CN1641094A - Ion exchange fiber and its fabric preparing method - Google Patents
Ion exchange fiber and its fabric preparing method Download PDFInfo
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Abstract
The invention includes a kind of ion-exchange fibre and its fabric preparation method, in particular the produce method in closed reactor. It adopt acrylic fibre or other fabric beforehand interaction with 1--60% consistency hydrazine hydrate under 100-150 degree.C at press stronger than 0.0MP and small or be equal to 0.5MP a in closed reactor then produce through dissolving in water in the alkaline condition or the acidity condition. The products produced by ion exchange fibre and its fabric preparation method in this invention, have super and strong adsorb ability for the harmful air and reborn abilities, and the preparation method of this invention system can obviously shorten the respond time and decrease original material depletion, raise the production efficiency, lower the production cost.
Description
One. technical field: the present invention relates to a kind of ion-exchange fibre and process for making such fabric thereof, particularly relate to a kind of ion-exchange fibre and fabric thereof the preparation method in closed reactor.
Two. background technology: ion-exchange fibre is novel absorption of a class and separation function fibrous material, and the application that its industrial preparation reaches in different field is one of swift and violent new and high technology of current development.Compare with the graininess ion-exchanger, ion exchange fiber material has following characteristics: (1) counter ion mass transfer is big apart from weak point, effective ratio area, thereby in the process with liquid film mass transfer and two kinds of major decision reaction speeds of skeleton carrier inner transmission matter, ion exchange fiber material all has tangible kinetics advantage than graininess ion exchange material.(2) ion exchange fiber material can use with various fabrics forms such as yarn, line, cloth, felts, and can carry out effective adsorption filtration to acid, the various polar gas micromolecule of alkali under certain condition.Thereby start the beginning of this chemisorbed separation means practical application under gas phase condition of ion-exchange.
In the world ion-exchange fibre being studied and used maximum countries at present is states such as Japan, the former Soviet Union.From late nineteen seventies, they have developed multiple novel ion-exchange and chelate fibre material, and for example: Muscovite FIBAN, VION series and Japanese IONEX, TIN series ion-exchange fibre have formed tandem products such as comprising anion, CATION, both sexes, chelating.Its Application Areas and production scale are also in enlarging rapidly.Domestic research and the application work that begins ion exchange fiber material from the seventies, wherein: Zhongshan University, Henan chemistry institute, Henan Province's fine chemistry industry key lab etc. successively develop the different kinds of ions exchanging fiber material, and have carried out many useful explorations in the different field application facet.But on the whole; China in this respect can be also rare for the ion-exchange fibre product of preparation of industrialization and practical application, and its work also is in the literature accumulation stage of laboratory research and application basically.
This problem undertaker once developed the anion exchanging fiber material with independent intellectual property rights.On this basis: we propose the imagination of exploitation cation exchange fibre by investigation and analysis and market applicating expedition to domestic and international lot of documents.At present: the cation exchange fibre of succeeding in developing both at home and abroad has multiple preparation route, wherein: the former Soviet Union, carries out the reaction that is hydrolyzed again of sulfonating reaction or polypropylene fiber again and prepares strong acid, weak acid ion-exchange fibre (for example: Byelorussia Fiban-K-1 and Fiban-K-4 ion-exchange fibre) respectively after irradiation grafting is introduced styrene by polypropylene fiber after irradiation grafting is introduced acrylonitrile.The common feature for preparing functional fibre in this way is the irradiation technique complexity, and gained material exchange capacity is low.In addition, it is more to generate spent acid in the production process, and it also is that they are difficult in the actual main cause of applying of gas absorption field of purification that the highly acid fiber is difficult for regeneration.Since the eighties, utilized the research and the actual fabrication report of acrylic fiber exploitation organic functions fiber to increase gradually both at home and abroad.For example: Russia, Japan and China are raw material with the acrylic fiber successively all, and the method that adopts the both-end based compound to react in the NaOH aqueous solution makes has appropriate cancellated cation exchange fibre
[1], but since in the acrylic fiber CN hydrolysis degree wayward, so the machinery of gained ion exchange fiber material and fiberizing performance often can not reach the requirement of actual use.Chinese invention patent CN 1054168C, the patent No. is 97112391.8, name is called has reported in " multi-dentate ion exchange chelating fibre and synthetic method thereof " that acrylic fiber carries out precrosslink with hydrazine hydrate solution earlier, and then hydrolysis prepares carboxy-containing acid group's high water-absorption fiber or ion-exchange fibre in NaOH solution, its physical and chemical performance of functional fibre material that adopts this method to obtain is greatly improved, but because the above-mentioned technological reaction time is longer, hydrazine hydrate solution concentration height, the raw materials consumption amount is big, the cost height, so that their preparation of industrialization is subjected to certain limitation.
Three. summary of the invention: the objective of the invention is: it is longer to overcome the present preparation ion-exchange fibre reaction time, and raw materials consumption is big, and the deficiency that cost is high provides a kind of ion-exchange fibre and fabric thereof the preparation method in closed reactor.
Technical scheme of the present invention is:
A kind of preparation method of ion-exchange fibre, adopt acrylic fiber and certain density hydrazine hydrate solution to carry out the precrosslink reaction at a certain temperature earlier, hydrolysis and preparing under alkali condition or under the acid condition again, precrosslink reaction, basic hydrolysis or acid hydrolytic reaction are to carry out in smaller or equal to the closed reactor of 0.5MPa greater than 0.0Mpa at pressure.
The concentration of hydrazine hydrate solution is 1～60% in the precrosslink reaction, the precrosslink reaction is to react 1～10 hour under 100～150 ℃ of conditions, the concentration of aqueous slkali is 1～40% in the basic hydrolysis, basic hydrolysis is to react 1～10 hour under 100～150 ℃ of conditions, the concentration of acid solution is 5～80% in the acid hydrolytic reaction, and acid hydrolytic reaction is to react 1～5 hour under 100～150 ℃ of conditions.
