CN105883920A - Preparation method of chromium trichloride - Google Patents

Abstract

The invention discloses a preparation method of chromium trichloride. The preparation method includes the following steps: 1) neutralizing chromium sulfate and a 8-15% sodium hydroxide solution to obtain chromium hydroxide; 2) performing a reaction to the chromium hydroxide with 2-2.5 times of hydrochloric acid to obtain a reaction liquid; 3) concentrating the reaction liquid, adding activated carbon, and filtering the reaction liquid through three stages: one activated carbon and two filter membranes, with temperature maintained at 50-60 DEG C to obtain a filtrate; and 4) spray-drying the filtrate to obtain the chromium trichloride. The preparation method increases yield and reduces content of impurities through selection and optimization on reaction liquid concentration and material proportion. In a drying method of a crystallization machine, the spray-drying method is employed preferably to replace a conventional organic solvent crystallization and vacuum drying method, so that the preparation method is environment-friendly, saves working time, reduces energy consumption and effectively controls water content. The preparation method is short in process, is low in cost, is short in time, is high in yield and content, is low in environment pollution and is very suitable for industrial production. The method aims to provide high-quality raw materials for chromium (III) medicine preparations.

Description

A kind of preparation method of chromium chloride

Technical field

The present invention relates to the novel preparation method of a kind of chromium chloride, belong to chemical field.

Background technology

Chromium chloride, chemical formula: CrCl3 6H2O, for green or bottle-green crystalline powder, it is dissolved in water, It is dissolved in ethanol, insoluble in ether.Green solution is become with water after seething with excitement for a long time.The scorchinggest hot, become Chrome green.Cl gas flow can distil, and carbon tetrachloride at 400 DEG C altogether heat can to obtain dynamics lazy The purple anhydride of property.Six water things have bottle green, light green color and three kinds of variants of purple, the most all become Become bottle green and purple mixture, but at DMSO, DMF, the organic solvent such as ethanol present blackish green. For chromic salts processed, chromium plating with make mordant etc..Printing and dyeing industry is used as mordant；Electroplating industry is used for chromium plating； Chemical industry is used for producing other chromic salts；Pigment industry is used for manufacturing various containing chromium pigment；Organic synthesis aspect For manufacturing chrome catalysts, it is possible to be used as decomposing agents.

Chromium chloride or a kind of specific medicament for treating diabetes, chromium is considered as the trace that body weight for humans is wanted Element.Although it is not appointed as recommended dietary supply (RDA) by national research council, but sets Determine adult's safety every day and suitable intake has been 50-200ug.While it is known that chromium at sugar and Lipid-metabolism plays an important role, but the mechanism of action in mankind's metabolism is still not very clear. It has been reported that chromium is important to sugar tolerance and insulin resistance.Chromium is bioactive with external in vivo Different it is verified that.Chromium deficiency can significantly be treated by inorganic trivalent chromium and other chromium organically combined.

The pharmacological action of chromium includes: 1. control blood sugar.Chromium has confactor effect necessary to insulin function. Or insulin can be improved be combined with cell surface receptor, or improve by the number stopped, make diabetic's Normalizing plasma glucose.2. reconcile lipid.Chromium can reduce total lipoprotein and low-density lipoprotein, serum cholesterol, and Improve high density sebum albumen.Chromium can significantly improve the insulin synthesis to albumen.3. control the most aging Process.In old man's body, chromium concn reduces, thus it is speculated that ageing process itself may lack with internal long-term chromium or consume The most relevant.

The synthetic method of the chromium chloride of document report has following several: carbon chromium chloridising prepares chromium chloride, hydrogen Chromium chloride is prepared in chromium oxide chlorination, the acid of chromium hydroxide hydrochloric acid molten prepares chromium chloride and chromic anhybride ethanol reduction legal system The methods such as standby chromium chloride.But because of the problem such as technology, preparation method all have that product content is low, yield is low, Cost is high or the various defects such as difficult industrialization.

Chinese patent CN201310374697 discloses the production method of a kind of chromium chloride hexahydrate, and the method uses Chromic anhybride ethanol reduction.Although this process route is the most briefly, easily operate, but during use a large amount of Organic solvent, production cost is high, yield is low and not environmentally.

