CN101362102A - Polyacrylonitrile fiber duplex metal complexes catalyst and preparation method thereof - Google Patents
Polyacrylonitrile fiber duplex metal complexes catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polyacrylonitrile fiber bimetallic complex catalyst and a preparation method thereof. The catalyst is characterized in that the appearance is between brownish yellow and yellowish green and is fiber-shaped; and the catalyst is formed by polyacrylonitrile fiber which is modified by hydrazine hydrate and hydroxylamine hydrochloride, and a coordination compound of iron ion and copper ion, wherein, the contents of iron ion and copper ion are 11.60mg/g to 26.10mg/g and 11.15mg/g to 28.30mg/g respectively. The preparation method adopts the following steps: 1. the pre-treatment of the polyacrylonitrile fiber; 2. modified reaction of the hydrazine hydrate of the polyacrylonitrile fiber and hydroxylamine hydrochloride; 3. the preparation of mixed solution of iron ion and copper ion; 4. the coordination reaction of the modified polyacrylonitrile fiber and metal ions; therefore, the fiber-shaped polyacrylonitrile fiber bimetallic complex catalyst with the color between brownish yellow and pale green is obtained. The catalyst has good catalytic activity, is applicable to the degradation of dyes in the basic printing and dyeing wastewater and has high reuse rate.
Description
Technical field
The present invention relates to a kind of chemical catalyst technology, be specially a kind of polyacrylonitrile fiber duplex metal complexes catalyst that the dyeing waste water dyestuff is degraded and preparation method thereof that is used for promoting, international monopoly Main classification number plan is Int.Cl.B01 J 29/00 (2006.01) I.
Background technology
Textile industry is one of bigger department of China's discharging amount of industrial wastewater.According to incompletely statistics, nearly 1,000,000,000 tons of the wastewater flow rate of the annual discharging of textile industry occupies the 6th of China's discharged volume of industrial waste water, and wherein the dyeing waste water discharge capacity accounts for 80% of textile waste discharge capacity.Therefore as seen, the environmental pollution problem of textile industry mainly is the pollution of dyeing waste water.In this external printing and dyeing processing, comprise fiber article dyeing processing and post processing (fixation, wash and the soap etc.) waste water that process produced, it is big to have the water yield, colourity height, the feature of complicated component (containing dyestuff, auxiliary agent, soda acid, fiber impurity and inorganic salts etc.).The analysis showed that dyestuff is the component that has the greatest impact in the dyeing waste-water, the color of waste water is mainly derived from that part of dyestuff of fixing in the process of dying and being washed.According to estimates, about more than 70 ten thousand tons of the amount of dye of the annual printing and dyeing industry use in the whole world at present, the amount of dye of losing in the printing and dyeing process is about 10-20%, and wherein major part enters in the dyeing waste water.That is to say that if the treated just discharging of dyeing waste water, then annual will have the dyestuff that is no less than 100,000 tons finally to enter among the human habitat to be dissolved or dispersed in form in the water.Therefore, the harmless treatment of dyeing waste-water just becomes the key technology that wastewater in textile printing and dyeing industry is handled.
