CN1379012A - Process for preparing calcium magnesium acetate by vacuum distillation method - Google Patents
Process for preparing calcium magnesium acetate by vacuum distillation method Download PDFInfo
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- CN1379012A CN1379012A CN 02117083 CN02117083A CN1379012A CN 1379012 A CN1379012 A CN 1379012A CN 02117083 CN02117083 CN 02117083 CN 02117083 A CN02117083 A CN 02117083A CN 1379012 A CN1379012 A CN 1379012A
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- calcium
- solution
- calcium magnesium
- reaction
- distillation
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- 238000000034 method Methods 0.000 title claims abstract description 13
- LUYGICHXYUCIFA-UHFFFAOYSA-H calcium;dimagnesium;hexaacetate Chemical compound [Mg+2].[Mg+2].[Ca+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O LUYGICHXYUCIFA-UHFFFAOYSA-H 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 238000005292 vacuum distillation Methods 0.000 title claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000011575 calcium Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 8
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 238000004821 distillation Methods 0.000 claims description 21
- 229960000583 acetic acid Drugs 0.000 claims description 16
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 13
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims description 12
- 239000012362 glacial acetic acid Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- ZORPJCONVDWMSP-UHFFFAOYSA-J calcium;magnesium;tetraacetate Chemical class [Mg+2].[Ca+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O ZORPJCONVDWMSP-UHFFFAOYSA-J 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- YLUIKWVQCKSMCF-UHFFFAOYSA-N calcium;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[Mg+2].[Ca+2] YLUIKWVQCKSMCF-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 5
- 238000010669 acid-base reaction Methods 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 150000002681 magnesium compounds Chemical class 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 229910052749 magnesium Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 1
- -1 Dichlorodiphenyl Acetate calcium magnesium salts Chemical class 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for preparing calcium magnesium acetate includes such steps as mixing Ca and Mg compound (the mole ratio of Ca:Mg is 3-4:6-7) with solution of acetic acid, to form a solution with concentration of (3-5) mol/L, reaction at 40-90 deg.C for 1-3 hr, filtering, vacuum distilling concentration at 45-90 deg.C and under -0.08-0.1 MPa for 1-5 hr, and drying. Its advantages are simple process, low reaction temp. and high purity of product.
Description
Technical field
The present invention relates to a kind of method, belong to the fine chemistry industry preparing technical field with process for preparing calcium magnesium acetate by vacuum distillation.
Background technology
(Calcium Magnesium Acetate CMA) is the calcium magnesium acetate composite salt to calcium acetate magnesium salt, is a kind of new environmental-protecting chemical product that the U.S. developed for alternative motorway deicing agent (sodium-chlor) the beginning of the eighties.The good water solubility of CMA, fusing point is low, and is biodegradable, compares with sodium-chlor, can reduce in vehicle, the highway foundation facility chlorion to the pollution of concrete, corrosion of metal and surface water.Research in recent years finds that also CMA has the NO that removes the coal combustion generation
x, SO
2And the HCl effect of PVC burning generation, with the control topsoil.U.S. Pat 4699725 and US4913831 have reported the microcosmic composition of measuring CMA with x-ray diffraction method and " TGA-GC-MSD " (differential thermal-thermogravimetric analysis) respectively, to being familiar with and analyzing CMA and played certain directive function.At present, the method of introducing with the acetic acid synthesized calcium magnesium salts of acid-base reaction mainly is a U.S. Pat 4913831, the principal feature of its production technique is: reactions steps is the emulsion of the certain density calcium magnesium oxide of preparation (and calcium carbonate and magnesium carbonate) earlier, adds acetic acid reaction then; Product dehydration, dispersion, drying and granulation process carry out in a design complex apparatus simultaneously.Patent US4588512 has then mainly introduced by gravel or coagulating agent Dichlorodiphenyl Acetate calcium magnesium salts slurries granulating and drying.The major defect of above technology has 2 points, and the one, because granulating and drying equipment complexity to the temperature requirement in the entire reaction course very high (being not less than 90 ℃), causes acetic acid volatilization loss bigger, cause that product purity descends; The 2nd, the required water yield will enter velocity of flow and the drying effect that drying plant carries out granulating and drying with fluid and do not stop to regulate in the reaction process, causes the dehydration energy consumption bigger.
Summary of the invention
The purpose of this invention is to provide the method that a kind of preparation technology and equipment are simple, temperature of reaction is low, product purity is high with the acetic acid synthesized calcium magnesium salts of distillation under vacuum.
