CN1013103B

CN1013103B - Preparation technique of hydrous ferrous sulphate

Info

Publication number: CN1013103B
Application number: CN 87102022
Authority: CN
Inventors: 唐国干
Original assignee: Individual
Current assignee: Individual
Priority date: 1987-05-06
Filing date: 1987-05-06
Publication date: 1991-07-10
Also published as: CN87102022A

Abstract

The present invention relates to a technique for preparing ferrous sulfate monohydrate with high purity and hard oxidation. The technique takes coarse green vitriol prepared by the oxidation of pyritic in moist air or green vitriol which is a by-product for preparing titanium pigment as a raw material, and the ferrous sulfate monohydrate is prepared by the working procedures of washing, boiling, extracting, concentration, crystallization, drying, etc. The technique has the advantages of simple preparation and low cost, the obtained products are hard to oxidize or deteriorate in the moist air, and therefore, the technique enlarges application ranges. The ferrous sulfate monohydrate is suitable for being used as a raw material of a feed additive and can also be used in the fields of aquatic product, agriculture, chemical industry, medical treatment and food service industry.

Description

Preparation technique of hydrous ferrous sulphate

The present invention relates to a kind ofly prepare the purity height, be difficult for the ferrous sulfate monohydrate (Feso of oxidation ₄H ₂O) technology.

In chemical industry dictionary and national chemical reagent products catalogue, point out ferrous sulfate (Feso ₄7H ₂O), be commonly called as green whetstone, blue-greenish colour monoclinic crystal, proportion 1.899(14.8 ℃), 64 ℃ of fusing points, lose six molecular crystal water at 90 ℃, lose whole crystal water, weathering gradually in air at 300 ℃, and oxidation and be tawny, anhydride is a white powder, and proportion is 3.4, then becomes blue-greenish colour again with the water effect, water-soluble, be dissolved in ethanol hardly, reductive action is arranged, natural product has melanterite, can be by iron and dilute sulphuric acid effect and make, specification GB664-77, the ferrous sulfate that the domestic market produces is iron vitriol (Feso ₄7H ₂O), many because of containing crystal water, in dry air weathering, be the rapid deterioration by oxidation of wind in damp atmosphere, thereby limited its application.Still there is not the producer that produces ferrous sulfate monohydrate at home, national standard and province's standard of not working out ferrous sulfate monohydrate yet.Looking into USP4055631 open day the 77,10, the 25th, is raw material with the green vitriol, uses double evaporation-cooling to reduce crystal water, is heated to 56.5～64.8 ℃ at saturated ferrous sulfate for the first time and makes Feso ₄7H ₂O transfers Feso to ₄4H ₂O for the second time is to heat and make Feso at 75～90 ℃ ₄H ₂O, its quality is not good enough.

Task of the present invention provides a kind of green vitriol that utilizes, and prepares the purity height, is difficult for the technology of the ferrous sulfate monohydrate of oxidation, and this prepared is simple, and cost is low, and its products obtained therefrom is difficult for deterioration by oxidation in damp atmosphere, thereby enlarges its range of application.

To achieve these goals, solution of the present invention is, utilizes operations such as green vitriol is put forward through cleaning, boiling, concentrated, crystallization, drying and makes, and it is characterized in that utilizing sulfurous iron ore (Fes ₂) product-green vitriol of paying of the thick green vitriol that makes through oxidation in damp atmosphere or preparation titanium dioxide makes raw material, after cleaning surfactant suspension impurity, put into iron pan or enamel reaction still, the water or the deionization exchanged water that add six times of amounts dissolve, and add 10% steel cuttings, in advance at 10%Na ₂CO ₃Boil in the solution, after oil removing is derusted, and it is clean with the tap water flushing, heated and boiled is to pH value 4.5～5.5 then, filter, if heavy metal content is less than 0.002% in the green vitriol, do not need removal of impurities, when heavy metal content greater than 0.002% the time, for removing the heavy metal in the product, can in solution, feed hydrogen sulfide, make it generate insoluble vitriol and remove, the clean steel cuttings that in filtrate, still adds green vitriol amount 10%, to absorb residual sulfuric acid root in the filtrate, thereby stablize acidity, filtrate is concentrated into 1/3～1/4 of original volume, left standstill crystallisation by cooling 12～14 hours, Tc is advisable at 10～25 ℃, with crystallization with a small amount of 95% washing with alcohol, and dry surperficial moisture content with whizzer, and in stainless steel drying plant or loft drier, carry out drying then, be heated to 30～40 ℃ earlier, remove partial crystallization water, be heated to 90～120 ℃ then and dewater, remove six molecular crystal water, after crushed, obtain high purity, be difficult for oxidation white or linen ferrous sulfate monohydrate crystalline powder, in time be encapsulated in lucifuge the bottle in or in the packaging vessel.

