CN1974003A - Homogenous catalyst system for catalyzing decomposition of oxygen-releasing agent hydrogen peroxide - Google Patents

Homogenous catalyst system for catalyzing decomposition of oxygen-releasing agent hydrogen peroxide Download PDF

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CN1974003A
CN1974003A CN 200610165521 CN200610165521A CN1974003A CN 1974003 A CN1974003 A CN 1974003A CN 200610165521 CN200610165521 CN 200610165521 CN 200610165521 A CN200610165521 A CN 200610165521A CN 1974003 A CN1974003 A CN 1974003A
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hydrogen peroxide
homogeneous catalysis
catalysis system
acid
oxygen
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CN1974003B (en
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刘振东
陈小斌
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Beijing Institute of Clothing Technology
Beijing Institute Fashion Technology
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Beijing Institute Fashion Technology
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Abstract

The homogeneous catalyst system for catalyzing decomposition of oxygen releasing agent hydrogen peroxide includes oxo acid, oxo salt or peroxy acid complex of VIb metal; iodine, hydroiodic acid or its salt; and alkali cocatalyst hydroxide, strong base-weak acid salt or organic base compound. The composite catalyst system is used in the decomposition of oxygen releasing agent hydrogen peroxide and can reach unexpected effect. It has high catalytic activity, smooth oxygen release, capacity of forming homogeneous solution with water, reuseability, long shelf life and environment friendship.

