cost is higher.
G.CN101548733A and CN101747441A disclose respectively taking wood pulp cellulose as raw material, with ethanol waterSolution is reaction medium, the method by solvent legal system for sodium carboxymethylcellulose. Lower (the solvent of liquid-solid ratio of these two kinds of methodsBe about 2:1～3:1 with the mass ratio of raw material), reduce to a certain extent production cost. But CN101548733A gained producesThe viscosity of product is lower, the not enough 50mPas of viscosity of 2% aqueous solution; Though the viscosity of CN101747441A products obtained therefrom is higher,But in course of reaction, added crosslinking agent, and in this patent documentation the concrete condition of undeclared this crosslinking agent (as the structure of matterOr title, dosage etc. are all not mentioned). CN102822204A also discloses a kind of taking wood pulp cellulose as raw material, with isopropyl alcoholThe aqueous solution is reaction medium, the method by solvent legal system for sodium carboxymethylcellulose. The product substitution value that this method makes is not high,But its aqueous solution has excellent viscosity, turbidity and transmission value. But the shortcoming of this method is also clearly: 1. solvent cost tooHigh. First, the cost of isopropyl alcohol will be significantly higher than ethanol conventional in other patents; The liquid-solid ratio of reacting described in this method in addition,Also higher (mass ratio of isopropyl alcohol and raw material is about 11:1～15:1). 2. technological process complexity. For example, this method proposes, and uses hydrogenPotassium oxide carries out quaternization, uses the sodium chloride saturated solution that contains 20% (mass fraction) after whole preparation feedback finishes againMethanol wash product, make sodium ion replace potassium ion, just obtain sodium carboxymethylcellulose, although this operation has strengthened productGel characteristic, but greatly increased undoubtedly the upper difficulty of operation, improved manpower and materials cost.
H.CN101367878A discloses a kind of taking pomace as raw material, taking ethanol water as reaction medium, passes throughSolvent legal system is for the method for sodium carboxymethylcellulose. The weak point of this method is that the organic solvent amount expending is larger, is providingEmbodiment in, 4g raw material just can complete reaction with the high concentration ethanol solution (volumetric concentration is 95%) of about 60mL, produceCost is high.
I.CN101993499A and CN102304186A disclose respectively taking cotton stalk as raw material and have prepared carboxymethyl celluloseThe method of element sodium. These two kinds of methods all need be using volume fraction as 95% the high concentration ethanol aqueous solution as reaction medium, whereinCN102304186A also needs microwave to complete reaction.
J.CN102887957A discloses taking furfural dregs as raw material, the side by solvent legal system for sodium carboxymethylcelluloseMethod. This method is carried out quaternization with hydrophily method after in advance furfural dregs being carried out desanding, acid and boils, extracts, bleaches, then with ethanol waterSolution is that reaction medium carries out etherification reaction.
K. US Patent No. 7,022,837B2 discloses with the sulfate pulp of cork or hardwood or sulfite pulpFor raw material, the method by solvent legal system for sodium carboxymethylcellulose. This method is soaked paper pulp with low-concentration sodium hydroxide solution in advance16～24 hours, then centrifugal, dry, then after being soaked in water and spending the night, in 99% isopropyl alcohol, alkalize and etherification reaction.The product viscosity that this method obtains is very high, but too loaded down with trivial details to the pre-treatment step of raw material, has greatly extended the production cycle; AndReaction is used more expensive high concentration aqueous isopropanol, and liquid-solid ratio is very high (about 20:1) also.
In sum, prepare the multiplex inert organic solvents of CMC as reaction medium using non-cotton raw material both at home and abroad, production costHigher. Though and lower-cost hydrophily method has indivedual application examples, the performance of products obtained therefrom is unsatisfactory, is difficult to meet each rowThe demand of industry.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of sodium carboxymethylcellulose, the present invention is with wood pulp or secondary stockFor raw material, prepare the sodium carboxymethylcellulose of different viscosities and substitution value by semidry method. The inventive method raw material sources are extensive,Preparation cost is lower, and properties of product can regulate and control.
For reaching above-mentioned purpose, the invention provides a kind of preparation method of sodium carboxymethylcellulose, described method is with wood pulpOr paper pulp is raw material, comprise the steps:
(1) quaternization: by raw material taking water as medium and NaOH carry out quaternization and obtain alkali cellulose;
(2) etherification reaction: the alkali cellulose of step (1) and chloroacetic acid are carried out to etherification reaction and obtain carboxymethyl celluloseSodium crude product;
(3) neutralization and washing: the sodium carboxymethylcellulose crude product of step (2) is neutralized in the aqueous solution of alcohol, andIn alcohol, wash;
(4) dry processing: will obtain sodium carboxymethylcellulose after dry the solid matter obtaining in step (3) processing.
The present invention takes semidry method to prepare sodium carboxymethylcellulose, and semidry method and traditional hydrophily method and solvent method technique are allThere is essential distinction. Semidry method without organic solvent, only using a small amount of water as reaction medium, coordinates pulverizer in course of reactionHigh speed shear react, significantly reduced preparation cost, simplified equipment, products obtained therefrom is functional.
