CN105566091A - Preparation method of copper lead salicylate complex - Google Patents
Preparation method of copper lead salicylate complex Download PDFInfo
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- CN105566091A CN105566091A CN201510951859.5A CN201510951859A CN105566091A CN 105566091 A CN105566091 A CN 105566091A CN 201510951859 A CN201510951859 A CN 201510951859A CN 105566091 A CN105566091 A CN 105566091A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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Abstract
The invention belongs to the field of organic chemical industry synthesis, and particularly relates to a preparation method of copper lead salicylate, which comprises the following steps: by using a sodium salicylate water solution as a substrate and polyacrylamide as an assistant, dropwisely adding an equal mole of nitrate mixed water solution under the coupled actions of mechanical stirring and ultrasonic until the reaction product precipitates, heating, reacting, aging, centrifugating, and carrying out quick drying by microwave coupled steam heating to obtain the uniform double-base propellant solid catalyst copper lead salicylate. According to the method, the salicylic acid and nitrates of lead and copper react by using the polyacrylamide as a homogeneous precipitant; the coupled actions of mechanical stirring and ultrasonic are utilized to prevent the product precipitate from wrapping the raw material or byproduct sodium nitrate, so that the product is uniform and pure; the quick drying mode of microwave coupled steam heating is adopted for drying, thereby avoiding the defect of different internal and external properties of the product due to the charred outside and tender inside in the traditional drying; and by adopting different copper/lead proportions, one technique can be utilized to obtain a series of catalysts with different properties.
Description
Technical field
The invention belongs to organic chemical industry and synthesize field, be specifically related to a kind of lead salicylate copper complex preparation method.
Background technology
Lead salicylate copper complex double-base propellent burningrate catalyst is one of burningrate catalyst of American-European countries's exploitation also widespread use, propelling agent of good performance after the seventies in last century.
It is reported, lead salicylate copper complex has three kinds of synthetic methods in the world:
1, pressed powder oxides lead (oxidation lead and yellow-collation) and cupric oxide powder are suspended in water, under strong stirring, add Whitfield's ointment and are heated to reaction more than 24 hours of boiling.
2, plumbous oxide and ventilation breather (malachite green) two kinds of powder arts are distributed in water, add the heating of Whitfield's ointment strong stirring 65 in batches.C reacts, until become homogeneous mashed prod, filters to obtain finished product.
3, by water miscible mantoquita and lead salt formation homogeneous phase solution soluble in water, then Whitfield's ointment is added, after stirring, heating, intensification. regulate pH with tertiary sodium phosphate 20% aqueous solution, after reaction terminates, reaction solution is fine particle shape unit for uniform suspension.The product filtered.
The Master's thesis of the Zhang Fuqiang of University Of Tianjin have studied " burningrate catalyst of double-base propellent--the synthesis technique of copper-lead inner complex (CLCP) ", and lead salicylate copper complex is one of them.In paper, synthesis technique is:: cupric nitrate, lead nitrate in aqueous with salicylism reaction 30 minutes, then with trisodium phosphate aqueous solution as chelatropic reaction pH value regulator, 80.During CpH=5.5, react 5 hours, obtain product through washing, dry, dry.Obtain the Whitfield's ointment lead bronze that technical indicator is qualified, productive rate 94%.
The Hou Zhulin of Beijing Institute of Technology once studied the application of Cupric salicylate lead salt, and result shows: to xLDB propelling agent, unitary lead salicylate and unitary Cupric salicylate composite, when the two ratio is 1.5:0.5, xLDB can be made to advance chaste tree pressure index to reduce by 27.1%.
Xi'an 204 Li Jizhen etc. should be used as the meticulous research caused also once to Whitfield's ointment copper-lead.
The inventive method there is not yet bibliographical information, the application of ultrasonic wave, polyacrylamide make product particle evenly, stable performance; Microwave drying makes that product surface is long-pending large, surface can not coking, and sampling obtains the result in front.
Summary of the invention
The invention provides a kind of lead salicylate copper complex preparation method, with the sodium salicylate aqueous solution for substrate, polyacrylamide is auxiliary agent, under mechanical stirring and ultrasonic wave-coupled effect, drip equimolar mixed nitrate aqueous solution, question response thing is separated out, and then through intensification, reaction aging, centrifugal and microwave coupling steam heating rapid drying, obtains uniform double-base rocket solid catalyst Whitfield's ointment copper-lead; When lead nitrate, the change of cupric nitrate ratio, obtain a series of catalyzer that performance is different because of the change of lead bronze ratio.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of lead salicylate copper complex preparation method, said method comprising the steps of:
1) by soluble in water for 1 mole of water poplar acid sodium, be heated to 50 ± 3 DEG C, filter for subsequent use;
2) by plumbous for n molar nitric acid water-soluble with (1-n) molar nitric acid copper, be heated to 45 ± 3 DEG C, filter for subsequent use, wherein 0<n<1;
3) by step 1) the sodium salicylate aqueous temperature that obtains maintains 50 ± 3 DEG C, adds step 2) mixed nitrate solution that obtains;
4) reinforced complete, be warming up to 85 ± 5 DEG C, reaction aging 4Hr;
5) be cooled to 50 ± 5 DEG C, centrifugal solid-liquid is separated;
6) solid crude product 45-50 DEG C of deionized water wash is less than 3ppm to nitrate radical, till polyacrylamide inspection does not measure;
7) wet product is after heat drying, obtain moisture lower than 0.05% rocket solid catalyzer Whitfield's ointment lead bronze.
