CN104003864A - Fatty acid alkaline-earth metal salt and preparation method thereof - Google Patents
Fatty acid alkaline-earth metal salt and preparation method thereof Download PDFInfo
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- CN104003864A CN104003864A CN201410253458.8A CN201410253458A CN104003864A CN 104003864 A CN104003864 A CN 104003864A CN 201410253458 A CN201410253458 A CN 201410253458A CN 104003864 A CN104003864 A CN 104003864A
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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
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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Abstract
The invention discloses a fatty acid alkaline-earth metal salt. The fatty acid alkaline-earth metal salt is of a structure shown in the following formula: CH3(CH2)nCOO-M-OOC(CH2)nCH3, wherein M is Mg<2+>, Ca<2+>, Ba<2+>, n is equal to 6-18, and the fatty acid alkaline-earth metal salt is white powder at normal temperature. A preparation method of the fatty acid alkaline-earth metal salt comprises the following steps: carrying out a salifying reaction on molten fatty acid and calcium or barium alkaline metal oxide or hydroxide powder under the action of a catalyst at a certain temperature, then cooling, rolling, and crushing, so that the powdery product is obtained. Compared with the traditional technology, the fatty acid alkaline-earth metal salt has the advantages that industrial production of the fatty acid alkaline-earth metal salt by adopting a melting method is realized, the production cost is saved, the energy consumption is reduced, the production cycle is shortened, pollution to the environment is less and real energy conservation and emission reduction are realized.
Description
Technical field
The present invention relates to one and be widely used in coating, rubber, plastics, powder metallurgy, paper, material of construction, pharmaceutical industry etc., make the fatty acid alkali salt in the fields such as the polishing of furniture lacquering agent, rubber and plastic thermo-stabilizer and lubricant, powder metallurgy releasing agent, paper coating lubricant, building materials hydrophobizing agent and tablet vehicle and preparation method thereof.
Background technology
The preparation technology who produces on the market at present fatty acid metal salt probably divides four kinds, double decomposition (claiming again water law two-step approach), water law single stage method, scorification, semi-melting method or direct method; And the wherein three kinds of processing methodes of only having that can produce fatty acid alkali salt: double decomposition (claiming water law two-step approach), water law single stage method, semi-melting method or direct method.Double decomposition is commonly called as WATER-WASHING METHOD or wet method, and whole reaction is carried out in water, first the lipid acid of melting and buck is carried out to saponification reaction, and then carries out replacement(metathesis)reaction with alkaline-earth metal ions, and gained system is through dehydration, washing, the dry finished product that makes.Water law single stage method is to improve on water law two-step process basis, reaction does not need to carry out saponification and replacement(metathesis)reaction, but the lipid acid of melting is directly reacted and makes finished product through dehydrating with alkaline earth metal oxide or hydroxide powder under the prerequisite of water as medium; Semi-melting method or direct method are that the lipid acid of melting reacts and directly makes solid finished product at the temperature below the melting point of generated fatty acid alkali salt with alkaline earth metal oxide or hydroxide powder.Also do not find at present scorification technique to be realized to the technology appearance that fatty acid alkali salt industrialization is produced.
Double decomposition technique is being produced into using a large amount of water to wash final product to remove the residual of alkaline-earth metal and acid ion, and the waste water environmental pollution producing in process is larger, and production process very complicated, is eliminated just gradually.Although water law single stage method is improved and improved metathesis process, produces and still needs with large water gaging (final product and water ratio are probably in left and right, 1:5～8), the baking needed electric energy to product and the consumption of water are all very large, and production cost is higher.Semi-melting method or direct method will be carried out salt-forming reaction at low temperatures, have implemented great difficulty, and temperature of reaction is low, and alkaline-earth metal reactive behavior also just decreases; And solid-state or semi-vitreous lipid acid contacts with powdery alkali soil metal oxide or oxyhydroxide, want reaction thoroughly, must there is contact area as much as possible (fineness of powder is more carefully better); And solid matter is enough powerful to the requirement of reaction unit stirring power simultaneously, and power consumption is very large, and second scorification of many factors or direct method technique are difficult to realize in practice, and moulding product is also rarely found.