Because the price of wood pulp piece or waste paper lumps is far below purified cotton, also reduce the cost of raw material. Use in addition waste paperSlurry is prepared sodium carboxymethylcellulose and is also had and turn waste into wealth, and recycles the significance of waste paper resource.
According to preparation method of the present invention, in step (1), preferred described quaternization is by raw material and solid hydrogen-oxygenChange after sodium and sodium hydrate aqueous solution are placed in consersion unit and carry out quaternization;
According to preparation method of the present invention, in step (1), can also preferred described quaternization be by consersion unitCycle periodic running is to react;
According to preparation method of the present invention, the cycle periodic running in step (1) quaternization is that reaction is establishedThe capable 0.5-5min of received shipment, then leave standstill 10-30min, to complete an alkalization cycle;
Wherein preferably repeat 2-10 cycle;
Specifically for example consersion unit is moved to 0.5-5min, leave standstill 10-30min, complete one-period, 0.5-reruns5min, leaves standstill 10-30min, completes second period, is so cycled to repeat 2-8 cycle.
According to any described preparation method above, reaction total time that wherein can also preferred steps (1) quaternizationFor 0.5-3h.
The quaternization that wherein the present invention can also preferred steps (1) is at room temperature to carry out.
According to preparation method of the present invention, in step (1), solid sodium hydroxide quality is described material quality0.3-2 doubly; Sodium hydrate aqueous solution mass concentration is 20-50%, the 1-2.5 that sodium hydrate aqueous solution quality is material qualityDoubly; Preferred described NaOH adds with the form of spray or dropping.
According to preparation method of the present invention, it in step (2), is the alkali fibre that solid chloroacetic acid is joined to step (1)In dimension element, carry out etherification reaction;
According to preparation method of the present invention, in step (2), can also preferred described etherification reaction be by consersion unitCycle periodic running is to react;
According to preparation method of the present invention, the cycle periodic running in step (2) etherification reaction is that reaction is establishedThe capable 0.5-5min of received shipment, then at 20-40 DEG C, leave standstill 10-30min, to complete an etherificate cycle;
Wherein preferably repeat 4-16 cycle;
According to any described preparation method above, wherein more preferably the reaction total time of described etherification reaction is 2-6h.
According to preparation method of the present invention, the 0.5-5 that in step (2), chloroacetic acid quality is described material qualityDoubly.
According to preparation method of the present invention, in preferred steps of the present invention (2) etherification reaction, chloroacetic acid is point 1-4 timeAdd, and add in the time that each cycle starts.
Wherein the present invention more preferably chloroacetic acid be point evenly to add for 1-4 time.
Wherein be understandable that, adding of chloroacetic acid is to belong to an operation in the etherificate cycle; Work as chloroacetic acidAfter adding, the etherificate cycle subsequently no longer adds chloroacetic acid;
Specifically for example, as chloroacetic acid, gradation adds fashionablely, and the beginning in each etherificate cycle all adds chloroacetic acid, until oneMonoxone finishes.
More specifically can be for example, as chloroacetic acid adds fashionablely several times, each etherificate cycle starts first to add chloroacetic acid,Again consersion unit is moved to 0.5-5min, then leave standstill 10-30min at 20-40 DEG C, to complete an etherificate cycle; When a chlorineAfter acetic acid finishes, if after continue operation, no longer add chloroacetic acid, only consersion unit is moved to 0.5-5min, thenAt 20-40 DEG C, leave standstill 10-30min, complete an etherificate cycle.
According to preparation method of the present invention, the neutralization of preferred steps (3) and washing are by the carboxymethyl fibre of step (2)Tie up plain sodium crude product transfer in the aqueous solution of alcohol, stir after with acid solution neutralization, then with filtering after alcohol washing;
According to preparation method of the present invention, in step (3), the aqueous solution of alcohol is the aqueous solution of methyl alcohol and/or ethanol;
Wherein more preferably the volume ratio of alcohol and water is 7:3-9.5:0.5.
According to preparation method of the present invention, wherein the present invention can also preferred steps (3) in by the carboxylic first of step (2)Base sodium cellulosate crude product is transferred in the aqueous solution of alcohol and is stirred 5～10min, and it is fully disperseed.
According to preparation method of the present invention, wherein the neutralization of the present invention described in can also preferred steps (3) is to adjustWhole pH value to 7 ± 0.5.
According to preparation method of the present invention, wherein the present invention after neutralization finishes in can also preferred steps (3), continuesStir 10-30min.
According to preparation method of the present invention, the acid solution described in step (3) is hydrochloric acid or acetum.
According to preparation method of the present invention, described in step (3), be by the solution after step (3) neutralization with alcohol washingFilter, gained solid is added and in alcohol, stirs 5-10min.
According to preparation method of the present invention, in the further preferred steps of the present invention (3), the alcohol of washing use is ethanol.