Precrosslink reaction is to carry out in pressure is the closed reactor of 0.1～0.3MPa, the concentration of hydrazine hydrate solution is 5～40% in the precrosslink reaction, the precrosslink reaction is to react 1～5 hour under 100～130 ℃ of conditions, the concentration of aqueous slkali is 1～20% in the basic hydrolysis, basic hydrolysis is to react 1～8 hour under 100～130 ℃ of conditions, the concentration of acid solution is 20～60% in the acid hydrolytic reaction, and acid hydrolytic reaction is to react 1～5 hour under 100～130 ℃ of conditions.
Precrosslink reaction is to carry out in pressure is the closed reactor of 0.1～0.25MPa, the concentration of hydrazine hydrate solution is 8～20% in the precrosslink reaction, the precrosslink reaction is to react 2～5 hours under 110～120 ℃ of conditions, the concentration of aqueous slkali is 3～10% in the basic hydrolysis, basic hydrolysis is to react 2～5 hours under 110～130 ℃ of conditions, the concentration of acid solution is 30～50% in the acid hydrolytic reaction, and acid hydrolytic reaction is to react 2～5 hours under 110～130 ℃ of conditions.
Aqueous slkali in the basic hydrolysis is a sodium hydroxide solution, or is potassium hydroxide solution, or is lithium hydroxide solution, and the acid solution in the acid hydrolytic reaction is a hydrochloric acid solution, or is sulfuric acid solution, or is salpeter solution, or is phosphoric acid solution.
A kind of preparation method of fabrics treated by ion exchanging, adopt acrylic fiber fabric and certain density hydrazine hydrate solution to carry out the precrosslink reaction at a certain temperature earlier, hydrolysis and preparing under alkali condition or under the acid condition again, precrosslink reaction, basic hydrolysis or acid hydrolytic reaction are to carry out in smaller or equal to the closed reactor of 0.5MPa greater than 0.0Mpa at pressure.
The concentration of hydrazine hydrate solution is 1～60% in the precrosslink reaction, the precrosslink reaction is to react 1～10 hour under 100～150 ℃ of conditions, the concentration of aqueous slkali is 1～40% in the basic hydrolysis, basic hydrolysis is to react 1～10 hour under 100～150 ℃ of conditions, the concentration of acid solution is 5～80% in the acid hydrolytic reaction, and acid hydrolytic reaction is to react 1～5 hour under 100～150 ℃ of conditions.
Precrosslink reaction is to carry out in pressure is the closed reactor of 0.1～0.3MPa, the concentration of hydrazine hydrate solution is 5～40% in the precrosslink reaction, the precrosslink reaction is to react 1～5 hour under 100～130 ℃ of conditions, the concentration of aqueous slkali is 1～20% in the basic hydrolysis, basic hydrolysis is to react 1～8 hour under 100～130 ℃ of conditions, the concentration of acid solution is 20～60% in the acid hydrolytic reaction, and acid hydrolytic reaction is to react 1～5 hour under 100～130 ℃ of conditions.
Precrosslink reaction is to carry out in pressure is the closed reactor of 0.1～0.25MPa, the concentration of hydrazine hydrate solution is 8～20% in the precrosslink reaction, the precrosslink reaction is to react 2～5 hours under 110～120 ℃ of conditions, the concentration of aqueous slkali is 3～10% in the basic hydrolysis, basic hydrolysis is to react 2～5 hours under 110～130 ℃ of conditions, the concentration of acid solution is 30～50% in the acid hydrolytic reaction, and acid hydrolytic reaction is to react 2～5 hours under 110～130 ℃ of conditions.
Aqueous slkali in the basic hydrolysis is a sodium hydroxide solution, or is potassium hydroxide solution, or is lithium hydroxide solution, and the acid solution in the acid hydrolytic reaction is a hydrochloric acid solution, or is sulfuric acid solution, or is salpeter solution, or is phosphoric acid solution.
Positive beneficial effect of the present invention is:
1. ion-exchange fibre of the present invention and process for making such fabric thereof can obviously shorten the reaction time, reduce raw materials consumption, enhance productivity, and reduce production costs.The present invention adopts acrylic fiber and fabric thereof to carry out the precrosslink reaction at a certain temperature earlier with certain density hydrazine hydrate solution in closed reaction vessel, the new synthesis process of prepared in reaction ion-exchange fibre and fabric thereof again is hydrolyzed in alkalescence or acid solution, owing to be reflected in the enclosed system and finish, therefore this method compared with prior art, not only can make the reaction time shorten significantly by the rising of reaction temperature, but also avoided the volatilizing loss of raw material such as hydrazine hydrate in original technology effectively, originally in uncovered system, 1 ton of ion-exchange fibre of average every production, consumption of raw material hydrazine hydrate (80%) is 800Kg, be reflected in the enclosed system now and finish, 1 ton of ion-exchange fibre of average every production, consumption of raw material hydrazine hydrate (80%) only are 153Kg.In the general condition scope, it is original 1/5～1/3 that the raw material hydrazine hydrate only consumes, and just can reach same preparation effect, facts have proved that the present invention can save material in a large number, obviously improved production efficiency, greatly reduce production cost, have remarkable economical and social benefit, be worthy to be popularized.
2. the ion-exchange fibre or the fabric product that use ion-exchange fibre of the present invention and process for making such fabric thereof to produce have the ability of superpower absorption pernicious gas.As a kind of reactive polymer material, ion-exchange fibre of the present invention soaks transition through NaOH or hydrochloric acid solution, can obtain the ion-exchange fibre or the fabric product of sodium type or two kinds of specifications of Hydrogen, and can be respectively to sour gas (SO
2, HCl, Cl
2, HF), alkaline gas (NH
3And primary, the second month in a season, uncle's organic amine etc.) carry out effectively, adsorption filtration fast.The sodium type product of particularly above-mentioned fiber or fabric has very strong suction moisture-retaining capacity, thus effectively realized normal temperature, often under the wet condition to the high-efficiency dynamic adsorption cleaning of above-mentioned pernicious gas.
