CN204933427U - Paste state bed reactor - Google Patents
Paste state bed reactor Download PDFInfo
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- CN204933427U CN204933427U CN201520658989.5U CN201520658989U CN204933427U CN 204933427 U CN204933427 U CN 204933427U CN 201520658989 U CN201520658989 U CN 201520658989U CN 204933427 U CN204933427 U CN 204933427U
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- tedge
- expanding reach
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- cooler
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Abstract
The utility model discloses a kind of paste state bed reactor, comprise tedge, expanding reach, cooler, catalyst settler, filter; Be connected to expanding reach on tedge top, tedge part extend into expanding reach, the tedge in expanding reach is provided with slurries return port, communicates with reative cell; Be connected with cooler bottom tedge, cooler and tedge are integral types; Catalyst settler by tangential way from middle part charging, catalyst settler top equipment has the barrier of certain altitude to form standing district, catalyst settler top is connected with gas-liquid separation chamber by balance pipe, bottom is connected with cooler, filter top is connected with gas-liquid separation chamber by balance pipe, filter bottom is connected with cooler, and filter is provided with backwash facility; Tedge bottom is provided with liquid phase feed entrance and gas phase feed(raw material)inlet; Tedge inside is reative cell, is provided with liquid feed distributor and gas feed distributor bottom reative cell.The utility model hydrogenation efficiency reaches 14-16g/l hydride.
Description
Technical field
The utility model belongs to technical field of chemical engineering, is specifically related to a kind of paste state bed reactor, particularly relates to the paste state bed reactor of hydrogenation process in process for prepairng hydrogen peroxide by anthraquinone technique.
Background technology
Hydrogen peroxide is a kind of important Inorganic Chemicals, and it is widely used in the numerous areas such as papermaking, weaving, chemicals synthesis, military project, electronics, food processing, medicine, cosmetics, environmental protection, metallurgy.Producing water and oxygen after peroxide decomposition, to environment non-secondary pollution, is a kind of green chemical.Generally adopt the anthraquinone production carrying out hydrogen peroxide both at home and abroad at present.Process for prepairng hydrogen peroxide by anthraquinone is using anthraquinone derivative as working material, and under the effect of catalyst, the anthraquinone derivative hydrogenation of will dissolve in organic solvent with hydrogen, generates corresponding hydrogen anthraquinone.Then, hydrogen anthraquinone oxidation Hydrogen Peroxide and anthraquinone derivative.Finally, obtain certain density aqueous hydrogen peroxide solution as product with the hydrogen peroxide in water extraction organic solvent, the working solution containing anthraquinone derivative and organic solvent is then recycled.Wherein, the efficiency of anthraquinone hydrogenation process directly determines output and the concentration of hydrogen peroxide, marginal to the production tool of whole hydrogen peroxide.At present domestic the most frequently used in anthraquinone hydrogenation process be down-type fixed-bed reactor, i.e. trickle bed reactor, but fixed bed reactors exist that catalyst use efficiency is low, reaction selectivity is low, temperature distributing disproportionation is even in bed, catalyst local liquid holdup is large and working solution is degraded serious problem.Adopt fixed bed reactors to carry out hydrogenation process, hydrogen effect is generally only 6 ~ 7g/L hydride.And the reactor adopting gas and liquid flowing to move upward is the better selection carrying out anthraquinone derivative hydrogenation process.This type of reactor comprises tubular type suspended-bed reactor, bubbling bed reactor and paste state bed reactor.Also flow in the process of flowing at gas-liquid two-phase, working solution and hydrogen anthraquinone mixed solution are as continuous phase, and hydrogen (or hydrogen and inert gas gaseous mixture) is as decentralized photo, both the treating capacity of working solution and the utilization rate of catalyst can have been improved, increase anthraquinone conversion ratio, overcome again fixed bde catalyst bed local liquid holdup large, the problem of the working solution degraded that temperature distributing disproportionation causes.Large-scale hydrogen peroxide manufacture device newly-built abroad generally adopts up flow type fluid bed to carry out hydrogenation, and hydrogen effect generally can reach more than 12g/L hydride.