The present invention proposes a kind of method with process for preparing calcium magnesium acetate by vacuum distillation, with Glacial acetic acid or acetum and calcium magnesium oxide or calcium carbonate and magnesium carbonate is raw material, it is characterized in that: calcium, magnesium compound are added in the acetum and mix, the calcium magnesium acetate salts solution of reaction gained concentrates through underpressure distillation, drying gets granular calcium acetate magnesium salt again, and its concrete preparation technology carries out as follows:
(1) acid-base reaction: in reaction tank, add deionized water under the room temperature earlier, slowly add Glacial acetic acid, be made into the solution of concentration for (3～5) mol/L, the calcium magnesium compound that will crush in advance then drops in the reaction tank with stoichiometric ratio, be aided with stirring, the mol ratio of calcium magnesium compound is Ca: Mg=3～4: 6～7, temperature of reaction is controlled at (40～90) ℃, reaction times is (1～3) hour, adjust pH value in the solution between 7～10, stopped reaction by adding the small amount of calcium magnesium compound at last;
(2) filter: the solution of step (1) preparation is filtered, and liquid phase is carried out underpressure distillation, the recycling of solid phase calcium magnesium oxide;
(3) underpressure distillation: the liquid of step (2) preparation is steamed moisture in the solution under the condition of decompression, distillation pressure is (0.08～-0.1) MPa, distillation temperature is (45～90) ℃, and distillation time is (1～5) hour, concentrates the calcium acetate magnesium solution and reaches white thick crystal and get final product.
In this preparation method, step in the acid-base reaction (1) also can take to add earlier under the room temperature deionized water in reaction tank, add CaO then, MgO, be made into calcium oxide, magnesium oxide mixed emulsion, the mol ratio of calcium magnesium compound is Ca: Mg=3～4: 6～7, slowly adds Glacial acetic acid again, its strength of solution is (3～5) mol/L, and stirs the condition that makes it set by step (1) and react.
Because the present invention adopts conventional vacuum distillation equipment to dehydrate, operational path is simple, temperature of reaction is low, product purity obviously improves, the acetate ion rate of loss was about for 0.01% (the acetate ion rate of loss is about 2% during air distillation, and temperature required when recording air distillation is 125 ℃～130 ℃).And the mother liquid obtained product concentration height of this technological reaction, dehydration is simple, greatly the energy efficient of limit.
Description of drawings
Fig. 1 is the X-ray diffractogram of the embodiment of the invention.
Embodiment
Below for adopting method of the present invention to prepare the embodiment of calcium acetate magnesium salt.
Embodiment 1:
Get the 500ml deionized water under the room temperature, slowly add Glacial acetic acid 2.878mol, the CaO of property adding 0.483mol again, 1.100mol MgO, and stir and to make it to react 1.5hr, solution is displaing yellow slightly, temperature of reaction is 45 ± 5 ℃, use mol ratio Ca: Mg=3: 7 calcium magnesium compound is regulated pH value, shows weakly alkaline pH=7.4 until solution, static afterwards centrifugal, filter to isolate excessive calcium oxide magnesium.Record mother liquor pH=9.11.
Mother liquor to be put into Rotary Evaporators, carry out underpressure distillation, pressure is-0.096～-0.098MPa, temperature is 50 ± 5 ℃, a large amount of white crystals are separated out in underpressure distillation 1.5 hours, measure the distillate volume.Use the high-pressure liquid chromatography distillate, acetate ion concentration is 2.475 * 10
-3Mol/L, pH=4.60, the acetic acid rate of loss is 0.01%.
Embodiment 2:
Get the 500ml deionized water under the room temperature, slowly add Glacial acetic acid 4.029mol, the CaO of property adding 0.672mol again, 1.34mol MgO, and stir and to make it to react 2hr, solution is displaing yellow slightly, temperature of reaction is 70 ± 5 ℃, use mol ratio Ca: Mg=3: 6 calcium magnesium compound is regulated pH value, shows weakly alkaline pH=8.5 until solution, static afterwards centrifugal, filter to isolate excessive calcium oxide magnesium.Record mother liquor pH=9.56.
Mother liquor is put into Rotary Evaporators, carry out underpressure distillation, pressure is-0.095～-0.098 MPa, and temperature is 75 ± 5 ℃, and a large amount of white crystals are separated out in underpressure distillation 3.5 hours, measure the distillate volume.Use the high-pressure liquid chromatography distillate, acetate ion concentration is 3.755 * 10
-3Mol/L, pH=4.16, the acetic acid rate of loss is 0.012%.
Embodiment 3:
Get the 500ml deionized water under the room temperature, the CaO that adds 0.483mol, 1.100mol MgO, be made into calcium oxide, magnesium oxide mixed emulsion, slowly adding Glacial acetic acid 2.878mol, and stirring makes it to take place, and controlled temperature is between 85 ± 5 ℃, the complete reaction required time is about 3 hours, and is mother liquid obtained similar with embodiment 1.
