CN101942712B - Recovery method of N-methylmorpholine oxide solvent in process of producing regenerated cellulose fibre by solvent method - Google Patents
Recovery method of N-methylmorpholine oxide solvent in process of producing regenerated cellulose fibre by solvent method Download PDFInfo
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- CN101942712B CN101942712B CN2009100884459A CN200910088445A CN101942712B CN 101942712 B CN101942712 B CN 101942712B CN 2009100884459 A CN2009100884459 A CN 2009100884459A CN 200910088445 A CN200910088445 A CN 200910088445A CN 101942712 B CN101942712 B CN 101942712B
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Abstract
The invention relates to a recovery method of an N-methylmorpholine oxide (NMMO) solvent in a process of producing regenerated cellulose fibre by a solvent method in a spinning technology. The technical scheme of the invention is designed as follows: a NMMO aqueous solution with the mass concentration of 50% is taken as a coagulating bath of the regenerated cellulose fibre; the circulation of the coagulating bath is optimally controlled so that the mass concentration of the coagulating bath of the NMMO aqueous solution in a coagulating bath-loading container is controlled to be 50%; and multiple impurities in recovery liquid, namely a coagulating bath solution, are removed through rough filtration, microporous membrane microfiltration, anion exchange resin treatment, cation exchange resin treatment and hydrogen peroxide oxidization, thereby achieving the recovery of the NMMO solvent.
Description
Technical field
The present invention relates to solvent method in the spinning technique and produce the recovery method of N-methylmorpholine oxide (NMMO) solvent in the regenerated celulose fibre process.
Technical background
N-methylmorpholine oxide (NMMO) is a kind of innoxious solvent; It is to be made through hydrogen peroxide oxidation by N-methylmorpholine, is that the technology of the indirect dissolving cellulos pulp of solvent feedstock production regenerated celulose fibre receives increasing attention in recent years with N-methylmorpholine oxide (mass concentration is 50%).Because the NMMO price is very high, external manufacturer quite payes attention to reclaiming NMMO, has proposed the technical scheme of multiple recovery NMMO, to search out producing the most practical technical method.To prepare the process of regenerated celulose fibre be a pure physical process to NMMO dissolving cellulos pulp in theory; But in practical operation a lot of chemical side reactions can take place; Cause fiber degradation, NMMO to decompose like meeting; Even uncontrollable thermal response etc., therefore in the coagulating bath that utilizes this spinning technique production regenerated celulose fibre, having a lot of impurity needs to handle.Such as: microorganism, suspended impurity (cellulose strand and undissolved pulp raw material or catabolite), NMMO, foreign pigment, N-methylmorpholine, morpholine and metal ion.
Generally be that the use mass concentration is 10～30% the NMMO aqueous solution in the coagulating bath of the NMMO method production regenerated celulose fibre in the existing spinning technique production; Recycle the NMMO solvent; The general operations such as coarse filtration, smart filter, anion exchange resin, cationic ion-exchange resin, hydrogen peroxide oxidation that all adopt are earlier removed the impurity in the coagulating bath; Concentrate the recovery that the mass concentration that makes the NMMO solvent reaches about 87% and then accomplishes the NMMO solvent through reduction vaporization again, but adopt reduction vaporization concentration technology technology very high temperature and vacuum requirements.Generally adopt single effect evaporator to carry out reduction vaporization and concentrate recovery NMMO, vacuum degree control is in 15～18Kpa scope, and heating and temperature control is 110～120 ℃ of scopes, and evaporating temperature is controlled at 74～76 ℃ of scopes, and water vapour is recycled through condenser.The disclosed NMMO method of evaporating of Chinese patent CN101088993A reclaims NMMO through two vapo(u)rization system evaporation and concentration, and one imitates heating and temperature control 100～105 ℃ of scopes, and evaporating temperature is controlled at 50～70 ℃ of scopes, and vacuum degree control is in 10～15Kpa scope; Two imitate heating and temperature control 100～105 ℃ of scopes, and evaporating temperature is controlled at 80～95 ℃ of scopes, and vacuum degree control makes the mass concentration of NMMO reach 80～87% scopes in 2～10Kpa scope.The recovery method of NMMO solvent during the disclosed a kind of solvent method fiber of Chinese patent CN101280476A is produced; Adopt triple effect evaporator to carry out reduction vaporization and reclaimed the NMMO solvent; One imitates heating and temperature control 82～86 ℃ of scopes, and evaporating temperature is controlled at 70～74 ℃ of scopes; Two imitate heating and temperature control 70～74 ℃ of scopes, and evaporating temperature is controlled at 58～62 ℃ of scopes; The triple effect heating and temperature control is 58～62 ℃ of scopes, and evaporating temperature is controlled at 46～50 ℃ of scopes.Although concentrating the mass concentration of the NMMO that can make recovery, reduction vaporization reaches about 87%; Contain some volatile matters such as amine and solvent etc. in the condensed water but can make during evaporation and concentration; Adopt reverse osmosis or cationic ion-exchange resin effectively to separate residual amine, amine oxide and other material, but the condensed water recycling make the NMMO solvent run off easily.The evaporation concentration device investment is big, and arts demand consumes a large amount of water, electricity, vapour etc., will handle the impurity in the condensed water in addition, and the technology of very complicated causes the production cost of NMMO solvent method regenerated celulose fibre to improve, and is difficult to realize industrial the popularization.
Summary of the invention
The objective of the invention is to overcome when the NMMO solvent method is produced regenerated celulose fibre in the existing spinning technique production utilizes the reduction vaporization concentration technique to reclaim the deficiency of NMMO solvent; A kind of suitability for industrialized production that is adapted to is provided, and the solvent method of more convenient operation is produced the method for the recycling of NMMO solvent in the regenerated celulose fibre process.
Technical scheme of the present invention is to be that 50% the NMMO aqueous solution is the coagulating bath of regenerated celulose fibre through design with mass concentration; The circulation of optimal control coagulating bath; Make the mass concentration of loading the NMMO aqueous coagulation bath in the coagulating bath container be controlled at 50%; Removing recovery liquid through coarse filtration, microporous barrier micro-filtration, anion exchange process, cationic ion-exchange resin processing, hydrogen peroxide oxidation is the plurality of impurities in the coagulating bath solution, thereby realizes the recovery of NMMO solvent.
The recovery method that solvent method of the present invention is produced N-methylmorpholine oxide (NMMO) solvent in the regenerated celulose fibre may further comprise the steps:
(1) in the spinning technique that solvent method prepares regenerated celulose fibre is produced, be that 50% N-methylmorpholine oxide water solution (being commercially available NMMO solvent) is the indirect dissolving cellulos pulp of solvent feedstock production regenerated celulose fibre (the NMMO aqueous solution and cellulose pulp raw material are that 85～90% o'clock cellulose pulps promptly dissolve in the mass concentration of 90～120 ℃ of following mixed dehydrations to the NMMO aqueous solution) with mass concentration; With mass concentration is that 50% the NMMO aqueous solution is the coagulating bath of regenerated celulose fibre;
(2) along with the carrying out of spinning technique; Add mass concentration in the coagulating bath of step (1) and be 10～25% the NMMO aqueous solution; Make simultaneously contain mass concentration be 50% NMMO aqueous coagulation bath discharge load coagulating bath container in receiving slit; Make under the effective circulation of NMMO aqueous coagulation bath; Make the mass concentration of loading the NMMO aqueous coagulation bath in the coagulating bath container be controlled at 50% (through controlling the flow velocity that in the coagulating bath of step (1) adding mass concentration is 10～25% the NMMO aqueous solution; And make that to contain mass concentration be the flow velocity that 50% NMMO aqueous coagulation bath is discharged the container that loads coagulating bath, can effectively control load the NMMO aqueous coagulation bath in the coagulating bath container mass concentration 50%), in receiving slit, obtain containing mass concentration and be the recovery liquid of 50% the NMMO aqueous solution;
