CN110040781B - Method and device for producing sodium tungstate by using waste hydrogenation catalyst - Google Patents
Method and device for producing sodium tungstate by using waste hydrogenation catalyst Download PDFInfo
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- CN110040781B CN110040781B CN201910348300.1A CN201910348300A CN110040781B CN 110040781 B CN110040781 B CN 110040781B CN 201910348300 A CN201910348300 A CN 201910348300A CN 110040781 B CN110040781 B CN 110040781B
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Abstract
The invention relates to a method and a device for producing sodium tungstate by using a novel waste hydrogenation catalyst, wherein the method comprises the following steps: drying the waste hydrogenation catalyst by drying equipment to remove oil and water in the waste hydrogenation catalyst to obtain a dried material; crushing the dried material by crushing equipment to obtain a crushed material; adding the crushed material, water and the additive 1 into a high-pressure oxygen leaching device according to a certain proportion; and (3) carrying out solid-liquid separation on the reacted materials to obtain filter residues and filtrate, wherein the filter residues are used as raw materials for recovering cobalt (nickel), the solution is a sodium tungstate solution, and the obtained sodium tungstate solution is evaporated and crystallized to obtain sodium tungstate. The method for producing sodium tungstate by using the waste hydrogenation catalyst is suitable for recycling the waste hydrogenation catalyst, so that resources are recycled, the environmental pollution is reduced, valuable metals such as tungsten and nickel in the waste hydrogenation catalyst are recycled, and the method has great popularization significance.
Description
Technical Field
The invention relates to a waste hydrogenation catalyst recycling technology, in particular to a method and a device for producing sodium tungstate by using a waste hydrogenation catalyst.
Background
The catalyst is mainly applied to the chemical industry, particularly the petroleum industry and the environmental management industry, and a large amount of catalysts are used every year. After the catalyst is recycled for many times in the using process, the activity is reduced or the catalyst is permanently poisoned, so that the catalyst cannot be regenerated and used. If the waste catalyst is directly discharged, on one hand, the environment pollution is caused, and on the other hand, the valuable metal loss is caused, so that the development of the waste catalyst recycling technology is beneficial to the full utilization of resources. However, the recovery method of the spent hydrogenation catalyst in the prior art is mainly a "roast-leaching method".
The existing technology has various defects, the main process is sodium carbonate sintering-normal pressure water leaching, the mixed sodium carbonate roasting is carried out at the temperature of about 800 ℃, the roasted materials are leached by water, and the purpose of recovering tungsten is achieved.
The oxidation roasting-ammonia leaching method is to oxidize and roast the waste catalyst at about 800 deg.c, and the roasted material is ammonia leached and converted into ammonium tungstate to recover tungsten.
Disclosure of Invention
The invention aims to solve the problems of poor operation environment, long flow, large labor capacity, high roasting equipment requirement, high energy consumption and low recovery rate of the existing waste hydrogenation catalyst recovery technology, and provides a method and a device for producing sodium tungstate by using waste hydrogenation catalysts.
In order to achieve the above object, the present invention provides a method for producing sodium tungstate by using a spent hydrogenation catalyst, comprising the following steps:
preparation of a drying material: drying the waste hydrogenation catalyst, and removing oil and water in the waste hydrogenation catalyst to obtain a dried material;
preparing a crushed material: crushing the obtained dried material to obtain a crushed material;
preparing a slurry mixing liquid: mixing water, an additive and the obtained crushed materials together to obtain a slurry, wherein the additive is at least one of solid alkali and liquid alkali; wherein the solid-liquid mass ratio is 1: 3-1: 10, and the addition amount of the additive is 1.5-5 times of the theoretical value; wherein the solid-liquid mass ratio is the weight ratio of the weight of the waste hydrogenation catalyst to the weight of water;
preparation of reacted materials: feeding the obtained slurry into a high-pressure oxygen leaching device for reaction, and blowing oxygen all the time in the reaction process to obtain a reacted material;
preparation of sodium tungstate solution: carrying out solid-liquid separation on the obtained reacted materials to obtain filter residues and filtrate, wherein the filter residues can be used as a raw material for recovering cobalt (nickel), and the filtrate is sodium tungstate solution;
preparation of sodium tungstate: and (3) carrying out evaporative crystallization on the obtained sodium tungstate solution to obtain sodium tungstate.