The present invention compared with prior art has following advantage:

1. this product is white or canescence crystalline powder, odorless, and content is 95～98%, is a kind of high purity, is difficult for the ferrous sulfate monohydrate of oxidation; And USP4055631 uses double evaporation-cooling, and to reduce crystal water, its quality is not good enough.

2. this technology prices of raw and semifnished materials are cheap, and cost is low, are to utilize sulfurous iron ore (Fes ₂) byproduct-green vitriol of oxidation makes in damp atmosphere thick green vitriol or preparation titanium dioxide is made raw material, and domestic most employing iron and dilute sulphuric acid prepare iron vitriol;

3. of many uses, the anaemia and the raw material of making fodder additives that in herding, are used for livestock and poultry, on aquatic products, add copper sulfate with this product, be used to prevent and treat the rotted gill disease of fish, on agricultural, can make weedicide, on chemical industry, be used as water purification agent, gas scavenger, and be used to make ink, pigment, metal surface sanitas.As hematinic, its contained iron is synthetic blood red dirty raw material in the body, can treat modal hypoferric anemia, can be used as additive on food in medical treatment.

Technical process of the present invention is: thick green vitriol clean → boils to be carried → concentrates → crystallization → drying → pulverizing → packing → finished product.

Embodiment one:

Get sulfurous iron ore (Fes ₂) 3 kilograms of the thick green vitriols that make, remove its surperficial suspended impurity with the tap water flushing after, be put in iron pan or the enamel reaction still, add ion exchanged water and dissolve for 18 kilograms, and add 0.3 kilogram of steel cuttings, its steel cuttings is in advance through 10%Na ₂CO ₃Solution boils, and it is clean with the tap water flushing, heated and boiled is evaporated to pH value 4.5～5.5 and filters then, in case of necessity (when heavy metal content greater than 0.002%) for removing heavy metal in the product, can in solution, feed hydrogen sulfide, make it generate insoluble vitriol and remove, in filtrate, still add 0.3 kilogram of clean steel cuttings,, stablize acidity to absorb remaining sulfate radical, be concentrated into original volume 1/3～1/4, left standstill crystallisation by cooling 12～14 hours, room temperature is 20 ℃, with crystallization with a small amount of 95% washing with alcohol, and dry surperficial moisture content with whizzer, moisture eliminator is put in crystallization carried out drying, remove partial crystallization water at 40 ℃ earlier, be warming up to 90～100 ℃ then and dewater, make 0.75 kilogram of ferrous sulfate monohydrate white powder, after tested result: Feso ₄Content is 85.54%, calculates Feso ₄H ₂O content is 95.67% or Feso ₄7H ₂O content is 156.44%: acidity: show blue, pH value is 3.0～4.0.Heavy metal content is 0.002%; Arsenic salt: the arsenic spot does not show.

Embodiment two:

Get 5 kilograms of preparation titanium dioxide byproduct-green vitriols, after removing surfactant suspension impurity with tap water flushing, put into iron pan or enamel reaction still, add 0.5 kilogram of 30 kilograms of ion exchanged waters and clean steel cuttings, its steel cuttings pretreatment process is identical with embodiment one, heated and boiled to pH value 4.5～5.5 filters then, it is identical with embodiment one to remove in the product heavy metal method in case of necessity, in filtrate, still add 0.5 kilogram of clean steel cuttings, be concentrated into 1/3～1/4 of original volume, left standstill crystallisation by cooling 12～14 hours, room temperature is 15 ℃, and crystallization with a small amount of 95% washing with alcohol, and is dried surperficial moisture content with whizzer, put into loft drier and carry out drying, be heated to 40 ℃ earlier and remove partial crystallization water, be heated to 90～100 ℃ then and dewater, remove six molecular crystal water, make 2.2 kilograms of ferrous sulfate monohydrate white powders, after tested result: Feso ₄Content is 86.66%, calculates Feso ₄H ₂O content is 96.88%, or Feso ₄7H ₂O content is 158.64%, and acidity shows blue, and pH value is 3.0～4.0, and heavy metal content is 0.002%, arsenic salt: the arsenic spot does not show.

The present invention is along with the material purity difference, and recovery rate is generally 25～50%.

Claims

1, a kind of technology of preparation-aqueous ferrous sulfate, be through washing, boil carry, concentrate, operation such as crystallization, drying and making, it is characterized in that making raw material with green vitriol, after cleaning surfactant suspension impurity, add the water of 6 times of amounts or the clean steel cuttings of ion exchanged water and 10%, boil, filtering and impurity removing, still adding 10% clean steel cuttings in filtrate concentrates, leave standstill crystallisation by cooling, after a small amount of 95% washing with alcohol, carry out drying and dehydrating, crystals dried temperature is divided two constant temperature stages: the fs is 30～40 ℃, and subordinate phase is 90～120 ℃.

2, technology according to claim 1 is characterized in that heavy metal content for removing the heavy metal in the product, can feed hydrogen sulfide greater than 0.002 o'clock in the green vitriol in solution.