WO2020029488A1 - 淤浆法制备黄原酸盐的方法及系统 - Google Patents

淤浆法制备黄原酸盐的方法及系统 Download PDF

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WO2020029488A1
WO2020029488A1 PCT/CN2018/119611 CN2018119611W WO2020029488A1 WO 2020029488 A1 WO2020029488 A1 WO 2020029488A1 CN 2018119611 W CN2018119611 W CN 2018119611W WO 2020029488 A1 WO2020029488 A1 WO 2020029488A1
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reaction
solvent
xanthate
alcohol
reactor
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French (fr)
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钟宏
马鑫
王帅
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Central South University
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
    • C07C329/12—Dithiocarbonic acids; Derivatives thereof
    • C07C329/14—Esters of dithiocarbonic acids
    • C07C329/16—Esters of dithiocarbonic acids having sulfur atoms of dithiocarbonic groups bound to acyclic carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/002—Inorganic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/14—Flotation machines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
    • C07C329/12—Dithiocarbonic acids; Derivatives thereof
    • C07C329/14—Esters of dithiocarbonic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/008—Organic compounds containing oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/012—Organic compounds containing sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/007—Modifying reagents for adjusting pH or conductivity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/02—Collectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00—Specified materials treated by the flotation agents; Specified applications
    • B03D2203/02—Ores

Definitions

  • the invention relates to the technical field of preparation methods of chemical ore dressing agents, in particular to a method and system for preparing xanthate by a slurry method.
  • Xanthate also called xanthate or dithiocarbonate, has the structural formula: In the formula, R is a hydrocarbon group of a different carbon chain, and M is usually Na or K. Xanthate was first synthesized by Zeise in 1815. It was not until 1925 that Keller discovered that xanthate could be used as a flotation collector for non-ferrous metal sulfide ores. Xanthate was widely used in metal sulfide mines and to recover metals. Sulfide minerals have greatly promoted the development of the mineral flotation industry. Today, xanthates are still the most versatile and important sulfide ore collector.
  • the industrial production of xanthate is mainly carried out by the kneader method.
  • This method is to add alcohol and carbon disulfide to the kneader, and then add powdery caustic in batches to knead the xanthate.
  • the kneader method has the following problems in the production of xanthate: the requirements for the particle size of the alkali are fine and the energy consumption of powder alkali operation is high; and the reaction of synthesizing xanthate is exothermic and requires a high-power refrigerator to strictly control the reaction temperature.
  • the kneader method is difficult to achieve closed production, there is a small amount of volatilization loss such as carbon disulfide in the production process, and the temperature is not easy to control during the production process, resulting in incomplete reactions, more side reactions, and products. Low purity.
  • the xanthanate product produced by the kneader method contains water and high impurity content, especially unreacted caustic, which leads to a short shelf life of the product (Tian Xishuang, Wang Yongxin. Discussion on the production method of xanthate. Nonferrous metals (mineral part) 1991 ( 03): 30 ⁇ 31; Xiong Xun.
  • liquid xanthate is unstable and difficult to store, which greatly limits its application (Yang Xiaoling, Zhang Hongliang. Synthesis of liquid sodium isopropylxanthogen. Applied Chemistry, 2010, 39 (6): 895-897 ).
  • the existing solvent method for preparing xanthate is to react caustic alkali, carbon disulfide and alcohol in an organic solvent medium to generate xanthate. After the reaction is completed, the reaction slurry is transferred to a drying device (such as a rake type). Dryer, etc.) to remove the solvent to obtain xanthate product.
  • a drying device such as a rake type). Dryer, etc.
  • the reaction When the xanthate is synthesized by the reaction of alcohol, carbon disulfide and caustic, the reaction itself is an exothermic process, the reaction rate is fast, and the reaction exotherm is large, although the presence of organic solvents slows down the severity of the reaction and avoids excessive local temperature While the side reactions are exacerbated, a large amount of cooling water is still required in the reaction process to remove the heat released by the reaction and control the reaction temperature. After the reaction is completed, it needs to be heated to a certain temperature, and the solvent is removed by distillation. The entire process is complicated, the energy utilization rate is low, and the energy consumption is high.
  • the present invention provides a method and a system for preparing xanthate by a slurry method.
  • the method can not only reduce the volatilization loss of carbon disulfide, but also control the temperature of the preparation process and the purity of the obtained product. High; the prepared xanthate is stable and easy to store; the amount of solvent required in the production process is small and the operation is simple; the reaction process reduces the use of cooling water and has low energy consumption.
  • the present invention provides a method for preparing xanthate by a slurry method, including the following steps:
  • the powdered xanthate is transferred to a granulation device for granulation; the granules obtained after the granulation are dried and dehydrated to obtain a granular xanthate.
  • step 1) 2-tert-butoxyethanol needs to be added.
  • the added amount of the 2-tert-butoxyethanol is 5% to 10% by weight of the alcohol.
  • the addition of the 2-tert-butoxyethanol makes the powder product have a certain viscosity, which is beneficial to the subsequent granulation.
  • the molar ratio of the alcohol, caustic alkali, and carbon disulfide is 1: 1 to 1.05: 1 to 3, and the volume of the dichloromethane is 0.5 to 5 times the volume of the alcohol.
  • the system pressure in the step 2) is controlled at -0.01 to -0.08 MPa; the temperature in the system is maintained at 10 to 80 ° C.
  • the alcohol includes a C 2 to C 12 fatty alcohol, a fusel oil, a C 2 to C 10 alkoxy ether alcohol, or a combination thereof.
  • the C 2 -C 12 fatty alcohol is selected from the group consisting of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, pentanol, isoamyl alcohol, neopentyl alcohol, n-hexanol, isohexanol, and methyl alcohol.
  • the C 2 to C 10 alkoxy ether alcohol is selected from the group consisting of 2-methoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 2-tert-butoxyethanol, and 2-hexyloxy One or more of ethyl alcohol, 2-methoxypropanol, 2-ethoxypropanol, and 2-butoxypropanol.
  • reaction is continued for 0.5 to 6 hours.
  • the base is caustic.
  • the caustic alkali is sodium hydroxide or potassium hydroxide, and includes powder, granule or flake.
  • the reaction temperature of the xanthate synthesis of the present invention is 0 to 70 ° C, and the reaction time is 0.5 to 6 hours.
  • the temperature in the reactor can be adjusted by adjusting the pressure of the solvent distillation and controlling the evaporation rate of the solvent.
  • the present invention provides a system for implementing the above-mentioned slurry method for preparing xanthate, comprising a reaction device, a solvent recovery device, a granulation device, and a drying device which are interconnected;
  • the reaction device includes a slurry reactor, a raw material inlet, a powder outlet, an air outlet, and an agitator; the raw material inlet, the powder outlet, and the air outlet are disposed on the slurry reactor;
  • the agitator is installed in a slurry reactor;
  • the solvent recovery device includes a dust collector, a condenser, a vacuum pump, and a plurality of activated carbon adsorption columns connected in sequence;
  • the dust collector is connected with an air outlet
  • the condenser and several activated carbon adsorption columns are connected to a solvent storage tank;
  • the granulating equipment includes a granulating equipment body, a powder feeding port and a granule discharging port;
  • the powder feeding port and the granule discharging port are separately arranged at both ends of the granulation equipment body;
  • the powder feeding port is connected with the powder discharging port
  • the drying equipment includes a drying equipment body, a drying jacket, a particle feed port, an exhaust port, and a product discharge port;
  • the exhaust port is connected to a dust collector.