Further, in the step of preparing the drying material, the waste hydrogenation catalyst is a waste hydrogenation catalyst, or powder or broken strips generated in the production process of the hydrogenation catalyst, floor plates or poisoned waste hydrogenation catalyst which cannot be regenerated, wherein the mass of the alumina and the silica accounts for 60-100%, the mass of the tungsten accounts for 0-30% of the oxide, and the mass of the cobalt or nickel oxide accounts for 0-10%.
Further, in the step of preparing the drying material, the drying temperature is 80-180 ℃, and the drying time is 12-48 h; oil and water in the waste catalyst are removed, and the crushing and reaction in the next procedure are facilitated.
Preferably, the drying temperature is 100-150 ℃, and the drying time is 24-36 h.
Further, in the preparation of the crushed material, the crushed material passes through a 60-mesh screen; preferably, the mixture is sieved by a 100-mesh sieve; more preferably, the mixture is sieved through a 140-mesh sieve. The catalyst is used for reducing the particle size of the waste hydrogenation catalyst, increasing the specific surface area, increasing the contact area between the catalyst and an additive, facilitating the chemical reaction and improving the recovery rate of tungsten.
Further, in the step of preparing the size mixing liquid, the solid-liquid mass ratio is 1: 4-1: 6, and the addition amount of the additive is 2-3.5 times of the theoretical value. Wherein the solid-liquid mass ratio is the weight ratio of the waste catalyst to the water, and 1:4 is 1g of the waste catalyst added with 4ml of water; the addition amount of the additive is 2-3 times of the theoretical addition amount required by tungsten reaction in the additive. It is assumed that when the additive is sodium hydroxide, the theoretical value of the additive is calculated according to the following formula: the molecular weight of the alkali is multiplied by 2/232 multiplied by the weight of the waste hydrogenation catalyst multiplied by the weight of tungsten oxide multiplied by 1-oil mass percentage-water mass percentage.
Further, in the step of preparing the reacted material, the reaction conditions are as follows: rotating speed is 200-600 r/min, temperature is 120-180 ℃, oxygen pressure is 0.5-2.0 MPa, heat preservation time is 1-4 h, oxygen is always blown in during the reaction process, oxygen partial pressure is guaranteed to be unchanged, and the heat preservation time is up to discharging;
preferably, the rotating speed is 400-500 r/min, the temperature is 140-160 ℃, the oxygen pressure is 1.3-1.8 MPa, and the heat preservation time is 2-3 h. The reaction condition of the step is that the waste hydrogenation catalyst can carry out chemical reaction with the additive under the condition, so that tungsten in the waste catalyst is converted into sodium tungstate under the condition, and further the tungsten in the waste catalyst is recycled; the strengthening of the reaction condition is beneficial to the leaching of tungsten in the waste catalyst and the improvement of the recovery rate of tungsten.
Further, in the step of preparing sodium tungstate, the conditions of evaporative crystallization are that the vacuum degree is 0.01-0.03 MPa, and the obtained sodium tungstate solution is concentrated to 30-40% of the initial volume through concentration. And reducing the volume of water through negative pressure evaporation to ensure that the sodium tungstate solution is supersaturated and separated out.
The invention also provides a device for producing sodium tungstate by using the waste hydrogenation catalyst, which is characterized by comprising dust collection equipment, drying equipment, crushing equipment, a size mixing tank, a material beating pump, high-pressure oxygen leaching equipment, a material discharging tank, a material beating pump, solid-liquid separation equipment, a concentrated tank, a material beating pump, concentration equipment, drying equipment and packaging equipment which are sequentially connected.
The invention also protects the product prepared by the method for producing sodium tungstate by using the waste hydrogenation catalyst, which comprises sodium tungstate solution or sodium tungstate.
Has the advantages that:
in the method for producing sodium tungstate by using the waste hydrogenation catalyst, tungsten in the waste hydrogenation catalyst is converted into sodium tungstate, so that tungsten resources in the waste hydrogenation catalyst are effectively utilized, the tungsten resources are effectively utilized, and the environmental pressure is relieved.