Description

The homogeneous catalysis system that a kind of catalysis oxygen-releasing agent hydrogen peroxide decomposes
Technical field
The present invention relates to homogeneous catalysis system and the application aspect system oxygen thereof that a kind of catalysis oxygen-releasing agent hydrogen peroxide decomposes.
Technical background
Hydrogen peroxide is as a kind of oxidant, because its environment amenable characteristic is generally paid attention in recent years.Simple also is the interested problem of scientific worker with the KI decomposition of hydrogen peroxide in recent years, people such as Xiang Mingli " Southwest Nationalities College's journal. natural science edition " the 28th the 3rd phase of volume and the 29th volume the 1st phase delivered respectively " hydrogen peroxide KI catalytic decomposition put should in new phenomenon " reach " to the query of " hydrogen peroxide KI catalytic decomposition " catalysis notion " two pieces of papers, to the mechanism of KI decomposition of hydrogen peroxide and the phenomenon in reacting study.
Forefathers study hydrogen peroxide mostly, and various catalyst are to its catalyticing decomposition action under the alkalescent situation in acidity, and the catalytic activity of its catalyst is lower, and reaction activity is higher.The alkali metal salt of the oxyacid of VIb family metal and iodide such as sodium tungstate and KI all were used as the catalyst that decomposes respectively, but catalytic activity is all very low.The inventor finds unexpectedly with these two kinds of catalyst that as composite catalyst the catalyst system and catalyzing as oxygen-releasing agent hydrogen peroxide decomposes has obtained beyond thought effect.The catalytic activity height, oxygen release is steady, and catalyst system and catalyzing and water form homogeneous phase solution, and can use repeatedly, and the length because of standing time does not lose activity.
Summary of the invention
The homogeneous catalysis system that a kind of catalysis oxygen-releasing agent hydrogen peroxide of the present invention decomposes, its composition comprises:
(1) oxyacid of VIb family metal, oxysalt or peroxy acid complex, as wolframic acid, tungstates, peroxide wolframic acid, peroxide tungstates or can generate the compound Molybdenum Suan, Molybdenum hydrochlorate etc. of the tungsten of peroxide wolframic acid with the hydrogen peroxide reaction, specifically as wolframic acid, peroxide wolframic acid, sodium tungstate, potassium tungstate, Molybdenum acid Na, Molybdenum acid potassium, peroxide sodium tungstate, peroxide potassium tungstate etc., preferred sodium tungstate or potassium tungstate.
(2) iodine, hydroiodic acid or its salt; Concrete as iodine, hydroiodic acid, sodium iodide, KI etc., preferred sodium iodide or KI.
(3) alkaline promoter comprises the salt or the organic base compounds of hydroxide, strong base weak acid; Concrete as potash, sodium carbonate, sodium metasilicate, potassium hydroxide, NaOH, hexamethylenetetramine etc., preferred sodium carbonate.
The mol ratio of (1) and (2) two kinds of catalytic components is 100: 1～1: 100 in the catalyst system and catalyzing, be preferably 10: 1～1: 10 with 6: 4～4: 6 for good;
Homogeneous catalytic reaction of the present invention carries out in the presence of a kind of alkaline promoter, the inventor finds, under the situation that other condition is fixed, increase along with system neutral and alkali co-catalyst quality, oxygenous speed should be added the alkali of different amounts with different application requirements according to required oxygen release speed also in the increase that is directly proportional.Generally speaking, steady for aerogenesis, select the use amount of suitable alkaline promoter, among the present invention the alkali use amount generally in 0.001～10mol/L scope, with 0.01～1mol/L for well.
In the homogeneous catalytic reaction of the present invention, along with the rising of reaction temperature in the system, oxygenous speed is also obviously accelerated, should be according to the product oxygen speed of different demands, select suitable temperature, general reaction temperature is controlled between 0 ℃～40 ℃, with 0 ℃～20 ℃ for well.
In the homogeneous catalytic reaction of the present invention, also should adjust catalyst concn with different application requirements according to required oxygen release speed, catalyst concn generally is controlled at 2 * 10 -3Mol～8 * 10 -3Mol is with 3 * 10 -3Mol～5 * 10 -3Mol is for well.
Embodiment
