CN1247841C - Solvent recovery process for solvent method cellulose fiber preparation - Google Patents
Solvent recovery process for solvent method cellulose fiber preparation Download PDFInfo
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- CN1247841C CN1247841C CNB2004100543358A CN200410054335A CN1247841C CN 1247841 C CN1247841 C CN 1247841C CN B2004100543358 A CNB2004100543358 A CN B2004100543358A CN 200410054335 A CN200410054335 A CN 200410054335A CN 1247841 C CN1247841 C CN 1247841C
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Abstract
The present invention relates to technology of solvent recovery in the process of preparing cellulose fiber by a solvent method. Firstly, suspended impurities larger than 9 mu m in spinning productive cycle waste liquid are removed by rough filtration; then, solid impurities larger than 1 mu m are removed by a micropore ceramic tube and a refined filtration system of which the outer wall is coated with a sintered zirconium dioxide film; subsequently, colored decomposing substances are removed by anion exchange resin; afterwards, metallic ions and morpholine are removed by reasonably selecting cation exchange resin and utilizing the adsorption force of the cation exchange resin according to the characteristics of the selecting exchange sequence that metallic ions are not smaller than morpholine which is larger than NMM which is larger than NMMO; and finally, the NMM is oxidized to the NMMO. The five processing sequences synthetically form recovery system engineering, remove various impurities, effectively recover the solvent NMMO and enhances fibre quality and technology safety. The technology is feasible, and has high efficiency.
Description
Technical field
The present invention relates in the chemical fibre manufacturing solvent recovery process in the cellulose fiber by solvent method spinning production process, specifically be meant by comprehensive multiple recovery method, in spinning production cycle waste liquid, remove plurality of impurities, reclaim the technology of solvent N-methylmorpholine oxide (NMMO) effectively.
Background technology
Patent (US92 was just arranged as far back as the thirties in 20th century, 179,181) available tertiary amino oxides NMMO is proposed, be that the direct dissolving cellulos of N-methylmorpholine oxide is produced the cellulose fiber by solvent method Lyocell that performance is better than viscose glue, it is formed and still belongs to cellulosic structure, product abandonment thing natural degradation is considered to the very good a kind of environmental protection fiber of combination property.It has the comfortableness of cotton fiber, the intensity of polyester fiber, and the soft matter attitude of the drapability of viscose and silk is subjected to liking of people deeply, and its market prospects are very wide.
For this reason, from the seventies in 20th century so far, under scientist's the joint efforts, applied for or disclose up to a hundred patents of relevant Lyocell fiber at home and abroad, the related Lyocell fiber production of these patents can be divided into three part main technique technology: (1) uses NMMO/H by a certain percentage
2O makes solvent, makes cellulose dissolution make cellulose spinning solution; (2) spinning solution is through spinning pack and at rare NMMO/H
2Be spun into tow in the coagulating bath of O, make fiber through post processing then; (3) in water lotion and coagulating bath, assemble gradually by spinning as the solvent NMMO of spinning solution, in order to reach the recycle of NMMO, and remove the various impurity that produce in the technology, set up the solvent recovery engineering.
After deliberation, following several material is arranged in the solution that the NMMO solvent reclaims from coagulating bath and water lotion after through high-temperature digestion and spinning:
1.N-methyl morpholine oxide (NMMO)
It is the primary solvent of dissolving cellulos pulp, must be to its recycling as much as possible.
2. suspended impurity
It is mainly derived from the dissolving and spinning process of cellulose pulp, the cellulose that does not dissolve and degrade, and these suspended impurity parts exist with undissolved colloidal form with dissolved state, part.Because their existence not only can cause the solvent recovery process difficulty, and has reduced the quality of recovered solvent, thereby has influenced the recycle once more of recovery solvent.
3. foreign pigment
It mainly is coloured decomposed substance that NMMO and cellulose are at high temperature produced, and this material mainly is organic anion, and its existence can cause fiber quality to descend, and makes the finished fiber yellowing, has reduced the rate of recovery of NMMO simultaneously.
4. morpholine (M), N-methylmorpholine (NMM)
When the spinning solution that makes for the dissolution with solvents cellulose with NMMO is subjected to high temperature, NMMO decomposes easily, wherein NMMO mainly decomposes generation N-methylmorpholine (NMM), morpholine (M), owing to existence and the accumulation of these catabolites in reclaiming solvent, can reduce the solubility property of solvent gradually.In addition, morpholine can partly be converted into N-nitrosomorpholine under certain condition, and N-nitrosomorpholine is a kind ofly to be difficult to remove and very strong carcinogenic chemical, this shows the importance that morpholine is removed in the solvent recovery process.