As further optimization, described sodium salicylate is synthesized then and there by Whitfield's ointment hydro-oxidation sodium water solution.
As further optimization, described step 3) in the adding procedure of mixed nitrate solution carry out under ultrasonic wave and mechanical stirring coupling.
As further optimization, described step 4) in reaction aging carry out under ultrasonic wave and mechanical stirring coupling.
As further optimization, described step 5) in process of cooling carry out under ultrasonic wave and mechanical stirring coupling.
As further optimization, described step 6) described in prepare the polyacrylamide of deionized water containing 5-10ppm of reaction solution.
As further optimization, described step 8) in wet product heat drying mode be microwave coupling steam heating.
As further optimization, described 0<n<1, when n changes, obtains a series of lead bronze ratio difference and the discrepant lead salicylate copper catalyst of performance.
The beneficial effect that the present invention has:
The present invention takes Whitfield's ointment and nitrate that is plumbous, copper to be that precipitation from homogeneous solution agent is reacted at polyacrylamide; Utilize mechanical stirring and ultrasonic wave-coupled effect, avoid product precipitation and sandwich raw material or by product SODIUMNITRATE, make product evenly pure; Microwave coupling steam heating rapid drying mode is taked in oven dry, avoids the drawback that traditional drying " outer burnt interior tender " causes nature difference inside and outside product; Adopt the copper-lead ratio of different ratios, a technique can obtain the catalyzer of a series of different properties.
Embodiment
In order to make content of the present invention more easily and be expressly understood, below according to specific embodiment, the present invention is further detailed explanation.
A kind of lead salicylate copper complex preparation method, with the sodium salicylate aqueous solution for substrate, polyacrylamide is auxiliary agent, under mechanical stirring and ultrasonic wave-coupled effect, drip equimolar mixed nitrate aqueous solution, question response thing is separated out, and then through intensification, reaction aging, centrifugal and microwave coupling steam heating rapid drying, obtains uniform double-base rocket solid catalyst Whitfield's ointment copper-lead; When lead nitrate, the change of cupric nitrate ratio, obtain a series of catalyzer that performance is different because of the change of lead bronze ratio.
Embodiment 1:
1) by soluble in water for 1 mole of water poplar acid sodium, be heated to 50 ± 3 DEG C, filter for subsequent use;
2) by plumbous for 0.5 molar nitric acid and 0.5 molar nitric acid copper is water-soluble, be heated to 45 ± 3 DEG C, filter for subsequent use;
3) by step 1) temperature of the sodium salicylate aqueous solution that obtains maintains 50 ± 3 DEG C, under ultrasonic wave and mechanical stirring coupling, adds step 2) mixed nitrate solution;
5) reinforced complete, be warming up to 85 ± 5 DEG C, reaction aging 4Hr under ultrasonic wave and mechanical stirring coupling;
6) under ultrasonic wave and mechanical stirring coupling, be chilled to 50 ± 5 DEG C, centrifugal solid-liquid is separated;
7) solid crude product 45-50 DEG C of deionized water wash is less than 3ppm to nitrate radical, till polyacrylamide inspection does not measure;
8) wet product is after the drying of microwave coupling steam heating, obtain moisture lower than 0.05% rocket solid catalyzer: Whitfield's ointment lead bronze, yield 87%, lead bronze is than for 1:1.
Embodiment 2:
1) by soluble in water for 1 mole of water poplar acid sodium, be heated to 50 ± 3 DEG C, filter for subsequent use;
2) by plumbous for 0.9 molar nitric acid and 0.1 molar nitric acid copper is water-soluble, be heated to 45 ± 3 DEG C, filter for subsequent use;
3) by step 1) temperature of the sodium salicylate aqueous solution that obtains maintains 50 ± 3 DEG C, under ultrasonic wave and mechanical stirring coupling, adds step 2) mixed nitrate solution;
5) reinforced complete, be warming up to 85 ± 5 DEG C, reaction aging 4Hr under ultrasonic wave and mechanical stirring coupling;
6) under ultrasonic wave and mechanical stirring coupling, be chilled to 50 ± 5 DEG C, centrifugal solid-liquid is separated;
7) solid crude product 45-50 DEG C of deionized water wash is less than 3ppm to nitrate radical, till polyacrylamide inspection does not measure;
8) wet product is after the drying of microwave coupling steam heating, obtain moisture lower than 0.05% rocket solid catalyzer: Whitfield's ointment lead bronze, yield 88%, lead bronze is than for 9:1.