According to the method, a proper amount of additive is added for sodium treatment according to the tungsten content in the waste hydrogenation catalyst (the additive is added according to the tungsten content in the waste hydrogenation catalyst, so that on one hand, tungsten in the waste catalyst is dissolved out, and on the other hand, the cost is saved under the condition that the tungsten is dissolved out), and the additive and the waste hydrogenation catalyst are subjected to high-pressure oxygen leaching after being subjected to size mixing, so that the phenomenon that a roasting furnace is formed in the traditional pyrometallurgical process is avoided, and the production efficiency is improved.
Further, the high-pressure oxygen leaching solution is subjected to solid-liquid separation equipment to obtain a sodium tungstate solution, and finally, the tungsten recovery rate is up to about 98% through evaporation and crystallization.
In a word, the method for producing sodium tungstate by using the waste hydrogenation catalyst is suitable for recycling various waste hydrogenation catalysts, such as crushed materials and floor materials generated in the production process of the hydrogenation catalyst, poisoned waste hydrogenation catalysts which cannot be recycled, and the like.
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In order to illustrate the technical solution of the present invention more clearly, the drawings will be briefly described below, and it is apparent that the drawings in the following description relate only to some embodiments of the present invention and are not intended to limit the present invention.
Fig. 1 is a schematic diagram of a device connection provided by an embodiment of the present invention.
Detailed Description
The definitions of some of the terms used in the present invention are given below, and other non-mentioned terms have definitions and meanings known in the art:
waste hydrogenation catalyst: the waste poisoned hydrogenation catalyst can not be regenerated and used by the crushed aggregates and floor materials produced in the production process of the hydrogenation catalyst. In a preferred embodiment of the present invention, the spent hydrogenation catalyst mainly comprises: the weight ratio of the aluminum oxide to the silicon oxide is 60-100%, the weight ratio of the tungsten calculated by the oxide is 0-30%, and the weight ratio of the cobalt (nickel) calculated by the oxide is 0-10%. It should be noted that the above-mentioned contents of elements are only necessary for satisfying disclosure, and do not constitute a limitation to the scheme itself, and the method provided by the present invention is applicable to the spent hydrogenation catalysts obtained by the commercial and existing processing methods.
The source of the spent hydrogenation catalyst in the present invention is not particularly limited, and the spent hydrogenation catalyst may be obtained commercially or may be a waste material produced in the conventional hydrogenation catalyst production process. According to a preferred embodiment of the present invention, the spent hydrogenation catalyst is crushed material, flooring material, poisoned spent hydrogenation catalyst which cannot be reused, or the like, generated during the production process. It should be noted that the spent hydrogenation catalyst is crushed or ground for reuse.
The method provided by the invention has no special limitation on equipment for drying the waste hydrogenation catalyst, and adopts universal drying equipment, wherein the drying temperature is preferably 80-180 ℃, the drying time is 12-48 h, the drying temperature is preferably 100-150 ℃, the drying time is 24-36 h, the drying temperature is more preferably 120-130 ℃, and the drying time is 28-32 h.
In the method provided by the invention, equipment for crushing the waste hydrogenation catalyst is not particularly limited, and common crushing equipment can be adopted, wherein in the step two, the crushed material preferably passes through a 60-mesh screen, the crushed material preferably passes through a 100-mesh screen, and the crushed material more preferably passes through a 140-mesh screen.
In the method provided by the invention, the additive can be liquid caustic soda, can also be flake caustic soda, and can also be a mixture of the liquid caustic soda and the flake caustic soda. Wherein the addition proportion of the additive 1 is 1.5-5 times of the theoretical value, and the solid-liquid mass ratio is 1: 3-1: 10; preferably, the additive is liquid alkali (low in price), and the addition proportion is 2-3.5 times of the theoretical value, wherein when the alkali is sodium hydroxide, the theoretical value of the alkali is calculated according to the following formula: the molecular weight of alkali is multiplied by 2/232 multiplied by the weight of the waste hydrogenation catalyst multiplied by (1-oil content mass percentage-water content mass percentage) multiplied by the tungsten oxide mass percentage, and the solid-liquid mass ratio is 1: 4-1: 6. (oil moisture means oil and moisture contained in the spent hydrogenation catalyst; oil and moisture analysis method-method for analyzing oil and moisture content in the spent hydrogenation catalyst by differential gravimetry; and tungsten oxide mass percent means tungsten oxide mass percent in the spent hydrogenation catalyst.)