US4428923 discloses a kind of tubular type suspension bed hydrogenation reactor system of process for prepairng hydrogen peroxide by anthraquinone, and reactor becomes pass-over offset system, is connected between horizontal tube and vertical tube by elbow, and each section of pipe has identical nominal diameter.Pipe is outer has sleeve pipe for heating and cooling, and hydrogenation process just carries out in the reactor.Before working solution and hydrogen enter hydrogenator, first through a venturi mixer premix, catalyst is along with working solution together continuous-flow, and working solution and hydrogen react, and after the reaction through a separator, catalyst is carried out preliminary being separated with hydride; A special hydride filter must be used after separation to be again separated with catalyst by hydride, and hydrogenation efficiency is 12g/L hydride.
CN1298369A provides a kind of bubbling bed reactor.Reactor is preferably vertical type bubbling tower, in reactor, at least part of hydraulic diameter that comprises is between the through hole of 1 to 10mm or flow path member, be generally bed, knitted fabric, open-celled foams or filler, be generally and structure like SulzerBX earthfill rockfill concrete riprap RCC, pass through for working solution or hydrogen.Ensure that the sidewall roughness of flow path member is 0.5 to 5 times of catalyst average grain diameter, working solution enters reactor with gas phase together with reactor lower part, under catalyst action, carry out hydrogenation reaction, enter equipment for separating liquid from solid after reaction and carry out being separated of hydride and catalyst.This reaction system can carry out the operation of interval and continuous two kinds of modes, and hydrogenation efficiency can reach more than 15g/L hydride.
CN1817838A discloses a kind of fluidized-bed reactor being applicable to anthraquinone working solution hydrogenation.This reactor body is divided into upper and lower two parts, and bottom is hydrogenation body region, and top has expanding reach structure and is beneficial to gas-liquid separation, and inside reactor is void tower, and hydrogenation efficiency can reach 9.9g/L hydride.
CN104549065 provides a kind of slurry bed circulatory flow reactor and applies and a kind of method of producing hydrogen peroxide, the expanding reach that described slurry bed circulatory flow reactor comprises tedge, tedge top caliber expands and solid-liquid separator, described expanding reach is communicated with solid-liquid separator top, is communicated with bottom described solid-liquid separator with bottom tedge; The three phase separator of double-sleeve structure is set in described expanding reach, feed(raw material)inlet is provided with bottom described tedge, described expanding reach top is provided with gas vent, arranges filter assemblies in described solid-liquid separator, and described solid-liquid separator top after filtration assembly arranges purified liquor outlet.Adopt this slurry bed circulatory flow reactor high as gas-liquid-solid three-phase separative efficiency in the method for hydrogenation reactor production hydrogen peroxide, avoid catalyst local excessive hydrogenation, reduce the possibility of excessive hydrogenation, hydrogen effect is high, can obtain the hydrogen peroxide product of higher concentration.
Summary of the invention
The purpose of this utility model is to provide a kind of paste state bed reactor, and this reactor is applicable to gas-liquid-solid three-phase slurry reactor and is separated, and is specially adapted to hydriding process in process for prepairng hydrogen peroxide by anthraquinone technique.
For reaching this object, the technical scheme that the utility model proposes is:
A kind of paste state bed reactor, is characterized in that: comprise tedge, expanding reach, cooler, catalyst settler, filter; Tedge inside is reative cell; Be connected to expanding reach on tedge top, tedge part extend into expanding reach, the tedge in expanding reach is provided with slurries return port, communicates with reative cell; Be connected with cooler bottom tedge, cooler and tedge are integral types; Expanding reach top is gas-liquid separation chamber, top is provided with reaction gas outlet, expanding reach middle and lower part is the pre-decanting zone of catalyst, in catalyst sedimentation, district is provided with baffle plate, expanding reach baffle plate isolated area lower open, upper guard-plate is provided with perforate, and expanding reach baffle plate isolated area is connected by tangential feed pipe with catalyst settler; Catalyst settler by tangential way from middle part charging, top, catalyst sedimentation district is provided with the barrier with standing function, catalyst settler top is connected with gas-liquid separation chamber by balance pipe, bottom is connected with cooler by catalyst pulp pipe, and barrier top is connected with filter by reactant liquor overflow pipe; Be provided with filter assemblies in filter, filter top is connected with gas-liquid separation chamber by balance pipe, and after filtering, clear liquid is discharged by filter purified liquor outlet, and filter bottom is connected with cooler by catalyst pulp pipe, filters and is provided with backwash facility; Tedge bottom is provided with liquid phase feed entrance and gas phase feed(raw material)inlet; Liquid feed distributor and gas feed distributor is provided with bottom reative cell.
The utility model is provided with the fluid redistributor with refrigerating function in reative cell.