Summary of the invention

In the technology of preparing of existing chromium chloride, or technique is the longest；Or follow-up when crystallizing, gained Required grade solvent effluent volume is big；Or it is the highest directly to add impurity treatment degree when organic solvent crystallizes； Various reasons, causes impurity, yield level cost to become the difficult problem that the needs of this production solve.

It is an object of the invention to by reaction solution concentration, the screening of material proportion and optimization are reached improve yield, Reduce the purpose of magazine.By changing crystallizer drying means, preferably spray drying method substitutes traditional organic Solvent crystal, vacuum drying method, reached environmental protection, saved man-hour, reduce energy consumption, effectively control moisture Purpose.Production operation step is brief, cost is lower, the most shorter, yield is higher, content is higher, right The pollution of environment is less, is especially suitable for industrialized production.It is intended that trivalent chromium medicine preparation provides the former of high-quality Material.

For achieving the above object, the present invention adopts the following technical scheme that

The preparation method of a kind of chromium chloride, comprises the steps:

1) sodium hydroxide solution of chromium sulfate and 8-15% occurs to neutralize reaction and obtains chromium hydroxide.

2) step 1) chromium hydroxide that synthesizes and 2-2.5 times amount hydrochloric acid reaction obtain reactant liquor.

3) will reactant liquor concentrate after add activated carbon, keep feed liquid 50-60 DEG C through activated carbon, two The three-stage filtration of secondary filter membrane, takes filtrate.

4) chromium chloride finished product is obtained after filtrate is spray-dried.

The concrete concrete synthetic route of chromium oxide following (being only exemplified by signal):

6NaOH+Cr2(SO4)3→3Na2SO4+2Cr(OH)3+6HCL→2CrCl3

The preparation method of chromium chloride of the present invention, described step 1) neutralize the NaOH selected in reaction The concentration of solution is 8-15%, preferably 12%.

The preparation method of chromium chloride of the present invention, described step 2) middle dropping 2-2.5, times amount hydrochloric acid, excellent Elect 2 times amount as.

The preparation method of chromium chloride of the present invention, described step 4) in drying means for being spray-dried.

As a kind of preferred forms of the present invention, described preparation method comprises the steps:

1), under room temperature, in enamel tank, chromium sulfate is slowly added dropwise the hydrogen of 10% by the purified water of 3 times amount after dissolving Sodium hydroxide solution occurs to neutralize reaction 1 hour, after filtration, at 70-80 degree, filter cake is carried out vacuum drying and obtains hydrogen Chromium oxide.

2), under room temperature, in enamel tank, add chromium hydroxide, add 5 times amount purified water stirring and dissolving.Drip The hydrochloric acid adding 2.2 times amount reacts, and 30min drips, and 90 DEG C of reactions obtain reactant liquor in 2 hours.

3) by reactant liquor in 80 DEG C～85 DEG C, vacuum is not more than under the conditions of-0.08mp, after being concentrated into half Add 5% and enter activated carbon decolorizing 30min, keep feed liquid at 50-60 DEG C through an activated carbon, twice filter membrane Three-stage filtration, takes filtrate.

4) filtrate obtains chromium chloride finished product after drying in 70-75 DEG C of spray-dried device.

The most obvious feature of the present invention is exactly that the concentration controlling NaOH and the amount of hydrochloric acid and addition reaches control Impurity processed, the purpose of raising yield.Secondly, preferably crystallization dry run, use the spray drying to instead of The process of organic solvent crystallization, substantially increases yield and the yield of product, and decreases pollution, reduces Cost.Simply, easily operate, damage ratio conventional method is much smaller, and considering cost is low for whole technical process, Process is suitable for industrial production.

Accompanying drawing explanation

Fig. 1 is the process chart of preparation method of the present invention.

Detailed description of the invention

Following example are used for illustrating the present invention, but are not limited to the scope of the present invention.If not specializing, The conventional means that technological means used in embodiment is well known to those skilled in the art, raw materials used is Commercial goods.