The Fenton oxidizing process is exactly one of key technology of treatment of dyeing wastewater, is bringing into play more and more important effect.The Fenton oxidizing process is based on Fe
2+And H
2O
2(being commonly referred to Fenton reagent) produces a kind of high-level oxidation technology of hydroxyl free radical.It has good oxidative degradation effect for being difficult to biodegradable organic pollution such as dyestuff etc.But the Fenton oxidizing process also exists technical problem in application: promptly must use down at acid condition (pH=2-5), and after the reaction end, iron ion can remain in the solution, causes secondary pollution.For addressing this problem, the heterogeneous Fenton photochemical catalyst that iron ion is fixed in the support materials surface arises at the historic moment.It not only has advantages of high catalytic activity, and can overcome the above-mentioned shortcoming of Fenton oxidizing process.In heterogeneous Fenton photochemical catalyst R﹠D process, although molecular sieve, Nafion film and ion exchange resin etc. all once were used as support materials, because the catalyst activity of its preparation is not high or cost an arm and a leg etc. former thereby limit their use.Polyacrylonitrile fibre has good stability to oxidant commonly used, and has the light fastness that is higher than other fiber.The more important thing is that after polyacrylonitrile fibre and metal ion formed complex, its intensity did not significantly reduce.In addition, polyacrylonitrile fibre can also carry out blending with other fiber or interweave the higher and cheap composite of preparation stability.Because above-mentioned reason polyacrylonitrile fibre is considered to have the support materials of potentiality of developing on a large scale very much.People such as the V.V.Ishtchenko of Britain have made iron modified acrylic fibre catalyst by the adsorption reaction between modified acrylic fibre and the iron ion, and use it in the oxidative degradation of waste water from dyestuff [referring to the modified acrylic fibre Preparation of catalysts and to the optimization of hydrogen peroxide decomposes, Ishtchenko V V, Huddersman K D, Vitkovskaya R F.Production of a modified PAN fibrouscatalyst and its optimisation towards the decomposition of hydrogen peroxide[J] .Appl Catal A, 2003,242:123-137.].Studies show that although this catalyst can promote the oxidative degradation of dyestuff in water, the applicability under alkali condition is not high, and reusability is poor, has influenced applying of this technology.
Summary of the invention
At the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is that a kind of polyacrylonitrile fiber duplex metal complexes catalyst and preparation method thereof is provided.This catalyst is used for promoting the degraded of dyeing waste water dyestuff, not only has the catalytic activity higher than existing catalyst, and particularly can be under alkali condition to waste water in dyestuff carry out decolored degradation, have universality, simultaneously the repeat usage height.Advantages such as it is simple that this method for preparing catalyst has technology, with low cost, and industrializing implementation is easy.
The technical scheme that the present invention solves described catalyst technology problem is: design a kind of polyacrylonitrile fiber duplex metal complexes catalyst, it is characterized in that this catalyst outward appearance is pale brown look to yellow green, fiber shape, be made of the polyacrylonitrile fibre of hydrazine hydrate and hydroxylamine hydrochloride modification and iron ion and copper ion complexation reaction thing, the iron ion wherein and the content of copper ion are respectively 11.60-26.10mg/g and 11.15-28.30mg/g.
The technical scheme that the present invention solves described method for preparing catalyst technical problem is: design a kind of preparation method of polyacrylonitrile fiber duplex metal complexes catalyst of the present invention, it adopts following technology:
1. the preliminary treatment of polyacrylonitrile fibre: use and contain volumetric concentration and take out after 20-40 minutes, wash dry for standby 2-3 times as the nonionic surfactant water-soluble liquid carrying out washing treatment polyacrylonitrile fibre yarn of 2.0g/L;
2. the modified-reaction of polyacrylonitrile fibre: accurately the described preliminary treatment polyacrylonitrile fibre of weighing is to predetermined weight, immerse volumetric concentration and be respectively in the hydrazine hydrate and hydroxylamine hydrochloride mixed aqueous solution of 20-50g/L and 28-70g/L, the volume ratio of polyacrylonitrile fibre weight and mixed aqueous solution is 1:40; With NaOH the pH value of mixed aqueous solution is transferred to 9.2-9.8, reaction 2-6 hour under 95-98 ℃ and stirring condition then, the polyacrylonitrile fibre with modification after the reaction takes out, with dry for standby after the distilled water washing 3-5 times;
3. the preparation of iron copper metal ion mixed solution: use the metallic ion mixed liquor of copper sulphate and iron chloride preparation molar concentration as 0.1M, requiring the iron ion in this mixed solution and the molar concentration rate of copper ion is 1-3:3-1, then the gained mixed solution is left standstill filter after 2-5 hours standby;
4. the complexation reaction of modified acrylic fibre and metal ion: gained modified acrylic fibers polyacrylonitrile fibre is immersed in the described metallic ion mixed liquor, after reacting 12-24 hour under normal temperature and the stirring condition, oven dry after using distilled water to wash 3-5 times, gained complexation reaction thing are fibrous pale brown look to absinthe-green polyacrylonitrile fiber duplex metal complexes catalyst.
