CN102659162A - Method for preparing calcium bromide through using tetrabutylammonium bromide crystallization mother solution - Google Patents
Method for preparing calcium bromide through using tetrabutylammonium bromide crystallization mother solution Download PDFInfo
- Publication number
- CN102659162A CN102659162A CN2012101002698A CN201210100269A CN102659162A CN 102659162 A CN102659162 A CN 102659162A CN 2012101002698 A CN2012101002698 A CN 2012101002698A CN 201210100269 A CN201210100269 A CN 201210100269A CN 102659162 A CN102659162 A CN 102659162A
- Authority
- CN
- China
- Prior art keywords
- bromide
- mother solution
- calcium bromide
- tetrabutyl amonium
- calcium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
A method for producing calcium bromide through using a tetrabutylammonium bromide crystallization mother solution can improve the resource utilization rate. The method comprises the following processes: adding the tetrabutylammonium bromide crystallization mother solution and a catalyst to a reactor according to a mass ratio of 10-100:0.001-600, stirring, reacting at -10-320DEG C for 0.05-20h, and carrying out reduced pressure distillation, wherein the catalyst is composed of Al2O3, SiO2, CaSO4, CaO, CaCO3, Ca(OH)2, graphite, active carbon and fluorite; adding water to residual materials after the reduced pressure distillation according to a mass ratio of the tetrabutylammonium bromide crystallization mother solution to water of 1-100:1-500, stirring at 20-120DEG C for 0.1-10h, and separating to obtain a primary filtrate containing calcium bromide; adding active carbon and/or atlapulgite to the primary filtrate containing calcium bromide to decolor, filtering or centrifugalizing to obtain a secondary filtrate containing calcium bromide, and carrying out evaporative concentration, cooling crystallization, filtering or centrifugalizing, and vacuum drying to obtain calcium bromide products containing above 98% by mass of calcium bromide, which has a yield of 5-60% of the mass of the tetrabutylammonium bromide crystallization mother solution.
Description
Technical field
A kind of method of utilizing the Tetrabutyl amonium bromide crystalline mother solution to prepare Calcium Bromide involved in the present invention is industry disposal of waste gas, water and industrial residue of environmental chemical engineering field and the efficient method of utilizing of a kind of novel chemical by-product resource utilization of utilizing the aspect.
Background technology
Tetrabutyl amonium bromide has good phase-transfer catalysis performance as a kind of quaternary ammonium salt cationic surfactant, in Fine Organic Chemical article such as aldehyde, ketone, ester, ether and carboxylic acid synthetic, is widely used.Utilize the catalyzer of Tetrabutyl amonium bromide, not only can improve the condition and the yield that improves product of reaction, but also the reaction that can make some be difficult under normal operation carry out is accomplished smoothly as heterogeneous reaction system.As under alkaline condition, being catalyzer, can realize Resorcinol and epichlorohydrin reaction and generate the Resorcinol diglycidylether with the Tetrabutyl amonium bromide; In the presence of sodium hydroxide, Tetrabutyl amonium bromide can catalysis methanol and the 1 reaction generate triethyl orthoformate; In cardiovascular new drug pentoxifylline synthetic, use Tetrabutyl amonium bromide as phase-transfer catalyst, not only product yield is much higher than the yield of the non-phase-transfer catalyst operational path of present domestic employing, and reaction conditions also is further improved.
The synthetic of Tetrabutyl amonium bromide generally is in ethanol, acetonitrile isopolarity solvent; Generate the feed liquid that contains Tetrabutyl amonium bromide earlier through Tributylamine and positive NBB direct reaction; Then through distillating recovering solvent and unreacted Tributylamine and positive NBB; Obtain the Tetrabutyl amonium bromide wet stock through cooling or freezing and crystallizing, filtration or spinning, recrystallization again, at last the Tetrabutyl amonium bromide wet stock that obtains is carried out vacuum-drying to obtain the Tetrabutyl amonium bromide product.In the technology of this preparation Tetrabutyl amonium bromide, a large amount of crystalline mother solutions that contains Tetrabutyl amonium bromide and a small amount of positive NBB and Tributylamine is arranged.Because this crystalline mother solution is difficult to reclaim Tetrabutyl amonium bromide product wherein through direct spissated method, thereby being utilized in of it still is on the lower level now.How to realize the higher value application of Tetrabutyl amonium bromide crystalline mother solution better, be the problem that people are concerned about always.