The preparation of embodiment 1 chromium chloride

1), under room temperature, in enamel tank, 50kg chromium sulfate and the purified water of 150kg, stirring and dissolving are added. There is neutralization reaction 1 hour, by filter cake at 70-80 after filtration in the sodium hydroxide solution 320L being slowly added dropwise 8% Degree carries out vacuum drying and obtains chromium hydroxide 15.45kg.

2) under room temperature, in enamel tank, add 15.45kg chromium hydroxide obtained in the previous step, add 77.25kg Purified water stirring and dissolving.Dropping 30.9kg concentrated hydrochloric acid reacts, and 30min drips, and 90 DEG C of reactions 2 are little Time obtain 112L reactant liquor.

3) by reactant liquor in 80 DEG C～85 DEG C, vacuum is not more than under the conditions of-0.08mp, after being concentrated into 56L Add 0.75kg and enter activated carbon decolorizing 30min, keep feed liquid at 50-60 DEG C through activated carbon, twice filter membrane Three-stage filtration, take filtrate.

4) filtrate obtains 19.35kg chromium chloride finished product after drying in 70-75 DEG C of spray-dried device.Total recovery 60%, content 99.5%.

The preparation (preferred plan) of embodiment 2 chromium chloride

1), under room temperature, in enamel tank, 50kg chromium sulfate and the purified water of 150kg, stirring and dissolving are added. There is neutralization reaction 1 hour, by filter cake at 70-80 after filtration in the sodium hydroxide solution 250L being slowly added dropwise 10% Degree carries out vacuum drying and obtains chromium hydroxide 16.15kg.

2) under room temperature, in enamel tank, add 16.15kg chromium hydroxide obtained in the previous step, add 80.75kg Purified water stirring and dissolving.Dropping 32.3kg concentrated hydrochloric acid reacts, and 30min drips, and 90 DEG C of reactions 2 are little Time obtain 118L reactant liquor.

3) by reactant liquor in 80 DEG C～85 DEG C, vacuum is not more than under the conditions of-0.08mp, after being concentrated into 59L Add 0.8kg and enter activated carbon decolorizing 30min, keep feed liquid at 50-60 DEG C through activated carbon, twice filter membrane Three-stage filtration, take filtrate.

4) filtrate obtains 19.85kg chromium chloride finished product after drying in 70-75 DEG C of spray-dried device.Total recovery 61.5%, content 99.4%.

The preparation of embodiment 3 chromium chloride

1), under room temperature, in enamel tank, 50kg chromium sulfate and the purified water of 150kg, stirring and dissolving are added. There is neutralization reaction 1 hour in the sodium hydroxide solution 166.7L being slowly added dropwise 15%, is existed by filter cake after filtration 70-80 degree carries out vacuum drying and obtains chromium hydroxide 16.10kg.

2) under room temperature, in enamel tank, add 16.10kg chromium hydroxide obtained in the previous step, add 80.5kg Purified water stirring and dissolving.Dropping 32.2kg concentrated hydrochloric acid reacts, and 30min drips, and 90 DEG C of reactions 2 are little Time obtain 115L reactant liquor.

3) by reactant liquor in 80 DEG C～85 DEG C, vacuum be not more than under the conditions of-0.08mp, be concentrated into 55.5L After add 0.8kg and enter activated carbon decolorizing 30min, keep feed liquid at 50-60 DEG C through activated carbon, twice filter The three-stage filtration of film, takes filtrate.

4) filtrate obtains 19.90kg chromium chloride finished product after drying in 70-75 DEG C of spray-dried device.Total recovery 61.7%, content 99.0%.

The preparation of embodiment 4 chromium chloride

1), under room temperature, in enamel tank, 50kg chromium sulfate and the purified water of 150kg, stirring and dissolving are added. There is neutralization reaction 1 hour, by filter cake at 70-80 after filtration in the sodium hydroxide solution 250L being slowly added dropwise 10% Degree carries out vacuum drying and obtains chromium hydroxide 16.15kg.

2) under room temperature, in enamel tank, add obtained in the previous step 16,15kg chromium hydroxide, add 80.75kg Purified water stirring and dissolving.Dropping 32.3kg concentrated hydrochloric acid reacts, and 25min drips, and 90 DEG C of reactions 2 are little Time obtain 118L reactant liquor.

