CN104447409A - Synthesis method of hydroxyoximate - Google Patents
Synthesis method of hydroxyoximate Download PDFInfo
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- CN104447409A CN104447409A CN201410633799.8A CN201410633799A CN104447409A CN 104447409 A CN104447409 A CN 104447409A CN 201410633799 A CN201410633799 A CN 201410633799A CN 104447409 A CN104447409 A CN 104447409A
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- hydroximic acid
- acid salt
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- fatty acid
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- 238000001308 synthesis method Methods 0.000 title abstract 5
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- -1 fatty acid ester Chemical class 0.000 claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 34
- 239000000194 fatty acid Substances 0.000 claims abstract description 34
- 229930195729 fatty acid Natural products 0.000 claims abstract description 34
- 239000003513 alkali Substances 0.000 claims abstract description 33
- 239000003518 caustics Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 238000004821 distillation Methods 0.000 claims abstract description 13
- 238000005188 flotation Methods 0.000 claims abstract description 10
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 145
- 150000003839 salts Chemical class 0.000 claims description 69
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 33
- 238000010189 synthetic method Methods 0.000 claims description 31
- 150000002632 lipids Chemical class 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- 238000000605 extraction Methods 0.000 claims description 11
- 238000007127 saponification reaction Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 230000001351 cycling effect Effects 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 7
- 230000032050 esterification Effects 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 150000004665 fatty acids Chemical class 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000007039 two-step reaction Methods 0.000 abstract description 2
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 abstract 2
- 239000013043 chemical agent Substances 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 8
- 239000005642 Oleic acid Substances 0.000 description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 8
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000006146 oximation reaction Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000003556 assay Methods 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 4
- JGHZJRVDZXSNKQ-UHFFFAOYSA-N methyl octanoate Chemical compound CCCCCCCC(=O)OC JGHZJRVDZXSNKQ-UHFFFAOYSA-N 0.000 description 4
- HBROZNQEVUILML-UHFFFAOYSA-N salicylhydroxamic acid Chemical compound ONC(=O)C1=CC=CC=C1O HBROZNQEVUILML-UHFFFAOYSA-N 0.000 description 4
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229940070765 laurate Drugs 0.000 description 2
- 229940095102 methyl benzoate Drugs 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 239000009637 wintergreen oil Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 241000406668 Loxodonta cyclotis Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a synthesis method of hydroxamate. The hydroxamate is synthesized from fatty acid, short chain alcohol, dodecyl sulfonic acid, hydroxylamine hydrochloride and caustic alkali by two steps; and the synthesis method comprises the following steps of adding fatty acid, short chain alcohol and dodecyl sulfonic acid into a reactor, stirring and reacting at a constant temperature of 75 DEG C-100 DEG C; carrying out reduced pressure distillation on the reactants to obtain fatty acid ester; adding hydroxylamine hydrochloride into another reactor, adding caustic alkali in batches while stirring, and mixing; adding fatty acid ester and reacting for 3-5 hours at 40 DEG C-60 DEG C to obtain a hydroxamate solution; and rapidly cooling the hydroxamate solution to obtain the solid hydroxamate. By the synthesis method, the conversion between acid-alkali environment for the esterification and hydroximation two-step reaction is avoided, the synthesized product needs not to be subjected to processing steps such as acidification, impurity removal and purification and the obtained product can be organically combined with flotation industry. The synthesis method has the advantages that the operation is simple, the yield of the product is high, the generation of a large amount of acidic wastewater is avoided and the cost of chemical agents is effectively decreased.
Description
Technical field
The present invention relates to a kind of synthetic method of highly effective chelating flotation collector, particularly the synthetic method of place's hydroximic acid salt.
Background technology
The structural formula of hydroximic acid molecule is RC (=O) NHOH, the Sauerstoffatom in molecule and nitrogen-atoms all with lone-pair electron, can with Fe
3+, Cu
2+, Zn
2+, Ni
2+be combined into stable complex compound Deng metal ion, hydroximic acid is successfully applied in the test of multi mineral flotation separation.Hydroximic acid has the history of nearly 70 years as flotation collector, achieves good flotation effect, widely uses in the flotation in the ore deposits such as cassiterite ore deposit, ilmenite, tungsten ore, rare-earth mineral, phosphorus ore, zinc ore, copper oxide ore.In the beneficiation test of the polymetallic ore of complexity, it is successfully crucial with hydroximic acid to be that flotation collector has become many ore-dressing techniques.Hydroximic acid is as the flotation collector of oxidized ore, and possessing advantage that is efficient, low toxicity, is the medicament extremely with development prospect.