Calcium Bromide is crystallization of a kind of colourless oblique policy shape or crystal block, odorless, and it is salty and bitter to distinguish the flavor of, and very strong water absorbability is arranged, and can be used for treating diseases such as epilepsy, tetany, at sea also is widely used in the oil production.Calcium Bromide is very easily water-soluble, and the aqueous solution that water-soluble back generates manifests neutrality; Calcium Bromide also has certain solubility in ethanol, acetone and acid, but is slightly soluble in methyl alcohol, liquefied ammonia, and is insoluble to ether or chloroform.Calcium Bromide can form double salt with alkali metal halide.Calcium Bromide can be through the preparation of ferrous bromide method, and its process is following: iron filings are joined in the reactor drum that fills water, under agitation add bromine more in batches, under 40 ℃, react the generation ferrous bromide then; With the calcium hydroxide adjust pH to alkalescence and be heated to and boil; Remove ferrous hydroxide through cooling, separation then; Filtrating is left standstill generation Calcium Bromide bullion through evaporating, be cooled to 30 ℃, and the Calcium Bromide bullion that obtains can obtain Calcium Bromide through decolouring, filtration, evaporation concentration, crystallisation by cooling again.Prepare Calcium Bromide by this method and need consume a large amount of bromines.Owing to contain a large amount of bromine negative ions in the Tetrabutyl amonium bromide crystalline mother solution, therefore utilize the Tetrabutyl amonium bromide crystalline mother solution can prepare Calcium Bromide.
Utilizing the Tetrabutyl amonium bromide crystalline mother solution to prepare in the research process of Calcium Bromide; A lot of technical information have been contacted about Tetrabutyl amonium bromide preparation and application facet; Wherein have mainly comprising of certain reference value: " synthesizing of phase-transfer catalyst Tetrabutyl amonium bromide and benzyltriethylammoinium chloride " (Soviet Union's salt science and technology; 2006 the 2nd phases), " Tetrabutyl amonium bromide building-up reactions dynamics research " (Beijing Union University's journal; 1994 the 4th phases), " synthesizing of Tetrabutyl amonium bromide " (Henan Medical Univ.'s journal; 1994 the 3rd phases), " the synthetic improvement of tetra-n-butyl ammonium bromide " (Liaoning chemical industry; 1999 the 4th phases), " the big monomer of quaternary ammonium salt catalysis synthetic end allyl group polyoxyalkylene " (applied chemistry; 1994 the 3rd phases), " preparation of Tetrabutyl amonium bromide and 4-butyl ammonium hydrogen sulfate " (chemical reagent, 1997 the 3rd phases), " Electrolyte-Solvent Interaction.I.Tetrabutylammonium Bromide in Methanol-Nitrobenzene Mixtures " (J.Am.Chem.Soc., the 1st phase of nineteen fifty), " study on the synthesis of Resorcinol diglycidylether " (meticulous and specialty chemicals; 2010 the 10th phases), " trimethyl orthoacetate is synthesized in phase transfer method catalysis " (Tianjin chemical industry, 2003 the 6th phases); " novel method-urea reduction method of Calcium Bromide preparation " (dimension mill College of Education journal, 1996 the 3rd phases); " producing the discussion of Calcium Bromide by the elementary bromine absorption process " (Soviet Union's salt science and technology, 2000 the 1st phases).
