Method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphorite washing fine silt

Abstract

The invention discloses a method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphorite washing fine silt, which belongs to the technical field of phosphorite beneficiation, and comprises the following steps: carrying out dense dehydration on the washing fine silt, adding an agent for sufficient mass transfer and dispersion, desliming by adopting table flotation equipment, carrying out flotation desiliconization on the deslimed material for primary enrichment, and carrying out secondary enrichment on the deslimed material for later use; and sulfur rough concentrate and gravity separation tailings are obtained through secondary enrichment of gravity separation equipment, sulfur concentrate is obtained through flotation of the sulfur rough concentrate, and phosphate concentrate is obtained through flotation after the flotation tailings and the gravity separation tailings are combined. The method mainly aims at ultra-high-fineness and ultra-difficult-to-separate fine silt products generated in the phosphorite mine pretreatment process, the impurity removal and enrichment efficiency is greatly improved by innovatively adopting a table floating dosing and desliming mode in phosphorite mineral separation, the technical bottleneck that the materials are difficult to treat and recover is broken through by combining efficient utilization of gravity separation equipment, and the method is suitable for industrial production. And the overall recovery rate of phosphorite mining and utilization is increased, and collaborative recovery of the valuable element sulfur of phosphorite is achieved.

Description

Technical Field

[0001] The invention belongs to the technical field of phosphate ore dressing, and in particular relates to a method for collaboratively recovering sulfur concentrate and phosphate concentrate from phosphate ore water-washed fine mud. Background Art

[0002] Phosphate rock is an important raw material for the chemical production of yellow phosphorus, phosphoric acid, fertilizers and various fine phosphorus chemical raw materials, and has important life value and strategic significance. In the process of processing medium and low-grade phosphate rock, water washing and other methods are often used for pretreatment, which produces a large amount of water-washed fine mud. This type of phosphorus-containing fine mud has the characteristics of large mud content, high gangue mineral content, fine particle size (-0.074mm-accounting for more than 90%, -0.038mm-accounting for more than 75%), and low content of valuable minerals (sulfide minerals). It cannot be reasonably recycled, resulting in a decrease in the comprehensive allocation efficiency of phosphate rock resources and a waste of associated sulfide mineral resources.

[0003] Based on the characteristics of this type of fine mud, it cannot be recycled and processed by a single gravity separation method. However, when flotation is used for separation, the mutual covering phenomenon of fine particles of different minerals and the non-selective coagulation effect between fine muds will seriously affect the separation of flotation reagents. At the same time, the fine particles have a large specific surface area, which will lead to a significant increase in the amount of reagents used. During the flotation process, a high content of fine particles will make the mechanical entrainment phenomenon prominent and affect the collision probability between the reagent and the target mineral, thereby affecting the structure and stability of the foam layer, and having a great impact on the process efficiency and equipment stability. Generally, the desludging process is used before flotation to eliminate the influence of ore mud and achieve a certain pre-enrichment effect, but the separation and targeting of fine mud materials by conventional gravity separation equipment are poor, which will cause excessive loss rates of sulfur minerals and phosphate minerals, and the overall efficiency of the operation is too low.

[0004] Based on the above technical bottlenecks, it is necessary to develop a mineral processing method with simple and efficient process, convenient and stable operation, and low cost to recover the valuable phosphorus and sulfur elements in the fine mud. Summary of the invention

[0005] The purpose of the present invention is to overcome the deficiencies in the above-mentioned prior art. In view of the fact that the existing process equipment technology is unable to process and recover phosphate ore fine mud products, a method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washed fine mud is provided. The purpose is to efficiently remove impurities and conduct cascade enrichment to respectively recover sulfur minerals and phosphate minerals. The process is simple and efficient, the operation is convenient and stable, and the cost is economical and low.

[0006] To achieve the above object, the technical solution adopted by the present invention is: a method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud, characterized in that it comprises the following steps:

[0007] Step 1: flotation and desludging treatment of phosphate ore water-washed fine mud slurry, including the following steps:

[0008] Step 101, dehydrating the phosphate ore water-washed fine mud slurry to a mass concentration of 25% to 40% to obtain a dense dehydrated water-washed fine mud slurry, adding a flotation agent to the dense dehydrated water-washed fine mud slurry and stirring and dispersing the mixture to obtain a homogeneous dispersed particle suspension;

[0009] Step 102, the homogeneous dispersed particle suspension obtained in step 101 is sorted and deslimed by a floating shaking table to obtain tailings product I and deslimed coarse concentrate slurry;

[0010] Step 2: The deslimed coarse concentrate slurry is enriched in stages, comprising the following steps:

[0011] Step 201, the deslimed coarse concentrate slurry obtained in step 102 is subjected to primary enrichment, and the specific operation of the primary enrichment is: using thickened return water to adjust the mass concentration of the deslimed coarse concentrate slurry to 20% to 30%, then adding a desiliconizing agent to the deslimed coarse concentrate slurry for reverse flotation desiliconization to obtain a foam product and a primary enriched desiliconized coarse concentrate, and performing a scavenging operation on the foam product to obtain a tailings product II;

[0012] Step 202, using a gravity separation device to perform secondary gravity separation on the primary enriched and desiliconized coarse concentrate obtained in step 201 to obtain sulfur coarse concentrate slurry and gravity separation tailings;

[0013] Step 3: flotation the sulfur concentrate pulp twice, comprising the following steps:

[0014] Step 301, adjusting the mass concentration of the sulfur concentrate slurry obtained in step 202 to 25% to 35% by using dense return water, and then adding a sulfur flotation agent to the sulfur concentrate slurry for positive flotation to obtain sulfur concentrate product III and sulfur flotation tailings;

[0015] Step 302, combining the sulfur flotation tailings obtained in step 301 and the gravity separation tailings obtained in step 202, adding acidic wastewater and adjusting the pH value of the pulp to 4.5-5.5 to obtain a weakly acidic pulp;

[0016] Step 303: adding a demagnesiumizing agent to the weakly acidic slurry obtained in step 302 for reverse flotation to obtain demagnesiumizing tailings product IV and phosphate concentrate product V.

[0017] The above-mentioned method for collaboratively recovering sulfur concentrate and phosphate concentrate from phosphate ore washed fine mud is characterized in that the phosphate ore washed fine mud slurry in step one is the phosphate ore washed fine mud produced in the phosphate mine pretreatment process, and the sulfur content in the phosphate ore washed fine mud slurry accounts for 2% to 6% by mass, and the phosphorus content accounts for 7% to 13% by mass; the washed fine mud with a particle size less than 0.074 mm in the phosphate ore washed fine mud slurry accounts for 85% to 95% by mass, and the washed fine mud with a particle size less than 0.038 mm accounts for 75% to 85% by mass; the mass concentration of the phosphate ore washed fine mud slurry is 8% to 15%.

[0018] The above-mentioned method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud is characterized in that the floating agent in step 101 includes a dispersant and a foaming agent, and the specific operation of adding the floating agent is: the homogeneous dispersed particle suspension is placed in a stirring barrel, the floating agent is added to the stirring barrel, and then stirred for 10 minutes to 30 minutes;

[0019] The dosage of the floating agent is 400-1200g / t phosphate rock washed fine mud slurry, the mass ratio of the dispersant to the foaming agent is 5:1-15:1, the dispersant is one or a combination of sodium hexametaphosphate, sodium pyrophosphate, and hydroxypropyl starch; the foaming agent is one or a combination of methyl isobutyl carbinol, ethylene glycol, and pine oil.

[0020] The above-mentioned method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washed fine mud is characterized in that the single-unit feed rate of the floating shaking table in step 102 is 8L / min~15L / min, the table slope is 0~5 degrees, and the water replenishment amount is 4L / min~8L / min; the yield of the tailings product I is 25%~35%.

[0021] The above-mentioned method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washed fine mud is characterized in that the desiliconization agent in step 201 is composed of the following raw materials in percentage by mass: 0% to 40% polyethylene glycol monolauramide, 10% to 25% 2-ethoxyethylamine, 15% to 25% nonylphenol polyoxyethylene ether phosphate, 15% to 20% polyethylene glycol, 5% to 15% aviation kerosene and 5% to 15% octylphenol polyoxyethylene ether amine; the dosage of the desiliconization agent is 100 to 300 g / t phosphate ore washed fine mud slurry.

[0022] The above-mentioned method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washed fine mud is characterized in that the gravity separation equipment in step 202 is one or a combination of a cone concentrator and a fine particle shaking table, the feed rate of the gravity separation equipment is 10L / min~15L / min, the overflow concentration during gravity separation is 8%~15%, and the mass percentage of sulfur in the sulfur rough concentrate slurry is 10%~17%.

[0023] The above-mentioned method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore water-washed fine mud is characterized in that the sulfur flotation reagent in step 301 includes a collector and an activator, the amount of the collector is 200-600 g / t of phosphate ore water-washed fine mud slurry, and the amount of the activator is 300-1500 g / t of phosphate ore water-washed fine mud slurry; the positive flotation is carried out in a stirring barrel, and before the positive flotation, the collector and the activator are successively added to the stirring barrel and stirred for 2 min to 5 min respectively;

[0024] The activator is a mixed solution of an inorganic acid and an inorganic salt in a mass ratio of 5:1-10:1, wherein the inorganic acid is one or a combination of phosphoric acid, oxalic acid, nitric acid, and ammonium bisulfate, and the inorganic salt is one or a combination of copper sulfate, ferrous sulfate, ammonium trichloride, and sodium copper ethylenediaminetetraacetate;

[0025] The collector is a combination of two or more of sodium amyl xanthate, sodium isoamyl xanthate, sodium butyl xanthate, butyl ammonium black medicine, diethyl disulfide, 1,3-bis(benzyloxycarbonyl)-2-methyl-2-thiourea, S-(4-chlorobenzyl)isothiourea ammonium chloride and dimethyl dithiocarbamate.

[0026] The above-mentioned method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washed fine mud is characterized in that the specific operation of the combination in step 302 is: the gravity separation tailings and the sulfur flotation tailings are fed into a stirring barrel together and stirred for 2min to 5min, and the acidic adjuster is phosphoric acid and / or sulfuric acid; the demagnesium agent in step 303 is a fatty acid anion collector, and the amount of the demagnesium agent is 600 to 1500g / t phosphate ore washed fine mud slurry.

[0027] The above-mentioned method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud is characterized in that the fatty acid anion collector is oleic acid or cyclohexane acid.

[0028] The above-mentioned method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washed fine mud is characterized in that the reverse flotation in step 201 and step 303 is a one-roughing-one-sweeping closed-circuit flotation, and the forward flotation in step 301 is a one-roughing-one-fine closed-circuit flotation; in the reverse flotation and forward flotation, the middlings are returned sequentially.

[0029] Compared with the prior art, the present invention has the following advantages:

[0030] 1. The present invention recovers sulfur and phosphorus minerals from phosphate ore water-washed fine mud, solving the technical problem that such ultra-high fineness and ultra-difficult to separate materials cannot be effectively recycled and utilized. By means of efficient impurity removal and step-by-step enrichment, the technical feasibility of recovering concentrate products from fine mud with low sulfur and phosphorus contents is achieved.

[0031] 2. The present invention adopts a flotation method for desliming in phosphate ore for the first time. The flotation agent achieves multiple effects and directional strengthening effects of a single agent through synergistic compatibility, effectively eliminating the covering and mudification effects of ore mud particles, while eliminating the harmful effects of non-selective coagulation between fine particles, avoiding the problem of non-selective entrainment of foam in the subsequent flotation process, greatly increasing the desliming efficiency and improving the enrichment effect.

[0032] 3. Based on material characteristics and technical requirements, the present invention has developed a new combined mineral processing process of "stage flotation desludging - cascade enrichment - secondary flotation" for phosphate ore fine mud. A relatively high-quality sulfur concentrate is obtained by cascade enrichment in the manner of "stage flotation - flotation - gravity separation". A primary flotation is used for impurity removal and a secondary flotation is used for enrichment to obtain relatively high-quality sulfur and phosphate concentrates, respectively. The gravity separation efficiency is greatly improved and the process cost is reduced. The reagents used for flotation are all common and easily available items with low cost and stable effect.