According to preparation method of the present invention, the dry processing of preferred steps (4) is the solid obtaining in step (3)Material is dried, is pulverized, sieving obtains sodium carboxymethylcellulose;
According to preparation method of the present invention, wherein the oven dry in step (4) is the conventional drying condition in this area,The present invention is preferably dried 6h at 60 DEG C.
According to preparation method of the present invention, sieving in the further preferred steps of the present invention (4) was 60 mesh sieves.
According to preparation method of the present invention, can also preferred consersion unit of the present invention be wherein pulverizer,Material is sheared to pulverizing.
According to preparation method of the present invention, before the quaternization of step (1), first raw material is pulverized and doneDry.
Wherein said dry the dry of this area ordinary meaning that should be understood to, is for example generally dry rear weightless ratio notExceed 10%.
Wherein the present invention is preferably broken to raw meal and becomes floccule fluffy, the hard core of nothing.
According to preparation method of the present invention, described wood pulp is softwood pulp or hardwood pulp; Described softwood pulp is excellentElect Korean pine wood pulp and/or spruce pulp as, described hardwood pulp is preferably one in birch wood pulp, eucalyptus wood pulp and willow wood pulpPlant or several mixing; Described paper pulp is secondary stock.
Wherein said secondary stock should be understood to conventionally described secondary stock of this area, for example produce with waste paper, warpThe paper pulp of deinking or not deinking.
The preferred secondary stock of the present invention is as the secondary stock of grass raw material and/or raw material of wood pulp; Described grass raw material exampleAs one or more mixed in rice grass as raw material, wheat straw raw material, cotton stalk class raw material, corn class raw material and giantreed class raw materialClose.
In sum, the invention provides a kind of taking wood pulp or secondary stock as raw material, by the semidry process of original creation, systemThe method of standby sodium carboxymethylcellulose. This method production cost is low; Production equipment is loosely required, and convenient operation, has improved equipmentUtilization ratio; Add indegree, pulverizer running time, reaction temperature and whole by adjusting dosage, the reagent of reaction reagentReact the time used, can make the carboxymethyl cellulose of different viscosities and substitution value, product can be used for oil drilling, washesWash, the industry such as weaving, toothpaste, food. Particularly, compared with prior art, preparation method provided by the invention has followingBeneficial effect:
(1) method of the present invention is taking wood pulp or secondary stock as raw material, and softwood pulp is (as Korean pine wood pulp, spruce pulpDeng), hardwood pulp (as birch wood pulp, eucalyptus wood pulp, willow wood pulp etc.) or various secondary stock be (by the waste paper reclaiming as useless filmPaper, useless brown paper, disregard message paper etc. make through making beating) all can be used as the raw materials of this law. With the conventional purified cotton of traditional handicraftRaw material is compared, and these raw material sources are abundant, and low price, has reduced cost.
(2) method of the present invention does not add inert organic solvents completely in carboxymethylation reaction process, significantly reducesProduction cost.
(3) method of the present invention relies on a small amount of (in sodium hydroxide solution) water as reaction medium, to coordinate powderThe high speed shear of broken machine can realize cellulosic carboxy methylation without organic solvent in the situation that. In course of reaction, thingMaterial both existed with form of suspension unlike in solvent method technique, also can as hydrophily method technique, not form the glue of pasty stateGroup. In the alkalization stage, material exists with slightly moistening wadding fibrous form; With the loose humidity of one in the etherificate stageSmall, flexible particle shape exist. Therefore semidry method has essential distinction with hydrophily method technique and solvent method technique before.Under the high speed shear effect of pulverizer, reaction reagent is easily deeply to material crystal region inside, thus improve reaction can andDegree and efficiency, obtain the good carboxy methylation product of performance.
(4) method of the present invention is looser to production equipment requirement, and main reactions steps is in pulverizerComplete; Do not need the repeatedly defeated transfer of pump of reaction mass, convenient operation; And pulverizer intermittent duty in course of reaction, power consumption isLow, also save to a certain extent the energy, manpower, reduce cost. In addition, pulverizer except can for reaction, also completeEntirely can, for the pulverizing in advance of raw material or the pulverising step of final products, make an equipment run through whole preparation flow, realShow the efficient utilization of equipment.
(5) because method of the present invention can be taking waste paper lumps as raw material, make qualified low-viscosity carboxymethyl fibreTie up plain product, therefore also have and turn waste into wealth, recycle the significance of waste paper resource.
Brief description of the drawings
Fig. 1 is the schematic diagram that carboxymethyl cellulose changes into sodium carboxymethylcellulose;
Fig. 2 is preparation method's of the present invention flow chart;
Fig. 3 is the infared spectrum of raw material of wood pulp of the present invention;
Fig. 4 is the infared spectrum of the sodium carboxymethylcellulose that obtains of the embodiment of the present invention 1;
Fig. 5 is the infared spectrum of the sodium carboxymethylcellulose that obtains of the embodiment of the present invention 2;
Fig. 6 is the infared spectrum of the sodium carboxymethylcellulose that obtains of the embodiment of the present invention 3;
Fig. 7 is the infared spectrum of secondary stock raw material of the present invention;
Fig. 8 is the infared spectrum of the sodium carboxymethylcellulose that obtains of the embodiment of the present invention 4;
Fig. 9 is the infared spectrum of the sodium carboxymethylcellulose that obtains of the embodiment of the present invention 5.