Soap-film method is adopted in experiment, and in magnetic agitation, and thermostatic water-circulator bath or ice bath (temperature error ± 0.5 ℃) are measured the O that the catalyst decomposing hydrogen dioxide solution is emitted 2Volume, during experiment earlier with catalyst, hydrogen peroxide, be made into certain density solution.Get 25mlH during reaction 2O 2, 25ml water, certain mass alkaline promoter place the 100ml reaction bulb, start agitator and thermostatted water, also catalyst (total amount 10ml) is measured simultaneously and put into test tube and place thermostatted water constant temperature, add catalyst in the reactor rapidly when treating temperature constant and install instrument to desired temperature, extrude a bubble more rapidly, when soap-film arrives scale, begin to clock, read H by eudiometer tube with stopwatch 2O 2Decompose the oxygen amount Vt that emits.Write down a secondary data every 1min, up to the per minute gas production less than 1ml.
Description of drawings: Fig. 1 is an Experimental equipment.
Embodiment 1
With Na2WO 4·2H 2O (A), KI (B) are made into the solution of 0.025mol/L separately, hydrogen peroxide is made into the solution that concentration is 0.78mol/L, the control temperature is at 0 ℃, sodium carbonate amount 1.5g, catalyst total mole number 0.00025mol, reaction system cumulative volume 60ml, A is 7: 3 than B mol ratio, tests by above-mentioned steps. The results are shown in Table 1.
Embodiment 2
Other condition only changes A into 6: 4 than B mol ratio with embodiment 1, experimentizes by above-mentioned steps.The results are shown in Table 1.
Embodiment 3
Other condition only changes A into 5: 5 than B mol ratio with embodiment 1, experimentizes by above-mentioned steps.The results are shown in Table 1.
Embodiment 4
Other condition only changes A into 4: 6 than B mol ratio with embodiment 1, experimentizes by above-mentioned steps.The results are shown in Table 1.
Embodiment 5
Other condition only changes A into 3: 7 than B mol ratio with embodiment 1, experimentizes by above-mentioned steps.The results are shown in Table 1.
Embodiment 6
The control temperature is made into solution, the reaction system cumulative volume 60ml that concentration is 0.78mol/L to hydrogen peroxide at 0 ℃, sodium carbonate amount 1.5g, and A is 4: 6 than B mol ratio, the catalyst total concentration is 0.0042mol/L, experimentizes by above-mentioned steps.The results are shown in Table 2.
Embodiment 7
Other condition only changes catalyst concn into 0.0050mol/L with embodiment 6, the results are shown in Table 2.
Embodiment 8
Other condition only changes catalyst concn into 0.0067mol/L with embodiment 6, the results are shown in Table 2.
Embodiment 9
Other condition only changes catalyst concn into 0.0083mol/L with embodiment 6, the results are shown in Table 2.
Embodiment 10
With Na 2WO 42H 2O (A), KI (B) are made into the solution of 0.03mol/L separately.Hydrogen peroxide is made into the solution that concentration is 0.78mol/L, controls temperature at 0 ℃, sodium carbonate amount 1.5g, catalyst total mole number 0.0003mol, reaction system cumulative volume 60ml, A is 5: 5 than B mol ratio, experimentizes by above-mentioned steps.Tested the back and placed 30% the hydrogen peroxide that adds 2ml after 3 days again, but need not add catalyst, so repeated four times.The 1st, 5 time the results are shown in Table 3.
Embodiment 11
With Na 2WO 42H 2O (A), KI (B) are made into the solution of 0.025mol/L separately.The control temperature is made into the solution that concentration is 0.78mol/L to hydrogen peroxide at 0 ℃, catalyst total mole number 0.00025mol, and reaction system cumulative volume 60ml, A is 4: 6 than B mol ratio, sodium carbonate amount 0.5g (0.078mol/L) experimentizes by above-mentioned steps.The results are shown in Table 4.
Embodiment 12
Other condition only changes the sodium carbonate amount into 1.0g (0.156mol/L) and experimentizes with embodiment 11.The results are shown in Table 4.
Embodiment 13
Other condition only changes the sodium carbonate amount into 2.0g (0.312mol/L) and experimentizes with embodiment 11.The results are shown in Table 4.
Embodiment 14
Other condition only changes the sodium carbonate amount into 3.0g (0.468mol/L) and experimentizes with embodiment 11.The results are shown in Table 4.
Embodiment 15
Other condition only changes the sodium carbonate amount into 4.0g (0.630mol/L) and experimentizes with embodiment 11.The results are shown in Table 4.
Embodiment 16
Other condition only changes the sodium carbonate amount into 5.0g (0.780mol/L) and experimentizes with embodiment 11.The results are shown in Table 4.
Embodiment 17
With Na 2WO 42H 2O (A), KI (B) are made into the solution of 0.03mol/L separately.The control temperature is made into the solution that concentration is 0.78mol/L to hydrogen peroxide at 0 ℃, sodium carbonate amount 1.5g, and catalyst total mole number 0.0003mol, reaction system cumulative volume 60ml, A is 5: 5 than B mol ratio, experimentizes by above-mentioned steps.The results are shown in Table 5.
Comparative Examples 1
Commercially available oxygen is upright that oxygen release agent 2.1g is dissolved in the 50ml water, be stirred in 0 ℃ of following constant temperature, Na 2WO 42H 2O (A), KI (B) are made into the solution of 0.03mol/L separately.Control temperature at 0 ℃, catalyst total mole number 0.0003mol, A is 5: 5 than B mol ratio, experimentizes by above-mentioned steps.The results are shown in Table 5.
