CN111957325A - Regeneration device and regeneration process of furfuryl alcohol waste catalyst - Google Patents
Regeneration device and regeneration process of furfuryl alcohol waste catalyst Download PDFInfo
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- CN111957325A CN111957325A CN202010924651.5A CN202010924651A CN111957325A CN 111957325 A CN111957325 A CN 111957325A CN 202010924651 A CN202010924651 A CN 202010924651A CN 111957325 A CN111957325 A CN 111957325A
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- furfuryl alcohol
- catalyst
- regeneration
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- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 title claims abstract description 396
- 239000003054 catalyst Substances 0.000 title claims abstract description 208
- 230000008929 regeneration Effects 0.000 title claims abstract description 106
- 238000011069 regeneration method Methods 0.000 title claims abstract description 106
- 239000002699 waste material Substances 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000008569 process Effects 0.000 title claims abstract description 28
- 238000004140 cleaning Methods 0.000 claims abstract description 123
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 52
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 52
- 239000007788 liquid Substances 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 230000001172 regenerating effect Effects 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 26
- 238000012216 screening Methods 0.000 claims abstract description 22
- 238000012856 packing Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 96
- 239000000463 material Substances 0.000 claims description 89
- 239000007787 solid Substances 0.000 claims description 84
- 238000004090 dissolution Methods 0.000 claims description 77
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 76
- 238000003756 stirring Methods 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 229910001868 water Inorganic materials 0.000 claims description 51
- 239000002245 particle Substances 0.000 claims description 48
- 239000002244 precipitate Substances 0.000 claims description 45
- 238000005406 washing Methods 0.000 claims description 45
- -1 copper hydroxide-silicon dioxide Chemical compound 0.000 claims description 37
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 32
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 32
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 32
- 238000010992 reflux Methods 0.000 claims description 29
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 24
- 239000007791 liquid phase Substances 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 24
- 239000010865 sewage Substances 0.000 claims description 21
- 239000011343 solid material Substances 0.000 claims description 18
- 238000007873 sieving Methods 0.000 claims description 17
- 239000006228 supernatant Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000012071 phase Substances 0.000 claims description 15
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000292 calcium oxide Substances 0.000 claims description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 11
- 238000003825 pressing Methods 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 6
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 230000005484 gravity Effects 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 239000007790 solid phase Substances 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 4
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000004891 communication Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
- B01J38/66—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts using ammonia or derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/68—Liquid treating or treating in liquid phase, e.g. dissolved or suspended including substantial dissolution or chemical precipitation of a catalyst component in the ultimate reconstitution of the catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/72—Regeneration or reactivation of catalysts, in general including segregation of diverse particles
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to a regeneration device and a regeneration process of a furfuryl alcohol waste catalyst; the device comprises at least one furfuryl alcohol waste catalyst bin; at least one furfuryl alcohol waste catalyst dissolving and regenerating unit for ensuring the solubility of the copper sulfate solution and realizing the regeneration of the copper sulfate solution; at least one cleaning unit for cleaning the solid-liquid mixture produced by the regeneration unit; at least one crushing unit for drying and crushing the catalyst; the furfuryl alcohol waste catalyst bin is connected with a screening machine through a furfuryl alcohol waste catalyst dissolving and regenerating unit, a cleaning unit and a crushing unit, a screen underflow channel of the screening machine is communicated with the packing machine, and a screen overflow channel of the screening machine is communicated with the crushing unit; the method has the advantages of simple structure, reasonable flow design, simple and controllable operation, capability of realizing the regeneration of the furfuryl alcohol waste catalyst, reduction of the production cost of the furfuryl alcohol and environmental friendliness.
Description
Technical Field
The invention belongs to the technical field of furfuryl alcohol waste catalyst regeneration, and particularly relates to a regeneration device and a regeneration process of a furfuryl alcohol waste catalyst.
Background
Furfuryl alcohol is an important chemical raw material; at present, two methods of liquid phase hydrogenation and gas phase hydrogenation are industrially used for preparing furfuryl alcohol by catalytic hydrogenation of furfural, and the production device and the catalyst used in the gas phase method are introduced abroad and have high price; at present, most of the furfuryl alcohol manufacturers at home still adopt a liquid-phase medium-pressure or high-pressure hydrogenation method for production. The liquid-phase medium-pressure or high-pressure hydrogenation method mainly comprises the following steps: the furfural and hydrogen react in a high-pressure liquid phase under the action of a solid catalyst, after the reaction is finished, the mixture is put into a pool for natural or mechanical sedimentation, supernatant liquid is pumped to a rectifying tower for refining, and solid waste generated by the catalyst used in the production process of the lower-layer solid is sold for disposal. The catalyst used in furfuryl alcohol production is often deactivated after being used once, so that the catalyst is used along with waste, cannot be directly recycled, and is large in use amount. The catalyst is used in a large amount in the furfuryl alcohol production process, and can be used only once, so that the production cost is greatly increased, and the used waste catalyst needs to be temporarily stored in a field in the process of treatment for sale, thereby seriously polluting the field environment. At present, the residual organic matters in the waste catalyst are evaporated in a high-efficiency mode to obtain a high recovery rate, and the regeneration of the waste catalyst part is treated by a common vacuum drying oven, so that the treatment capacity is small due to the limitation of equipment, the recovery rate is low, the operation time is long, and the method can not be continuously operated and can not be applied to industrial production. Therefore, in order to reduce the production cost of furfuryl alcohol and the pollution to the environment and realize the high-efficiency recycling of the furfuryl alcohol catalyst, a technology for regenerating the waste furfuryl alcohol catalyst is an urgent problem to be solved.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a regeneration device and a regeneration process of a furfuryl alcohol waste catalyst, which have the advantages of simple structure, reasonable flow design, simplicity and controllability in operation, capability of realizing regeneration of the furfuryl alcohol waste catalyst, reduction of the production cost of furfuryl alcohol and environmental friendliness.
The purpose of the invention is realized as follows: an apparatus for regenerating a furfuryl alcohol spent catalyst, the apparatus comprising: at least one furfuryl alcohol spent catalyst bin; at least one furfuryl alcohol waste catalyst dissolving and regenerating unit for ensuring the solubility of the copper sulfate solution and realizing the regeneration of the copper sulfate solution; at least one cleaning unit for cleaning the solid-liquid mixture produced by the regeneration unit; at least one crushing unit for drying and crushing the catalyst; the furfuryl alcohol waste catalyst bin is connected with a screening machine through a furfuryl alcohol waste catalyst dissolving and regenerating unit, a cleaning unit and a crushing unit, a screen underflow channel of the screening machine is communicated with the packing machine, and a screen overflow channel of the screening machine is communicated with the crushing unit.
Preferably, the furfuryl alcohol waste catalyst dissolving and regenerating unit comprises a metering belt connected with a discharging port of a furfuryl alcohol waste catalyst bin, and a discharging end of the metering belt is communicated with the regenerating tank sequentially through the dissolving reaction tank and the clarifying tank.
Preferably, the top of the dissolution reaction tank is provided with a furfuryl alcohol waste catalyst inlet, a dilute sulfuric acid inlet and a reflux port, the outside of the dissolution reaction tank is provided with a heat exchange jacket, and the inside of the dissolution reaction tank is provided with a stirring device with a first stirring motor.
Preferably, the upper part of the clarifying tank is provided with a supernatant outlet connected with the regeneration tank, the lower part of the clarifying tank is of a cone-bucket-shaped structure, and the bottom of the clarifying tank is connected with a reflux port of the dissolution reaction tank through a reflux pump.
Preferably, a stirring device with a second stirring motor is arranged inside the regeneration tank, and a copper sulfate solution inlet, ammonia water and silica sol adding port connected with a supernatant outlet are formed in the top of the regeneration tank; the bottom of the regeneration tank is provided with a solid-liquid mixed material outlet connected with the cleaning unit.
Preferably, the cleaning unit comprises a baffle plate with an angle of 45-60 degrees arranged inside the material cleaning bin; the baffle divides the interior of the material cleaning bin into a filtering cavity and a cleaning cavity; a track is arranged between the baffle at the top of the filter cavity and the inner wall of the material cleaning bin, a filter plate is arranged at the top of the track, and the bottom of the filter plate is matched with the track through a small wheel; the track extends to the upper part of the outer wall of the baffle on one side of the cleaning cavity; a hydraulic cylinder is fixedly arranged on the outer side of the filter cavity, and the piston end of the hydraulic cylinder penetrates through the material cleaning bin and is hinged with one side of the filter plate; a first sewage draining port is formed in the lower part of the material cleaning bin corresponding to the filter cavity; an overflow plate is arranged between the baffle in the cleaning cavity and the inner wall of the material cleaning bin, and a second sewage outlet is formed in the lower part of the material cleaning bin corresponding to the outer side of the overflow plate; the top of the filter plate when the hydraulic cylinder is at the initial position is provided with a distributor communicated with a solid-liquid mixed material outlet of the regeneration tank; and a spraying device connected with a washing water pipeline is arranged at the top of the cleaning cavity.
