CN105566091B - A kind of lead salicylate copper complex preparation method - Google Patents
A kind of lead salicylate copper complex preparation method Download PDFInfo
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- CN105566091B CN105566091B CN201510951859.5A CN201510951859A CN105566091B CN 105566091 B CN105566091 B CN 105566091B CN 201510951859 A CN201510951859 A CN 201510951859A CN 105566091 B CN105566091 B CN 105566091B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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 organic chemical industries to synthesize field, more particularly to a kind of lead salicylate copper complex preparation method, the preparation method is using sodium salicylate aqueous solution as substrate, polyacrylamide is auxiliary agent, under mechanical agitation and ultrasonic wave-coupled effect, equimolar mixed nitrate aqueous solution is added dropwise, waits for that reactant is precipitated, then rapid draing is heated through heating, reaction aging, centrifugation and microwave coupling steam, obtains uniform double-base rocket solid catalyst salicylic acid copper-lead.The present invention takes salicylic acid and the nitrate of lead, copper to be reacted for homogeneous precipitation agent in polyacrylamide；It is acted on using mechanical agitation and ultrasonic wave-coupled, avoids product precipitation and sandwich raw material or by-product sodium nitrate, keep product uniformly pure；Drying takes microwave coupling steam to heat rapid draing mode, avoids the drawbacks of traditional drying " tender in outer coke " causes nature difference inside and outside product；Using the copper-lead ratio of different proportion, a technique can obtain a series of catalyst of different properties.
Description
Technical field
The invention belongs to organic chemical industries to synthesize field, and in particular to a kind of lead salicylate copper complex preparation method.
Background technology
Lead salicylate copper complex double base propellant burningrate catalyst is that American-European countries's exploitation is simultaneously after the seventies in last century
One of the burningrate catalyst of propellant widely applied, of good performance.
It is reported that there are three types of synthetic methods for lead salicylate copper complex in the world：
1, solid powder oxides lead (oxidation lead and yellow-collation) and cupric oxide powder are suspended in water, under strong stirring, addition water
Poplar acid is heated to boiling reaction 24 hours or more.
2, two kinds of powder arts of lead oxide and basic copper carbonate (malachite green) are distributed in water, and salicylic acid strength is added portionwise and stirs
Heating is mixed 65.C reacts, until becoming uniform paste, filters to obtain finished product.
3, by water-soluble mantoquita and lead salt formation homogeneous phase solution soluble in water, salicylic acid is then added, after stirring evenly,
Heating, heating adjust pH with 20% aqueous solution of tertiary sodium phosphate, and after reaction, reaction solution is in fine particle shape unit for uniform suspension.
The product of filtering.
The Master's thesis of the Zhang Fuqiang of University Of Tianjin has studied the " burningrate catalyst of double base propellant -- copper-lead chelate
(CLCP) synthesis technology ", lead salicylate copper complex are one of them.Synthesis technology is in paper：：Copper nitrate, plumbi nitras
In aqueous solution with salicylism reaction 30 minutes, then with trisodium phosphate aqueous solution as chelatropic reaction pH adjusting agent, 80.
It when C pH=5.5, reacts 5 hours, obtains product through washing, dry, drying.The salicylic acid lead bronze of technical indicator qualification is obtained, is produced
Rate 94%.
The Hou Zhulin of Beijing Institute of Technology once studied the application of Cupric salicylate lead salt, the results showed that：To xLDB propellants,
Unitary lead salicylate is compounded with unitary Cupric salicylate, and the two ratio is 1.5：When 0.5, it can make xLDB that chaste tree pressure index be promoted to reduce
27.1%.
Xi'an 204 Li Jizhen etc. careful research was also once done to the application of salicylic acid copper-lead.
For the method for the present invention there is not yet document report, the application of ultrasonic wave, polyacrylamide makes that product particle is uniform, performance is steady
It is fixed；Microwave drying make product table area is big, surface will not coking, sampling obtained positive result.
Invention content
The present invention provides a kind of lead salicylate copper complex preparation method, using sodium salicylate aqueous solution as substrate, polypropylene
Amide is auxiliary agent, under mechanical agitation and ultrasonic wave-coupled effect, equimolar mixed nitrate aqueous solution is added dropwise, waits for reactant
It is precipitated, then heats rapid draing through heating, reaction aging, centrifugation and microwave coupling steam, it is solid to obtain uniform double-base rocket
Body catalyst salicylic acid copper-lead；When plumbi nitras, the variation of copper nitrate ratio, a series of performances due to lead bronze ratio changes are obtained not
Same catalyst.