In the utility model, tedge ratio of height to diameter is 4/1 ~ 20/1.
In the utility model, the cylindrical shell shell footpath of expanding reach is 1.2/1 ~ 2/1 with rising shell footpath ratio.
The ratio of height to diameter 0.5/1 ~ 4/1 of expanding reach cylindrical shell in the utility model.
In the utility model, the aspect ratio of height and expanding reach cylindrical shell that tedge stretches into expanding reach is 0.3 ~ 0.6.
Filter assemblies of the present utility model is two or more sets.
Cooler of the present utility model is ripple tube cooler.
Paste state bed reactor described in the utility model is applied in process for prepairng hydrogen peroxide by anthraquinone, during work, working solution enters liquid feed distributor by liquid phase feed feed entrance, hydrogen-containing gas enters gas feed distributor by phase feed feed entrance, mix with the slurries in tedge and move upward, under hydrogenation catalyst effect, the anthraquinone derivative in working solution carries out hydrogenation reaction and obtains hydrogen anthraquinone in tedge; After hydrogenation reaction, material is after tedge reaction, and enter expanding reach, the gas-liquid separation chamber on expanding reach top carries out gas-liquid separation, and reacting gas discharges reactor from reaction gas outlet; Carry out solid-liquid initial gross separation in expansion middle and lower part, the slurries that partially catalyzed agent concentration is high turn back to reative cell from slurries return port, and the reactant liquor of remove portion catalyst granules enters catalyst settler from the top overflow of expanding reach baffle plate isolated area with tangential way; At catalyst settler, hydrogenation reaction solution carries out waterpower and gravitational settling, and leave standstill effect through catalyst settler grid, slurries bottom catalyst settler return cooler by tube connector, the gas-liquid separation chamber top of the gas phase Returning reactor on top, the reactant liquor after sedimentation separation catalyst enters filter from the overflow of grid top; In the filter, reactant liquor after filtration assembly carries out isolated by filtration, and clear liquid is discharged from purified liquor outlet and obtained hydride, and hydride obtains the oxidation solution containing hydrogen peroxide in oxidation reactor with oxygen reaction; Oxidation solution obtains hydrogenperoxide steam generator and working solution through extract and separate, and gaseous substance turns back to reactor gas-liquid separation chamber top, and slurries are back to cooler from filter bottom by tube connector; After the slurries come from catalyst sedimentation room and filter carry out heat exchange cooler, again enter tedge and carry out hydrogenation reaction.
The outlet of unloading of hydrogenation catalyst is located at filter and cooler connecting tube top, adds entrance and is located at filter and cooling connecting tube bottom.
In the method that the utility model provides, the reaction temperature in described paste state bed reactor is 35 ~ 80 DEG C, preferably 55 ~ 75 DEG C; Reaction pressure is 0.1 ~ 0.5MPa, preferably 0.2 ~ 0.3MPa.
The beneficial effects of the utility model are:
Cooler of the present utility model and tedge are integral type, so both achieve the cooling of circulation fluid, serve again recycle liquid distributor effect, make circulation fluid evenly can enter reative cell; Have the redistributor of refrigerating function reaction zone being provided with, realization response liquid gas-solid Three-phase Flow is even, improves the mass-transfer performance of fluid, controls the variations in temperature of reactant liquor simultaneously.The enforcement of these technical schemes, improves hydrogenation efficiency, and hydrogenation efficiency reaches 14-16g/L hydride.
The hydrogenation unit preparing the method for hydrogen peroxide provided adopts paste state bed reactor, the top of tedge extend into expanding reach, the expanding reach on reactor top is gas-liquid separation chamber and catalyst sedimentation Disengagement zone, catalyst carries out pre-sedimentation in catalyst sedimentation Disengagement zone, bottom, catalyst sedimentation Disengagement zone is provided with slurries return port and is connected with reative cell, slurries containing high concentration catalyst return reative cell from this slurries return port, baffle plate is provided with in middle and upper part, catalyst sedimentation Disengagement zone, light liquid after the pre-sedimentation of catalyst enters baffle plate isolated area, perforate is arranged at baffle plate top, gas enters gas-liquid separation chamber from perforate, in isolated area, the slurries of remove portion catalyst enter catalyst settler by the tangential feed pipe of catalyst settler, catalyst settler top is provided with the barrier possessing standing function, and the reactant liquor on barrier top enters filter by tube overflow, the enforcement of these technical schemes, the expanding reach gas-liquid separation chamber of reactor achieves gas-liquid separation, catalyst sedimentation Disengagement zone realizes solid-liquid pre-separation, slurries high for catalyst concn are returned reative cell simultaneously, so both improve reative cell middle and upper part catalyst concn, when reactant concentration gradient reduces, obtain high hydrogenation efficiency, reduce again the catalyst concn 20%-30% in reactant liquor, alleviate downstream catalyst segregational load, before filter, catalyst settler is set, catalyst settler is separated 60%-70% catalyst again further, so significantly alleviate filter loading, 70% of filter area can be reduced, the filter assemblies cycle of operation obtains significant prolongation, compared with the direct filtration not adding catalyst settler, filter assemblies can extend 2-3 doubly running time, and the backwash frequency reduces 60%-80%.
