CN102219199A - Method for cogenerating calcium hydroxide and sodium chloride by magnesium hydrogen phosphate heptahydrate prepared by boric sludge - Google Patents

Abstract

A method for cogenerating calcium hydroxide and sodium chloride by magnesium hydrogen phosphate heptahydrate prepared by boric sludge, relating to three wastes treatment and comprehensive utilization in inorganic chemical industry. Boric sludge is obtained by acid leaching recovery and purification synthesis so as to prepare heptahydrate magnesium hydrogen phosphate and then cogenerate calcium hydroxide and sodium chloride. The method comprises the steps as follows: conducting acid leaching recovery: heating boric sludge by steam, conducting liquid-solid separation by using a whirling centrifugal machine, then obtaining filtrate containing boric acid for processing; adding hydrochloric acid in a filter cake containing magnesium oxide for reaction, then generating magnesium chloride solution, calcium chloride solution and manganese chloride solution; filtering filter cake silicon dioxide for processing; conducting purification synthesis: removing impurity in the recovered filtrate by magnesium hydroxide so as to generate precipitation of hydroxide of calcium chloride and manganese chloride respectively, and filtering so as to obtain calcium hydroxide and manganic hydroxide; adding dibasic sodium phosphate in magnesium chloride in the filtrate for reaction so as to obtain mixture solution of heptahydrate magnesium hydrogen phosphate and sodium chloride; filtering so as to obtain filter cake heptahydrate magnesium hydrogen phosphate; conducting reduced pressure distillation on the filtrate, and when the solution is saturated, cooling the solution so as to separate out sodium chloride crystallization. According to the method, the economical benefits of boric sludge waste materials are improved.

Description

The method that is equipped with secondary magnesium phosphate seven water thing co-producing calcium hydroxides and sodium-chlor with boric sludge

Technical field

The present invention relates to the technical field of the inorganic chemical industry disposal of three wastes and comprehensive utilization, particularly a kind of method that is equipped with secondary magnesium phosphate seven water thing co-producing calcium hydroxides and sodium-chlor with boric sludge.

Background technology

Boron mud is with szaibelyite (2MgOB ₂O ₃H ₂O) be raw material, by roasting, pulverizing, mix, take the carbon water law to produce borax (Na with soda ash ₂B ₄O ₇10H ₂O), remaining solid waste after washing, crystallisation process extract borax.Produce one ton of borax and can produce 4 tons of boron mud, a borax plant that produces 8000 tons per year, can produce boron mud every year is 3.2 ten thousand tons.Because the quantity discharged of boron mud is bigger, the multiple comprehensive Utilization Ways of present domestic employing except that producing Magnesium Carbonate Light 41-45 and magnesium oxide and plastic and rubber filler, also has the coal of producing boron magnesium phosphorus composite fertilizer, making honeycomb briquette reinforced and do architectural borax etc.

Magnesium in the boron mud generally all is that the form with magnesiumcarbonate exists, and is sometimes also different and difference arranged along with the mineral products of szaibelyite.The component of producing Magnesium Carbonate Light 41-45 boron mud is such: magnesium oxide 38%, silicon-dioxide 20%, carbonic acid gas 17%, boron oxide 3%, calcium oxide 3%, manganese oxide 0.11%, other are moisture content.

One should improve constantly the value of output object to the utilization of boron mud, and some markets of output product in short supply, that added value is big is to improve the economic benefit that boron mud utilizes.

Two, well-known, the utilization of boron mud is relevant with magnesium, and magnesium-containing compound is very extensive in each field application, and wherein seven water secondary magnesium phosphates can be used as accessory substance, Ph conditioning agent, stablizer, wrapping material softening agent etc., and purposes is very extensive.

Summary of the invention

The present invention is intended at the utilization of boron mud and the market requirement, and a kind of method that is equipped with secondary magnesium phosphate seven water thing co-producing calcium hydroxides and sodium-chlor with boric sludge is provided.