The technical solution adopted by the present invention to solve the technical problems is：
A kind of lead salicylate copper complex preparation method, the described method comprises the following steps：
1) 1 mole of sodium salicylate is soluble in water, 50 ± 3 DEG C are heated to, filtering is spare；
2) n molar nitric acids lead and (1-n) molar nitric acid copper are dissolved in water, are heated to 45 ± 3 DEG C, filtering is spare, wherein 0<n
<1；
3) the sodium salicylate aqueous temperature that step 1) obtains is maintained 50 ± 3 DEG C, the mixing that step 2) obtains is added
Nitrate solution；
4) charging is finished, and is warming up to 85 ± 5 DEG C, reaction aging 4Hr；
5) 50 ± 5 DEG C are cooled to, centrifugal solid-liquid separation；
6) solid crude product is washed with 45-50 DEG C of deionized water to nitrate anion and is less than 3ppm, polyacrylamide inspection does not measure
Until；
7) after the heated drying of wet product, the rocket solid catalyst salicylic acid lead bronze that moisture is less than 0.05% is obtained.
As advanced optimizing, the sodium salicylate adds sodium hydrate aqueous solution to synthesize on the spot by salicylic acid.
As advanced optimizing, the adding procedure of mixed nitrate solution is in ultrasonic wave and mechanical agitation in the step 3)
It is carried out under coupling.
As advanced optimizing, reaction aging carries out under ultrasonic wave and mechanical agitation coupling in the step 4).
As advanced optimizing, cooling procedure carries out under ultrasonic wave and mechanical agitation coupling in the step 5).
As advanced optimizing, polypropylene of the deionized water containing 5-10ppm of reaction solution is prepared described in the step 6)
Amide.
As advanced optimizing, wet product heat drying method heats for microwave coupling steam in the step 8).
As advanced optimizing, described 0<n<1, when n changes, obtains a series of lead bronze ratios differences and performance is variant
Lead salicylate copper catalyst.
The device have the advantages that：
The present invention takes salicylic acid and the nitrate of lead, copper to be reacted for homogeneous precipitation agent in polyacrylamide；It utilizes
Mechanical agitation and ultrasonic wave-coupled effect avoid product precipitation and sandwich raw material or by-product sodium nitrate, keep product uniformly pure；
Drying takes microwave coupling steam to heat rapid draing mode, avoids traditional drying " tender in outer coke " and causes property inside and outside product
The drawbacks of difference；Using the copper-lead ratio of different proportion, a technique can obtain a series of catalyst of different properties.
Specific implementation mode
In order to make the content of present invention be easier and be expressly understood, below according to specific embodiment, the present invention is made into one
Step detailed description.
A kind of lead salicylate copper complex preparation method, using sodium salicylate aqueous solution as substrate, polyacrylamide is auxiliary agent,
Under mechanical agitation and ultrasonic wave-coupled effect, equimolar mixed nitrate aqueous solution is added dropwise, waits for that reactant is precipitated, then passes through
Heating, reaction aging, centrifugation and microwave coupling steam heat rapid draing, obtain uniform double-base rocket solid catalyst bigcatkin willow
Sour copper-lead；When plumbi nitras, the variation of copper nitrate ratio, a series of different catalyst of performance due to lead bronze ratio changes are obtained.
Embodiment 1：
1) 1 mole of sodium salicylate is soluble in water, 50 ± 3 DEG C are heated to, filtering is spare；
2) 0.5 molar nitric acid lead and 0.5 molar nitric acid copper are dissolved in water, are heated to 45 ± 3 DEG C, filtering is spare；
3) temperature for the sodium salicylate aqueous solution that step 1) obtains is maintained 50 ± 3 DEG C, in ultrasonic wave and mechanical agitation
Under coupling, the mixed nitrate solution of step 2) is added；
5) charging is finished, and is warming up to 85 ± 5 DEG C, the reaction aging 4Hr under ultrasonic wave and mechanical agitation coupling；
6) it is cooled to 50 ± 5 DEG C under ultrasonic wave and mechanical agitation coupling, centrifugal solid-liquid separation；
7) solid crude product with 45-50 DEG C of deionized water wash to nitrate anion be less than 3ppm, polyacrylamide inspection do not measure for
Only；
8) wet product obtains the rocket solid catalyst that moisture is less than 0.05% after microwave coupling steam heat drying：Water
Poplar acid lead bronze, yield 87%, lead bronze ratio are 1:1.
