CN114534906B - Beneficiation method for molybdenum-containing high-zinc complex magnesium silicate-modified silicon-stuck-rock copper ore - Google Patents

Abstract

The invention discloses a beneficiation method for molybdenum-containing high-zinc complex magnesium silicate altered skarn-type copper ore, which includes one-stage grinding, copper-molybdenum-zinc talc mixed roughing, two-stage grinding, and copper-molybdenum-zinc talc mixing. Selection, copper-molybdenum-zinc talc flotation separation, molybdenum-zinc-talc gravity separation, and molybdenum-zinc column separation steps. The full flotation process of the present invention does not inhibit easily floating magnesium silicate minerals such as talc, but instead utilizes centrifugal gravity separation to remove them, thus avoiding the inhibition of the target sulfide metal minerals caused by macromolecular inhibitors in traditional mineral processing that inhibit easily floating gangue. , and tailings filtration and other problems, to maximize the recovery rate of the target sulfide polymetallic minerals.

Description

A mineral processing method for complex magnesium silicate altered skarn-type copper deposits containing molybdenum and high zinc

Technical field

The invention belongs to the field of mineral processing technology, and specifically relates to an ore dressing method for complex magnesium silicate altered skarn-type copper ores containing molybdenum and high zinc.

Background technique

Copper is widely used in electric power, electronic industry, construction and transportation, aerospace military industry, light industry and daily necessities, and has an important strategic position. Easy-selected porphyry copper contributes more than 70% of the world's copper, and there are many preliminary studies. However, easy-to-select copper resources are facing depletion with continuous development, and skarn-type complex copper resources are increasingly valued by mineral processing workers.

The copper minerals in the molybdenum-containing high-zinc complex magnesium silicate altered skarn-type copper ores are mainly chalcopyrite and some chalcocite and cobalt blue, the zinc minerals are mainly sphalerite, and the molybdenum minerals are mainly molybdenum. The main gangue minerals are talc, serpentine, tremolite, chlorite, hornblende and kaolinite. This type of complex magnesium silicate altered polymetallic minerals often has the following difficulties: First, layered magnesium silicate minerals such as talc have natural surface hydrophobicity and good floatability like molybdenite. Conventional inhibition of talc is difficult to achieve. Effective separation; secondly, there are often a large number of unavoidable ions in complex altered ore slurries. For example, Cu ²⁺ brought during the formation of secondary copper will have a strong activation effect on sphalerite, making sphalerite extremely floatable. Well, if the unavoidable ion influence cannot be effectively eliminated and the surface pretreatment of sphalerite cannot be effectively eliminated, sphalerite will be difficult to suppress; furthermore, in order to achieve mineral dissociation and surface pretreatment, the mineral particle size will inevitably be reduced, and some minerals cannot Avoid facing the problem of fine particle flotation separation; in summary, due to the particularity of ore properties, copper-molybdenum-zinc minerals and some magnesium silicate minerals have "indifferent" floatability, which poses a huge problem to the separation and recovery of polymetallic minerals. challenge. At present, mines mainly deal with this type of ore by partial priority flotation and mixed flotation. When the partial priority flotation process inhibits sphalerite at the front end of the process, it depends on the flotability of sphalerite and the unavoidable ionic strength of the slurry. , when there are inevitably more ions and the flotability of sphalerite is better, the inhibitory effect of sphalerite is not ideal and inhibits copper minerals; although mixed flotation avoids the suppression of copper minerals caused by sphalerite at the front end of the process However, it is difficult to solve the problem of "no difference" floatability of copper, molybdenum and zinc minerals during multi-metal separation. Forcibly inhibiting separation will cause greater harm to other target metals, and the product quality will be poor; in addition, the current mines are prone to floating magnesium silicon such as talc. Acid salts are usually pre-removed by flotation or inhibited by polymer inhibitors. Depending on the floatability of gangue, both will cause the loss of the target mineral to varying degrees. The existing process is not suitable for the separation of this type of complex magnesium silicate alteration polymetallic ores.

Contents of the invention

Aiming at the "no difference" floatability of chalcopyrite, sphalerite and molybdenite from the complex alteration of talc, serpentine, actinolite and angular shale, high zinc-containing molybdenum refractory copper ores, the present invention provides a Ore dressing technology and method for a molybdenum- and high-zinc complex magnesium silicate alteration skarn-type copper deposit.

The object of the present invention is achieved in this way, including one-stage grinding, copper-molybdenum-zinc talc mixed rough separation, two-stage grinding, copper-molybdenum-zinc talc mixed selection, copper-molybdenum-zinc talc flotation separation, and molybdenum-zinc-talc gravity separation. Separation and molybdenum-zinc column separation steps include:

A. One-stage grinding: Grind the crushed copper ore in one stage to obtain material a. The grinding fineness is -74μm accounting for 55~65%;

B. Copper-molybdenum-zinc talc mixed roughing: add pyrite inhibitor, collector and foaming agent to material a in sequence, and obtain copper-molybdenum-zinc talc mixed coarse concentrate b and roughing tailings c after one rough separation. ; Add collector and foaming agent to the roughing tailings c in sequence to perform a sweep to obtain the sweeping foam d and tailings e; the sweeping foam returns to the roughing step;

C. Second-stage grinding: Add sulfur inhibitors to the copper-molybdenum-zinc talc mixed coarse concentrate b and perform second-stage grinding to obtain material f. The grinding fineness is -74 μm accounting for 80~85%;

D. Mixed selection of copper-molybdenum-zinc talc: Add collector and foaming agent to material f in sequence, and obtain first-stage selection, second-stage selection and third-stage selection to obtain copper-molybdenum-zinc talc mixed concentrate. g and tailings h; the foam selected in the first stage goes to the second stage, and the foam selected in the second stage goes to the third stage. The foam in the third stage is copper-molybdenum-zinc talc concentrate, and the selected tailings return to the upper level of concentrate in turn. Selecting; a collector and a foaming agent are added to the selected tailings in sequence for a stage of fine sweeping and selection. The foam in one stage of fine sweeping and selection returns to the first stage of fine selection. The collectors and foaming agents are added to the tailings of a stage of fine sweeping and selection in sequence and enter the second stage of fine cleaning. Sweeping and sorting, the foam in the second stage of fine sweeping and sorting returns to the first stage of fine sweeping and sorting, and the tailings in the second stage of fine sweeping and sorting are tailings h;