Summary of the invention
A kind of invention that utilizes the Tetrabutyl amonium bromide crystalline mother solution to prepare the method for Calcium Bromide; Mainly be in order to realize that with the Tetrabutyl amonium bromide crystalline mother solution be the inorganic fine chemicals Calcium Bromide of basic raw material preparation production; Thereby improve the preparation cost of efficiency of resource, reduction Tetrabutyl amonium bromide, reduce the pollution of chemical industry " three wastes " environment.
Technical scheme of the present invention is: utilize catalyzer to promote that under hot conditions the Tetrabutyl amonium bromide that is present in the Tetrabutyl amonium bromide crystalline mother solution is decomposed into organic cpds such as Tributylamine, butylene, butanols, and obtain containing the mixture of Tributylamine through underpressure distillation; After underpressure distillation, remain in adding zero(ppm) water or deionized water in the material in the reactor drum then, and heated and stirred; Last warp successively filters or spinning obtains containing solution, activated carbon and/or activated decoloration, filtration or spinning, evaporation concentration, crystallisation by cooling, filtration or spinning, the vacuum-drying of Calcium Bromide, and obtains the Calcium Bromide product.
The Tetrabutyl amonium bromide crystalline mother solution with by aluminium sesquioxide, silicon-dioxide, calcium sulfate, quicklime, lime carbonate, calcium hydroxide, Graphite Powder 99, gac, fluorite by mass ratio 0.001～100: 0.001～100: 0.001～100: 0.001～100: 0.001～100: 0.001～100: 0.001～100: 0.001～100: 0.001～300 catalyzer that constitutes is by mass ratio 10～100: 0.001～600 joins in the reactor drum, stirs also and under-10 ℃～320 ℃, reacts 0.05～20 hour; In vacuum tightness is that 0.001～100kPa, temperature are under 10 ℃～360 ℃ the condition reacting rear material to be carried out underpressure distillation to obtain containing the distillate of Tributylamine; After underpressure distillation, remain in the material in the reactor drum mass ratio by Tetrabutyl amonium bromide crystalline mother solution and water and be 1～100: 1～500 and add zero(ppm) water or deionized water; And refilter or spinning after 0.1～10 hour 20～120 ℃ of following heated and stirred, obtain containing the first-time filtrate of Calcium Bromide; In the first-time filtrate that contains Calcium Bromide, be to add activated carbon and/or activated decoloration at 1～500: 1～300, and filtration or spinning obtain containing the secondary filtrating of Calcium Bromide by the mass ratio of Tetrabutyl amonium bromide crystalline mother solution and activated carbon and/or atlapulgite; The secondary filtrating that contains Calcium Bromide is through evaporation concentration, crystallisation by cooling, filtration or spinning, vacuum-drying, promptly obtains the quality percentage composition greater than 98% Calcium Bromide product with the yield with respect to Tetrabutyl amonium bromide crystalline mother solution quality 5%～60%.
The practical implementation method
Provide some embodiment below, so that the present invention is described further.
Embodiment 1:
1000 gram Tetrabutyl amonium bromide crystalline mother solutions with 10 grams by aluminium sesquioxide, silicon-dioxide, calcium sulfate, quicklime, lime carbonate, calcium hydroxide, Graphite Powder 99, gac, fluorite by mass ratio 0.001: 10: 1: 0.1: 0.001: 0.1: the catalyzer that constitutes at 100: 0.001: 10 joined in the reactor drum, stirred also and under 10 ℃, reacted 20 hours; In vacuum tightness is that 0.1kPa, temperature are under 260 ℃ the condition reacting rear material to be carried out underpressure distillation, obtains containing the distillate of Tributylamine; After underpressure distillation, remain in the material in the reactor drum mass ratio by Tetrabutyl amonium bromide crystalline mother solution and water and be 100: 500 and add zero(ppm) water or deionized water; And refilter or spinning after 5 hours 40 ℃ of following heated and stirred, obtain containing the first-time filtrate of Calcium Bromide; In the first-time filtrate that contains Calcium Bromide, be to add activated carbon and/or activated decoloration at 10: 10, and filtration or spinning obtain containing the secondary filtrating of Calcium Bromide by the mass ratio of Tetrabutyl amonium bromide crystalline mother solution and activated carbon and/or atlapulgite; The secondary filtrating that contains Calcium Bromide is through evaporation concentration, crystallisation by cooling, filtration or spinning, vacuum-drying, promptly obtains the quality percentage composition greater than 98% Calcium Bromide product with the yield with respect to Tetrabutyl amonium bromide crystalline mother solution quality 15%.