Wherein: the flow velocity that adds mass concentration in the coagulating bath of step (1) and be 10～25% the NMMO aqueous solution is 0.54～340kg/h; Make that to contain mass concentration be that the flow velocity that 50% NMMO aqueous coagulation bath is discharged the container that loads coagulating bath is 1.11～570kg/h;
(3) with obtain in step (2) receiving slit contain mass concentration be the recovery liquid of 50% the NMMO aqueous solution through the stainless steel filtering net coarse filtration, remove the solid suspended impurity of particle diameter greater than 10 μ m;
Described stainless steel filtering net coarse filtration is that the mass concentration that contains that step (2) is obtained is that the recovery liquid of 50% the NMMO aqueous solution flows through the stainless steel filtering net that layer aperture, upper, middle and lower is respectively 25～38 μ m, 15～24 μ m, 10 μ m with the flow velocity of 5～20kg/h;
(4) will handle the recovery liquid that contains the NMMO aqueous solution that obtains through step (3) and remove the impurity of particle diameter less than 10 μ m through the microporous barrier micro-filtration;
Described microporous barrier specification is: aperture 0.1～0.6 μ m, membrane flux is 100～1000L/m
2H, filter pressure 0.01～0.3Mpa;
Described microporous barrier is a kind of in microporous membrane of polyethersulfone, microporous polyurethane film, cellulose mixture microporous barrier, ultra-high molecular mass polyethylene micropore film, microporous polypropylene membrane, polyvinylidene fluoride microporous film, microporous teflon membran, ceramic microporous membranes or the glass microporous barrier.
(5) the recovery liquid that contains NMMO that step (4) is obtained is crossed the anion exchange tower that is filled with anion exchange resin to remove the foreign pigment that reclaims in the liquid; And then the cation exchange tower that is filled with cationic ion-exchange resin excessively obtains containing the recovery liquid of N-methylmorpholine and N-methylmorpholine oxide to remove metal ion and the morpholine that reclaims in the liquid;
Described anion exchange resin is the epoxy type anion exchange resin of macroreticular weakly base band primary amine groups; The granularity of described anion exchange resin is 20～40 orders; The be equipped with amount of anion exchange resin in anion exchange tower is 30～80% of this exchange column volume, and the flow velocity that the recovery liquid that contains the N-methylmorpholine oxide water solution is crossed the anion exchange tower that is filled with anion exchange resin is 3～6BV/h; Described cationic ion-exchange resin is macropore faintly acid band carboxylic acid group's a acrylic acid type cation exchange resin; The granularity of described cationic ion-exchange resin is 20～40 orders; The be equipped with amount of cationic ion-exchange resin in cation exchange tower is 30～80% of this exchange column volume, and the flow velocity that the recovery liquid that contains the N-methylmorpholine oxide water solution is crossed the cation exchange tower that is filled with cationic ion-exchange resin is 3～6BV/h;
(6) the recovery liquid that contains N-methylmorpholine and N-methylmorpholine oxide that step (5) is obtained obtains mass concentration behind hydrogen peroxide oxidation be 50% N-methylmorpholine oxide water solution; The mass concentration that obtains is that 50% N-methylmorpholine oxide water solution can directly be used for step (1) dissolving cellulos pulp feedstock production regenerated celulose fibre indirectly.
Described hydrogen peroxide oxidation technology is: using mass concentration is the recovery liquid that contains N-methylmorpholine and N-methylmorpholine oxide that 20～60% aqueous hydrogen peroxide solution oxidation step (5) obtains; Wherein: containing the recovery liquid of N-methylmorpholine and N-methylmorpholine oxide and the weight ratio of aqueous hydrogen peroxide solution is 1: 700～1000; Oxidizing temperature is 50～90 ℃, and oxidization time is 1～5 hour.
The degree of polymerization of described cellulose pulp raw material is 300～1200, the mass content of alpha-cellulose >=93%.
Described cellulose pulp raw material is selected from least a in the group that the cotton pulp dregs of rice, bamboo pulp, wood pulps, reed straw pulp, maize straw pulp, cotton stalk pulp, straw pulp, wheat straw pulp, bagasse pulp etc. are formed.