  • the stirrer includes a ribbon stirrer or a spiral stirrer.
  • the raw material feed port includes an alkali feed port, an alcohol feed port, a dichloromethane feed port, and a carbon disulfide feed port;
  • the alkali feed port is connected to an alkali storage tank;
  • the alcohol feed port Connected to an alcohol metering tank;
  • the dichloromethane feed port is connected to a dichloromethane metering tank;
  • the carbon disulfide feed port is connected to a carbon disulfide metering tank.
  • the slurry reactor is provided with a heating jacket; the heating jacket is connected to a heating device.
  • activated carbon adsorption columns can be directly communicated with a vent valve communicating with the atmosphere, or can be directly communicated with a vacuum pump through an intake valve.
  • a number of the activated carbon adsorption columns are connected to the head and the tail respectively through a pipeline, and are switched in parallel or in series through a valve switch; preferably, there are three activated carbon adsorption columns, and two activated carbon adsorption columns are connected in series by adjusting a valve for For adsorption, another adsorption column is used in parallel with the previous two activated carbon adsorption columns for desorption or standby.
  • the activated carbon adsorption column comprises an activated carbon adsorption column I, an activated carbon adsorption column II, and an activated carbon adsorption column III.
  • the two activated carbon adsorption columns are used in series with an adsorption solvent to be discharged into the atmosphere, and another activated carbon adsorption column is connected in parallel with them for subsequent follow-up. Spare or desorb.
  • the granulating equipment is a screw extruder or a roll compactor.
  • the screw extruder is a single screw extruder or a twin screw extruder.
  • the granulating device is a twin-screw extruder.
  • the drying jacket comprises a drying jacket body, a steam inlet pipe and a condensate water outlet; the steam inlet pipe and the condensate water outlet are arranged on both sides of the drying jacket body.
  • the drying equipment is a multilayer disk dryer, a rotary cylinder dryer or a belt dryer. Further preferably, the drying device is a multilayer disc dryer.
  • the solvent storage tank includes a water discharge valve and a solvent valve.
  • the method of the present invention completes the processes of reaction, solvent removal and drying and dehydration in a slurry reactor, the main reaction device of the system.
  • the operation is simple, has the characteristics of fast mixing speed, high efficiency, and fast discharge, and can meet the requirements. Vacuum feeding, no need for dust.
  • the solvent in the slurry reactor is evaporated by a vacuum pump during the reaction, thereby taking away most of the heat released by the xanthate preparation, which can reduce the cooling water required during the reaction and also reduce the reaction temperature.
  • the solvent recovery system After all the solvents removed in the method of the present invention enter the solvent recovery system, they are directly recovered after dust removal and condensation, and the gas is discharged without pollution after adsorption. After the recovered solvent enters the solvent storage tank, the liquid water and the solvent are separated and floated. It can act as a water seal on the upper layer of the solvent, and can be discharged through the drain valve when the amount of water has accumulated to a certain amount.
  • the xanthate product prepared by the present invention has high purity and yield, few impurities, simple and convenient preparation process operation, low cost, environmental friendliness, and easy industrialized production.
  • the invention provides a method and a system for preparing xanthate by a slurry method.
  • the specific advantages are as follows:
  • the reaction system is in the form of a slurry, the system is uniform, the mass and heat transfer of the reaction system are relatively uniform, and the reactants are fully contacted, which is conducive to the reaction.
  • reaction solvent a mixture of dichloromethane and carbon disulfide is used as a reaction solvent, and the reaction is performed under a condition of less than 1 atmosphere.
  • the reaction heat is removed by the evaporation of the solvent to control the reaction temperature. Because the solvent vaporization can take away the reaction heat more efficiently, the amount of solvent can be significantly reduced.
  • the minimum amount of solvent is only 1.0 times the volume of the alcohol of the raw material, which reduces the energy required for solvent evaporation and overcomes the disadvantage of the solvent method that requires a large amount of solvent.
  • the boiling point of dichloromethane is 39.8 ° C
  • the boiling point of carbon disulfide is 46.5 ° C
  • the boiling point is lower
  • the boiling point of dichloromethane is lower than the boiling point of carbon disulfide, which is easier to volatilize, remove heat, and facilitate the recycling of solvents.
  • the dichloromethane has flame retardant effect.
  • the closed flash point of the reactant carbon disulfide is -30 ° C. When the dichloromethane is added, the closed flash point is significantly increased (as shown in FIG. 2).
  • the dichloromethane volume fraction is 50. At%, the closed flash point is increased to 31.2 ⁇ 1 ° C, which indicates that the use of dichloromethane as the reaction solvent can effectively improve the safety of the process.
  • the slurry reactor used in the preparation process of the present invention integrates the functions of reaction, solvent removal and drying and dehydration, and is easy to operate. Moreover, the slurry reactor has fast mixing speed, high efficiency, fast discharge, and can Meet the advantages of vacuum feeding and no dust.
  • the system of the present invention integrates reaction equipment, solvent recovery equipment, granulation equipment drying equipment, and material drying equipment.
  • the components are connected simply and effectively, and it is easy to realize automatic control of the production line. It has high energy efficiency and low energy consumption.
  • FIG. 1 is a schematic diagram of a system structure according to a preferred embodiment of the present invention.
  • reaction device 1-1—slurry reactor; 1-2—alkali storage tank; 1-3—alcohol metering tank; 1-4—methylene chloride metering tank; 1-5—carbon disulfide metering tank; 1— 6—Powder outlet
  • 2 Solvent recovery device: 2-1—Dust collector; 2-2—Condenser; 2-3—Vacuum pump; 2-4—Activated carbon adsorption column I; 2-5—Activated carbon adsorption column II; 2-6—Activated carbon adsorption Column III; 2-7—solvent storage tank;
  • Figure 2 shows the closed flash point test results for a mixed solution of dichloromethane and carbon disulfide.
  • the various reagents and raw materials used in the present invention are all commercially available products or products that can be prepared by known methods.
