CN100348500C

CN100348500C - Method for producing ammonium molybdate from high-impurity ferro-molybdenum

Info

Publication number: CN100348500C
Application number: CNB2006100316349A
Authority: CN
Inventors: 王学文; 肖连生; 龚柏凡; 李青刚
Original assignee: Central South University
Current assignee: Central South University
Priority date: 2006-05-11
Filing date: 2006-05-11
Publication date: 2007-11-14
Anticipated expiration: 2026-05-11
Also published as: CN1850623A

Abstract

The present invention relates to a method for producing ammonium molybdate from ferro-molybdenum with high impurity content, which comprises the processes: the ferro-molybdenum with high impurity content and sodium carbonate are mechanically activated and roasted, sand is roasted to be stirred and leached out by adding water, inorganic acid is added to leached liquid to regulate the ph value, molybdenum is exchanged by weak base anion resin irons, an ammonium molybdate solution is statically placed to settle vanadium, magnesium chloride is purified to remove P, As and Si, the vanadium is deep removed by the exchange of strong base anion resin ions, ammonium molybdate is crystallized, etc. The present invention has the advantages of strong technology adaptability, good quality of the ammonium molybdate and high Mo recovery rate; furthermore, the total technology yield can reach more than 90%, and the quality of the produced ammonium molybdate is higher than that of a secondary grade of the national standard.

Description

A kind of method of producing ammonium molybdate from high-impurity ferro-molybdenum

Technical field the present invention relates to a kind of particularly carbon containing nickel-molybdenum ore method of smelting the producing ammonium molybdate from high-impurity ferro-molybdenum obtain of high impurity ferro-molybdenum of utilizing.

Background technology carbon containing nickel-molybdenum ore difficulty is selected difficult smelting, after this ore deposit exploits out, adopts electric furnace to be smelt high impurity ferro-molybdenum mostly, and its typical chemical ingredients is: Mo10～20%, Fe55～70%, Ni4.5～10%, P4.5～6%, SiO ₂10～15%, V ₂O ₅0.5～3%, As0.3～1%.Ferro-molybdenum is mainly used in steel industry, but the ferro-molybdenum that is used for steel industry has strict restriction to the content of impurity such as P.Therefore, high impurity ferro-molybdenum has only in advance that impurity such as effective elimination P just can be used for steel industry.Yet the technology that does not have maturation to be suitable at present can be with the impurity removals such as P in the high impurity molybdenum-iron.

The traditional technology that with the brightness concentrated molybdenum ore is the raw material production ammonium molybdate is for producing ammonium molybdate from high-impurity ferro-molybdenum and inapplicable, because high impurity ferro-molybdenum fusing point is low, maturing temperature is controlled under its fusing point and will could incites somebody to action wherein molybdenum oxidation through the repeated multiple times roasting, calcining leaches with ammoniacal liquor, the leaching yield of Mo also only 80～85%, the ammonium molybdate solution that leaching obtains contains impurity such as a large amount of P, As, Si, V, Ni, and the ammonium molybdate quality that does not have the crystallization of strong purification means to obtain is also poor.

Summary of the invention removes the impurity P in the high impurity ferro-molybdenum in order effectively to utilize high impurity ferro-molybdenum, for steel industry provides acceptable material, the invention provides a kind of method of producing ammonium molybdate from high-impurity ferro-molybdenum.