Detailed description of the invention
Describe below the beneficial effect of implementation process of the present invention and generation by specific embodiment in detail, be intended to help to readReader understands essence of the present invention and feature better, not as restriction that can practical range to this case.
In each embodiment, equipment used and material are by buying on market, and concrete condition is as follows:
Wood pulp piece is purchased from precious the people live in plenty the Paper Co., Ltd of Tianjin moral; Waste paper lumps, remittance rich plastics in Jiangmen City of Guangdong Province haveLimit company; Pulverizer is family's board 150g vertical type all steel electric household pulverizer (invariablenes turning speed: 28000 turn/min, volume stillDetermine power 900W), Yongkang City, Zhejiang Province Shan Zhu trade Co., Ltd; NaOH, absolute methanol, absolute ethyl alcohol, concentrated hydrochloric acid (matterAmount mark 36.5%), Yi Li fine chemicals Co., Ltd of Beijing; Chloroacetic acid, Tianjin good fortune chemical reagent factory in morning; Acetic acid(mass fraction 60%), modern east, Beijing fine chemicals Co., Ltd.
Unlike the prior art, the inventive method not with an organic solvent, is alkalizing in alkalization and etherification reactionIn reaction, only use a small amount of water (water of sodium hydroxide solution in quaternization) as reaction medium; The present invention is just in neutralizationRelate to the use of a small amount of organic solvent with washing process, such as the 15-20 that in step (3), the aqueous solution quality of alcohol is material qualityDoubly (being preferably 20 times); For example the alcohol quality of the middle washing of step (3) use is doubly (being preferably 10 times) of 8-12 of material quality again.
Embodiment 1
This example, taking wood pulp piece as raw material, has made qualified drilling fluid low viscosity carboxymethyl cellulose by semidry methodSodium.
(1) preparation: wood pulp piece is put into pulverizer and pulverize, until raw material becomes fluffy, cotton-shaped without hard core from bulkThing. Cotton-shaped raw material is put into baking oven dry.
In pulverizer, add the dried cotton-shaped raw material of wood pulp of 10g, 6.03g granular solids NaOH, then withIt is 25% sodium hydrate aqueous solution that the form of spray adds 15.46g mass concentration. Start pulverizer 2min. After pulverizing,Pulverizer is at room temperature left standstill to 20min, complete an alkalization cycle. And then pulverize-standing alkalization process,Altogether repeat 3 cycles. The whole quaternization time is 1.1h.
To the disposable 13.5g solid chloroacetic acid that adds in pulverizer, then start pulverizer 2min. After pulverizing,By pulverizer be placed in temperature be 25 DEG C insulating box leave standstill 30min, complete an etherificate cycle. And then carry out powderBroken-standing etherification procedure, repeats 8 cycles altogether. The whole etherification reaction time is 4.27h.
Material in pulverizer is transferred to one the beaker that 200mL volumetric concentration is 75% ethanol-water solution is housedIn. By the material stirring 5min in ethanol-water solution. Under stirring condition, slowly splash into mass concentration and be 10% salt acid-solubleLiquid, until the pH=7 of suspension stops dripping acid solution, continues to stir 10min.
Suspension is carried out to vacuum filtration or press filtration, then the solid of gained is moved to one 100mL absolute ethyl alcohol is housedIn container, by the material stirring 5～10min in absolute ethyl alcohol, then suspension is carried out to vacuum filtration.
By the solid matter of gained after filtering dry 6h in the insulating box of 60 DEG C, taken out, pulverize, cross 60 mesh sieves.By weighing products, obtain low-viscosity sodium carboxymethyl cellulose 17.16g. Preparation flow as shown in Figure 2.
(2) performance evaluation and sign:
1. drilling fluid additive performance evaluation: by American Petroleum Institute (API) (AmericanPetroleumInstitute)" drilling fluid materials specification " (API13A:SpecificationforDrillingFluidsMaterials, 2010Version) in " technical grade low viscosity carboxymethyl cellulose " described evaluation method the performance of the present embodiment product is evaluated. CommentValency the results are shown in Table 1:
Table 1 embodiment 1 properties of product evaluation
Embodiment 1 products obtained therefrom is the drilling fluid technical grade low viscosity carboxylic first that performance meets international standard as shown in Table 1Base sodium cellulosate.
2. the mensuration of substitution value: in National Standard of the People's Republic of China's " food additives sodium carboxymethylcellulose "Assay method (ashing method) substitution value of this routine products obtained therefrom is measured. Record substitution value DS=0.698.