Embodiment 2:
1000 gram Tetrabutyl amonium bromide crystalline mother solutions with 50 grams by aluminium sesquioxide, silicon-dioxide, calcium sulfate, quicklime, lime carbonate, calcium hydroxide, Graphite Powder 99, gac, fluorite by mass ratio 0.1: 10: 1: 10: 0.1: 10: the catalyzer that constitutes at 1: 0.1 joined in the reactor drum, stirred also and under 50 ℃, reacted 2 hours; In vacuum tightness is that 1kPa, temperature are under 220 ℃ the condition reacting rear material to be carried out underpressure distillation, obtains containing the distillate of Tributylamine; After underpressure distillation, remain in the material in the reactor drum mass ratio by Tetrabutyl amonium bromide crystalline mother solution and water and be 30: 100 and add zero(ppm) water or deionized water; And refilter or spinning after 1 hour 80 ℃ of following heated and stirred, obtain containing the first-time filtrate of Calcium Bromide; In the first-time filtrate that contains Calcium Bromide, be to add activated carbon and/or activated decoloration at 10: 70, and filtration or spinning obtain containing the secondary filtrating of Calcium Bromide by the mass ratio of Tetrabutyl amonium bromide crystalline mother solution and activated carbon and/or atlapulgite; The secondary filtrating that contains Calcium Bromide is through evaporation concentration, crystallisation by cooling, filtration or spinning, vacuum-drying, promptly obtains the quality percentage composition greater than 98% Calcium Bromide product with the yield with respect to Tetrabutyl amonium bromide crystalline mother solution quality 20%.
Embodiment 3:
1000 gram Tetrabutyl amonium bromide crystalline mother solutions with 100 grams by aluminium sesquioxide, silicon-dioxide, calcium sulfate, quicklime, lime carbonate, calcium hydroxide, Graphite Powder 99, gac, fluorite by mass ratio 0.01: 100: 10: 10: 0.1: 10: the catalyzer that constitutes at 1: 0.1 joined in the reactor drum, stirred also and under 70 ℃, reacted 0.5 hour; In vacuum tightness is that 10kPa, temperature are under 280 ℃ the condition reacting rear material to be carried out underpressure distillation, obtains containing the distillate of Tributylamine; After underpressure distillation, remain in the material in the reactor drum mass ratio by Tetrabutyl amonium bromide crystalline mother solution and water and be 60: 400 and add zero(ppm) water or deionized water; And refilter or spinning after 10 hours 100 ℃ of following heated and stirred, obtain containing the first-time filtrate of Calcium Bromide; In the first-time filtrate that contains Calcium Bromide, be to add activated carbon and/or activated decoloration at 80: 10, and filtration or spinning obtain containing the secondary filtrating of Calcium Bromide by the mass ratio of Tetrabutyl amonium bromide crystalline mother solution and activated carbon and/or atlapulgite; The secondary filtrating that contains Calcium Bromide is through evaporation concentration, crystallisation by cooling, filtration or spinning, vacuum-drying, promptly obtains the quality percentage composition greater than 98% Calcium Bromide product with the yield with respect to Tetrabutyl amonium bromide crystalline mother solution quality 35%.