5. metal ion
It is mainly from the parts of used cellulose pulp or employed hardware and pipeline etc.
Metal ion is iron ion and copper ion particularly, can impel NMMO and cellulosic degraded under the condition of high temperature.Even a large amount of heat of producing of this reaction can make system have blast may, therefore must remove metal ion, especially iron ion and copper ion.
From on can find out that the solvent recovery engineering plays an important role in the Lyocell fiber production, in recent years, people have carried out a large amount of research in this area, form many patents and article report, now with the classification of relevant NMMO solvent recovery patent, can be divided into following several:
1. filtration method: with WO93/11287, patents such as WO97/07268 are representative.In WO93/11287, only use the coarse filtration process, can filter out, but some irregular little suspended impurities still exist some big suspended impurities.In WO97/07268, make flocculant make suspended impurity agglomeration not of uniform size flocculate into big suspended impurity earlier, remove by depth-type filtration again, although to suspended impurity remove more thorough, but the extra adding of flocculant has also increased the burden that reclaims, and has brought potential threat to reclaiming technology simultaneously.Above-mentioned patented technology is only used single filtration decontamination method, can only remove suspended impurity, can not remove other soluble impurity of existing in the solvent such as morpholine etc., can not remove the coloring matter and the ion that form in the solution.
2. absorption method: with EP-A-0488988, US5, patents such as 502,188 are representative.All to adopt aluminium oxide, silica and/or active carbon as adsorbent, the method for absorption is comparatively thorough to foreign pigment absorption for they, and shortcoming is that active ingredient NMMO and NMM also partly are adsorbed, thereby has reduced solvent recovering yield.This method also exists the low problem of effective rate of utilization of desorption and adsorbent when industry is used.
3. oxidizing process: with US 5,904,818, WO97/07138, DE-A-140259, EP-A-0320690, FR-A-8808039, US5, patents such as 216,154 are representative.These patents all come oxidation to reclaim N-methylmorpholine in the liquid with hydrogen peroxide, make its regeneration N-methylmorpholine oxide, but the morpholine that occurs in oxidizing process can be oxidized to easily carcinogenic and this material of N-nitrosomorpholine that be difficult to remove, certainly the patent that has proposes to utilize carboxylic acid halides to suppress the generation of nitrosamine, or in the presence of carbon dioxide the oxidation methyl morpholine, though stoped the generation of N-nitro compound like this, but but introduced new chemicals, made the whole recovery process complications.
4. ion-exchange: handle the patent and the report of NMMO solvent recovery in recent years about ion-exchange-resin process, with DD-A-254199, EP-A-427701, DD-A-274435 etc. are representative.In DD-A-254199, use band-CH
2N (CH
3)
2The uncle of type presses the anion exchange resin of the styrene/divinyl benzene copolymer of group, and this method can be removed foreign pigment, but but can not remove fully morpholine and metal ion.In DD-A-274435, adopt the cationic ion-exchange resin of the styrene/divinyl benzene copolymer of sulfonic acid group, though this method can be removed morpholine, but part NMMO and NMM are also removed simultaneously, thereby have reduced solvent recovering rate, in addition, it can not be removed foreign pigment.
Summary of the invention
The objective of the invention is to be to provide one to remove plurality of impurities in the circulation waste liquid in the process that the Lyocell fibre spinning is produced, reclaim the systemic recycling engineering of solvent N-methylmorpholine oxide effectively, this recycling engineering is that multiple relevant recovery technology and the equipment by solvent is combined.
For addressing this problem, adopt following technical scheme:
Formulate a kind of impurity such as suspended impurity in the Lyocell fibre spinning production cycle waste liquid, foreign pigment, morpholine, metal ion of removing, and effectively reclaim the system recoveries engineering of solvent N-methylmorpholine oxide, this system is that five processing methods are formed, and is comprehensively formed a complete recycling engineering by coarse filtration, essence filter, resin anion (R.A.) exchange processing, cation resin exchange processing, oxidation processes five big operations.
Concrete technological process is pressed: 1, coarse filtration; 2, smart filter; 3, the resin anion (R.A.) exchange is handled; 4, cation resin exchange is handled; 5, oxidation processes.