E. Copper-molybdenum-zinc talc flotation separation: Add copper inhibitors, collectors and foaming agents to the copper-molybdenum-zinc talc mixed concentrate in sequence and enter rough selection. Add copper inhibitors and collectors to the foam in rough selection. The first stage of selection is carried out, and the copper inhibitor is added to the foam of the first stage of selection for the second stage of selection. The foam of the second stage of selection is molybdenum zinc talc mixed concentrate i, the tailings of the second stage of selection are returned to the first stage of selection, and the tailings of the first stage of selection are returned to Rough selection, the rough selection tailings are sequentially added with collectors and foaming agents for sweeping, the foam is returned to rough selection, and the sweeping tailings are the final copper concentrate j;

F. Molybdenum-zinc-talc gravity separation: The molybdenum-zinc-talc mixed concentrate i is concentrated and dehydrated, and then enters the centrifugal gravity selection for rough selection. The centrifugal gravity selection rough selection of the light products enters the centrifugal gravity selection for selection, and the centrifugal gravity selection selects the light products. For the final talc product, centrifugal gravity selection selects heavy products, returns to centrifugal gravity selection for rough selection, centrifugal gravity selection for rough selection, and centrifugal gravity selection for rough selection. The heavy product of sweeping is molybdenum-zinc mixed concentrate k;

G. Molybdenum-zinc column separation: Concentrate and dehydrate the molybdenum-zinc mixed concentrate k, add unavoidable ion pretreatment agent for scrubbing to obtain slurry l, add zinc inhibitors and collectors to the slurry l in sequence for rough selection, rough selection The foam is sequentially added with zinc inhibitors and collectors for one-stage selection, the first-stage selection foam is added with zinc inhibitors and collectors for the second-stage selection, the second-stage selection foam is added with zinc inhibitors for the third-stage selection, and the third-stage selection foam is The foam of the first-stage selection is the final molybdenum concentrate product m. The tailings of the third-stage selection return to the second-stage selection, the tailings of the second-stage selection return to the first-stage selection, the tailings of the first-stage selection return to the rough selection, and the tailings of the rough selection return to the rough selection. The collector is scavenged, the scavenged concentrate is returned to roughing, and the scavenged tailings are the final zinc concentrate product n.

The specific operations are as follows:

A. One-stage grinding: Grind the crushed copper ore in one stage. The grinding fineness is -74μm accounting for 55~65%.

B. Copper-molybdenum-zinc talc mixed rough selection: A certain amount of pyrite inhibitor is added to the grinding product in one stage, and a collector and foaming agent are added in sequence. After one rough selection, the rough concentrate is a copper-molybdenum-zinc talc mixed rough concentrate. Mine, roughing tailings are sequentially added with collectors and foaming agents for a sweep. The swept foam is returned to roughing, and the swept tailings are tailings 1.

C. Second-stage grinding: Add sulfur inhibitors to the copper-molybdenum-zinc talc mixed coarse concentrate obtained in step B for second-stage grinding. The grinding fineness is -74 μm accounting for 80~85%.

D. Copper-molybdenum-zinc talc mixed selection: add collector and foaming agent to the pulp ground in step C in sequence, and after one stage of selection, the foam selected in the first stage enters the second stage of selection, and the foam selected in the second stage enters the third stage Selected, the three-stage selected foam is copper-molybdenum-zinc talc mixed concentrate, and the selected tailings are returned to the previous level of selection in turn. A collector and a foaming agent are added to the first stage of fine selection tailings in turn to carry out the first stage of fine sweep and selection. The foam in the first stage of fine sweep and selection returns to the first stage of fine sweep and selection. The collector and foaming agent are added to the first stage of fine sweep and selection tailings in order to enter the second stage of fine sweep and selection. The foam is returned to the first stage of fine sweeping and sorting, and the tailings of the second stage of fine sweeping and sorting are tailings 2.

E. Copper-molybdenum-zinc talc flotation separation: Add copper inhibitor, collector, and foaming agent to the copper-molybdenum-zinc talc mixed concentrate produced in the three stages of step D in sequence to enter roughing, and add copper to the roughing foam in sequence. Inhibitors and collectors are used for one-stage selection, and copper inhibitors are added to the foam for the first-stage selection for the second-stage selection. The second-stage selection foam is molybdenum-zinc talc mixed concentrate, and the tailings from the second-stage selection are returned to the first-stage selection. The selected tailings are returned to roughing, and collectors and foaming agents are added to the roughing tailings in turn for sweeping. The foamed tailings are swept back to roughing. The sweeping tailings are the final copper concentrate.

F. Molybdenum zinc-talc gravity separation: Concentrate and dehydrate the foam selected in the second stage of step E, remove some unavoidable ions with water, and concentrate the product to a given concentration into centrifugal gravity selection for rough selection, and centrifuge gravity selection for rough selection. The product enters the centrifugal gravity selection and the light product is selected as the final talc product. The centrifugal gravity selection selects the heavy product and returns to the centrifugal gravity selection for rough selection. The centrifugal gravity selection rough selection heavy product enters the centrifugal gravity selection and sweeps. The centrifugal gravity selection The light products are returned to the centrifugal gravity separation for rough selection, and the heavy products are the molybdenum-zinc mixed concentrate.

G. Molybdenum-Zinc Column Separation: Concentrate and dehydrate the molybdenum-zinc mixed concentrate in step F, remove some unavoidable ions with water, add the unavoidable ion pretreatment agent to the concentrated product with a certain concentration, and enter the stirring mill for scrubbing under established conditions. To eliminate unavoidable ions in the slurry, the slurry after stirring, friction and scrubbing is sequentially added with zinc inhibitors and collectors and enters the flotation column for rough selection. The rough separation foam is sequentially added with zinc inhibitors and collectors for a stage of selection. The first-stage selection foam is sequentially added with zinc inhibitors and collectors for the second-stage selection. The second-stage selection foam is added with zinc inhibitors for the third-stage selection. The third-stage selection foam is the final molybdenum concentrate product. The third-stage selection is The tailings are returned to the second stage of beneficiation, the second stage beneficiation tailings are returned to the first stage of beneficiation, the first stage beneficiation tailings are returned to roughing, the roughing tailings are added with collectors for sweeping, and the sweeping concentrates are returned to roughing and sweeping. The tailings are the final zinc concentrate product.