Sodium type ion-exchange fibre and fabric thereof are a kind of chemisorbed processes to the absorption of deleterious acidic gas, are based on the salt and the strong acid reaction of weak acid, and the acidity of sour gas only just can be adsorbed greater than carboxylic acid, and the strong more adsorption effect of acidity is good more.We have investigated the dynamic adsorption of sodium type ion-exchange fibre to pernicious gases such as sulfur dioxide, hydrogen chloride, hydrogen fluoride in the air, the results are shown in following table:
Sodium type ion-exchange fibre is to the dynamic adsorption of pernicious gas
| Sorbing material | Material weight (g) | The pernicious gas kind | Gas concentration (mg/m 3) | Time of break-through (min) |
| The carboxylic acid type fiber | ????1.0 | ????SO 2 | ????2000 | ????100 |
| ????HCL | ????1000 | ????107 | ||
| ????HF | ????150 | ????104 |
For further checking the feasibility of ion-exchange fibre and fabric practical application on respiratory personal protective equipment filtrate thereof, we entrust country (Beijing) articles for labour protection quality supervision and test center to carry out ion-exchange fibre to SO by national relevant technologies standard (GB/T2892-1995 " filtermask canister method for testing performance " and GB2890-1995 " filtermask general technical specifications ")
2And NH
3The test that effectively penetrates adsorption capacity and respiratory resistance of two kinds of representative acid, alkali gas, and obtained good test result (seeing the following form).As can be seen: in the fiber dry weight only is under the situation of carbon leaching material 1/4, and ion exchange fiber material can reach the national standard that traditional breathing breathing mask purifies these gas absorption to the filtration result of pernicious gas sulfur dioxide and ammonia.In addition, height that sodium type, Hydrogen ion-exchange fibre itself are had is inhaled moisture-retaining capacity, and after the coordination Adsorption of Cu, Ag metal ion effectively the excellent function of filtering aldehydes organic molecule and various germs more make it in common, become possibility as office work environment regenerating air purifying filtrate under the low-humidity environment condition.
H type, Na type ion-exchange fibre are as the The performance test results of anti-poison respirator filtrate
Air flow resistance when the dense stream of heavy gas penetrates
Material
Amount, g degree, mg/m
3Amount, between L/min, min power, Pa
Na type 19.5 2000 (SO
2) 30 37.8 54.9
H type 23.8 1000 (NH
3) 30 25.1 33.3
3. when fabrics treated by ion exchanging is as the gas purification filtrate, has low pressure drop characteristic preferably.Ion-exchange fibre in actual applications, suitable form of fabric is one of key factor that can it successful Application, and experimental result shows: 1) ion-exchange fibre of the present invention mixes with polypropylene fiber about 25%, through combing, lapping, technologies such as thermoforming can be processed into the adhesive type non-weaving cloth.2) acrylic fibers knitting wool is crosslinked through hydrazine, and basic hydrolysis can further be processed into the ion-exchange fibre knitted fabric after making ion-exchange fibre knitting wool.3) acrylic yarn is woven into that to carry out hydrazine behind the acrylic fibers gauze more crosslinked, and basic hydrolysis can make the ion-exchange fibre gauze.In above-mentioned three kinds of form of fabric, therefore two kinds of form of fabric of ion-exchange fibre knitted fabric and gauze as the gas purification filtrate time, have better low pressure drop characteristic than the ion exchange fiber non-woven that huddles long-pending form because fabric is effective arrangement.
4. detect through national articles for labour protection quality supervision and test center: the articles for labour protection that ion-exchange fibre of the present invention is made are at absorption SO
2, NH
3The every index in aspect all reaches or is better than national standard.Present domestic labour protection is with the malicious box of filter, and each is with 4#, about 90 grams of 7# active carbon, and 4#, 7# active carbon producer price are about 1.5 ten thousand yuan/T, and being folded to each, to filter malicious box be 1.35 yuan/.And ion-exchange fibre of the present invention reaches above-mentioned filter toxic effect fruit, and consumption only is 1/3 to 1/5 of 4#, a 7# active carbon, and can regenerate repeatedly and do not influence its serviceability 10 times.So even fiber consumption is 1/3 of an active carbon, and uses by regeneration and to calculate for 5 times, the single use cost is also filtered 40% of malicious box less than granular activated carbon, is folded to each and filters its cost of malicious box and be no more than 0.54 yuan/, therefore has good economy and society benefit.
5. ion-exchange fibre or its fabric have superpower power of regeneration.Ion-exchange fibre and fabric thereof are after recycling for 20 times, its exchange capacity with not do not use before compare slightly and rise, result after soda acid soaks is similar to ion-exchange fibre or its fabric, this also should be summed up as a small amount of unreacted itrile group in the ion-exchange fibre carrier (thereby-in repeatedly acid-base solution soaks the cause that hydrolysis forms new carboxyl takes place CN).The IR collection of illustrative plates of ion-exchange fibre sample before and after contrast is used removes 2242cm
-1Do not have other significant change outside place's absworption peak dies down, further specify ion-exchange fibre and have the chemical stability that can be repeatedly used, referring to Fig. 1 and Fig. 2.
Four. description of drawings:
Fig. 1 is the IR figure of ion-exchange fibre;
Fig. 2 is the IR spectrogram of 20 use regeneration back ion-exchange fibres.
Five. the specific embodiment:
Embodiment 1: in reactor, add 1% hydrazine hydrate 80kg, acrylic fiber 3kg, and the closed reactor agitating heating, in 130 ℃, 0.3MPa reaction 2 hours, cooling discharge, washing and drying got cross filament.
Add 1% sodium hydroxide solution 125kg, above-mentioned cross filament in reactor, in the closed reactor agitating heating, in 150 ℃, 0.5MPa reaction 1 hour, cooling discharge, washing and drying got sodium type ion-exchange fibre.
Add 5% hydrochloric acid solution 50kg, above-mentioned sodium type ion-exchange fibre in reactor, made the transition 6 hours, washing and drying gets the Hydrogen ion-exchange fibre.
Embodiment 2: in reactor, add 5% hydrazine hydrate 80kg, acrylic fiber 5kg, and the closed reactor agitating heating, in 100 ℃, 0.02MPa reaction 5 hours, cooling discharge, washing and drying got cross filament.