So seek a kind of technique simple, workable, be beneficial to industrialization, prepare efficiently the commercial run of fatty acid alkali salt, be the demand of current industry member
Summary of the invention
In order to overcome the deficiency of existing production technology, solve traditional technology high energy consumption, heavily contaminated, expensive problem, scorification technique is carried out improvement and perfection by the present invention, solve the problem that this technique can only be produced melting fatty acid zinc salt for a long time, realized smoothly fatty acid alkali salt industrialization and produce.
How to solve alkaline earth metal oxide or oxyhydroxide and fatty acid response violent, the product viscosity of generation is large, and reaction later stage difficulties in dispersion and colour-change etc., be the emphasis of this subject study.
For solving the problems of the technologies described above adopted technical scheme: a kind of fatty acid alkali salt, is characterized in that: described fatty acid alkali salt has as shown in the formula structure: CH
3(CH
2)
ncOO-M-OOC (CH
2)
ncH
3, wherein M is Mg
2+, Ca
2+, Ba
2+, n=6～18, are white powder under normal temperature.
The preparation method of described fatty acid alkali salt is: under certain temperature and catalyst action, carry out salt-forming reaction by the lipid acid of melting and oxide compound or the hydroxide powder of calcium or magnesium or barium alkaline-earth metal, then through overcooling roll sheet, fragmentation makes powdered product.
Described lipid acid is C
8～C
20saturated fatty acid.If carbon number is less than 8, the oxide compound of lipid acid and alkaline-earth metal or oxyhydroxide, especially too fast with oxyhydroxide speed of response, cause preparation process to be difficult to carry out smoothly; If carbon number is greater than 20, because reactive behavior is too low, and need to add too much catalyst reaction, when extending the reaction times, finally can affect purity, the color and luster of product.
The oxide compound of described alkaline-earth metal or the size distribution of hydroxide powder are 1～50 micron.If particle diameter is less than 1 micron, while dispersion, easily produce aggregate in the lipid acid of melting, be unfavorable for disperseing; If particle diameter is greater than 50 microns, corresponding contact area obviously reduces, make solid-liquid phase reaction be difficult to thoroughly carry out, can only make the oxide compound of alkaline-earth metal or the add-on of oxyhydroxide obviously be greater than equivalence ratio, just can make the value of free acid drop in qualified scope, the final like this quality that can have influence on product.
Gradation ground, toward the oxide compound or the hydroxide powder that add alkaline-earth metal in the lipid acid of melting, is generally 3～5 times (depending on the total input amount of material that participates in reacting), and will slowly adds.Alkaline earth metal oxide or oxyhydroxide and fatty acid response are violent, if once add or add too fast fast, can cause reaction to form bulk cohesion, and viscosity increases suddenly, is difficult for disperseing, and reaction is difficult to carry out smoothly; And add too much (more than 5 times) of indegree, and the reaction times extends, and product can, because of oxidation variable color, affect quality product.
The temperature of salt-forming reaction is controlled at 135～145 DEG C, temperature of reaction can not be too high can not be too low.Because when excess Temperature, product can be because of high temperature oxidation variable color; If temperature is too low, reactive behavior reduces, and speed of response slows down, and viscosity also can increase, and is unfavorable for the carrying out of reaction.
Water as catalyst dilution is filtration process water, and its add-on is 1～3% of lipid acid quality.If water add-on is greater than 3%, can make reaction more violent, reaction is difficult to control, and can be increased in product residual; If water add-on is less than 1%, speed of response slows down, and extends reaction time.
Described catalyzer can be an acidic catalyst, as organic acid or organic dibasic acid, can be also oxygenant, as hydrogen peroxide.Organic acid can be one or more in formic acid, acetic acid, propionic acid, tosic acid; Organic dibasic acid can be oxalic acid, propanedioic acid, succinic acid, one or more in phthalic acid, terephthalic acid.If consider the catalytic effect of reaction, can select organic dibasic acid and tosic acid; If consider the purity of final final product, select hydrogen peroxide to be advisable; Comprehensive assessment reactive behavior and the feature of environmental protection, choose with hydrogen peroxide or acetic acid or both arrange in pairs or groups use more reasonable.Catalyst levels is 0.5～1% of lipid acid quality.If catalyst levels is less than 0.5%, reactive behavior is too low, and speed of response is slow, extends reaction time; If catalyst levels is greater than 1%, because speed of response is too fast, can make reaction more violent, reaction is difficult to control.