In the method provided by the invention, the reaction conditions in the high-pressure oxygen leaching process are that the rotating speed is as follows: 200-600 r/min, 120-180 ℃, 0.5-2.0 MPa of oxygen pressure and 1-4 h of heat preservation time, wherein oxygen is always blown in during the reaction process to ensure that the oxygen partial pressure is not changed, and the heat preservation time is up to discharging. The reaction conditions of the preferred hyperbaric oxygen leaching process are the rotation speed: 400-500 r/min, 140-160 ℃, 1.3-1.8 MPa of oxygen pressure and 2-3 h of heat preservation time, wherein oxygen is always blown in during the reaction process, the oxygen partial pressure is ensured to be unchanged, and the heat preservation time is up to the discharge.
In the method of the present invention, the solid-liquid separation apparatus used is not particularly limited as long as it can separate a solid phase from a liquid phase. In order to improve the recovery rate, the filter residue is washed in the filtering process, the obtained water phase is combined into the filtrate, and the obtained residue phase is dried by blowing. The obtained filter residue is rich in cobalt (nickel) and can be used as a raw material for producing a cobalt product (nickel product).
In the method of the present invention, the conditions for evaporative crystallization of the sodium tungstate solution are not particularly limited. For example, the feed liquid may be concentrated to 30 to 40% of the initial volume of the feed liquid by concentration at a vacuum of 0.01 to 0.03MPa, preferably to 33 to 38%, for example 35%, for example 36% of the initial volume by concentration at a vacuum of 0.02 MPa. The impurity content is mainly controlled by controlling the residual volume of the concentrated feed liquid in the concentration process, and the more the residual mother liquid is, the lower the impurity content in the crystallized product is.
The method for producing sodium tungstate by using the waste hydrogenation catalyst is mainly characterized in that the steps are orderly matched, so that tungsten in the waste hydrogenation catalyst is separated from other impurities and converted into sodium tungstate, and a wet smelting method is mainly used, so that the traditional pyrometallurgical method is abandoned. Other methods such as drying, crushing, filtering, evaporating and crystallizing the raw materials can be the same as those in the prior art, and those skilled in the art can know that the methods are not described herein.
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.
The test methods used below included:
the tungsten content detection method comprises the following steps: WO in tungsten-X-ray fluorescence measurement of tungsten waste in waste hydrogenation catalyst 3 Co, Ni, Fe, Cu, Cr, etc.; a method for measuring the content of tungsten trioxide in a solution by a tungsten-tungsten concentration meter in a sodium tungstate solution; colorimetric method for determining total tungsten content in cobalt (nickel) slag by tungsten-potassium thiocyanate.
The waste hydrogenation catalyst used in the embodiment is a conventional commercial waste hydrogenation catalyst, and is mainly derived from waste hydrogenation catalysts such as crushed aggregates and floor materials which are generated in the production process, and poisoned waste hydrogenation catalysts which cannot be regenerated, wherein the mass ratio of alumina and silica is 60-100%, the mass ratio of tungsten is 0-30% by weight calculated on oxide, and the mass ratio of cobalt (nickel) is 0-10% by weight calculated on oxide.