The synthetic method of hydroximic acid mainly contains hydroxylamine assay, nitroparaffins rearrangement method, nitroparaffins reduction method, thermo-cracking preparing process, acid amides oxidation style, biological enzyme conversion method and solid-phase synthesis etc.Hydroxylamine assay, because technique is simple, technical difficulty is little and not high to equipment requirements, is the most frequently used synthetic method of hydroximic acid.Due to processing condition, other synthetic method requires that higher use is little, also have no suitability for industrialized production report.Hydroxylamine assay synthesis technique generates hydroximic acid with carboxylic acid or carboxylic acid derivative for nucleophilic substitution reaction occurs in the basic conditions for raw material and free hydroxylamine, azanol-ester method in hydroxylamine assay is the most frequently used method of current industrial synthesis hydroximic acid, synthesis technique is the first Acrawax under the katalysis of an acidic catalyst by the lipid acid of suitable carbon chain lengths and lower alcohol, there is hydroxyl oximation reaction in the basic conditions with free azanol in the ester of synthesis, is then acidified with acid and can obtains corresponding hydroximic acid.
Although the simple and easy handling of azanol-ester method synthesis technique, but the complicated loaded down with trivial details hydroximic acid product loss of effective components that makes of intermediate treatment process is too much, generally in esterification the vitriol oil is used to be catalyzer, shortcomings such as there is etching apparatus, contaminate environment, to be difficultly separated, by product is many, selectivity of product is low.In synthesis technique, esterification and hydroxyl oximation reaction acid-basicity are completely contradicted, and cause simple two-step reaction will experience the conversion of three soda acid solvent environment, can produce a large amount of industrial acidic wastewaters, this causes white elephant to environment.Obtain as hydroximic acid salts solution after hydroxyl oximation reaction terminates, expect the solid phase prod about hydroximic acid, industrial sulfuric acid or the hydrochloric acid of normally adopting is by acidified for hydroximic acid the thick product of hydroximic acid, and thick product acidifying obtained repeatedly can obtain the highly purified hydroximic acid crystal product of part after recrystallization.In acidization meeting, have the generation of a large amount of acid waste water, acidization has part hydroximic acid not separate out simultaneously, and this can cause the reduction greatly of product yield.The solubleness of hydroximic acid in water is very little, when Floatation Industry is applied, need to add caustic alkali or ammonia solvent, the acidifying precipitation before and after this and Alkaline solubilization not only cause the generation of the loss of part hydroximic acid and a large amount of acid waste water, and making complicated operation, cost increases greatly.
Summary of the invention
Technical problem to be solved by this invention is for the deficiencies in the prior art, and propose a kind of synthetic method of new hydroximic acid salt, the method is simple to operate, and product yield is high, avoids the generation of a large amount of acid waste water, effectively reduces reagent cost.
Technical problem to be solved by this invention is realized by following technical scheme.The present invention is a kind of synthetic method of hydroximic acid salt, is characterized in: the method uses lipid acid, short chain alcohol, dodecyl sodium sulfonate, oxammonium hydrochloride and caustic alkali to synthesize hydroximic acid salt in two steps, and its concrete steps are as follows:
(1) preparation of fatty acid ester: add lipid acid, short chain alcohol and dodecyl sodium sulfonate in the reactor, the ratio of the amount of three is, lipid acid: short chain alcohol: dodecyl sodium sulfonate=1:3 ~ 8:0.10 ~ 0.15, constant temperature stirring reaction 4 ~ 8 hours at 75 DEG C ~ 100 DEG C; Reactant underpressure distillation, obtains fatty acid ester, reclaims unreacted alcohol;
(2) preparation of hydroximic acid salt: add hydroxylamine hydrochloride solution in another reactor, add caustic alkali under agitation in batches, oxammonium hydrochloride is 1:2 ~ 2.2 with the ratio of the amount of substance of caustic alkali, is uniformly mixed 10 ~ 20 minutes after adding caustic alkali; Add fatty acid ester, fatty acid ester is 1:1.0 ~ 1.2 with the ratio of the amount of substance of oxammonium hydrochloride, after adding fatty acid ester, reacts 3 ~ 5 hours at 40 DEG C ~ 60 DEG C; The hydroximic acid salts solution fast cooling obtained obtains hydroximic acid salt solid.