In reactor, add 3% sodium hydroxide solution 80kg, above-mentioned cross filament, the closed reactor agitating heating, in 100 ℃, 0.02MPa reaction 4 hours, cooling discharge, washing and drying got sodium type ion-exchange fibre.
Add 5% hydrochloric acid solution 50kg, above-mentioned sodium type ion-exchange fibre in reactor, made the transition 10 hours, washing and drying gets the Hydrogen ion-exchange fibre.
Embodiment 3: in reactor, add 10% hydrazine hydrate 100kg, acrylic fiber 4kg, and the closed reactor agitating heating, in 100 ℃, 0.02MPa reaction 10 hours, cooling discharge, washing and drying got cross filament.
In reactor, add 10% sodium hydroxide solution 80kg, above-mentioned cross filament, the closed reactor agitating heating, in 100 ℃, 0.05MPa reaction 4 hours, cooling discharge, washing and drying got sodium type ion-exchange fibre.
Add 5% hydrochloric acid solution 50kg, above-mentioned sodium type ion-exchange fibre in reactor, made the transition 10 hours, washing and drying gets the Hydrogen ion-exchange fibre.
Embodiment 4: in reactor, add 15% hydrazine hydrate 100kg, acrylic fiber 5.4kg, and the closed reactor agitating heating, in 110 ℃, 0.3MPa reaction 1 hour, cooling discharge, washing and drying got cross filament.
In reactor, add 5% sodium hydroxide solution 80kg, above-mentioned cross filament, the closed reactor agitating heating, in 100 ℃, 0.2MPa reaction 5 hours, cooling discharge, washing and drying got sodium type ion-exchange fibre.
Add 5% hydrochloric acid solution 50kg, above-mentioned sodium type ion-exchange fibre in reactor, made the transition 10 hours, washing and drying gets the Hydrogen ion-exchange fibre.
Embodiment 5: in reactor, add 40% hydrazine hydrate 100kg, acrylic fiber 5.0kg, and the closed reactor agitating heating, in 120 ℃, 0.35MPa reaction 1 hour, cooling discharge, washing and drying got cross filament.
In reactor, add 20% sodium hydroxide solution 80kg, above-mentioned cross filament, the closed reactor agitating heating, in 120 ℃, 0.4MPa reaction 5 hours, cooling discharge, washing and drying got sodium type ion-exchange fibre.
Add 5% hydrochloric acid solution 50kg, above-mentioned sodium type ion-exchange fibre in reactor, made the transition 10 hours, washing and drying gets the Hydrogen ion-exchange fibre.
Embodiment 6: in reactor, add 5% hydrazine hydrate 100kg, acrylic fiber 3.1kg, and the closed reactor agitating heating, in 100 ℃, 0.02MPa reaction 5 hours, cooling discharge, washing and drying got cross filament.
In reactor, add 1% sodium hydroxide solution 80kg, above-mentioned cross filament, the closed reactor agitating heating, in 100 ℃, 0.02MPa reaction 5 hours, cooling discharge, washing and drying got sodium type ion-exchange fibre.
Add 5% hydrochloric acid solution 50kg, above-mentioned sodium type ion-exchange fibre in reactor, made the transition 15 hours, washing and drying gets the Hydrogen ion-exchange fibre.
Embodiment 7: in reactor, add 35% hydrazine hydrate 100kg, acrylic fiber 4.9kg, and the closed reactor agitating heating, in 150 ℃, 0.5MPa reaction 2 hours, cooling discharge, washing and drying got cross filament.
In reactor, add 15% sodium hydroxide solution 80kg, above-mentioned cross filament, the closed reactor agitating heating, in 110 ℃, 0.2MPa reaction 10 hours, cooling discharge, washing and drying got sodium type ion-exchange fibre.
Add 10% hydrochloric acid solution 50kg, above-mentioned sodium type ion-exchange fibre in reactor, made the transition 8 hours, washing and drying gets the Hydrogen ion-exchange fibre.
Embodiment 8: in reactor, add 20% hydrazine hydrate 100kg, acrylic fiber 5.0kg, and the closed reactor agitating heating, in 150 ℃, 0.5MPa reaction 2 hours, cooling discharge, washing and drying got cross filament.
In reactor, add 15% sodium hydroxide solution 80kg, above-mentioned cross filament, the closed reactor agitating heating, in 110 ℃, 0.2MPa reaction 7 hours, cooling discharge, washing and drying got sodium type ion-exchange fibre.
Add 10% hydrochloric acid solution 50kg, above-mentioned sodium type ion-exchange fibre in reactor, made the transition 8 hours, washing and drying gets the Hydrogen ion-exchange fibre.
Embodiment 9: in reactor, add 20% hydrazine hydrate 600g, acrylic fiber 23.1g, and the closed reactor agitating heating, in 150 ℃, 0.5MPa reaction 2 hours, cooling discharge, washing and drying got cross filament.
In reactor, add 15% sodium hydroxide solution 600g, above-mentioned cross filament, the closed reactor agitating heating, in 130 ℃, 0.4MPa reaction 4 hours, cooling discharge, washing and drying got sodium type ion-exchange fibre.
Add 10% hydrochloric acid solution 600g, above-mentioned sodium type ion-exchange fibre in reactor, made the transition 12 hours, washing and drying gets the Hydrogen ion-exchange fibre.
Embodiment 10: in reactor, add 8% hydrazine hydrate 400g, acrylic fiber 24.7g, and the closed reactor agitating heating, in 110 ℃, 0.3MPa reaction 5 hours, cooling discharge, washing and drying got cross filament.
In reactor, add 5% sodium hydroxide solution 500g, above-mentioned cross filament, the closed reactor agitating heating, in 120 ℃, 0.2MPa reaction 4 hours, cooling discharge, washing and drying got sodium type ion-exchange fibre.
Add 10% hydrochloric acid solution 400g, above-mentioned sodium type ion-exchange fibre in reactor, made the transition 7 hours, washing and drying gets the Hydrogen ion-exchange fibre.