Comparative Examples 2
Other condition is with embodiment 1, and catalyst only adopts the identical A component of total mole number and embodiment 1, the results are shown in Table 6.
Comparative Examples 3
Other condition is with embodiment 1, and catalyst only adopts the identical B component of total mole number and embodiment 1, the results are shown in Table 6.
Embodiment 18
KI (B) is made into the solution of 0.03mol/L.Hydrogen peroxide is made into the solution that concentration is 0.78mol/L, controls temperature at 0 ℃, sodium carbonate amount 1.5g, reaction system cumulative volume 60ml, A adopt 0.05g peroxide sodium tungstate, and wherein the peroxide sodium tungstate is with reference to synthetic [(1) Shi Xiaobo of following document, Yue Bin, Lin Bingfa etc., WPTA-H 2O 2-KOH system prepares the research of peroxide potassium tungstate, SCI, 1993,14 (4): 450-453; (2) Lv Xilun, inorganic peroxy compounds chemistry, Beijing, Science Press, 1987:70-86].Experimentize by above-mentioned steps.The results are shown in Table 7.
Embodiment 19
KI (B) is made into the solution of 0.03mol/L.Hydrogen peroxide is made into the solution that concentration is 0.78mol/L, controls temperature at 0 ℃, sodium carbonate amount 1.5g, reaction system cumulative volume 60ml, A adopt 0.07g peroxide sodium tungstate, and wherein peroxide sodium tungstate reference example 18 described documents are synthetic.Experimentize by above-mentioned steps.The results are shown in Table 7.
Embodiment 20
With Na 2WO 42H 2O (A), be made into the solution of 0.03mol/L.Hydrogen peroxide is made into the solution that concentration is 0.78mol/L, sodium carbonate amount 1.5g, catalyst total mole number 0.0003mol, reaction system cumulative volume 60ml, B adopts the 0.0196g iodine, and A is that 5: 2.5 control temperature are at 0 ℃ than B mol ratio, experimentize by above-mentioned steps, the results are shown in Table 8.
Embodiment 21
With Na 2WO 42H 2O (A), KI (B) are made into the solution of 0.03mol/L separately.The control temperature is made into the solution that concentration is 0.78mol/L to hydrogen peroxide at 0 ℃, catalyst total mole number 0.0003mol, and reaction system cumulative volume 60ml, A is 5: 5 than B mol ratio, sodium metasilicate (NaSiO 39H 2O) 2g (0.128mol/L) experimentizes by above-mentioned steps.The results are shown in Table 9.
Embodiment 22
With Na 2WO 42H 2O (A), KI (B) are made into the solution of 0.03mol/L separately.The control temperature is made into the solution that concentration is 0.78mol/L to hydrogen peroxide at 0 ℃, catalyst total mole number 0.0003mol, and reaction system cumulative volume 60ml, A is 5: 5 than B mol ratio, hexamethylenetetramine 3g (0.357mol/L) experimentizes by above-mentioned steps.The results are shown in Table 10.
Embodiment 23
With Na 2WO 42H 2O (A), KI (B) are made into the solution of 0.03mol/L separately, and hydrogen peroxide is made into the solution that concentration is 0.78mol/L, and the control temperature is at 0 ℃, sodium carbonate amount 1.5g, catalyst total mole number 0.0003mol, reaction system cumulative volume 60ml, A is 98: 2 than B mol ratio, experimentizes by above-mentioned steps.The results are shown in Table 11.
Embodiment 24
With Na 2WO 42H 2O (A), KI (B) are made into the solution of 0.03mol/L separately, and hydrogen peroxide is made into the solution that concentration is 0.78mol/L, and the control temperature is at 0 ℃, sodium carbonate amount 1.5g, catalyst total mole number 0.0003mol, reaction system cumulative volume 60ml, A is 2: 98 than B mol ratio, experimentizes by above-mentioned steps.The results are shown in Table 12.
Table 1
Figure A20061016552100111
Table 2
Figure A20061016552100121
Table 3
Table 4
Figure A20061016552100141
37.0 3.32
38.0 2.93
39.0 2.76
40.0 2.46
41.0 2.13
42.0 1.94
43.0 1.61
44.0 1.33
45.0 1.05
46.0 0.91
Table 5
Figure A20061016552100151
Table 6
Table 7
Time/min Embodiment 18 Embodiment 19
1.0 15.14(ml) 20.58(ml)
2.0 17.36 24.36
3.0 17.22 23.65
4.0 16.51 23.18
5.0 16.65 22.00
6.0 15.42 21.76
7.0 15.33 20.34
8.0 15.14 18.45
9.0 15.61 17.98
10.0 13.72 13.72
11.0 13.25 11.35
12.0 13.25 7.57
13.0 10.88 4.26
14.0 10.41 2.84
15.0 8.51 1.66
16.0 7.33 1.18
17.0 4.97 0.57
18.0 3.31
19.0 1.89
20.0 1.42
21.0 0.95
Table 8
Time/min Embodiment 20
1.0 20.34
2.0 22.47
3.0 21.29
4.0 21.29
5.0 19.87
6.0 19.87
7.0 18.92
8.0 17.50
9.0 15.61
10.0 14.19
11.0 12.30
12.0 8.51
13.0 6.62
14.0 3.55
15.0 2.60
16.0 1.18
Table 9
Time/min Embodiment 21
1.0 14.66(ml)
2.0 15.37
3.0 15.85
4.0 15.37
5.0 14.43
6.0 14.19
7.0 12.54
8.0 11.59
9.0 9.93
10.0 7.57
11.0 5.68
12.0 4.49
13.0 3.55
14.0 3.07
15.0 2.60
16.0 1.89
17.0 1.66
18.0 1.51
19.0 1.42
20.0 1.18
21.0 1.00
Table 10
Time/min Embodiment 22
5.0 13.72(ml)
10.0 14.19
15.0 13.72
20.0 13.72
25.0 13.25
30.0 10.41
Table 11
Time/min Embodiment 23
5.0 8.57(ml)
10.0 9.62
15.0 9.52
20.0 9.62
25.0 9.52
30.0 9.71
Table 12
Time/min Embodiment 24
5.0 8.29(ml)
10.0 8.10
15.0 8.19
20.0 8.19
25.0 7.81
30.0 8.10