Further, the process conditions for the mixed coarse selection of copper-molybdenum-zinc talc described in step B are to add pyrite inhibitor 2000~3000 g/ton, stir for 3~5 minutes, add collector 40~60 g/ton, Foaming agent 30~40g/ton, stir for 3~4 minutes; the process conditions for copper-molybdenum-zinc talc mixing and sweeping are to add collector 20~30g/ton, foaming agent 15~20g/ton, stir for 3 ~4 minutes;

Further, the process conditions for the copper-molybdenum-zinc talc mixed selection 1 described in step D are to add a collector of 20 to 30 g/ton, a foaming agent of 10 to 20 g/ton, and stir for 3 to 4 minutes; The process conditions of zinc talc mixed concentrate sweeping 1 are to add collector 10~15g/ton, foaming agent 5~10g/ton, stir for 3~4 minutes; the process conditions of copper molybdenum zinc talc mixed concentrate sweeping 2 To add collector 5~7.5g/ton, foaming agent 2.5~5g/ton, stir for 3~4 minutes;

Further, the copper-molybdenum-zinc talc flotation separation and roughing process conditions described in step E are to add 200~300 g/ton of copper inhibitor, stir for 3~5 minutes, add 20~30 g/ton of collector, 10~20g/ton of foaming agent, stir for 3~4 minutes; copper-molybdenum-zinc talc flotation separation and selection 1 process conditions are to add 50~100g/ton of copper inhibitor, stir for 3~5 minutes, add capture Agent 5~15g/ton, stir for 3~4 minutes; copper-molybdenum-zinc talc flotation separation and selection 2 process conditions are to add copper inhibitor 30~50g/ton, stir for 3-5 minutes; copper-molybdenum-zinc talc The flotation separation and sweeping process conditions include adding collector 10~15g/ton, foaming agent 5~10g/ton, and stirring for 3~4 minutes;

Further, the concentration concentration of molybdenum zinc-talc before gravity separation and separation described in step F is 40%~60%, the rough selection speed of centrifugal gravity selection is 600~800r/min, and the selection speed of centrifugal gravity selection is 700~900r/min. Centrifugal gravity selection sweep speed 600~800r/min;

Further, the process conditions of step G for concentration and stirring mill scrubbing before molybdenum-zinc column separation are: the concentration of the concentrated product is 50%~60%, 100~200 g/ton of unavoidable ion pretreatment agent is added to the stirring mill, and the scrubbing time is 2~3 minutes, the stirring mill uses ceramic balls, the diameter of the ceramic balls is 6~12mm, the filling rate is 40~55%, and the stirring speed is about 90~120r/min; the molybdenum-zinc column separation roughing process conditions are to add zinc inhibitor 1000~ 1500 g/ton, stir for 3 to 5 minutes, collector 30 to 60 g/ton, stir for 3 to 4 minutes; molybdenum-zinc column separation and selection 1 process conditions are to add zinc inhibitor 300 to 500 g/ton, Stir for 3 to 5 minutes, collect agent 10 to 20 g/ton, stir for 3 to 4 minutes; molybdenum-zinc column separation and selection 2 process conditions are to add zinc inhibitor 200 to 300 g/ton, stir for 3 to 5 minutes , collector 5~10g/ton, stir for 3~4 minutes; molybdenum-zinc column separation and selection 3 process conditions are to add zinc inhibitor 100~200g/ton, stir for 3~5 minutes; molybdenum-zinc column The process conditions for separation and sweeping are to add 15 to 30 grams/ton of collector and stir for 3 to 4 minutes;

Further, the pyrite inhibitor described in step B is calcium oxide. The collector is one or two of isopropyl ethyl thiocarbamate and allyl pentoxanate and one or two of isopentyl xanthate, butyl xanthate, and butylammonium xanthate. Several combinations are used, one or two of isopropyl ethyl thiocarbamate and allyl penxanthate account for 40% to 60%, isopentyl xanthate, butyl xanthate, butylammonium One or several types of black medicine account for 40% to 60%. The foaming agent is pine alcohol oil or 24K.

Further, the sulfur inhibitor described in step C is calcium oxide, and the dosage is 500~1000 g/ton;

Further, the collector described in step D is one or two of isopropyl ethyl thiocarbamate and allyl pentoxylate used in combination with butylammonium black liquor. One or both of thiocarbamate and allyl pentoxanate account for 60% to 80%, and butylammonium black drug accounts for 20% to 40%. The foaming agent is pine alcohol oil or 24K.

Further, the copper inhibitor described in step E is a mixture of sodium thioglycolate modified small molecule product and thioglycolic acid modified small molecule product, the sodium thioglycolate modified small molecule product accounts for 40% to 60%, and the thioglycolic acid modified small molecule product accounts for 40% to 60%. Modified small molecule products account for 40% to 60%. The collector is one or two of emulsified diesel and emulsified kerosene used in combination with butylammonium black powder. The collector is one or two of emulsified diesel and emulsified kerosene. Accounting for 30% to 50%, butylammonium black drug accounts for 50% to 70%. The foaming agent is 24K.

Further, the unavoidable ion pretreatment agent described in step G is one or two of sodium sulfide or calcium oxide, the zinc inhibitor is two or three of zinc sulfate, sodium sulfite and sodium sulfide, and the collector is It is one or both of emulsified diesel or emulsified kerosene.

Compared with the existing technology, the advantages of the present invention are:

1. The total flotation process of the present invention does not inhibit easily floating magnesium silicate minerals such as talc, but uses centrifugal gravity separation to remove them, avoiding the target sulfide metals caused when macromolecular inhibitors inhibit easily floating gangue in traditional mineral processing. Mineral suppression, tailings filtration and other problems can maximize the recovery rate of target sulfide polymetallic minerals.

2. Before producing the copper concentrate product, the present invention adapts to the strong floatability of sphalerite activated by unavoidable ions, does not inhibit sphalerite in the whole process, and avoids the yellowing caused by forcibly inhibiting sphalerite in a high-concentration unavoidable ion environment. The loss of target metal minerals such as copper ore and chalcocite is simplified while ensuring the recovery rate of copper minerals to the greatest extent.