  • the present invention provides a system for implementing a method for preparing a xanthate by a slurry method, which includes a reaction device 1, a solvent recovery device 2, a granulation device 3, and a drying device 4 which are interconnected;
  • the reaction device 1 includes a slurry reactor 1-1, a raw material inlet, a powder outlet 1-6, an air outlet, and an agitator; the raw material inlet, a powder outlet 1-6, and an air outlet It is arranged on the slurry reactor 1-1; the stirrer is installed in the slurry reactor 1-1; preferably, the stirrer includes a spiral ribbon stirrer or a spiral stirrer; the spiral ribbon stirrer The stirrer is a single-spiral ribbon stirrer or a double-spiral ribbon stirrer; it is even more preferably a double-spiral ribbon stirrer, which is conducive to the stirring of sludge-like products prepared by the slurry method and the subsequent removal of solvents; preferably, the raw materials are fed into
  • the feed port includes an alkali feed port, an alcohol feed port, a dichloromethane feed port and a carbon disulfide feed port; the alkali feed port is connected to an alkali storage tank 1-2;
  • the solvent recovery device 2 includes a dust collector 2-1, a condenser 2-2, a vacuum pump 2-3, and a plurality of activated carbon adsorption columns, which are sequentially connected;
  • the dust collector 2-1 is connected to the air outlet; the solvent in the slurry reactor 1-1 is wrapped with dust into the dust collector 2-1, and after the dust is removed in the dust collector 2-1, it enters the follow-up installation;
  • the condenser 2-1 and several activated carbon adsorption columns are connected to the solvent storage tank 2-7;
  • a plurality of the activated carbon adsorption columns are connected to each other through a pipe; the plurality of activated carbon adsorption columns are connected to a head and a tail respectively through a pipe, and are switched in parallel or in series through a valve switch; preferably, the activated carbon adsorption columns are three, two Each activated carbon adsorption column is connected in series for adsorption by adjusting the valve, and the other adsorption column is connected in parallel with the previous two activated carbon adsorption columns for desorption or standby.
  • Each adsorption column can be directly connected to the air vent valve connected to the atmosphere, or directly connected to the vacuum pump 2-3 through the intake valve; as in this embodiment, the activated carbon adsorption column includes activated carbon adsorption column I2-4, activated carbon adsorption column II 2-5, activated carbon adsorption column III2-6, two activated carbon adsorption columns are used in series with the adsorption solvent and discharged into the atmosphere, and another activated carbon adsorption column is connected in parallel with them for subsequent backup or desorption;
  • the granulation equipment 3 includes a granulation equipment body, a powder feeding port 3-1 and a granule discharging port 3-2;
  • the powder feed port 3-1 and the granule discharge port 3-2 are respectively arranged at both ends of the granulation equipment body; preferably, the granulation equipment is a screw extruder or a double-roller agglomerator, in which the screw is extruded
  • the machine is a single-screw extruder or a twin-screw extruder; a further preferred granulation device is a twin-screw extruder; the powder xanthanate is made into a granular xanthanate to facilitate subsequent products;
  • the powder feeding port 3-1 is connected to the powder discharging port 1-6;
  • the drying equipment 4 includes a drying equipment body, a drying jacket, a particle feeding port 4-1, an exhaust port 4-2, and a product discharging port 4-4.
  • the drying jacket includes a drying jacket body
  • the steam inlet pipe 4-3 and the condensate water outlet 4-5; the steam inlet pipe 4-3 and the condensate water outlet 4-5 are arranged on both sides of the drying jacket body; the exhaust port 4-2 and The dust collector 2-1 is connected. Ensure that the exhaust gas is free from pollution.
  • the drying equipment is a multilayer disk dryer, a rotary cylinder dryer, a belt dryer, and further preferably, the drying equipment is a multilayer disk dryer.
  • Example 2 The system of Example 1 was used to prepare sodium isobutyl xanthate
  • Hot water at 50 to 80 ° C. was passed into the reactor jacket, and dried under the conditions of a vacuum of -0.04 to -0.05 MPa for 1 h to obtain a powdery sodium isobutyl xanthate product, and the solvent was recovered at the same time.
  • the reactor discharge valve was opened, and the sodium xanthate powder obtained by the reaction was transferred to a twin-screw extruder for granulation to obtain sodium xanthate particles having a size of about 4 ⁇ 6 to 12 (mm).
  • the prepared sodium xanthate particles are sent to a disc dryer to further remove the residual solvent and part of the moisture.
  • the drying temperature is 50 to 120 ° C, and a dried granular sodium isobutyl xanthate product is obtained and recovered at the same time. Solvent.
  • Example 3 The system of Example 1 was used to prepare sodium isobutyl xanthate
  • Hot water at 50 to 80 ° C. was passed into the reactor jacket, and dried under the conditions of a vacuum of -0.04 to -0.05 MPa for 1 h to obtain a powdery sodium isobutyl xanthate product, and the solvent was recovered at the same time.
  • the reactor discharge valve was opened, and the sodium xanthate powder obtained by the reaction was transferred to a twin-screw extruder for granulation to obtain sodium xanthate particles having a size of about 4 ⁇ 6-12 (mm).
  • the prepared sodium xanthate particles are sent to a disc dryer to further remove the residual solvent and part of the moisture.
  • the drying temperature is 50 to 120 ° C, and a dried granular sodium isobutyl xanthate product is obtained and recovered at the same time. Solvent.
  • Example 4 The system of Example 1 was used to prepare sodium isobutyl xanthate
  • Hot water at 70 to 80 ° C. was passed into the reactor jacket, and the vacuum was dried under the conditions of -0.04 to -0.05 MPa for 2 h to obtain a powdery sodium isobutyl xanthate product, and the solvent was recovered at the same time.
  • Example 5 The system of Example 1 was used to prepare sodium ethyl xanthate
  • Hot water at 70 to 90 ° C. was passed through the reactor jacket, and the vacuum degree was -0.03 to -0.05 MPa for 1 h to obtain a powdery sodium sodium xanthate product, and the solvent was recovered at the same time.
  • the reactor discharge valve was opened, and the sodium xanthate powder obtained by the reaction was transferred to a twin-screw extruder for granulation to obtain ethyl xanthate particles having a size of about 4 ⁇ 6 to 12 (mm).
  • the obtained sodium ethyl xanthate pellets are sent to a disc dryer to further remove the residual solvent and part of the water.
  • the drying temperature is 50 to 120 ° C, and a dried granular sodium ethyl xanthate product is obtained. Recover the solvent.
  • Example 6 The system of Example 1 was used to prepare sodium n-butyl xanthate
  • the vacuum pump and the condenser control the evaporation rate of the solvent in the reaction by adjusting the degree of vacuum, and then the reaction temperature in the reactor is maintained at 25-30 ° C, and the reaction is held for 2.5 hours. At this time, the materials in the reactor are in the form of mud. .
  • Hot water at 50 to 80 ° C. was passed through the reactor jacket and dried under the conditions of a vacuum of -0.05 to -0.06 MPa for 2.5 h to obtain a powdery sodium n-butyl xanthate product, and the solvent was recovered at the same time.
  • Example 7 The mixed sodium xanthate was prepared using the device in Example 1.
  • the vacuum pump and condenser in the solvent recovery system control the evaporation rate of the solvent in the reaction by adjusting the degree of vacuum, and then the reaction temperature in the reactor is maintained at 25-30 ° C, and the reaction is maintained for 2.5 hours.
  • the material is in the form of mud.
  • Hot water at 50 to 80 ° C was passed through the reactor jacket, and the vacuum was dried for 1 h under the conditions of -0.04 to -0.05 MPa to obtain a powdery mixed sodium xanthate product, and the solvent was recovered at the same time.
  • the reactor discharge valve was opened, and the sodium xanthate powder obtained by the reaction was transferred to a twin-screw extruder for granulation to obtain mixed sodium xanthate particles having a size of about 4 ⁇ 6 to 12 (mm).
  • the prepared mixed sodium xanthate particles are sent to a disc dryer to further remove the residual solvent and part of the moisture.