Embodiment 2：
1) 1 mole of sodium salicylate is soluble in water, 50 ± 3 DEG C are heated to, filtering is spare；
2) 0.9 molar nitric acid lead and 0.1 molar nitric acid copper are dissolved in water, are heated to 45 ± 3 DEG C, filtering is spare；
3) temperature for the sodium salicylate aqueous solution that step 1) obtains is maintained 50 ± 3 DEG C, in ultrasonic wave and mechanical agitation
Under coupling, the mixed nitrate solution of step 2) is added；
5) charging is finished, and is warming up to 85 ± 5 DEG C, the reaction aging 4Hr under ultrasonic wave and mechanical agitation coupling；
6) it is cooled to 50 ± 5 DEG C under ultrasonic wave and mechanical agitation coupling, centrifugal solid-liquid separation；
7) solid crude product with 45-50 DEG C of deionized water wash to nitrate anion be less than 3ppm, polyacrylamide inspection do not measure for
Only；
8) wet product obtains the rocket solid catalyst that moisture is less than 0.05% after microwave coupling steam heat drying：Water
Poplar acid lead bronze, yield 88%, lead bronze ratio are 9:1.
Embodiment 3：
1) 1 mole of sodium salicylate is soluble in water, 50 ± 3 DEG C are heated to, filtering is spare；
2) 0.4 molar nitric acid lead and 0.6 molar nitric acid copper are dissolved in water, are heated to 45 ± 3 DEG C, filtering is spare；
3) temperature for the sodium salicylate aqueous solution that step 1) obtains is maintained 50 ± 3 DEG C, in ultrasonic wave and mechanical agitation
Under coupling, the mixed nitrate solution of step 2) is added；
5) charging is finished, and is warming up to 85 ± 5 DEG C, the reaction aging 4Hr under ultrasonic wave and mechanical agitation coupling；
6) it is cooled to 50 ± 5 DEG C under ultrasonic wave and mechanical agitation coupling, centrifugal solid-liquid separation；
7) solid crude product with 45-50 DEG C of deionized water wash to nitrate anion be less than 3ppm, polyacrylamide inspection do not measure for
Only；
8) wet product obtains the rocket solid catalyst that moisture is less than 0.05% after microwave coupling steam heat drying：Water
Poplar acid lead bronze, yield 86.5%, lead bronze ratio are 2:3.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical solution and advantageous effect
It describes in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the guarantor of the present invention
Within the scope of shield.
Claims (3)
1. a kind of lead salicylate copper complex preparation method, which is characterized in that the described method comprises the following steps：
1) 1 mole of sodium salicylate is soluble in water, 50 ± 3 DEG C are heated to, filtering is spare；The sodium salicylate adds hydrogen by salicylic acid
Aqueous solution of sodium oxide synthesizes on the spot；
2) n molar nitric acids lead and (1-n) molar nitric acid copper are dissolved in water, are heated to 45 ± 3 DEG C, filtering is spare, wherein 0<n<1；
3) the sodium salicylate aqueous temperature that step 1) obtains is maintained 50 ± 3 DEG C, the mixed nitrate that step 2) obtains is added
The adding procedure of salting liquid, the mixed nitrate solution carries out under ultrasonic wave and mechanical agitation coupling；
4) charging is finished, and is warming up to 85 ± 5 DEG C, reaction aging 4Hr, reaction aging under ultrasonic wave and mechanical agitation coupling into
Row；
5) 50 ± 5 DEG C are cooled to, centrifugal solid-liquid separation, cooling procedure carries out under ultrasonic wave and mechanical agitation coupling；
6) solid crude product is washed with 45-50 DEG C of deionized water to nitrate anion and is less than 3ppm, until polyacrylamide inspection does not measure,
Prepare polyacrylamide of the deionized water containing 5-10ppm of reaction solution；
7) after the heated drying of wet product, the rocket solid catalyst salicylic acid lead bronze that moisture is less than 0.05% is obtained.
2. a kind of lead salicylate copper complex preparation method according to claim 1, it is characterised in that：In the step 7)
Wet product heat drying method heats for microwave coupling steam.
3. a kind of lead salicylate copper complex preparation method according to claim 1, it is characterised in that：Described 0<n<1, when
When n changes, a series of lead bronze ratios differences and the discrepant lead salicylate copper catalyst of performance are obtained.
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| US6024810A (en) * | 1998-10-06 | 2000-02-15 | Atlantic Research Corporation | Castable double base solid rocket propellant containing ballistic modifier pasted in an inert polymer |
| CN101642709B (en) * | 2008-08-04 | 2011-07-20 | 深圳大学 | CuO-PbO/carbon nano-tube composite powder and preparation method thereof |
| CN101711985A (en) * | 2008-10-06 | 2010-05-26 | 天津市化学试剂研究所 | Method for preparing copper-lead complex salt |
| CN102059142B (en) * | 2010-11-27 | 2012-07-25 | 中北大学 | Method for preparing copper plumbum chelate/mesoporous carbon composite material |
| CN102836733A (en) * | 2012-09-06 | 2012-12-26 | 南京理工大学 | Preparation method of energetic bimetallic nitro complex |
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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. |
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