The recovery method of N-methylmorpholine oxide (NMMO) solvent is energy-conservation, simple in the solvent method production regenerated celulose fibre of the present invention, technological process short, the production less investment.The mass concentration that contains of replenishing concentration, flow velocity and the discharge of rare NMMO aqueous solution in the into coagulating bath through optimal control is that the mass concentration that the flow velocity of 50% the NMMO aqueous solution is controlled the NMMO aqueous solution in the coagulating bath is 50%.Utilize mass concentration to do coagulating bath for the 50%NMMO aqueous solution, not only this solvent of recycling is convenient, can also solve traditional reduction vaporization enrichment facility and bring expensive problem.The filter screen that adopts and the aperture of microporous barrier are littler than the aperture of suspended impurity in the coagulating bath and microorganism; Can effectively remove solid suspended impurity and microorganism; Both do not introduced the chemicals of flocculant and so on; Simplify traditional coarse filtration, smart filter recovery technology again, also alleviated the postorder processing burden, prolonged the life-span of ion exchange resin; Through the choose reasonable anion and cation exchange resin, utilize the selection exchange adsorption capacity of ion exchange resin to impurity, reach the purpose of removing metal ion, morpholine, coloring matter, stoped the generation of N-nitrosomorpholine; The N-methylmorpholine and the N-methylmorpholine oxide that utilize hydrogen peroxide oxidation to reclaim in the liquid at last generate NMMO, to accomplish the recovery of NMMO solvent.Whole technology has been avoided the operation of decompression, high temperature, and the NMMO solvent recovering yield reaches more than 95%, is adapted to suitability for industrialized production, more convenient operation.
Description of drawings
Fig. 1. comprise the spinning technique schematic flow sheet of the recovery method of NMMO solvent in the solvent method production regenerated celulose fibre of the present invention.
The specific embodiment
Embodiment 1
See also Fig. 1.
(1) in the spinning technique of solvent method preparation regeneration reed fiber is produced, be that 50% the NMMO aqueous solution is that solvent dissolves reed pulp (polymer 302, the mass content 95.6% of alpha-cellulose) preparation regeneration reed fiber indirectly with commercially available mass concentration; With mass concentration is that 50% the NMMO aqueous solution is the coagulating bath of regeneration reed fiber;
(2) along with the carrying out of spinning technique; Adding mass concentration in the coagulating bath of step (1) with the flow velocity of 340kg/h is 25% the NMMO aqueous solution; Simultaneously with the flow velocity of 570kg/h make contain mass concentration be 50% the NMMO aqueous solution discharge load coagulating bath container in receiving slit; Make under the effective circulation of NMMO aqueous coagulation bath; Make the mass concentration of loading the NMMO aqueous coagulation bath in the coagulating bath container be controlled at 50%, in receiving slit, obtain containing mass concentration and be the recovery liquid of 50% the NMMO aqueous solution;
(3) be that the recovery liquid of 50% the NMMO aqueous solution is respectively the stainless steel filtering net of 38 μ m (400 order), 24 μ m (525 order), 10 μ m (1250 order) with the flow velocity of 10kg/h through upper, middle and lower layer specification with the mass concentration that contains that obtains in step (2) receiving slit, remove the solid suspended impurity of particle diameter greater than 10 μ m;
(4) will handle the recovery liquid that contains the NMMO aqueous solution obtain through super high molecular weight (2,500,000) polyethene microporous membrane (average pore size 0.3 μ m, membrane flux 1000L/m through step (3)
2H, filter pressure 0.3Mpa) micro-filtration is removed the impurity of particle diameter less than 10 μ m;
(5) the recovery liquid that contains the NMMO aqueous solution that step (4) is obtained is crossed epoxy type anion exchange resin (granularity 30 orders that are filled with macroreticular weakly base band primary amine groups; The anion exchange resin amount of being equipped with is 80% of this exchange column volume; The flow velocity that the recovery liquid that contains the NMMO aqueous solution is crossed the anion exchange tower that is filled with anion exchange resin is 6BV/h; Shanghai Resin Factory Co., Ltd.'s product) anion exchange tower; Removing the foreign pigment that reclaims in the liquid, and then cross the acrylic acid type cation exchange resin that is filled with macropore faintly acid band carboxylic acid group (granularity 20 orders, the cationic ion-exchange resin amount of being equipped with is 30% of this exchange column volume; The flow velocity that the recovery liquid that contains the NMMO aqueous solution is crossed the cation exchange tower that is filled with cationic ion-exchange resin is 3BV/h; Shanghai Resin Factory Co., Ltd.'s product) cation exchange tower to remove metal ion and the morpholine that reclaims in the liquid, obtains containing the recovery liquid of N-methylmorpholine and N-methylmorpholine oxide;