  • the drying temperature is 50 to 120 ° C, and a dry granular mixed sodium xanthate product is obtained, and the solvent is recovered at the same time. .
  • Example 8 The mixed sodium xanthate was prepared using the device in Example 1.
  • the condenser by adjusting the degree of vacuum, the evaporation rate of the solvent in the reaction is controlled, and then the reaction temperature in the reactor is maintained at 25 to 30 ° C, and the reaction is maintained for 2.5 hours. At this time, the materials in the reactor are in the form of mud.
  • Hot water at 50 to 80 ° C was passed through the reactor jacket, and the vacuum was dried for 1 h under the conditions of -0.04 to -0.05 MPa to obtain a powdery mixed sodium xanthate product, and the solvent was recovered at the same time.
  • the reactor discharge valve was opened, and the sodium xanthate powder obtained by the reaction was transferred to a twin-screw extruder for granulation to obtain mixed sodium xanthate particles having a size of about 4 ⁇ 6 to 12 (mm).
  • the prepared mixed sodium xanthate particles are sent to a disc dryer to further remove the residual solvent and part of the moisture.
  • the drying temperature is 50 to 120 ° C, and a dry granular mixed sodium xanthate product is obtained, and the solvent is recovered at the same time. .
  • Analysis shows that the average product content is 90.77%, the free base content is 0.16%, the moisture content is 3.78%, and the yield of the product based on sodium hydroxide is 92.79%.
  • the sodium xanthate prepared in the examples of the present invention has high purity, low free base content, low moisture content, and high product yield.

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Abstract

公开了一种淤浆法制备黄原酸盐的方法及系统，所述方法通过在淤浆反应器中加入二氯甲烷和二硫化碳混合物作反应溶剂，然后加入醇和苛性碱与二硫化碳反应，反应在低于1个大气压的条件下进行，溶剂蒸发移走反应放出的热量；反应完毕后继续减压蒸馏，脱除溶剂和水，得到黄原酸盐；将黄原酸盐转入造粒设备中造粒，然后进入干燥设备中干燥，得到产品。所述方法在一套由反应设备、溶剂回收设备、造粒设备和干燥设备组成的系统中进行，其中反应系统的主体设备是淤浆反应器。该方法具有效率高、能耗低、安全性好、环境友好、操作方便等优点，减少了反应过程所需的冷却水，易于实现工业化。

Description

淤浆法制备黄原酸盐的方法及系统 技术领域
本发明涉及化工选矿药剂制备方法技术领域，具体来说，涉及一种淤浆法制备黄原酸盐的方法及系统。
背景技术
黄原酸盐，也称黄药或二硫代碳酸盐，其结构式为：
Figure PCTCN2018119611-appb-000001
式中，R为不同碳链的烃基等，M通常为Na或K。黄原酸盐于1815年由Zeise首次合成，直到1925年Keller发现黄原酸盐可以用作有色金属硫化矿浮选捕收剂，黄原酸盐才被广泛地应用于金属硫化矿山以及回收金属硫化矿物，极大地推动了矿物浮选工业的发展。时至今日，黄原酸盐仍是最通用、最重要的硫化矿捕收剂。
目前工业生产黄原酸盐主要采用混捏机法，该方法是将醇和二硫化碳加入混捏机中，然后分批加入粉状苛性碱混捏合成黄原酸盐。混捏机法生产黄原酸盐存在以下问题：对碱的粒度要求较细，粉碱作业能耗高；而且合成黄原酸盐反应放热剧烈，需采用大功率冷冻机来严格控制反应温度，否则不仅会严重影响产品质量，还可能导致危险；混捏机法难以做到封闭生产，生产过程存在少量二硫化碳等挥发损失，而且生产过程中温度的不易控制致使反应不完全，副反应较多，产品纯度低。混捏机法生产的黄原酸盐产品中含水，杂质含量较高，尤其是未反应的苛性碱，导致产品保质期较短(田喜双,王永信.黄药生产方 法探讨.有色金属(选矿部分)1991(03):30～31；熊薪.黄原酸盐合成工艺的生产实践.铜业工程,2003(2):29～31)。也有文献报道采用湿碱法制备黄原酸盐，该法是在制醇钠时，加入少量水润湿烧碱，避免烧碱结块，使反应完全，制得的醇钠再与二硫化碳作用生成液体黄原酸盐(即黄原酸盐水溶液)。液体黄原酸盐产品具有生产成本低、使用时不需要溶解、操作容易、产品中游离碱量可控等优点，该工艺主要适用于小型土法生产。但由于液体黄原酸盐不稳定，不易储存，极大地限制了对其的应用(杨晓玲，张红亮.液体异丙基黄原酸钠的合成.应用化工,2010,39(6):895-897)。