Salt-forming reaction requires to vacuumize 1～1.5 hour.Vacuumizing is to add water in order to get rid of in reaction generation and process, reduces product moisture; Also prevent uncovered reaction from causing product oxidation and affect product color simultaneously.
Roll sheet equipment can water flowing cooling, accelerate reaction product by molten state to solid-state transition, avoid time lengthening to cause product oxidation stain, shorten the production cycle simultaneously.
Powder if accomplish industry standard require particle diameter, the mechanical disintegration of configurable high velocity impact formula, also can select micronizer mill; Product cut size scope is adjustable, all can (determine according to client's actual requirement) for 25～100 microns.
Compared with prior art, tool of the present invention has the following advantages:
(1) realized the industrialization of scorification explained hereafter fatty acid alkali salt, saved production cost than traditional technology, reduced energy consumption, shortened the production cycle, environmental pollution is less, accomplishes real energy-saving and emission-reduction.
(2) this technique is suitable for the salt-forming reaction of multiple lipid acid and alkaline earth metal oxide or hydroxide powder, is easy to processing, is applicable to serialization, the production of mass-producing ground.
(3) this technique preparing product purity is high, and water ratio is low, applied widely; Processing flexibly, can be made sheet, also can be processed into superfine powder, meets different clients' demand.
Embodiment
In order to understand better the present invention, below in conjunction with specific embodiment, the invention will be further described, but the present invention's scope required for protection is not limited to the scope that embodiment records.
The preparation method of embodiment 1 calcium stearate
800kg stearic acid (acid number 210) is heated to 140 DEG C, dividing and adding total amount for four times is calcium hydroxide (>=96%) the dispersion reaction of 120kg, and coordinate that point to add total amount for four times be glacial acetic acid aqueous solution (containing the Glacial acetic acid 4kg) catalyzed reaction of 24kg, vacuumize 1.5 hours.Then the cooling sheet that rolls becomes solid sheet, pulverizes and makes calcium stearate product through the pulverizer of high velocity impact formula.Its quality index is: calcium contents 6.9%; Weight loss on heating≤1.0%; Fusing point >=140 DEG C; Free acid≤0.5%.Fineness≤75 μ m.
The preparation method of embodiment 2 calcium stearates
800kg stearic acid (acid number 210) is heated to 140 DEG C, dividing and adding total amount for four times is calcium oxide (>=95%) the dispersion reaction of 91kg, and coordinate that point to add total amount for four times be glacial acetic acid aqueous solution (containing the Glacial acetic acid 4kg) catalyzed reaction of 24kg, vacuumize 1.5 hours.Then the cooling sheet that rolls becomes solid sheet, pulverizes and makes calcium stearate product through the pulverizer of high velocity impact formula.Its quality index is: calcium contents 7.0%; Weight loss on heating≤1.0%; Fusing point >=145 DEG C; Free acid≤0.7%.Fineness≤75 μ m.
The preparation method of embodiment 3 Magnesium Stearates
900kg stearic acid (acid number 210) is heated to 135 DEG C, dividing and adding total amount for three times is the magnesium oxide (>=96.0%) of 76kg, disperse reaction, and coordinate that point to add total amount for three times be hydrogen peroxide solution (containing the hydrogen peroxide 7kg) catalyzed reaction of 30kg, vacuumize 1 hour.Then the cooling sheet that rolls becomes solid, pulverizes and makes Magnesium Stearate product through micronizer mill.Its quality index is: Mg content 4.8%; Weight loss on heating≤1.5%; Fusing point >=120 DEG C; Free acid≤2.0%; Fineness≤75 μ m.