(6) it is that promptly to obtain mass concentration after 60% the aqueous hydrogen peroxide solution oxidation be 50% the NMMO aqueous solution that the recovery liquid that contains N-methylmorpholine and N-methylmorpholine oxide that step (5) is obtained uses mass concentration, and resulting mass concentration is that 50% the NMMO aqueous solution can directly be used for step (1) and dissolves reed pulp preparation regeneration reed fiber indirectly;
Described hydrogen peroxide oxidation technology is: containing the recovery liquid of N-methylmorpholine and N-methylmorpholine oxide and the weight ratio of aqueous hydrogen peroxide solution is 1: 1000, and oxidizing temperature is 90 ℃, and oxidization time is 5 hours.
Embodiment 2
(1) in the spinning technique that solvent method prepares regenerated bamboo fiber is produced, be that 50% the NMMO aqueous solution is that solvent dissolves bamboo pulp (degree of polymerization is 773, the mass content 93.2% of alpha-cellulose) preparation regenerated bamboo fiber indirectly with commercially available mass concentration; With mass concentration is that 50% the NMMO aqueous solution is the coagulating bath of regenerated bamboo fiber;
(2) along with the carrying out of spinning technique; Adding mass concentration in the coagulating bath of step (1) with the flow velocity of 0.54kg/h is 10% the NMMO aqueous solution; Simultaneously with the flow velocity of 1.11kg/h make contain mass concentration be 50% the NMMO aqueous solution discharge load coagulating bath container in receiving slit; Make under the effective circulation of NMMO aqueous coagulation bath; Make the mass concentration of loading the NMMO aqueous coagulation bath in the coagulating bath container be controlled at 50%, in receiving slit, obtain containing mass concentration and be the recovery liquid of 50% the NMMO aqueous solution;
(3) with obtain in step (2) receiving slit contain mass concentration be the recovery liquid of 50% the NMMO aqueous solution with the flow velocity of 20kg/h through three layers of stainless steel filtering net coarse filtration; Its upper, middle and lower layer specification is respectively the stainless steel filtering net of 25 μ m (500 order), 15 μ m (1000 order), 10 μ m (1250 order), removes the solid suspended impurity of particle diameter greater than 10 μ m;
(4) will handle the recovery liquid that contains the NMMO aqueous solution obtain through microporous polypropylene membrane (average pore size 0.1 μ m, membrane flux 500L/m through step (3)
2H, filter pressure 0.1Mpa) micro-filtration is removed the impurity of particle diameter less than 10 μ m;
(5) the recovery liquid that contains the NMMO aqueous solution that step (4) is obtained is crossed epoxy type anion exchange resin (granularity 20 orders that are filled with macroreticular weakly base band primary amine groups; The anion exchange resin amount of being equipped with is 50% of this exchange column volume; The flow velocity that the recovery liquid that contains the NMMO aqueous solution is crossed the anion exchange tower that is filled with anion exchange resin is 4BV/h; Shanghai Resin Factory Co., Ltd.'s product) anion exchange tower is to remove the foreign pigment that reclaims in the liquid; And then mistake is filled with macropore faintly acid band carboxylic acid group's acrylic acid type cation exchange resin (granularity 30 orders; The cationic ion-exchange resin amount of being equipped with is 80% of this exchange column volume; The flow velocity that the recovery liquid that contains the NMMO aqueous solution is crossed the cation exchange tower that is filled with cationic ion-exchange resin is 6BV/h; Shanghai Resin Factory Co., Ltd.'s product) cation exchange tower to remove metal ion and the morpholine that reclaims in the liquid, obtains containing the recovery liquid of N-methylmorpholine and N-methylmorpholine oxide;
(6) it is that promptly to obtain mass concentration after 40% the aqueous hydrogen peroxide solution oxidation be 50% the NMMO aqueous solution that the recovery liquid that contains N-methylmorpholine and N-methylmorpholine oxide that step (5) is obtained uses mass concentration, and resulting mass concentration is that 50% the NMMO aqueous solution can directly be used for step (1) and dissolves bamboo pulp indirectly and prepare regenerated bamboo fiber;
Described hydrogen peroxide oxidation technology is: containing the recovery liquid of N-methylmorpholine and N-methylmorpholine oxide and the weight ratio of aqueous hydrogen peroxide solution is 1: 800, and oxidizing temperature is 50 ℃, and oxidization time is 1 hour.