Embodiment 4:
1000 gram Tetrabutyl amonium bromide crystalline mother solutions with 200 grams by aluminium sesquioxide, silicon-dioxide, calcium sulfate, quicklime, lime carbonate, calcium hydroxide, Graphite Powder 99, gac, fluorite by mass ratio 10: 1: 10: 10: 0.1: 10: the catalyzer that constitutes at 1: 100 joined in the reactor drum, stirred also and under 60 ℃, reacted 0.05 hour; In vacuum tightness is that 12kPa, temperature are under 240 ℃ the condition reacting rear material to be carried out underpressure distillation, obtains containing the distillate of Tributylamine; After underpressure distillation, remain in the material in the reactor drum mass ratio by Tetrabutyl amonium bromide crystalline mother solution and water and be 30: 300 and add zero(ppm) water or deionized water; And refilter or spinning after 5 hours 85 ℃ of following heated and stirred, obtain containing the first-time filtrate of Calcium Bromide; In the first-time filtrate that contains Calcium Bromide, be to add activated carbon and/or activated decoloration at 55: 136, and filtration or spinning obtain containing the secondary filtrating of Calcium Bromide by the mass ratio of Tetrabutyl amonium bromide crystalline mother solution and activated carbon and/or atlapulgite; The secondary filtrating that contains Calcium Bromide is through evaporation concentration, crystallisation by cooling, filtration or spinning, vacuum-drying, promptly obtains the quality percentage composition greater than 98% Calcium Bromide product with the yield with respect to Tetrabutyl amonium bromide crystalline mother solution quality 30%.
Embodiment 5:
1000 gram Tetrabutyl amonium bromide crystalline mother solutions with 300 grams by aluminium sesquioxide, silicon-dioxide, calcium sulfate, quicklime, lime carbonate, calcium hydroxide, Graphite Powder 99, gac, fluorite by mass ratio 18: 10: 2: 10: 9: 10: the catalyzer that constitutes at 1: 200 joined in the reactor drum, stirred also and under 60 ℃, reacted 0.5 hour; In vacuum tightness is that 15kPa, temperature are under 260 ℃ the condition reacting rear material to be carried out underpressure distillation, obtains containing the distillate of Tributylamine; After underpressure distillation, remain in the material in the reactor drum mass ratio by Tetrabutyl amonium bromide crystalline mother solution and water and be 300: 100 and add zero(ppm) water or deionized water; And refilter or spinning after 4 hours 75 ℃ of following heated and stirred, obtain containing the first-time filtrate of Calcium Bromide; In the first-time filtrate that contains Calcium Bromide, be to add activated carbon and/or activated decoloration at 100: 18, and filtration or spinning obtain containing the secondary filtrating of Calcium Bromide by the mass ratio of Tetrabutyl amonium bromide crystalline mother solution and activated carbon and/or atlapulgite; The secondary filtrating that contains Calcium Bromide is through evaporation concentration, crystallisation by cooling, filtration or spinning, vacuum-drying, promptly obtains the quality percentage composition greater than 98% Calcium Bromide product with the yield with respect to Tetrabutyl amonium bromide crystalline mother solution quality 32%.
Embodiment 6:
1000 gram Tetrabutyl amonium bromide crystalline mother solutions with 400 grams by aluminium sesquioxide, silicon-dioxide, calcium sulfate, quicklime, lime carbonate, calcium hydroxide, Graphite Powder 99, gac, fluorite by mass ratio 15: 9: 2: 7: 9: 100: the catalyzer that constitutes at 1: 300 joined in the reactor drum, stirred also and under 100 ℃, reacted 0.1 hour; In vacuum tightness is that 12kPa, temperature are under 270 ℃ the condition reacting rear material to be carried out underpressure distillation, obtains containing the distillate of Tributylamine; After underpressure distillation, remain in the material in the reactor drum mass ratio by Tetrabutyl amonium bromide crystalline mother solution and water and be 70: 200 and add zero(ppm) water or deionized water; And refilter or spinning after 7 hours 40 ℃ of following heated and stirred, obtain containing the first-time filtrate of Calcium Bromide; In the first-time filtrate that contains Calcium Bromide, be to add activated carbon and/or activated decoloration at 190: 26, and filtration or spinning obtain containing the secondary filtrating of Calcium Bromide by the mass ratio of Tetrabutyl amonium bromide crystalline mother solution and activated carbon and/or atlapulgite; The secondary filtrating that contains Calcium Bromide is through evaporation concentration, crystallisation by cooling, filtration or spinning, vacuum-drying, promptly obtains the quality percentage composition greater than 98% Calcium Bromide product with the yield with respect to Tetrabutyl amonium bromide crystalline mother solution quality 19%.