Described coarse filtration is that the circulation waste liquid that will be produced in the spinning production process flows through the filtering container that has filter medium anthracite, float stone and gravel with 6～14m/h flow velocity, to remove the suspended solid of particle diameter greater than 9 μ m, its technical parameter: filter medium anthracite, float stone and the gravel of adopting pack in the filtering container with capacity such as each sections of upper, middle and lower respectively, its particle diameter is respectively 10～20mm, 5～10mm, 2～4mm.
Described smart filter is that filter liquor after the coarse filtration is scribbled netted uniform zirconium oxide film by earthenware and the earthenware outer wall that tube wall has micropore, and can remove particle diameter is the treatment process of 1～9 μ m suspended impurity.
Its technological parameter:
(1) micropore ceramic tube that is adopted, its porosity are 25～60%, and average pore size is 2 μ m～5 μ m, and its caliber is 0.4～0.85 times of smart filter inside diameter of vessel.
(2) zirconium oxide film of earthenware outer wall is that the particle of 0.3 μ m～15 μ m is formed by particle diameter, and it is the uniform zirconia ceramics film of netted densification of 0.2 μ m～11 μ m that the suspended particles sintering process of this particle by routine formed average pore size.
(3) operating pressure is 30kPa～250kPa, and the feeding flow velocity is 0.05m/s～0.3m/s.
It is to be with the filter liquor feeding of look to be equipped with in the conventional exchange column of anion exchange resin essence filter back that described resin anion (R.A.) exchange is handled, and after the anion exchange by both, removes the contained band colored foreign of its filter liquor.
Its technological parameter and step:
(1) resin that is adopted is meant band-OH
-The macropore strong basic anion-exchange resin of the polystyrene of the quaternary amines of type, specification are granularity 20～40 orders, and the resin equipped amount is 0.3～0.7 times of this exchange column volume.
(2) the feeding flow velocity is per hour to flow through 2～5 times resin bed volume.
(3) when 2～6 times of bed volumes are collected eluate, need to survey the absorbance of corresponding filter liquor.When the absorbance of filter liquor was 0.25～0.4, the resin adsorption value reached capacity, stopped exchange.
It is the filter liquor after the resin anion (R.A.) exchange processing to be fed be equipped with in the conventional exchange column of cationic ion-exchange resin that described cation resin exchange is handled, by cation exchange group on the resin and the band CATION in the filter liquor or there are all substances of CATION tendency group to carry out optionally ion-exchange, for reaching Selective Separation and, selecting following technology and processing step until the purpose of impurity such as final removal metal ion and morpholine:
(1) resin that is adopted is meant band H
+The macroporous strong-acid cation-exchange resin of the polystyrene of the sulfonic acid group of type, specification are granularity 20～40 orders, and the resin equipped amount is 0.3～0.7 times of this exchange column volume.This resin has different exchange absorption affinities to materials such as metal ion, morpholines, the size of its exchange absorption affinity must by the metal ion＞＞order of morpholine＞N-methylmorpholine＞N-methylmorpholine oxide arranges.
(2) the feeding flow velocity is per hour to flow through 3～6 times resin bed volume.
(3) when 7～14 times of bed volumes are collected filter liquor, measure iron ion and copper ion and N-methylmorpholine oxide respectively, the concentration of N-methylmorpholine and morpholine.Containing morpholine in eluate is 15ppm, and when metal ion was 0.1ppm, it was saturated to regard resin as, stops exchange.
Described oxidation processes is the filter liquor that contains N-methylmorpholine and N-methylmorpholine oxide after coming the oxidative cationic resins exchange to handle with hydrogen peroxide, makes N-methylmorpholine change into the N-methylmorpholine oxide.
Its technological parameter and step:
(1) 20～40% aqueous hydrogen peroxide solution and filter liquor are 1: 800～1300 to mix stirring in the evaporation reaction device according to weight ratio.
(2) reaction temperature is 40～80 ℃, and the reaction time is 1～5 hour.