Embodiment 11: in reactor, add 8% hydrazine hydrate 200g, acrylic fiber 8.0g, and the closed reactor agitating heating, in 110 ℃, 0.2MPa reaction 1 hour, cooling discharge, washing and drying got cross filament.
In reactor, add 2% sodium hydroxide solution 250g, above-mentioned cross filament, the closed reactor agitating heating, in 120 ℃, 0.25MPa reaction 2 hours, cooling discharge, washing and drying got sodium type ion-exchange fibre.
Add 10% hydrochloric acid solution 400g, above-mentioned sodium type ion-exchange fibre in reactor, made the transition 7 hours, washing and drying gets the Hydrogen ion-exchange fibre.
Embodiment 12: in reactor, add 12% hydrazine hydrate 200g, acrylic fiber 8.2g, and the closed reactor agitating heating, in 130 ℃, 0.47MPa reaction 1 hour, cooling discharge, washing and drying got cross filament.
In reactor, add 2% sodium hydroxide solution 250g, above-mentioned cross filament, the closed reactor agitating heating, in 120 ℃, 0.25MPa reaction 1 hour, cooling discharge, washing and drying got sodium type ion-exchange fibre.
Add 10% hydrochloric acid solution 400g, above-mentioned sodium type ion-exchange fibre in reactor, made the transition 7 hours, washing and drying gets the Hydrogen ion-exchange fibre.
Embodiment 13: in reactor, add 60% hydrazine hydrate 600g, acrylic fiber 23.1g, and the closed reactor agitating heating, in 100 ℃, 0.02MPa reaction 1 hour, cooling discharge, washing and drying got cross filament.
In reactor, add 40% potassium hydroxide solution 600g, above-mentioned cross filament, the closed reactor agitating heating, in 100 ℃, 0.02MPa reaction 1 hour, cooling discharge, washing and drying got sodium type ion-exchange fibre.
Add 10% hydrochloric acid solution 600g, above-mentioned sodium type ion-exchange fibre in reactor, made the transition 12 hours, washing and drying gets the Hydrogen ion-exchange fibre.
Embodiment 14: in reactor, add 8% hydrazine hydrate 400g, acrylic fiber 24.7g, and the closed reactor agitating heating, in 110 ℃, 0.3MPa reaction 5 hours, cooling discharge, washing and drying got cross filament.
In reactor, add 5% potassium hydroxide solution 500g, above-mentioned cross filament, the closed reactor agitating heating, in 120 ℃, 0.2MPa reaction 4 hours, cooling discharge, washing and drying got sodium type ion-exchange fibre.
Add 10% hydrochloric acid solution 400g, above-mentioned sodium type ion-exchange fibre in reactor, made the transition 7 hours, washing and drying gets the Hydrogen ion-exchange fibre.
Embodiment 15: in reactor, add 8% hydrazine hydrate 400g, acrylic fiber 24.7g, and the closed reactor agitating heating, in 110 ℃, 0.3MPa reaction 5 hours, cooling discharge, washing and drying got cross filament.
In reactor, add 10% lithium hydroxide solution 500g, above-mentioned cross filament, the closed reactor agitating heating, in 120 ℃, 0.2 Pa reaction 5 hours, cooling discharge, washing and drying got sodium type ion-exchange fibre.
Add 10% sulfuric acid solution 400g, above-mentioned sodium type ion-exchange fibre in reactor, made the transition 7 hours, washing and drying gets the Hydrogen ion-exchange fibre.
Embodiment 16: in reactor, add 20% hydrazine hydrate 600g, acrylic fiber 23.1g, and the closed reactor agitating heating, in 150 ℃, 0.5MPa reaction 2 hours, cooling discharge, washing and drying got cross filament.
In reactor, add 25% lithium hydroxide solution 600g, above-mentioned cross filament, the closed reactor agitating heating, in 130 ℃, 0.4MPa reaction 3 hours, cooling discharge, washing and drying got sodium type ion-exchange fibre.
Add 10% hydrochloric acid solution 600g, above-mentioned sodium type ion-exchange fibre in reactor, made the transition 12 hours, washing and drying gets the Hydrogen ion-exchange fibre.
Embodiment 17: in reactor, add 18% hydrazine hydrate 200g, acrylic fiber 8.5g, and the closed reactor agitating heating, in 110 ℃, 0.07MPa reaction 3 hours, cooling discharge, washing and drying got cross filament.
In reactor, add above-mentioned cross filament, 20% hydrochloric acid solution 200ml, in 100 ℃, 0.02MPa reaction 3 hours, cooling discharge, washing and drying got the Hydrogen ion-exchange fibre.
Add 10% potassium hydroxide solution 400g, above-mentioned Hydrogen ion-exchange fibre in reactor, made the transition 7 hours, washing and drying gets sodium type ion-exchange fibre.
Embodiment 18: in reactor, add 18% hydrazine hydrate 200g, acrylic fiber 8.5g, and the closed reactor agitating heating, in 110 ℃, 0.07MPa reaction 3 hours, cooling discharge, washing and drying got cross filament.
In reactor, add above-mentioned cross filament 2.8g, 80% sulfuric acid solution 200g, in 100 ℃, 0.02MPa reaction 1 hour, cooling discharge, washing and drying got the Hydrogen ion-exchange fibre.
Add 10% sodium hydroxide solution 400g, above-mentioned Hydrogen ion-exchange fibre in reactor, made the transition 7 hours, washing and drying gets sodium type ion-exchange fibre.
Embodiment 19: in reactor, add 18% hydrazine hydrate 200g, acrylic fiber 8.5g, and the closed reactor agitating heating, in 110 ℃, 0.07MPa reaction 3 hours, cooling discharge, washing and drying got cross filament.
In reactor, add above-mentioned cross filament 2.8g, 10% salpeter solution 200g, in 150 ℃, 0.5MPa reaction 5 hours, cooling discharge, washing and drying got the Hydrogen ion-exchange fibre.