Preferably, the crushing unit comprises a filter press connected with a feeding pump, and a solid material outlet of the filter press is connected with the secondary crusher sequentially through the primary crusher and the dryer; the filter press is provided with a liquid phase discharge port.
Preferably, a gas phase outlet at the top of the dryer is connected with the tail gas treatment device through a cyclone separator, and a solid material outlet at the bottom of the cyclone separator is connected with an inlet of the secondary crusher.
Preferably, the oversize material channel of the screening machine is communicated with the feed inlet of the primary crusher through a conveying belt.
A regeneration process of a regeneration device of a furfuryl alcohol waste catalyst comprises the following steps:
step 1: preheating a dissolution reaction tank and a dryer before feeding of a system, wherein the internal temperature of the dissolution reaction tank after preheating is not less than 60 ℃, and the internal temperature of the dryer after preheating is not less than 150 ℃;
step 2: the furfuryl alcohol waste catalyst in the furfuryl alcohol waste catalyst bin enters a dissolution reaction tank through a metering belt; the furfuryl alcohol waste catalyst is the furfuryl alcohol waste catalyst after organic matters are recovered;
and step 3: adding dilute sulfuric acid into a dissolution reaction tank through a dilute sulfuric acid inlet, keeping the temperature in the dissolution reaction tank at 60-90 ℃ through a heat exchange jacket, starting a corresponding stirring device by starting a first stirring motor, and enabling the dilute sulfuric acid to react with the furfuryl alcohol waste catalyst rapidly to be dissolved to generate a copper sulfate solution containing a small amount of calcium sulfate and calcium oxide; the concentration of the dilute sulfuric acid is 50-68 percent; the molar ratio of the dilute sulfuric acid to the furfuryl alcohol spent catalyst is 2.5: 1;
and 4, step 4: the copper sulfate solution generated in the step 3 and a small amount of mixture of calcium sulfate and calcium oxide enter a clarifying tank from a dissolution reaction tank; clarifying the mixture in a clarifying tank, depositing a small amount of clarified solids at the bottom of the clarifying tank, and allowing the settled solids to enter a dissolution reaction tank through a reflux pump and a reflux port of the dissolution reaction tank for dissolution reaction again;
and 5: the mixture obtained in the step 4 is clarified in a clarifying tank and then enters a regeneration tank through a supernatant outlet, ammonia water and silica sol are added into the regeneration tank through an ammonia water and silica sol adding port, and meanwhile, a second stirring motor is started to start a corresponding stirring device, so that the ammonia water, the silica sol and a copper sulfate solution are fully reacted at normal temperature and normal pressure, and a solid-liquid mixture with the main components of copper hydroxide-silicon dioxide precipitate and ammonium sulfate, water, silicon dioxide and trace copper ammonia complex compound is generated; the volume ratio of the copper sulfate solution to the ammonia water to the silica sol is as follows: 1:1.8: 1.5;
step 6: uniformly distributing the solid-liquid mixture in the step 5 on the top of the filter plate through a distributor; the liquid phase enters the filter cavity through the filter plate and is discharged from the first drain outlet; when the solid-liquid mixture is subjected to solid-liquid separation by the filter plate, starting the hydraulic cylinder, extending out of the piston end of the hydraulic cylinder to enable the filter plate to move forwards along the rail, and when the filter plate moves onto the rail on the upper part of the outer wall of the baffle plate, allowing the copper hydroxide-silicon dioxide precipitate to enter the bottom of the cleaning cavity under the action of gravity; retracting the telescopic end of the hydraulic cylinder and enabling the telescopic end to be in an initial state, and at the moment, enabling the filter plate to be at the bottom of the distributor and repeating the work;
and 7: when the copper hydroxide-silicon dioxide precipitate is positioned at the bottom of the cleaning cavity, cleaning the copper hydroxide-silicon dioxide precipitate by using the washing water in the washing water pipeline through a spraying device to remove impurities on the surface of the copper hydroxide-silicon dioxide precipitate, and overflowing excessive washing water through an overflow plate and discharging the excessive washing water through a second sewage outlet;
and 8: the copper hydroxide-silicon dioxide precipitate after the water washing by the material cleaner and the washing water which does not overflow are pumped into a filter press by a feeding pump, and are subjected to filter pressing and drying by the filter press to prepare a catalyst filter cake; the pressure of the filter press is 0.8-1.2 MPa; the washing liquid after filter pressing of the filter press is discharged through a liquid phase discharge port;
and step 9: the catalyst filter cake in the step 8 is subjected to primary crushing by a primary crusher, the catalyst solid particles after the primary crushing are sent to a dryer for drying and activation, and the dried and activated catalyst solid particles enter a secondary crusher for secondary crushing; the temperature in the dryer is as follows: the water content of the catalyst solid after passing through the dryer is less than or equal to 2.5 percent at the temperature of 150-200 ℃; the granularity of the catalyst solid particles after the second crushing is less than or equal to 350 meshes;
step 10: feeding the re-crushed catalyst solid particles in the step 9 into a sieving machine for sieving, and feeding the sieved undersize materials into a packaging machine through an undersize material channel for packaging and then using or selling; the particle size of solid particles of the undersize product is not more than 350 meshes;
step 11: the oversize products screened in the step 10 are sent into a primary crusher through a conveying belt, and the step 8 and the step 9 are repeated;
step 12: in the step 9, in the process of drying the catalyst solid particles after the first-stage crushing in the dryer, the dried gas enters a cyclone separator, gas-solid separation is carried out through the cyclone separator, and the gas phase after the gas-solid separation is subjected to tail gas treatment through a tail gas treatment device; and (3) enabling the solid phase subjected to gas-solid separation to enter a secondary crusher through a solid material outlet at the bottom of the cyclone separator and an inlet of the secondary crusher to be crushed again together with the dried and activated catalyst solid particles in the step (8) in the secondary crusher.
The invention has the advantages of simple structure, reasonable flow design, simple and controllable operation, realization of regeneration of the furfuryl alcohol waste catalyst, reduction of the furfuryl alcohol production cost and environmental friendliness.
Drawings
FIG. 1 is a schematic structural diagram of a furfuryl alcohol spent catalyst dissolving and regenerating unit according to the present invention.
FIG. 2 is a schematic view of the structure of the cleaning unit of the present invention.
FIG. 3 is a schematic view showing the positional relationship of the baffle, filter plate and overflow plate according to the present invention.
Fig. 4 is a schematic view of the construction of the crushing unit of the present invention.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, embodiments of the present invention will now be described with reference to the accompanying drawings, in which like reference numerals refer to like parts throughout. For the sake of simplicity, only the parts relevant to the invention are schematically shown in the drawings, and they do not represent the actual structure as a product.
As shown in fig. 1, 2, 3 and 4, the present invention is a regeneration device and a regeneration process of furfuryl alcohol waste catalyst, the device comprises: at least one furfuryl alcohol spent catalyst bin 1; at least one furfuryl alcohol waste catalyst dissolving and regenerating unit for ensuring the solubility of the copper sulfate solution and realizing the regeneration of the copper sulfate solution; at least one cleaning unit for cleaning the solid-liquid mixture produced by the regeneration unit; at least one crushing unit for drying and crushing the catalyst; the furfuryl alcohol waste catalyst bin 1 is connected with the screening machine 14 through a furfuryl alcohol waste catalyst dissolving and regenerating unit, a cleaning unit and a crushing unit, a screen underflow channel of the screening machine 14 is communicated with the packing machine 38, and a screen overflow channel of the screening machine 14 is communicated with the crushing unit. The invention can make the reaction faster and more accurate and can ensure the recovery rate of the waste catalyst by arranging the furfuryl alcohol waste catalyst dissolving and regenerating unit for ensuring the solubility of the copper sulfate solution; the solid precipitate generated by the reaction can be cleaned by arranging the cleaning unit so as to achieve the purposes of removing impurities and ensuring the purity and quality of the regenerated catalyst.
Further, the furfuryl alcohol waste catalyst dissolving and regenerating unit comprises a metering belt 2 connected with a discharge port of a furfuryl alcohol waste catalyst bin 1, and a discharge end of the metering belt 2 is communicated with a regenerating tank 6 sequentially through a dissolving reaction tank 3 and a clarifying tank 4. The amount of the furfuryl alcohol waste catalyst can be accurately determined by arranging the metering belt 2, so that the addition amount of the dilute sulfuric acid is determined, and the purpose of controlling the solubility of the copper sulfate solution from the source is achieved.