Compared with prior art, polyacrylonitrile fiber duplex metal complexes catalyst of the present invention has higher catalytic activity, be specially adapted under alkali condition to promote the degraded of dyestuff in the dyeing waste water, and it is fast to have a dye decolored degradation, characteristics such as recycling rate of waterused height.Characteristics such as it is simple, with low cost that Preparation of catalysts method of the present invention has technology, do not need special installation, operates easily, and industrialization promotion is easy.
Description of drawings
Fig. 1 is three kinds of embodiment (PAN-Fe-Cu-1, PAN-Fe-Cu-2 and PAN-Fe-Cu-3) and prior art catalyst (PAN-Fe) effect contrast figure's (test condition: reactive red MS:50mol/L, H to the catalytic action of reactive red MS oxidative degradation under the pH=6 condition of catalyst of the present invention
2O
2: 0.003mol/L, catalyst: 4.0g/L, pH=6.0; Radiant light: ultraviolet light (365nm): 490 μ W/cm
2, visible light (400-1000nm): 5065 μ W/cm
2);
Fig. 2 is three kinds of embodiment PAN-Fe-Cu-1, PAN-Fe-Cu-2 and PAN-Fe-Cu-3 of catalyst of the present invention) under the condition of different pH (=2,4,6,8,10), be applied to percent of decolourization variation comparison diagram (testing time is 80 minutes, the same Fig. 1 of other test condition) in the reaction of reactive red MS oxidative decoloration with prior art catalyst (PAN-Fe);
Fig. 3 is a kind of embodiment of catalyst of the present invention (PAN-Fe-Cu-1) percent of decolourization change curve (the same Fig. 1 of test condition) to reactive red MS when reusing;
Percent of decolourization change curve (contrast) to reactive red MS when Fig. 4 is prior art catalyst (PAN-Fe) repeated use is schemed (the same Fig. 1 of test condition).
The specific embodiment
Be described in further detail the present invention below in conjunction with embodiment and accompanying drawing thereof:
The polyacrylonitrile fiber duplex metal complexes catalyst (hereinafter to be referred as catalyst) of the present invention's design, it is characterized in that this catalyst outward appearance is pale brown look to yellow green, fiber shape, be made of the polyacrylonitrile fibre of hydrazine hydrate and hydroxylamine hydrochloride modification and iron ion and copper ion coordination thing, the iron ion wherein and the content of copper ion are respectively 11.60-26.10mg/g and 11.15-28.30mg/g.
Catalyst of the present invention is series of products.In the content range of described iron ion and copper ion, when its iron ion and content of copper ion were close, activity of such catalysts obviously strengthened, and was applicable to the processing of high concentration dyeing waste-water; When the content of copper ion in its catalyst was high relatively, catalyst had higher alkali resistance, was applicable to the processing of alkalescence or meta-alkalescence dyeing waste-water.But the content range of described iron ion and copper ion is the preferable range value.As required, the catalyst prod of actual fabrication is not limited to this content range value.Simultaneously, though catalyst of the present invention is fibrous, also be made as other shapes easily, as granule or particulate etc.
As everyone knows, the pH value of dyeing waste water mostly is alkalescence greatly.For existing homogeneous phase Fenton reaction system, because the catalyst iron ion is distributed in the solution with the form of free state, when the pH of solution value was higher than 6, iron ion can produce flocculation even precipitation, thereby make catalyst lose catalytic activity, reduce even lose its catalysis.(brief note is PAN-Fe to the polyacrylonitrile fibre iron heterogeneous catalysis of prior art, PAN wherein represents polyacrylonitrile fibre, Fe represents iron ion) only be suitable under acid condition, bringing into play catalytic action, and under alkali condition, its catalytic action then descends significantly.Catalyst of the present invention is exactly the improvement of doing at the deficiency of homogeneous phase Fenton reaction and prior art PAN-Fe.
Different with the heterogeneous catalysis of prior art, catalyst of the present invention is polyacrylonitrile fiber duplex metal complexes (a complexation reaction thing), brief note is PAN-Fe-Cu-X (PAN wherein represents polyacrylonitrile fibre, and Fe and Cu represent iron ion and copper ion respectively, and X is a specifications parameter).Its remarkable structural feature is to contain copper and iron two metal ion species.Unique coordination structure make its not only aspect catalytic activity apparently higher than polyacrylonitrile fibre iron heterogeneous catalysis, and importantly under alkali condition, still have advantages of high catalytic activity.As a kind of follow-on heterogeneous Fenton catalysts, catalyst of the present invention not only can make dyestuff under alkalescence decolored degradation take place, and reusability is good.