[0033] The present invention is further described in detail below through the accompanying drawings and examples. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 It is a process flow chart of the present invention. DETAILED DESCRIPTION

[0035] In order to further understand the content of the present invention, the present invention is further described in detail in conjunction with the accompanying drawings and embodiments. The following embodiments are only used to illustrate the content of the present invention, but not to limit the scope of the present invention.

[0036] A method for synergistically recovering sulfur and phosphate concentrate from phosphate ore water-washed fine mud is disclosed. The sulfur concentrate and phosphate concentrate are recovered from the water-washed fine mud of a mine in Yichang City, Hubei Province. The main components and particle size composition of the fine mud are shown in Table 1 and Table 2, respectively.

[0037] Table 1

[0038]

[0039]

[0040] Table 2

[0041]

[0042] Example 1

[0043] A method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud comprises the following steps:

[0044] Step 1: flotation and desludging treatment of phosphate ore water-washed fine mud slurry, including the following steps:

[0045] Step 101, dehydrating the phosphate ore water-washed fine mud slurry to a mass concentration of 32% to obtain a dense dehydrated water-washed fine mud slurry, adding a flotation agent to the dense dehydrated water-washed fine mud slurry and stirring and dispersing the mixture to obtain a homogeneous dispersed particle suspension;

[0046] The floating agent includes a dispersant and a foaming agent. The specific operation of adding the floating agent is as follows: the homogeneous dispersed particle suspension is placed in a stirring barrel, the floating agent is added to the stirring barrel, and then stirred at a high speed for 20 minutes;

[0047] The dosage of the floating agent is 1000g / t phosphate rock washed fine mud slurry, the mass ratio of the dispersant to the foaming agent is 5:1, the dispersant is a combination of sodium hexametaphosphate and hydroxypropyl starch; the foaming agent is methyl isobutyl carbinol.

[0048] Step 102, the homogeneous dispersed particle suspension obtained in step 101 is sorted and deslimed by a floating shaking table to obtain tailings product I and deslimed coarse concentrate slurry;

[0049] The single floating shaking table has a feed rate of 10 L / min, a table slope of 3 degrees, and a water replenishment rate of 5 L / min; the yield of the tailings product I is 25% to 35%.

[0050] The phosphate ore washed fine mud slurry described in step one is the phosphate ore washed fine mud produced in the pretreatment process of the phosphate ore mine, and the sulfur content in the phosphate ore washed fine mud slurry accounts for 2% to 6% by mass, and the phosphorus content accounts for 7% to 13% by mass; the washed fine mud with a particle size less than 0.074 mm in the phosphate ore washed fine mud slurry accounts for 85% to 95% by mass, and the washed fine mud with a particle size less than 0.038 mm accounts for 75% to 85% by mass; the mass concentration of the phosphate ore washed fine mud slurry is 8% to 15%.

[0051] Step 2: The deslimed coarse concentrate slurry is enriched in stages, comprising the following steps:

[0052] Step 201, the deslimed coarse concentrate slurry obtained in step 102 is subjected to primary enrichment, and the specific operation of the primary enrichment is: using thickened return water to adjust the mass concentration of the deslimed coarse concentrate slurry to 28%, then adding a desiliconizing agent to the deslimed coarse concentrate slurry for reverse flotation desiliconization to obtain a foam product and a primary enriched desiliconized coarse concentrate, and performing a scavenging operation on the foam product to obtain a tailings product II; wherein the reverse flotation is a one-roughing and one-scavenging closed-circuit flotation, and the middlings are returned in sequence;

[0053] The desiliconizing agent is composed of the following raw materials in percentage by mass: 20% polyethylene glycol monolauramide, 15% 2-ethoxyethylamine, 20% nonylphenol polyoxyethylene ether phosphate, 15% polyethylene glycol, 15% aviation kerosene and 15% octylphenol polyoxyethylene ether amine; the dosage of the desiliconizing agent is 200g / t phosphate rock washed fine mud slurry.

[0054] Step 202, using a gravity separation device to perform secondary gravity separation on the primary enriched and desiliconized coarse concentrate obtained in step 201 to obtain sulfur coarse concentrate slurry and gravity separation tailings;

[0055] The gravity separation equipment is a cone concentrator, the feed rate of the gravity separation equipment is 13L / min, the overflow concentration during gravity separation is 13%, and the mass percentage of sulfur in the sulfur rough concentrate slurry is 10% to 17%.

[0056] Step 3: flotation the sulfur concentrate pulp twice, comprising the following steps:

[0057] Step 301, adjusting the mass concentration of the sulfur concentrate pulp obtained in step 202 to 30% by using dense return water, and then adding sulfur flotation reagent to the sulfur concentrate pulp for positive flotation to obtain sulfur concentrate product III and sulfur flotation tailings; the positive flotation is a one-coarse and one-fine closed-circuit flotation, and the middlings are returned in sequence;

[0058] The sulfur flotation reagent includes a collector and an activator, wherein the collector is used in an amount of 300 g / t of phosphate rock water-washed fine mud slurry, and the activator is used in an amount of 600 g / t of phosphate rock water-washed fine mud slurry; the positive flotation is carried out in a stirring barrel, and before the positive flotation, the collector and the activator are successively added to the stirring barrel and stirred for 3 minutes respectively;

[0059] The activator is a mixed solution of an inorganic acid and an inorganic salt in a mass ratio of 6:1, wherein the inorganic acid is a combination of phosphoric acid and oxalic acid, and the inorganic salt is copper sulfate; the collector is a combination of sodium amyl xanthate and 1,3-bis(benzyloxycarbonyl)-2-methyl-2-thiourea.

[0060] Step 302: combining the sulfur flotation tailings obtained in step 301 and the gravity separation tailings obtained in step 202, adding acidic wastewater and adjusting the pH value of the pulp to 4.8 to obtain a weakly acidic pulp;

[0061] The specific operation of the merging is: the gravity separation tailings and the sulfur flotation tailings are fed into a stirring barrel together and stirred for 3 minutes, and the acidic adjuster is phosphoric acid; the demagnesiumizing agent in step 303 is a fatty acid anion collector, and the dosage of the demagnesiumizing agent is 1200g / t phosphate rock washed fine mud slurry; the fatty acid anion collector is oleic acid.

[0062] Step 303, adding a demagnesizing agent to the weakly acidic slurry obtained in step 302 for reverse flotation to obtain demagnesized tailings product IV and phosphate concentrate product V; the reverse flotation is a one-roughing and one-sweeping closed-circuit flotation, and the middlings are returned in sequence.

[0063] In Example 1, a sulfur concentrate product with a yield of 7.37%, a sulfur grade of 35.08%, and a recovery rate of 75.82% was finally obtained; at the same time, a phosphate concentrate product with a yield of 27.51% was obtained, with a phosphorus grade of 26.18% and a recovery rate of 74.02%.

[0064] Example 2

[0065] A method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud comprises the following steps:

[0066] Step 1: flotation and desludging treatment of phosphate ore water-washed fine mud slurry, including the following steps:

[0067] Step 101, dehydrating the phosphate ore water-washed fine mud slurry to a mass concentration of 32% to obtain a dense dehydrated water-washed fine mud slurry, adding a flotation agent to the dense dehydrated water-washed fine mud slurry and stirring and dispersing the mixture to obtain a homogeneous dispersed particle suspension;

[0068] The floating agent includes a dispersant and a foaming agent. The specific operation of adding the floating agent is as follows: the homogeneous dispersed particle suspension is placed in a stirring barrel, the floating agent is added to the stirring barrel, and then stirred at a high speed for 20 minutes;

[0069] The dosage of the floating agent is 1200g / t phosphate rock washed fine mud slurry, the mass ratio of the dispersant to the foaming agent is 9:1, the dispersant is a combination of sodium hexametaphosphate and sodium pyrophosphate; the foaming agent is methyl isobutyl carbinol.

[0070] Step 102, the homogeneous dispersed particle suspension obtained in step 101 is sorted and deslimed by a floating shaking table to obtain tailings product I and deslimed coarse concentrate slurry;

[0071] The single floating shaking table has a feed rate of 10 L / min, a table slope of 3 degrees, and a water replenishment rate of 5 L / min; the yield of the tailings product I is 25% to 35%.

[0072] The phosphate ore washed fine mud slurry described in step one is the phosphate ore washed fine mud produced in the pretreatment process of the phosphate ore mine, and the sulfur content in the phosphate ore washed fine mud slurry accounts for 2% to 6% by mass, and the phosphorus content accounts for 7% to 13% by mass; the washed fine mud with a particle size less than 0.074 mm in the phosphate ore washed fine mud slurry accounts for 85% to 95% by mass, and the washed fine mud with a particle size less than 0.038 mm accounts for 75% to 85% by mass; the mass concentration of the phosphate ore washed fine mud slurry is 8% to 15%.

[0073] Step 2: The deslimed coarse concentrate slurry is enriched in stages, comprising the following steps:

[0074] Step 201, the deslimed coarse concentrate slurry obtained in step 102 is subjected to primary enrichment, and the specific operation of the primary enrichment is: using thickened return water to adjust the mass concentration of the deslimed coarse concentrate slurry to 28%, then adding a desiliconizing agent to the deslimed coarse concentrate slurry for reverse flotation desiliconization to obtain a foam product and a primary enriched desiliconized coarse concentrate, and performing a scavenging operation on the foam product to obtain a tailings product II; wherein the reverse flotation is a one-roughing and one-scavenging closed-circuit flotation, and the middlings are returned in sequence;

[0075] The desiliconizing agent is composed of the following raw materials in percentage by mass: 40% polyethylene glycol monolauramide, 10% 2-ethoxyethylamine, 15% nonylphenol polyoxyethylene ether phosphate, 20% polyethylene glycol, 10% aviation kerosene and 5% octylphenol polyoxyethylene ether amine; the dosage of the desiliconizing agent is 200g / t phosphate rock washed fine mud slurry.

[0076] Step 202, using a gravity separation device to perform secondary gravity separation on the primary enriched and desiliconized coarse concentrate obtained in step 201 to obtain sulfur coarse concentrate slurry and gravity separation tailings;

[0077] The gravity separation equipment is a cone concentrator, the feed rate of the gravity separation equipment is 13L / min, the overflow concentration during gravity separation is 13%, and the mass percentage of sulfur in the sulfur rough concentrate slurry is 10% to 17%.

[0078] Step 3: flotation the sulfur concentrate pulp twice, comprising the following steps:

[0079] Step 301, adjusting the mass concentration of the sulfur concentrate pulp obtained in step 202 to 30% by using dense return water, and then adding sulfur flotation reagent to the sulfur concentrate pulp for positive flotation to obtain sulfur concentrate product III and sulfur flotation tailings; the positive flotation is a one-coarse and one-fine closed-circuit flotation, and the middlings are returned in sequence;

[0080] The sulfur flotation reagent includes a collector and an activator, wherein the collector is used in an amount of 300 g / t of phosphate rock water-washed fine mud slurry, and the activator is used in an amount of 600 g / t of phosphate rock water-washed fine mud slurry; the positive flotation is carried out in a stirring barrel, and before the positive flotation, the collector and the activator are successively added to the stirring barrel and stirred for 3 minutes respectively;

[0081] The activator is a mixed solution of an inorganic acid and an inorganic salt in a mass ratio of 7:1, wherein the inorganic acid is a combination of oxalic acid and nitric acid, and the inorganic salt is ferrous sulfate; the collector is a combination of sodium butyl xanthate and S-(4-chlorobenzyl)isothiourea ammonium chloride.

[0082] Step 302: combining the sulfur flotation tailings obtained in step 301 and the gravity separation tailings obtained in step 202, adding acidic wastewater and adjusting the pH value of the pulp to 4.8 to obtain a weakly acidic pulp;

[0083] The specific operation of the merging is: the gravity separation tailings and the sulfur flotation tailings are fed into a stirring barrel together and stirred for 3 minutes, and the acidic adjuster is phosphoric acid; the demagnesiumizing agent in step 303 is a fatty acid anion collector, and the dosage of the demagnesiumizing agent is 1200g / t phosphate rock washed fine mud slurry; the fatty acid anion collector is oleic acid.