3. The second-stage grinding product of the present invention is equipped with multiple selection operations, using the hydrophobicity differences of minerals to screen the floatability of gangue minerals and further remove the magnesium silicate gangue minerals with relatively poor floatability. Prevent this part of gangue minerals from entering the copper-molybdenum-zinc talc flotation separation operation due to mechanical entrainment, water flow entrainment and other factors, avoid the final copper concentrate product from being contaminated by this part of gangue minerals with poor floatability, and ensure the high quality of copper concentrate products. Pure quality.

4. The present invention uses the organic small molecule copper inhibitor D402 in the copper-molybdenum-zinc talc flotation separation operation, which avoids the simultaneous use of the traditional copper inhibitor sodium sulfide and other copper inhibitors on sphalerite when inhibiting copper minerals such as chalcopyrite and chalcocite. The inhibition caused by this process can better achieve the separation of copper minerals and zinc minerals.

5. The present invention uses centrifugal gravity separation to remove talc, which not only simplifies the pharmaceutical system, but also strengthens the recovery of fine-grained molybdenite and sphalerite, and is more in line with the advantages of back-end column separation and sorting.

6. The present invention sets up concentration and dehydration operations from flotation to gravity separation, gravity separation and then to flotation to meet the concentration requirements of the operation. At the same time, some unavoidable ions in the slurry are removed with the concentration overflow water, plus pretreatment in the stirring mill. Chemical scrubbing can fully interfere with unavoidable ions, further reduce the floatability of sphalerite in the lower stage of operation, and improve the molybdenum and zinc separation efficiency.

7. The slurry after stirring and friction is separated by a jet flotation column. The mineralized area and mineralization intensity are greater, and the characteristics of high bubble dispersion, many fine bubbles, low turbulence, and high enrichment ratio are more suitable for the industry. The separation of minerals with small buoyancy differences can produce molybdenum concentrate products and zinc concentrate products with lower mutual content.

8. The reagents used in the present invention are all conventional flotation reagents and are environmentally friendly.

Description of the drawings

Figure 1 is a schematic diagram of the process flow of the present invention.

Detailed ways

The present invention will be further described below with reference to the examples and drawings, but the present invention is not limited in any way. Any transformation or replacement based on the teachings of the present invention falls within the protection scope of the present invention.

The mineral processing method of the molybdenum-containing high-zinc complex magnesium silicate altered skarn-type copper ore of the present invention is characterized by comprising one stage of grinding, rough separation of copper-molybdenum-zinc talc mixture, two-stage grinding, and mixing of copper-molybdenum-zinc talc. The steps of selection, copper-molybdenum-zinc talc flotation separation, molybdenum-zinc-talc gravity separation, and molybdenum-zinc column separation include:

A. One-stage grinding: Grind the crushed copper ore in one stage to obtain material a. The grinding fineness is -74μm accounting for 55~65%;

B. Copper-molybdenum-zinc talc mixed roughing: add pyrite inhibitor, collector and foaming agent to material a in sequence, and obtain copper-molybdenum-zinc talc mixed coarse concentrate b and roughing tailings c after one rough separation. ; Add collector and foaming agent to the roughing tailings c in sequence to perform a sweep to obtain the sweeping foam d and tailings e; the sweeping foam returns to the roughing step;

C. Second-stage grinding: Add sulfur inhibitors to the copper-molybdenum-zinc talc mixed coarse concentrate b and perform second-stage grinding to obtain material f. The grinding fineness is -74 μm accounting for 80~85%;

D. Mixed selection of copper-molybdenum-zinc talc: Add collector and foaming agent to material f in sequence, and obtain first-stage selection, second-stage selection and third-stage selection to obtain copper-molybdenum-zinc talc mixed concentrate. g and tailings h; the foam selected in the first stage goes to the second stage, and the foam selected in the second stage goes to the third stage. The foam in the third stage is copper-molybdenum-zinc talc concentrate, and the selected tailings return to the upper level of concentrate in turn. Selecting; a collector and a foaming agent are added to the selected tailings in sequence for a stage of fine sweeping and selection. The foam in one stage of fine sweeping and selection returns to the first stage of fine selection. The collectors and foaming agents are added to the tailings of a stage of fine sweeping and selection in sequence and enter the second stage of fine cleaning. Sweeping and sorting, the foam in the second stage of fine sweeping and sorting returns to the first stage of fine sweeping and sorting, and the tailings in the second stage of fine sweeping and sorting are tailings h;

E. Copper-molybdenum-zinc talc flotation separation: Add copper inhibitors, collectors and foaming agents to the copper-molybdenum-zinc talc mixed concentrate in sequence and enter rough selection. Add copper inhibitors and collectors to the foam in rough selection. The first stage of selection is carried out, and the copper inhibitor is added to the foam of the first stage of selection for the second stage of selection. The foam of the second stage of selection is molybdenum zinc talc mixed concentrate i, the tailings of the second stage of selection are returned to the first stage of selection, and the tailings of the first stage of selection are returned to Rough selection, the rough selection tailings are sequentially added with collectors and foaming agents for sweeping, the foam is returned to rough selection, and the sweeping tailings are the final copper concentrate j;

F. Molybdenum-zinc-talc gravity separation: The molybdenum-zinc-talc mixed concentrate i is concentrated and dehydrated, and then enters the centrifugal gravity selection for rough selection. The centrifugal gravity selection rough selection of the light products enters the centrifugal gravity selection for selection, and the centrifugal gravity selection selects the light products. For the final talc product, centrifugal gravity selection selects heavy products, returns to centrifugal gravity selection for rough selection, centrifugal gravity selection for rough selection, and centrifugal gravity selection for rough selection. The heavy product of sweeping is molybdenum-zinc mixed concentrate k;

G. Molybdenum-zinc column separation: Concentrate and dehydrate the molybdenum-zinc mixed concentrate k, add unavoidable ion pretreatment agent for scrubbing to obtain slurry l, add zinc inhibitors and collectors to the slurry l in sequence for rough selection, rough selection The foam is sequentially added with zinc inhibitors and collectors for one-stage selection, the first-stage selection foam is added with zinc inhibitors and collectors for the second-stage selection, the second-stage selection foam is added with zinc inhibitors for the third-stage selection, and the third-stage selection foam is The foam of the first-stage selection is the final molybdenum concentrate product m. The tailings of the third-stage selection return to the second-stage selection, the tailings of the second-stage selection return to the first-stage selection, the tailings of the first-stage selection return to the rough selection, and the tailings of the rough selection return to the rough selection. The collector is scavenged, the scavenged concentrate is returned to roughing, and the scavenged tailings are the final zinc concentrate product n.