3. characterize: this routine products obtained therefrom is characterized with infrared spectrum. For the ease of contrast, provide the red of raw material of wood pulpExternal spectrum figure, is shown in Fig. 3. The infrared spectrogram of this routine gained CMC product is shown in Fig. 4. From the contrast of Fig. 3 and Fig. 4, at carboxymethylAfter changing reaction, at wave number 1620cm-1There is a new strong absworption peak in place, this is the characteristic peak of C=O stretching vibration. In addition,Be 1430cm in wave number-1Place and 1310cm-1Two peaks that place occurs are respectively-CH2-scissoring vibration characteristic peak and-face of OHInterior flexural vibrations characteristic peak. The appearance explanation of these new characteristic peaks has a large amount of-CH in the molecule of product2COOH structure,Therefore, products obtained therefrom is sodium carboxymethylcellulose.
Embodiment 2
This example, taking wood pulp piece as raw material, has made qualified drilling fluid medium viscosity carboxymethyl cellulose by semidry methodSodium. This example is with the main distinction of embodiment 1: in quaternization process, solid sodium hydroxide and sodium hydroxide solutionConsumption difference; The asynchronism(-nization) of pulverizer single operation; The asynchronism(-nization) of quaternization and etherification reaction; Chloroacetic acid at twiceAdd in the ratio of 1:1.
(1) preparation: wood pulp piece is put into pulverizer and pulverize, until raw material becomes fluffy, cotton-shaped without hard core from bulkThing. Cotton-shaped raw material is put into baking oven dry.
In pulverizer, add the dried cotton-shaped raw material of wood pulp of 10g, 5.3g chip solid NaOH, then to dripForm to add 17.85g mass concentration be 25% sodium hydrate aqueous solution. Start pulverizer 1min. After pulverizing, by powderBroken machine at room temperature leaves standstill 30min, completes an alkalization cycle. And then pulverize-standing alkalization process, altogetherRepeat 3 cycles. The whole quaternization time is 1.55h.
In pulverizer, add 10.19g solid chloroacetic acid, then start pulverizer 2min. After pulverizing, will pulverizeMachine be placed in temperature be 25 DEG C insulating box leave standstill 30min, complete an etherificate cycle. And then add 10.19g chloroetheneAcid, and again pulverize-standing etherification procedure, repeat 6 etherificate cycles altogether. The whole etherification reaction time is 3.2h.
All the other preparation processes are identical with embodiment 1. By weighing products, obtain medium viscosity sodium carboxymethylcellulose 14.51g.
(2) performance evaluation and sign:
1. drilling fluid additive performance evaluation: with reference to the People's Republic of China's oil and gas industry standard SY5093-92---in sanlose for drilling fluid (CMC), " in sticky sanlose " described evaluation method is to thisThe performance of embodiment product is evaluated. Evaluation result is in table 2:
Table 2 embodiment 2 properties of product evaluations
As shown in Table 2, embodiment 2 products obtained therefroms are performance drilling fluids of meeting national standard with in sticky carboxymethyl celluloseSodium.
3. characterize: this routine products obtained therefrom is characterized with infrared spectrum. Spectrogram is shown in Fig. 5. The feature of known routine productPeak and embodiment 1 product are similar, illustrate that products obtained therefrom is sodium carboxymethylcellulose.
Embodiment 3
This example, taking wood pulp piece as raw material, has made qualified drilling fluid high viscosity carboxymethyl cellulose by semidry methodSodium. This example is with the main distinction of embodiment 1: in quaternization process, solid sodium hydroxide and sodium hydroxide solutionConsumption difference; The concentration difference of sodium hydroxide solution; The asynchronism(-nization) of pulverizer single operation; The environment temperature of etherification reaction is notWith; The total time difference of etherification reaction; Chloroacetic acid adds in the ratio of 1:2 at twice.
(1) preparation: wood pulp piece is put into pulverizer and pulverize, until raw material becomes fluffy, cotton-shaped without hard core from bulkThing. Cotton-shaped raw material is put into baking oven dry.
In pulverizer, add the dried cotton-shaped raw material of wood pulp of 10g, 5.78g granular solids NaOH, then withIt is 33.3% sodium hydrate aqueous solution that the form of spray adds 23.40g mass concentration. Start pulverizer 1min. Pulverize completeAfter, pulverizer is at room temperature left standstill to 20min, complete an alkalization cycle. And then pulverize-standing alkalizationJourney, repeats 3 cycles altogether. The whole quaternization time is 1.1h.
First in pulverizer, add 7.06g solid chloroacetic acid, then start pulverizer 0.5min. After pulverizing, willPulverizer be placed in temperature be 35 DEG C insulating box leave standstill 20min, complete an etherificate cycle. And then add 14.12g chlorineAcetic acid, and again pulverize-standing etherification procedure, pulverize-leave standstill 6 etherificate cycles altogether. The whole etherification reaction timeFor 2.05h.
All the other preparation processes are identical with embodiment 1. By weighing products, obtain high-viscosity sodium carboxymethyl cellulose 15.01g.
(2) performance evaluation and sign:
1. drilling fluid additive performance evaluation: by American Petroleum Institute (API) (AmericanPetroleumInstitute)" drilling fluid materials specification " (API13A:SpecificationforDrillingFluidsMaterials, 2010Version) in " technical grade high viscosity carboxymethyl cellulose " described evaluation method the performance of the present embodiment product is evaluated. CommentValency the results are shown in Table 3:
Table 3 embodiment 3 properties of product evaluations (drilling fluid additive)
As shown in Table 3, embodiment 3 products obtained therefroms are high sticky carboxymethyl celluloses for drilling fluid that performance meets international standardSodium.