Add 10% sodium hydroxide solution 400g, above-mentioned FFC-1 Hydrogen ion-exchange fibre in reactor, made the transition 7 hours, washing and drying gets sodium type ion-exchange fibre.
Embodiment 20: in reactor, add 18% hydrazine hydrate 200g, acrylic fiber 8.5g, and the closed reactor agitating heating, in 110 ℃, 0.07MPa reaction 3 hours, cooling discharge, washing and drying got cross filament.
In reactor, add above-mentioned cross filament 3.1g, 40% salpeter solution 200g, in 120 ℃, 0.05MPa reaction 1 hour, cooling discharge, washing and drying got the Hydrogen ion-exchange fibre.
Add 10% sodium hydroxide solution 400g, above-mentioned Hydrogen ion-exchange fibre in reactor, made the transition 7 hours, washing and drying gets sodium type ion-exchange fibre.
Embodiment 21: in reactor, add 18% hydrazine hydrate 200g, acrylic fiber 8.5g, and the closed reactor agitating heating, in 110 ℃, 0.07MPa reaction 3 hours, cooling discharge, washing and drying got cross filament.
In reactor, add above-mentioned cross filament 2.8g, 10% phosphoric acid solution 200g, in 150 ℃, 0.5MPa reaction 5 hours, cooling discharge, washing and drying got the Hydrogen ion-exchange fibre.
Add 10% sodium hydroxide solution 400g, above-mentioned Hydrogen ion-exchange fibre in reactor, made the transition 7 hours, washing and drying gets sodium type ion-exchange fibre.
Embodiment 22: in reactor, add 18% hydrazine hydrate 200g, acrylic fiber 8.5g, and the closed reactor agitating heating, in 110 ℃, 0.07MPa reaction 3 hours, cooling discharge, washing and drying got cross filament.
In reactor, add above-mentioned cross filament 3.1g, 20% phosphoric acid solution 200g, in 120 ℃, 0.05MPa reaction 1 hour, cooling discharge, washing and drying got the Hydrogen ion-exchange fibre.
Add 10% sodium hydroxide solution 400g, above-mentioned Hydrogen ion-exchange fibre in reactor, made the transition 7 hours, washing and drying gets sodium type ion-exchange fibre.
Embodiment 23: in reactor, add 18% hydrazine hydrate 200g, acrylic fiber 8.5g, and the closed reactor agitating heating, in 110 ℃, 0.07MPa reaction 3 hours, cooling discharge, washing and drying got cross filament.
In reactor, add above-mentioned cross filament 2.5g, 20% sulfuric acid solution 200ml, in 100 ℃, 0.02MPa reaction 3 hours, cooling discharge, washing and drying got the Hydrogen ion-exchange fibre.
Add 10% sodium hydroxide solution 400g, above-mentioned Hydrogen ion-exchange fibre in reactor, made the transition 7 hours, washing and drying gets sodium type ion-exchange fibre.
Embodiment 24: in reactor, add 18% hydrazine hydrate 200g, acrylic fiber 8.5g, and the closed reactor agitating heating, in 110 ℃, 0.07MPa reaction 3 hours, cooling discharge, washing and drying got cross filament.
In reactor, add above-mentioned cross filament 2.8g, 50% sulfuric acid solution 200g, in 100 ℃, 0.02MPa reaction 5 hours, cooling discharge, washing and drying got the Hydrogen ion-exchange fibre.
Add 10% sodium hydroxide solution 400g, above-mentioned Hydrogen ion-exchange fibre in reactor, made the transition 7 hours, washing and drying gets sodium type ion-exchange fibre.
Embodiment 25: in reactor, add 18% hydrazine hydrate 200g, acrylic fiber 8.5g, and the closed reactor agitating heating, in 110 ℃, 0.07MPa reaction 3 hours, cooling discharge, washing and drying got cross filament.
In reactor, add above-mentioned cross filament 2.8g, 10% sulfuric acid solution 200g, in 150 ℃, 0.5MPa reaction 5 hours, cooling discharge, washing and drying got the Hydrogen ion-exchange fibre.
Add 10% sodium hydroxide solution 400g, above-mentioned Hydrogen ion-exchange fibre in reactor, made the transition 7 hours, washing and drying gets sodium type ion-exchange fibre.
Embodiment 26: in reactor, add 18% hydrazine hydrate 200g, acrylic fiber 8.5g, and the closed reactor agitating heating, in 110 ℃, 0.07MPa reaction 3 hours, cooling discharge, washing and drying got cross filament.
In reactor, add above-mentioned cross filament 3.1g, 80% sulfuric acid solution 200g, in 120 ℃, 0.05MPa reaction 1 hour, cooling discharge, washing and drying got 1 Hydrogen ion-exchange fibre.
Add 10% sodium hydroxide solution 400g, above-mentioned Hydrogen ion-exchange fibre in reactor, made the transition 7 hours, washing and drying gets sodium type ion-exchange fibre.
Embodiment 27: in reactor, add 5% hydrazine hydrate 100kg, acrylic fiber 3.1kg, and the closed reactor agitating heating, in 120 ℃, 0.2MPa reaction 4 hours, cooling discharge, washing and drying got cross filament.
In reactor, add 1% sodium hydroxide solution 80kg, above-mentioned cross filament, the closed reactor agitating heating, in 120 ℃, 0.2MPa reaction 5 hours, cooling discharge, washing and drying got sodium type ion-exchange fibre.
Add 5% hydrochloric acid solution 50kg, above-mentioned sodium type ion-exchange fibre in reactor, made the transition 15 hours, washing and drying gets the Hydrogen ion-exchange fibre.
Embodiment 28: in reactor, add 10% hydrazine hydrate 100kg, acrylic fiber 4.9kg, and the closed reactor agitating heating, in 110 ℃, 0.1MPa reaction 3 hours, cooling discharge, washing and drying got cross filament.
In reactor, add 10% sodium hydroxide solution 80kg, above-mentioned cross filament, the closed reactor agitating heating, in 120 ℃, 0.2MPa reaction 5 hours, cooling discharge, washing and drying got sodium type ion-exchange fibre.