有文献报道采用溶剂法合成黄原酸盐，溶剂法合成的黄原酸盐产品具有纯度和收率高的优点，但通常所需要的溶剂量大、操作工艺复杂、能耗高、生产成本较高(施先义，覃雪媚，邓钟燕.丁基钠黄药合成工艺的改进[J].化工技术与开发，2006，35(4)：47-48；胡正吉，汪世跃，王庆久，曲志强.溶剂法生产异丁基钾黄药[J].有色矿冶，1999(4)：16-18；Konrad Baessler，Georg Polz.Process for the manufacture of alkali xanthates[P].AU1713170A，1970-7-3；田喜双，王永信.黄药生产方法探讨[J].有色金属(选矿部分)1991(03)：30-31；A.M.Ahmed,K.Ibrahim,O.R.Anna,P.F.Jr John.Synthesis,characterization and luminescent properties of dinuclear Gold(I)xanthate complexes:X-ray structure of[Au 2(n-Buxanthate) 2][J].Inorg Chem 2004,43:3833-3839；黄军.一种丁基黄原酸钠的合成工艺[P].CN102050769A，2011-05-11；马鑫，钟宏，王帅，胡元，肖静晶.溶剂法合成异丁基黄原酸钠[J].江西理工大学学报,2012,3(5)：1～5；钟宏，刘广义，马鑫，王帅，曹占芳.一种黄原酸盐的合成方法[P].CN102690218A,2012-09-26；刘广义,黄耀国.黄原酸盐的制备方法[P].CN 105384669 A.2016-03-09)。
现有的溶剂法制备黄原酸盐工艺，是将苛性碱、二硫化碳和醇在有机溶剂介质中反应生成黄原酸盐，反应完成后，将反应得到的浆料转入干燥装置(如耙式干燥机等)脱除溶剂得到黄原酸盐产品。用醇、二硫化碳和苛性碱反应合成黄原酸盐时，反应本身是放热过程，反应速率较快，反应放热量大，尽管有机溶剂的存在减缓了反应的剧烈程度，避免了局部温度过高而加剧副反应，但反应过程仍需大量的冷却水来移走反应放出的热量，控制反应温度。反应完成后，又需加热至一定温度，蒸馏脱除溶剂，整个工艺过程复杂，能源利用率低，能耗高。
发明内容
针对相关技术中的上述技术问题，本发明提供了一种淤浆法制备黄原酸盐的方法及系统，所述方法不仅能够减少二硫化碳的挥发损失，且制备过程温度可控，所得产物的纯度高；制备的黄原酸盐稳定、易储存；生产过程所需溶剂量少，操作简单；反应过程减少冷却水的使用，能耗低。
为实现上述技术目的，本发明的技术方案是这样实现的：
一方面，本发明提供一种淤浆法制备黄原酸盐的方法，包括如下步骤：
1)将二氯甲烷和二硫化碳加入淤浆反应器内搅拌混合，再加入醇和碱，搅拌反应；
2)待反应体系温度开始上升时，开启真空泵并调节体系压力以控制反应体系的温度，回收溶剂；
3)待溶剂基本回收完成后，向淤浆反应器的加热夹套中通入热水或蒸汽加热促进溶剂脱除，制得粉末状黄原酸盐。
进一步地，所述粉末状黄原酸盐转入造粒设备进行造粒；造粒后所得颗粒 进行干燥脱水，即得颗粒状黄原酸盐。
进一步地，所述步骤1)中还需加入2-叔丁氧基乙醇。
进一步地，所述2-叔丁氧基乙醇的添加量为醇重量的5％～10％。所述2-叔丁氧基乙醇的加入使得粉末产品具有一定的黏性，利于后续造粒。
进一步地，所述醇、苛性碱、二硫化碳的摩尔比为1:1～1.05:1～3，所述二氯甲烷的体积为醇体积的0.5～5倍。
进一步地，所述步骤2)中体系压力控制在-0.01～-0.08MPa；所述体系内的温度维持在10～80℃。
进一步地，所述醇包括C 2～C 12脂肪醇、杂醇油、C 2～C 10烃氧基醚醇或其组合。
进一步地，所述C 2～C 12脂肪醇选自乙醇、正丙醇、异丙醇、正丁醇、异丁醇、戊醇、异戊醇、新戊醇、正己醇、异己醇、甲基异丁基甲醇、正辛醇、异辛醇、十二醇中的一种或几种。
进一步地，所述C 2～C 10烃氧基醚醇选自2-甲氧基乙醇、2-丙氧基乙醇、2-丁氧基乙醇、2-叔丁氧基乙醇、2-己氧基乙醇、2-甲氧基丙醇、2-乙氧基丙醇、2-丁氧基丙醇中的一种或几种。
进一步地，所述反应持续0.5～6小时。
进一步地，所述碱为苛性碱。所述苛性碱为氢氧化钠或氢氧化钾，包括粉末状或颗粒状或片状。
本发明黄原酸盐合成的反应温度为0～70℃，反应时间为0.5～6小时，可通过调节溶剂蒸馏的压强，控制溶剂蒸发速率，从而调节反应器内的温度。
另一方面，本发明提供一种实现上述淤浆法制备黄原酸盐方法的系统，包括相互连通的反应装置、溶剂回收装置、造粒设备和干燥设备；
所述反应装置包括淤浆反应器、原料进料口、粉末出料口、出气口和搅拌器；所述原料进料口、粉末出料口和出气口设置在所述淤浆反应器上；所述搅拌器安装在淤浆反应器内；
所述溶剂回收装置包括依次连通的除尘器、冷凝器、真空泵和若干活性炭吸附柱；
所述除尘器与出气口连接；
所述冷凝器和若干活性炭吸附柱均与溶剂储罐连接；
若干所述活性炭吸附柱通过管道相互连接；
所述造粒设备包括造粒设备本体、粉末进料口和颗粒出料口；
所述粉末进料口和颗粒出料口分设在造粒设备本体两端；
所述粉末进料口与粉末出料口相接；
所述干燥设备包括干燥设备本体、干燥夹套、颗粒进料口、排气口和产物出料口；
所述排气口与除尘器连接。
优选地，所述搅拌器包括螺带搅拌器或螺旋搅拌器。
进一步地，所述原料进料口包括碱进料口、醇进料口、二氯甲烷进料口和二硫化碳进料口；所述碱进料口与碱储罐连接；所述醇进料口与醇计量罐连接；所述二氯甲烷进料口与二氯甲烷计量罐连接；所述二硫化碳进料口与二硫化碳计量罐连接。
进一步地，所述淤浆反应器外套设有加热夹套；所述加热夹套与加热设备连接。
进一步地，若干所述活性炭吸附柱均可直接与连通大气的放气阀连通，也可通过进气阀与真空泵直接连通。若干所述活性炭吸附柱通过管道使头部、尾 部分别相连，通过阀门切换，使之并联或串联；优选地，所述活性炭吸附柱为三个，两个活性炭吸附柱通过调节阀门实现串联用于吸附，另一吸附柱与之前两个活性炭吸附柱并联用于脱附或备用。优选地，所述活性炭吸附柱包括活性炭吸附柱I、活性炭吸附柱II、活性炭吸附柱III，通过两个活性炭吸附柱串联配合使用吸附溶剂后排入大气，另一个活性炭吸附柱与它们并联做后续备用或脱附。
进一步地，所述造粒设备为螺旋挤压机或对辊压团机。进一步优选地，螺杆挤压机为单螺杆挤压机或双螺杆挤压机。进一步优选地，所述造粒装置为双螺杆挤压机。
进一步地，所述干燥夹套包括干燥夹套本体、进汽管和冷凝水排出口；所述进汽管和冷凝水排出口分设在干燥夹套本体两侧。