2. food additives performance evaluation: the product making by the present embodiment, solution viscosity is higher, can be used for food workIn industry. By National Standard of the People's Republic of China GB1904-2005---described in food additives sodium carboxymethylcelluloseEvaluation method is evaluated the performance of the present embodiment product. Evaluation result is in table 4:
Table 4 embodiment 3 properties of product evaluations (food additives)
As shown in Table 4, embodiment 3 products obtained therefroms are food additives carboxymethyl celluloses that performance meets national standardSodium. Press the naming rule described in GB1904-2005, this product type is FL9.
3. characterize: this routine products obtained therefrom is characterized with infrared spectrum. Spectrogram is shown in Fig. 6. The feature of known routine productPeak and embodiment 1 product are similar, illustrate that products obtained therefrom is sodium carboxymethylcellulose.
Embodiment 4
This example, taking waste paper lumps as raw material, has made qualified drilling fluid low viscosity carboxymethyl cellulose by semidry methodSodium. This example is with the main distinction of embodiment 1: raw materials is waste paper lumps; In quaternization process, solid hydrogen oxidationThe consumption of sodium and sodium hydroxide solution is different; The concentration difference of sodium hydroxide solution; The asynchronism(-nization) of pulverizer single operation; EtherChange the environment temperature difference of reaction; The total time difference of quaternization; Chloroacetic acid adds in the ratio of 1:1 at twice.
(1) preparation: waste paper lumps is put into pulverizer and pulverize, until raw material becomes wadding fluffy, the hard core of nothing from bulkShape thing. Cotton-shaped raw material is put into baking oven dry.
In pulverizer, add the dried cotton-shaped secondary stock raw material of 10g, 6.73g granular solids NaOH, thenAdd the sodium hydrate aqueous solution of 13.60g mass concentration as 40% taking the form dripping. Start pulverizer 1min. Pulverize completeAfter, pulverizer is at room temperature left standstill to 20min, complete an alkalization cycle. And then pulverize-standing alkalizationJourney, repeats 6 cycles altogether. The whole quaternization time is 2.1h.
First in pulverizer, add 7.61g solid chloroacetic acid, then start pulverizer 1min. After pulverizing, by powderBroken machine be placed in temperature be 35 DEG C insulating box leave standstill 20min, complete an etherificate cycle. And then add 7.61g chloroetheneAcid, and again pulverize-standing etherification procedure, pulverize-leave standstill 12 etherificate cycles altogether. The whole etherification reaction time is4.2h。
All the other preparation processes are identical with embodiment 1. By weighing products, obtain low-viscosity sodium carboxymethyl cellulose 13.88g.
(2) performance evaluation and sign:
1. drilling fluid additive performance evaluation: by American Petroleum Institute (API) (AmericanPetroleumInstitute)" drilling fluid materials specification " (API13A:SpecificationforDrillingFluidsMaterials, 2010Version) in " technical grade low viscosity carboxymethyl cellulose " described evaluation method the performance of the present embodiment product is evaluated. CommentValency the results are shown in Table 5:
Table 5 embodiment 4 properties of product evaluations
Embodiment 4 products obtained therefroms are drilling fluid technical grade low viscosity carboxylic first that performance meets international standard as shown in Table 5Base sodium cellulosate.
2. the mensuration of substitution value: in National Standard of the People's Republic of China's " food additives sodium carboxymethylcellulose "Assay method (ashing method) substitution value of this routine products obtained therefrom is measured. Record substitution value DS=0.731.
3. characterize: this routine products obtained therefrom is characterized with infrared spectrum. For the ease of contrast, provide secondary stock raw materialInfrared spectrogram, is shown in Fig. 7. The infrared spectrogram of this routine gained CMC product is shown in Fig. 8. Known example of contrast by Fig. 7 and Fig. 8 producedThe characteristic peak of product and embodiment 1 product are similar, illustrate that products obtained therefrom is sodium carboxymethylcellulose.
Embodiment 5
This example, taking waste paper lumps as raw material, has made qualified drilling fluid low viscosity carboxymethyl cellulose by semidry methodSodium. This example is with the main distinction of embodiment 1: in quaternization process, solid sodium hydroxide and sodium hydroxide solutionConsumption difference; The concentration difference of sodium hydroxide solution; The asynchronism(-nization) of pulverizer single operation; Quaternization and etherification reactionAsynchronism(-nization); The environment temperature difference of etherification reaction; Chloroacetic acid adds in the ratio of 2:1 at twice. In and time, product is putIn methanol-water solution, neutralize with Acetic Acid-Water solution.
(1) preparation: waste paper lumps is put into pulverizer and pulverize, until raw material becomes wadding fluffy, the hard core of nothing from bulkShape thing. Cotton-shaped raw material is put into baking oven dry.