[0084] Step 303, adding a demagnesizing agent to the weakly acidic slurry obtained in step 302 for reverse flotation to obtain demagnesized tailings product IV and phosphate concentrate product V; the reverse flotation is a one-roughing and one-sweeping closed-circuit flotation, and the middlings are returned in sequence.

[0085] In Example 2, a sulfur concentrate product with a yield of 8.01% was finally obtained, of which sulfur was 33.79% and the recovery rate was 79.37%; at the same time, a phosphate concentrate product with a yield of 28.46% was obtained, of which the phosphorus grade was 25.37% and the recovery rate was 74.21%.

[0086] Example 3

[0087] A method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud comprises the following steps:

[0088] Step 1: flotation and desludging treatment of phosphate ore water-washed fine mud slurry, including the following steps:

[0089] Step 101, dehydrating the phosphate ore water-washed fine mud slurry to a mass concentration of 32% to obtain a dense dehydrated water-washed fine mud slurry, adding a flotation agent to the dense dehydrated water-washed fine mud slurry and stirring and dispersing the mixture to obtain a homogeneous dispersed particle suspension;

[0090] The floating agent includes a dispersant and a foaming agent. The specific operation of adding the floating agent is as follows: the homogeneous dispersed particle suspension is placed in a stirring barrel, the floating agent is added to the stirring barrel, and then stirred at a high speed for 30 minutes;

[0091] The dosage of the floating agent is 1000g / t phosphate rock washed fine mud slurry, the mass ratio of the dispersant to the foaming agent is 8:1, the dispersant is a combination of sodium hexametaphosphate and hydroxypropyl starch; the foaming agent is methyl isobutyl carbinol.

[0092] Step 102, the homogeneous dispersed particle suspension obtained in step 101 is sorted and deslimed by a floating shaking table to obtain tailings product I and deslimed coarse concentrate slurry;

[0093] The single floating shaking table has a feed rate of 12 L / min, a table slope of 2.5 degrees, and a water replenishment rate of 4.5 L / min; the yield of the tailings product I is 25% to 35%.

[0094] The phosphate ore washed fine mud slurry described in step one is the phosphate ore washed fine mud produced in the pretreatment process of the phosphate ore mine, and the sulfur content in the phosphate ore washed fine mud slurry accounts for 2% to 6% by mass, and the phosphorus content accounts for 7% to 13% by mass; the washed fine mud with a particle size less than 0.074 mm in the phosphate ore washed fine mud slurry accounts for 85% to 95% by mass, and the washed fine mud with a particle size less than 0.038 mm accounts for 75% to 85% by mass; the mass concentration of the phosphate ore washed fine mud slurry is 8% to 15%.

[0095] Step 2: The deslimed coarse concentrate slurry is enriched in stages, comprising the following steps:

[0096] Step 201, the deslimed coarse concentrate slurry obtained in step 102 is subjected to primary enrichment, and the specific operation of the primary enrichment is: using thickened return water to adjust the mass concentration of the deslimed coarse concentrate slurry to 28%, then adding a desiliconizing agent to the deslimed coarse concentrate slurry for reverse flotation desiliconization to obtain a foam product and a primary enriched desiliconized coarse concentrate, and performing a scavenging operation on the foam product to obtain a tailings product II; wherein the reverse flotation is a one-roughing and one-scavenging closed-circuit flotation, and the middlings are returned in sequence;

[0097] The desiliconizing agent is composed of the following raw materials in percentage by mass: 20% polyethylene glycol monolauramide, 25% 2-ethoxyethylamine, 25% nonylphenol polyoxyethylene ether phosphate, 15% polyethylene glycol, 5% aviation kerosene and 10% octylphenol polyoxyethylene ether amine; the dosage of the desiliconizing agent is 200g / t phosphate rock washed fine mud slurry.

[0098] Step 202, using a gravity separation device to perform secondary gravity separation on the primary enriched and desiliconized coarse concentrate obtained in step 201 to obtain sulfur coarse concentrate slurry and gravity separation tailings;

[0099] The gravity separation equipment is a cone concentrator, the feed rate of the gravity separation equipment is 13L / min, the overflow concentration during gravity separation is 13%, and the mass percentage of sulfur in the sulfur rough concentrate slurry is 10% to 17%.

[0100] Step 3: flotation the sulfur concentrate pulp twice, comprising the following steps:

[0101] Step 301, adjusting the mass concentration of the sulfur concentrate pulp obtained in step 202 to 30% by using dense return water, and then adding sulfur flotation reagent to the sulfur concentrate pulp for positive flotation to obtain sulfur concentrate product III and sulfur flotation tailings; the positive flotation is a one-coarse and one-fine closed-circuit flotation, and the middlings are returned in sequence;

[0102] The sulfur flotation reagent includes a collector and an activator, wherein the collector is used in an amount of 300 g / t of phosphate rock water-washed fine mud slurry, and the activator is used in an amount of 600 g / t of phosphate rock water-washed fine mud slurry; the positive flotation is carried out in a stirring barrel, and before the positive flotation, the collector and the activator are successively added to the stirring barrel and stirred for 3 minutes respectively;

[0103] The activator is a mixed solution of an inorganic acid and an inorganic salt in a mass ratio of 7:1, wherein the inorganic acid is a combination of nitric acid and ammonium bisulfate, and the inorganic salt is ammonium trichloride; the collector is a combination of butyl ammonium black medicine, diethyl disulfide and dimethyl dithiocarbamate.

[0104] Step 302: combining the sulfur flotation tailings obtained in step 301 and the gravity separation tailings obtained in step 202, adding acidic wastewater and adjusting the pH value of the pulp to 4.8 to obtain a weakly acidic pulp;

[0105] The specific operation of the merging is: the gravity separation tailings and the sulfur flotation tailings are fed into a stirring barrel together and stirred for 3 minutes, the acidic adjuster is a combination of phosphoric acid and sulfuric acid, wherein the mass ratio of phosphoric acid to sulfuric acid is 1:1; the demagnesiumizing agent in step 303 is a fatty acid anion collector, and the dosage of the demagnesiumizing agent is 1200g / t phosphate rock washed fine mud slurry; the fatty acid anion collector is cyclohexane acid.

[0106] Step 303, adding a demagnesizing agent to the weakly acidic slurry obtained in step 302 for reverse flotation to obtain demagnesized tailings product IV and phosphate concentrate product V; the reverse flotation is a one-roughing and one-sweeping closed-circuit flotation, and the middlings are returned in sequence.

[0107] In Example 3, a sulfur concentrate product with a yield of 7.85% was finally obtained, wherein the sulfur grade was 36.17% and the recovery rate was 83.27%; meanwhile, a phosphate concentrate product with a yield of 26.39% was obtained, wherein the phosphorus grade was 28.16% and the recovery rate was 76.38%.

[0108] Example 4

[0109] A method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud comprises the following steps:

[0110] Step 1: flotation and desludging treatment of phosphate ore water-washed fine mud slurry, including the following steps:

[0111] Step 101, dehydrating the phosphate ore water-washed fine mud slurry to a mass concentration of 32% to obtain a dense dehydrated water-washed fine mud slurry, adding a flotation agent to the dense dehydrated water-washed fine mud slurry and stirring and dispersing the mixture to obtain a homogeneous dispersed particle suspension;

[0112] The floating agent includes a dispersant and a foaming agent. The specific operation of adding the floating agent is as follows: the homogeneous dispersed particle suspension is placed in a stirring barrel, the floating agent is added to the stirring barrel, and then stirred at a high speed for 20 minutes;

[0113] The dosage of the floating agent is 1000g / t phosphate rock washed fine mud slurry, the mass ratio of the dispersant to the foaming agent is 5:1, the dispersant is a combination of sodium hexametaphosphate, sodium pyrophosphate and hydroxypropyl starch; the foaming agent is a combination of pine oil and ethylene glycol.

[0114] Step 102, the homogeneous dispersed particle suspension obtained in step 101 is sorted and deslimed by a floating shaking table to obtain tailings product I and deslimed coarse concentrate slurry;

[0115] The single floating shaking table has a feed rate of 10 L / min, a table slope of 3 degrees, and a water replenishment rate of 5 L / min; the yield of the tailings product I is 25% to 35%.

[0116] The phosphate ore washed fine mud slurry described in step one is the phosphate ore washed fine mud produced in the pretreatment process of the phosphate ore mine, and the sulfur content in the phosphate ore washed fine mud slurry accounts for 2% to 6% by mass, and the phosphorus content accounts for 7% to 13% by mass; the washed fine mud with a particle size less than 0.074 mm in the phosphate ore washed fine mud slurry accounts for 85% to 95% by mass, and the washed fine mud with a particle size less than 0.038 mm accounts for 75% to 85% by mass; the mass concentration of the phosphate ore washed fine mud slurry is 8% to 15%.

[0117] Step 2: The deslimed coarse concentrate slurry is enriched in stages, comprising the following steps:

[0118] Step 201, the deslimed coarse concentrate slurry obtained in step 102 is subjected to primary enrichment, and the specific operation of the primary enrichment is: using thickened return water to adjust the mass concentration of the deslimed coarse concentrate slurry to 28%, then adding a desiliconizing agent to the deslimed coarse concentrate slurry for reverse flotation desiliconization to obtain a foam product and a primary enriched desiliconized coarse concentrate, and performing a scavenging operation on the foam product to obtain a tailings product II; wherein the reverse flotation is a one-roughing and one-scavenging closed-circuit flotation, and the middlings are returned in sequence;

[0119] The desiliconizing agent is composed of the following raw materials in percentage by mass: 20% polyethylene glycol monolauramide, 25% 2-ethoxyethylamine, 25% nonylphenol polyoxyethylene ether phosphate, 15% polyethylene glycol, 5% aviation kerosene and 10% octylphenol polyoxyethylene ether amine; the dosage of the desiliconizing agent is 200g / t phosphate rock washed fine mud slurry.

[0120] Step 202, using a gravity separation device to perform secondary gravity separation on the primary enriched and desiliconized coarse concentrate obtained in step 201 to obtain sulfur coarse concentrate slurry and gravity separation tailings;

[0121] The gravity separation equipment is a fine-grained shaking table, wherein the shaking table inclination angle is 3.5 degrees, the feed rate of the gravity separation equipment is 10L / min, the overflow concentration during gravity separation is 14%, and the mass percentage of sulfur in the sulfur rough concentrate slurry is 10% to 17%.

[0122] Step 3: flotation the sulfur concentrate pulp twice, comprising the following steps:

[0123] Step 301, adjusting the mass concentration of the sulfur concentrate pulp obtained in step 202 to 30% by using dense return water, and then adding sulfur flotation reagent to the sulfur concentrate pulp for positive flotation to obtain sulfur concentrate product III and sulfur flotation tailings; the positive flotation is a one-coarse and one-fine closed-circuit flotation, and the middlings are returned in sequence;

[0124] The sulfur flotation reagent includes a collector and an activator, wherein the collector is used in an amount of 300 g / t of phosphate rock water-washed fine mud slurry, and the activator is used in an amount of 600 g / t of phosphate rock water-washed fine mud slurry; the positive flotation is carried out in a stirring barrel, and before the positive flotation, the collector and the activator are successively added to the stirring barrel and stirred for 3 minutes respectively;

[0125] The activator is a mixed solution of an inorganic acid and an inorganic salt in a mass ratio of 5:1, wherein the inorganic acid is a combination of phosphoric acid and nitric acid, and the inorganic salt is ethylenediaminetetraacetic acid; the collector is a combination of sodium isopentyl xanthate, sodium butyl xanthate and S-(4-chlorobenzyl) isothiourea ammonium chloride.