Cooler and tedge are set to integral type by the utility model, and are ripple tube coolers.So both can play cooling heat transferring effect, play the effect of slurry feed distributor simultaneously, and enable catalyst slurry be evenly distributed in reative cell; The application of glass stria tube formula cooler prevents the deposition of catalyst in cooler, can make cooler long-term operation.
By the enforcement of these technical schemes above, hydrogenation efficiency reaches 15-16g/L hydride, and the filter area of filter assemblies decreases more than 60%, and filter assemblies can extend 2-3 doubly running time, and the backwash frequency reduces 60%-80%.
figure said by accompanying drawing
Fig. 1 paste state bed reactor schematic diagram.
In figure: 1-tedge; 2-expanding reach; 3-catalyst settler; 4-filter; 5-cooler; 6-liquid feed distributor; 7-gas feed distributor; 8-reative cell; 9-gas-liquid separation chamber; 10-reaction gas outlet; 11-bubble; 12-solid catalyst particle; 13-liquid phase feed entrance; 14-phase feed entrance; 15-cooling water inlet; 16 coolant outlets; 17-purified liquor outlet; 18-filter assemblies; 19-slurries return port; 20-baffle plate; 21-settler tangential feed pipe; 22-settler barrier; 23-exhaust outlet, the overflow pipe of 24-catalyst settler and filter; 25-fluid redistributor; 26-cooling water inlet; 27 coolant outlets.
Detailed description of the invention
Below by concrete example, the present invention will be described, but do not form the further restriction to invention.
Below describe the specific embodiment of the present invention in detail:
Embodiment 1
Paste state bed reactor as shown in Figure 1, comprises tedge 1, expanding reach 2, cooler 5, catalyst settler 3, filter 4; Be connected to expanding reach on tedge top, tedge part extend into expanding reach, the tedge in expanding reach is provided with slurries return port 19, communicates with reative cell 8; Be connected with cooler 5 bottom tedge, cooler 5 and tedge 1 are integral types; Expanding reach top is gas-liquid separation chamber 9, top is provided with reaction gas outlet 10, expanding reach middle and lower part is the pre-decanting zone of catalyst, be provided with baffle plate 20 in the pre-decanting zone of catalyst and form baffle plate isolated area, lower open, upper guard-plate is provided with perforate 23, and baffle plate isolated area is connected by tangential feed pipe 21 with catalyst settler 3; Catalyst settler 3 is by tangential way from middle part charging, and catalyst settler top is provided with barrier 22, and catalyst settler top is connected with gas-liquid separation chamber 9 by balance pipe, and bottom is connected with cooler 5, and barrier top is connected with filter 4; Be provided with filter assemblies 18 in filter, filter top is connected with gas-liquid separation chamber by balance pipe, and after filtering, clear liquid is discharged by filter purified liquor outlet, and filter bottom is connected with cooler 5, and filter is provided with backwash facility; Tedge bottom is provided with liquid phase feed entrance 13 and gas phase feed(raw material)inlet 14; Tedge inside is reative cell 8, is provided with liquid feed distributor 6 and gas feed distributor 7 bottom reative cell.
The outlet of unloading of hydrogenation catalyst is located at filter and cooler connecting tube top, adds entrance and is located at filter and cooling connecting tube bottom.
Three groups of fluid redistributors 25 are provided with in reative cell.
Tedge ratio of height to diameter is 10/1.
The diameter of expanding reach cylindrical shell is 1.5/1 with tedge diameter ratio.
The ratio of height to diameter 2/1 of expanding reach cylindrical shell.
The aspect ratio of height and expanding reach cylindrical shell that tedge stretches out expanding reach is 0.6.