The preparation method of embodiment 4 Magnesium Stearates
900kg stearic acid (acid number 210) is heated to 135 DEG C, add 105kg magnesium hydroxide (>=96.0%) (divide and slowly add for three times), and coordinate that point to add total amount for three times be hydrogen peroxide solution (containing the hydrogen peroxide 7kg) catalyzed reaction of 30kg, vacuumize 1 hour.Then the cooling sheet that rolls becomes solid, pulverizes and makes Magnesium Stearate product through micronizer mill.Its quality index is: Mg content 4.8%; Weight loss on heating≤1.5%; Fusing point >=120 DEG C; Free acid≤1.5%; Fineness≤75 μ m.
The preparation method of embodiment 5 barium stearates
800kg stearic acid (acid number 210) is heated to 140 DEG C, dividing and adding total amount for four times is that 238.6kg barium oxide (>=96.0%) disperses reaction, and coordinate that point to add total amount for four times be glacial acetic acid aqueous solution (containing the Glacial acetic acid 4kg) catalyzed reaction of 24kg, vacuumize 1 hour.Then the cooling sheet that rolls becomes solid sheet, pulverizes and makes barium stearate product through micronizer mill.Its quality index is: barium content 20%; Weight loss on heating≤0.5%; Fusing point >=210 DEG C; Free acid≤0.5%.
Remarks: the mixing acid that the stearic acid (acid number 210) using in above case study on implementation is 18 carbonic acid that contain 60% Palmitic acid and 40%.
Subordinate list: HG/T3667-2000 Zinic stearas industry standard, pharmacopeia 2005 editions in the quality index of Magnesium Stearate, the industry standard of HG/T2424-1993 calcium stearate and the industry standard of HG/T2338-1992 barium stearate:
Table 1 Magnesium Stearate
| Project | Index |
| Outward appearance | White fine-powder |
| Content of magnesia % | 6.5-7.5 |
| Weight loss on heating %≤ | 5.0 |
| Vitriol %≤ | 0.6 |
| Muriate %≤ | 0.15 |
| Molysite %≤ | 0.01 |
| Heavy metal %≤ | 0.0001 |
Table 2 calcium stearate
Table 3 barium stearate
Claims (9)
1. a fatty acid alkali salt, is characterized in that: described fatty acid alkali salt has as shown in the formula structure: CH
3(CH
2)
ncOO-M-OOC (CH
2)
ncH
3, wherein M is Mg
2+, Ca
2+, Ba
2+, n=6～18, are white powder under normal temperature.
2. the preparation method of fatty acid alkali salt according to claim 1, described preparation technology is: under certain temperature and catalyst action, carry out salt-forming reaction by the lipid acid of melting and oxide compound or the hydroxide powder of calcium or magnesium or barium alkaline-earth metal, then through overcooling roll sheet, fragmentation makes powdered product.
3. the preparation method of fatty acid alkali salt according to claim 2, described preparation technology comprises the steps:
(1) by lipid acid heating and melting, and be warming up to 130～135 DEG C;
(2) the slow gradation of system obtaining to step (1) adds oxide compound or the hydroxide powder of calcium or magnesium or barium alkaline-earth metal; The oxide compound or the hydroxide powder that often add an alkaline-earth metal just add immediately once through water-reducible catalyst reaction;
(3) system step (2) being obtained vacuumizes reaction 1～1.5 hour at 135～145 DEG C, then cooling, roll sheet, pulverize obtain fatty acid alkaline earth salt product.
4. the preparation method of fatty acid alkali salt according to claim 2, is characterized in that: described lipid acid is C
8～C
20saturated fatty acid.
5. the preparation method of fatty acid alkali salt according to claim 2, is characterized in that: described catalyzer is hydrogen peroxide or organic acid or organic dibasic acid.
6. the preparation method of fatty acid alkali salt according to claim 5, is characterized in that: described organic acid is one or more in formic acid, acetic acid, propionic acid and tosic acid.
7. the preparation method of fatty acid alkali salt according to claim 5, is characterized in that: described organic dibasic acid is oxalic acid, propanedioic acid, succinic acid, one or more in phthalic acid and terephthalic acid.
8. the preparation method of fatty acid alkali salt according to claim 2, is characterized in that: the oxide compound of described alkaline-earth metal or the size distribution of hydroxide powder are 1～50 micron.