Embodiment 3:
1) by soluble in water for 1 mole of water poplar acid sodium, be heated to 50 ± 3 DEG C, filter for subsequent use;
2) by plumbous for 0.4 molar nitric acid and 0.6 molar nitric acid copper is water-soluble, be heated to 45 ± 3 DEG C, filter for subsequent use;
3) by step 1) temperature of the sodium salicylate aqueous solution that obtains maintains 50 ± 3 DEG C, under ultrasonic wave and mechanical stirring coupling, adds step 2) mixed nitrate solution;
5) reinforced complete, be warming up to 85 ± 5 DEG C, reaction aging 4Hr under ultrasonic wave and mechanical stirring coupling;
6) under ultrasonic wave and mechanical stirring coupling, be chilled to 50 ± 5 DEG C, centrifugal solid-liquid is separated;
7) solid crude product 45-50 DEG C of deionized water wash is less than 3ppm to nitrate radical, till polyacrylamide inspection does not measure;
8) wet product is after the drying of microwave coupling steam heating, obtain moisture lower than 0.05% rocket solid catalyzer: Whitfield's ointment lead bronze, yield 86.5%, lead bronze is than for 2:3.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. a lead salicylate copper complex preparation method, is characterized in that, said method comprising the steps of:
1) by soluble in water for 1 mole of water poplar acid sodium, be heated to 50 ± 3 DEG C, filter for subsequent use;
2) by plumbous for n molar nitric acid water-soluble with (1-n) molar nitric acid copper, be heated to 45 ± 3 DEG C, filter for subsequent use, wherein 0<n<1;
3) by step 1) the sodium salicylate aqueous temperature that obtains maintains 50 ± 3 DEG C, adds step 2) mixed nitrate solution that obtains;
4) reinforced complete, be warming up to 85 ± 5 DEG C, reaction aging 4Hr;
5) be cooled to 50 ± 5 DEG C, centrifugal solid-liquid is separated;
6) solid crude product 45-50 DEG C of deionized water wash is less than 3ppm to nitrate radical, till polyacrylamide inspection does not measure;
7) wet product is after heat drying, obtain moisture lower than 0.05% rocket solid catalyzer Whitfield's ointment lead bronze.
2. a kind of lead salicylate copper complex preparation method according to claim 1, is characterized in that: described sodium salicylate is synthesized then and there by Whitfield's ointment hydro-oxidation sodium water solution.
3. a kind of lead salicylate copper complex preparation method according to claim 1, is characterized in that: described step 3) in the adding procedure of mixed nitrate solution carry out under ultrasonic wave and mechanical stirring coupling.
4. a kind of lead salicylate copper complex preparation method according to claim 1, is characterized in that: described step 4) in reaction aging carry out under ultrasonic wave and mechanical stirring coupling.
5. a kind of lead salicylate copper complex preparation method according to claim 1, is characterized in that: described step 5) in process of cooling carry out under ultrasonic wave and mechanical stirring coupling.
6. a kind of lead salicylate copper complex preparation method according to claim 1, is characterized in that: described step 6) described in prepare reaction solution deionized water containing the polyacrylamide of 5-10ppm.
7. a kind of lead salicylate copper complex preparation method according to claim 1, is characterized in that: described step 8) in wet product heat drying mode be microwave coupling steam heating.
8. a kind of lead salicylate copper complex preparation method according to claim 1, it is characterized in that: described 0<n<1, when n changes, obtain a series of lead bronze ratio difference and the discrepant lead salicylate copper catalyst of performance.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106311325A (en) * | 2016-08-09 | 2017-01-11 | 山西北方兴安化学工业有限公司 | Preparation method of lead tannin catalyst |
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Cited By (1)
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| CN106311325A (en) * | 2016-08-09 | 2017-01-11 | 山西北方兴安化学工业有限公司 | Preparation method of lead tannin catalyst |
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Effective date of registration: 20190514 Address after: No. 1600 Yuegong Road, Jinshan District, Shanghai, 201507 Patentee after: Shanghai Wokai Biotechnology Co., Ltd. Address before: 200072 No. 801 Hutai Road, Zhabei District, Shanghai Patentee before: Sinopharm Chemical Reagent Co., Ltd. |