Add 10% hydrochloric acid solution 50kg, above-mentioned sodium type ion-exchange fibre in reactor, made the transition 8 hours, washing and drying gets the Hydrogen ion-exchange fibre.
Embodiment 29: in reactor, add 18% hydrazine hydrate 200g, acrylic fiber 8.5g, and the closed reactor agitating heating, in 110 ℃, 0.1MPa reaction 3 hours, cooling discharge, washing and drying got cross filament.
In reactor, add above-mentioned cross filament, 50% sulfuric acid solution 200g, in 120 ℃, 0.2MPa reaction 5 hours, cooling discharge, washing and drying got the Hydrogen ion-exchange fibre.
Add 10% sodium hydroxide solution 400g, above-mentioned Hydrogen ion-exchange fibre in reactor, made the transition 7 hours, washing and drying gets sodium type ion-exchange fibre.
Embodiment 30: in reactor, add 18% hydrazine hydrate 200g, acrylic fiber 8.5g, and the closed reactor agitating heating, in 110 ℃, 0.1MPa reaction 3 hours, cooling discharge, washing and drying got cross filament.
In reactor, add above-mentioned cross filament, 40% sulfuric acid solution 200g, in 120 ℃, 0.2MPa reaction 4 hours, cooling discharge, washing and drying got the Hydrogen ion-exchange fibre.
Add 10% sodium hydroxide solution 400g, above-mentioned Hydrogen ion-exchange fibre in reactor, made the transition 7 hours, washing and drying gets sodium type ion-exchange fibre.
Embodiment 31: get dry Hydrogen ion-exchange fibre 20g, abundant (fiber moisture about 20%) dress Filter column after the balance in T=22 ℃, the air ambient of RH (relative humidity)=85%.With ammonia content=760mg/m
3Air with the speed of 15L/min. evenly by the Filter column of above-mentioned fiber is housed, detect ammonia gas penetrativity, time of break-through 50.2min with instructions phenolphthalein solution.
Embodiment 32: get dry sodium type ion-exchange fibre 20g, abundant (fiber moisture about 25%) dress Filter column after the balance in T=22 ℃, the air ambient of RH (relative humidity)=85%.With content of sulfur dioxide=2000mg/m
3Air with the speed of 15L/min. evenly by the Filter column of above-mentioned fiber is housed, detect sulfur dioxide gas penetrativity, time of break-through 75.7min with the potassium permanganate indicator solution.
Embodiment 33: the Hydrogen ion-exchange fibre 20g that gets moisture about 20% is placed on the about 10m of volume
3, the about 3mg/m of ammonia content
3Confined space in.24h. after, ammonia content is reduced to about 0.2mg/m
3
Embodiment 34: carboxylic acid type (Na type) ion-exchange fibre is a kind of chemisorbed process to the absorption of deleterious acidic gas, be based on the salt and the strong acid reaction of weak acid, the acidity of sour gas only just can be adsorbed greater than carboxylic acid, and the strong more adsorption effect of acidity is good more.We have investigated the dynamic adsorption of carboxylic acid type fiber to pernicious gases such as sulfur dioxide, hydrogen chloride, hydrogen fluoride in the air, the results are shown in following table:
Carboxylic Ion Exchange Fibers is to the dynamic adsorption of pernicious gas
| Sorbing material | Material weight (g) | The pernicious gas kind | Gas concentration (mg/m 3) | Time of break-through (min) |
| The carboxylic acid type fiber | ????1.0 | ????SO 2 | ????2000 | ????100 |
| ????HCL | ????1000 | ????107 | ||
| ????HF | ????150 | ????104 |
Embodiment 35: use ion-exchange fibre of the present invention and make the individual protection mouth mask, using through the workman in certain resin processing plant all has filtering effect preferably to hydrogen chloride gas and chlorine.
Embodiment 36: use ion-exchange fibre of the present invention and make the individual protection mouth mask, using through the workman in Henan Province technology ﹠ development Co. has filtering effect preferably to front three ammonia.
Claims (10)
1. the preparation method of an ion-exchange fibre, adopt acrylic fiber and certain density hydrazine hydrate solution to carry out the precrosslink reaction at a certain temperature earlier, hydrolysis and preparing under alkali condition or under the acid condition again is characterized in that: precrosslink reaction, basic hydrolysis or acid hydrolytic reaction are to carry out in smaller or equal to the closed reactor of 0.5MPa greater than 0.0Mpa at pressure.
2. the preparation method of ion-exchange fibre according to claim 1, it is characterized in that: the concentration of hydrazine hydrate solution is 1～60% in the precrosslink reaction, the precrosslink reaction is to react 1～10 hour under 100～150 ℃ of conditions, the concentration of aqueous slkali is 1～40% in the basic hydrolysis, basic hydrolysis is to react 1～10 hour under 100～150 ℃ of conditions, the concentration of acid solution is 5～80% in the acid hydrolytic reaction, and acid hydrolytic reaction is to react 1～5 hour under 100～150 ℃ of conditions.
3. the preparation method of ion-exchange fibre according to claim 1 and 2, it is characterized in that: precrosslink reaction is to carry out in pressure is the closed reactor of 0.1～0.3MPa, the concentration of hydrazine hydrate solution is 5～40% in the precrosslink reaction, the precrosslink reaction is to react 1～5 hour under 100～130 ℃ of conditions, the concentration of aqueous slkali is 1～20% in the basic hydrolysis, basic hydrolysis is to react 1～8 hour under 100～130 ℃ of conditions, the concentration of acid solution is 20～60% in the acid hydrolytic reaction, and acid hydrolytic reaction is to react 1～5 hour under 100～130 ℃ of conditions.
4. the preparation method of ion-exchange fibre according to claim 1 and 2, it is characterized in that: precrosslink reaction is to carry out in pressure is the closed reactor of 0.1～0.25MPa, the concentration of hydrazine hydrate solution is 8～20% in the precrosslink reaction, the precrosslink reaction is to react 2～5 hours under 110～120 ℃ of conditions, the concentration of aqueous slkali is 3～10% in the basic hydrolysis, basic hydrolysis is to react 2～5 hours under 110～130 ℃ of conditions, the concentration of acid solution is 30～50% in the acid hydrolytic reaction, and acid hydrolytic reaction is to react 2～5 hours under 110～130 ℃ of conditions.