Experimental study shows, at catalyst of the present invention (PAN-Fe-Cu-1, PAN-Fe-Cu-2 and PAN-Fe-Cu-3, referring to embodiment 1-3) exist down, the percent of decolourization of reactive red MS is far above the percent of decolourization (referring to Fig. 1) of reactive red MS in the presence of the prior art catalyst.This illustrates that catalyst of the present invention has higher catalytic activity to the oxidative degradation of dyestuff in the dyeing waste-water, and more dyestuff is decomposed, and especially shows the most outstandingly with PAN-Fe-Cu-1.
The catalyst of prior art (PAN-Fe), catalytic effect to the oxidative degradation of reactive red MS under acid condition is comparatively desirable, but when the pH value rises to alkalescence, its percent of decolourization has decline by a relatively large margin, and after the pH value is raised to 8, percent of decolourization fall behind its 80min is near 70%, and it is bigger to show that the PAN-Fe catalytic activity is influenced by alkalescence, (referring to Fig. 2) promptly poor for applicability under alkali condition.Although catalyst P AN-Fe-Cu-1 of the present invention and PAN-Fe-Cu-2 also have similar trend, percent of decolourization reduction amplitude reduces to some extent in the presence of it.It should be noted that after pH is raised to 8 remarkable reduction does not take place the percent of decolourization of dyestuff in the presence of PAN-Fe-Cu-3, the reduction amplitude is less than 20%, the reduction amplitude of the percent of decolourization under the catalyst that is starkly lower than technology exists; And when the pH value is raised to 10, in the presence of PAN-Fe-Cu-3, still can reach 80%, be higher than 2 times more than (referring to Fig. 2) of prior art the percent of decolourization of reactive red MS when the 80min.This shows that catalyst P AN-Fe-Cu-3 of the present invention not only has outstanding catalytic activity under acid condition, and its catalytic activity is still good under alkali condition, has outstanding pervasive performance.
Catalyst of the present invention not only has outstanding base catalysis activity, but also has good reusability.Existing P AN-Fe catalyst is when repeating (for the second time) use, and its catalytic activity just can descend significantly, and catalyst of the present invention still keeps advantages of high catalytic activity after reusing three times, still can promote the degradation and decolorization reaction of dyestuff well.Following experimental study shows: under the condition of identical use amount and pH=6, the catalyst P AN-Fe-Cu-1 and the existing PAN-Fe catalyst of an embodiment of the present invention are reused three times in reactive red MS oxidative degradation respectively, investigated the variation of reactive red MS percent of decolourization.Catalyst of the present invention is when reusing for the third time, the percent of decolourization fall of its reactive red MS is in 30%, and at prior art PAN-Fe catalyst when reusing for the second time, the percent of decolourization fall of its reactive red MS has just surpassed 50% (referring to Fig. 3 and Fig. 4).This explanation catalyst P AN-Fe-Cu-1 has very high reusability, can repeatedly be applied in the decolorization of dyeing degradation treatment, and can significantly improve service efficiency, reduce use cost, have good practicality, industrial applications has tangible economic benefit.