The pyrite inhibitor described in step B is calcium oxide, the dosage is 2000~3000 g/ton, and the stirring time is 3~5 min; the collector is isopropylethyl thiocarbamate, One or two types of allyl pentoxylate are used in combination with one or more types of isopentyl xanthate, butyl xanthate, and butylammonium xanthate. The dosage is 40~60 g/ton. Isopropyl xanthate One or two of ethylthiocarbamate and allyl penxanthate account for 40% to 60%, and one or two of isopentyl xanthate, butyl xanthate, and butylammonium black Several types account for 40% to 60%; the foaming agent is pine alcohol oil or 24K, and the dosage is 30 to 40 grams/ton.

The sulfur inhibitor described in step C is calcium oxide, and the dosage is 500 to 1000 grams/ton.

The collector described in step D is one or two of isopropylethylthiocarbamate and allyl pentoxylate used in combination with butylammonium black liquor. Isopropylethylthiocarbamate One or two types of carbamate and allyl pentoxanthate account for 60% to 80%, and butylammonium black drug accounts for 20% to 40%. The foaming agent is pine alcohol oil or 24K.

In step E, the copper inhibitor is a mixture of sodium thioglycolate-modified small molecule products and thioglycolic acid-modified small molecule products. The sodium thioglycolate-modified small molecule products account for 40% to 60%, and the thioglycolic acid-modified small molecule products account for 40% to 60%. 40% to 60%; the collector is one or both of emulsified diesel and emulsified kerosene used together with butylammonium black powder, and the collector is one or both of emulsified diesel and emulsified kerosene accounting for 30% ~50%, and butylammonium black drug accounts for 50%~70%; the foaming agent is 24K.

The centrifugal gravity selection roughing speed described in step F is 600~800r/min, the centrifugal gravity selection selection speed is 700~900r/min, and the centrifugal gravity selection sweeping speed is 600~800r/min.

The unavoidable ion pretreatment agent described in step G is one or both of sodium sulfide or calcium oxide; the zinc inhibitor is two or three of zinc sulfate, sodium sulfite and sodium sulfide, and the The collector is one or both of emulsified diesel or emulsified kerosene.

The present invention will be further described below with specific implementation examples:

Example 1

A dressing plant in Nianqing, Tibet, contains 0.59% copper, 0.015% molybdenum, 0.39% zinc, and 16.35% magnesium. The main metal minerals are sulfide minerals (chalcopyrite, chalcocite, covellite, molybdenite and sphalerite). Zinc ore), easy magnesium silicate minerals are mainly talc and serpentine. Talc and molybdenite have good natural floatability. Affected by the unavoidable ions of the ore slurry, sphalerite has excellent floatability. Talc and various metals The difference in floatability between minerals is very small and difficult to separate. The above mineral samples are processed through the following process steps:

A. One-stage grinding: Grind the crushed copper ore in one stage, and the grinding fineness is -74μm accounting for 65%.

B. Copper-molybdenum-zinc talc mixed rough selection: The first-stage grinding product is used for copper-molybdenum-zinc talc mixed rough selection. The process conditions for copper-molybdenum-zinc talc mixed rough selection are to add 3000 g/ton of calcium oxide, stir for 5 minutes, and add isopropyl in turn. 30 g/ton of ethylthiocarbamate, 20 g/ton of butyl xanthate and 30 g/ton of 24K, stir for 3 minutes, and after a rough separation, the rough concentrate is a copper-molybdenum-zinc talc mixed coarse concentrate. , add 15 g/ton of isopropyl ethyl thiocarbamate, 10 g/ton butyl xanthate and 15 g/ton 24K to the roughing tailings in sequence, stir for 3 minutes, and perform a sweep to remove the foam. Return to roughing and sweep the tailings into tailings 1.

C. Second-stage grinding: Add 800 g/ton of calcium oxide to the copper-molybdenum-zinc talc mixed coarse concentrate obtained in step B, and perform second-stage grinding. The grinding fineness is -74 μm accounting for 85%.

D. Copper-molybdenum-zinc talc mixed selection: The copper-molybdenum-zinc talc mixed selection process is to add 20 g/ton of isopropyl ethyl thiocarbamate and 10 g of butylammonium black powder to the pulp ground in step C. / ton, 24K10 g/ton, stir for 3 minutes, after one stage of selection, the foam selected in the first stage enters the second stage selection, the foam selected in the second stage enters the third stage selection, the foam selected in the third stage is a mixture of copper, molybdenum and zinc talc Mine, the selected tailings are returned to the previous level of selection in turn. To a section of selected tailings, add 10 g/ton of isopropyl ethyl thiocarbamate, 5 g/ton of butylammonium black liquor, and 5 g/ton of 24K in sequence, stir for 3 minutes, and perform one stage of fine sweeping and one stage of fine sweeping. The foam returns to a section of fine selection, and a section of fine sweep tailings is added in sequence with 5 g/ton of isopropyl ethyl thiocarbamate, 2.5 g/ton of butylammonium black powder, and 2.5 g/ton of 24K, and stir for 3 minutes. Entering the second stage of fine sweeping and sorting, the foam in the second stage of fine sweeping and sorting returns to the first stage of fine sweeping and sorting, and the tailings of the second stage of fine sweeping and sorting are tailings 2.