Embodiment 7:
1000 gram Tetrabutyl amonium bromide crystalline mother solutions with 600 grams by aluminium sesquioxide, silicon-dioxide, calcium sulfate, quicklime, lime carbonate, calcium hydroxide, Graphite Powder 99, gac, fluorite by mass ratio 15: 9: 70: 7: 9: 100: the catalyzer that constitutes at 100: 300 joined in the reactor drum, stirred also and under 180 ℃, reacted 1 hour; In vacuum tightness is that 12kPa, temperature are under 290 ℃ the condition reacting rear material to be carried out underpressure distillation, obtains containing the distillate of Tributylamine; After underpressure distillation, remain in the material in the reactor drum mass ratio by Tetrabutyl amonium bromide crystalline mother solution and water and be 130: 190 and add zero(ppm) water or deionized water; And refilter or spinning after 0.1 hour 40 ℃ of following heated and stirred, obtain containing the first-time filtrate of Calcium Bromide; In the first-time filtrate that contains Calcium Bromide, be to add activated carbon and/or activated decoloration at 70: 10, and filtration or spinning obtain containing the secondary filtrating of Calcium Bromide by the mass ratio of Tetrabutyl amonium bromide crystalline mother solution and activated carbon and/or atlapulgite; The secondary filtrating that contains Calcium Bromide is through evaporation concentration, crystallisation by cooling, filtration or spinning, vacuum-drying, promptly obtains the quality percentage composition greater than 98% Calcium Bromide product with the yield with respect to Tetrabutyl amonium bromide crystalline mother solution quality 27%.
Embodiment 8:
1000 gram Tetrabutyl amonium bromide crystalline mother solutions with 1800 grams by aluminium sesquioxide, silicon-dioxide, calcium sulfate, quicklime, lime carbonate, calcium hydroxide, Graphite Powder 99, gac, fluorite by mass ratio 15: 90: 68: 7: 9: 100: the catalyzer that constitutes at 100: 300 joined in the reactor drum, stirred also and under 200 ℃, reacted 1 hour; In vacuum tightness is that 15kPa, temperature are under 240 ℃ the condition reacting rear material to be carried out underpressure distillation, obtains containing the distillate of Tributylamine; After underpressure distillation, remain in the material in the reactor drum mass ratio by Tetrabutyl amonium bromide crystalline mother solution and water and be 100: 500 and add zero(ppm) water or deionized water; And refilter or spinning after 5 hours 120 ℃ of following heated and stirred, obtain containing the first-time filtrate of Calcium Bromide; In the first-time filtrate that contains Calcium Bromide, be to add activated carbon and/or activated decoloration at 190: 98, and filtration or spinning obtain containing the secondary filtrating of Calcium Bromide by the mass ratio of Tetrabutyl amonium bromide crystalline mother solution and activated carbon and/or atlapulgite; The secondary filtrating that contains Calcium Bromide is through evaporation concentration, crystallisation by cooling, filtration or spinning, vacuum-drying, promptly obtains the quality percentage composition greater than 98% Calcium Bromide product with the yield with respect to Tetrabutyl amonium bromide crystalline mother solution quality 31%.