The present invention has designed the preparation method (abbreviation preparation method) of described polyacrylonitrile fiber duplex metal complexes catalyst simultaneously, and it is a foundation with catalyst of the present invention, adopts following technology preparation:
1. the preliminary treatment of polyacrylonitrile fibre: use and contain volumetric concentration and be the nonionic surfactant water-soluble liquid carrying out washing treatment polyacrylonitrile fibre (also can adopt yarn or knitting wool) of 2.0g/L 20-40 minutes, take out washing 2-3 times after, dry for standby;
2. the modified-reaction of polyacrylonitrile fibre: accurately the described preliminary treatment polyacrylonitrile fibre of weighing is to predetermined weight, and the immersion volumetric concentration is respectively in the hydrazine hydrate and hydroxylamine hydrochloride mixed aqueous solution of 20-50g/L and 28-70g/L, the volume ratio of polyacrylonitrile fibre weight and described mixed aqueous solution is 1:40, and the pH of described mixed aqueous solution is transferred to 9.2-9.8 with NaOH, reaction 2-6 hour under 95-98 ℃ and stirring condition then, after the reaction modified acrylic fibre is taken out, extremely neutral with the distilled water cyclic washing, general washing 3-5 times, dry for standby then;
3. the preparation of iron copper metal ion mixed solution: use the metallic ion mixed liquor of copper sulphate and iron chloride preparation molar concentration as 0.1M, the molar concentration rate that requires iron ion in this mixed solution and copper ion is preferred but be not limited to 1-3:3-1, after then the gained mixed solution being left standstill 2-5 hours, filter standby;
4. the complexation reaction of modified acrylic fibre and metal ion: the gained modified acrylic fibre is immersed in the described metallic ion mixed liquor, after reacting 12-24 hour under normal temperature and the stirring condition, use the distilled water cyclic washing 3-5 times, to there not being chlorion, oven dry, gained complexation reaction thing are fibrous pale brown look to absinthe-green polyacrylonitrile fiber duplex metal complexes catalyst.
The present invention adopts following method that the metal in the gained catalyst (iron and copper) ion concentration is measured: after complexation reaction is finished, reaction residue and described cleaning solution (distilled water) are mixed constant volume, use then compleximetry measure respectively wherein iron ion and the concentration of copper ion, and then calculate the iron ion in the gained catalyst and the content of copper ion respectively.After measured and calculate: the iron ion of gained catalyst and content of copper ion are respectively 11.60-26.10mg/g and 11.15-28.30mg/g.
The essence of preparation method of the present invention and prior art is not both, in the Preparation of catalysts process, in ferric chloride solution, added an amount of copper sulphate, make the copper ion and the iron ion that contain debita spissitudo in the solution simultaneously, and complexation reaction can take place with iron ion in copper ion jointly that increase newly on the modified acrylic fibre surface, form polyacrylonitrile fiber duplex metal complexes, thereby improved catalytic activity, adaptability and the reuse of catalyst.Preparation method's technology of the present invention is simple, with low cost, does not need special installation, operation easily, and industrialization promotion is easy.
The place that the inventive method is not addressed is applicable to prior art.
Introduce specific embodiments of the invention below, but the present invention is not subjected to the restriction of embodiment:
Embodiment 1
1. the preliminary treatment of polyacrylonitrile fibre: use and contain volumetric concentration and be the non-ionic surface active agent JFC solution washing polyacrylonitrile fibre yarn of 2.0g/L 30 minutes, take out after washing 2 times, dry for standby.
2. the modified-reaction of polyacrylonitrile fibre: accurately the above-mentioned preliminary treatment polyacrylonitrile of weighing yarn is to predetermined weight, and the immersion volumetric concentration is in the mixed aqueous solution of the hydrazine hydrate of 30g/L and the hydroxylamine hydrochloride that volumetric concentration is 42g/L, make its bath raio (ratio that refers to employed fibre weight and mixed aqueous solution volume) be 1:40, and the pH value of mixed aqueous solution is transferred to 9.5 with NaOH, reaction 2 hours under 98 ℃ and stirring condition then, flaxen modified acrylic fibre fiber is taken out, and dry with behind the distilled water cyclic washing 3 times.
3. the preparation of iron copper metal ion mixed solution: use copper sulphate and iron chloride compound concentration metallic ion mixed liquor as 0.1M, wherein the molar concentration rate of iron ion and copper ion is 1:1, the volumetric concentration that is both is respectively 0.5M, after then the gained mixed solution being left standstill 4 hours, filter standby;
4. the complexation reaction of modified acrylic fibre and metal ion: gained modified acrylic fibers polyacrylonitrile fibre is immersed in the described metallic ion mixed liquor, after reacting 24 hours under normal temperature and the stirring condition, use the distilled water cyclic washing 5 times, oven dry promptly obtains fibrous yellowish green polyacrylonitrile fiber duplex metal complexes catalyst (being designated as PAN-Fe-Cu-1) then.