Furthermore, a furfuryl alcohol waste catalyst inlet 16, a dilute sulfuric acid inlet 17 and a reflux port 18 are arranged at the top of the dissolution reaction tank 3, a heat exchange jacket 20 is arranged outside the dissolution reaction tank 3, and a stirring device with a first stirring motor 19 is arranged inside the dissolution reaction tank 3. The upper part of the clarifying tank 4 is provided with a supernatant outlet connected with the regeneration tank 6, the lower part of the clarifying tank 4 is of a cone-bucket-shaped structure, and the bottom of the clarifying tank is connected with a reflux port 18 of the dissolution reaction tank 3 through a reflux pump 5. The solution reaction tank 3 is provided with a reflux port 18, a heat exchange jacket 20 and a stirring device with a first stirring motor 19, and aims to accelerate the reaction; especially when a solid precipitate (which includes undissolved spent catalyst or other insolubles) appears in the mixture in the clarifier 4, it can be recycled into the dissolution reaction tank 3 for further reaction. The lower part of the clarifying tank 4 is of a cone hopper-shaped structure, so that solid can be conveniently deposited at the bottom, insoluble solid precipitates in the later period can be conveniently discharged, the funnel-shaped structure, the reflux pump 5 and the reflux port 18 form a reflux system, and the reflux system is matched with the heat exchange jacket 20 and a stirring device with a first stirring motor 19, so that the dilute sulfuric acid and the furfuryl alcohol waste catalyst can be ensured to quickly react, the reaction is ensured to be more complete, and the purpose of ensuring the solubility of the copper sulfate solution is achieved.
Furthermore, a stirring device with a second stirring motor 21 is arranged inside the regeneration tank 6, and a copper sulfate solution inlet 22 and an ammonia water and silica sol adding port 23 which are connected with a supernatant outlet are arranged at the top of the regeneration tank 6; the bottom of the regeneration tank 6 is provided with a solid-liquid mixed material outlet 24 connected with a cleaning unit. The regeneration tank is mainly used for regeneration reaction, the addition amount of ammonia water and silica sol in the regeneration reaction is based on the solubility of the copper sulfate solution, and the solubility of the copper sulfate solution can be ensured only if the furfuryl alcohol waste catalyst dissolving and regenerating unit ensures that the copper sulfate solution can be fully dissolved and reacted; when the solubility of the copper sulfate solution is determined, adding ammonia water and silica sol in a determined proportion to fully perform a regeneration reaction, wherein the copper hydroxide-silica precipitate generated after the regeneration reaction contains impurities, and immediately entering a cleaning unit to effectively clean the copper hydroxide-silica precipitate after the regeneration reaction so as to achieve the purpose of removing impurities in order to ensure the quality of the copper hydroxide-silica precipitate and facilitate the reuse of a catalyst; in the invention, the stirring devices in the stirring device with the first stirring motor 19 and the stirring device with the second stirring motor 21 both comprise the stirring shaft and the stirring blades sleeved on the stirring shaft, and the structures are conventional and are not repeated; take the agitating unit of taking first agitator motor 19 as an example, it sets up on the lateral wall of dissolving reaction tank 3, and it not only avoids the material to influence the problem that useless catalyst dissolves in the dissolving tank uneven distribution of vertical direction concentration, also plays the effect of once breaking and the purpose that improves dissolution efficiency to the material.
Further, the cleaning unit comprises a baffle 25 with an angle of 45-60 degrees arranged inside the material cleaning bin 7; the baffle 25 divides the interior of the material cleaning bin 7 into a filtering cavity and a cleaning cavity; a track 26 is arranged between the baffle 25 at the top of the filter cavity and the inner wall of the material cleaning bin 7, a filter plate 27 is arranged at the top of the track 26, and the bottom of the filter plate 27 is matched with the track 26 through a small wheel 28; the rail 26 extends to the upper part of the outer wall of the baffle 25 at one side of the cleaning cavity; a hydraulic cylinder 29 is fixedly arranged on the outer side of the filter cavity, and the piston end of the hydraulic cylinder 29 penetrates through the material cleaning bin 7 and is hinged with one side of the filter plate 27; a first sewage discharge port 30 is formed in the lower part of the material cleaning bin 7 corresponding to the filter cavity; an overflow plate 31 is arranged between the baffle 25 in the cleaning cavity and the inner wall of the material cleaning bin 7, and a second sewage draining outlet 32 is arranged at the lower part of the material cleaning bin 7 corresponding to the outer side of the overflow plate 31; the top of the filter plate 27 when the hydraulic cylinder 29 is at the initial position is provided with a distributor 33 communicated with the solid-liquid mixed material outlet 24 of the regeneration tank 6; the top of the washing chamber is provided with a shower 35 connected to a washing water pipe 34. The cleaning unit comprises a filter cavity and a cleaning cavity, wherein the filter cavity is mainly used for filtering and removing impurities from a liquid phase after a regeneration reaction, and the cleaning cavity is mainly used for cleaning a small amount of solid impurities in copper hydroxide-silicon dioxide precipitate; in order to ensure high efficiency and convenient operation in the cleaning process, a trolley form with a filter plate 27 is adopted in the filter cavity, the trolley runs along a track 26 and is powered by a hydraulic cylinder 29, liquid phase filtered by the filter plate 27 is discharged from a first sewage discharge port 30, and solid precipitates are conveyed to the cleaning cavity by the trolley for cleaning; in the cleaning process, a large amount of washing water is adopted to clean the solid precipitate, and the excessive washing water is discharged through the overflow plate 31 and the second sewage outlet 32; the solid precipitate after washing and a small amount of washing water are passed through a filter press 9 in a crushing unit to remove water; above-mentioned in-process filter 27 not only plays the purpose of filtering regeneration reaction liquid phase, can also play the purpose of transporting the solid deposit to reach convenient operation and carry out abundant washing with the characteristics of guaranteeing the regenerated catalyst quality to the solid deposit.
Further, the crushing unit comprises a filter press 9 connected with the feeding pump 8, and a solid material outlet of the filter press 9 is connected with a secondary crusher 13 through a primary crusher 10 and a dryer 11 in sequence; the filter press 9 is provided with a liquid phase discharge 36. In the invention, the filter press 9 is adopted to carry out preliminary drying on the catalyst, thus laying a foundation for crushing in the primary crusher 10; the dryer 11 of the present invention dries and activates the material crushed by the primary crusher 10, and particularly, dries the material crushed by the primary crusher 10, so as to achieve the purpose of rapid and sufficient drying and activation.
Further, a gas phase outlet at the top of the dryer 11 is connected with the tail gas treatment device 37 through the cyclone separator 12, and a solid material outlet at the bottom of the cyclone separator 12 is connected with an inlet of the secondary crusher 13. Through setting up cyclone 12 not only can be effectual discharge the waste heat gas can also effectively retrieve the catalyst dust granule in the waste heat gas to reach the mesh of fully retrieving the catalyst.
Preferably, the oversize passage of the sizer 14 is in communication with the feed inlet of the primary crusher 10 by a conveyor belt 15. By recycling oversize material channel materials of the sieving machine 14, the quality of the catalyst can be effectively ensured.