[0126] Step 302: combining the sulfur flotation tailings obtained in step 301 and the gravity separation tailings obtained in step 202, adding acidic wastewater and adjusting the pH value of the pulp to 4.8 to obtain a weakly acidic pulp;

[0127] The specific operation of the merging is: the gravity separation tailings and the sulfur flotation tailings are fed into a stirring barrel together and stirred for 3 minutes, and the acidic adjuster is sulfuric acid; the demagnesiumizing agent in step 303 is a fatty acid anion collector, and the dosage of the demagnesiumizing agent is 1200g / t phosphate rock washed fine mud slurry; the fatty acid anion collector is cyclohexane acid.

[0128] Step 303, adding a demagnesizing agent to the weakly acidic slurry obtained in step 302 for reverse flotation to obtain demagnesized tailings product IV and phosphate concentrate product V; the reverse flotation is a one-roughing and one-sweeping closed-circuit flotation, and the middlings are returned in sequence.

[0129] In Example 4, a sulfur concentrate product with a yield of 6.77%, a sulfur grade of 35.89%, and a recovery rate of 71.25% was finally obtained; at the same time, a phosphate concentrate product with a yield of 28.34% was obtained, with a phosphorus grade of 27.65% and a recovery rate of 80.54%.

[0130] Example 5

[0131] A method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud comprises the following steps:

[0132] Step 1: flotation and desludging treatment of phosphate ore water-washed fine mud slurry, including the following steps:

[0133] Step 101, dehydrating the phosphate ore water-washed fine mud slurry to a mass concentration of 25% to obtain a dense dehydrated water-washed fine mud slurry, adding a flotation agent to the dense dehydrated water-washed fine mud slurry and stirring and dispersing the mixture to obtain a homogeneous dispersed particle suspension;

[0134] The floating agent includes a dispersant and a foaming agent. The specific operation of adding the floating agent is as follows: the homogeneous dispersed particle suspension is placed in a stirring barrel, the floating agent is added to the stirring barrel, and then stirred at a high speed for 12 minutes;

[0135] The dosage of the floating agent is 400g / t phosphate rock water-washed fine mud slurry, the mass ratio of the dispersant to the foaming agent is 15:1, the dispersant is a combination of sodium pyrophosphate and hydroxypropyl starch; the foaming agent is pine oil.

[0136] Step 102, the homogeneous dispersed particle suspension obtained in step 101 is sorted and deslimed by a floating shaking table to obtain tailings product I and deslimed coarse concentrate slurry;

[0137] The single floating shaking table has a feed rate of 8 L / min, a table slope of 5 degrees, and a water replenishment rate of 8 L / min; the yield of the tailings product I is 25% to 35%.

[0138] The phosphate ore washed fine mud slurry described in step one is the phosphate ore washed fine mud produced in the pretreatment process of the phosphate ore mine, and the sulfur content in the phosphate ore washed fine mud slurry accounts for 2% to 6% by mass, and the phosphorus content accounts for 7% to 13% by mass; the washed fine mud with a particle size less than 0.074 mm in the phosphate ore washed fine mud slurry accounts for 85% to 95% by mass, and the washed fine mud with a particle size less than 0.038 mm accounts for 75% to 85% by mass; the mass concentration of the phosphate ore washed fine mud slurry is 8% to 15%.

[0139] Step 2: The deslimed coarse concentrate slurry is enriched in stages, comprising the following steps:

[0140] Step 201, the deslimed coarse concentrate slurry obtained in step 102 is subjected to primary enrichment, and the specific operation of the primary enrichment is: using thickened return water to adjust the mass concentration of the deslimed coarse concentrate slurry to 20%, then adding a desiliconizing agent to the deslimed coarse concentrate slurry for reverse flotation desiliconization to obtain a foam product and a primary enriched desiliconized coarse concentrate, and performing a scavenging operation on the foam product to obtain a tailings product II; wherein the reverse flotation is a one-roughing and one-scavenging closed-circuit flotation, and the middlings are returned in sequence;

[0141] The desiliconizing agent is composed of the following raw materials in percentage by mass: 0% polyethylene glycol monolauramide, 25% 2-ethoxyethylamine, 25% nonylphenol polyoxyethylene ether phosphate, 20% polyethylene glycol, 15% aviation kerosene and 15% octylphenol polyoxyethylene ether amine; the dosage of the desiliconizing agent is 100g / t phosphate rock washed fine mud slurry.

[0142] Step 202, using a gravity separation device to perform secondary gravity separation on the primary enriched and desiliconized coarse concentrate obtained in step 201 to obtain sulfur coarse concentrate slurry and gravity separation tailings;

[0143] The gravity separation equipment is a cone concentrator, the feed rate of the gravity separation equipment is 15L / min, the overflow concentration during gravity separation is 15%, and the mass percentage of sulfur in the sulfur rough concentrate slurry is 10% to 17%.

[0144] Step 3: flotation the sulfur concentrate pulp twice, comprising the following steps:

[0145] Step 301, adjusting the mass concentration of the sulfur concentrate pulp obtained in step 202 to 25% by using dense return water, and then adding sulfur flotation reagent to the sulfur concentrate pulp for positive flotation to obtain sulfur concentrate product III and sulfur flotation tailings; the positive flotation is a one-coarse and one-fine closed-circuit flotation, and the middlings are returned in sequence;

[0146] The sulfur flotation reagent includes a collector and an activator, wherein the collector is used in an amount of 200 g / t of phosphate rock water-washed fine mud slurry, and the activator is used in an amount of 300 g / t of phosphate rock water-washed fine mud slurry; the positive flotation is carried out in a stirring barrel, and before the positive flotation, the collector and the activator are successively added to the stirring barrel and stirred for 2 minutes respectively;

[0147] The activator is a mixed solution of an inorganic acid and an inorganic salt in a mass ratio of 5:1, wherein the inorganic acid is a combination of phosphoric acid and ammonium bisulfate, and the inorganic salt is a combination of copper sulfate and sodium copper ethylenediaminetetraacetate; the collector is a combination of sodium amyl xanthate, sodium isopentyl xanthate, sodium butyl xanthate and 1,3-bis(benzyloxycarbonyl)-2-methyl-2-thiourea.

[0148] Step 302: combining the sulfur flotation tailings obtained in step 301 and the gravity separation tailings obtained in step 202, adding acidic wastewater and adjusting the pH value of the pulp to 4.5 to obtain a weakly acidic pulp;

[0149] The specific operation of the merging is: the gravity separation tailings and the sulfur flotation tailings are fed into a stirring barrel together and stirred for 2 minutes, and the acidic adjuster is phosphoric acid; the demagnesiumizing agent in step 303 is a fatty acid anion collector, and the amount of the demagnesiumizing agent is 600g / t phosphate rock washed fine mud slurry; the fatty acid anion collector is oleic acid.

[0150] Step 303, adding a demagnesizing agent to the weakly acidic slurry obtained in step 302 for reverse flotation to obtain demagnesized tailings product IV and phosphate concentrate product V; the reverse flotation is a one-roughing and one-sweeping closed-circuit flotation, and the middlings are returned in sequence.

[0151] In Example 5, a sulfur concentrate product with a yield of 7.41% was finally obtained, wherein the sulfur grade was 34.36% and the recovery rate was 80.63%; meanwhile, a phosphate concentrate product with a yield of 28.12% was obtained, wherein the phosphorus grade was 26.13% and the recovery rate was 75.53%.

[0152] Example 6

[0153] A method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud comprises the following steps:

[0154] Step 1: flotation and desludging treatment of phosphate ore water-washed fine mud slurry, including the following steps:

[0155] Step 101, dehydrating the phosphate ore water-washed fine mud slurry to a mass concentration of 40% to obtain a dense dehydrated water-washed fine mud slurry, adding a flotation agent to the dense dehydrated water-washed fine mud slurry and stirring and dispersing the mixture to obtain a homogeneous dispersed particle suspension;

[0156] The floating agent includes a dispersant and a foaming agent. The specific operation of adding the floating agent is as follows: the homogeneous dispersed particle suspension is placed in a stirring barrel, the floating agent is added to the stirring barrel, and then stirred at a high speed for 30 minutes;

[0157] The dosage of the floating agent is 1200g / t phosphate rock washed fine mud slurry, the mass ratio of the dispersant to the foaming agent is 8:1, the dispersant is a combination of sodium hexametaphosphate and hydroxypropyl starch; the foaming agent is ethylene glycol.

[0158] Step 102, the homogeneous dispersed particle suspension obtained in step 101 is sorted and deslimed by a floating shaking table to obtain tailings product I and deslimed coarse concentrate slurry;

[0159] The single floating shaking table has a ore feeding rate of 15 / min, a table slope of 0 degrees, and a water replenishment rate of 4L / min; the yield of the tailings product I is 25% to 35%.

[0160] The phosphate ore washed fine mud slurry described in step one is the phosphate ore washed fine mud produced in the pretreatment process of the phosphate ore mine, and the sulfur content in the phosphate ore washed fine mud slurry accounts for 2% to 6% by mass, and the phosphorus content accounts for 7% to 13% by mass; the washed fine mud with a particle size less than 0.074 mm in the phosphate ore washed fine mud slurry accounts for 85% to 95% by mass, and the washed fine mud with a particle size less than 0.038 mm accounts for 75% to 85% by mass; the mass concentration of the phosphate ore washed fine mud slurry is 8% to 15%.

[0161] Step 2: The deslimed coarse concentrate slurry is enriched in stages, comprising the following steps:

[0162] Step 201, the deslimed coarse concentrate slurry obtained in step 102 is subjected to primary enrichment, and the specific operation of the primary enrichment is: using dense return water to adjust the mass concentration of the deslimed coarse concentrate slurry to 30%, then adding a desiliconizing agent to the deslimed coarse concentrate slurry for reverse flotation desiliconization to obtain a foam product and a primary enrichment desiliconized coarse concentrate, and performing a scavenging operation on the foam product to obtain a tailings product II; wherein the reverse flotation is a one-roughing and one-scavenging closed-circuit flotation, and the middlings are returned in sequence;

[0163] The desiliconizing agent is composed of the following raw materials in percentage by mass: 25% polyethylene glycol monolauramide, 18% 2-ethoxyethylamine, 15% nonylphenol polyoxyethylene ether phosphate, 17% polyethylene glycol, 15% aviation kerosene and 10% octylphenol polyoxyethylene ether amine; the dosage of the desiliconizing agent is 300g / t phosphate rock washed fine mud slurry.

[0164] Step 202, using a gravity separation device to perform secondary gravity separation on the primary enriched and desiliconized coarse concentrate obtained in step 201 to obtain sulfur coarse concentrate slurry and gravity separation tailings;

[0165] The gravity separation equipment is a cone concentrator, the feed rate of the gravity separation equipment is 10 / min, the overflow concentration during gravity separation is 8%, and the mass percentage of sulfur in the sulfur rough concentrate slurry is 10% to 17%.

[0166] Step 3: flotation the sulfur concentrate pulp twice, comprising the following steps:

[0167] Step 301, adjusting the mass concentration of the sulfur concentrate pulp obtained in step 202 to 35% by using dense return water, and then adding sulfur flotation reagent to the sulfur concentrate pulp for positive flotation to obtain sulfur concentrate product III and sulfur flotation tailings; the positive flotation is a one-coarse and one-fine closed-circuit flotation, and the middlings are returned in sequence;

[0168] The sulfur flotation reagent includes a collector and an activator, wherein the collector is used in an amount of 600 g / t of phosphate rock water-washed fine mud slurry, and the activator is used in an amount of 1500 g / t of phosphate rock water-washed fine mud slurry; the positive flotation is carried out in a stirring barrel, and before the positive flotation, the collector and the activator are successively added to the stirring barrel and stirred for 5 minutes respectively;

[0169] The activator is a mixed solution of an inorganic acid and an inorganic salt in a mass ratio of 5:1, wherein the inorganic acid is a combination of oxalic acid and nitric acid, and the inorganic salt is a combination of ferrous sulfate and ammonium trichloride; the collector is a combination of sodium butyl xanthate, butyl ammonium black medicine, diethyl disulfide, 1,3-bis(benzyloxycarbonyl)-2-methyl-2-thiourea and S-(4-chlorobenzyl)isothiourea ammonium chloride.