Example 1
The method for producing sodium tungstate by using the waste hydrogenation catalyst comprises the following steps:
preparation of a drying material: taking 250g of a waste hydrogenation catalyst (30% by mass of tungsten oxide, 5% by mass of cobalt oxide, 40% by mass of aluminum oxide, 25% by mass of silicon oxide, 3% by mass of oil and 5% by mass of water), and drying the waste hydrogenation catalyst at the drying temperature of 80 ℃ for 48 hours to obtain a dried material;
preparing a crushed material: crushing the dried material by crushing equipment, and sieving by a 200-mesh sieve to obtain a crushed material;
preparing a slurry mixing liquid: adding flake caustic soda into the crushed material, wherein the adding proportion of the flake caustic soda is 2 times of the theoretical value, adding water for size mixing, and obtaining size mixing liquid with a solid-to-liquid ratio of 1: 5; (wherein when the alkali is sodium hydroxide, the theoretical value of the alkali is calculated according to the following formula, the molecular weight of the alkali is multiplied by 2/232 multiplied by the weight of the waste hydrogenation catalyst multiplied by (1-oil part mass percent-water mass percent) multiplied by the tungsten oxide mass percent)
Preparation of reacted materials: feeding the slurry into a high-pressure oxygen leaching device, wherein the reaction conditions are that the rotating speed is as follows: 440r/min, 160 ℃, 1.4MPa of oxygen pressure and 3 hours of heat preservation time, wherein oxygen is blown in all the time in the reaction process to ensure that the oxygen partial pressure is unchanged, and the material is discharged after the heat preservation time, thus obtaining the reacted material.
Preparation of sodium tungstate solution: and D, filtering the feed liquid obtained in the step four, and washing the filter residue for three times by using heated non-saline water to obtain cobalt-containing filter residue and a sodium tungstate solution. The sodium tungstate solution in the residual trace slag can be washed clean by washing, and the recovery rate is improved.
Preparation of sodium tungstate: and (3) evaporating and crystallizing the sodium tungstate solution to obtain sodium tungstate, and concentrating the feed liquid to 35% of the volume of the initial feed liquid by concentration under the vacuum degree of 0.03MPa, wherein the recovery rate of tungsten is 98.5%.
The embodiment adopts a device for producing sodium tungstate by using a waste hydrogenation catalyst, which comprises a dust collecting device, a drying device, a crushing device, a size mixing tank, a material beating pump, a high-pressure oxygen leaching device, a discharge tank, a solid-liquid separation device, a concentrated tank, a concentration device, a drying device and a packaging device as shown in figure 1, wherein the drying device and the crushing device are connected with the dust collecting device, the drying device is connected with the crushing device, the crushing device is connected with the size mixing tank, the size mixing tank is connected with the high-pressure oxygen leaching device through the material beating pump, the high-pressure oxygen leaching device is connected with the discharge tank, the discharge tank is connected with the solid-liquid separation device through the material beating pump, the solid-liquid separation device is connected with the concentrated tank, the concentrated tank is connected with the concentration device through the material beating pump, and the concentration device is connected with the drying device, the drying equipment is connected with the packaging equipment.
The method comprises the steps of drying the waste hydrogenation catalyst in drying equipment, enabling the obtained dried material to enter crushing equipment for crushing, obtaining a crushed material through a sieve, sending the crushed material into a size mixing tank, adding an additive and water for size mixing to obtain a size mixing liquid, sending the size mixing liquid into high-pressure oxygen soaking equipment through a material mixing pump, discharging the material to a discharging tank after reaction, sending the material into solid-liquid separation equipment through the material mixing pump to separate filter residue and filtrate, enabling the filter residue to serve as a raw material for recovering cobalt, enabling the filtrate to enter a concentrated tank, sending the obtained sodium tungstate solution into concentration equipment through the material mixing pump for evaporation and crystallization to obtain sodium tungstate, placing the sodium tungstate in the drying equipment for drying to obtain a finished sodium tungstate product, and packaging through packaging equipment for storage and transportation.
The device adopts universal unit equipment, such as drying equipment and crushing equipment, combines the process of the invention, recovers and treats the waste hydrogenation catalyst, abandons the traditional pyrometallurgical process, has high tungsten recovery rate, and has great popularization significance.