A kind of method of producing ammonium molybdate from high-impurity ferro-molybdenum mainly may further comprise the steps: high impurity ferro-molybdenum and yellow soda ash mechanical activating roasting, calcining add water agitation leach, weak base negative resin ion-exchange molybdenum, ammonium molybdate solution and leave standstill after precipitation, the precipitation solution and purify with magnesium chloride and remove after P, As and Si, the purification solution and get ammonium molybdate with strong base negative resin ion-exchange deeply removing vanadium, except that solution crystallization behind the vanadium.But solution direct evaporation condensing crystal ammonium molybdate also can add hydrochloric acid or nitric acid neutralization precipitation crystallization ammonium molybdate behind the purification and impurity removal.Concrete processing parameter is: Na ₂CO ₃Extraordinarily go into by 0.5～0.8 of roasting reactive chemistry metering; The granularity of grinding the back material is negative 200 orders; 450～700 ℃ of maturing temperatures, roasting time 30～60min; Water logging solid-liquid weight ratio 1: 4～8; 45～100 ℃ of extraction temperatures, extraction time 0.5～3h; Leach liquor adds mineral acid (hydrochloric acid, sulfuric acid or nitric acid) adjust pH 2.5～5.0; Feed liquid is by 30～90min duration of contact of weak base (macroporous type or gel-type) negative resin ion exchange column; Negative molybdenum resin ammoniacal liquor (4～8mol/L NH ₃) desorb; Resin after the desorb is regenerated with hydrochloric acid (1.2～2.5 mol/L HCl); The ammonium molybdate solution room temperature that desorb obtains left standstill precipitation 0.0～2.0 day; Magnesium chloride is extraordinarily gone into by purifying reaction (P and As) stoichiometric 1.0～1.5,40～80 ℃ of insulation 0.5～1h; Purify back solution and add hydrochloric acid or nitric acid adjust pH 6.0～8.5; Solution is by 20～100min duration of contact of highly basic (macroporous type or gel-type) negative resin ion exchange column after the acid adjustment; Negative vanadium resin is with 2.0～6.0mol/L HCl solution or 0.2～1mol/L NaOH and 2.0～4.0mol/L NaCl mixing solutions desorption and regeneration; Ammonium molybdate solution can be evaporated to density 1.36～1.40g/cm ³Crystallisation by cooling also can 30～60 ℃ be extraordinarily gone into nitric acid or hydrochloric acid precipitated crystal by 1.0～1.1 of the heavy reactive chemistry metering of acid.

The present invention is with high impurity ferro-molybdenum and the levigate roasting of yellow soda ash mixing, and the molybdenum oxidation gets more thorough, and the leaching yield of molybdenum can reach 95～98%; Weak basic anion exchange resin absorption molybdenum, with the absorption of isopoly-acid root or heteropolyacid velamen, loading capacity reaches 60～130mg/ml to molybdenum in pH value 2.5～5.0, and the ammonium molybdate solution that obtains is metal ion such as iron content nickel not, do not need through ammonium sulfide purification and impurity removal operation, can avoid effectively that sulphur exceeds standard in the product; Increase the magnesium chloride cleaning section, but the P in the effective elimination ammonium molybdate solution, As, Si, the adaptive faculty that this had not only guaranteed quality product but also improved technology; Contain vanadium ammonium molybdate solution through leaving standstill precipitation, ion-exchange deeply removing vanadium, can improve ammonium molybdate product appearance quality and use properties; Ion-exchange is returned ion-exchange absorption molybdenum operation recovery V and Mo wherein except that the vanadium liquid of separating that vanadium obtains, and the total recovery that makes whole technology Mo is more than 90%, and the ammonium molybdate quality of output is more than the GB secondary.

Description of drawings

Fig. 1: producing ammonium molybdate from high-impurity ferro-molybdenum process flow diagram.

Embodiment

Below in conjunction with embodiment, the present invention is further described:

Embodiment 1

It is levigate to negative 200 orders to get 2kg high impurity ferro-molybdenum powder and 1kg anhydrous sodium carbonate mixing, 630 ℃ of roasting 60min of retort furnace, solid-liquid was than 1: 4,85 ℃ are leached 1h, leach liquor adds sour adjust pH 3.5, weak base negative resin (D314) absorption 60min duration of contact, molybdenum stripping liquid room temperature left standstill precipitation 2 days, added MgCl by 1.2 times 60 ℃ that purify the reactive chemistry metering ₂Be incubated 1 hour, purify back liquid and add hydrochloric acid adjust pH to 6.5, liquid contacts the 60min deeply removing vanadium with strong base negative resin (D231) after the acid adjustment, except that the 1.05 times 50 ℃ adding nitric acid crystallization ammonium molybdates of liquid behind the vanadium by the heavy reactive chemistry metering of acid.(%) is as follows for the experimental result of producing ammonium molybdate from high-impurity ferro-molybdenum:

	Mo	Fe	Ni	P	As	Si	V
	Mo	Fe	Ni	P	As	Si	V	Ferro-molybdenum	13.90	59.63	7.69	4.37	0.56	5.31	0.95
Leached mud	0.52	51.40	6.63	0.75	0.19	1.85	0.21	Ferro-molybdenum	13.90	59.63	7.69	4.37	0.56	5.31	0.95
Leached mud	0.52	51.40	6.63	0.75	0.19	1.85	0.21	Ammonium molybdate	58.21	0.0005	0.0005	0.0005	0.0001	0.0009	0.0015