Embodiment 3
(1) in the spinning technique that solvent method prepares the regeneration cotton fiber is produced, be that 50% the NMMO aqueous solution is that solvent dissolves the cotton pulp dregs of rice (degree of polymerization is 1193, the mass content 98.1% of alpha-cellulose) preparation regeneration cotton fiber indirectly with commercially available mass concentration; With mass concentration is that 50% the NMMO aqueous solution is the coagulating bath of regeneration cotton fiber;
(2) along with the carrying out of spinning technique; Adding mass concentration in the coagulating bath of step (1) with the flow velocity of 121kg/h is 15% the NMMO aqueous solution; Simultaneously with the flow velocity of 236kg/h make contain mass concentration be 50% the NMMO aqueous solution discharge load coagulating bath container in receiving slit; Make under the effective circulation of NMMO aqueous coagulation bath; Make the mass concentration of loading the NMMO aqueous coagulation bath in the coagulating bath container be controlled at 50%, in receiving slit, obtain containing mass concentration and be the recovery liquid of 50% the NMMO aqueous solution;
(3) with obtain in step (2) receiving slit contain mass concentration be the recovery liquid of 50% the NMMO aqueous solution with the flow velocity of 5 kg/h through three layers of stainless steel filtering net coarse filtration; Its upper, middle and lower layer specification is respectively 33 μ m (425 order), 23 μ m (625 order), the filtration of 10 μ m (1250 order) stainless steel filtering net, removes the solid suspended impurity of particle diameter greater than 10 μ m;
(4) will handle the recovery liquid that contains the NMMO aqueous solution obtain through ceramic microporous membranes (average pore size 0.6 μ m, membrane flux 100L/m through step (3)
2H, filter pressure 0.01Mpa) micro-filtration is removed the impurity of particle diameter less than 10 μ m;
(5) the recovery liquid that contains the NMMO aqueous solution that step (4) is obtained is crossed epoxy type anion exchange resin (granularity 40 orders that are filled with macroreticular weakly base band primary amine groups; The anion exchange resin amount of being equipped with is 30% of this exchange column volume; The flow velocity that the recovery liquid that contains the NMMO aqueous solution is crossed the anion exchange tower that is filled with anion exchange resin is 3BV/h; Shanghai Resin Factory Co., Ltd.'s product) anion exchange tower is to remove the foreign pigment that reclaims in the liquid; And then mistake is filled with macropore faintly acid band carboxylic acid group's acrylic acid type cation exchange resin (granularity 40 orders; The cationic ion-exchange resin amount of being equipped with is 60% of this exchange column volume; The flow velocity that the recovery liquid that contains the NMMO aqueous solution is crossed the cation exchange tower that is filled with cationic ion-exchange resin is 4BV/h; Shanghai Resin Factory Co., Ltd.'s product) cation exchange tower to remove metal ion and the morpholine that reclaims in the liquid, obtains containing the recovery liquid of N-methylmorpholine and N-methylmorpholine oxide;
(6) it is that promptly to obtain mass concentration after 20% the aqueous hydrogen peroxide solution oxidation be 50% the NMMO aqueous solution that the recovery liquid that contains N-methylmorpholine and N-methylmorpholine oxide that step (5) is obtained uses mass concentration, and resulting mass concentration is that 50% the NMMO aqueous solution can directly be used for step (1) and dissolves the cotton pulp dregs of rice indirectly and prepare the regeneration cotton fiber;
Described hydrogen peroxide oxidation technology is: containing the recovery liquid of N-methylmorpholine and N-methylmorpholine oxide and the weight ratio of aqueous hydrogen peroxide solution is 1: 700, and oxidizing temperature is 70C, and oxidization time is 3 hours.