Example 2
The method for producing sodium tungstate by using the waste hydrogenation catalyst comprises the following steps:
preparation of a drying material: taking 300g of a waste hydrogenation catalyst (10% by mass of tungsten oxide, 10% by mass of nickel oxide, 50% by mass of aluminum oxide, 30% by mass of silicon oxide, 2% by mass of oil and 1% by mass of water), and drying the waste hydrogenation catalyst at the drying temperature of 120 ℃ for 30h to obtain a dried material;
preparing a crushed material: crushing the dried material by crushing equipment, and screening the crushed material by a 60-mesh screen to obtain a crushed material;
preparing a slurry mixing liquid: adding liquid caustic soda into the crushed material in a proportion of 1.5 times of the theoretical value of the addition of the liquid caustic soda, adding water for size mixing, wherein the solid-to-liquid ratio is 1:4, and obtaining size mixing liquid;
preparation of reacted materials: feeding the slurry into a high-pressure oxygen leaching device, wherein the reaction conditions are that the rotating speed is as follows: 200r/min, 120 ℃, 2.0MPa of oxygen pressure and 4 hours of heat preservation time, blowing oxygen in the reaction process all the time to ensure that the oxygen partial pressure is unchanged, and discharging after the heat preservation time to obtain the reacted material.
Preparation of sodium tungstate solution: and D, filtering the feed liquid obtained in the step four, and washing the filter residue for three times by using heated non-saline water to obtain nickel-containing filter residue and a sodium tungstate solution. The sodium tungstate solution in the residual trace slag can be washed clean by washing, and the recovery rate is improved.
Preparation of sodium tungstate: and (3) evaporating and crystallizing the sodium tungstate solution to obtain sodium tungstate, and concentrating the feed liquid to 37% of the volume of the initial feed liquid by concentration under the vacuum degree of 0.02MPa, wherein the recovery rate of tungsten is 98.7%.
The example used an apparatus for producing sodium tungstate from a spent hydrogenation catalyst similar to that of example 1.
Example 3
The method for producing sodium tungstate by using the waste hydrogenation catalyst comprises the following steps:
preparation of a drying material: taking 280g of waste hydrogenation catalyst (the mass content of tungsten oxide is 3%, the mass content of cobalt oxide is 2%, the mass content of aluminum oxide is 60%, the mass content of silicon oxide is 35%, the mass content of oil is 1%, and the mass content of water is 6%), drying the waste hydrogenation catalyst at the drying temperature of 180 ℃ for 36h to obtain a dried material;
preparing a crushed material: crushing the dried material by crushing equipment, and sieving by a 100-mesh sieve to obtain a crushed material;
preparing a slurry mixing liquid: adding flake caustic soda into the crushed material, wherein the addition proportion of the flake caustic soda is 5 times of the theoretical value, adding water for size mixing, and obtaining size mixing liquid with the solid-liquid ratio of 1: 6;
preparation of reacted materials: feeding the slurry into a high-pressure oxygen leaching device, wherein the reaction conditions are that the rotating speed is as follows: 600r/min, 140 ℃, 1.3MPa of oxygen pressure and 3 hours of heat preservation time, blowing oxygen in the reaction process all the time to ensure that the oxygen partial pressure is unchanged, and discharging after the heat preservation time to obtain the reacted material.
Preparation of sodium tungstate solution: and D, filtering the feed liquid obtained in the step four, and washing the filter residue three times by using heated non-saline water to obtain cobalt-containing filter residue and a sodium tungstate solution. The sodium tungstate solution in the residual trace slag can be washed clean by washing, and the recovery rate is improved.
Preparation of sodium tungstate: and (3) evaporating and crystallizing the sodium tungstate solution to obtain sodium tungstate, and concentrating the feed liquid to 38% of the volume of the initial feed liquid by concentration under the vacuum degree of 0.03MPa, wherein the recovery rate of tungsten is 97.2%.
The example used an apparatus for producing sodium tungstate from a spent hydrogenation catalyst similar to that of example 1.