Advantage of the present invention is to adopt multiple recovery method in the preparation of cellulose fiber by solvent method is produced, and these method synthesis can be formed a complete recycling engineering, promptly according to five big operations such as coarse filtration, smart filter, resin anion (R.A.) exchange processing, cation resin exchange processing, oxidation processes, and the storage tank that operation is produced about five inter process arrangements are used for balance, can not only remove the plurality of impurities in the spinning production cycle waste liquid like this, and can reclaim solvent N-methylmorpholine oxide effectively, make feasible process of the present invention, efficient; Arranged smart filter after the coarse filtration operation, be used to remove a large amount of little suspended solid impurities, this essence filtering system is to finish by the zirconium oxide film through oversintering that micropore ceramic tube and its outer wall scribble, it can remove the solid impurity greater than 1 μ m, so both there be not to introduce chemicals as flocculant and so on, simplify recovery technology, also alleviated the burden of back operation, increased the life-span of ion exchange resin simultaneously; Adopt the ion exchange resin of cloudy earlier back sun to come integrated treatment through recovery liquid thick, smart filter again, anion exchange resin has been removed coloured decomposed substance that NMMO and cellulose are at high temperature produced, and has improved fiber quality, and finished fiber is bleached; By rational selection large porous strong acid cation exchange resin, utilize this resin that metal ion, morpholine, N-methylmorpholine and N-methylmorpholine oxide are had the exchange absorption affinity, with and the absorption affinity size be by the metal ion＞＞the tactic characteristic of morpholine＞N-methylmorpholine＞N-methylmorpholine oxide, removed metal ion wherein, avoided the degraded at high temperature of NMMO and cellulose, process safety is improved; Simultaneously, cationic ion-exchange resin adsorbs morpholine by selectable, and then has stoped the generation that strong carcinogen N-nitrosomorpholine is arranged; Finishing operation of the present invention is oxidation, only deposit N-methylmorpholine and N-methylmorpholine oxide in the filter liquor this moment, by oxidation N-methylmorpholine is oxidized to the N-methylmorpholine oxide, thereby avoided the particularly shortcoming of oxidation technology under the situation that impurity such as metal and morpholine exist, improved the rate of recovery of N-methylmorpholine oxide greatly.
Description of drawings:
Accompanying drawing 1 is process chart of the present invention:
Accompanying drawing 2 is smart filtering system schematic flow sheet: among the figure
1. lead channel 2. feed liquor flowmeters 3. feed liquor valves 4. Pressure gauges 5. smart filter tower shells
6. micropore ceramic tube 7. zirconium oxide films 8. return valves 9. liquid valves 10. liquid outlet grooves 11. return flow meters 12. water pumps
The specific embodiment:
As Fig. 1, concrete technological process is pressed: 1, coarse filtration; 2, smart filter; 3, the resin anion (R.A.) exchange is handled; 4, cation resin exchange is handled; 5, oxidation processes; 6, solvent recovery storage tank.Wherein:
1, coarse filtration, it is 1m that the circulation waste liquid that is produced in producing is flow through length with the 10m/h flow velocity, internal diameter is the stainless steel Filter column of 10cm, each section of upper, middle and lower in the post is equipped with highly anthracite, float stone and gravel for capacity such as 25cm respectively as filter medium, and its particle diameter is respectively 10～20mm, 5～10mm, 2～4mm.Removed bigger suspended solid, collected the coarse filtration fluid then and be stored in the storage tank (1).
2, smart filter, through after the coarse filtration, bigger suspended impurity is removed, but still old less suspended particles, particularly particle diameter exist less than the suspended particles of 9 μ m in filter liquor, therefore must further filter again, as Fig. 2, be smart filtering system schematic flow sheet of the present invention, wherein:
The capital equipment of smart filtering system is smart filter tower, and it is made up of the zirconium oxide film 7 of smart filter tower shell 5, micropore ceramic tube 6 and earthenware outer wall, and smart filter tower shell 5 is that internal diameter is 12cm, and height is the stainless steel cylinder of 50cm.The micropore ceramic tube 6 that is adopted is to be 5.5cm by an internal diameter, and external diameter is 7cm, longly is 50cm, and its porosity is 37～40%, and average pore size is that the micropore ceramic tube of 2 μ m～5 μ m is formed.It is the uniform zirconia ceramics film of netted densification of 1 μ m that the suspended particles sintering process that the zirconium oxide film 7 on earthenware surface is the Zirconia particles that is respectively 2 μ m by average grain diameter by routine has formed average pore size.