A regeneration process of a regeneration device of a furfuryl alcohol waste catalyst comprises the following steps:
step 1: preheating a dissolution reaction tank 3 and a dryer 11 before feeding of a system, wherein the internal temperature of the dissolution reaction tank 3 after preheating is not less than 60 ℃, and the internal temperature of the dryer after preheating is not less than 150 ℃;
step 2: the furfuryl alcohol waste catalyst in the furfuryl alcohol waste catalyst bin 1 enters a dissolution reaction tank 3 through a metering belt 2; the furfuryl alcohol waste catalyst is the furfuryl alcohol waste catalyst after organic matters are recovered;
and step 3: dilute sulfuric acid is added into the dissolution reaction tank 3 through a dilute sulfuric acid inlet 17, the temperature in the dissolution reaction tank 3 is kept at 60-90 ℃ through a heat exchange jacket 20, a corresponding stirring device is started by starting a first stirring motor 19, and the dilute sulfuric acid and the furfuryl alcohol waste catalyst are quickly reacted and dissolved to generate a copper sulfate solution containing a small amount of calcium sulfate and calcium oxide; the concentration of the dilute sulfuric acid is 50-68 percent; the molar ratio of the dilute sulfuric acid to the furfuryl alcohol spent catalyst is 2.5: 1;
and 4, step 4: the copper sulfate solution generated in the step 3 and a small amount of mixture of calcium sulfate and calcium oxide enter a clarifying tank 4 from a dissolution reaction tank 3; the mixture is clarified in a clarifying tank 4, a small amount of clarified solid is deposited at the bottom of the clarifying tank 4 and enters a dissolution reaction tank 3 through a reflux pump 5 and a reflux port 18 of the dissolution reaction tank 3 for dissolution reaction again;
and 5: the mixture obtained in the step 4 is clarified in the clarifying tank 4 and then enters the regeneration tank 6 through a supernatant outlet, ammonia water and silica sol are added into the regeneration tank 6 through an ammonia water and silica sol adding port 26, meanwhile, a second stirring motor 21 is started to start a corresponding stirring device, so that the ammonia water, the silica sol and a copper sulfate solution are fully reacted at normal temperature and normal pressure, and a solid-liquid mixture with the main components of copper hydroxide-silicon dioxide precipitate and ammonium sulfate, water, silicon dioxide and a trace amount of copper ammine complex compound is generated; the volume ratio of the copper sulfate solution to the ammonia water to the silica sol is as follows: 1:1.8: 1.5;
step 6: the solid-liquid mixture in the step 5 is uniformly distributed on the top of the filter plate 27 through a distributor 33; the liquid phase enters the filter cavity through the filter plate 27 and is discharged from the first drain outlet 30; when the solid-liquid mixture is subjected to solid-liquid separation by the filter plate 27, the hydraulic cylinder 29 is started, the piston end of the hydraulic cylinder 29 extends out to enable the filter plate 27 to move forwards along the rail 26, and when the filter plate 27 moves to the rail on the upper part of the outer wall of the baffle plate 25, the copper hydroxide-silicon dioxide precipitate enters the bottom of the cleaning cavity under the action of gravity; retracting the telescopic end of the hydraulic cylinder 29 and bringing it to the initial state, in which the filter plate 27 is at the bottom of the distributor 33 and repeating the above work;
and 7: when the copper hydroxide-silicon dioxide precipitate is positioned at the bottom of the cleaning cavity, the washing water in the washing water pipeline 34 cleans the copper hydroxide-silicon dioxide precipitate through the spraying device 35 to remove impurities on the surface of the copper hydroxide-silicon dioxide precipitate, and the excessive washing water overflows through the overflow plate 31 and is discharged through the second sewage outlet 32;
and 8: the copper hydroxide-silicon dioxide precipitate and the washing water which is not overflowed after the material cleaner filters the water and is washed are sent to a filter press 9 through a feed pump 8, and the catalyst filter cake is prepared after filter pressing and drying through the filter press 9; the pressure of the filter press 9 is 0.8-1.2 MPa; the washing liquid after filter pressing of the filter press 9 is discharged through a liquid phase discharge port 36;
and step 9: the catalyst filter cake in the step 8 is subjected to primary crushing by a primary crusher 10, the catalyst solid particles after the primary crushing are sent to a dryer 11 for drying and activation, and the dried and activated catalyst solid particles enter a secondary crusher 13 for secondary crushing; the temperature in the dryer 11 is: the water content of the catalyst solid after passing through the dryer 11 is less than or equal to 2.5 percent at the temperature of 150-200 ℃; the granularity of the catalyst solid particles after the second crushing is less than or equal to 350 meshes;
step 10: the catalyst solid particles crushed again in the step 9 enter a sieving machine 14 for sieving, and the sieved undersize materials enter a packing machine 38 through an undersize material channel to be packed for use or sold; the particle size of solid particles of the undersize product is not more than 350 meshes;
step 11: the oversize material screened in the step 10 is sent into a primary crusher 10 through a conveying belt 15, and the step 8 and the step 9 are repeated;
step 12: in the process of drying the catalyst solid particles after the first-stage crushing in the step 9 in the dryer 11, the dried gas enters the cyclone separator 12, the gas-solid separation is performed through the cyclone separator 12, and the gas phase after the gas-solid separation is subjected to tail gas treatment through the tail gas treatment device 37; the solid phase after the gas-solid separation enters the secondary crusher 13 through a solid material outlet at the bottom of the cyclone separator 12 and an inlet of the secondary crusher 13 to be crushed again together with the catalyst solid particles dried and activated in the step 8 in the secondary crusher 13.
The regeneration process of the regeneration device of the waste furfuryl alcohol catalyst not only breaks through the technical problem that the traditional process cannot realize industrialized regeneration of the furfuryl alcohol catalyst, but also improves the regeneration activity of the furfuryl alcohol catalyst; through the regeneration process, the treatment cost can be greatly reduced, and the cost can be saved by about 16 ten thousand yuan per year. In addition, the regeneration process realizes the recycling of the catalyst, saves the use cost of the catalyst, and can save the cost of 175 ten thousand yuan per year on the purchase cost of the catalyst. In conclusion, the furfuryl alcohol waste catalyst regeneration process can avoid the treatment cost of the waste catalyst, ensure that the regenerated catalyst has extremely high activity, greatly reduce the storage pressure of the waste catalyst and has great significance to environmental protection; the method has the characteristics of continuous production, simple structure, reasonable flow design, thorough recovery and effective improvement of product yield, not only can effectively reduce the pressure of environmental protection, but also lays a foundation for the industrial production of the regeneration process of the furfuryl alcohol waste catalyst.
The present invention will now be further illustrated with reference to examples in order to explain the present invention in more detail. The specific embodiment is as follows:
example 1
An apparatus for regenerating a furfuryl alcohol spent catalyst, the apparatus comprising: at least one furfuryl alcohol spent catalyst bin 1; at least one furfuryl alcohol waste catalyst dissolving and regenerating unit for ensuring the solubility of the copper sulfate solution and realizing the regeneration of the copper sulfate solution; at least one cleaning unit for cleaning the solid-liquid mixture produced by the regeneration unit; at least one crushing unit for drying and crushing the catalyst; the furfuryl alcohol waste catalyst bin 1 is connected with the screening machine 14 through a furfuryl alcohol waste catalyst dissolving and regenerating unit, a cleaning unit and a crushing unit, a screen underflow channel of the screening machine 14 is communicated with the packing machine 38, and a screen overflow channel of the screening machine 14 is communicated with the crushing unit. The furfuryl alcohol waste catalyst dissolving and regenerating unit comprises a metering belt 2 connected with a discharge port of a furfuryl alcohol waste catalyst bin 1, and a discharge end of the metering belt 2 is communicated with a regenerating tank 6 sequentially through a dissolving reaction tank 3 and a clarifying tank 4. The top of the dissolution reaction tank 3 is provided with a furfuryl alcohol waste catalyst inlet 16, a dilute sulfuric acid inlet 17 and a reflux port 18, the outside of the dissolution reaction tank 3 is provided with a heat exchange jacket 20, and the inside of the dissolution reaction tank 3 is provided with a stirring device with a first stirring motor 19. A stirring device with a second stirring motor 21 is arranged inside the regeneration tank 6, and a copper sulfate solution inlet 22 and an ammonia water and silica sol adding port 23 which are connected with a supernatant outlet are arranged at the top of the regeneration tank 6; the bottom of the regeneration tank 6 is provided with a solid-liquid mixed material outlet 24 connected with a cleaning unit. The cleaning unit comprises a baffle 25 with an angle of 45-60 degrees arranged inside the material cleaning bin 7; the baffle 25 divides the interior of the material cleaning bin 7 into a filtering cavity and a cleaning cavity; a track 26 is arranged between the baffle 25 at the top of the filter cavity and the inner wall of the material cleaning bin 7, a filter plate 27 is arranged at the top of the track 26, and the bottom of the filter plate 27 is matched with the track 26 through a small wheel 28; the rail 26 extends to the upper part of the outer wall of the baffle 25 at one side of the cleaning cavity; a hydraulic cylinder 29 is fixedly arranged on the outer side of the filter cavity, and the piston end of the hydraulic cylinder 29 penetrates through the material cleaning bin 7 and is hinged with one side of the filter plate 27; a first sewage discharge port 30 is formed in the lower part of the material cleaning bin 7 corresponding to the filter cavity; an overflow plate 31 is arranged between the baffle 25 in the cleaning cavity and the inner wall of the material cleaning bin 7, and a second sewage draining outlet 32 is arranged at the lower part of the material cleaning bin 7 corresponding to the outer side of the overflow plate 31; the top of the filter plate 27 when the hydraulic cylinder 29 is at the initial position is provided with a distributor 33 communicated with the solid-liquid mixed material outlet 24 of the regeneration tank 6; the top of the washing chamber is provided with a shower 35 connected to a washing water pipe 34. The crushing unit comprises a filter press 9 connected with a feed pump 8, and a solid material outlet of the filter press 9 is connected with a secondary crusher 13 through a primary crusher 10 and a dryer 11 in sequence; the filter press 9 is provided with a liquid phase discharge 36. The gas phase outlet at the top of the dryer 11 is connected with the tail gas treatment device 37 through the cyclone separator 12, and the solid material outlet at the bottom of the cyclone separator 12 is connected with the inlet of the secondary crusher 13. The oversize material channel of the sieving machine 14 is communicated with the feeding hole of the primary crusher 10 through a conveying belt 15.