In pulverizer, add the dried cotton-shaped secondary stock raw material of 10g, 3.4g granular solids NaOH, then withIt is 33.3% sodium hydrate aqueous solution that the form of spray adds 22.20g mass concentration. Start pulverizer 3min. Pulverize completeAfter, pulverizer is at room temperature left standstill to 10min, complete an alkalization cycle. And then pulverize-standing alkalizationJourney, repeats 8 cycles altogether. The whole quaternization time is 1.73h.
First in pulverizer, add 10.14g solid chloroacetic acid, then start pulverizer 2min. After pulverizing, by powderBroken machine be placed in temperature be 40 DEG C insulating box leave standstill 20min, complete an etherificate cycle. And then add 5.07g chloroetheneAcid, and again pulverize-standing etherification procedure, pulverize-leave standstill 15 etherificate cycles altogether. The whole etherification reaction time is5.5h。
Material in pulverizer is transferred to one the beaker that 200mL volumetric concentration is 80% methanol-water solution is housedIn. By the material stirring 5min in methanol-water solution. Under stirring condition, slowly splash into mass concentration and be 60% Acetic Acid-WaterSolution, until the pH=7 of suspension stops dripping acid solution, continues to stir 10min.
All the other preparation processes are identical with embodiment 1. By weighing products, obtain low-viscosity sodium carboxymethyl cellulose 16.08g.
(2) performance evaluation and sign:
1. drilling fluid additive performance evaluation: by American Petroleum Institute (API) (AmericanPetroleumInstitute)" drilling fluid materials specification " (API13A:SpecificationforDrillingFluidsMaterials, 2010Version) in " technical grade low viscosity carboxymethyl cellulose " described evaluation method the performance of the present embodiment product is evaluated. CommentValency the results are shown in Table 6:
Table 6 embodiment 5 properties of product evaluations
Embodiment 5 products obtained therefroms are drilling fluid technical grade low viscosity carboxylic first that performance meets international standard as shown in Table 6Base sodium cellulosate.
2. the mensuration of substitution value: in National Standard of the People's Republic of China's " food additives sodium carboxymethylcellulose "Assay method (ashing method) substitution value of this routine products obtained therefrom is measured. Record substitution value DS=1.246. With embodiment4 compare, and the substitution value of this routine products obtained therefrom is higher, but solution viscosity is lower.
3. characterize: this routine products obtained therefrom is characterized with infrared spectrum. Spectrogram is shown in Fig. 9. The feature of known routine productPeak and embodiment 1 product are similar, illustrate that products obtained therefrom is sodium carboxymethylcellulose.
Comparative example 1
This example is taking wood pulp piece as raw material, and alcohol-water mixed solution is reaction medium, and it is qualified to make by traditional solvent methodDrilling fluid medium viscosity sodium carboxymethylcellulose, to contrast solvent method and two kinds of preparation technologies of semidry method.
(1) preparation: wood pulp piece is put into pulverizer and pulverize, until raw material becomes fluffy, cotton-shaped without hard core from bulkThing. Cotton-shaped raw material is put into baking oven dry.
In there-necked flask, add the dried cotton-shaped raw material of wood pulp of 10g. 8g solid sodium hydroxide is dissolved in to 200mL80%Ethanol water in, and pour there-necked flask into. Flask is placed in to the water bath with thermostatic control of 30 DEG C and stirs, make material evenDisperse, carry out quaternization. After reaction 1.5h, water bath with thermostatic control is warming up to 60 DEG C, adds 20mL to be dissolved with 22.5g chloroacetic acid80% ethanol water, continues to stir, and carries out etherification reaction. After reaction 3h, the reactant in there-necked flask is poured in beaker,Under stirring condition, slowly splash into mass concentration and be 10% hydrochloric acid solution, until the pH=7 of suspension stops dripping acid solution,Continue to stir 10min.
Suspension is carried out to vacuum filtration or press filtration, then the solid of gained is moved to one 100mL absolute ethyl alcohol is housedIn container, by the material stirring 10min in absolute ethyl alcohol, then suspension is carried out to vacuum filtration.
By the solid matter of gained after filtering dry 6h in the insulating box of 60 DEG C, taken out, pulverize, cross 60 mesh sieves.By weighing products, obtain medium viscosity sodium carboxymethylcellulose 14.86g.
(2) performance evaluation and sign:
1. drilling fluid additive performance evaluation: with reference to the People's Republic of China's oil and gas industry standard SY5093-92---in sanlose for drilling fluid (CMC), " in sticky sanlose " described evaluation method is to thisThe performance of embodiment product is evaluated. Evaluation result is in table 7:
The 1 properties of product evaluation of table 7 comparative example
As shown in Table 7, comparative example 1 gained solvent method product be the performance drilling fluid that meets national standard with in sticky carboxymethylSodium cellulosate. Compared with semidry method product (embodiment 2), the Efficient Adhesive Promotion of solvent method product slightly well, but reduces the energy of filter lossPower and substitution value are slightly low. The Performance Ratio of the two is more approaching in general. Obviously, adopt semidry process economizing dereaction JieIn the situation of matter (ethanol water), make the sodium carboxymethylcellulose close with solvent method properties of product.