The coarse filtration fluid is as follows by the concrete steps of smart filtering system:
Start the water pump 12 that the lower end of lead channel 1 is connected to, the coarse filtration fluid flows out from lead channel 1, through feed liquor flowmeter 2 and liquid flowing valve 3, at operating pressure is under the 150kPa condition, speed with 0.1m/s flows to smart filter tower, this moment liquid stream press both direction mobile, part coarse filtration fluid flow direction is the axial flow by the micropore ceramic tube 6 that is parallel to smart filter tower, and the return valve 8 that is equipped with by shell 5 lower-left ends is back in the lead channel 1 through return flow meter 11 and water pump 12 successively, and this moment, filter liquor was through smart filter; Another part coarse filtration fluid is to flow by the direction perpendicular to the micropore ceramic tube 6 of smart filter tower, see through the zirconium oxide film 7 that scribbles on the outer wall of micropore ceramic tube 6 earlier, enter again in the micropore ceramic tube 6 and filter, the liquid valve 9 that is connected to from the bottom of micropore ceramic tube 6 flows in the liquid outlet groove 10 at last, and the filter liquor that obtains is stored in the storage tank (2).After testing, the particle diameter of the filter liquor in the storage tank (2) has reached the effect of smart filter less than 1 μ m, but smart filtrate color this moment absorbance A under detection wavelength 330nm place is 0.9, is dark brown, also needs further to remove.
3, the resin anion (R.A.) exchange is handled,
It is 1m that filter liquor in the storage tank (2) is flow through length with 3 times of flow velocitys to the resin bed volume per hour, internal diameter is the lucite exchange column of 2.5cm, it is 1 liter that volume is housed in the post, and granularity is 30 purpose anion exchange resin (Bayer company products), and this resin is band OH
-The macropore strong basic anion-exchange resin of the polystyrene of the quaternary amines of type.Collect eluate every 4 times of resin bed volumes, when eluate is 110 times of resin bed volumes, this moment, the absorbance of eluate was 0.34, and the color of eluate has deepened Huang gradually, illustrates that resin can not decolour again, promptly reached the saturated adsorptive value of resin, then stop exchange, eluate is stored in storage tank (3), though removed the band colored foreign, but metal ion and morpholine also in eluate, also need be further processed.
After testing, each composition in the eluate of storage tank (3) is composed as follows:
Iron ion: 87ppm, copper ion: 44ppm (measuring) with atomic absorption spectrography (AAS);
N-methylmorpholine oxide: 10.432 * 10
4Ppm, N-methylmorpholine: 893ppm, morpholine: 474ppm (method with HPLC is measured).
4, cation resin exchange is handled,
It is 1m that filter liquor after the resin anion (R.A.) exchange is handled in the storage tank (3) is flow through length with 4 times the flow velocity of resin bed volume per hour, internal diameter is the lucite exchange column of 2.5cm, it is 1 liter that volume is housed in the post, granularity is 30 purpose cationic ion-exchange resins (Bayer company products), and this resin is band H
+The macroporous strong-acid cation-exchange resin of the polystyrene of the sulfonic acid group of type.When 10 times of bed volumes are collected eluate, measure the concentration of iron ion and copper ion and N-methylmorpholine oxide, N-methylmorpholine and morpholine.
The used resin of the present invention is to metal ion, morpholine, the exchange absorption affinity of N-methylmorpholine and N-methylmorpholine oxide is different, size of its exchange absorption affinity be according to metal ion＞＞order of morpholine＞N-methylmorpholine＞N-methylmorpholine oxide arranges, when beginning, four kinds of components all are attracted on the exchanger resin, when reaching the saturated extent of adsorption of resin, resin at first begins wash-out to the N-methylmorpholine oxide of absorption affinity minimum and comes out, only contain N-methylmorpholine oxide in the filter liquor this moment, along with the 50 times of bed volumes that constantly increase to the feed quantity of resin end, the N-methylmorpholine oxide that is attracted on the ion exchange column is almost replaced by N-methylmorpholine and morpholine, when feed quantity during greater than 50 times of bed volumes, the N-methylmorpholine that is adsorbed on the resin just begins to be cemented out gradually until all being displaced by morpholine, when constantly increasing to 140 bed volumes along with feed quantity, it is saturated that morpholine on the resin has reached absorption, promptly feeding the morpholine that adsorbs in the liquid can not be again by resin adsorption, this moment, morpholine began to appear in the filter liquor, simultaneously, because resin is very big to the saturated extent of adsorption of metal ion, so when morpholine washes out, metal ion still rests on the resin, the iron ion in the filter liquor and the concentration of copper ion all are lower than 0.1ppm, the concentration of morpholine is less than 15ppm, at this moment, although iron, the quantity not sufficient of copper metal ion and morpholine is with the recycling of the oxidation operation that influences the back, but resin has exchanged fully and has adsorbed morpholine, and reached its saturated extent of adsorption, then should stop exchange, at this moment, the amount of three kinds of key components is respectively in the filter liquor:
N-methylmorpholine oxide: 10.431 * 10
4Ppm, N-methylmorpholine: 890ppm, except that the N-methylmorpholine oxide, also there is N-methylmorpholine in morpholine: 13ppm (method with HPLC is measured) in storage tank (4) the storage filter liquor, must carry out next step processing again.