The synthetic method of a kind of hydroximic acid salt of the present invention, its further preferred technical scheme or technical characteristic as follows:
1, after hydroximic acid salts solution fast cooling obtains hydroximic acid salt solid, in solution, remaining hydroximic acid salt uses lipid acid extraction saponification to obtain hydroximic acid combined capturing and collecting agent; The present invention extracts the lipid acid that hydroximic acid salt uses can select different lipid acid and consumption according to the actual type of ore, can prepare the combined capturing and collecting agent with different performance;
In the preparation of 2, step (1) fatty acid ester: the ratio of the amount of lipid acid, short chain alcohol, dodecyl sodium sulfonate three is 1:5:0.12; In the preparation of step (2) hydroximic acid salt: oxammonium hydrochloride is 1:2 with the ratio of the amount of substance of caustic alkali; Fatty acid ester is 1:1.1 with the ratio of the amount of substance of oxammonium hydrochloride;
3, described lipid acid comprises C
6~ C
12aliphatics, alicyclic and phenyl ring race, and the mixture of different carbon chain;
4, the unreacted alcohol cycling and reutilization obtained will can be reclaimed;
5, described short chain alcohol is preferably methyl alcohol or ethanol;
6, described caustic alkali is preferably sodium hydroxide or potassium hydroxide;
7, vacuum distillation temperature is preferably 40 DEG C ~ 60 DEG C.
8, the charge temperature of caustic alkali preferably controls below 30 DEG C.
The purposes of hydroximic acid combined capturing and collecting agent in the flotation of oxidized ore obtained by synthetic method of a kind of hydroximic acid salt of the present invention.
The inventive method take dodecyl sodium sulfonate as catalyst for esterification reaction, avoid soda acid converting process complicated in traditional synthesis, dodecyl sodium sulfonate can make emulsifying agent in hydroxyl oximation reaction simultaneously has promoter action to reaction, therefore, esterification terminate after by reacting with free hydroxylamine after simple underpressure distillation process.In addition, hydroximic acid is less demanding to product purity when Floatation Industry uses as collecting agent, the collecting agents such as normal and lipid acid combinationally use, therefore, reacted pyrosol fast cooling can be obtained the hydroximic acid salt solid that part is purer, can directly apply in Floatation Industry, the hydroximic acid salt lipid acid in solution residue extracts after saponification, and product also can directly use in Floatation Industry.
Compared with the synthesis technique of existing hydroximic acid, the present invention has the following advantages:
1. use dodecyl sodium sulfonate to be catalyzer in the esterification reaction, avoid the generation of the vitriol oil to the corrosion of equipment and a large amount of acid waste water;
2. the simple convenient operation of the treating processes after esterification, dodecyl sodium sulfonate can be used as emulsifying agent has promoter action to hydroxyl oximation reaction, can improve the synthesis yield of hydroximic acid salt;
3. hydroxyl oximation reaction terminate after by lower the temperature and extraction obtains hydroximic acid salt solid, without the need to acidifying purification step, avoid the loss of hydroximic acid and the generation of a large amount of acid waste water;
4. product is hydroximic acid salt solid, and Floatation Industry directly can dissolve use, without the need to adding alkali dissolution;
5. according to the type of actual ore, by means of only the type and the consumption that change extraction lipid acid, the hydroximic acid combined capturing and collecting agent that performance perameter is different can be prepared.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of synthetic method of the present invention.
Embodiment
The present invention is further illustrated by following examples, but not by the restriction of these embodiments.In embodiment, unless otherwise specified all numbers and percentage ratio all refer to quality.