[0170] Step 302, combining the sulfur flotation tailings obtained in step 301 and the gravity separation tailings obtained in step 202, adding acidic wastewater and adjusting the pH value of the pulp to 5.5 to obtain a weakly acidic pulp;

[0171] The specific operation of the merging is: the gravity separation tailings and the sulfur flotation tailings are fed into a stirring barrel together and stirred for 5 minutes, and the acidic adjuster is sulfuric acid; the demagnesiumizing agent in step 303 is a fatty acid anion collector, and the dosage of the demagnesiumizing agent is 1500g / t phosphate rock water-washed fine mud slurry; the fatty acid anion collector is cyclohexane acid.

[0172] Step 303, adding a demagnesizing agent to the weakly acidic slurry obtained in step 302 for reverse flotation to obtain demagnesized tailings product IV and phosphate concentrate product V; the reverse flotation is a one-roughing and one-sweeping closed-circuit flotation, and the middlings are returned in sequence.

[0173] In Example 6, a sulfur concentrate product with a yield of 6.88%, a sulfur grade of 37.11%, and a recovery rate of 75.34% was finally obtained; at the same time, a phosphate concentrate product with a yield of 27.78%, a phosphorus grade of 28.11%, and a recovery rate of 79.54% was obtained.

[0174] Example 7

[0175] A method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud comprises the following steps:

[0176] Step 1: flotation and desludging treatment of phosphate ore water-washed fine mud slurry, including the following steps:

[0177] Step 101, dehydrating the phosphate ore water-washed fine mud slurry to a mass concentration of 32% to obtain a dense dehydrated water-washed fine mud slurry, adding a flotation agent to the dense dehydrated water-washed fine mud slurry and stirring and dispersing the mixture to obtain a homogeneous dispersed particle suspension;

[0178] The floating agent includes a dispersant and a foaming agent. The specific operation of adding the floating agent is as follows: the homogeneous dispersed particle suspension is placed in a stirring barrel, the floating agent is added to the stirring barrel, and then stirred at a high speed for 23 minutes;

[0179] The dosage of the floating agent is 800g / t phosphate rock washed fine mud slurry, the mass ratio of the dispersant to the foaming agent is 10:1, the dispersant is sodium hexametaphosphate; the foaming agent is ethylene glycol.

[0180] Step 102, the homogeneous dispersed particle suspension obtained in step 101 is sorted and deslimed by a floating shaking table to obtain tailings product I and deslimed coarse concentrate slurry;

[0181] The single floating shaking table has a feed rate of 12 L / min, a table slope of 2.5 degrees, and a water replenishment rate of 6 L / min; the yield of the tailings product I is 25% to 35%.

[0182] The phosphate ore washed fine mud slurry described in step one is the phosphate ore washed fine mud produced in the pretreatment process of the phosphate ore mine, and the sulfur content in the phosphate ore washed fine mud slurry accounts for 2% to 6% by mass, and the phosphorus content accounts for 7% to 13% by mass; the washed fine mud with a particle size less than 0.074 mm in the phosphate ore washed fine mud slurry accounts for 85% to 95% by mass, and the washed fine mud with a particle size less than 0.038 mm accounts for 75% to 85% by mass; the mass concentration of the phosphate ore washed fine mud slurry is 8% to 15%.

[0183] Step 2: The deslimed coarse concentrate slurry is enriched in stages, comprising the following steps:

[0184] Step 201, the deslimed coarse concentrate slurry obtained in step 102 is subjected to primary enrichment, and the specific operation of the primary enrichment is: using dense return water to adjust the mass concentration of the deslimed coarse concentrate slurry to 25%, then adding a desiliconizing agent to the deslimed coarse concentrate slurry for reverse flotation desiliconization to obtain a foam product and a primary enrichment desiliconized coarse concentrate, and performing a scavenging operation on the foam product to obtain tailings product II; wherein the reverse flotation is a one-roughing and one-scavenging closed-circuit flotation, and the middlings are returned in sequence;

[0185] The desiliconizing agent is composed of the following raw materials in percentage by mass: 20% polyethylene glycol monolauramide, 15% 2-ethoxyethylamine, 20% nonylphenol polyoxyethylene ether phosphate, 15% polyethylene glycol, 15% aviation kerosene and 15% octylphenol polyoxyethylene ether amine; the dosage of the desiliconizing agent is 200g / t phosphate rock washed fine mud slurry.

[0186] Step 202, using a gravity separation device to perform secondary gravity separation on the primary enriched and desiliconized coarse concentrate obtained in step 201 to obtain sulfur coarse concentrate slurry and gravity separation tailings;

[0187] The gravity separation equipment is a fine-grained shaking table, wherein the shaking table inclination angle is 3.5 degrees, the feed rate of the gravity separation equipment is 13L / min, the overflow concentration during gravity separation is 11%, and the mass percentage of sulfur in the sulfur rough concentrate slurry is 10% to 17%.

[0188] Step 3: flotation the sulfur concentrate pulp twice, comprising the following steps:

[0189] Step 301, adjusting the mass concentration of the sulfur concentrate pulp obtained in step 202 to 26% by using thickened return water, and then adding sulfur flotation reagent to the sulfur concentrate pulp for positive flotation to obtain sulfur concentrate product III and sulfur flotation tailings; the positive flotation is a one-rough and one-fine closed-circuit flotation, and the middlings are returned in sequence;

[0190] The sulfur flotation reagent includes a collector and an activator, wherein the collector is used in an amount of 400 g / t of phosphate rock water-washed fine mud slurry, and the activator is used in an amount of 900 g / t of phosphate rock water-washed fine mud slurry; the positive flotation is carried out in a stirring barrel, and before the positive flotation, the collector and the activator are successively added to the stirring barrel and stirred for 2 minutes respectively;

[0191] The activator is a mixed solution of an inorganic acid and an inorganic salt in a mass ratio of 5:1, wherein the inorganic acid is a combination of phosphoric acid, oxalic acid and nitric acid, and the inorganic salt is ammonium trichloride and sodium copper ethylenediaminetetraacetate; the collector is a combination of sodium amyl xanthate, sodium isopentyl xanthate, sodium butyl xanthate, butyl ammonium black medicine and S-(4-chlorobenzyl) isothiourea ammonium chloride.

[0192] Step 302, combining the sulfur flotation tailings obtained in step 301 and the gravity separation tailings obtained in step 202, adding acidic wastewater and adjusting the pH value of the pulp to 5 to obtain a weakly acidic pulp;

[0193] The specific operation of the merging is: the gravity separation tailings and the sulfur flotation tailings are fed into a stirring barrel together and stirred for 2 minutes, the acidic adjuster is a combination of phosphoric acid and sulfuric acid, wherein the mass ratio of phosphoric acid to sulfuric acid is 1:1; the demagnesiumizing agent in step 303 is a fatty acid anion collector, and the dosage of the demagnesiumizing agent is 1050g / t phosphate rock washed fine mud slurry; the fatty acid anion collector is oleic acid.

[0194] Step 303, adding a demagnesizing agent to the weakly acidic slurry obtained in step 302 for reverse flotation to obtain demagnesized tailings product IV and phosphate concentrate product V; the reverse flotation is a one-roughing and one-sweeping closed-circuit flotation, and the middlings are returned in sequence.

[0195] In Example 7, a sulfur concentrate product with a yield of 8.12% was finally obtained, of which the sulfur grade was 34.45% and the recovery rate was 78.77%; at the same time, a phosphate concentrate product with a yield of 28.45% was obtained, of which the phosphorus grade was 26.23% and the recovery rate was 76.41%.

[0196] Example 8

[0197] A method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud comprises the following steps:

[0198] Step 1: flotation and desludging treatment of phosphate ore water-washed fine mud slurry, including the following steps:

[0199] Step 101, dehydrating the phosphate ore water-washed fine mud slurry to a mass concentration of 25% to obtain a dense dehydrated water-washed fine mud slurry, adding a flotation agent to the dense dehydrated water-washed fine mud slurry and stirring and dispersing the mixture to obtain a homogeneous dispersed particle suspension;

[0200] The floating agent includes a dispersant and a foaming agent. The specific operation of adding the floating agent is as follows: the homogeneous dispersed particle suspension is placed in a stirring barrel, the floating agent is added to the stirring barrel, and then stirred at a high speed for 12 minutes;

[0201] The dosage of the floating agent is 400g / t phosphate rock washed fine mud slurry, the mass ratio of the dispersant to the foaming agent is 15:1, the dispersant is sodium pyrophosphate; the foaming agent is methyl isobutyl carbinol.

[0202] Step 102, the homogeneous dispersed particle suspension obtained in step 101 is sorted and deslimed by a floating shaking table to obtain tailings product I and deslimed coarse concentrate slurry;

[0203] The single floating shaking table has a feed rate of 15 L / min, a table slope of 4 degrees, and a water replenishment rate of 7 L / min; the yield of the tailings product I is 25% to 35%.

[0204] The phosphate ore washed fine mud slurry described in step one is the phosphate ore washed fine mud produced in the pretreatment process of the phosphate ore mine, and the sulfur content in the phosphate ore washed fine mud slurry accounts for 2% to 6% by mass, and the phosphorus content accounts for 7% to 13% by mass; the washed fine mud with a particle size less than 0.074 mm in the phosphate ore washed fine mud slurry accounts for 85% to 95% by mass, and the washed fine mud with a particle size less than 0.038 mm accounts for 75% to 85% by mass; the mass concentration of the phosphate ore washed fine mud slurry is 8% to 15%.

[0205] Step 2: The deslimed coarse concentrate slurry is enriched in stages, comprising the following steps:

[0206] Step 201, the deslimed coarse concentrate slurry obtained in step 102 is subjected to primary enrichment, and the specific operation of the primary enrichment is: using thickened return water to adjust the mass concentration of the deslimed coarse concentrate slurry to 23%, then adding a desiliconizing agent to the deslimed coarse concentrate slurry for reverse flotation desiliconization to obtain a foam product and a primary enriched desiliconized coarse concentrate, and performing a scavenging operation on the foam product to obtain a tailings product II; wherein the reverse flotation is a one-roughing and one-scavenging closed-circuit flotation, and the middlings are returned in sequence;

[0207] The desiliconizing agent is composed of the following raw materials in percentage by mass: 0% polyethylene glycol monolauramide, 25% 2-ethoxyethylamine, 25% nonylphenol polyoxyethylene ether phosphate, 20% polyethylene glycol, 15% aviation kerosene and 15% octylphenol polyoxyethylene ether amine; the dosage of the desiliconizing agent is 200g / t phosphate rock washed fine mud slurry.

[0208] Step 202, using a gravity separation device to perform secondary gravity separation on the primary enriched and desiliconized coarse concentrate obtained in step 201 to obtain sulfur coarse concentrate slurry and gravity separation tailings;

[0209] The gravity separation equipment is a fine-grained shaking table, wherein the shaking table inclination angle is 3.5 degrees, the feed rate of the gravity separation equipment is 14L / min, the overflow concentration during gravity separation is 14%, and the mass percentage of sulfur in the sulfur rough concentrate slurry is 10% to 17%.

[0210] Step 3: flotation the sulfur concentrate pulp twice, comprising the following steps:

[0211] Step 301, adjusting the mass concentration of the sulfur concentrate pulp obtained in step 202 to 28% by using dense return water, and then adding sulfur flotation reagent to the sulfur concentrate pulp for positive flotation to obtain sulfur concentrate product III and sulfur flotation tailings; the positive flotation is a one-coarse and one-fine closed-circuit flotation, and the middlings are returned in sequence;

[0212] The sulfur flotation reagent includes a collector and an activator, wherein the collector is used in an amount of 500 g / t of phosphate rock water-washed fine mud slurry, and the activator is used in an amount of 1000 g / t of phosphate rock water-washed fine mud slurry; the positive flotation is carried out in a stirring barrel, and before the positive flotation, the collector and the activator are successively added to the stirring barrel and stirred for 3 minutes respectively;

[0213] The activator is a mixed solution of an inorganic acid and an inorganic salt in a mass ratio of 5:1, wherein the inorganic acid is a combination of oxalic acid, nitric acid and ammonium bisulfate, and the inorganic salt is a combination of copper sulfate and ferrous sulfate; the collector is a combination of sodium butyl xanthate, butyl ammonium black medicine, diethyl disulfide, 1,3-bis(benzyloxycarbonyl)-2-methyl-2-thiourea and S-(4-chlorobenzyl)isothiourea ammonium chloride.