5. the preparation method of ion-exchange fibre according to claim 1 and 2, it is characterized in that: the aqueous slkali in the basic hydrolysis is a sodium hydroxide solution, or be potassium hydroxide solution, or be lithium hydroxide solution, acid solution in the acid hydrolytic reaction is a hydrochloric acid solution, or be sulfuric acid solution, or be salpeter solution, or be phosphoric acid solution.
6. the preparation method of a fabrics treated by ion exchanging, adopt acrylic fiber fabric and certain density hydrazine hydrate solution to carry out the precrosslink reaction at a certain temperature earlier, hydrolysis and preparing under alkali condition or under the acid condition again is characterized in that: precrosslink reaction, basic hydrolysis or acid hydrolytic reaction are to carry out in smaller or equal to the closed reactor of 0.5MPa greater than 0.0Mpa at pressure.
7. the preparation method of fabrics treated by ion exchanging according to claim 6, it is characterized in that: the concentration of hydrazine hydrate solution is 1～60% in the precrosslink reaction, the precrosslink reaction is to react 1～10 hour under 100～150 ℃ of conditions, the concentration of aqueous slkali is 1～40% in the basic hydrolysis, basic hydrolysis is to react 1～10 hour under 100～150 ℃ of conditions, the concentration of acid solution is 5～80% in the acid hydrolytic reaction, and acid hydrolytic reaction is to react 1～5 hour under 100～150 ℃ of conditions.
8. according to the preparation method of claim 6 or 7 described fabrics treated by ion exchanging, it is characterized in that: precrosslink reaction is to carry out in pressure is the closed reactor of 0.1～0.3MPa, the concentration of hydrazine hydrate solution is 5～40% in the precrosslink reaction, the precrosslink reaction is to react 1～5 hour under 100～130 ℃ of conditions, the concentration of aqueous slkali is 1～20% in the basic hydrolysis, basic hydrolysis is to react 1～8 hour under 100～130 ℃ of conditions, the concentration of acid solution is 20～60% in the acid hydrolytic reaction, and acid hydrolytic reaction is to react 1～5 hour under 100～130 ℃ of conditions.
9. according to the preparation method of claim 6 or 7 described fabrics treated by ion exchanging, it is characterized in that: precrosslink reaction is to carry out in pressure is the closed reactor of 0.1～0.25MPa, the concentration of hydrazine hydrate solution is 8～20% in the precrosslink reaction, the precrosslink reaction is to react 2～5 hours under 110～120 ℃ of conditions, the concentration of aqueous slkali is 3～10% in the basic hydrolysis, basic hydrolysis is to react 2～5 hours under 110～130 ℃ of conditions, the concentration of acid solution is 30～50% in the acid hydrolytic reaction, and acid hydrolytic reaction is to react 2～5 hours under 110～130 ℃ of conditions.
10. according to the preparation method of claim 6 or 7 described fabrics treated by ion exchanging, it is characterized in that: the aqueous slkali in the basic hydrolysis is a sodium hydroxide solution, or be potassium hydroxide solution, or be lithium hydroxide solution, acid solution in the acid hydrolytic reaction is a hydrochloric acid solution, or be sulfuric acid solution, or be salpeter solution, or be phosphoric acid solution.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101579640A (en) * | 2008-05-15 | 2009-11-18 | 赵鹏雷 | Preparation method and use method of heterogeneous oxidation catalyst |
| CN103015162A (en) * | 2012-11-30 | 2013-04-03 | 吴江市超维纺织有限公司 | Method for producing antibacterial and deodorizing polyacrylonitrile fibers |
| CN103693711A (en) * | 2013-11-12 | 2014-04-02 | 郑州大学 | Method for treating nickel/copper-containing electroplating wastewater by using weak acid ion exchange fibers |
| CN107938321A (en) * | 2017-11-30 | 2018-04-20 | 郑州大学 | A kind of fiber solid support method of fluorescence carbon nanomaterial |
| CN108147584A (en) * | 2017-12-31 | 2018-06-12 | 邯郸派瑞电器有限公司 | A kind of method using PAN-PEI amido chelate fibre Treatment of Copper sewage |
| CN112301003A (en) * | 2019-07-26 | 2021-02-02 | 佛山市安芯纤维科技有限公司 | Carboxylic acid type cation exchange fiber and its fabric use in adsorption filtration of influenza virus |
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2004
- 2004-11-23 CN CNB2004100602750A patent/CN1262706C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101579640A (en) * | 2008-05-15 | 2009-11-18 | 赵鹏雷 | Preparation method and use method of heterogeneous oxidation catalyst |
| CN103015162A (en) * | 2012-11-30 | 2013-04-03 | 吴江市超维纺织有限公司 | Method for producing antibacterial and deodorizing polyacrylonitrile fibers |
| CN103693711A (en) * | 2013-11-12 | 2014-04-02 | 郑州大学 | Method for treating nickel/copper-containing electroplating wastewater by using weak acid ion exchange fibers |
| CN103693711B (en) * | 2013-11-12 | 2015-11-04 | 郑州大学 | Utilize weak acidic ion-exchange fiber process nickeliferous/method of copper-contained electroplating waste water |
| CN107938321A (en) * | 2017-11-30 | 2018-04-20 | 郑州大学 | A kind of fiber solid support method of fluorescence carbon nanomaterial |
| CN108147584A (en) * | 2017-12-31 | 2018-06-12 | 邯郸派瑞电器有限公司 | A kind of method using PAN-PEI amido chelate fibre Treatment of Copper sewage |
| CN112301003A (en) * | 2019-07-26 | 2021-02-02 | 佛山市安芯纤维科技有限公司 | Carboxylic acid type cation exchange fiber and its fabric use in adsorption filtration of influenza virus |
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| CN1262706C (en) | 2006-07-05 |
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