For achieving the above object, be equipped with the technical scheme of method of secondary magnesium phosphate seven water thing co-producing calcium hydroxides and sodium-chlor with boric sludge as follows in the present invention:

Be equipped with the method for secondary magnesium phosphate seven water thing co-producing calcium hydroxides and sodium-chlor with boric sludge, boron mud by acidleach recovery, purifying synthesis technique, made seven water secondary magnesium phosphates, simultaneously co-producing calcium hydroxide and sodium-chlor:

Technology is reclaimed in described acidleach: boron mud was kept 1-2 hour to 60-80 ℃ with steam heating, with the liquid-solid separation of drying whizzer, obtained the filtrate deep processing separately based on boric acid then; Magnesium oxide in the filter cake boron mud and hydrochloric acid react in first corrosion-resistant reactor by the mass ratio 1 of pure substance: 1.63-2.03, stir; Reaction generates magnesium chloride, calcium chloride and manganese chloride solution; Filtration obtains the deep processing separately of filter cake silicon-dioxide; Clarifying filtrate is done further purifying;

Described purifying synthesis technique is: reclaim clear filtrate that technology obtains with an amount of magnesium hydroxide impurity and purification through acidleach, make calcium chloride and Manganous chloride tetrahydrate generate precipitation of hydroxide respectively, washing after filtration, drying and crushing, sizing screening, packing obtain calcium hydroxide and manganous hydroxide product respectively; Gained filtrate is the magnesium chloride clear liquor; Magnesium chloride and sodium hydrogen phosphate react in second corrosion-resistant reactor by the mass ratio 1 of pure substance: 1.63-2.03 in the clear liquor, stir; Obtain seven water secondary magnesium phosphates and sodium-chlor mixed solution; Filter, filter cake is through washing drying, drying and crushing, being packaged to be seven water secondary magnesium phosphate products; Filtrate is sent into the underpressure distillation device and is carried out underpressure distillation, when solution reaches capacity concentration distillate is ejected, and separates out through being cooled to the sodium-chlor crystallization, obtains the sodium chloride crystal product through washing, drying, pulverizing.

The used boron mud of the present invention is for producing the boron mud of Magnesium Carbonate Light 41-45, and its component is: magnesium oxide, silicon-dioxide, carbonic acid gas, boron oxide, calcium oxide, manganese oxide and moisture.What certainly, other boron mud of similar components also can adapt to the present invention is equipped with the method for magnesium basic carbonate coproduction calcium and manganese oxyhydroxide with boric sludge.

Chemical equation of the present invention is:

MgO+2HCl＝＝＝＝MgCl ₂+H ₂O

CaO+2HCl＝＝＝＝CaCl ₂+H ₂O

MnO+2HCl＝＝＝＝MnCl ₂+H ₂O

CaCl ₂+Mg(OH) ₂＝＝＝＝MgCl ₂+Ca(OH) ₂

MnCl ₂+Mg(OH) ₂＝＝＝＝MgCl ₂+Mn(OH) ₂

MgCl ₂+Na ₂HPO ₃+7H ₂O＝＝＝＝MgHPO ₃·7H ₂O+2NaCl

Beneficial effect of the present invention is: one, and provide a kind of and be equipped with the method for secondary magnesium phosphate seven water thing co-producing calcium hydroxides and sodium-chlor with boric sludge, can effectively handle boron mud waste material.Its two, preparation comprises seven water secondary magnesium phosphates, calcium hydroxide and sodium-chlor, all serves many purposes, remarkable in economical benefits has improved the economic benefit of handling boron mud waste material.Its three, preparation purity height, quality is guaranteed.

Embodiment

Embodiment one

Be equipped with the method for secondary magnesium phosphate seven water thing co-producing calcium hydroxides and sodium-chlor with boric sludge, boron mud by acidleach recovery, purifying synthesis technique, is made seven water secondary magnesium phosphates, simultaneously co-producing calcium hydroxide and sodium-chlor; The used boron mud of the present invention is for producing the boron mud of Magnesium Carbonate Light 41-45, and its component is: magnesium oxide 38%, silicon-dioxide 20%, carbonic acid gas 17%, boron oxide 3%, calcium oxide 3%, manganese oxide 0.11%, other are moisture.