Embodiment 2

It is levigate to negative 160 orders to get 2kg high impurity ferro-molybdenum powder and 1.2kg anhydrous sodium carbonate mixing, 600 ℃ of roasting 50min of groom's stove, solid-liquid was than 1: 4,80 ℃ are leached 2h, leach liquor adds sour adjust pH 3.1, weak base negative resin (D332) absorption 60min duration of contact, molybdenum stripping liquid room temperature left standstill precipitation 1.5 days, added MgCl by 1.1 times 60 ℃ that purify the reactive chemistry metering ₂Be incubated 0.5 hour, purify back liquid and add hydrochloric acid adjust pH to 6.6, liquid contacts the 60min deeply removing vanadium with strong base negative resin (201 * 7) after the acid adjustment, except that liquid evaporation concentration to density behind the vanadium is 1.39g/cm ³, the crystallisation by cooling ammonium molybdate.(%) is as follows for the experimental result of producing ammonium molybdate from high-impurity ferro-molybdenum:

	Mo	Ni	Fe	V	P	As	Si
	Mo	Ni	Fe	V	P	As	Si	Ferro-molybdenum	21.31	9.42	54.46	1.27	5.14	0.43	5.11
Leached mud	0.43	8.12	46.95	0.17	0.86	0.17	1.68	Ferro-molybdenum	21.31	9.42	54.46	1.27	5.14	0.43	5.11
Leached mud	0.43	8.12	46.95	0.17	0.86	0.17	1.68	Ammonium molybdate	56.71	0.0005	0.0005	0.0013	0.0005	0.0005	0.0008

Embodiment 3

It is levigate to negative 180 orders to get 3kg high impurity ferro-molybdenum powder and 1.2kg anhydrous sodium carbonate mixing, 580 ℃ of roasting 60min of groom's stove, solid-liquid was than 1: 4,90 ℃ are leached 1h, leach liquor adds sour adjust pH 3.5, weak base negative resin (D315) absorption 60min duration of contact adds MgCl by 1.2 times 60 ℃ that purify the reactive chemistry metering ₂Be incubated 1 hour, purify back liquid and add hydrochloric acid adjust pH to 6.5, liquid contacts 60min absorption vanadium after the acid adjustment with strong base negative resin (D252), except that the 1.0 times 55 ℃ adding nitric acid crystallization ammonium molybdates of liquid behind the vanadium by the heavy reactive chemistry metering of acid.The experimental result (%) that ferro-molybdenum is produced ammonium molybdate is as follows:

	Mo	Fe	Ni	P	As	Si	V
	Mo	Fe	Ni	P	As	Si	V	Ferro-molybdenum	11.4	68.31	4.78	5.72	1.033	4.72	0.27
Leached mud	0.41	58.38	4.09	0.81	0.35	2.36	0.15	Ferro-molybdenum	11.4	68.31	4.78	5.72	1.033	4.72	0.27
Leached mud	0.41	58.38	4.09	0.81	0.35	2.36	0.15	Ammonium molybdate	58.41	0.0005	0.0005	0.0005	0.0001	0.0009	0.0015

Claims

1, a kind of method of producing ammonium molybdate from high-impurity ferro-molybdenum is characterized in that: comprise that mainly high impurity ferro-molybdenum and yellow soda ash mechanical activating roasting, calcining add water agitation leach, weak base negative resin ion-exchange molybdenum, ammonium molybdate solution and leave standstill after precipitation, the precipitation solution and purify with magnesium chloride and remove after P, As and Si, the purification solution and get ammonium molybdate with strong base negative resin ion-exchange deeply removing vanadium, except that solution crystallization behind the vanadium;

Concrete processing parameter is: Na ₂CO ₃Extraordinarily go into by 0.5～0.8 of roasting reactive chemistry metering, grind negative 200 orders of granularity of back material, 450～700 ℃ of maturing temperatures, roasting time 30～60min;

Water logging solid-liquid weight ratio 1: 4～8,45～100 ℃ of extraction temperatures, extraction time 0.5～3h, leach liquor add mineral acid adjust pH 2.5～5.0;

Feed liquid is born the ammoniacal liquor desorb of molybdenum resin by 30～90min duration of contact of weak base negative resin ion exchange column, the resin regeneration of hydrochloric acid after the desorb, and the ammonium molybdate solution room temperature that desorb obtains left standstill precipitation 0.0～2.0 day;

Magnesium chloride is extraordinarily gone into by P and As stoichiometric 1.0～1.5 in the purification reaction, 40～80 ℃ of insulation 0.5～1h; Purify back solution and add hydrochloric acid or nitric acid adjust pH 6.0～8.5, solution is by 20～100min duration of contact of strong base negative resin ion exchange column after the acid adjustment; Negative vanadium resin is regenerated with 2.0～6.0mol/L HCl solution stripping; Ammonium molybdate solution transpiration cooling crystallization.