The mensuration of iron ion and content of copper ion in the gained catalyst: after complexation reaction is finished, with reaction residue and cleaning solution mixing constant volume, use compleximetry to measure the wherein concentration of iron ion and copper ion respectively then, and calculate iron copper two metal ion species content in the catalyst.After measured and calculate: iron ion and content of copper ion among this catalyst P AN-Fe-Cu-1 are respectively 13.89mg/g and 14.25mg/g.
The volumetric concentration of hydrazine hydrate among the embodiment 1 and hydroxylamine hydrochloride mixed aqueous solution is adjusted into 25g/L and 55g/L respectively, and the pH value transfers to 9.2; The iron ion in the described metallic ion mixed liquor and the molar concentration rate of copper ion are adjusted into 3:1, be that ferric chloride in aqueous solution and copper sulfate solution volumetric concentration are respectively 0.075mol/L and 0.025mol/L, all the other promptly prepare second kind of polyacrylonitrile fiber duplex metal complexes catalyst (being designated as PAN-Fe-Cu-2) with embodiment 1.
After measured and calculate, iron ion in this catalyst and content of copper ion are respectively 25.84mg/g and 11.91mg/g.
Embodiment 3:
The hydrazine hydrate of embodiment 1 and the volumetric concentration of hydroxylamine hydrochloride mixed aqueous solution are adjusted into 45g/L and 40g/L respectively, and the pH value transfers to 9.8; The iron ion in the described metallic ion mixed liquor and the molar concentration rate of copper ion are adjusted into 1:3, be that ferric chloride in aqueous solution and copper sulfate solution volumetric concentration are respectively 0.025mol/L and 0.075mol/L, all the other promptly prepare the third polyacrylonitrile fiber duplex metal complexes catalyst (being designated as PAN-Fe-Cu-3) with embodiment 1.
After measured and calculate, iron ion in this catalyst and content of copper ion are respectively 11.69mg/g and 27.52mg/g.
Comparative Examples:
Present embodiment is the effect Comparative Examples.The catalyst (PAN-Fe) of use prior art for preparing is documented in the table 1 with the metal ion content correction data of the catalyst (being PAN-Fe-Cu-1, PAN-Fe-Cu-2 and PAN-Fe-Cu-3) of the embodiment of the invention 1-3 gained.
Table 1: the metal ion content contrast table of three kinds of catalyst
In the table 1, W
FeRepresent the content of iron ion in the catalyst; W
CuRepresent the content of copper ion in the catalyst.Wherein the PAN-Fe method for preparing catalyst is to use the mixed solution that the ferric chloride solution of 0.1mol/L replaces iron ion among the embodiment 1 and copper ion to be 0.05mol/L, and all the other are with embodiment 1.
The catalytic activity of catalyst can use the decolorizing printing and dyeing waste water rate to measure usually, concrete grammar is as target contaminant with reactive red MS, use the catalyst and the hydrogen peroxide (0.003mol/L) of identical weight (being generally 4.0g/L), under the condition of pH=6, carry out the oxidative degradation of particular dye, according to its catalytic activity of numerical Evaluation of percent of decolourization.Use said method that described four kinds of catalyst are applied to compare their catalytic activity in the azo dyes reactive red MS oxidative degradation commonly used at present in the present invention respectively, test result as shown in Figure 1.As can be seen from Figure 1, at catalyst of the present invention, especially under the existence of PAN-Fe-Cu-1, the percent of decolourization of reactive red MS is along with the prolongation in reaction time raises fast, and in the identical reaction time, the percent of decolourization level of catalyst of the present invention is significantly higher than the percent of decolourization level under the existence of prior art catalyst, and actual proof catalyst of the present invention has higher catalytic activity, can promote the decolorizing printing and dyeing waste water degraded better.Simultaneously, catalyst of the present invention also has the basic dyeing of being applicable to waste water (referring to Fig. 2), and the characteristics of reusable rate height (referring to Fig. 3).
Claims (8)
1. polyacrylonitrile fiber duplex metal complexes catalyst, it is characterized in that this catalyst outward appearance is pale brown look to yellow green, fiber shape, be made of the polyacrylonitrile fibre of hydrazine hydrate and hydroxylamine hydrochloride modification and iron ion and copper ion complexation reaction thing, the iron ion wherein and the content of copper ion are respectively 11.60-26.10mg/g and 11.15-28.30mg/g.