Example 4
The method for producing sodium tungstate by using the waste hydrogenation catalyst comprises the following steps:
preparation of a drying material: taking 350g of waste hydrogenation catalyst (the mass content of tungsten oxide is 15%, the mass content of cobalt oxide is 6%, the mass content of aluminum oxide is 55%, the mass content of silicon oxide is 24%, the mass content of oil is 1%, and the mass content of water is 1%), drying the waste hydrogenation catalyst at the drying temperature of 100 ℃ for 12h to obtain a dried material;
preparing a crushed material: crushing the dried material by crushing equipment, and sieving by a 60-mesh sieve to obtain a crushed material;
preparing a slurry mixing liquid: adding flake caustic soda into the crushed material, wherein the addition proportion of the flake caustic soda is 3.5 times of the theoretical value, adding water for size mixing, and obtaining size mixing liquid with the solid-liquid ratio of 1: 4;
preparation of reacted materials: feeding the slurry into a high-pressure oxygen leaching device, wherein the reaction conditions are that the rotating speed is as follows: 400r/min, 155 ℃, 1.5MPa of oxygen pressure and 3 hours of heat preservation time, wherein oxygen is blown in all the time in the reaction process to ensure that the oxygen partial pressure is unchanged, and the reaction material is obtained after the heat preservation time is up to discharge.
Preparation of sodium tungstate solution: and D, filtering the feed liquid obtained in the step four, and washing the filter residue for three times by using heated non-saline water to obtain cobalt-containing filter residue and a sodium tungstate solution. The sodium tungstate solution in the residual trace slag can be washed clean by washing, and the recovery rate is improved.
Preparation of sodium tungstate: and (3) evaporating and crystallizing the sodium tungstate solution to obtain sodium tungstate, and concentrating the feed liquid to 39% of the volume of the initial feed liquid by concentration under the vacuum degree of 0.02MPa, wherein the recovery rate of tungsten is 98.8%.
The example used an apparatus for producing sodium tungstate from a spent hydrogenation catalyst similar to that of example 1.
Example 5
The method for producing sodium tungstate by using the waste hydrogenation catalyst comprises the following steps:
preparation of a drying material: taking 250g of a waste hydrogenation catalyst (the mass content of tungsten oxide is 20%, the mass content of nickel oxide is 10%, the mass content of aluminum oxide is 30%, the mass content of silicon oxide is 40%, the mass content of oil is 2%, and the mass content of water is 4%), drying the waste hydrogenation catalyst at the drying temperature of 130 ℃ for 24h to obtain a dried material;
preparing a crushed material: crushing the dried material by crushing equipment, and sieving by a 140-mesh sieve to obtain a crushed material;
preparing a slurry mixing liquid: adding flake caustic soda into the crushed material in a proportion of 2.8 times of the theoretical value of the flake caustic soda, adding water for size mixing, wherein the solid-to-liquid ratio is 1:5, and obtaining size mixing liquid;
preparation of reacted materials: feeding the slurry into a high-pressure oxygen leaching device, wherein the reaction conditions are that the rotating speed is as follows: 500r/min, 160 ℃, 0.5MPa of oxygen pressure and 1h of heat preservation time, wherein oxygen is blown in all the time in the reaction process to ensure that the oxygen partial pressure is unchanged, and the reaction material is obtained after the heat preservation time is up to discharge.
Preparation of sodium tungstate solution: and D, filtering the feed liquid obtained in the step four, and washing the filter residue for three times by using heated non-saline water to obtain nickel-containing filter residue and a sodium tungstate solution. The sodium tungstate solution in the residual trace slag can be washed clean by washing, and the recovery rate is improved.
Preparation of sodium tungstate: and (3) evaporating and crystallizing the sodium tungstate solution to obtain sodium tungstate, and concentrating the feed liquid to 35% of the volume of the initial feed liquid by concentration under the vacuum degree of 0.02MPa, wherein the recovery rate of tungsten is 98.9%.
The example used an apparatus for producing sodium tungstate from a spent hydrogenation catalyst similar to that of example 1.
Comparative example 1
Other conditions were not changed, and only oxygen was introduced into example 1 instead of oxygen, and the final tungsten recovery rate was only 58.6%.