Technology is reclaimed in acidleach: get 500Kg boron mud and kept 1-2 hour to 60-80 ℃ with steam heating, with the liquid-solid separation of drying whizzer, obtain the filtrate deep processing separately based on boric acid then; Magnesium oxide in the filter cake boron mud (pure quality is 190Kg) and hydrochloric acid react in first corrosion-resistant reactor by the mass ratio of pure substance 1: 1.63, stir; Reaction generates magnesium chloride, calcium chloride and manganese chloride solution; Filtration obtains the deep processing separately of filter cake silicon-dioxide; Clarifying filtrate is done further purifying;

The purifying synthesis technique is: reclaim clear filtrate that technology obtains with an amount of magnesium hydroxide impurity and purification through acidleach, make calcium chloride and Manganous chloride tetrahydrate generate precipitation of hydroxide respectively, washing after filtration, drying and crushing, sizing screening, packing obtain calcium hydroxide and a small amount of manganous hydroxide product respectively; Gained filtrate is the magnesium chloride clear liquor; Magnesium chloride in the clear liquor (it is 403Kg that previous reaction generates the pure quality of magnesium chloride altogether) and sodium hydrogen phosphate react in second corrosion-resistant reactor by the mass ratio of pure substance at 1: 1.63, stir; Obtain seven water secondary magnesium phosphates and sodium-chlor mixed solution; Filter, filter cake is through washing drying, drying and crushing, being packaged to be seven water secondary magnesium phosphate product 1199Kg; Filtrate is sent into the underpressure distillation device and is carried out underpressure distillation, when solution reaches capacity concentration distillate is ejected, and separates out through being cooled to the sodium-chlor crystallization, obtains sodium chloride crystal product 610Kg through washing, drying, pulverizing.

Embodiment two

Be equipped with the method for secondary magnesium phosphate seven water thing co-producing calcium hydroxides and sodium-chlor with boric sludge, boron mud by acidleach recovery, purifying synthesis technique, is made seven water secondary magnesium phosphates, simultaneously co-producing calcium hydroxide and sodium-chlor; The used boron mud of the present invention is for producing the boron mud of Magnesium Carbonate Light 41-45, and its component is: magnesium oxide 38%, silicon-dioxide 20%, carbonic acid gas 17%, boron oxide 3%, calcium oxide 3%, manganese oxide 0.11%, other are moisture.

Technology is reclaimed in acidleach: get 500Kg boron mud and kept 1-2 hour to 60-80 ℃ with steam heating, with the liquid-solid separation of drying whizzer, obtain the filtrate deep processing separately based on boric acid then; Magnesium oxide in the filter cake boron mud (pure quality is 190Kg) and hydrochloric acid react in first corrosion-resistant reactor by the mass ratio of pure substance 1: 1.83, stir; Reaction generates magnesium chloride, calcium chloride and manganese chloride solution; Filtration obtains the deep processing separately of filter cake silicon-dioxide; Clarifying filtrate is done further purifying;

The purifying synthesis technique is: reclaim clear filtrate that technology obtains with an amount of magnesium hydroxide impurity and purification through acidleach, make calcium chloride and Manganous chloride tetrahydrate generate precipitation of hydroxide respectively, washing after filtration, drying and crushing, sizing screening, packing obtain calcium hydroxide and a small amount of manganous hydroxide product respectively; Gained filtrate is the magnesium chloride clear liquor; Magnesium chloride in the clear liquor (it is 452Kg that previous reaction generates the pure quality of magnesium chloride altogether) and sodium hydrogen phosphate react in second corrosion-resistant reactor by the mass ratio of pure substance at 1: 1.83, stir; Obtain seven water secondary magnesium phosphates and sodium-chlor mixed solution; Filter, filter cake is through washing drying, drying and crushing, being packaged to be seven water secondary magnesium phosphate product 1510Kg; Filtrate is sent into the underpressure distillation device and is carried out underpressure distillation, when solution reaches capacity concentration distillate is ejected, and separates out through being cooled to the sodium-chlor crystallization, obtains sodium chloride crystal product 768Kg through washing, drying, pulverizing.

Embodiment three

Be equipped with the method for secondary magnesium phosphate seven water thing co-producing calcium hydroxides and sodium-chlor with boric sludge, boron mud by acidleach recovery, purifying synthesis technique, is made seven water secondary magnesium phosphates, simultaneously co-producing calcium hydroxide and sodium-chlor; The used boron mud of the present invention is for producing the boron mud of Magnesium Carbonate Light 41-45, and its component is: magnesium oxide 38%, silicon-dioxide 20%, carbonic acid gas 17%, boron oxide 3%, calcium oxide 3%, manganese oxide 0.11%, other are moisture.