E. Copper-molybdenum-zinc talc flotation separation: The copper-molybdenum-zinc talc flotation separation process conditions are: add the copper-molybdenum-zinc talc mixed concentrate produced in the three stages of step D in sequence and add sodium thioglycolate modified small molecule product 150 g/ton, thioglycolic acid modified small molecule product 120 g/ton, stir for 4 minutes, add emulsified diesel oil 8 g/ton, butylammonium black powder 12 g/ton, 24K 10 g/ton, stir for 3 minutes, enter rough selection , coarsely select the foam and add 50 g/ton of sodium thioglycolate modified small molecule product, 30 g/ton of thioglycolic acid modified small molecule product, stir for 4 minutes, 4 g/ton of emulsified diesel oil, and 6 g/ton of butylammonium black liquor. , stir for 3 minutes, perform one stage of selection, add 30 g/ton of sodium thioglycolate modified small molecule product to the foam in the first stage, and 20 g/ton of thioglycolic acid modified small molecule product, stir for 4 minutes, perform the second stage of selection, The second-stage selection foam is a mixed concentrate of molybdenum-zinc talc. The second-stage selection tailings are returned to the first-stage selection, and the first-stage selection tailings are returned to the rough selection. The rough selection tailings are sequentially added with 4 g/ton of emulsified diesel oil and butylammonium black liquor. 6g/ton, 24K5g/ton, stir for 3 minutes, sweep, sweep the foam back to roughing, and sweep the tailings into the final copper concentrate.

F. Molybdenum zinc-talc gravity separation: The molybdenum zinc-talc gravity separation process conditions are to concentrate and dehydrate the selected foam in the second stage of step E, remove some unavoidable ions with water, and concentrate the product to a concentration of 50% into the rotating speed Centrifugal gravity selection at 700 r/min for rough selection, centrifugal gravity selection for rough selection, the light products enter the centrifuge gravity selection at 800 r/min for selection, the centrifugal gravity selection selects the light products as the final talc product, and the centrifugal gravity selection selects the heavy products and returns to centrifugation Gravity selection and rough selection, centrifugal gravity selection and rough selection. The heavy products enter the centrifugal gravity selection and sweep at a speed of 700r/min. The centrifugal gravity selection sweeps and sweeps the light products and returns to the centrifugal gravity selection and rough selection. The heavy products of centrifugal gravity selection and sweep are molybdenum and zinc mixed concentrates. .

G. Molybdenum-Zinc Column Separation: The molybdenum-zinc column separation process conditions are to concentrate and dehydrate the molybdenum-zinc mixed concentrate in step F, remove some unavoidable ions with water, and add 150 grams of sodium sulfide to the 60% concentrated product. / ton, enter the stirring friction scrubbing, use 8mm diameter ceramic balls for scrubbing, the filling rate is 40%, the stirring speed is 100 r/min, the slurry after stirring friction scrubbing is sequentially added with 800g/ton of zinc sulfate and 400g/ton of sodium sulfite. Stir for 4 minutes, emulsified diesel oil 40g/ton, stir for 3 minutes, enter the flotation column for rough separation, add 200g/ton of zinc sulfate and 100g/ton of sodium sulfite to the coarse separation foam, stir for 4 minutes, and add 15g/ton of emulsified diesel oil. tons, stir for 3 minutes, and perform a selection. Add 150 g/ton of zinc sulfate and 75 g/ton of sodium sulfite to the first stage of foam selection, stir for 4 minutes, stir for 3 minutes, and stir for 3 minutes to carry out the second stage of foam selection. Add 100 g of zinc sulfate to the second stage of foam selection. / ton, 50 g/ton of sodium sulfite, stir for 4 minutes, perform three-stage selection, the foam of the third-stage selection is the final molybdenum concentrate product, the tailings of the third-stage selection return to the second-stage selection, and the tailings of the second-stage selection return There is a section of fine selection, and the tailings of a section of fine selection are returned to rough selection. 20 g/ton of emulsified diesel oil is added to the coarse tailings, stirred for 3 minutes, and then swept. The sweep concentrate is returned to rough selection. The sweep tailings are the final zinc concentrate. product.

Using the above process to process the ore, the copper concentrate can be obtained with a Cu grade of 25.29% and a Cu recovery rate of 86.20%; the molybdenum concentrate has a Mo grade of 32.62% and a Mo recovery rate of 67.95%; the zinc concentrate has a Zn grade of 41.02% and a Zn recovery rate of 71.33 % technical indicators. Improved the comprehensive utilization rate of mineral resources.

Example 2

A dressing plant in Inner Mongolia contains 0.51% copper, 0.017% molybdenum, 0.31% zinc, and 15.19% magnesium. The main metal minerals are sulfide minerals (chalcopyrite, cobaltite, cobalt blue, molybdenite, and sphalerite. ore), easy magnesium silicate minerals are mainly talc. Talc and molybdenite have good natural floatability. Affected by unavoidable ions in the ore slurry, sphalerite has excellent floatability. The floatability between talc and various metal minerals The difference is extremely small and difficult to separate. The above mineral samples are processed through the following process steps:

A. One-stage grinding: Grind the crushed copper ore in one stage, and the grinding fineness is -74μm accounting for 60%.

B. Copper-molybdenum-zinc talc mixed rough selection: The first-stage grinding product is used for copper-molybdenum-zinc talc mixed rough selection. The process conditions for copper-molybdenum-zinc talc mixed rough selection are to add 2500 g/ton of calcium oxide, stir for 5 minutes, and add amyl yellow in sequence. Acid allyl ester 30 g/ton, isopentyl xanthate 20 g/ton and 24K 30 g/ton, stir for 3 minutes, and undergo a rough selection. The rough concentrate is a copper-molybdenum-zinc talc mixed coarse concentrate, and the rough separation tail The ore is sequentially added with 13 g/ton of allyl pentoxylate, 9 g/ton of isopentyl xanthate and 20 g/ton of 24K, stir for 3 minutes, and perform a sweep. The swept foam is returned to roughing and the tailings are swept. For tailings 1.

C. Second-stage grinding: Add 700 g/ton of calcium oxide to the copper-molybdenum-zinc talc mixed coarse concentrate obtained in step B for second-stage grinding. The grinding fineness is -74 μm accounting for 80%.