A regeneration process of a regeneration device of a furfuryl alcohol waste catalyst comprises the following steps:
step 1: preheating a dissolution reaction tank 3 and a dryer 11 before feeding of a system, wherein the internal temperature of the dissolution reaction tank 3 after preheating is not less than 60 ℃, and the internal temperature of the dryer after preheating is not less than 150 ℃;
step 2: the furfuryl alcohol waste catalyst in the furfuryl alcohol waste catalyst bin 1 enters a dissolution reaction tank 3 through a metering belt 2; the furfuryl alcohol waste catalyst is the furfuryl alcohol waste catalyst after organic matters are recovered;
and step 3: dilute sulfuric acid is added into the dissolution reaction tank 3 through a dilute sulfuric acid inlet 17, the temperature in the dissolution reaction tank 3 is kept at 60 ℃ through a heat exchange jacket 20, a corresponding stirring device is started by starting a first stirring motor 19, and the dilute sulfuric acid and the furfuryl alcohol waste catalyst are quickly reacted and dissolved to generate a copper sulfate solution containing a small amount of calcium sulfate and calcium oxide; the concentration of the dilute sulfuric acid is 50%; the molar ratio of the dilute sulfuric acid to the furfuryl alcohol spent catalyst is 2.5: 1;
and 4, step 4: the copper sulfate solution generated in the step 3 and a small amount of mixture of calcium sulfate and calcium oxide enter a clarifying tank 4 from a dissolution reaction tank 3; the mixture is clarified in a clarifying tank 4, a small amount of clarified solid is deposited at the bottom of the clarifying tank 4 and enters a dissolution reaction tank 3 through a reflux pump 5 and a reflux port 18 of the dissolution reaction tank 3 for dissolution reaction again;
and 5: the mixture obtained in the step 4 is clarified in the clarifying tank 4 and then enters the regeneration tank 6 through a supernatant outlet, ammonia water and silica sol are added into the regeneration tank 6 through an ammonia water and silica sol adding port 26, meanwhile, a second stirring motor 21 is started to start a corresponding stirring device, so that the ammonia water, the silica sol and a copper sulfate solution are fully reacted at normal temperature and normal pressure, and a solid-liquid mixture with the main components of copper hydroxide-silicon dioxide precipitate and ammonium sulfate, water, silicon dioxide and a trace amount of copper ammine complex compound is generated; the volume ratio of the copper sulfate solution to the ammonia water to the silica sol is as follows: 1:1.8: 1.5;
step 6: the solid-liquid mixture in the step 5 is uniformly distributed on the top of the filter plate 27 through a distributor 33; the liquid phase enters the filter cavity through the filter plate 27 and is discharged from the first drain outlet 30; when the solid-liquid mixture is subjected to solid-liquid separation by the filter plate 27, the hydraulic cylinder 29 is started, the piston end of the hydraulic cylinder 29 extends out to enable the filter plate 27 to move forwards along the rail 26, and when the filter plate 27 moves to the rail on the upper part of the outer wall of the baffle plate 25, the copper hydroxide-silicon dioxide precipitate enters the bottom of the cleaning cavity under the action of gravity; retracting the telescopic end of the hydraulic cylinder 29 and bringing it to the initial state, in which the filter plate 27 is at the bottom of the distributor 33 and repeating the above work;
and 7: when the copper hydroxide-silicon dioxide precipitate is positioned at the bottom of the cleaning cavity, the washing water in the washing water pipeline 34 cleans the copper hydroxide-silicon dioxide precipitate through the spraying device 35 to remove impurities on the surface of the copper hydroxide-silicon dioxide precipitate, and the excessive washing water overflows through the overflow plate 31 and is discharged through the second sewage outlet 32;
and 8: the copper hydroxide-silicon dioxide precipitate and the washing water which is not overflowed after the material cleaner filters the water and is washed are sent to a filter press 9 through a feed pump 8, and the catalyst filter cake is prepared after filter pressing and drying through the filter press 9; the pressure of the filter press 9 is 0.8 MPa; the washing liquid after filter pressing of the filter press 9 is discharged through a liquid phase discharge port 36;
and step 9: the catalyst filter cake in the step 8 is subjected to primary crushing by a primary crusher 10, the catalyst solid particles after the primary crushing are sent to a dryer 11 for drying and activation, and the dried and activated catalyst solid particles enter a secondary crusher 13 for secondary crushing; the temperature in the dryer 11 is: the moisture content of the catalyst solid after passing through the dryer 11 is less than or equal to 2.5 percent at 150 ℃; the granularity of the catalyst solid particles after the second crushing is less than or equal to 350 meshes;
step 10: the catalyst solid particles crushed again in the step 9 enter a sieving machine 14 for sieving, and the sieved undersize materials enter a packing machine 38 through an undersize material channel to be packed for use or sold; the particle size of solid particles of the undersize product is not more than 350 meshes;
step 11: the oversize material screened in the step 10 is sent into a primary crusher 10 through a conveying belt 15, and the step 8 and the step 9 are repeated;
step 12: in the process of drying the catalyst solid particles after the first-stage crushing in the step 9 in the dryer 11, the dried gas enters the cyclone separator 12, the gas-solid separation is performed through the cyclone separator 12, and the gas phase after the gas-solid separation is subjected to tail gas treatment through the tail gas treatment device 37; the solid phase after the gas-solid separation enters the secondary crusher 13 through a solid material outlet at the bottom of the cyclone separator 12 and an inlet of the secondary crusher 13 to be crushed again together with the catalyst solid particles dried and activated in the step 8 in the secondary crusher 13.
Example 2
An apparatus for regenerating a furfuryl alcohol spent catalyst, the apparatus comprising: at least one furfuryl alcohol spent catalyst bin 1; at least one furfuryl alcohol waste catalyst dissolving and regenerating unit for ensuring the solubility of the copper sulfate solution and realizing the regeneration of the copper sulfate solution; at least one cleaning unit for cleaning the solid-liquid mixture produced by the regeneration unit; at least one crushing unit for drying and crushing the catalyst; the furfuryl alcohol waste catalyst bin 1 is connected with the screening machine 14 through a furfuryl alcohol waste catalyst dissolving and regenerating unit, a cleaning unit and a crushing unit, a screen underflow channel of the screening machine 14 is communicated with the packing machine 38, and a screen overflow channel of the screening machine 14 is communicated with the crushing unit. The furfuryl alcohol waste catalyst dissolving and regenerating unit comprises a metering belt 2 connected with a discharge port of a furfuryl alcohol waste catalyst bin 1, and a discharge end of the metering belt 2 is communicated with a regenerating tank 6 sequentially through a dissolving reaction tank 3 and a clarifying tank 4. The top of the dissolution reaction tank 3 is provided with a furfuryl alcohol waste catalyst inlet 16, a dilute sulfuric acid inlet 17 and a reflux port 18, the outside of the dissolution reaction tank 3 is provided with a heat exchange jacket 20, and the inside of the dissolution reaction tank 3 is provided with a stirring device with a first stirring motor 19. A stirring device with a second stirring motor 21 is arranged inside the regeneration tank 6, and a copper sulfate solution inlet 22 and an ammonia water and silica sol adding port 23 which are connected with a supernatant outlet are arranged at the top of the regeneration tank 6; the bottom of the regeneration tank 6 is provided with a solid-liquid mixed material outlet 24 connected with a cleaning unit. The cleaning unit comprises a baffle 25 with an angle of 45-60 degrees arranged inside the material cleaning bin 7; the baffle 25 divides the interior of the material cleaning bin 7 into a filtering cavity and a cleaning cavity; a track 26 is arranged between the baffle 25 at the top of the filter cavity and the inner wall of the material cleaning bin 7, a filter plate 27 is arranged at the top of the track 26, and the bottom of the filter plate 27 is matched with the track 26 through a small wheel 28; the rail 26 extends to the upper part of the outer wall of the baffle 25 at one side of the cleaning cavity; a hydraulic cylinder 29 is fixedly arranged on the outer side of the filter cavity, and the piston end of the hydraulic cylinder 29 penetrates through the material cleaning bin 7 and is hinged with one side of the filter plate 27; a first sewage discharge port 30 is formed in the lower part of the material cleaning bin 7 corresponding to the filter cavity; an overflow plate 31 is arranged between the baffle 25 in the cleaning cavity and the inner wall of the material cleaning bin 7, and a second sewage draining outlet 32 is arranged at the lower part of the material cleaning bin 7 corresponding to the outer side of the overflow plate 31; the top of the filter plate 27 when the hydraulic cylinder 29 is at the initial position is provided with a distributor 33 communicated with the solid-liquid mixed material outlet 24 of the regeneration tank 6; the top of the washing chamber is provided with a shower 35 connected to a washing water pipe 34. The crushing unit comprises a filter press 9 connected with a feed pump 8, and a solid material outlet of the filter press 9 is connected with a secondary crusher 13 through a primary crusher 10 and a dryer 11 in sequence; the filter press 9 is provided with a liquid phase discharge 36. The gas phase outlet at the top of the dryer 11 is connected with the tail gas treatment device 37 through the cyclone separator 12, and the solid material outlet at the bottom of the cyclone separator 12 is connected with the inlet of the secondary crusher 13. The oversize material channel of the sieving machine 14 is communicated with the feeding hole of the primary crusher 10 through a conveying belt 15.