[0214] Step 302: combining the sulfur flotation tailings obtained in step 301 and the gravity separation tailings obtained in step 202, adding acidic wastewater and adjusting the pH value of the pulp to 4.7 to obtain a weakly acidic pulp;

[0215] The specific operation of the merging is: the gravity separation tailings and the sulfur flotation tailings are fed into a stirring barrel together and stirred for 3 minutes, and the acidic adjuster is sulfuric acid; the demagnesiumizing agent in step 303 is a fatty acid anion collector, and the amount of the demagnesiumizing agent is 800g / t phosphate rock washed fine mud slurry; the fatty acid anion collector is cyclohexane acid.

[0216] Step 303, adding a demagnesizing agent to the weakly acidic slurry obtained in step 302 for reverse flotation to obtain demagnesized tailings product IV and phosphate concentrate product V; the reverse flotation is a one-roughing and one-sweeping closed-circuit flotation, and the middlings are returned in sequence.

[0217] In Example 8, a sulfur concentrate product with a yield of 6.95%, a sulfur grade of 35.46%, and a recovery rate of 73.95% was finally obtained; at the same time, a phosphate concentrate product with a yield of 28.1% was obtained, with a phosphorus grade of 26.19% and a recovery rate of 76.89%.

[0218] Example 9

[0219] A method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud comprises the following steps:

[0220] Step 1: flotation and desludging treatment of phosphate ore water-washed fine mud slurry, including the following steps:

[0221] Step 101, dehydrating the phosphate ore water-washed fine mud slurry to a mass concentration of 40% to obtain a dense dehydrated water-washed fine mud slurry, adding a flotation agent to the dense dehydrated water-washed fine mud slurry and stirring and dispersing the mixture to obtain a homogeneous dispersed particle suspension;

[0222] The floating agent includes a dispersant and a foaming agent. The specific operation of adding the floating agent is as follows: the homogeneous dispersed particle suspension is placed in a stirring barrel, the floating agent is added to the stirring barrel, and then stirred at a high speed for 10 minutes;

[0223] The dosage of the floating agent is 1000g / t phosphate rock washed fine mud slurry, the mass ratio of the dispersant to the foaming agent is 15:1, the dispersant is hydroxypropyl starch; and the foaming agent is pine oil.

[0224] Step 102, the homogeneous dispersed particle suspension obtained in step 101 is sorted and deslimed by a floating shaking table to obtain tailings product I and deslimed coarse concentrate slurry;

[0225] The single floating shaking table has a feed rate of 8 L / min, a table slope of 1 degree, and a water replenishment rate of 5 L / min; the yield of the tailings product I is 25% to 35%.

[0226] The phosphate ore washed fine mud slurry described in step one is the phosphate ore washed fine mud produced in the pretreatment process of the phosphate ore mine, and the sulfur content in the phosphate ore washed fine mud slurry accounts for 2% to 6% by mass, and the phosphorus content accounts for 7% to 13% by mass; the washed fine mud with a particle size less than 0.074 mm in the phosphate ore washed fine mud slurry accounts for 85% to 95% by mass, and the washed fine mud with a particle size less than 0.038 mm accounts for 75% to 85% by mass; the mass concentration of the phosphate ore washed fine mud slurry is 8% to 15%.

[0227] Step 2: The deslimed coarse concentrate slurry is enriched in stages, comprising the following steps:

[0228] Step 201, the deslimed coarse concentrate slurry obtained in step 102 is subjected to primary enrichment, and the specific operation of the primary enrichment is: using thickened return water to adjust the mass concentration of the deslimed coarse concentrate slurry to 29%, then adding a desiliconizing agent to the deslimed coarse concentrate slurry for reverse flotation desiliconization to obtain a foam product and a primary enriched desiliconized coarse concentrate, and performing a scavenging operation on the foam product to obtain a tailings product II; wherein the reverse flotation is a one-roughing and one-scavenging closed-circuit flotation, and the middlings are returned in sequence;

[0229] The desiliconizing agent is composed of the following raw materials in percentage by mass: 20% polyethylene glycol monolauramide, 25% 2-ethoxyethylamine, 25% nonylphenol polyoxyethylene ether phosphate, 15% polyethylene glycol, 5% aviation kerosene and 10% octylphenol polyoxyethylene ether amine; the dosage of the desiliconizing agent is 150g / t phosphate rock washed fine mud slurry.

[0230] Step 202, using a gravity separation device to perform secondary gravity separation on the primary enriched and desiliconized coarse concentrate obtained in step 201 to obtain sulfur coarse concentrate slurry and gravity separation tailings;

[0231] The gravity separation equipment is a combination of a cone concentrator and a fine-grained shaking table, wherein the shaking table has an inclination angle of 3.5 degrees, a feed rate of 15 L / min, an overflow concentration during gravity separation of 10%, and a sulfur mass percentage in the sulfur rough concentrate slurry of 10% to 17%.

[0232] Step 3: flotation the sulfur concentrate pulp twice, comprising the following steps:

[0233] Step 301, adjusting the mass concentration of the sulfur concentrate pulp obtained in step 202 to 32% by using dense return water, and then adding sulfur flotation reagent to the sulfur concentrate pulp for positive flotation to obtain sulfur concentrate product III and sulfur flotation tailings; the positive flotation is a one-coarse and one-fine closed-circuit flotation, and the middlings are returned in sequence;

[0234] The sulfur flotation reagent includes a collector and an activator, wherein the collector is used in an amount of 550 g / t of phosphate rock water-washed fine mud slurry, and the activator is used in an amount of 1300 g / t of phosphate rock water-washed fine mud slurry; the positive flotation is carried out in a stirring barrel, and before the positive flotation, the collector and the activator are successively added to the stirring barrel and stirred for 4 minutes respectively;

[0235] The activator is a mixed solution of an inorganic acid and an inorganic salt in a mass ratio of 5:1, wherein the inorganic acid is a combination of phosphoric acid, oxalic acid and nitric acid, and the inorganic salt is a combination of ferrous sulfate and ammonium trichloride; the collector is a combination of sodium amyl xanthate, sodium isopentyl xanthate, sodium butyl xanthate, butyl ammonium black medicine, diethyl disulfide and 1,3-bis(benzyloxycarbonyl)-2-methyl-2-thiourea.

[0236] Step 302, combining the sulfur flotation tailings obtained in step 301 and the gravity separation tailings obtained in step 202, adding acidic wastewater and adjusting the pH value of the pulp to 4.6 to obtain a weakly acidic pulp;

[0237] The specific operation of the merging is: the gravity separation tailings and the sulfur flotation tailings are fed into a stirring barrel together and stirred for 4 minutes, and the acidic adjuster is phosphoric acid; the demagnesiumizing agent in step 303 is a fatty acid anion collector, and the dosage of the demagnesiumizing agent is 1300g / t phosphate rock washed fine mud slurry; the fatty acid anion collector is oleic acid.

[0238] Step 303, adding a demagnesizing agent to the weakly acidic slurry obtained in step 302 for reverse flotation to obtain demagnesized tailings product IV and phosphate concentrate product V; the reverse flotation is a one-roughing and one-sweeping closed-circuit flotation, and the middlings are returned in sequence.

[0239] In Example 9, a sulfur concentrate product with a yield of 7.35%, a sulfur grade of 38.46%, and a recovery rate of 81.51% was finally obtained; at the same time, a phosphate concentrate product with a yield of 27.17% was obtained, with a phosphorus grade of 27.58% and a recovery rate of 77.46%.

[0240] Example 10

[0241] A method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud comprises the following steps:

[0242] Step 1: flotation and desludging treatment of phosphate ore water-washed fine mud slurry, including the following steps:

[0243] Step 101, dehydrating the phosphate ore water-washed fine mud slurry to a mass concentration of 30% to obtain a dense dehydrated water-washed fine mud slurry, adding a flotation agent to the dense dehydrated water-washed fine mud slurry and stirring and dispersing the mixture to obtain a homogeneous dispersed particle suspension;

[0244] The floating agent includes a dispersant and a foaming agent. The specific operation of adding the floating agent is as follows: the homogeneous dispersed particle suspension is placed in a stirring barrel, the floating agent is added to the stirring barrel, and then stirred at a high speed for 10 minutes;

[0245] The dosage of the floating agent is 600g / t phosphate rock washed fine mud slurry, the mass ratio of the dispersant to the foaming agent is 5:1, the dispersant is a combination of sodium hexametaphosphate, sodium pyrophosphate and hydroxypropyl starch; the foaming agent is a combination of methyl isobutyl carbinol, pine oil and ethylene glycol.

[0246] Step 102, the homogeneous dispersed particle suspension obtained in step 101 is sorted and deslimed by a floating shaking table to obtain tailings product I and deslimed coarse concentrate slurry;

[0247] The single floating shaking table has a feed rate of 13 L / min, a table slope of 2 degrees, and a water replenishment rate of 6 L / min; the yield of the tailings product I is 25% to 35%.

[0248] The phosphate ore washed fine mud slurry described in step one is the phosphate ore washed fine mud produced in the pretreatment process of the phosphate ore mine, and the sulfur content in the phosphate ore washed fine mud slurry accounts for 2% to 6% by mass, and the phosphorus content accounts for 7% to 13% by mass; the washed fine mud with a particle size less than 0.074 mm in the phosphate ore washed fine mud slurry accounts for 85% to 95% by mass, and the washed fine mud with a particle size less than 0.038 mm accounts for 75% to 85% by mass; the mass concentration of the phosphate ore washed fine mud slurry is 8% to 15%.

[0249] Step 2: The deslimed coarse concentrate slurry is enriched in stages, comprising the following steps:

[0250] Step 201, the deslimed coarse concentrate slurry obtained in step 102 is subjected to primary enrichment, and the specific operation of the primary enrichment is: using thickened return water to adjust the mass concentration of the deslimed coarse concentrate slurry to 23%, then adding a desiliconizing agent to the deslimed coarse concentrate slurry for reverse flotation desiliconization to obtain a foam product and a primary enriched desiliconized coarse concentrate, and performing a scavenging operation on the foam product to obtain a tailings product II; wherein the reverse flotation is a one-roughing and one-scavenging closed-circuit flotation, and the middlings are returned in sequence;

[0251] The desiliconizing agent is composed of the following raw materials in percentage by mass: 20% polyethylene glycol monolauramide, 25% 2-ethoxyethylamine, 25% nonylphenol polyoxyethylene ether phosphate, 15% polyethylene glycol, 5% aviation kerosene and 10% octylphenol polyoxyethylene ether amine; the dosage of the desiliconizing agent is 230g / t phosphate rock washed fine mud slurry.

[0252] Step 202, using a gravity separation device to perform secondary gravity separation on the primary enriched and desiliconized coarse concentrate obtained in step 201 to obtain sulfur coarse concentrate slurry and gravity separation tailings;

[0253] The gravity separation equipment is a cone concentrator, the feed rate of the gravity separation equipment is 12L / min, the overflow concentration during gravity separation is 12%, and the mass percentage of sulfur in the sulfur rough concentrate slurry is 10% to 17%.