Mother liquor to be put into Rotary Evaporators, carry out underpressure distillation, control pressure is-0.083～-0.086Mpa, all the other conditions are identical, and temperature required when recording underpressure distillation is 85 ± 5 ℃, and required time is 5hr.Acetate ion concentration is 6.635 * 10 in the distillate
-3Mol/L, pH=3.62, the acetic acid rate of loss is 0.015%.
Claims (2)
1, a kind of method with process for preparing calcium magnesium acetate by vacuum distillation, with Glacial acetic acid or acetum and calcium magnesium oxide or calcium carbonate and magnesium carbonate is raw material, it is characterized in that: calcium, magnesium compound are added in the acetum and mix, the calcium magnesium acetate salts solution of reaction gained concentrates through underpressure distillation, drying gets granular calcium acetate magnesium salt again, and its concrete preparation technology carries out as follows:
(1) acid-base reaction: in reaction tank, add deionized water under the room temperature earlier, slowly add Glacial acetic acid, be made into the solution of concentration for (3～5) mol/L, the calcium magnesium compound that will crush in advance then drops in the reaction tank with stoichiometric ratio, be aided with stirring, the mol ratio of calcium magnesium compound is Ca: Mg=3～4: 6～7, temperature of reaction is controlled at (40～90) ℃, reaction times is (1～3) hour, adjust pH value in the solution between 7～10, stopped reaction by adding the small amount of calcium magnesium compound at last;
(2) filter: the solution of step (1) preparation is filtered, and liquid phase is carried out underpressure distillation, the recycling of solid phase calcium magnesium oxide;
(3) underpressure distillation: the liquid of step (2) preparation is steamed moisture in the solution under the condition of decompression, distillation pressure is (0.08～-0.1) MPa, distillation temperature is (45～90) ℃, and distillation time is (1～5) hour, concentrates the calcium acetate magnesium solution and reaches white thick crystal and get final product.
2, according to the described a kind of method of claim 1 with process for preparing calcium magnesium acetate by vacuum distillation, it is characterized in that: step (1) also can take to add earlier under the room temperature deionized water in reaction tank, add CaO then, MgO, be made into calcium oxide, magnesium oxide mixed emulsion, the mol ratio of calcium magnesium compound is Ca: Mg=3～4: 6～7, slowly adds Glacial acetic acid again, its strength of solution is (3～5) mol/L, and stirs the condition that makes it set by step (1) and react.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021170835A CN1164555C (en) | 2002-04-29 | 2002-04-29 | Process for preparing calcium magnesium acetate by vacuum distillation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021170835A CN1164555C (en) | 2002-04-29 | 2002-04-29 | Process for preparing calcium magnesium acetate by vacuum distillation method |
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| Publication Number | Publication Date |
|---|---|
| CN1379012A true CN1379012A (en) | 2002-11-13 |
| CN1164555C CN1164555C (en) | 2004-09-01 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864599A (en) * | 2014-04-01 | 2014-06-18 | 福建源鑫环保科技有限公司 | Method for preparing calcium-magnesium acetate by utilizing steel slag |
| CN103865486A (en) * | 2014-03-21 | 2014-06-18 | 大连理工大学 | Method for preparing environmen-friendly carboxylic calcium magnesium salt snow-melting agent by using smoke desulfation waste |
| CN104355984A (en) * | 2014-11-25 | 2015-02-18 | 姜升林 | Preparation process and application of calcium magnesium acetate |
| CN104557506A (en) * | 2014-12-08 | 2015-04-29 | 长沙罗斯科技有限公司 | Preparation technology of stannous acetate |
-
2002
- 2002-04-29 CN CNB021170835A patent/CN1164555C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865486A (en) * | 2014-03-21 | 2014-06-18 | 大连理工大学 | Method for preparing environmen-friendly carboxylic calcium magnesium salt snow-melting agent by using smoke desulfation waste |
| CN103865486B (en) * | 2014-03-21 | 2015-10-28 | 大连理工大学 | A kind of method utilizing flue gas desulfurization waste to prepare environment-friendly type calcium magnesium carboxylate snow-melting agent |
| CN103864599A (en) * | 2014-04-01 | 2014-06-18 | 福建源鑫环保科技有限公司 | Method for preparing calcium-magnesium acetate by utilizing steel slag |
| CN104355984A (en) * | 2014-11-25 | 2015-02-18 | 姜升林 | Preparation process and application of calcium magnesium acetate |
| CN104355984B (en) * | 2014-11-25 | 2016-03-23 | 姜升林 | The preparation technology of calcium magnesium acetate and application |
| CN104557506A (en) * | 2014-12-08 | 2015-04-29 | 长沙罗斯科技有限公司 | Preparation technology of stannous acetate |
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| Publication number | Publication date |
|---|---|
| CN1164555C (en) | 2004-09-01 |
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