Comparative example 2
Other conditions are not changed, the addition amount of the liquid caustic soda in the example 2 is changed from 2.5 times of the theoretical value to 1.1 times of the theoretical value, and the final recovery rate of the tungsten is only 78.5 percent.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (11)
1. A method for producing sodium tungstate by using a waste hydrogenation catalyst is characterized by comprising the following steps:
preparation of a drying material: drying the waste hydrogenation catalyst, and removing oil and water in the waste hydrogenation catalyst to obtain a dried material;
preparing a crushed material: crushing the obtained dried material to obtain a crushed material;
preparing a slurry mixing liquid: mixing water, an additive and the obtained crushed materials together to obtain a slurry, wherein the additive is at least one of solid alkali and liquid alkali; wherein the solid-liquid mass ratio is 1:4, and the addition of the additive is 1.5 times of the theoretical value; the solid-liquid mass ratio is the weight ratio of the weight of the waste hydrogenation catalyst to the weight of water;
preparation of reacted materials: feeding the obtained slurry into a high-pressure oxygen leaching device for reaction, and blowing oxygen all the time in the reaction process to obtain a reacted material;
preparation of sodium tungstate solution: carrying out solid-liquid separation on the obtained reacted materials to obtain filter residues and filtrate, wherein the filter residues can be used as raw materials for recovering cobalt or nickel, and the filtrate is sodium tungstate solution;
preparation of sodium tungstate: and (3) carrying out evaporative crystallization on the obtained sodium tungstate solution to obtain sodium tungstate.
2. The method for producing sodium tungstate using the waste hydrogenation catalyst as claimed in claim 1, wherein in the step of preparing the drying material, the waste hydrogenation catalyst is a waste hydrogenation catalyst, or powder or strips produced in the production process of the hydrogenation catalyst, a floor slab material or a poisoned waste hydrogenation catalyst which cannot be regenerated, wherein the mass ratio of the alumina to the silica is 60-100%, the mass ratio of the tungsten is 0-30% by mass based on the oxide, and the mass ratio of the cobalt or nickel oxide is 0-10% by mass.
3. The method for producing sodium tungstate using the spent hydrogenation catalyst as set forth in claim 1, wherein: in the preparation step of the drying material, the drying temperature is 80-180 ℃, and the drying time is 12-48 h.
4. The method for producing sodium tungstate using the spent hydrogenation catalyst according to claim 3, wherein: the drying temperature is 100-150 ℃, and the drying time is 24-36 h.
5. The method for producing sodium tungstate using the spent hydrogenation catalyst as set forth in claim 1, wherein: in the preparation of the crushed material, the crushed material passes through a 60-mesh screen.
6. The method for producing sodium tungstate using the spent hydrogenation catalyst according to claim 1, wherein: in the preparation of the crushed material, the crushed material passes through a 100-mesh screen.
7. The method for producing sodium tungstate using the spent hydrogenation catalyst as set forth in claim 1, wherein: in the preparation of the crushed material, the crushed material passes through a 140-mesh screen.
8. The method for producing sodium tungstate using the spent hydrogenation catalyst according to claim 1, wherein: in the preparation step of the reacted materials, the reaction conditions are as follows: the rotating speed is 200-600 r/min, the temperature is 120-180 ℃, the oxygen pressure is 0.5-2.0 MPa, the heat preservation time is 1-4 h, oxygen is blown in all the time in the reaction process, the oxygen partial pressure is guaranteed to be unchanged, and the heat preservation time is up to discharging.
9. The method for producing sodium tungstate using the spent hydrogenation catalyst as set forth in claim 8, wherein: the rotating speed is 400-500 r/min, the temperature is 140-160 ℃, the oxygen pressure is 1.3-1.8 MPa, and the heat preservation time is 2-3 h.
10. The method for producing sodium tungstate using the spent hydrogenation catalyst as set forth in claim 1, wherein: in the preparation step of the sodium tungstate, the evaporative crystallization is performed under the condition that the vacuum degree is 0.01-0.03 MPa, and the obtained sodium tungstate solution is concentrated to 30-40% of the initial volume through concentration.
11. An apparatus for producing sodium tungstate by using the spent hydrogenation catalyst according to any one of claims 1 to 10, which comprises a dust collecting device, a drying device, a crushing device, a size mixing tank, a material beating pump, a high-pressure oxygen leaching device, a discharging tank, a material beating pump, a solid-liquid separation device, a concentrate tank, a material beating pump, a concentrating device, a drying device and a packaging device which are connected in sequence.
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