[0254] Step 3: flotation the sulfur concentrate pulp twice, comprising the following steps:

[0255] Step 301, adjusting the mass concentration of the sulfur concentrate pulp obtained in step 202 to 34% by using dense return water, and then adding sulfur flotation reagent to the sulfur concentrate pulp for positive flotation to obtain sulfur concentrate product III and sulfur flotation tailings; the positive flotation is a one-coarse and one-fine closed-circuit flotation, and the middlings are returned in sequence;

[0256] The sulfur flotation reagent includes a collector and an activator, wherein the collector is used in an amount of 300 g / t of phosphate rock water-washed fine mud slurry, and the activator is used in an amount of 1500 g / t of phosphate rock water-washed fine mud slurry; the positive flotation is carried out in a stirring barrel, and before the positive flotation, the collector and the activator are successively added to the stirring barrel and stirred for 5 minutes respectively;

[0257] The activator is a mixed solution of an inorganic acid and an inorganic salt in a mass ratio of 10:1, wherein the inorganic acid is a combination of phosphoric acid, oxalic acid, nitric acid and ammonium bisulfate, and the inorganic salt is sodium copper ethylenediaminetetraacetate; the collector is a combination of sodium butyl xanthate, butyl ammonium black medicine, diethyl disulfide, 1,3-bis(benzyloxycarbonyl)-2-methyl-2-thiourea, S-(4-chlorobenzyl)isothiourea ammonium chloride and dimethyl dithiocarbamate.

[0258] Step 302, combining the sulfur flotation tailings obtained in step 301 and the gravity separation tailings obtained in step 202, adding acidic wastewater and adjusting the pH value of the pulp to 5.2 to obtain a weakly acidic pulp;

[0259] The specific operation of the merging is: the gravity separation tailings and the sulfur flotation tailings are fed into a stirring barrel together and stirred for 5 minutes, and the acidic adjuster is phosphoric acid; the demagnesiumizing agent in step 303 is a fatty acid anion collector, and the amount of the demagnesiumizing agent is 800g / t phosphate rock washed fine mud slurry; the fatty acid anion collector is oleic acid.

[0260] Step 303, adding a demagnesizing agent to the weakly acidic slurry obtained in step 302 for reverse flotation to obtain demagnesized tailings product IV and phosphate concentrate product V; the reverse flotation is a one-roughing and one-sweeping closed-circuit flotation, and the middlings are returned in sequence.

[0261] In Example 10, a sulfur concentrate product with a yield of 7.85%, a sulfur grade of 35.43%, and a recovery rate of 78.53% was finally obtained; at the same time, a phosphate concentrate product with a yield of 28.37% was obtained, with a phosphorus grade of 25.98% and a recovery rate of 79.45%.

[0262] Embodiment 11

[0263] A method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud comprises the following steps:

[0264] Step 1: flotation and desludging treatment of phosphate ore water-washed fine mud slurry, including the following steps:

[0265] Step 101, dehydrating the phosphate ore water-washed fine mud slurry to a mass concentration of 30% to obtain a dense dehydrated water-washed fine mud slurry, adding a flotation agent to the dense dehydrated water-washed fine mud slurry and stirring and dispersing the mixture to obtain a homogeneous dispersed particle suspension;

[0266] The floating agent includes a dispersant and a foaming agent. The specific operation of adding the floating agent is as follows: the homogeneous dispersed particle suspension is placed in a stirring barrel, the floating agent is added to the stirring barrel, and then stirred at a high speed for 11 minutes;

[0267] The dosage of the floating agent is 700g / t phosphate rock washed fine mud slurry, the mass ratio of the dispersant to the foaming agent is 8:1, the dispersant is a combination of sodium hexametaphosphate and hydroxypropyl starch; the foaming agent is methyl isobutyl carbinol.

[0268] Step 102, the homogeneous dispersed particle suspension obtained in step 101 is sorted and deslimed by a floating shaking table to obtain tailings product I and deslimed coarse concentrate slurry;

[0269] The single floating shaking table has a ore feeding capacity of 14 L / min, a table slope of 3 degrees, and a water replenishment capacity of 7 L / min; the yield of the tailings product I is 25% to 35%.

[0270] The phosphate ore washed fine mud slurry described in step one is the phosphate ore washed fine mud produced in the pretreatment process of the phosphate ore mine, and the sulfur content in the phosphate ore washed fine mud slurry accounts for 2% to 6% by mass, and the phosphorus content accounts for 7% to 13% by mass; the washed fine mud with a particle size less than 0.074 mm in the phosphate ore washed fine mud slurry accounts for 85% to 95% by mass, and the washed fine mud with a particle size less than 0.038 mm accounts for 75% to 85% by mass; the mass concentration of the phosphate ore washed fine mud slurry is 8% to 15%.

[0271] Step 2: The deslimed coarse concentrate slurry is enriched in stages, comprising the following steps:

[0272] Step 201, the deslimed coarse concentrate slurry obtained in step 102 is subjected to primary enrichment, and the specific operation of the primary enrichment is: using thickened return water to adjust the mass concentration of the deslimed coarse concentrate slurry to 23%, then adding a desiliconizing agent to the deslimed coarse concentrate slurry for reverse flotation desiliconization to obtain a foam product and a primary enriched desiliconized coarse concentrate, and performing a scavenging operation on the foam product to obtain a tailings product II; wherein the reverse flotation is a one-roughing and one-scavenging closed-circuit flotation, and the middlings are returned in sequence;

[0273] The desiliconizing agent is composed of the following raw materials in percentage by mass: 20% polyethylene glycol monolauramide, 25% 2-ethoxyethylamine, 25% nonylphenol polyoxyethylene ether phosphate, 15% polyethylene glycol, 5% aviation kerosene and 10% octylphenol polyoxyethylene ether amine; the dosage of the desiliconizing agent is 200g / t phosphate rock washed fine mud slurry.

[0274] Step 202, using a gravity separation device to perform secondary gravity separation on the primary enriched and desiliconized coarse concentrate obtained in step 201 to obtain sulfur coarse concentrate slurry and gravity separation tailings;

[0275] The gravity separation equipment is a cone concentrator, the feed rate of the gravity separation equipment is 13L / min, the overflow concentration during gravity separation is 12%, and the mass percentage of sulfur in the sulfur rough concentrate slurry is 10% to 17%.

[0276] Step 3: flotation the sulfur concentrate pulp twice, comprising the following steps:

[0277] Step 301, adjusting the mass concentration of the sulfur concentrate pulp obtained in step 202 to 25% by using dense return water, and then adding sulfur flotation reagent to the sulfur concentrate pulp for positive flotation to obtain sulfur concentrate product III and sulfur flotation tailings; the positive flotation is a one-coarse and one-fine closed-circuit flotation, and the middlings are returned in sequence;

[0278] The sulfur flotation reagent includes a collector and an activator, wherein the collector is used in an amount of 300 g / t of phosphate rock water-washed fine mud slurry, and the activator is used in an amount of 1500 g / t of phosphate rock water-washed fine mud slurry; the positive flotation is carried out in a stirring barrel, and before the positive flotation, the collector and the activator are successively added to the stirring barrel and stirred for 3 minutes respectively;

[0279] The activator is a mixed solution of an inorganic acid and an inorganic salt in a mass ratio of 5:1, wherein the inorganic acid is a combination of phosphoric acid, oxalic acid, nitric acid and ammonium bisulfate, and the inorganic salt is a combination of copper sulfate, ferrous sulfate, ammonium trichloride and sodium copper ethylenediaminetetraacetate; the collector is a combination of sodium amyl xanthate, sodium isopentyl xanthate, sodium butyl xanthate, butyl ammonium black medicine, diethyl disulfide, 1,3-bis(benzyloxycarbonyl)-2-methyl-2-thiourea and S-(4-chlorobenzyl)isothiourea ammonium chloride.

[0280] Step 302: combining the sulfur flotation tailings obtained in step 301 and the gravity separation tailings obtained in step 202, adding acidic wastewater and adjusting the pH value of the pulp to 5.3 to obtain a weakly acidic pulp;

[0281] The specific operation of the merging is: the gravity separation tailings and the sulfur flotation tailings are fed into a stirring barrel together and stirred for 3 minutes, and the acidic adjuster is sulfuric acid; the demagnesiumizing agent in step 303 is a fatty acid anion collector, and the amount of the demagnesiumizing agent is 800g / t phosphate rock water-washed fine mud slurry; the fatty acid anion collector is oleic acid.

[0282] Step 303, adding a demagnesizing agent to the weakly acidic slurry obtained in step 302 for reverse flotation to obtain demagnesized tailings product IV and phosphate concentrate product V; the reverse flotation is a one-roughing and one-sweeping closed-circuit flotation, and the middlings are returned in sequence.

[0283] In Example 11, a sulfur concentrate product with a yield of 6.82% was finally obtained, with a sulfur grade of 37.13% and a recovery rate of 76.24%; at the same time, a phosphate concentrate product with a yield of 26.98% was obtained, with a phosphorus grade of 26.92% and a recovery rate of 80.23%.

[0284] Example 12

[0285] A method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud comprises the following steps:

[0286] Step 1: flotation and desludging treatment of phosphate ore water-washed fine mud slurry, including the following steps:

[0287] Step 101, dehydrating the phosphate ore water-washed fine mud slurry to a mass concentration of 30% to obtain a dense dehydrated water-washed fine mud slurry, adding a flotation agent to the dense dehydrated water-washed fine mud slurry and stirring and dispersing the mixture to obtain a homogeneous dispersed particle suspension;

[0288] The floating agent includes a dispersant and a foaming agent. The specific operation of adding the floating agent is as follows: the homogeneous dispersed particle suspension is placed in a stirring barrel, the floating agent is added to the stirring barrel, and then stirred at a high speed for 12 minutes;

[0289] The dosage of the floating agent is 750g / t phosphate rock washed fine mud slurry, the mass ratio of the dispersant to the foaming agent is 8:1, the dispersant is a combination of sodium hexametaphosphate and hydroxypropyl starch; the foaming agent is methyl isobutyl carbinol.

[0290] Step 102, the homogeneous dispersed particle suspension obtained in step 101 is sorted and deslimed by a floating shaking table to obtain tailings product I and deslimed coarse concentrate slurry;

[0291] The single floating shaking table has a feed rate of 15 L / min, a table slope of 4 degrees, and a water replenishment rate of 8 L / min; the yield of the tailings product I is 25% to 35%.

[0292] The phosphate ore washed fine mud slurry described in step one is the phosphate ore washed fine mud produced in the pretreatment process of the phosphate ore mine, and the sulfur content in the phosphate ore washed fine mud slurry accounts for 2% to 6% by mass, and the phosphorus content accounts for 7% to 13% by mass; the washed fine mud with a particle size less than 0.074 mm in the phosphate ore washed fine mud slurry accounts for 85% to 95% by mass, and the washed fine mud with a particle size less than 0.038 mm accounts for 75% to 85% by mass; the mass concentration of the phosphate ore washed fine mud slurry is 8% to 15%.

[0293] Step 2: The deslimed coarse concentrate slurry is enriched in stages, comprising the following steps:

[0294] Step 201, the deslimed coarse concentrate slurry obtained in step 102 is subjected to primary enrichment, and the specific operation of the primary enrichment is: using thickened return water to adjust the mass concentration of the deslimed coarse concentrate slurry to 23%, then adding a desiliconizing agent to the deslimed coarse concentrate slurry for reverse flotation desiliconization to obtain a foam product and a primary enriched desiliconized coarse concentrate, and performing a scavenging operation on the foam product to obtain a tailings product II; wherein the reverse flotation is a one-roughing and one-scavenging closed-circuit flotation, and the middlings are returned in sequence;

[0295] The desiliconizing agent is composed of the following raw materials in percentage by mass: 20% polyethylene glycol monolauramide, 25% 2-ethoxyethylamine, 25% nonylphenol polyoxyethylene ether phosphate, 15% polyethylene glycol, 5% aviation kerosene and 10% octylphenol polyoxyethylene ether amine; the dosage of the desiliconizing agent is 280g / t phosphate rock washed fine mud slurry.

[0296] Step 202, using a gravity separation device to perform secondary gravity separation on the primary enriched and desiliconized coarse concentrate obtained in step 201 to obtain sulfur coarse concentrate slurry and gravity separation tailings;

[0297] The gravity separation equipment is a cone concentrator, the feed rate of the gravity separation equipment is 14L / min, the overflow concentration during gravity separation is 12%, and the mass percentage of sulfur in the sulfur rough concentrate slurry is 10% to 17%.