Embodiment 1, with reference to accompanying drawing 1, a kind of synthetic method of hydroximic acid salt, the method uses lipid acid, short chain alcohol, dodecyl sodium sulfonate, oxammonium hydrochloride and caustic alkali to synthesize hydroximic acid salt in two steps, and its concrete steps are as follows:
(1) preparation of fatty acid ester: add lipid acid, short chain alcohol and dodecyl sodium sulfonate in the reactor, the ratio of the amount of three is, lipid acid: short chain alcohol: dodecyl sodium sulfonate=1:3:0.10, constant temperature stirring reaction 4 hours at 75 DEG C DEG C; Reactant underpressure distillation, obtains fatty acid ester, reclaims unreacted alcohol;
(2) preparation of hydroximic acid salt: add hydroxylamine hydrochloride solution in another reactor, add caustic alkali under agitation in batches, oxammonium hydrochloride is 1:2 with the ratio of the amount of substance of caustic alkali, is uniformly mixed 10 minutes after adding caustic alkali; Add fatty acid ester, fatty acid ester is 1:1.0 with the ratio of the amount of substance of oxammonium hydrochloride, after adding fatty acid ester, reacts 3 hours at 40 DEG C; The hydroximic acid salts solution fast cooling obtained obtains hydroximic acid salt solid.
Embodiment 2, a kind of synthetic method of hydroximic acid salt, the method uses lipid acid, short chain alcohol, dodecyl sodium sulfonate, oxammonium hydrochloride and caustic alkali to synthesize hydroximic acid salt in two steps, and its concrete steps are as follows:
(1) preparation of fatty acid ester: add lipid acid, short chain alcohol and dodecyl sodium sulfonate in the reactor, the ratio of the amount of three is, lipid acid: short chain alcohol: dodecyl sodium sulfonate=1:8:0.15, constant temperature stirring reaction 8 hours at 100 DEG C; Reactant underpressure distillation, obtains fatty acid ester, reclaims unreacted alcohol;
(2) preparation of hydroximic acid salt: add hydroxylamine hydrochloride solution in another reactor, add caustic alkali under agitation in batches, oxammonium hydrochloride is 1:2.2 with the ratio of the amount of substance of caustic alkali, is uniformly mixed 20 minutes after adding caustic alkali; Add fatty acid ester, fatty acid ester is 1:1.2 with the ratio of the amount of substance of oxammonium hydrochloride, after adding fatty acid ester, reacts 5 hours at 60 DEG C; The hydroximic acid salts solution fast cooling obtained obtains hydroximic acid salt solid.
Embodiment 3, a kind of synthetic method of hydroximic acid salt, the method uses lipid acid, short chain alcohol, dodecyl sodium sulfonate, oxammonium hydrochloride and caustic alkali to synthesize hydroximic acid salt in two steps, and its concrete steps are as follows:
(1) preparation of fatty acid ester: add lipid acid, short chain alcohol and dodecyl sodium sulfonate in the reactor, the ratio of the amount of three is, lipid acid: short chain alcohol: dodecyl sodium sulfonate=1:5:0.12, constant temperature stirring reaction 6 hours at 85 DEG C; Reactant underpressure distillation, obtains fatty acid ester, reclaims unreacted alcohol;
(2) preparation of hydroximic acid salt: add hydroxylamine hydrochloride solution in another reactor, add caustic alkali under agitation in batches, oxammonium hydrochloride is 1:2 with the ratio of the amount of substance of caustic alkali, is uniformly mixed 15 minutes after adding caustic alkali; Add fatty acid ester, fatty acid ester is 1:1.1 with the ratio of the amount of substance of oxammonium hydrochloride, after adding fatty acid ester, reacts 4 hours at 50 DEG C; The hydroximic acid salts solution fast cooling obtained obtains hydroximic acid salt solid.
Embodiment 4, in the synthetic method of a kind of hydroximic acid salt described in embodiment 1 or 2 or 3: after hydroximic acid salts solution fast cooling obtains hydroximic acid salt solid, in solution, remaining hydroximic acid salt uses lipid acid extraction saponification to obtain hydroximic acid combined capturing and collecting agent.
Embodiment 5, in the synthetic method of a kind of hydroximic acid salt of embodiment 1-4 described in any one: described lipid acid comprises C
6~ C
12aliphatics, alicyclic and phenyl ring race, and the mixture of different carbon chain.