D. Copper-molybdenum-zinc talc mixed selection: The copper-molybdenum-zinc talc mixed selection process is to add 18 g/ton of allyl pentaxate, 8 g/ton of butylammonium black powder, and 10 g of 24K to the pulp ground in step C. / ton, stir for 3 minutes, after one stage of selection, the foam selected in the first stage enters the second stage of selection, and the foam selected in the second stage enters the third stage of selection. The foam selected in the third stage is a copper-molybdenum-zinc talc mixed concentrate, and the selected tail The mines return to the previous level of selection in turn. To a section of selected tailings, add 8 g/ton of allyl pentaxanoate, 3 g/ton of butylammonium black liquor, and 5 g/ton of 24K in sequence. Stir for 3 minutes. Perform a section of fine sweeping and selection, and a section of fine sweeping of foam to return to the first section of selection. , add 4 g/ton of allyl pentoxanate, 2 g/ton of butylammonium black liquor, and 2.5 g/ton of 24K to the tailings in the first stage of fine sweeping and sorting. Stir for 3 minutes and enter the second stage of fine sweeping and sorting. The fine sweeping and sorting foam returns to the first stage of fine sweeping and sorting, and the tailings of the second stage of fine sweeping and sorting are tailings 2.

E. Copper-molybdenum-zinc talc flotation separation: The copper-molybdenum-zinc talc flotation separation process conditions are: add the copper-molybdenum-zinc talc mixed concentrate produced in the three stages of step D in sequence and add sodium thioglycolate modified small molecule product 150 g/ton, thioglycolic acid modified small molecule product 120 g/ton, stir for 4 minutes, add emulsified diesel oil 8 g/ton, butylammonium black powder 12 g/ton, 24K 10 g/ton, stir for 3 minutes, enter rough selection , coarsely select the foam and add 50 g/ton of sodium thioglycolate modified small molecule product, 30 g/ton of thioglycolic acid modified small molecule product, stir for 4 minutes, 4 g/ton of emulsified diesel oil, and 6 g/ton of butylammonium black liquor. , stir for 3 minutes, perform one stage of selection, add 25 g/ton of sodium thioglycolate modified small molecule product to the foam in the first stage, and 20 g/ton of thioglycolic acid modified small molecule product, stir for 4 minutes, perform the second stage of selection, The second-stage selection foam is a mixed concentrate of molybdenum-zinc talc. The second-stage selection tailings are returned to the first-stage selection, and the first-stage selection tailings are returned to the rough selection. The rough selection tailings are sequentially added with 4 g/ton of emulsified diesel oil and butylammonium black liquor. 6g/ton, 24K5g/ton, stir for 3 minutes, sweep, sweep the foam back to roughing, and sweep the tailings into the final copper concentrate.

F. Molybdenum zinc-talc gravity separation: The molybdenum zinc-talc gravity separation process conditions are to concentrate and dehydrate the selected foam in the second stage of step E, remove some unavoidable ions with water, and concentrate the product to a concentration of 45% into the rotating speed 600 r/min centrifugal gravity selection for rough selection, centrifugal gravity selection for rough selection, light products enter the centrifugal gravity selection at 700 r/min for selection, centrifugal gravity selection selects light products as the final talc product, centrifugal gravity selection selects heavy products and returns to centrifugation Gravity selection and rough selection, centrifugal gravity selection and rough selection. The heavy products enter the centrifugal gravity selection and sweep at a speed of 600r/min. The centrifugal gravity selection sweeps and sweeps the light products and returns to the centrifugal gravity selection and rough selection. The heavy product of centrifugal gravity selection and sweep is molybdenum and zinc mixed concentrate. .

G. Molybdenum-Zinc Column Separation: The molybdenum-zinc column separation process conditions are to concentrate and dehydrate the molybdenum-zinc mixed concentrate in step F, remove some unavoidable ions with water, and add 170 grams of sodium sulfide to the 55% concentrated product. / ton, enter the stirring friction scrubbing, use 6mm diameter ceramic balls for scrubbing, the filling rate is 45%, the stirring speed is 90 r/min, and the slurry after stirring friction scrubbing is sequentially added with 800g/ton of zinc sulfate and 300g/ton of sodium sulfide. , stir for 4 minutes, emulsified diesel oil 40g/ton, stir for 3 minutes, enter the flotation column for rough separation, add 200g/ton of zinc sulfate and 80g/ton of sodium sulfide to the coarse separation foam, stir for 4 minutes, emulsified diesel oil 15 g/ton, stir for 3 minutes, and carry out a section of selection. In the first stage of foam selection, add 150 g/ton of zinc sulfate and 60 g/ton of sodium sulfide in sequence, stir for 4 minutes, and stir for 3 minutes of emulsified diesel oil. Then proceed to the second stage of foam selection. In the second stage of foam selection, add 100 g of zinc sulfate. g/ton, sodium sulfide 40 g/ton, stir for 4 minutes, perform three-stage selection, the foam of the third-stage selection is the final molybdenum concentrate product, the tailings of the third-stage selection return to the second-stage selection, and the tailings of the second-stage selection The ore is returned to a section of fine selection, and the tailings of a section of fine selection are returned to rough selection. 20 g/ton of emulsified diesel oil is added to the rough selection tailings, stirred for 3 minutes, and then swept. The sweep concentrate is returned to rough selection, and the sweep tailings are the final zinc. Concentrate products.

Using the above process to process the ore, the copper concentrate can be obtained with a Cu grade of 24.77% and a Cu recovery rate of 85.35%; the molybdenum concentrate has a Mo grade of 34.17% and a Mo recovery rate of 71.21%; the zinc concentrate has a Zn grade of 40.76% and a Zn recovery rate of 68.71 % technical indicators. Improved the comprehensive utilization rate of mineral resources.

Claims (7)