Claims (10)
1. a solvent method is produced the recovery method of N-methylmorpholine oxide solvent in the regenerated celulose fibre, it is characterized in that this method may further comprise the steps:
(1) in the spinning technique that solvent method prepares regenerated celulose fibre is produced, be that 50% N-methylmorpholine oxide water solution is the indirect dissolving cellulos pulp of a solvent feedstock production regenerated celulose fibre with mass concentration; With mass concentration is that 50% N-methylmorpholine oxide water solution is the coagulating bath of regenerated celulose fibre;
(2) along with the carrying out of spinning technique; Add mass concentration in the coagulating bath of step (1) and be 10～25% N-methylmorpholine oxide water solution; Make simultaneously contain mass concentration be 50% N-methylmorpholine oxide water solution coagulating bath discharge load coagulating bath container in receiving slit; Make under the effective circulation of N-methylmorpholine oxide water solution coagulating bath; Make the mass concentration of loading the N-methylmorpholine oxide water solution coagulating bath in the coagulating bath container be controlled at 50%, in receiving slit, obtain containing mass concentration and be the recovery liquid of 50% N-methylmorpholine oxide;
Wherein: the flow velocity that adds mass concentration in the coagulating bath of step (1) and be 10～25% N-methylmorpholine oxide water solution is 0.54～340kg/h; Make that to contain mass concentration be that the flow velocity that the container that loads coagulating bath is discharged in 50% N-methylmorpholine oxide water solution coagulating bath is 1.11～570kg/h;
(3) with obtain in step (2) receiving slit contain mass concentration be the recovery liquid of 50% N-methylmorpholine oxide through the stainless steel filtering net coarse filtration, remove the solid suspended impurity of particle diameter greater than 10 μ m;
(4) will handle the recovery liquid that contains the N-methylmorpholine oxide that obtains through step (3) and remove the impurity of particle diameter less than 10 μ m through the microporous barrier micro-filtration;
(5) the recovery liquid that contains the N-methylmorpholine oxide that step (4) is obtained is crossed the anion exchange tower that is filled with anion exchange resin to remove the foreign pigment that reclaims in the liquid; And then the cation exchange tower that is filled with cationic ion-exchange resin excessively obtains containing the recovery liquid of N-methylmorpholine and N-methylmorpholine oxide to remove metal ion and the morpholine that reclaims in the liquid;
(6) the recovery liquid that contains N-methylmorpholine and N-methylmorpholine oxide that step (5) is obtained obtains mass concentration behind hydrogen peroxide oxidation be 50% N-methylmorpholine oxide water solution.
2. recovery method according to claim 1 is characterized in that: the mass concentration that step (6) obtains is that 50% N-methylmorpholine oxide water solution directly is used for step (1) dissolving cellulos pulp feedstock production regenerated celulose fibre indirectly.
3. recovery method according to claim 1 is characterized in that: described stainless steel filtering net coarse filtration is that the mass concentration that contains that step (2) is obtained is that the recovery liquid of 50% N-methylmorpholine oxide flows through the stainless steel filtering net that layer aperture, upper, middle and lower is respectively 25～38 μ m, 15～24 μ m, 10 μ m with the flow velocity of 5～20kg/h.