Embodiment 6, in the synthetic method of a kind of hydroximic acid salt of embodiment 1-5 described in any one: will reclaim the unreacted alcohol cycling and reutilization obtained.
Embodiment 7, in the synthetic method of a kind of hydroximic acid salt of embodiment 1-6 described in any one: described short chain alcohol is methyl alcohol or ethanol.
Embodiment 8, in the synthetic method of a kind of hydroximic acid salt of embodiment 1-7 described in any one: described caustic alkali is sodium hydroxide or potassium hydroxide.
Embodiment 9, in the synthetic method of a kind of hydroximic acid salt of embodiment 1-8 described in any one: vacuum distillation temperature is 40 DEG C ~ 60 DEG C.
Embodiment 10, in the synthetic method of a kind of hydroximic acid salt of embodiment 1-9 described in any one: the charge temperature of caustic alkali controls below 30 DEG C.
Embodiment 11, the preparation experiment of benzyl hydroximic acid sodium:
Add 122 parts of phenylformic acid in the reactor, 192 parts of methyl alcohol and 39.2 parts of dodecyl sodium sulfonates, constant temperature stirring reaction 6 hours at 80 DEG C, by reaction mixture underpressure distillation at 40 DEG C ~ 60 DEG C after reaction terminates, the methyl alcohol reclaimed is recycling, obtains the methyl benzoate of about 175 parts and the mixture of dodecyl sodium sulfonate.76.4 parts of hydroxylamine hydrochloride solution are added in another reactor, add 88 parts of sodium hydroxide under the mild stirring of room in batches, be uniformly mixed 10 ~ 20 minutes, make oxammonium hydrochloride fully free, add the methyl benzoate of 175 parts and the mixture of dodecyl sodium sulfonate, react 3 hours at temperature of reaction is 45 DEG C.The hydroximic acid salts solution obtained is by obtaining the benzyl hydroximic acid sodium solid that 118 parts of purity are 78.3% after fast cooling filtration drying, the total content of the remaining benzyl hydroximic acid sodium in solution is 50 parts, if with the oleic acid of 387 parts extraction and saponification can obtain benzyl hydroximic acid and oleic acid mass ratio is the combined capturing and collecting agent of 1:9.
Embodiment 12, the preparation experiment of Using Salicyl Hydroximic Acid sodium:
Add 138 parts of Whitfield's ointments in the reactor, 192 parts of methyl alcohol and 39.2 parts of dodecyl sodium sulfonates, constant temperature stirring reaction 5 hours at 80 DEG C, by reaction mixture underpressure distillation at 40 DEG C ~ 60 DEG C after reaction terminates, the methyl alcohol reclaimed is recycling, obtains the wintergreen oil of about 190 parts and the mixture of dodecyl sodium sulfonate.76.4 parts of hydroxylamine hydrochloride solution are added in another reactor, add 88 parts of sodium hydroxide under the mild stirring of room in batches, be uniformly mixed 10 ~ 20 minutes, make oxammonium hydrochloride fully free, add the wintergreen oil of 190 parts and the mixture of dodecyl sodium sulfonate, react 3 hours at temperature of reaction is 50 DEG C.The hydroximic acid salts solution obtained is by obtaining the Using Salicyl Hydroximic Acid sodium solid that 132 parts of purity are 79.6% after fast cooling filtration drying, the total content of the remaining Using Salicyl Hydroximic Acid sodium in solution is 55 parts, if with the oleic acid of 913 parts extraction and saponification can obtain Using Salicyl Hydroximic Acid and oleic acid mass ratio is the combined capturing and collecting agent of 5:95.
Embodiment 13, the preparation experiment of n-octyl sodium alkyl hydroxamate:
Add 144 parts of n-caprylic acid in the reactor, 224 parts of methyl alcohol and 39.2 parts of dodecyl sodium sulfonates, constant temperature stirring reaction 6 hours at 90 DEG C, by reaction mixture underpressure distillation at 40 DEG C ~ 60 DEG C after reaction terminates, the methyl alcohol reclaimed is recycling, obtains the methyl caprylate of about 196 parts and the mixture of dodecyl sodium sulfonate.76.4 parts of hydroxylamine hydrochloride solution are added in another reactor, add 88 parts of sodium hydroxide under the mild stirring of room in batches, be uniformly mixed 10 ~ 20 minutes, make oxammonium hydrochloride fully free, add the methyl caprylate of 196 parts and the mixture of dodecyl sodium sulfonate, react 3 hours at temperature of reaction is 55 DEG C.The hydroximic acid salts solution obtained is by obtaining the n-octyl sodium alkyl hydroxamate solid that 144 parts of purity are 77.8% after fast cooling filtration drying, the total content of the remaining n-octyl sodium alkyl hydroxamate in solution is 49 parts, if with the stearic acid of 387 parts extraction and saponification can obtain n-octyl hydroximic acid and stearic acid mass ratio is the combined capturing and collecting agent of 1:9.