A regeneration process of a regeneration device of a furfuryl alcohol waste catalyst comprises the following steps:
step 1: preheating a dissolution reaction tank 3 and a dryer 11 before feeding of a system, wherein the internal temperature of the dissolution reaction tank 3 after preheating is not less than 60 ℃, and the internal temperature of the dryer after preheating is not less than 150 ℃;
step 2: the furfuryl alcohol waste catalyst in the furfuryl alcohol waste catalyst bin 1 enters a dissolution reaction tank 3 through a metering belt 2; the furfuryl alcohol waste catalyst is the furfuryl alcohol waste catalyst after organic matters are recovered;
and step 3: dilute sulfuric acid is added into the dissolution reaction tank 3 through a dilute sulfuric acid inlet 17, the temperature in the dissolution reaction tank 3 is kept at 90 ℃ through a heat exchange jacket 20, a corresponding stirring device is started by starting a first stirring motor 19, and the dilute sulfuric acid and the furfuryl alcohol waste catalyst are quickly reacted and dissolved to generate a copper sulfate solution containing a small amount of calcium sulfate and calcium oxide; the concentration of the dilute sulfuric acid is 68 percent; the molar ratio of the dilute sulfuric acid to the furfuryl alcohol spent catalyst is 2.5: 1;
and 4, step 4: the copper sulfate solution generated in the step 3 and a small amount of mixture of calcium sulfate and calcium oxide enter a clarifying tank 4 from a dissolution reaction tank 3; the mixture is clarified in a clarifying tank 4, a small amount of clarified solid is deposited at the bottom of the clarifying tank 4 and enters a dissolution reaction tank 3 through a reflux pump 5 and a reflux port 18 of the dissolution reaction tank 3 for dissolution reaction again;
and 5: the mixture obtained in the step 4 is clarified in the clarifying tank 4 and then enters the regeneration tank 6 through a supernatant outlet, ammonia water and silica sol are added into the regeneration tank 6 through an ammonia water and silica sol adding port 26, meanwhile, a second stirring motor 21 is started to start a corresponding stirring device, so that the ammonia water, the silica sol and a copper sulfate solution are fully reacted at normal temperature and normal pressure, and a solid-liquid mixture with the main components of copper hydroxide-silicon dioxide precipitate and ammonium sulfate, water, silicon dioxide and a trace amount of copper ammine complex compound is generated; the volume ratio of the copper sulfate solution to the ammonia water to the silica sol is as follows: 1:1.8: 1.5;
step 6: the solid-liquid mixture in the step 5 is uniformly distributed on the top of the filter plate 27 through a distributor 33; the liquid phase enters the filter cavity through the filter plate 27 and is discharged from the first drain outlet 30; when the solid-liquid mixture is subjected to solid-liquid separation by the filter plate 27, the hydraulic cylinder 29 is started, the piston end of the hydraulic cylinder 29 extends out to enable the filter plate 27 to move forwards along the rail 26, and when the filter plate 27 moves to the rail on the upper part of the outer wall of the baffle plate 25, the copper hydroxide-silicon dioxide precipitate enters the bottom of the cleaning cavity under the action of gravity; retracting the telescopic end of the hydraulic cylinder 29 and bringing it to the initial state, in which the filter plate 27 is at the bottom of the distributor 33 and repeating the above work;
and 7: when the copper hydroxide-silicon dioxide precipitate is positioned at the bottom of the cleaning cavity, the washing water in the washing water pipeline 34 cleans the copper hydroxide-silicon dioxide precipitate through the spraying device 35 to remove impurities on the surface of the copper hydroxide-silicon dioxide precipitate, and the excessive washing water overflows through the overflow plate 31 and is discharged through the second sewage outlet 32;
and 8: the copper hydroxide-silicon dioxide precipitate and the washing water which is not overflowed after the material cleaner filters the water and is washed are sent to a filter press 9 through a feed pump 8, and the catalyst filter cake is prepared after filter pressing and drying through the filter press 9; the pressure of the filter press 9 is 1.2 MPa; the washing liquid after filter pressing of the filter press 9 is discharged through a liquid phase discharge port 36;
and step 9: the catalyst filter cake in the step 8 is subjected to primary crushing by a primary crusher 10, the catalyst solid particles after the primary crushing are sent to a dryer 11 for drying and activation, and the dried and activated catalyst solid particles enter a secondary crusher 13 for secondary crushing; the temperature in the dryer 11 is: the water content of the catalyst solid after passing through the dryer 11 is less than or equal to 2.5 percent at the temperature of 200 ℃; the granularity of the catalyst solid particles after the second crushing is less than or equal to 350 meshes;
step 10: the catalyst solid particles crushed again in the step 9 enter a sieving machine 14 for sieving, and the sieved undersize materials enter a packing machine 38 through an undersize material channel to be packed for use or sold; the particle size of solid particles of the undersize product is not more than 350 meshes;
step 11: the oversize material screened in the step 10 is sent into a primary crusher 10 through a conveying belt 15, and the step 8 and the step 9 are repeated;
step 12: in the process of drying the catalyst solid particles after the first-stage crushing in the step 9 in the dryer 11, the dried gas enters the cyclone separator 12, the gas-solid separation is performed through the cyclone separator 12, and the gas phase after the gas-solid separation is subjected to tail gas treatment through the tail gas treatment device 37; the solid phase after the gas-solid separation enters the secondary crusher 13 through a solid material outlet at the bottom of the cyclone separator 12 and an inlet of the secondary crusher 13 to be crushed again together with the catalyst solid particles dried and activated in the step 8 in the secondary crusher 13.
Example 3
An apparatus for regenerating a furfuryl alcohol spent catalyst, the apparatus comprising: at least one furfuryl alcohol spent catalyst bin 1; at least one furfuryl alcohol waste catalyst dissolving and regenerating unit for ensuring the solubility of the copper sulfate solution and realizing the regeneration of the copper sulfate solution; at least one cleaning unit for cleaning the solid-liquid mixture produced by the regeneration unit; at least one crushing unit for drying and crushing the catalyst; the furfuryl alcohol waste catalyst bin 1 is connected with the screening machine 14 through a furfuryl alcohol waste catalyst dissolving and regenerating unit, a cleaning unit and a crushing unit, a screen underflow channel of the screening machine 14 is communicated with the packing machine 38, and a screen overflow channel of the screening machine 14 is communicated with the crushing unit. The furfuryl alcohol waste catalyst dissolving and regenerating unit comprises a metering belt 2 connected with a discharge port of a furfuryl alcohol waste catalyst bin 1, and a discharge end of the metering belt 2 is communicated with a regenerating tank 6 sequentially through a dissolving reaction tank 3 and a clarifying tank 4. The top of the dissolution reaction tank 3 is provided with a furfuryl alcohol waste catalyst inlet 16, a dilute sulfuric acid inlet 17 and a reflux port 18, the outside of the dissolution reaction tank 3 is provided with a heat exchange jacket 20, and the inside of the dissolution reaction tank 3 is provided with a stirring device with a first stirring motor 19. A stirring device with a second stirring motor 21 is arranged inside the regeneration tank 6, and a copper sulfate solution inlet 22 and an ammonia water and silica sol adding port 23 which are connected with a supernatant outlet are arranged at the top of the regeneration tank 6; the bottom of the regeneration tank 6 is provided with a solid-liquid mixed material outlet 24 connected with a cleaning unit. The cleaning unit comprises a baffle 25 with an angle of 45-60 degrees arranged inside the material cleaning bin 7; the baffle 25 divides the interior of the material cleaning bin 7 into a filtering cavity and a cleaning cavity; a track 26 is arranged between the baffle 25 at the top of the filter cavity and the inner wall of the material cleaning bin 7, a filter plate 27 is arranged at the top of the track 26, and the bottom of the filter plate 27 is matched with the track 26 through a small wheel 28; the rail 26 extends to the upper part of the outer wall of the baffle 25 at one side of the cleaning cavity; a hydraulic cylinder 29 is fixedly arranged on the outer side of the filter cavity, and the piston end of the hydraulic cylinder 29 penetrates through the material cleaning bin 7 and is hinged with one side of the filter plate 27; a first sewage discharge port 30 is formed in the lower part of the material cleaning bin 7 corresponding to the filter cavity; an overflow plate 31 is arranged between the baffle 25 in the cleaning cavity and the inner wall of the material cleaning bin 7, and a second sewage draining outlet 32 is arranged at the lower part of the material cleaning bin 7 corresponding to the outer side of the overflow plate 31; the top of the filter plate 27 when the hydraulic cylinder 29 is at the initial position is provided with a distributor 33 communicated with the solid-liquid mixed material outlet 24 of the regeneration tank 6; the top of the washing chamber is provided with a shower 35 connected to a washing water pipe 34. The crushing unit comprises a filter press 9 connected with a feed pump 8, and a solid material outlet of the filter press 9 is connected with a secondary crusher 13 through a primary crusher 10 and a dryer 11 in sequence; the filter press 9 is provided with a liquid phase discharge 36. The gas phase outlet at the top of the dryer 11 is connected with the tail gas treatment device 37 through the cyclone separator 12, and the solid material outlet at the bottom of the cyclone separator 12 is connected with the inlet of the secondary crusher 13. The oversize material channel of the sieving machine 14 is communicated with the feeding hole of the primary crusher 10 through a conveying belt 15.