Technology is reclaimed in acidleach: get 500Kg boron mud and kept 1-2 hour to 60-80 ℃ with steam heating, with the liquid-solid separation of drying whizzer, obtain the filtrate deep processing separately based on boric acid then; Magnesium oxide in the filter cake boron mud (pure quality is 190Kg) and hydrochloric acid react in first corrosion-resistant reactor by the mass ratio of pure substance 1: 2.03, stir; Reaction generates magnesium chloride, calcium chloride and manganese chloride solution; Filtration obtains the deep processing separately of filter cake silicon-dioxide; Clarifying filtrate is done further purifying;

The purifying synthesis technique is: reclaim clear filtrate that technology obtains with an amount of magnesium hydroxide impurity and purification through acidleach, make calcium chloride and Manganous chloride tetrahydrate generate precipitation of hydroxide respectively, washing after filtration, drying and crushing, sizing screening, packing obtain calcium hydroxide and a small amount of manganous hydroxide product respectively; Gained filtrate is the magnesium chloride clear liquor; Magnesium chloride in the clear liquor (it is 502Kg that previous reaction generates the pure quality of magnesium chloride altogether) and sodium hydrogen phosphate react in second corrosion-resistant reactor by the mass ratio of pure substance at 1: 2.03, stir; Obtain seven water secondary magnesium phosphates and sodium-chlor mixed solution; Filter, filter cake is through washing drying, drying and crushing, being packaged to be seven water secondary magnesium phosphate product 1860Kg; Filtrate is sent into the underpressure distillation device and is carried out underpressure distillation, when solution reaches capacity concentration distillate is ejected, and separates out through being cooled to the sodium-chlor crystallization, obtains sodium chloride crystal product 946Kg through washing, drying, pulverizing.

Claims (2)

1. be equipped with the method for secondary magnesium phosphate seven water thing co-producing calcium hydroxides and sodium-chlor with boric sludge, it is characterized in that: boron mud makes seven water secondary magnesium phosphates by acidleach recovery, purifying synthesis technique, simultaneously co-producing calcium hydroxide and sodium-chlor:

Technology is reclaimed in described acidleach: boron mud was kept 1-2 hour to 60-80 ℃ with steam heating, with the liquid-solid separation of drying whizzer, obtained the filtrate deep processing separately based on boric acid then; Magnesium oxide in the filter cake boron mud and hydrochloric acid react in first corrosion-resistant reactor by the mass ratio 1 of pure substance: 1.63-2.03, stir; Reaction generates magnesium chloride, calcium chloride and manganese chloride solution; Filtration obtains the deep processing separately of filter cake silicon-dioxide; Clarifying filtrate is done further purifying;

Described purifying synthesis technique is: reclaim clear filtrate that technology obtains with an amount of magnesium hydroxide impurity and purification through acidleach, make calcium chloride and Manganous chloride tetrahydrate generate precipitation of hydroxide respectively, washing after filtration, drying and crushing, sizing screening, packing obtain calcium hydroxide and manganous hydroxide product respectively; Gained filtrate is the magnesium chloride clear liquor; Magnesium chloride and sodium hydrogen phosphate react in second corrosion-resistant reactor by the mass ratio 1 of pure substance: 1.63-2.03 in the clear liquor, stir; Obtain seven water secondary magnesium phosphates and sodium-chlor mixed solution; Filter, filter cake is through washing drying, drying and crushing, being packaged to be seven water secondary magnesium phosphate products; Filtrate is sent into the underpressure distillation device and is carried out underpressure distillation, when solution reaches capacity concentration distillate is ejected, and separates out through being cooled to the sodium-chlor crystallization, obtains the sodium chloride crystal product through washing, drying, pulverizing.

2. according to claim 1ly be equipped with the method for magnesium basic carbonate coproduction calcium and manganese oxyhydroxide, it is characterized in that with boric sludge: described boron mud, contain magnesium oxide, silicon-dioxide, carbonic acid gas, boron oxide, calcium oxide, manganese oxide and moisture in its component.