5, oxidation processes,
Come oxidation storage tank (4) to contain the filter liquor of N-methylmorpholine and N-methylmorpholine oxide with hydrogen peroxide, make N-methylmorpholine change into the N-methylmorpholine oxide.Filter liquor in 150 liters of storage tanks (4) is mixed stirring with 0.15 liter 30% aqueous hydrogen peroxide solution in 200 liters evaporation reaction device, reaction temperature is 60 ℃, and the reaction time is 2.5 hours.(measure) after measured, have 10.515 * 10 respectively after the oxidation in the solution with the method for HPLC
4The N-methylmorpholine oxide of ppm and the N-methylmorpholine of 52ppm, then the oxidation productive rate is about 94%.
With the solution after the oxidation is that the aqueous solution of N-methylmorpholine oxide is stored in the solvent recovery storage tank, just can continue circulation and be used for dissolving spinning technology.
Claims (5)
1, the technology of solvent recovery in the cellulose fiber by solvent method preparation process, it is characterized in that, described recovery technology is made up of coarse filtration, smart filter, resin anion (R.A.) exchange processing, cation resin exchange processing, oxidation processes five big operations, and according to recycling engineering of the comprehensive composition of said sequence, specific as follows:
(a) described coarse filtration is that the circulation waste liquid that will be produced in the spinning production process flows through the filtering container that has filter medium anthracite, float stone and gravel with 6～14 meters/hour flow velocitys, to remove the suspended solid of particle diameter greater than 9 μ m;
(b) described smart filter is that filter liquor with coarse filtration scribbles netted uniform zirconium oxide film by earthenware and the earthenware outer wall that tube wall has micropore, removing particle diameter is the treatment process of the suspended impurity of 1～9 μ m, its technological parameter: operating pressure is 30kPa～250kPa, and the feeding flow velocity is 0.05 meter per second～0.3 meter per second;
(c) described resin anion (R.A.) exchange processing is to be with the filter liquor feeding of look to be equipped with in the conventional exchange column of anion exchange resin essence filter back, after the anion exchange by both, remove the band colored foreign that its filter liquor includes, its technological parameter: (1) feeding speed is per hour to flow through 2～5 times resin bed volume; (2) when 2～6 times resin bed volume is collected eluate, survey the absorbance of corresponding filter liquor, when its absorbance was 0.25～0.4, the resin adsorption value reached capacity, stopped exchange;
(d) to handle be that filter liquor feeding after the resin anion (R.A.) exchange is handled is equipped with in the conventional exchange column that Yanggao County's Ziwen changes resin for described cation resin exchange, by cation exchange group on the resin and the band CATION in the filter liquor or there are all substances of CATION tendency group to carry out optionally ion-exchange, for reaching Selective Separation and until the purpose of final removal metal ion and morpholine impurity, its technological parameter: (1) feeding flow velocity is for per hour flowing through 3～6 times resin bed volume; (2) when 7～14 times resin bed volume is collected filter liquor, measure iron ion and copper ion and N-methylmorpholine oxide respectively, the concentration of N-methylmorpholine and morpholine; Containing morpholine in eluate is 15ppm, and when metal ion was 0.1ppm, it was saturated to regard resin as, stops exchange;
(e) described oxidation processes is the filter liquor that contains N-methylmorpholine and N-methylmorpholine oxide after coming the oxidative cationic resins exchange to handle with hydrogen peroxide, make N-methylmorpholine change into the N-methylmorpholine oxide, its technological parameter: (1) 20～40% aqueous hydrogen peroxide solution and filter liquor are 1: 800～1300 to mix stirring in the evaporation reaction device according to weight ratio; (2) reaction temperature is 40～80 ℃, 1～5 hour reaction time.