A regeneration process of a regeneration device of a furfuryl alcohol waste catalyst comprises the following steps:
step 1: preheating a dissolution reaction tank 3 and a dryer 11 before feeding of a system, wherein the internal temperature of the dissolution reaction tank 3 after preheating is not less than 60 ℃, and the internal temperature of the dryer after preheating is not less than 150 ℃;
step 2: the furfuryl alcohol waste catalyst in the furfuryl alcohol waste catalyst bin 1 enters a dissolution reaction tank 3 through a metering belt 2; the furfuryl alcohol waste catalyst is the furfuryl alcohol waste catalyst after organic matters are recovered;
and step 3: dilute sulfuric acid is added into the dissolution reaction tank 3 through a dilute sulfuric acid inlet 17, the temperature in the dissolution reaction tank 3 is kept at 75 ℃ through a heat exchange jacket 20, a corresponding stirring device is started by starting a first stirring motor 19, and the dilute sulfuric acid and the furfuryl alcohol waste catalyst are quickly reacted and dissolved to generate a copper sulfate solution containing a small amount of calcium sulfate and calcium oxide; the concentration of the dilute sulfuric acid is 59 percent; the molar ratio of the dilute sulfuric acid to the furfuryl alcohol spent catalyst is 2.5: 1;
and 4, step 4: the copper sulfate solution generated in the step 3 and a small amount of mixture of calcium sulfate and calcium oxide enter a clarifying tank 4 from a dissolution reaction tank 3; the mixture is clarified in a clarifying tank 4, a small amount of clarified solid is deposited at the bottom of the clarifying tank 4 and enters a dissolution reaction tank 3 through a reflux pump 5 and a reflux port 18 of the dissolution reaction tank 3 for dissolution reaction again;
and 5: the mixture obtained in the step 4 is clarified in the clarifying tank 4 and then enters the regeneration tank 6 through a supernatant outlet, ammonia water and silica sol are added into the regeneration tank 6 through an ammonia water and silica sol adding port 26, meanwhile, a second stirring motor 21 is started to start a corresponding stirring device, so that the ammonia water, the silica sol and a copper sulfate solution are fully reacted at normal temperature and normal pressure, and a solid-liquid mixture with the main components of copper hydroxide-silicon dioxide precipitate and ammonium sulfate, water, silicon dioxide and a trace amount of copper ammine complex compound is generated; the volume ratio of the copper sulfate solution to the ammonia water to the silica sol is as follows: 1:1.8: 1.5;
step 6: the solid-liquid mixture in the step 5 is uniformly distributed on the top of the filter plate 27 through a distributor 33; the liquid phase enters the filter cavity through the filter plate 27 and is discharged from the first drain outlet 30; when the solid-liquid mixture is subjected to solid-liquid separation by the filter plate 27, the hydraulic cylinder 29 is started, the piston end of the hydraulic cylinder 29 extends out to enable the filter plate 27 to move forwards along the rail 26, and when the filter plate 27 moves to the rail on the upper part of the outer wall of the baffle plate 25, the copper hydroxide-silicon dioxide precipitate enters the bottom of the cleaning cavity under the action of gravity; retracting the telescopic end of the hydraulic cylinder 29 and bringing it to the initial state, in which the filter plate 27 is at the bottom of the distributor 33 and repeating the above work;
and 7: when the copper hydroxide-silicon dioxide precipitate is positioned at the bottom of the cleaning cavity, the washing water in the washing water pipeline 34 cleans the copper hydroxide-silicon dioxide precipitate through the spraying device 35 to remove impurities on the surface of the copper hydroxide-silicon dioxide precipitate, and the excessive washing water overflows through the overflow plate 31 and is discharged through the second sewage outlet 32;
and 8: the copper hydroxide-silicon dioxide precipitate and the washing water which is not overflowed after the material cleaner filters the water and is washed are sent to a filter press 9 through a feed pump 8, and the catalyst filter cake is prepared after filter pressing and drying through the filter press 9; the pressure of the filter press 9 is 1.0 MPa; the washing liquid after filter pressing of the filter press 9 is discharged through a liquid phase discharge port 36;
and step 9: the catalyst filter cake in the step 8 is subjected to primary crushing by a primary crusher 10, the catalyst solid particles after the primary crushing are sent to a dryer 11 for drying and activation, and the dried and activated catalyst solid particles enter a secondary crusher 13 for secondary crushing; the temperature in the dryer 11 is: the moisture content of the catalyst solid after passing through the dryer 11 is less than or equal to 2.5 percent at 175 ℃; the granularity of the catalyst solid particles after the second crushing is less than or equal to 350 meshes;
step 10: the catalyst solid particles crushed again in the step 9 enter a sieving machine 14 for sieving, and the sieved undersize materials enter a packing machine 38 through an undersize material channel to be packed for use or sold; the particle size of solid particles of the undersize product is not more than 350 meshes;
step 11: the oversize material screened in the step 10 is sent into a primary crusher 10 through a conveying belt 15, and the step 8 and the step 9 are repeated;
step 12: in the process of drying the catalyst solid particles after the first-stage crushing in the step 9 in the dryer 11, the dried gas enters the cyclone separator 12, the gas-solid separation is performed through the cyclone separator 12, and the gas phase after the gas-solid separation is subjected to tail gas treatment through the tail gas treatment device 37; the solid phase after the gas-solid separation enters the secondary crusher 13 through a solid material outlet at the bottom of the cyclone separator 12 and an inlet of the secondary crusher 13 to be crushed again together with the catalyst solid particles dried and activated in the step 8 in the secondary crusher 13.
In the description of the present invention, it is to be noted that, unless otherwise explicitly specified or limited, the terms "connected," "connecting," and the like are to be construed broadly, and may, for example, be fixedly connected, integrally connected, or detachably connected; or communication between the interior of the two elements; they may be directly connected or indirectly connected through an intermediate, and those skilled in the art can understand the specific meaning of the above terms in the present invention according to specific situations. The above examples are merely illustrative of the feasible embodiments of the present invention and they are not intended to limit the scope of the present invention, and equivalent embodiments, modifications and alterations without departing from the technical spirit of the present invention are included in the scope of the present invention.
Claims (10)
1. A regeneration device of furfuryl alcohol dead catalyst which characterized in that: the device includes:
at least one furfuryl alcohol spent catalyst bin (1);
at least one furfuryl alcohol waste catalyst dissolving and regenerating unit for ensuring the solubility of the copper sulfate solution and realizing the regeneration of the copper sulfate solution;
at least one cleaning unit for cleaning the solid-liquid mixture produced by the regeneration unit;
at least one crushing unit for drying and crushing the catalyst;
the furfuryl alcohol waste catalyst bin (1) is connected with the screening machine (14) through a furfuryl alcohol waste catalyst dissolving and regenerating unit, a cleaning unit and a crushing unit, a screen underflow channel of the screening machine (14) is communicated with the packing machine (38), and a screen overflow channel of the screening machine (14) is communicated with the crushing unit.
2. The regeneration device of a furfuryl alcohol spent catalyst according to claim 1, wherein: the furfuryl alcohol waste catalyst dissolving and regenerating unit comprises a metering belt (2) connected with a discharge port of a furfuryl alcohol waste catalyst bin (1), and a discharge end of the metering belt (2) is communicated with a regenerating tank (6) sequentially through a dissolving reaction tank (3) and a clarifying tank (4).
3. A regeneration apparatus of furfuryl alcohol spent catalyst according to claim 2, characterized in that: the top of the dissolution reaction tank (3) is provided with a furfuryl alcohol waste catalyst inlet (16), a dilute sulfuric acid inlet (17) and a reflux port (18), the outside of the dissolution reaction tank (3) is provided with a heat exchange jacket (20), and the inside of the dissolution reaction tank (3) is provided with a stirring device with a first stirring motor (19).
4. A regeneration apparatus of furfuryl alcohol spent catalyst according to claim 2, characterized in that: the upper part of the clarifying tank (4) is provided with a supernatant outlet connected with the regeneration tank (6), the lower part of the clarifying tank (4) is of a cone-bucket-shaped structure, and the bottom of the clarifying tank is connected with a reflux port (18) of the dissolution reaction tank (3) through a reflux pump (5).