3) by reactant liquor in 80 DEG C～85 DEG C, vacuum is not more than under the conditions of-0.08mp, after being concentrated into 59L Add 0.8kg and enter activated carbon decolorizing 30min, keep feed liquid at 50-60 DEG C through activated carbon, twice filter membrane Three-stage filtration, take filtrate.

4) filtrate obtains 19.92kg chromium chloride finished product after drying in 70-75 DEG C of spray-dried device.Total recovery 61.7%, content 99.1%.

The preparation of embodiment 5 chromium chloride

1), under room temperature, in enamel tank, 50kg chromium sulfate and the purified water of 150kg, stirring and dissolving are added. There is neutralization reaction 1 hour, by filter cake at 70-80 after filtration in the sodium hydroxide solution 250L being slowly added dropwise 10% Degree carries out vacuum drying and obtains chromium hydroxide 16.15kg.

2) under room temperature, in enamel tank, add 16.15kg chromium hydroxide obtained in the previous step, add 80.75kg Purified water stirring and dissolving.Dropping 32.3kg concentrated hydrochloric acid reacts, and 35min drips, and 90 DEG C of reactions 2 are little Time obtain 118L reactant liquor.

3) by reactant liquor in 80 DEG C～85 DEG C, vacuum is not more than under the conditions of-0.08mp, after being concentrated into 59L Add 0.8kg and enter activated carbon decolorizing 30min, keep feed liquid at 50-60 DEG C through activated carbon, twice filter membrane Three-stage filtration, take filtrate.

4) filtrate obtains 19.78kg chromium chloride finished product after drying in 70-75 DEG C of spray-dried device.Total recovery 61.3%, content 99.5%.

Although, the present invention is described in detail the most with a general description of the specific embodiments, But on the basis of the present invention, can make some modifications or improvements it, this is to those skilled in the art Obviously.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all Belong to the scope of protection of present invention.

Claims (5)

1. the preparation method of a chromium chloride, it is characterised in that the production method of this chromium chloride includes following step Rapid:

1) sodium hydroxide solution of chromium sulfate and 8-15% occurs to neutralize reaction and obtains chromium hydroxide.

2) step 1) chromium hydroxide that synthesizes and 2-2.5 times amount hydrochloric acid reaction obtain reactant liquor.

3) will reactant liquor concentrate after add activated carbon, keep feed liquid 50-60 DEG C through activated carbon, two The three-stage filtration of secondary filter membrane, takes filtrate.

4) chromium chloride finished product is obtained after filtrate is spray-dried.

2. preparation method as claimed in claim 1, it is characterised in that described step 1) neutralization reaction The concentration of the sodium hydroxide solution of middle selection is 8-15%, preferably 12%.

3. preparation method as claimed in claim 1, it is characterised in that described step 2) middle dropping 2-2.5, Times amount hydrochloric acid, preferably 2 times amount.

4. preparation method as claimed in claim 1, it is characterised in that described step 4) in drying means For being spray-dried.

Method the most according to claim 1, it is characterised in that: comprise the steps:

1), under room temperature, in enamel tank, chromium sulfate is slowly added dropwise the hydrogen of 10% by the purified water of 3 times amount after dissolving Sodium hydroxide solution occurs to neutralize reaction 1 hour, after filtration, at 70-80 degree, filter cake is carried out vacuum drying and obtains hydrogen Chromium oxide.

2), under room temperature, in enamel tank, add chromium hydroxide, add 5 times amount purified water stirring and dissolving.Drip The hydrochloric acid adding 2.2 times amount reacts, and 30min drips, and 90 DEG C of reactions obtain reactant liquor in 2 hours.

3) by reactant liquor in 80 DEG C～85 DEG C, vacuum is not more than under the conditions of-0.08mp, after being concentrated into half Add 5% and enter activated carbon decolorizing 30min, keep feed liquid at 50-60 DEG C through an activated carbon, twice filter membrane Three-stage filtration, takes filtrate.

4) filtrate obtains chromium chloride finished product after drying in 70-75 DEG C of spray-dried device.