4. recovery method according to claim 1 is characterized in that: described microporous barrier specification is: aperture 0.1～0.6 μ m, membrane flux is 100～1000L/m
2H, filter pressure 0.01～0.3Mpa;
Described microporous barrier is a kind of in microporous membrane of polyethersulfone, microporous polyurethane film, cellulose mixture microporous barrier, polyethene microporous membrane, microporous polypropylene membrane, polyvinylidene fluoride microporous film, microporous teflon membran, ceramic microporous membranes or the glass microporous barrier.
5. recovery method according to claim 1; It is characterized in that: the be equipped with amount of described anion exchange resin in anion exchange tower is 30～80% of this exchange column volume, and the flow velocity that the recovery liquid that contains the N-methylmorpholine oxide is crossed the anion exchange tower that is filled with anion exchange resin is 3～6BV/h; The be equipped with amount of described cationic ion-exchange resin in cation exchange tower is 30～80% of this exchange column volume, and the flow velocity that the recovery liquid that contains the N-methylmorpholine oxide is crossed the cation exchange tower that is filled with cationic ion-exchange resin is 3～6BV/h.
6. according to claim 1 or 5 described recovery methods, it is characterized in that: described anion exchange resin is the epoxy type anion exchange resin of macroreticular weakly base band primary amine groups, and the granularity of described anion exchange resin is 20～40 orders; Described cationic ion-exchange resin is macropore faintly acid band carboxylic acid group's a acrylic acid type cation exchange resin, and the granularity of described cationic ion-exchange resin is 20～40 orders.
7. recovery method according to claim 1; It is characterized in that: described hydrogen peroxide oxidation technology is: using mass concentration is the recovery liquid that contains N-methylmorpholine and N-methylmorpholine oxide that 20～60% aqueous hydrogen peroxide solution oxidation step (5) obtains; Wherein: containing the recovery liquid of N-methylmorpholine and N-methylmorpholine oxide and the weight ratio of aqueous hydrogen peroxide solution is 1: 700～1000; Oxidizing temperature is 50～90 ℃, and oxidization time is 1～5 hour.
8. recovery method according to claim 1 and 2 is characterized in that: the degree of polymerization of described cellulose pulp raw material is 300～1200, the mass content of alpha-cellulose >=93%.
9. recovery method according to claim 1 and 2 is characterized in that: described cellulose pulp raw material is selected from least a in the group that the cotton pulp dregs of rice, bamboo pulp, wood pulps, reed straw pulp, maize straw pulp, cotton stalk pulp, straw pulp, wheat straw pulp, bagasse pulp are formed.
10. recovery method according to claim 8 is characterized in that: described cellulose pulp raw material is selected from least a in the group that the cotton pulp dregs of rice, bamboo pulp, wood pulps, reed straw pulp, maize straw pulp, cotton stalk pulp, straw pulp, wheat straw pulp, bagasse pulp are formed.
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| CN2009100884459A CN101942712B (en) | 2009-07-07 | 2009-07-07 | Recovery method of N-methylmorpholine oxide solvent in process of producing regenerated cellulose fibre by solvent method |
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| AT521561A5 (en) * | 2016-07-22 | 2022-09-15 | China Textile Academy | Process for the production of cellulose fibers |
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| CN108452548B (en) * | 2017-02-22 | 2020-08-04 | 中国石化仪征化纤有限责任公司 | Device and method for recovering organic solvent in flammable and explosive high-viscosity polymer waste |
| CN110393973B (en) * | 2018-04-24 | 2022-04-05 | 恒天纤维集团有限公司 | Method for controlling operation stability of solvent recovery circulation system |
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| CN114539186A (en) * | 2021-07-02 | 2022-05-27 | 华茂伟业绿色科技股份有限公司 | NMMO purification method and system and obtained NMMO hydrate crystal |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT521561A5 (en) * | 2016-07-22 | 2022-09-15 | China Textile Academy | Process for the production of cellulose fibers |
| AT521561B1 (en) * | 2016-07-22 | 2023-02-15 | China Textile Academy | Process for the production of cellulose fibers |
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