Fluidized bed reactor and arsenic compound adsorption system comprising same

Abstract

The invention provides a fluidized bed reactor and a system comprising the same for adsorbing arsenic compounds, the fluidized bed reactor comprises: a reactor main body provided with a gas material inlet, a gas material outlet, a purge gas inlet and a nozzle; the baffles comprise at least one upper baffle and at least one lower baffle, the upper baffles are arranged at the top of the reactor main body, and the lower baffles are arranged at the bottom of the reactor main body; and the at least one resistor is arranged on the baffle plate. The baffle plate and the resistor are arranged in the fluidized bed reactor, and gas raw materials can be dispersed into micron-sized small bubbles to fill the reactor under the action of micro-current, so that the gas-liquid-solid three-phase contact area is increased, the retention time of the bubbles in the reactor is prolonged, the mass transfer in the reaction is enhanced, and the adsorption efficiency is improved.

Description

Technical Field

[0001] The invention relates to the technical field of fluidized reaction and adsorption, in particular to a fluidized bed reactor and a system for adsorbing arsenic compounds comprising the fluidized bed reactor. Background Art

[0002] As one of the important basic organic chemical raw materials in industry, butyl octanol is an important raw material for synthesizing fine chemical products, and is mainly used to produce plasticizers, solvents, dehydrating agents, defoamers, dispersants, flotation agents, petroleum additives and synthetic fragrances. At present, the butyl octanol carbonyl synthesis process is widely used in China, with propylene, synthesis gas and hydrogen as raw materials, and triphenylphosphine complex rhodium as catalyst. Among them, propylene and synthesis gas often contain impurities such as H2O, S, O2, As and alkynes. Among these impurities, the presence of arsenic compounds, especially arsenic compounds, is likely to reduce the activity of the catalyst, and even poisoning and lose activity, affecting the normal production of the device. Arsenic compounds mainly exist in the form of gaseous arsenic oxide (As2O5) and arsenic hydride (AsH3). If the untreated arsenic-containing waste gas is diffused into the atmosphere, it will pollute the air, rivers, lakes and soil, and endanger human health. Therefore, in order to extend the life of the triphenylphosphine complex rhodium catalyst, improve the use efficiency of the catalyst, and reduce and eliminate the emission of arsenic-containing waste gas, effective treatment means are required.

[0003] In addition, in order to prevent the accumulation of inert components such as propane in the reaction system of the low-pressure carbonyl synthesis technology of butanol and to keep the system pressure constant, a part of the gas needs to be continuously discharged from the circulation loop of the system. The gas composition mainly includes CH4, C3H6, C3H8, C4H 80 (mixed butyraldehyde), H2, N2, H2S, CO, CO2, As2O5 and AsH3, among which C3H6 and C3H8 account for 30-40 mol%, a set of 2.5×10 5 The emission of off-gas from a 1,200 kg / h butyl octanol plant is about 1,200 kg / h. If the propylene and propane in these tail gases are not recovered, they will be burned as fuel, wasting a large amount of valuable resources and polluting the environment. In addition, under this synthesis method, arsenic-containing gas is often present in the waste gas. If the arsenic-containing gas flow is directly introduced into the atmosphere, it will cause greater pollution to the environment and is not suitable for subsequent recycling.

[0004] Therefore, a method for absorbing arsenide in 1,2-butanol synthesis gas is developed so that arsenide in each section of the material can be collected in time for detection, and the process method and process parameters can be adjusted in time according to the results to purify the raw materials, avoid or reduce the deactivation of the catalyst, extend the service life of the catalyst, and reduce economic losses.

[0005] Since arsenic has strong reducibility, the early removal of arsenic hydrogen generally adopts chemical absorption method, using strong oxidizing aqueous solution to react with arsenic to convert it into trivalent arsenic or pentavalent arsenic. At present, the research and application of purifying arsenic oxide and arsenic hydride by adsorbent is the most extensive. Single metal, metal oxide, composite metal oxide or sulfide is loaded on activated carbon, alumina and molecular sieve and modified, and combined with chemical adsorption, catalytic oxidation and other methods to remove arsenic oxide and arsenic hydride. Among them, the modified adsorbent is simple to prepare, has strong selective adsorption and no secondary pollution, and has gradually been widely used. As a carrier of adsorbent, activated carbon has the advantages of low cost, wide source, acid and alkali resistance, good adsorption performance, large specific surface area and non-toxicity, and is widely used in various adsorption fields. Physical activation method, chemical physics method, catalytic activation method and template method are all commonly used methods for preparing modified activated carbon adsorbents. At present, single metal compounds or bimetallic oxides such as copper, lead, zinc and palladium are mainly loaded as adsorbents.