2, the technology of solvent recovery in the cellulose fiber by solvent method preparation process according to claim 1, it is characterized in that, coarse filtration adopts filter medium anthracite, float stone and gravel to pack in the filtering container with capacity such as each sections of upper, middle and lower respectively, and its particle diameter is respectively 10～20mm, 5～10mm, 2～4mm.
3, the technology of solvent recovery is characterized in that in the cellulose fiber by solvent method preparation process according to claim 1, and the porosity of the micropore ceramic tube that smart filter is adopted is 25～60%, average pore size is 2 μ m～5 μ m, and its caliber is 0.4～0.85 times of smart filter inside diameter of vessel; The zirconium oxide film of earthenware outer wall is that the Zirconia particles of 0.3 μ m～15 μ m is formed by particle diameter, and the average pore size that the suspended particles sintering process by routine forms is the netted uniform zirconia ceramics film of 0.2 μ m～11 μ m.
4, the technology of solvent recovery in the cellulose fiber by solvent method preparation process according to claim 1, it is characterized in that, the anion exchange resin that is adopted is the macropore strong basic anion-exchange resin of polystyrene of the quaternary amines of band-OH-type, specification is granularity 20～40 orders, and the resin equipped amount is 0.3～0.7 times of this exchange column volume.
5, the technology of solvent recovery is characterized in that in the cellulose fiber by solvent method preparation process according to claim 1, and the cationic ion-exchange resin that is adopted is band H
+The macroporous strong-acid cation-exchange resin of the polystyrene of the sulfonic acid group of type, specification are granularity 20～40 orders, and the resin equipped amount is 0.3～0.7 times of this exchange column volume; This resin is to metal ion, and materials such as morpholine have different exchange absorption affinities, the size of its exchange absorption affinity must by the metal ion＞＞order of morpholine＞N-methylmorpholine＞N-methylmorpholine oxide arranges.
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| CN101089262B (en) * | 2006-06-13 | 2011-01-05 | 上海里奥纤维企业发展有限公司 | Recovery and purification method for solvent preparing cellulose fibre by solvent method |
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| CN100355960C (en) * | 2005-12-26 | 2007-12-19 | 东华大学 | Solvent recovery method for cellulose fiber preparation with ion liquid as solvent |
| CN101280476B (en) * | 2008-05-23 | 2010-04-14 | 宜宾丝丽雅集团有限公司 | Recovery method for NMMO solvent in fibre production by solvent method |
| CN101988216B (en) * | 2009-08-04 | 2014-08-06 | 上海太平洋纺织机械成套设备有限公司 | Method for circularly preparing solvents in Lyocell fiber preparation process |
| CN102234852B (en) * | 2010-04-21 | 2013-04-10 | 聚隆纤维股份有限公司 | Solvent recovery method of Lyocell fibers |
| CN102167465A (en) * | 2011-03-17 | 2011-08-31 | 天津工业大学 | Recovery method of spinning waste liquor by means of concentrating |
| TW201240721A (en) * | 2011-04-01 | 2012-10-16 | Acelon Chem & Fiber Corp | Energy-efficient N-methylmorpholine-N-oxide solvent recycling method |
| CN104711706B (en) * | 2015-03-17 | 2016-10-05 | 中国纺织科学研究院 | The retracting device of Lyocell fiber spinning solution waste material and recovery method |
| CN106283276B (en) * | 2016-08-30 | 2019-08-20 | 中国纺织科学研究院有限公司 | Solvent method produces the recovery method of N-methyl morpholine oxide during cellulose |
| CN108250160A (en) * | 2017-12-18 | 2018-07-06 | 山东雅美科技有限公司 | Utilize the method for RO reverse osmosis membrane technology concentration and recovery NMMO solvents |
| CN110055626A (en) * | 2019-04-23 | 2019-07-26 | 福建宏远集团有限公司 | A kind of recovery method of spinning N-methylmorpholine-N oxide solution |
| CN113546617B (en) * | 2021-08-10 | 2023-04-21 | 四川轻化工大学 | Mesophase pitch-based mesoporous carbon catalyst for decomposing residual hydrogen peroxide in N-methylmorpholine oxide product and preparation method thereof |
-
2004
- 2004-09-07 CN CNB2004100543358A patent/CN1247841C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101089262B (en) * | 2006-06-13 | 2011-01-05 | 上海里奥纤维企业发展有限公司 | Recovery and purification method for solvent preparing cellulose fibre by solvent method |
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