Embodiment 14, the preparation experiment of lauryl sodium alkyl hydroxamate:
Add 200 parts of lauric acid in the reactor, 256 parts of methyl alcohol and 39.2 parts of dodecyl sodium sulfonates, constant temperature stirring reaction 8 hours at 90 DEG C, by reaction mixture underpressure distillation at 40 DEG C ~ 60 DEG C after reaction terminates, the methyl alcohol reclaimed is recycling, obtains the Laurate methyl of about 252 parts and the mixture of dodecyl sodium sulfonate.76.4 parts of hydroxylamine hydrochloride solution are added in another reactor, add 88 parts of sodium hydroxide under the mild stirring of room in batches, be uniformly mixed 10 ~ 20 minutes, make oxammonium hydrochloride fully free, add the Laurate methyl of 252 parts and the mixture of dodecyl sodium sulfonate, react 4 hours at temperature of reaction is 55 DEG C.The hydroximic acid salts solution obtained is by obtaining the lauryl sodium alkyl hydroxamate solid that 175 parts of purity are 76.7% after fast cooling filtration drying, the total content of the remaining lauryl sodium alkyl hydroxamate in solution is 73 parts, if with the naphthenic acid of 596 parts extraction and saponification can obtain lauryl hydroximic acid and naphthenic acid mass ratio is the combined capturing and collecting agent of 1:9.
Embodiment 15, the preparation experiment of cyclohexyl methyl sodium alkyl hydroxamate:
Add 128 parts of heptanaphthenic acid in the reactor, 160 parts of methyl alcohol and 39.2 parts of dodecyl sodium sulfonates, constant temperature stirring reaction 5 hours at 90 DEG C, by reaction mixture underpressure distillation at 40 DEG C ~ 60 DEG C after reaction terminates, the methyl alcohol reclaimed is recycling, obtains the heptanaphthenic acid methyl esters of about 180 parts and the mixture of dodecyl sodium sulfonate.76.4 parts of hydroxylamine hydrochloride solution are added in another reactor, add 88 parts of sodium hydroxide under the mild stirring of room in batches, be uniformly mixed 10 ~ 20 minutes, make oxammonium hydrochloride fully free, add the heptanaphthenic acid methyl esters of 180 parts and the mixture of dodecyl sodium sulfonate, react 3 hours at temperature of reaction is 45 DEG C.The hydroximic acid salts solution obtained is by obtaining the cyclohexyl methyl sodium alkyl hydroxamate solid that 122 parts of purity are 78.5% after fast cooling filtration drying, the total content of the remaining cyclohexyl methyl sodium alkyl hydroxamate in solution is 52 parts, if with the oleic acid of 405 parts extraction and saponification can obtain cyclohexyl methyl hydroximic acid and oleic acid mass ratio is the combined capturing and collecting agent of 1:9.
Embodiment 16, C
8~ C
10the preparation experiment of mixing sodium alkyl hydroxamate:
Add 158 parts of C in the reactor
8~ C
10mixed fatty acid, 224 parts of methyl alcohol and 39.2 parts of dodecyl sodium sulfonates, constant temperature stirring reaction 6 hours at 90 DEG C, by reaction mixture underpressure distillation at 40 DEG C ~ 60 DEG C after reaction terminates, the methyl alcohol of recovery is recycling, obtains the C of about 210 parts
8~ C
10mixed methyl aliphatic ester and the mixture of dodecyl sodium sulfonate.In another reactor, add 76.4 parts of hydroxylamine hydrochloride solution, under the mild stirring of room, add 88 parts of sodium hydroxide in batches, be uniformly mixed 10 ~ 20 minutes, make oxammonium hydrochloride fully free, add 210 parts of C
8~ C
10mixed methyl aliphatic ester and the mixture of dodecyl sodium sulfonate, react 3 hours at temperature of reaction is 55 DEG C.The hydroximic acid salts solution obtained is the C of 76.5% by obtaining 146 parts of purity after fast cooling filtration drying
8~ C
10mixing sodium alkyl hydroxamate solid, the remaining C in solution
8~ C
10the total content of mixing sodium alkyl hydroxamate is 60 parts, if with the oleic acid of 479 parts extraction also saponification can obtain C
8~ C
10mixing hydroximic acid and oleic acid mass ratio are the combined capturing and collecting agent of 1:9.