9. the preparation method of fatty acid alkali salt according to claim 2, is characterized in that: described water is for filtering process water.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104726168A (en) * | 2015-02-05 | 2015-06-24 | 中山华明泰化工股份有限公司 | Lithium-zinc compound lubricant and preparation method thereof |
| CN110105209A (en) * | 2019-05-22 | 2019-08-09 | 广东信诚达科技有限公司 | δ-fatty acyl gluconate and preparation method thereof and PVC heat stabilizer |
| CN110386871A (en) * | 2019-08-27 | 2019-10-29 | 如皋市涤诺皂业有限公司 | A kind of production technology of magnesium stearate |
| CN111606799A (en) * | 2020-07-02 | 2020-09-01 | 中山华明泰科技股份有限公司 | Preparation method and application of medicinal composite vegetable fatty acid magnesium |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5274144A (en) * | 1990-06-15 | 1993-12-28 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of metal soaps |
| CN1127743A (en) * | 1995-01-25 | 1996-07-31 | 烟台市福山区齐鲁助剂厂 | Specific grade zinc stearate and its producing process |
| JPH1135518A (en) * | 1997-07-16 | 1999-02-09 | Mizusawa Ind Chem Ltd | Production of higher fatty acid salt |
| CN101337877A (en) * | 2008-08-07 | 2009-01-07 | 百利合化工（中山）有限公司 | Method for preparing higher fatty acid alkali salt |
| CN101648860A (en) * | 2009-07-02 | 2010-02-17 | 荀育军 | Production formula and novel process of barium stearate |
| CN102219667A (en) * | 2011-04-22 | 2011-10-19 | 中山市华明泰化工材料科技有限公司 | Higher fatty acid metal salt and preparation method thereof |
| CN102344354A (en) * | 2010-08-06 | 2012-02-08 | 南通新邦化工科技有限公司 | Calcium stearate fusion production process and calcium stearate reaction kettle thereof |
-
2014
- 2014-06-09 CN CN201410253458.8A patent/CN104003864A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5274144A (en) * | 1990-06-15 | 1993-12-28 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of metal soaps |
| CN1127743A (en) * | 1995-01-25 | 1996-07-31 | 烟台市福山区齐鲁助剂厂 | Specific grade zinc stearate and its producing process |
| JPH1135518A (en) * | 1997-07-16 | 1999-02-09 | Mizusawa Ind Chem Ltd | Production of higher fatty acid salt |
| CN101337877A (en) * | 2008-08-07 | 2009-01-07 | 百利合化工（中山）有限公司 | Method for preparing higher fatty acid alkali salt |
| CN101648860A (en) * | 2009-07-02 | 2010-02-17 | 荀育军 | Production formula and novel process of barium stearate |
| CN102344354A (en) * | 2010-08-06 | 2012-02-08 | 南通新邦化工科技有限公司 | Calcium stearate fusion production process and calcium stearate reaction kettle thereof |
| CN102219667A (en) * | 2011-04-22 | 2011-10-19 | 中山市华明泰化工材料科技有限公司 | Higher fatty acid metal salt and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104726168A (en) * | 2015-02-05 | 2015-06-24 | 中山华明泰化工股份有限公司 | Lithium-zinc compound lubricant and preparation method thereof |
| CN110105209A (en) * | 2019-05-22 | 2019-08-09 | 广东信诚达科技有限公司 | δ-fatty acyl gluconate and preparation method thereof and PVC heat stabilizer |
| CN110105209B (en) * | 2019-05-22 | 2022-04-08 | 广东信诚达科技有限公司 | Delta-fatty acyl gluconate and preparation method thereof, and PVC heat stabilizer |
| CN110386871A (en) * | 2019-08-27 | 2019-10-29 | 如皋市涤诺皂业有限公司 | A kind of production technology of magnesium stearate |
| CN111606799A (en) * | 2020-07-02 | 2020-09-01 | 中山华明泰科技股份有限公司 | Preparation method and application of medicinal composite vegetable fatty acid magnesium |
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Application publication date: 20140827 |