进一步地，所述的干燥设备为多层圆盘干燥器、回转圆筒干燥器或带式干燥机。进一步优选地，所述干燥设备为多层圆盘干燥器。
进一步地，所述溶剂储罐包括放水阀和溶剂阀。
本发明的方法在所述系统的主体反应装置——淤浆反应器内完成反应、溶剂脱除和干燥脱水的过程，操作简单，具有混合速度快、效率高、出料快的特点，能够满足真空上料、无粉尘的需求。
本发明的方法在反应过程中通过真空泵将淤浆反应器内的溶剂蒸发，进而带走黄原酸盐制备放出的大部分热量，可减少反应过程中所需的冷却水，也降低了反应温度，加快了投料速度，缩短生产周期；通过真空泵可维持反应在低于1个大气压的情况下进行，回收溶剂同时降低反应热量；通过调节真空泵的压力实现调节溶剂蒸发速度，进而控制反应体系的温度；
本发明的方法中脱除的所有的溶剂进入溶剂回收系统后，经过除尘、冷凝 后直接回收，气体经过吸附后无污染排放；回收的溶剂进入溶剂储罐后，液体水与溶剂分层且浮于溶剂上层，可起到水封作用，当水的量累积至一定量后可通过放水阀排出。
本发明制备的黄原酸盐产品纯度和收率高，杂质少，而且制备过程操作简便，成本低，环境友好，易于实现工业化生产。
本发明的有益效果：
本发明提供一种淤浆法制备黄原酸盐的方法及系统，具体优势如下：
(1)本发明的方法制备黄原酸盐时，反应体系呈淤浆状，体系均一，反应体系的传质、传热相对均匀，反应物接触充分，利于反应进行。
(2)本发明以二氯甲烷和二硫化碳混合物为反应溶剂，反应在低于1个大气压的条件下进行，利用溶剂的汽化移走反应热，控制反应温度。由于溶剂汽化可以更加高效地带走反应热，可明显减少溶剂的用量，溶剂的最小用量仅为原料醇体积的1.0倍，降低溶剂蒸发所需能耗，克服了溶剂法需要大量溶剂的缺点。
(3)二氯甲烷沸点为39.8℃，二硫化碳沸点为46.5℃，沸点较低，且二氯甲烷沸点低于二硫化碳沸点，更易于挥发，移走热量，易于实现溶剂的循环利用。且二氯甲烷具有阻燃的功效，反应物二硫化碳的闭口闪点为-30℃，当添加二氯甲烷后，闭口闪点明显提高(如图2所示)，例如二氯甲烷体积分数为50％时，闭口闪点提高为31.2±1℃，这说明采用二氯甲烷作为反应溶剂，可有效提高工艺的安全性。
(4)本发明制备过程中，采用的淤浆反应器，集反应、溶剂脱除及干燥脱水功能于一体，操作简单，而且淤浆反应器具有混合速度快、效率高、出料快，能满足真空上料、无粉尘的优点。
(5)本发明的系统集成了反应设备、溶剂回收设备、造粒设备干燥设备、物料干燥设备，各组件连接简单有效，易于实现生产线的自动化控制，能源利用效率高，能耗低。
(6)本发明的原料转化率、产品的收率和纯度高，能耗低、整个生产过程均在密闭体系中操作，无废气排放，环境友好，易于实现工业化。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本发明优选实施例的系统结构示意图；
标记说明：
1—反应装置：1-1—淤浆反应器；1-2—碱储罐；1-3—醇计量罐；1-4—二氯甲烷计量罐；1-5—二硫化碳计量罐；1-6—粉末出料口
2—溶剂回收装置：2-1—除尘器；2-2—冷凝器；2-3—真空泵；2-4—活性炭吸附柱I；2-5—活性炭吸附柱II；2-6—活性炭吸附柱III；2-7—溶剂储罐；
3—造粒设备：3-1—粉末进料口；3-2—颗粒出料口；
4—干燥设备：4-1—颗粒进料口；4-2—排气口；4-3—进汽管；4-4—产品出料口；4-5—冷凝水排出口；
图2是二氯甲烷与二硫化碳混合液的闭口闪点测试结果。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清 楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员所获得的所有其他实施例，都属于本发明保护的范围。
除非另有定义，下文中所使用的所有专业术语与本领域技术人员通常理解的含义相同。本文中所使用的专业术语只是为了描述具体实施例的目的，并不是旨在限制本发明的保护范围。
除有特别说明，本发明中用到的各种试剂、原料均为可以从市场上购买的商品或者可以通过公知的方法制得的产品。
实施例1
如图1所示，本发明提供一种实现淤浆法制备黄原酸盐方法的系统，包括相互连通的反应装置1、溶剂回收装置2、造粒设备3和干燥设备4；
所述反应装置1包括淤浆反应器1-1、原料进料口、粉末出料口1-6、出气口和搅拌器；所述原料进料口、粉末出料口1-6和出气口设置在所述淤浆反应器1-1上；所述搅拌器安装在淤浆反应器1-1内；优选地，所述搅拌器包括螺带搅拌器或螺旋搅拌器；所述螺带搅拌器为单螺带搅拌器或双螺带搅拌器；更进一步优选为双螺带搅拌器，利于淤浆法制备的泥团状产品的搅拌和后续溶剂的脱除；优选地，所述原料进料口包括碱进料口、醇进料口、二氯甲烷进料口和二硫化碳进料口；所述碱进料口与碱储罐1-2连接；所述醇进料口与醇计量罐1-3连接；所述二氯甲烷进料口与二氯甲烷计量罐1-4连接；所述二硫化碳进料口与二硫化碳计量罐1-5连接；优选地，所述淤浆反应器1-1外套设有加热夹套；所述加热夹套与加热设备连接；通过加热夹套的作用，利于后续对淤浆反应器1-1内残余的水或溶剂进行脱除；优选地，所述淤浆反应器1-1内还设置有温度检测装置和压力检测装置；所述温度检测装置和压力检测装置均 与控制器连接；所述控制器与真空泵2-3连接；通过温度检测装置和压力检测装置检测淤浆反应器1-1内的实施温度和压力，进而控制真空泵2-3的工作参数；
所述溶剂回收装置2包括依次连通的除尘器2-1、冷凝器2-2、真空泵2-3和若干活性炭吸附柱；
所述除尘器2-1与出气口连接；将淤浆反应器1-1内的溶剂以气体的形式裹带粉尘进入除尘器2-1，通过在除尘器2-1内去除粉尘后进入后续的装置；
所述冷凝器2-1和若干活性炭吸附柱均与溶剂储罐2-7连接；
若干所述活性炭吸附柱通过管道相互连接；若干所述活性炭吸附柱通过管道使头部、尾部分别相连，通过阀门切换，使之并联或串联；优选地，所述活性炭吸附柱为三个，两个活性炭吸附柱通过调节阀门实现串联用于吸附，另一吸附柱与之前两个活性炭吸附柱并联用于脱附或备用。各吸附柱均可直接与连通大气的放气阀连通，也可通过进气阀与真空泵2-3直接连通；如本实施例中，活性炭吸附柱包括活性炭吸附柱I 2-4、活性炭吸附柱II 2-5、活性炭吸附柱III2-6，通过两个活性炭吸附柱串联配合使用吸附溶剂后排入大气，另一个活性炭吸附柱与它们并联做后续备用或脱附；
所述造粒设备3包括造粒设备本体、粉末进料口3-1和颗粒出料口3-2；
所述粉末进料口3-1和颗粒出料口3-2分设在造粒设备本体两端；优选地，所述造粒设备为螺旋挤压机或对辊压团机，其中螺杆挤压机为单螺杆挤压机或双螺杆挤压机；进一步优选的造粒装置为双螺杆挤压机；通过将粉末黄原酸盐制成颗粒状黄原酸盐，利于后续成品；