5. A regeneration apparatus of furfuryl alcohol spent catalyst according to claim 2, characterized in that: a stirring device with a second stirring motor (21) is arranged inside the regeneration tank (6), and a copper sulfate solution inlet (22) connected with a supernatant outlet and an ammonia water and silica sol adding port (23) are arranged at the top of the regeneration tank (6); the bottom of the regeneration tank (6) is provided with a solid-liquid mixed material outlet (24) connected with the cleaning unit.
6. The regeneration device of a furfuryl alcohol spent catalyst according to claim 1, wherein: the cleaning unit comprises a material cleaning bin (7), and a baffle (25) with an angle of 45-60 degrees is arranged in the material cleaning bin;
the baffle (25) divides the interior of the material cleaning bin (7) into a filtering cavity and a cleaning cavity;
a track (26) is arranged between the baffle (25) at the top of the filter cavity and the inner wall of the material cleaning bin (7), a filter plate (27) is arranged at the top of the track (26), and the bottom of the filter plate (27) is matched with the track (26) through a small wheel (28); the track (26) extends to the upper part of the outer wall of the baffle (25) at one side of the cleaning cavity;
a hydraulic cylinder (29) is fixedly arranged on the outer side of the filter cavity, and the piston end of the hydraulic cylinder (29) penetrates through the material cleaning bin (7) and is hinged with one side of the filter plate (27);
a first sewage draining port (30) is arranged at the lower part of the material cleaning bin (7) corresponding to the filter cavity;
an overflow plate (31) is arranged between the baffle (25) in the cleaning cavity and the inner wall of the material cleaning bin (7), and a second sewage draining outlet (32) is arranged at the lower part of the material cleaning bin (7) corresponding to the outer side of the overflow plate (31);
a distributor (33) communicated with the solid-liquid mixed material outlet (24) of the regeneration tank (6) is arranged at the top of the filter plate (27) when the hydraulic cylinder (29) is at the initial position;
the top of the cleaning cavity is provided with a spraying device (35) connected with a washing water pipeline (34).
7. The regeneration device of a furfuryl alcohol spent catalyst according to claim 1, wherein: the crushing unit comprises a filter press (9) connected with a feeding pump (8), and a solid material outlet of the filter press (9) is connected with a secondary crusher (13) through a primary crusher (10) and a dryer (11) in sequence; the filter press (9) is provided with a liquid phase discharge port (36).
8. The regeneration device of a furfuryl alcohol spent catalyst according to claim 1, wherein: and a gas phase outlet at the top of the dryer (11) is connected with a tail gas treatment device (37) through a cyclone separator (12), and a solid material outlet at the bottom of the cyclone separator (12) is connected with an inlet of a secondary crusher (13).
9. The regeneration device of a furfuryl alcohol spent catalyst according to claim 1, wherein: and an oversize material channel of the sieving machine (14) is communicated with a feed inlet of the primary crusher (10) through a conveying belt (15).
10. A process for regenerating a device for regenerating a spent furfuryl alcohol catalyst according to claims 1 to 9, characterized in that: the regeneration process comprises the following steps:
step 1: preheating a dissolution reaction tank (3) and a dryer (11) before feeding of a system, wherein the internal temperature of the dissolution reaction tank (3) after preheating is not less than 60 ℃, and the internal temperature of the dryer after preheating is not less than 150 ℃;
step 2: the furfuryl alcohol waste catalyst in the furfuryl alcohol waste catalyst bin (1) enters a dissolution reaction tank (3) through a metering belt (2); the furfuryl alcohol waste catalyst is the furfuryl alcohol waste catalyst after organic matters are recovered;
and step 3: dilute sulfuric acid is added into the dissolution reaction tank (3) through a dilute sulfuric acid inlet (17), the temperature in the dissolution reaction tank (3) is kept at 60-90 ℃ through a heat exchange jacket (20), a corresponding stirring device is started by starting a first stirring motor (19), the dilute sulfuric acid and the furfuryl alcohol waste catalyst are quickly reacted and dissolved to generate a copper sulfate solution, and the copper sulfate solution contains a small amount of calcium sulfate and calcium oxide; the concentration of the dilute sulfuric acid is 50-68 percent; the molar ratio of the dilute sulfuric acid to the furfuryl alcohol spent catalyst is 2.5: 1;
and 4, step 4: the copper sulfate solution generated in the step 3 and a small amount of mixture of calcium sulfate and calcium oxide enter a clarifying tank (4) from a dissolution reaction tank (3); clarifying the mixture in a clarifying tank (4), depositing a small amount of clarified solids at the bottom of the clarifying tank (4) and entering a dissolution reaction tank (3) through a reflux pump (5) and a reflux port (18) of the dissolution reaction tank (3) to carry out dissolution reaction again;
and 5: the mixture obtained in the step 4 is clarified in a clarifying tank (4), enters a regeneration tank (6) through a supernatant outlet, ammonia water and silica sol are added into the regeneration tank (6) through an ammonia water and silica sol adding port (26), and meanwhile, a second stirring motor (21) is started to start a corresponding stirring device, so that the ammonia water, the silica sol and a copper sulfate solution are fully reacted at normal temperature and normal pressure to generate a solid-liquid mixture with main components of copper hydroxide-silicon dioxide precipitates and ammonium sulfate, water, silicon dioxide and trace copper-ammonia complex compounds; the volume ratio of the copper sulfate solution to the ammonia water to the silica sol is as follows: 1:1.8: 1.5;
step 6: enabling the solid-liquid mixture in the step 5 to uniformly distribute on the top of the filter plate (27) through a distributor (33); the liquid phase enters the filter cavity through the filter plate (27) and is discharged from the first sewage discharge port (30);
after solid-liquid separation of the solid-liquid mixture is realized by the filter plate (27), the hydraulic cylinder (29) is started, the piston end of the hydraulic cylinder (29) extends out to enable the filter plate (27) to move forwards along the track (26), and when the filter plate (27) moves onto the track on the upper part of the outer wall of the baffle plate (25), copper hydroxide-silicon dioxide precipitate enters the bottom of the cleaning cavity under the action of gravity; retracting the telescopic end of the hydraulic cylinder (29) and making it in an initial state, at which time the filter plate (27) is at the bottom of the distributor (33) and repeating the above-mentioned work;
and 7: when the copper hydroxide-silicon dioxide precipitate is positioned at the bottom of the cleaning cavity, cleaning water in a cleaning water pipeline (34) cleans the copper hydroxide-silicon dioxide precipitate through a spraying device (35) to remove impurities on the surface of the copper hydroxide-silicon dioxide precipitate, and excessive cleaning water overflows through an overflow plate (31) and is discharged through a second sewage outlet (32);
and 8: the copper hydroxide-silicon dioxide sediment after the water washing of the material cleaner and the washing water which does not overflow are sent to a filter press (9) through a feed pump (8), and are filter-pressed and dried by the filter press (9) to prepare a catalyst filter cake; the pressure of the filter press (9) is 0.8-1.2 MPa; the washing liquid after filter pressing of the filter press (9) is discharged through a liquid phase discharge port (36);
and step 9: the catalyst filter cake in the step 8 is subjected to primary crushing by a primary crusher (10), the catalyst solid particles subjected to primary crushing are sent to a dryer (11) for drying and activation, and the dried and activated catalyst solid particles enter a secondary crusher (13) for secondary crushing; the temperature in the dryer (11) is: the water content of the catalyst solid after passing through the dryer (11) is less than or equal to 2.5 percent at the temperature of 150-200 ℃; the granularity of the catalyst solid particles after the second crushing is less than or equal to 350 meshes;
step 10: the catalyst solid particles crushed again in the step 9 enter a sieving machine (14) for sieving, and the sieved undersize materials enter a packaging machine (38) through an undersize material channel for packaging and then using or selling; the particle size of solid particles of the undersize product is not more than 350 meshes;
step 11: the oversize material screened in the step 10 is sent into a primary crusher (10) through a conveying belt (15), and the step 8 and the step 9 are repeated;
step 12: in the step 9, in the process of drying the catalyst solid particles after the first-stage crushing in the dryer (11), the dried gas enters the cyclone separator (12), gas-solid separation is carried out through the cyclone separator (12), and the gas phase after the gas-solid separation is subjected to tail gas treatment through the tail gas treatment device (37); and the solid phase after gas-solid separation enters the secondary crusher (13) through a solid material outlet at the bottom of the cyclone separator (12) and an inlet of the secondary crusher (13) to be crushed again together with the catalyst solid particles dried and activated in the step 8 in the secondary crusher (13).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117960254A (en) * | 2024-04-02 | 2024-05-03 | 河南氢力能源有限公司 | Recovery and regeneration process of copper-silicon system spent catalyst in furfural hydrogenation reaction |
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