The filter assemblies used is two groups.
Working solution is entered liquid feed distributor by liquid phase feed feed entrance, hydrogen-containing gas enters gas feed distributor by phase feed feed entrance, mix with the slurries in tedge and move upward, under hydrogenation catalyst effect, the anthraquinone derivative in working solution carries out hydrogenation reaction and obtains hydrogen anthraquinone in tedge; After hydrogenation reaction, material is after tedge reaction is risen, and enter expanding reach, the gas-liquid separation chamber on expanding reach top carries out gas-liquid separation, and reacting gas discharges reactor from reaction gas outlet; Solid-liquid initial gross separation is carried out in expanding reach middle and lower part, the slurries that catalyst concn is high bottom expanding reach, turn back to reative cell from slurries return port, the baffle plate isolated area of expanding reach middle and upper part is containing the lower hydrogenation reaction solution of catalyst concn, inflow catalyst settler in the middle part of expanding reach; At catalyst settler, hydrogenation reaction solution carries out sedimentation separation, and bottom is the slurries containing catalyst, cooler is entered by tube connector, the gas-liquid separation chamber top of the gas phase Returning reactor at top, grid top is the hydrogenation reaction solution being separated rear catalyst, enters filter through overflow pipe; In the filter, reactant liquor enters isolated by filtration by filter assemblies, and clear liquid is discharged from purified liquor outlet and obtained hydride, and hydride obtains the oxidation solution containing hydrogen peroxide in oxidation reactor with oxygen reaction; Oxidation solution obtains hydrogenperoxide steam generator and working solution through extract and separate, and gaseous substance turns back to reactor gas-liquid separation chamber top, and the slurries containing catalyst enter cooler from filter bottom by tube connector; After the slurries come from catalyst sedimentation room and filter carry out heat exchange cooler, again enter tedge and carry out hydrogenation reaction.
The reaction temperature of paste state bed reactor is 35 ~ 80 DEG C; Reaction pressure is 0.1 ~ 0.5MPa, preferably 0.2 ~ 0.3MPa.
Embodiment 2
Hydrogen effect assay method: get 5mL hydride in separatory funnel, then add the heavy aromatics of 10mL and the H of 20mL
2sO
4solution (H
2sO
4be 1:4 with the volume ratio of water); Logical O in above-mentioned mixed solution
2, till bubbling is oxidizing to glassy yellow or crocus (about 10 ~ 15min); With pure water extractive reaction liquid 4 ~ 5 times, about 20mL water at every turn; With the KMnO of concentration 0.1mol/L in extract
4standard liquid is titrated to blush, and 30s is colour-fast is terminal.Then hydrogen effect (gH
2o
2/ L)=concentration of standard solution (0.1mol/L) × standard liquid volume (mL) × 17.01/5.
The catalyst adopted is: the palladium-carbon catalyst Pd110 that Yu Rui Chemical Co., Ltd. produces, and design parameter is as follows: bullion content 10% ± 0.2%, specific area>=950m
2/ g, metal surface area 85 ~ 105m
2/ g, carrier average grain diameter 100 μm.
Working solution is: 2-EAQ content is 120-180g/L, and solvent is made up of C10 aromatic hydrocarbons and trioctyl phosphate, the two 3:1 ratio mixing by volume.
Embodiment 3
Adopt the paste state bed reactor shown in accompanying drawing 1, wherein, reaction tedge is of a size of Φ 100 × 1000mm, and expanding reach is of a size of Φ 150 × 250mm, and the height that tedge grows expanding reach is 150mm; Filter has two groups of height to be the sintering metal filter element filtering assembly of 400mm, sets when each filter assemblies pressure reduction reaches 0.05MPa and carries out automatic backflushing, and backwash liquid reacts clear liquid after filtering.
Working solution inlet amount is 0.3m
3/ h, hydrogen feed amount is 5.0Nm
3/ h, reaction temperature 50-55 DEG C, reaction pressure 0.25-0.50MPa.
Filter assemblies life cycle is 60 hours, each backwashing time 40 seconds.
Hydrogenation efficiency reaches 12-14g/L hydride.
Embodiment 4
Adopt the paste state bed reactor shown in accompanying drawing 1, wherein, reaction tedge is of a size of Φ 100 × 1000mm, and expanding reach is of a size of Φ 150 × 250mm, and the height that tedge grows expanding reach is 150mm; Filter has two groups of height to be the sintering metal filter element filtering assembly of 400mm, sets when each filter assemblies pressure reduction reaches 0.05MPa and carries out automatic backflushing, and backwash liquid reacts clear liquid after filtering.Arrange at reative cell the fluid redistributor that a group has refrigerating function, redistributor is for being arranged in the middle part of reative cell.