所述粉末进料口3-1与粉末出料口1-6相接；
所述干燥设备4包括干燥设备本体、干燥夹套、颗粒进料口4-1、排气口 4-2和产物出料口4-4；优选地，所述干燥夹套包括干燥夹套本体、进汽管4-3和冷凝水排出口4-5；所述进汽管4-3和冷凝水排出口4-5分设在干燥夹套本体两侧；所述排气口4-2与除尘器2-1连接。保证排出的气体无污染。优选地，所述的干燥设备为多层圆盘干燥器、回转圆筒干燥器、带式干燥机，进一步优选地，所述干燥设备为多层圆盘干燥器。
实施例2运用实施例1的系统对异丁基黄原酸钠进行制备
将34.0份纯度为99％的二氯甲烷和18.3份纯度为99％的二硫化碳加入淤浆反应器中，开启反应器搅拌装置，然后将6.4份粒状氢氧化钠(纯度为99％)加到反应器中，然后将11.8份纯度为99％的异丁醇滴加入反应器内，随着反应的进行，反应器内物料温度迅速上升，打开溶剂回收系统中的真空泵及冷凝器，通过调节真空度的大小，从而控制反应内溶剂的蒸发速率，进而调节反应器内反应温度维持在25～30℃，保温反应2.5h，此时反应器内物料呈泥团状。
向反应器夹套通入50～80℃的热水，真空度为-0.04～-0.05MPa的条件下干燥1h，得到粉末状异丁基黄原酸钠产品，同时回收溶剂。
打开反应器放料阀，将反应得到的黄原酸钠粉末转入双螺杆挤压机造粒，得到规格约为Φ4×6～12(mm)的黄原酸钠颗粒。
将制得的黄原酸钠颗粒送入圆盘式干燥机进一步干燥脱除残余的溶剂和部分水分，干燥温度为50～120℃，得到干燥的粒状异丁基黄原酸钠产品，同时回收溶剂。
分析表明异丁基黄原酸钠产品纯度为91.16％，游离碱含量为0.11％，水分含量为2.92％，基于异丁醇的产品收率为95.68％，产品达到有色金属行业标准干燥品。
实施例3运用实施例1的系统对异丁基黄原酸钠进行制备
将34.0份纯度为99％的二氯甲烷、18.3份纯度为99％的二硫化碳和11.8份纯度为99％的异丁醇加入淤浆反应器中，开启反应器搅拌装置，然后将6.4份片氢氧化钠(纯度为99％)分批加到反应器中，随着反应的进行，反应器内物料温度迅速上升，打开溶剂回收系统中的真空泵及冷凝器，通过调节真空度的大小，从而控制反应内溶剂的蒸发速率，进而调节反应器内反应温度维持在25～30℃，保温反应3.5h，此时反应器内物料呈泥团状。
向反应器夹套通入50～80℃的热水，真空度为-0.04～-0.05MPa的条件下干燥1h，得到粉末状异丁基黄原酸钠产品，同时回收溶剂。
打开反应器放料阀，将反应得到的黄原酸钠粉末转入双螺杆挤压机造粒，得到规格约为Φ4×6～12(mm)的黄原酸钠颗粒。
将制得的黄原酸钠颗粒送入圆盘式干燥机进一步干燥脱除残余的溶剂和部分水分，干燥温度为50～120℃，得到干燥的粒状异丁基黄原酸钠产品，同时回收溶剂。
分析表明异丁基黄原酸钠产品纯度为90.39％，游离碱含量为0.08％，水分含量为3.48％，基于异丁醇的产品收率为96.13％，产品达到有色金属行业标准干燥品。
实施例4运用实施例1的系统对异丁基黄原酸钠进行制备
将27.2份纯度为99％的二氯甲烷和24.4份纯度为99％的二硫化碳加入淤浆反应器中，开启反应器搅拌装置，然后将6.4份粒状氢氧化钠(纯度为99％)加到反应器中，然后将11.8份纯度为99％的异丁醇滴加入反应器内，随着反应的进行，反应器内物料温度迅速上升，打开溶剂回收系统中的真空泵及冷凝器，通过调节真空度的大小，从而控制反应内溶剂的蒸发速率，进而调节反应器内反应温度维持在25～30℃，保温反应2.5h，此时反应器内物料呈泥团状。
向反应器夹套通入70～80℃的热水，真空度为-0.04～-0.05MPa的条件下干燥2h，得到粉末状异丁基黄原酸钠产品，同时回收溶剂。
分析表明异丁基黄原酸钠产品纯度为87.4％，游离碱含量为0.20％，基于异丁醇的产品收率为97.35％，产品达到有色金属行业标准特级品。
实施例5运用实施例1的系统对乙基黄原酸钠进行制备
将48.2份纯度为99％的二氯甲烷和16.2份纯度为99％的二硫化碳加入淤浆反应器中，开启反应器搅拌装置，然后将5.7份粒状氢氧化钠(纯度为99％)加到反应器中，然后将6.5份纯度为99％的无水乙醇滴加入反应器内，随着反应的进行，反应器内物料温度迅速上升，打开溶剂回收系统中的真空泵及冷凝器，通过调节真空度的大小，从而控制反应内溶剂的蒸发速率，进而调节反应器内反应温度维持在25～30℃，保温反应2.5h，此时反应器内物料呈泥团状。
向反应器夹套通入70～90℃的热水，真空度为-0.03～-0.05MPa的条件下干燥1h，得到粉末状乙基黄原酸钠产品，同时回收溶剂。
打开反应器放料阀，将反应得到的黄原酸钠粉末转入双螺杆挤压机造粒，得到规格约为Φ4×6～12(mm)的乙基黄原酸钠颗粒。
将制得的乙基黄原酸钠颗粒送入圆盘式干燥机进一步干燥脱除残余的溶剂和部分水分，干燥温度为50～120℃，得到干燥的粒状乙基黄原酸钠产品，同时回收溶剂。
分析表明乙基黄原酸盐产品纯度为92.03％，游离碱含量为0.11％，水分含量为2.13％，基于乙醇的产品收率为94.89％，产品达到有色金属行业标准干燥品。
实施例6运用实施例1的系统对正丁基黄原酸钠进行制备
将41.6份纯度为99％的二氯甲烷和16.0份纯度为99％的二硫化碳加入淤 浆反应器中，开启反应器搅拌装置，然后将5.6份粒状氢氧化钠(纯度为99％)加到反应器中，反应器内物料温度为28℃，然后将10.4份纯度为99％的正丁醇滴加入反应器内，随着反应的进行，反应器内物料温度迅速上升，打开溶剂回收系统中的真空泵及冷凝器，通过调节真空度的大小，从而控制反应内溶剂的蒸发速率，进而调节反应器内反应温度维持在25～30℃，保温反应2.5h，此时反应器内物料呈泥团状。
向反应器夹套通入50～80℃的热水，真空度为-0.05～-0.06MPa的条件下干燥2.5h，得到粉末状正丁基黄原酸钠产品，同时回收溶剂。
分析表明正丁基黄原酸钠产品纯度为84.7％，游离碱含量为0.09％，基于正丁醇的产品收率为95.73％，产品达到有色金属行业标准一级品。
实施例7使用实施例1中装置制备混合黄原酸钠
将34.0份纯度为99％的二氯甲烷和18.3份纯度为99％的二硫化碳加入淤浆反应器中，开启反应器搅拌装置，然后将6.4份粒状氢氧化钠(纯度为99％)加到反应器中，然后将11.4份纯度为99％的异丁醇和0.7份纯度为99％的2-叔丁氧基乙醇滴加入反应器内，随着反应的进行，反应器内物料温度迅速上升，打开溶剂回收系统中的真空泵及冷凝器，通过调节真空度的大小，从而控制反应内溶剂的蒸发速率，进而调节反应器内反应温度维持在25～30℃，保温反应2.5h，此时反应器内物料呈泥团状。