Claims (10)
1. a synthetic method for hydroximic acid salt, is characterized in that: the method uses lipid acid, short chain alcohol, dodecyl sodium sulfonate, oxammonium hydrochloride and caustic alkali to synthesize hydroximic acid salt in two steps, and its concrete steps are as follows:
(1) preparation of fatty acid ester: add lipid acid, short chain alcohol and dodecyl sodium sulfonate in the reactor, the ratio of the amount of three is, lipid acid: short chain alcohol: dodecyl sodium sulfonate=1:3 ~ 8:0.10 ~ 0.15, constant temperature stirring reaction 4 ~ 8 hours at 75 DEG C ~ 100 DEG C; Reactant underpressure distillation, obtains fatty acid ester, reclaims unreacted alcohol;
(2) preparation of hydroximic acid salt: add hydroxylamine hydrochloride solution in another reactor, add caustic alkali under agitation in batches, oxammonium hydrochloride is 1:2 ~ 2.2 with the ratio of the amount of substance of caustic alkali, is uniformly mixed 10 ~ 20 minutes after adding caustic alkali; Add fatty acid ester, fatty acid ester is 1:1.0 ~ 1.2 with the ratio of the amount of substance of oxammonium hydrochloride, after adding fatty acid ester, reacts 3 ~ 5 hours at 40 DEG C ~ 60 DEG C; The hydroximic acid salts solution fast cooling obtained obtains hydroximic acid salt solid.
2. the synthetic method of a kind of hydroximic acid salt according to claim 1, is characterized in that: after hydroximic acid salts solution fast cooling obtains hydroximic acid salt solid, and in solution, remaining hydroximic acid salt uses lipid acid extraction saponification to obtain hydroximic acid combined capturing and collecting agent.
3. the synthetic method of a kind of hydroximic acid salt according to claim 1 and 2, is characterized in that: in the preparation of step (1) fatty acid ester: the ratio of the amount of lipid acid, short chain alcohol, dodecyl sodium sulfonate three is 1:5:0.12; In the preparation of step (2) hydroximic acid salt: oxammonium hydrochloride is 1:2 with the ratio of the amount of substance of caustic alkali; Fatty acid ester is 1:1.1 with the ratio of the amount of substance of oxammonium hydrochloride.
4. the synthetic method of a kind of hydroximic acid salt according to claim 1 and 2, is characterized in that: described lipid acid comprises C
6~ C
12aliphatics, alicyclic and phenyl ring race, and the mixture of different carbon chain.
5. the synthetic method of a kind of hydroximic acid salt according to claim 1 and 2, is characterized in that: will reclaim the unreacted alcohol cycling and reutilization obtained.
6. the synthetic method of a kind of hydroximic acid salt according to claim 1 and 2, is characterized in that: described short chain alcohol is methyl alcohol or ethanol.
7. the synthetic method of a kind of hydroximic acid salt according to claim 1 and 2, is characterized in that: described caustic alkali is sodium hydroxide or potassium hydroxide.
8. the synthetic method of a kind of hydroximic acid salt according to claim 1 and 2, is characterized in that: vacuum distillation temperature is 40 DEG C ~ 60 DEG C.
9. the synthetic method of a kind of hydroximic acid salt according to claim 1 and 2, is characterized in that: the charge temperature of caustic alkali controls below 30 DEG C.
10. the purposes of hydroximic acid combined capturing and collecting agent in the flotation of oxidized ore obtained by synthetic method of a kind of hydroximic acid salt according to claim 2.
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