CN1974002B - Homogeneous catalyst system for catalyzing decomposition of oxygen-releasing agent sodium percarbonate - Google Patents
Homogeneous catalyst system for catalyzing decomposition of oxygen-releasing agent sodium percarbonate Download PDFInfo
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- CN1974002B CN1974002B CN 200610165520 CN200610165520A CN1974002B CN 1974002 B CN1974002 B CN 1974002B CN 200610165520 CN200610165520 CN 200610165520 CN 200610165520 A CN200610165520 A CN 200610165520A CN 1974002 B CN1974002 B CN 1974002B
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- sodium percarbonate
- oxygen
- releasing agent
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Abstract
The homogeneous catalyst system for catalyzing decomposition of oxygen releasing agent sodium percarbonate includes oxo acid, oxo salt or peroxy acid complex of VIb metal, and iodine, hydroiodic acid or its salt. The composite catalyst system is used in the decomposition of oxygen releasing agent sodium percarbonate 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
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 sodium percarbonate decomposes.
Technical background
SODIUM PERCARBONATE has good oxygen release effect as a kind of solid oxidizer, because its environment amenable characteristic is generally paid attention in recent years.
Simple is the interested problem of scientific worker with KI as the catalyst decomposes 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, the mechanism of KI decomposition of hydrogen peroxide and a little phenomena of course of reaction appearance are studied.
Forefathers have studied the catalyticing decomposition action that arrives the oxygen release agent hydrogen peroxide of various catalyst liquid towardses under the alkalescent situation in acidity mostly, 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 these two kinds of catalyst unexpectedly as composite catalyst, is used for the catalyst that the solid oxygen-releasing agent sodium percarbonate decomposes, and has obtained beyond thought effect.The catalytic activity height, oxygen release is steady, and catalyst system 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 catalyst system that a kind of catalysis oxygen-releasing agent sodium percarbonate 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.
The mol ratio of (1) and (2) two kinds of catalytic components is 100: 1～1: 100 in the catalyst system, be preferably 10: 1～1: 10 with 6: 4～4: 6 for good;
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
Experimental procedure: 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 catalyst and decomposed the O that SODIUM PERCARBONATE discharges
2Volume, during experiment earlier with catalyst, SODIUM PERCARBONATE, be made into certain density solution.The SODIUM PERCARBONATE of getting 50ml water, certain mass during reaction places 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 SODIUM PERCARBONATE by eudiometer tube and decompose the oxygen amount Vt that emits with stopwatch.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 0.03mol/L separately. Control temperature at 0 ℃, SODIUM PERCARBONATE amount 2.0g, catalyst total mole number 0.0003mol, 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
Control temperature at 0 ℃,, SODIUM PERCARBONATE 2.0g, reaction system cumulative volume 60ml, 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.The control temperature is at 0 ℃,, SODIUM PERCARBONATE amount 1.0g, 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 3.
Embodiment 11
Other condition only changes the SODIUM PERCARBONATE amount into 4.0g with embodiment 10, experimentizes by above-mentioned steps, the results are shown in Table 3.
Embodiment 12
With Na
2WO
42H
2O (A), KI (B) are made into the solution of 0.03mol/L separately.Control temperature at 10 ℃, SODIUM PERCARBONATE amount 2.0g, 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 4.
Embodiment 13
Other condition only changes reaction temperature into 20 ℃ with embodiment 12, experimentizes by above-mentioned steps, the results are shown in Table 4.
Embodiment 14
Other condition only changes reaction temperature into 30 ℃ with embodiment 12, experimentizes by above-mentioned steps, the results are shown in Table 4.
Embodiment 15
Other condition only changes reaction temperature into 40 ℃ with embodiment 12, experimentizes by above-mentioned steps, the results are shown in Table 4.
Embodiment 16
With Na
2WO
42H
2O (A), NaI (B) are made into the solution of 0.03mol/L separately.Control temperature at 0 ℃, SODIUM PERCARBONATE amount 2.0g, 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.
Embodiment 17
With Na
2WO
42H
2O (A), be made into the solution of 0.03mol/L.Control temperature at 0 ℃, SODIUM PERCARBONATE amount 2.0g, catalyst total mole number 0.0003mol, reaction system cumulative volume 60ml, B adopts the 0.0196g iodine, and A is 5: 2.5 than B mol ratio, experimentizes by above-mentioned steps, the results are shown in Table 5.
Comparative Examples 1
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 2
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
Adopt catalyst total amount 0.3g of the present invention in the system of 60ml, catalyst A and B mass ratio 2: 1 are under natural room temperature, no constant temperature do not have to stir, and catalysis 2g oxygen is upright as to carry the oxygen release agent, place and need not add catalyst again after 7 days, it is upright as to carry the oxygen release agent to continue catalysis 2g oxygen, so repeats four times.With the 1st time, the 2nd time, the results are shown in the table 7 of the 5th.
Comparative Examples 3
In the system of 60ml, adopt commercially available oxygen upright catalyst 0.3g, under natural room temperature, no constant temperature does not have and stirs, catalysis 2g oxygen is upright as to carry the oxygen release agent, places and need not add catalyst again after 7 days, continuation catalysis 2g oxygen stands to such an extent that carry the oxygen release agent, so repeats four times.With the 1st time, the 2nd time, the results are shown in the table 7 of the 5th.