Claims (10)

1, a kind of homogeneous catalysis system of catalysis oxygen-releasing agent hydrogen peroxide decomposition, its composition comprises:
(1) oxyacid of VIb family metal, oxysalt or peroxy acid complex;
(2) iodine, hydroiodic acid or its salt;
(3) alkaline promoter comprises the salt or the organic base compounds of hydroxide, strong base weak acid;
Wherein (1) is 100: 1～1: 100 with the mol ratio of (2) two kinds of compositions, and the use amount of alkaline promoter is 0.001～10mol/L.
2, homogeneous catalysis system according to claim 1, oxyacid, oxysalt or the peroxy acid complex of wherein said VIb family metal are wolframic acid, tungstates, peroxide wolframic acid, peroxide tungstates or the compound that can generate the tungsten of peroxide wolframic acid with the hydrogen peroxide reaction.
3, homogeneous catalysis system according to claim 2, the oxysalt of wherein said VIb family metal is sodium tungstate or potassium tungstate.
4, homogeneous catalysis system according to claim 1, described hydriodate are sodium iodide or KI.
5, homogeneous catalysis system according to claim 1, wherein said alkaline promoter are potash, sodium carbonate, sodium metasilicate, potassium hydroxide or NaOH.
6, homogeneous catalysis system according to claim 5, wherein said alkaline promoter are sodium carbonate.
7, homogeneous catalysis system according to claim 1, wherein the use amount of alkaline promoter is 0.01～1mol/L.
8, homogeneous catalysis system according to claim 1, wherein (1) is 10: 1～1: 10 with the mol ratio of (2) two kinds of compositions.
9, homogeneous catalysis system according to claim 8, wherein (1) is 6: 4～4: 6 with the mol ratio of (2) two kinds of compositions.
10, the application of any one described homogeneous catalysis system of claim 1～9 in the catalysis oxygen-releasing agent hydrogen peroxide decomposes.
CN 200610165521 2006-12-21 2006-12-21 Homogenous catalyst system for catalyzing decomposition of oxygen-releasing agent hydrogen peroxide Expired - Fee Related CN1974003B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103539072A (en) * 2013-09-24 2014-01-29 苏州创科微电子材料有限公司 Method of preparing oxygen by efficiently catalyzing hydrogen peroxide by nanomaterial
CN104646021A (en) * 2015-01-20 2015-05-27 郑州轻工业学院 Ferroferric oxide/silica/manganese dioxide catalyst and preparation method thereof
CN106087014A (en) * 2016-08-26 2016-11-09 苏州顾氏新材料有限公司 A kind of method of nano composite alloy plated material efficient catalytic producing oxygen from hydrogen peroxide
TWI646055B (en) * 2017-11-27 2019-01-01 陳世雄 Method and apparatus for decomposition of hydrogen peroxide in waste acid solution by liquid catalyst coupled with photocatalytic reaction
CN110562928A (en) * 2019-09-18 2019-12-13 吉林大学 Method for preparing oxygen by catalyzing hydrogen peroxide with alkali

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5425892A (en) * 1977-07-29 1979-02-27 Wako Pure Chem Ind Ltd Quantitative determination of hydrogen peroxide

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103539072A (en) * 2013-09-24 2014-01-29 苏州创科微电子材料有限公司 Method of preparing oxygen by efficiently catalyzing hydrogen peroxide by nanomaterial
CN104646021A (en) * 2015-01-20 2015-05-27 郑州轻工业学院 Ferroferric oxide/silica/manganese dioxide catalyst and preparation method thereof
CN106087014A (en) * 2016-08-26 2016-11-09 苏州顾氏新材料有限公司 A kind of method of nano composite alloy plated material efficient catalytic producing oxygen from hydrogen peroxide
TWI646055B (en) * 2017-11-27 2019-01-01 陳世雄 Method and apparatus for decomposition of hydrogen peroxide in waste acid solution by liquid catalyst coupled with photocatalytic reaction
CN110562928A (en) * 2019-09-18 2019-12-13 吉林大学 Method for preparing oxygen by catalyzing hydrogen peroxide with alkali

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