向反应器夹套通入50～80℃的热水，真空度为-0.04～-0.05MPa的条件下干燥1h，得到粉末状混合黄原酸钠产品，同时回收溶剂。
打开反应器放料阀，将反应得到的黄原酸钠粉末转入双螺杆挤压机造粒，得到规格约为Φ4×6～12(mm)的混合黄原酸钠颗粒。
将制得的混合黄原酸钠颗粒送入圆盘式干燥机进一步干燥脱除残余的溶 剂和部分水分，干燥温度为50～120℃，得到干燥的粒状混合黄原酸钠产品，同时回收溶剂。
分析表明混合黄原酸钠产品平均含量为90.23％，游离碱含量为0.18％，水分含量为3.41％，基于氢氧化钠的产品收率为93.09％。
实施例8使用实施例1中装置制备混合黄原酸钠
将34.0份纯度为99％的二氯甲烷和18.3份纯度为99％的二硫化碳加入淤浆反应器中，开启反应器搅拌装置，然后将6.4份粒状氢氧化钠(纯度为99％)加到反应器中，然后将9.1份混合醇(含异丁醇50％、无水乙醇50％)滴加入反应器内，随着反应的进行，反应器内物料温度迅速上升，打开溶剂回收系统中的真空泵及冷凝器，通过调节真空度的大小，从而控制反应内溶剂的蒸发速率，进而调节反应器内反应温度维持在25～30℃，保温反应2.5h，此时反应器内物料呈泥团状。
向反应器夹套通入50～80℃的热水，真空度为-0.04～-0.05MPa的条件下干燥1h，得到粉末状混合黄原酸钠产品，同时回收溶剂。
打开反应器放料阀，将反应得到的黄原酸钠粉末转入双螺杆挤压机造粒，得到规格约为Φ4×6～12(mm)的混合黄原酸钠颗粒。
将制得的混合黄原酸钠颗粒送入圆盘式干燥机进一步干燥脱除残余的溶剂和部分水分，干燥温度为50～120℃，得到干燥的粒状混合黄原酸钠产品，同时回收溶剂。分析表明产品平均含量为90.77％，游离碱含量为0.16％，水分含量为3.78％，基于氢氧化钠的产品收率为92.79％。
对照实施例1采用混捏机法制备异丁基黄原酸钠
将275.8份纯度为99％的二硫化碳和255.7份纯度为99％的异丁醇加入混捏机中，开启混捏并通冷冻盐水将该混合物冷却20℃以下，然后缓慢加入138.4 份粉末状氢氧化钠(纯度为99％)，控制碱加料时的反应温度低于35℃，加完碱后，在20～35℃下混捏反应4h，反应结束，得到粉末状的异丁基黄原酸钠产物。分析表明异丁基黄原酸钠纯度为84.12％，游离碱含量为0.46％，基于异丁醇的产品收率为91.74％，产品达到有色金属行业标准中一级品。
对照实施例2采用混捏机法制备乙基黄原酸钠
将343.8份纯度为99％的二硫化碳和198.1份纯度为99％的无水乙醇加入混捏机中，开启混捏并通冷冻盐水将该混合物冷却20℃以下，然后缓慢加入172.0份粉末状氢氧化钠(纯度为99％)，控制碱加料时的反应温度低于30℃，加完碱后，在20～35℃下混捏反应4h，反应结束，得到粉末状的乙基黄原酸钠产物。分析表明乙基黄原酸钠纯度为82.44％，游离碱含量为0.41％，基于乙醇的产品收率为90.65％，产品达到有色金属行业标准中一级品。
从两个对比实施例的结果可见，本发明实施例制备的黄原酸钠的纯度高，游离碱含量低，水分含量少，产品收率高。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种淤浆法制备黄原酸盐的方法，其特征在于，包括如下步骤：
    1)将二氯甲烷和二硫化碳加入淤浆反应器内搅拌混合，再加入醇和碱，搅拌反应；
    2)待反应体系温度开始上升时，开启真空泵并调节体系压力以控制反应体系的温度，回收溶剂；
    3)待溶剂基本回收完成后，向淤浆反应器的加热夹套中通入热水或蒸汽加热促进溶剂脱除，制得粉末状黄原酸盐。
  2. 根据权利要求1所述的方法，其特征在于，所述方法还包括将粉末状黄原酸盐转入造粒设备进行造粒；造粒后所得颗粒进行干燥脱水，即得颗粒状黄原酸盐。
  3. 根据权利要求1所述的方法，其特征在于，所述步骤1)中还需加入2-叔丁氧基乙醇。
  4. 根据权利要求1所述的方法，其特征在于，所述醇、苛性碱、二硫化碳的摩尔比为1:1～1.05:1～3，所述二氯甲烷的体积为醇体积的0.5～5倍。
  5. 根据权利要求1所述的方法，其特征在于，所述步骤2)中体系压力控制在-0.01～-0.08MPa；所述体系内的温度维持在10～80℃。
  6. 根据权利要求1所述的方法，其特征在于，所述醇包括C 2～C 12脂肪醇、杂醇油、C 2～C 10烃氧基醚醇或其组合。
  7. 根据权利要求1所述的方法，其特征在于，所述C 2～C 12脂肪醇选自乙醇、正丙醇、异丙醇、正丁醇、异丁醇、戊醇、异戊醇、新戊醇、正己醇、异己醇、甲基异丁基甲醇、正辛醇、异辛醇、十二醇中的一种或几种；所述C 2～C 10 烃氧基醚醇选自2-甲氧基乙醇、2-丙氧基乙醇、2-丁氧基乙醇、2-叔丁氧基乙醇、2-己氧基乙醇、2-甲氧基丙醇、2-乙氧基丙醇、2-丁氧基丙醇中的一种或几种。
  8. 根据权利要求1所述的方法，其特征在于，所述反应持续0.5～6小时。
  9. 一种用于实现权利要求1～8任一项所述淤浆法制备黄原酸盐方法的系统，其特征在于，包括相互连通的反应装置、溶剂回收装置、造粒设备和干燥设备；
    所述反应装置包括淤浆反应器、原料进料口、粉末出料口、出气口和搅拌器；所述原料进料口、粉末出料口和出气口设置在所述淤浆反应器上；所述搅拌器安装在淤浆反应器内；
    所述溶剂回收装置包括依次连通的除尘器、冷凝器、真空泵和若干活性炭吸附柱；
    所述除尘器与出气口连接；
    所述冷凝器和若干活性炭吸附柱均与溶剂储罐连接；
    若干所述活性炭吸附柱通过管道相互连接；
    所述造粒设备包括造粒设备本体、粉末进料口和颗粒出料口；
    所述粉末进料口和颗粒出料口分设在造粒设备本体两端；
    所述粉末进料口与粉末出料口相接；
    所述干燥设备包括干燥设备本体、干燥夹套、颗粒进料口、排气口和产物出料口；
    所述排气口与除尘器连接。
  10. 根据权利要求9所述的淤浆法制备黄原酸盐的系统，其特征在于，所述原料进料口包括碱进料口、醇进料口、二氯甲烷进料口和二硫化碳进料口； 所述碱进料口与碱储罐连接；所述醇进料口与醇计量罐连接；所述二氯甲烷进料口与二氯甲烷计量罐连接；所述二硫化碳进料口与二硫化碳计量罐连接；
    所述淤浆反应器外套设有加热夹套；所述加热夹套与加热设备连接；
    若干所述活性炭吸附柱均可直接与连通大气的放气阀连通，也可通过进气阀与真空泵直接连通；
    所述干燥夹套包括干燥夹套本体、进汽管和冷凝水排出口；所述进汽管和冷凝水排出口分设在干燥夹套本体两侧。
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