1. A beneficiation method for molybdenum-containing high-zinc complex magnesium silicate altered skarn type copper ore, which is characterized by including one stage of grinding, copper-molybdenum-zinc talc mixed roughing, two-stage grinding, copper-molybdenum-zinc Talc mixing and selection, copper-molybdenum-zinc talc flotation separation, molybdenum-zinc-talc gravity separation, and molybdenum-zinc column separation steps include: A. One-stage grinding: Grind the crushed copper ore in one stage to obtain material a. The grinding fineness is -74μm accounting for 55~65%; B. Copper-molybdenum-zinc talc mixed roughing: add pyrite inhibitor, collector and foaming agent to material a in sequence, and obtain copper-molybdenum-zinc talc mixed coarse concentrate b and roughing tailings c after one rough separation. ; Add collector and foaming agent to the roughing tailings c in sequence to perform a sweep to obtain the sweeping foam d and tailings e; the sweeping foam returns to the roughing step; C. Second-stage grinding: Add sulfur inhibitors to the copper-molybdenum-zinc talc mixed coarse concentrate b and perform second-stage grinding to obtain material f. The grinding fineness is -74 μm accounting for 80~85%; D. Mixed selection of copper-molybdenum-zinc talc: Add collector and foaming agent to material f in sequence, and obtain first-stage selection, second-stage selection and third-stage selection to obtain copper-molybdenum-zinc talc mixed concentrate. g and tailings h; the foam selected in the first stage goes to the second stage, and the foam selected in the second stage goes to the third stage. The foam in the third stage is copper-molybdenum-zinc talc concentrate, and the selected tailings return to the upper level of concentrate in turn. Selecting; a collector and a foaming agent are added to the selected tailings in sequence for a stage of fine sweeping and selection. The foam in one stage of fine sweeping and selection returns to the first stage of fine selection. The collectors and foaming agents are added to the tailings of a stage of fine sweeping and selection in sequence and enter the second stage of fine cleaning. Sweeping and sorting, the foam in the second stage of fine sweeping and sorting returns to the first stage of fine sweeping and sorting, and the tailings in the second stage of fine sweeping and sorting are tailings h; E. Copper-molybdenum-zinc talc flotation separation: Add copper inhibitors, collectors and foaming agents to the copper-molybdenum-zinc talc mixed concentrate in sequence and enter rough selection. Add copper inhibitors and collectors to the foam in rough selection. The first stage of selection is carried out, and the copper inhibitor is added to the foam of the first stage of selection for the second stage of selection. The foam of the second stage of selection is molybdenum zinc talc mixed concentrate i, the tailings of the second stage of selection are returned to the first stage of selection, and the tailings of the first stage of selection are returned to Rough selection, the rough selection tailings are sequentially added with collectors and foaming agents for sweeping, the foam is returned to rough selection, and the sweeping tailings are the final copper concentrate j; F. Molybdenum-zinc-talc gravity separation: The molybdenum-zinc-talc mixed concentrate i is concentrated and dehydrated, and then enters the centrifugal gravity selection for rough selection. The centrifugal gravity selection rough selection of the light products enters the centrifugal gravity selection for selection, and the centrifugal gravity selection selects the light products. For the final talc product, centrifugal gravity selection selects heavy products, returns to centrifugal gravity selection for rough selection, centrifugal gravity selection for rough selection, and centrifugal gravity selection for rough selection. The heavy product of sweeping is molybdenum-zinc mixed concentrate k; G. Molybdenum-zinc column separation: Concentrate and dehydrate the molybdenum-zinc mixed concentrate k, add unavoidable ion pretreatment agent for scrubbing to obtain slurry l, add zinc inhibitors and collectors to the slurry l in sequence for rough selection, rough selection The foam is sequentially added with zinc inhibitors and collectors for one-stage selection, the first-stage selection foam is added with zinc inhibitors and collectors for the second-stage selection, the second-stage selection foam is added with zinc inhibitors for the third-stage selection, and the third-stage selection foam is The foam of the first-stage selection is the final molybdenum concentrate product m. The tailings of the third-stage selection return to the second-stage selection, the tailings of the second-stage selection return to the first-stage selection, the tailings of the first-stage selection return to the rough selection, and the tailings of the rough selection return to the rough selection. The collector is scavenged, the scavenged concentrate is returned to roughing, and the scavenged tailings are the final zinc concentrate product n. 2. The beneficiation method of molybdenum-containing high-zinc complex magnesium silicate altered skarn type copper ore according to claim 1, characterized in that the pyrite inhibitor described in step B is calcium oxide, and the dosage It is 2000~3000g/ton, and the stirring time is 3~5min; the collector is one or two of isopropyl ethyl thiocarbamate, allyl pentoxylate and isopentyl One or more combinations of base xanthate, butyl xanthate, and butyl ammonium black base are used, the dosage is 40~60 g/ton, isopropylethyl thiocarbamate, allyl pentexanthate One or two of them account for 40% to 60%, and one or more of isopentyl xanthate, butyl xanthate, and butylammonium blackate account for 40% to 60%; the foaming agent is Pine alcohol oil or 24K, dosage 30~40g/ton. 3. The beneficiation method of molybdenum-containing high-zinc complex magnesium silicate altered skarn type copper ore according to claim 1, characterized in that the sulfur inhibitor described in step C is calcium oxide, and the dosage is 500 ~1000g/ton. 4. The beneficiation method for molybdenum-containing high-zinc complex magnesium silicate altered skarn-type copper ore according to claim 1, characterized in that the collector described in step D is isopropyl ethyl sulfide. One or both of isopropyl ethyl thiocarbamate and allyl pentoxylate are used together with butylammonium black drug, and one or both of isopropylethyl thiocarbamate and allyl pentoxate Two types account for 60% to 80%, and butylammonium black powder accounts for 20% to 40%. The foaming agent is pine alcohol oil or 24K. 5. The beneficiation method of molybdenum-containing high-zinc complex magnesium silicate altered skarn type copper ore according to claim 1, characterized in that in step E, the copper inhibitor is a sodium thioglycolate modified small molecule product and A mixture of modified small molecule products of thioglycolic acid, sodium thioglycolate modified small molecule products account for 40% to 60%, and thioglycolic acid modified small molecule products account for 40% to 60%; the collector is emulsified diesel, One or two kinds of emulsified kerosene are used together with butylammonium black powder. The collector is emulsified diesel oil and one or two kinds of emulsified kerosene accounting for 30% to 50%, and butylammonium black powder accounts for 50% to 70%; so The foaming agent mentioned above is 24K. 6. The beneficiation method of molybdenum-containing high-zinc complex magnesium silicate altered skarn type copper ore according to claim 1, characterized in that the centrifugal gravity separation roughing speed described in step F is 600~800r/ min, the centrifugal gravity selection and selection speed is 700~900r/min, and the centrifugal gravity selection and sweep speed is 600~800r/min. 7. The beneficiation method of molybdenum-containing high-zinc complex magnesium silicate altered skarn type copper ore according to claim 1, characterized in that the unavoidable ion pretreatment agent described in step G is sodium sulfide or oxidation One or two of calcium; the zinc inhibitor is two or three of zinc sulfate, sodium sulfite and sodium sulfide, and the collector is one or two of emulsified diesel or emulsified kerosene .