[0298] Step 3: flotation the sulfur concentrate pulp twice, comprising the following steps:

[0299] Step 301, adjusting the mass concentration of the sulfur concentrate pulp obtained in step 202 to 35% by using dense return water, and then adding sulfur flotation reagent to the sulfur concentrate pulp for positive flotation to obtain sulfur concentrate product III and sulfur flotation tailings; the positive flotation is a one-coarse and one-fine closed-circuit flotation, and the middlings are returned in sequence;

[0300] The sulfur flotation reagent includes a collector and an activator, wherein the collector is used in an amount of 300 g / t of phosphate rock water-washed fine mud slurry, and the activator is used in an amount of 1500 g / t of phosphate rock water-washed fine mud slurry; the positive flotation is carried out in a stirring barrel, and before the positive flotation, the collector and the activator are successively added to the stirring barrel and stirred for 3 minutes respectively;

[0301] The activator is a mixed solution of an inorganic acid and an inorganic salt in a mass ratio of 10:1, wherein the inorganic acid is phosphoric acid and the inorganic salt is copper sulfate; the collector is a combination of sodium amyl xanthate, sodium isoamyl xanthate, sodium butyl xanthate, butyl ammonium black medicine, diethyl disulfide, 1,3-bis(benzyloxycarbonyl)-2-methyl-2-thiourea and S-(4-chlorobenzyl)isothiourea ammonium chloride.

[0302] Step 302: combining the sulfur flotation tailings obtained in step 301 and the gravity separation tailings obtained in step 202, adding acidic wastewater and adjusting the pH value of the pulp to 4.5 to obtain a weakly acidic pulp;

[0303] The specific operation of the merging is: the gravity separation tailings and the sulfur flotation tailings are fed into a stirring barrel together and stirred for 3 minutes, and the acidic adjuster is sulfuric acid; the demagnesiumizing agent in step 303 is a fatty acid anion collector, and the amount of the demagnesiumizing agent is 800g / t phosphate rock water-washed fine mud slurry; the fatty acid anion collector is oleic acid.

[0304] Step 303, adding a demagnesizing agent to the weakly acidic slurry obtained in step 302 for reverse flotation to obtain demagnesized tailings product IV and phosphate concentrate product V; the reverse flotation is a one-roughing and one-sweeping closed-circuit flotation, and the middlings are returned in sequence.

[0305] In Example 12, a sulfur concentrate product with a yield of 7.15% was finally obtained, of which the sulfur grade was 38.41% and the recovery rate was 77.59%; at the same time, a phosphate concentrate product with a yield of 26.87% was obtained, of which the phosphorus grade was 27.13% and the recovery rate was 77.69%.

[0306] Comparative Example 1

[0307] The other conditions of this comparative example are consistent with those of Example 1, except that the mixed dispersant of sodium hexametaphosphate and sodium pyrophosphate and methyl isobutyl carbinol are not added in step 101. The experiment found that the material desludging yield was reduced, and the sulfur and phosphorus minerals were seriously entrained, the efficiency was greatly reduced, and the foam viscosity of the reverse flotation impurity removal process after desludging increased, and the impurity removal and enrichment effect was affected. The final product indicators of the experiment are shown in Table 3.

[0308] Table 3

[0309]

[0310] Comparative Example 2

[0311] The other conditions of this comparative example are consistent with those of Example 1, except that a hydrocyclone is used instead of a flotation dosing method for desludging, the feed rate is controlled to be 14L / min, the cyclone overflow concentration is 8%, and the subsequent process is consistent with Example 1. The experiment found that due to the poor sorting performance of the hydrocyclone and the ultra-high fineness of the raw material, more tailings need to be discarded to achieve a better enrichment effect. The final product indicators of the experiment are shown in Table 4.

[0312] Table 4

[0313]

[0314] Comparative Example 3

[0315] The other conditions of this comparative example are consistent with those of Example 1, except that the cone concentrator is not used for enrichment in step 202. The experiment found that since the sulfur was not further enriched before the flotation of the sulfur ore, and some slightly fine particles were not removed, the sulfur content of the flotation ore was low and the flotation foam separation performance decreased. The final product indicators of the experiment are shown in Table 5.

[0316] Table 5

[0317]

[0318] The final product indicators of Comparative Examples 1 to 3 were compared with the product indicators of Example 1, and the comparison results are shown in Table 6.

[0319] Table 6

[0320]

[0321]

[0322] As can be seen from the above table, after the process and reagents of the present invention are changed, it is impossible to achieve effective enrichment and recovery of sulfur and phosphorus minerals at the same time. Comparative Example 1 does not add a flotation reagent in step 101, resulting in reduced desludging efficiency, affected grades of sulfur and phosphorus mineral concentrates, and a significant decrease in recovery rate; Comparative Example 2 uses a hydrocyclone for desludging in step 101. Due to the slightly larger specific gravity of the sulfide ore, the grade and recovery rate of the sulfur concentrate are less affected, but the grade and recovery rate of the phosphorus concentrate are greatly affected; Comparative Example 3 does not use a cone concentrator for enrichment in step 202, resulting in a lower sulfur grade in the secondary flotation process, and a significant decrease in the grade of the sulfur concentrate.

[0323] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any way. Any simple modification, change and equivalent structural transformation made to the above embodiment based on the technical essence of the present invention still falls within the protection scope of the technical solution of the present invention.

Claims

1. A method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud, characterized in that: The following steps are involved: Step 1: flotation and desludging treatment of phosphate ore water-washed fine mud slurry, including the following steps: Step 101, dehydrating the phosphate ore water-washed fine mud slurry to a mass concentration of 25% to 40% to obtain a dense dehydrated water-washed fine mud slurry, adding a flotation agent to the dense dehydrated water-washed fine mud slurry and stirring and dispersing the mixture to obtain a homogeneous dispersed particle suspension; Step 102, the homogeneous dispersed particle suspension obtained in step 101 is sorted and deslimed by a floating shaking table to obtain tailings product I and deslimed coarse concentrate slurry; Step 2: The deslimed coarse concentrate slurry is enriched in stages, comprising the following steps: Step 201, the deslimed coarse concentrate slurry obtained in step 102 is subjected to primary enrichment, and the specific operation of the primary enrichment is: using thickened return water to adjust the mass concentration of the deslimed coarse concentrate slurry to 20% to 30%, then adding a desiliconizing agent to the deslimed coarse concentrate slurry for reverse flotation desiliconization to obtain a foam product and a primary enriched desiliconized coarse concentrate, and performing a scavenging operation on the foam product to obtain a tailings product II; Step 202, using a gravity separation device to perform secondary gravity separation on the primary enriched and desiliconized coarse concentrate obtained in step 201 to obtain sulfur coarse concentrate slurry and gravity separation tailings; Step 3: flotation the sulfur concentrate pulp twice, comprising the following steps: Step 301, adjusting the mass concentration of the sulfur concentrate slurry obtained in step 202 to 25% to 35% by using dense return water, and then adding a sulfur flotation agent to the sulfur concentrate slurry for positive flotation to obtain sulfur concentrate product III and sulfur flotation tailings; Step 302, combining the sulfur flotation tailings obtained in step 301 and the gravity separation tailings obtained in step 202, adding acidic wastewater and adjusting the pH value of the pulp to 4.5-5.5 to obtain a weakly acidic pulp; Step 303: adding a demagnesiumizing agent to the weakly acidic slurry obtained in step 302 for reverse flotation to obtain demagnesiumizing tailings product IV and phosphate concentrate product V.

2. The method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud according to claim 1, characterized in that: The phosphate ore washed fine mud slurry described in step one is the phosphate ore washed fine mud produced in the pretreatment process of the phosphate ore mine, and the sulfur content in the phosphate ore washed fine mud slurry accounts for 2% to 6% by mass, and the phosphorus content accounts for 7% to 13% by mass; the washed fine mud with a particle size less than 0.074 mm in the phosphate ore washed fine mud slurry accounts for 85% to 95% by mass, and the washed fine mud with a particle size less than 0.038 mm accounts for 75% to 85% by mass; the mass concentration of the phosphate ore washed fine mud slurry is 8% to 15%.

3. The method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud according to claim 1, characterized in that: The floating agent in step 101 includes a dispersant and a foaming agent. The specific operation of adding the floating agent is as follows: the homogeneous dispersed particle suspension is placed in a stirring barrel, the floating agent is added to the stirring barrel, and then stirred for 10 minutes to 30 minutes; The dosage of the floating agent is 400-1200g / t phosphate rock washed fine mud slurry, the mass ratio of the dispersant to the foaming agent is 5:1-15:1, the dispersant is one or a combination of sodium hexametaphosphate, sodium pyrophosphate, and hydroxypropyl starch; the foaming agent is one or a combination of methyl isobutyl carbinol, ethylene glycol, and pine oil.

4. The method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud according to claim 1, characterized in that: The single floating shaking table in step 102 has a feed rate of 8L / min to 15L / min, a table slope of 0 to 5 degrees, and a water replenishment rate of 4L / min to 8L / min; the yield of the tailings product I is 25% to 35%.

5. The method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud according to claim 1, characterized in that: The desiliconizing agent in step 201 is composed of the following raw materials in percentage by mass: 0% to 40% of polyethylene glycol monolauramide, 10% to 25% of 2-ethoxyethylamine, 15% to 25% of nonylphenol polyoxyethylene ether phosphate, 15% to 20% of polyethylene glycol, 5% to 15% of aviation kerosene and 5% to 15% of octylphenol polyoxyethylene ether amine; the dosage of the desiliconizing agent is 100 to 300 g / t of phosphate rock washed fine mud slurry.

6. The method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud according to claim 1, characterized in that: The gravity separation equipment in step 202 is one or a combination of a cone concentrator and a fine-grained shaking table. The feed rate of the gravity separation equipment is 10L / min to 15L / min, the overflow concentration during gravity separation is 8% to 15%, and the mass percentage of sulfur in the sulfur rough concentrate slurry is 10% to 17%.

7. The method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud according to claim 1, characterized in that: The sulfur flotation reagents in step 301 include a collector and an activator, wherein the amount of the collector is 200-600 g / t of phosphate rock water-washed fine mud slurry, and the amount of the activator is 300-1500 g / t of phosphate rock water-washed fine mud slurry; the forward flotation is carried out in a stirring barrel, and before the forward flotation, the collector and the activator are successively added to the stirring barrel and stirred for 2 min to 5 min respectively; The activator is a mixed solution of an inorganic acid and an inorganic salt in a mass ratio of 5:1-10:1, wherein the inorganic acid is one or a combination of phosphoric acid, oxalic acid, nitric acid, and ammonium bisulfate, and the inorganic salt is one or a combination of copper sulfate, ferrous sulfate, ammonium trichloride, and sodium copper ethylenediaminetetraacetate; The collector is a combination of two or more of sodium amyl xanthate, sodium isoamyl xanthate, sodium butyl xanthate, butyl ammonium black medicine, diethyl disulfide, 1,3-bis(benzyloxycarbonyl)-2-methyl-2-thiourea, S-(4-chlorobenzyl)isothiourea ammonium chloride and dimethyl dithiocarbamate.

8. The method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud according to claim 1, characterized in that: The specific operation of the merging in step 302 is: the gravity separation tailings and the sulfur flotation tailings are fed into a stirring barrel together and stirred for 2 minutes to 5 minutes, and the acidic adjuster is phosphoric acid and / or sulfuric acid; the demagnesium agent in step 303 is a fatty acid anion collector, and the amount of the demagnesium agent is 600 to 1500 g / t of phosphate rock washed fine mud slurry.

9. The method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud according to claim 8, characterized in that: The fatty acid anion collector is oleic acid or cyclohexane acid.

10. The method for synergistically recovering sulfur concentrate and phosphate concentrate from phosphate ore washing fine mud according to claim 1, characterized in that: The reverse flotation in step 201 and step 303 is a one-roughing-one-sweeping closed-circuit flotation, and the forward flotation in step 301 is a one-roughing-one-fine closed-circuit flotation; in the reverse flotation and forward flotation, the middlings are returned sequentially.

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