Claims (2)
1. method of utilizing the Tetrabutyl amonium bromide crystalline mother solution to prepare Calcium Bromide; It is characterized in that: the Tetrabutyl amonium bromide crystalline mother solution with by aluminium sesquioxide, silicon-dioxide, calcium sulfate, quicklime, lime carbonate, calcium hydroxide, Graphite Powder 99, gac, fluorite by mass ratio 0.001～100: 0.001～100: 0.001～100: 0.001～100: 0.001～100: 0.001～100: 0.001～100: 0.001～100: 0.001～300 catalyzer that constitutes is by mass ratio 10～100: 0.001～600 joins in the reactor drum, stirs also and under-10 ℃～320 ℃, reacts 0.05～20 hour; In vacuum tightness is that 0.001～100kPa, temperature are under 10 ℃～360 ℃ the condition reacting rear material to be carried out underpressure distillation to obtain containing the distillate of Tributylamine; After underpressure distillation, remain in the material in the reactor drum mass ratio by Tetrabutyl amonium bromide crystalline mother solution and water and be 1～100: 1～500 and add zero(ppm) water or deionized water; And refilter or spinning after 0.1～10 hour 20～120 ℃ of following heated and stirred, obtain containing the first-time filtrate of Calcium Bromide; In the first-time filtrate that contains Calcium Bromide, be to add activated carbon and/or activated decoloration at 1～500: 1～300, and filtration or spinning obtain containing the secondary filtrating of Calcium Bromide by the mass ratio of Tetrabutyl amonium bromide crystalline mother solution and activated carbon and/or atlapulgite; The secondary filtrating that contains Calcium Bromide is through evaporation concentration, crystallisation by cooling, filtration or spinning, vacuum-drying, promptly obtains the quality percentage composition greater than 98% Calcium Bromide product with the yield with respect to Tetrabutyl amonium bromide crystalline mother solution quality 5%～60%.
2. a kind of method of utilizing the Tetrabutyl amonium bromide crystalline mother solution to prepare Calcium Bromide according to claim 1 is characterized in that: obtain Calcium Bromide quality percentage composition greater than 98% Calcium Bromide product with the yield with respect to Tetrabutyl amonium bromide crystalline mother solution quality 5%～60%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101002698A CN102659162B (en) | 2012-03-28 | 2012-03-28 | Method for preparing calcium bromide through using tetrabutylammonium bromide crystallization mother solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101002698A CN102659162B (en) | 2012-03-28 | 2012-03-28 | Method for preparing calcium bromide through using tetrabutylammonium bromide crystallization mother solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102659162A true CN102659162A (en) | 2012-09-12 |
| CN102659162B CN102659162B (en) | 2013-12-04 |
Family
ID=46768784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101002698A Expired - Fee Related CN102659162B (en) | 2012-03-28 | 2012-03-28 | Method for preparing calcium bromide through using tetrabutylammonium bromide crystallization mother solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102659162B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107673979A (en) * | 2017-09-06 | 2018-02-09 | 肯特催化材料股份有限公司 | The recoverying and utilizing method of halogenation short chain quaternary ammonium waste salt |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008106346A2 (en) * | 2007-02-28 | 2008-09-04 | Albemarle Corporation | Processes for producing and using bromine products suitable for reducing mercury emissions during coal combustion |
| CN101618888A (en) * | 2009-08-03 | 2010-01-06 | 山东天信化工有限公司 | Method for preparing calcium bromide solution used for oil drilling |
-
2012
- 2012-03-28 CN CN2012101002698A patent/CN102659162B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008106346A2 (en) * | 2007-02-28 | 2008-09-04 | Albemarle Corporation | Processes for producing and using bromine products suitable for reducing mercury emissions during coal combustion |