Embodiment 19
KI (B) is made into the solution of 0.03mol/L.Control temperature at 0 ℃, SODIUM PERCARBONATE amount 2.0g, reaction system cumulative volume 60ml, A adopt 0.05g peroxide sodium tungstate, and the peroxide sodium tungstate is with reference to following document synthetic [(1) Shi Xiaobo, 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 8.
Embodiment 20
KI (B) is made into the solution of 0.03mol/L.Control temperature at 0 ℃, SODIUM PERCARBONATE amount 2.0g, reaction system cumulative volume 60ml, A adopt 0.07g peroxide sodium tungstate, and peroxide sodium tungstate reference example 19 documents are synthetic, 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,, control temperature at 0 ℃, SODIUM PERCARBONATE 2.0g, 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 9.
Embodiment 22
With Na
2WO
42H
2O (A), KI (B) are made into the solution of 0.03mol/L separately,, control temperature at 0 ℃, SODIUM PERCARBONATE 2.0g, 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 10.
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
Table 8
| Time/min | Embodiment 19 | Embodiment 20 |
| 1.0 | 13.25(ml) | 19.87(ml) |
| 2.0 | 14.62 | 21.29 |
| 3.0 | 13.53 | 21.29 |
| Time/min | Embodiment 19 | Embodiment 20 |
| 4.0 | 14.43 | 20.20 |
| 5.0 | 13.48 | 19.06 |
| 6.0 | 13.25 | 17.98 |
| 7.0 | 12.06 | 17.98 |
| 8.0 | 12.68 | 15.86 |
| 9.0 | 11.45 | 13.01 |
| 10.0 | 10.88 | 10.64 |
| 11.0 | 10.88 | 7.33 |
| 12.0 | 9.46 | 4.97 |
| 13.0 | 8.51 | 3.07 |
| 14.0 | 7.57 | 1.89 |
| 15.0 | 6.15 | 1.42 |
| 16.0 | 4.73 | 0.95 |
| 17.0 | 2.84 | |
| 18.0 | 2.60 | |
| 19.0 | 1.66 | |
| 20.0 | 1.18 | |
| 21.0 | 0.90 |
Table 9
| Time/min | Embodiment 21 |
| 5.0 | 7.81(ml) |
| 10.0 | 8.67 |
| 15.0 | 8.67 |
| 20.0 | 9.14 |
| 25.0 | 8.86 |
| 30.0 | 8.95 |
Table 10
| Time/min | Embodiment 22 |
| 5.0 | 5.43(ml) |
| 10.0 | 7.14 |
| 15.0 | 7.14 |
| 20.0 | 6.95 |
| 25.0 | 7.05 |
| 30.0 | 6.95 |
Claims (5)
1. the homogeneous catalyst that decomposes of a catalysis oxygen-releasing agent sodium percarbonate, form by (1) and (2) two components:
(1) oxyacid of group vib metal, oxysalt or peroxy acid complex;
(2) iodine, hydroiodic acid or its salt;
Wherein (1) is 6: 4～4: 6 with the mol ratio of (2) two kinds of compositions.
2. homogeneous catalyst according to claim 1, the oxyacid of wherein said group vib metal, oxysalt or peroxy acid complex are wolframic acid, tungstates, peroxide wolframic acid or peroxide tungstates.
3. homogeneous catalyst according to claim 2, the oxysalt of wherein said group vib metal are sodium tungstate or potassium tungstate.
4. homogeneous catalyst according to claim 1, described hydriodate are sodium iodide or KI.
5. the application of any one described homogeneous catalyst of claim 1～4 in the catalysis oxygen-releasing agent sodium percarbonate decomposes.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220332576A1 (en) * | 2021-04-16 | 2022-10-20 | The United States Of America, As Represented By The Secretary Of The Navy | Apparatus and Method for Generating Oxygen from Sodium Percarbonate and Water, Including Seawater |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4251629A (en) * | 1977-07-29 | 1981-02-17 | Wako Pure Chemical Industries, Ltd. | Determination of hydrogen peroxide |
-
2006
- 2006-12-21 CN CN 200610165520 patent/CN1974002B/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4251629A (en) * | 1977-07-29 | 1981-02-17 | Wako Pure Chemical Industries, Ltd. | Determination of hydrogen peroxide |
Non-Patent Citations (5)
| Title |
|---|
| JP昭60-84239A 1985.05.13 |
| 向明礼等.对"过氧化氢碘化钾催化分解"催化概念的质疑.西南民族学院学报·自然科学版29 1.2003,29(1),41-44. |
| 向明礼等.对"过氧化氢碘化钾催化分解"催化概念的质疑.西南民族学院学报·自然科学版29 1.2003,29(1),41-44. * |
| 吴洪达等.过氧化氢的分解反应.河池师专学报（自然科学版）22 2.2003,22(2),27-30. |
| 吴洪达等.过氧化氢的分解反应.河池师专学报(自然科学版)22 2.2003,22(2),27-30. * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220332576A1 (en) * | 2021-04-16 | 2022-10-20 | The United States Of America, As Represented By The Secretary Of The Navy | Apparatus and Method for Generating Oxygen from Sodium Percarbonate and Water, Including Seawater |
| US11845656B2 (en) * | 2021-04-16 | 2023-12-19 | United States Of America As Represented By The Secretary Of The Navy | Apparatus and method for generating oxygen from sodium percarbonate and water, including seawater |
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