Working solution inlet amount is 0.3m
3/ h, hydrogen feed amount is 5.0Nm
3/ h, reaction temperature 50-55 DEG C, reaction pressure 0.25-0.50MPa.
Filter assemblies life cycle is 60 hours, each backwashing time 40 seconds.
Hydrogenation efficiency reaches 15-16g/L hydride.
Claims (8)
1. a paste state bed reactor, is characterized in that: comprise tedge (1), expanding reach (2), cooler (5), catalyst settler (3), filter (4); Tedge top is connected to expanding reach (2), and tedge part extend into expanding reach (2), the tedge in expanding reach is provided with slurries return port (19), communicates with reative cell (8); Be connected with cooler (5) bottom tedge, cooler (5) and tedge (1) are integral types; Expanding reach top is gas-liquid separation chamber (9), top is provided with reaction gas outlet (10), expanding reach middle and lower part is the pre-decanting zone of catalyst, baffle plate (20) is provided with in the pre-decanting zone of catalyst, isolated area is formed between baffle plate and expanding reach cylindrical shell, isolated area bottom is unlimited, and upper guard-plate is provided with perforate (23), and expanding reach baffle plate isolated area is connected by tangential feed pipe (21) with catalyst settler (3); Catalyst settler top is provided with barrier (22), catalyst settler top is connected with gas-liquid separation chamber (9) by balance pipe, bottom is connected with cooler (5), and barrier top is overflow area, and overflow area is connected with filter (4) by overflow line (24); Be provided with filter assemblies (18) in filter, filter top is connected with gas-liquid separation chamber by balance pipe, and filter bottom is connected with cooler (5), and filter is provided with backwash facility; Tedge bottom is provided with liquid phase feed entrance (13) and gas phase feed(raw material)inlet (14); Tedge inside is reative cell (8), is provided with liquid feed distributor (6) and gas feed distributor (7) bottom reative cell.
2. paste state bed reactor according to claim 1, is characterized in that: be provided with the fluid redistributor (25) with refrigerating function in reative cell.
3. paste state bed reactor according to claim 1, is characterized in that: tedge ratio of height to diameter is 4/1 ~ 20/1.
4. paste state bed reactor according to claim 1, is characterized in that: the cylindrical shell shell footpath of expanding reach is 1.2/1 ~ 2/1 with rising shell footpath ratio.
5. paste state bed reactor according to claim 1, is characterized in that: the cylindrical shell ratio of height to diameter 0.5/1 ~ 4/1 of expanding reach.
6. paste state bed reactor according to claim 1, is characterized in that: the aspect ratio of height and expanding reach cylindrical shell that tedge stretches out expanding reach is 0.3 ~ 0.6.
7. paste state bed reactor according to claim 1, is characterized in that: filter assemblies is two or more sets.
8. paste state bed reactor according to claim 1, is characterized in that: cooler is ripple tube cooler.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201520658989.5U CN204933427U (en) | 2015-08-28 | 2015-08-28 | Paste state bed reactor |
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|---|---|---|---|
| CN201520658989.5U CN204933427U (en) | 2015-08-28 | 2015-08-28 | Paste state bed reactor |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105056845A (en) * | 2015-08-28 | 2015-11-18 | 湖南百利工程科技股份有限公司 | Slurry bed reactor and application of slurry bed reactor in producing hydrogen peroxide |
| CN111036149A (en) * | 2019-12-02 | 2020-04-21 | 河南金鹏化工有限公司 | Water-washing continuous production process and device for thiodicarb |
-
2015
- 2015-08-28 CN CN201520658989.5U patent/CN204933427U/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105056845A (en) * | 2015-08-28 | 2015-11-18 | 湖南百利工程科技股份有限公司 | Slurry bed reactor and application of slurry bed reactor in producing hydrogen peroxide |
| CN111036149A (en) * | 2019-12-02 | 2020-04-21 | 河南金鹏化工有限公司 | Water-washing continuous production process and device for thiodicarb |
| CN111036149B (en) * | 2019-12-02 | 2023-06-23 | 河南金鹏化工有限公司 | Thiodicarb water washing continuous production process and device |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160106 Termination date: 20180828 |
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