| CN101618888A (en) * | 2009-08-03 | 2010-01-06 | 山东天信化工有限公司 | Method for preparing calcium bromide solution used for oil drilling |
Non-Patent Citations (6)
| Title |
|---|
| 《Ind. Eng. Chem. Res》 19920131 Ronit Aizenberg et al. "New approach for the simple and economic preparation of inorganic bromide salts" 第431-434页 1-2 第31卷, 第1期 * |
| 《潍坊教育学院学报》 19961231 王景明 "溴化钙制备的新方法-尿素还原法" 第36-37、43页 1-2 , 第3期 * |
| 《辽宁化工》 19990731 王国喜等 "四正丁基溴化铵的合成改进" 第211-212页 1-2 第28卷, 第4期 * |
| RONIT AIZENBERG ET AL.: ""New approach for the simple and economic preparation of inorganic bromide salts"", 《IND. ENG. CHEM. RES》, vol. 31, no. 1, 31 January 1992 (1992-01-31), pages 431 - 434 * |
| 王国喜等: ""四正丁基溴化铵的合成改进"", 《辽宁化工》, vol. 28, no. 4, 31 July 1999 (1999-07-31), pages 211 - 212 * |
| 王景明: ""溴化钙制备的新方法-尿素还原法"", 《潍坊教育学院学报》, no. 3, 31 December 1996 (1996-12-31) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107673979A (en) * | 2017-09-06 | 2018-02-09 | 肯特催化材料股份有限公司 | The recoverying and utilizing method of halogenation short chain quaternary ammonium waste salt |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102659162B (en) | 2013-12-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111039310B (en) | Method for preparing sodium bicarbonate and co-producing ammonium sulfate from sodium sulfate | |
| CN104555953A (en) | Preparation method of hydrazine hydrate | |
| CN101857214B (en) | Method for producing potassium dihydrogen phosphate with double decomposition method | |
| CN101250115B (en) | Method for synthesizing 3-amido-1,2-propanediol by pipe reactor | |
| CN1962611A (en) | Process for preparing glycine using hydroxy-acetonitrile method | |
| CN107416872A (en) | The preparation method of magnalium carbonate form hydrotalcite | |
| EP1979299B1 (en) | Process for producing monopentaerythritol of high purity | |
| CN103896808A (en) | Method of preparing azodiisobutyronitrile | |
| CN103570568A (en) | Clean production process of glycine in coproduction with ammonium chloride | |
| CN111004162B (en) | Method and device for preparing L-selenocysteine by using sodium triacetoxyborohydride as reducing agent | |
| CN111039305A (en) | Method for preparing sodium bicarbonate and ammonium sulfate by sodium sulfate in short process | |
| CN102531055B (en) | The preparation method of sodium metavanadate/potassium metavanadate | |
| CN113120925B (en) | Method for recovering iodide from isophorone cracking material | |
| CN104387255B (en) | Preparation method of calcium formate | |
| CN106748900A (en) | A kind of Waste Sulfuric Acid prepares the environment-protection production method of paratoluenesulfonic acid sodium salt | |
| CN114180601A (en) | Green low-carbon process for producing sodium carbonate and caustic soda from waste salt and waste residues | |
| CN102659162B (en) | Method for preparing calcium bromide through using tetrabutylammonium bromide crystallization mother solution | |
| CN111393323A (en) | Environment-friendly clean production method of high-purity cyanoacetic acid, cyanoacetic ester and malonic ester | |
| CN103360262B (en) | Method for preparing tributylamine by utilizing tetrabutylammonium bromide crystallization mother liquor | |
| CN101092369A (en) | Method for preparing iminodiacetic acid by using raw material of hydroxy acetonitrile | |
| CN102351345B (en) | Method for recovering melamine from melamine waste water and co-producing desulfurizer | |
| CN103030661B (en) | The preparation method of ibronate sodium | |
| CN102177129B (en) | Method for preparing ammonium salts of fumaric or succinic acid | |
| CN111004184A (en) | Synthesis process of 4, 6-dichloropyrimidine | |
| CN103554182A (en) | Method for preparing glyphosate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131204 Termination date: 20190328 |