Claims (25)
1. a preparation method for sodium carboxymethylcellulose, is characterized in that, described method, taking wood pulp or paper pulp as raw material, comprisesFollowing steps:
(1) quaternization: by raw material taking water as medium and NaOH carry out quaternization and obtain alkali cellulose; Described alkalization is anti-Should be to carry out quaternization after raw material and solid sodium hydroxide and sodium hydrate aqueous solution are placed in to consersion unit; Solid hydrogen oxidationSodium quality is 0.3-2 times of described material quality; Sodium hydrate aqueous solution mass concentration is 20-50%, sodium hydrate aqueous solutionQuality is 1-2.5 times of material quality;
(2) etherification reaction: the alkali cellulose of step (1) and chloroacetic acid are carried out to etherification reaction, and to obtain sodium carboxymethylcellulose thickProduct;
(3) neutralization and washing: the sodium carboxymethylcellulose crude product of step (2) is neutralized in the aqueous solution of alcohol, and at alcoholIn wash;
(4) dry processing: will obtain sodium carboxymethylcellulose after dry the solid matter obtaining in step (3) processing.
2. preparation method according to claim 1, is characterized in that, sodium hydrate aqueous solution described in step (1) is with sprayThe form of drenching or drip adds.
3. preparation method according to claim 1, is characterized in that, the described quaternization of step (1) is by consersion unitCycle periodic running is to react.
4. preparation method according to claim 3, is characterized in that, the cycle batch (-type) fortune in step (1) quaternizationRow is that consersion unit is moved to 0.5-5min, then leaves standstill 10-30min, to complete an alkalization cycle.
5. preparation method according to claim 4, is characterized in that, the alkalization cycle of step (1) repeats 2-10 cycle.
6. preparation method according to claim 4, is characterized in that, the reaction total time of step (1) quaternization is0.5-3h。
7. preparation method according to claim 1, is characterized in that, described consersion unit is pulverizer.
8. preparation method according to claim 1, is characterized in that, in step (2), chloroacetic acid quality is described raw materialThe 0.5-5 of quality doubly.
9. preparation method according to claim 1, is characterized in that, the described etherification reaction of step (2) is by consersion unitCycle periodic running.
10. preparation method according to claim 9, is characterized in that, in step (2) etherification reaction, chloroacetic acid is a point 1-Add for 4 times, and add in the time that each cycle starts.
11. preparation methods according to claim 9, is characterized in that, the cycle batch (-type) fortune in step (2) etherification reactionRow is that consersion unit is moved to 0.5-5min, then leaves standstill 10-30min at 20-40 DEG C, to complete an etherificate cycle.
12. preparation methods according to claim 11, is characterized in that, the etherificate cycle of step (2) repeats 4-16 weekPhase.
13. preparation methods according to claim 11, is characterized in that, the reaction total time of the etherification reaction of step (2)For 2-6h.
14. preparation methods according to claim 1, is characterized in that, step (2) is that solid chloroacetic acid is joined to stepSuddenly in the alkali cellulose of (1), carry out etherification reaction and obtain sodium carboxymethylcellulose crude product.
15. preparation methods according to claim 1, is characterized in that, in step (3) aqueous solution of alcohol be methyl alcohol and/orThe aqueous solution of ethanol.
16. preparation methods according to claim 15, is characterized in that, in step (3), the volume ratio of alcohol and water is 7:3-9.5:0.5。
17. preparation methods according to claim 1, is characterized in that, step (3) is by the carboxymethyl cellulose of step (2)Element sodium crude product transfer to and stir in the aqueous solution of alcohol after with acid solution neutralization, then with filtering after alcohol washing.
18. preparation methods according to claim 17, is characterized in that, the acid solution described in step (3) is hydrochloric acid or vinegarAcid solution.
19. preparation methods according to claim 17, is characterized in that, step (3) is with filtering after ethanol washing.
20. preparation methods according to claim 1, is characterized in that, the dry processing of step (4) is by step (3)The solid matter obtaining is dried, is pulverized, sieving obtains sodium carboxymethylcellulose.
21. according to the preparation method described in claim 1～20 any one, it is characterized in that, in the quaternization of step (1)Before, first raw material is pulverized and is dried.
22. according to the preparation method described in claim 1～20 any one, it is characterized in that, described wood pulp is softwood pulpOr hardwood pulp; Described paper pulp is secondary stock.
23. preparation methods according to claim 22, is characterized in that, described softwood pulp is Korean pine wood pulp and/or cloudChina fir slurry.
24. preparation methods according to claim 22, is characterized in that, described hardwood pulp is birch wood pulp, eucalyptus woodThe mixing of one or more in slurry and willow wood pulp.
25. preparation methods according to claim 22, is characterized in that, described secondary stock is grass raw material and/or woodThe secondary stock of slurry raw material.
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| CN108611898B (en) * | 2018-04-17 | 2020-07-17 | 陕西科技大学 | Method for preparing carboxymethyl fiber by using water medium method and application thereof |
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