2. polyacrylonitrile fiber duplex metal complexes catalyst according to claim 1 is characterized in that the iron ion in the described catalyst and the content of copper ion are respectively 13.89mg/g and 14.25mg/g.
3. polyacrylonitrile fiber duplex metal complexes catalyst according to claim 1 is characterized in that the iron ion in the described catalyst and the content of copper ion are respectively 25.84mg/g and 11.91mg/g.
4. polyacrylonitrile fiber duplex metal complexes catalyst according to claim 1 is characterized in that the iron ion in the described catalyst and the content of copper ion are respectively 11.69mg/g and 27.52mg/g.
5. the preparation method of each described polyacrylonitrile fiber duplex metal complexes catalyst of claim 1-4, it adopts following technology:
(1). the preliminary treatment of polyacrylonitrile fibre: use and contain volumetric concentration and take out after 20-40 minutes, wash dry for standby 2-3 times as the nonionic surfactant water-soluble liquid carrying out washing treatment polyacrylonitrile fibre yarn of 2.0g/L;
(2). the modified-reaction of polyacrylonitrile fibre: accurately the described preliminary treatment polyacrylonitrile fibre of weighing is to predetermined weight, immerse volumetric concentration and be respectively in the hydrazine hydrate and hydroxylamine hydrochloride mixed aqueous solution of 20-50g/L and 28-70g/L, the volume ratio of polyacrylonitrile fibre weight and mixed aqueous solution is 1:40; With NaOH the pH value of mixed aqueous solution is transferred to 9.2-9.8, reaction 2-6 hour under 95-98 ℃ and stirring condition then, the polyacrylonitrile fibre with modification after the reaction takes out, with dry for standby after the distilled water washing 3-5 times;
(3). the preparation of iron copper metal ion mixed solution: use the metallic ion mixed liquor of copper sulphate and iron chloride preparation molar concentration as 0.1M, requiring the iron ion in this mixed solution and the molar concentration rate of copper ion is 1-3:3-1, then the gained mixed solution is left standstill filter after 2-5 hours standby;
(4). the complexation reaction of modified acrylic fibre and metal ion: gained modified acrylic fibers polyacrylonitrile fibre is immersed in the described metallic ion mixed liquor, after reacting 12-24 hour under normal temperature and the stirring condition, oven dry after using distilled water to wash 3-5 times, gained complexation reaction thing are fibrous pale brown look to absinthe-green polyacrylonitrile fiber duplex metal complexes catalyst.
6. according to the preparation method of the described polyacrylonitrile fiber duplex metal complexes catalyst of claim 5, it is characterized in that the volumetric concentration of described hydrazine hydrate and hydroxylamine hydrochloride mixed aqueous solution is respectively 30g/L and 42g/L, the pH value transfers to 9.5; The iron ion in the described metallic ion mixed liquor and the molar concentration rate of copper ion are 1:1.
7. according to the preparation method of the described polyacrylonitrile fiber duplex metal complexes catalyst of claim 5, it is characterized in that the volumetric concentration of described hydrazine hydrate and hydroxylamine hydrochloride mixed aqueous solution is adjusted into 25g/L and 55g/L respectively, the pH value transfers to 9.2; The iron ion in the described metallic ion mixed liquor and the molar concentration rate of copper ion are 3:1.
8. according to the preparation method of the described polyacrylonitrile fiber duplex metal complexes catalyst of claim 5, it is characterized in that the volumetric concentration of described hydrazine hydrate and hydroxylamine hydrochloride mixed aqueous solution is adjusted into 45g/L and 40g/L respectively, the pH value transfers to 9.8; The iron ion in the described metallic ion mixed liquor and the molar concentration rate of copper ion are 1:3.
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| CN1306080C (en) * | 2005-09-23 | 2007-03-21 | 东华大学 | Chemical fibre containing organic metal catalyst, production and use thereof |
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2008
- 2008-09-27 CN CN2008101518949A patent/CN101362102B/en not_active Expired - Fee Related
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