[0006] At present, the designs of devices used for reaction absorption are diverse, and the effects are also different. Usually, a fluidized bed is a reactor that uses gas or liquid to pass through a granular solid layer to put solid particles in a suspended motion state and carry out a gas-solid phase reaction process or a liquid-solid phase reaction process. It has high heat transfer efficiency, and the temperature in the bed is easy to maintain uniformity. A large number of solid particles can be easily transported back and forth. Because the particles are fine, the internal diffusion resistance can be eliminated, and the efficiency of catalysts, adsorbents, etc. can be fully utilized. Common types of fluidized beds include dispersed fluidized beds, bubbling beds, turbulent beds, and fast fluidized beds.

[0007] CN202021429752 discloses an adsorption fluidized bed reaction device, which is provided with an air inlet, an air outlet, a feed port and a discharge port which are in communication with the inside thereof, wherein the air inlet and the discharge port are arranged at the lower part of the adsorption fluidized bed reaction device, and the air outlet and the feed port are arranged at the upper part of the adsorption fluidized bed reaction device; a multi-layer fluidized bed is arranged from top to bottom inside the adsorption fluidized bed reaction device, and the multi-layer fluidized bed is provided with a fluidized area and a storage area which are interconnected, and the fluidized area of ​​the multi-layer fluidized bed is arranged in a stacked and separated manner, wherein the fluidized plate is one or more of a perforated plate, a screen, and a sintered porous plate. The adsorption fluidized bed reaction device is also provided with a timing controller for controlling the timing feeding of the feeder; the air outlet is provided with a concentration sensor; the air inlet extends to the inside of the adsorption fluidized bed reaction device and faces the bottom of the adsorption fluidized bed reaction device; a diffuser plate is provided in the air inlet.

[0008] CN104759204B relates to a flue gas circulating fluidized bed combined mercury and arsenic removal device, comprising an economizer (1), a selective catalytic reduction denitrification device (24), an air preheater (25), a fluidized bed reactor (14), a bag filter (16), a desulfurization tower (22) and a chimney (23) which are sequentially connected via a flue gas pipeline, wherein a shunt flue gas pipeline and a main flue gas pipeline are arranged in parallel between the economizer (1) and the fluidized bed reactor (14), the main flue gas pipeline is connected to the bottom port of the fluidized bed reactor (14), and the selective catalytic reduction denitrification device (24) is connected to the air preheater (25), a fluidized bed reactor (14), a bag filter (16), a desulfurization tower (22) and a chimney (23). The reduction denitration device (24) and the air preheater (25) are arranged in the main flue gas duct in sequence in accordance with the flue gas flow direction; the split flue gas duct is provided with a hydrogen bromide solution addition branch and an adsorbent addition branch in sequence from the economizer to the fluidized bed reactor, and the end of the split flue gas duct is connected to the lower part of the fluidized bed reactor through a flue gas nozzle (15), and the flue gas nozzle (15) is located above the bottom port of the fluidized bed reactor; an adsorbent recovery mechanism is provided below the bag filter (16), the feed inlet is connected to the bag filter, and the recovery port is connected to the fluidized bed reactor.

[0009] It can be seen from this that the existing fluidized bed reactor adsorption technology has a problem that after the reaction gas enters the reaction chamber, it is unevenly distributed in the reaction chamber and the contact with the solid phase reactants is insufficient, that is, the fluidized adsorption reaction is not carried out sufficiently, resulting in a reduced adsorption effect of the reactants, which seriously affects the adsorption effect. Summary of the invention

[0010] The main purpose of the present invention is to provide a fluidized bed reactor and a system for adsorbing arsenic compounds containing the same, so as to overcome the defects of the prior art such as insufficient contact between gas raw materials and solid raw materials and poor adsorption effect of reactants.

[0011] In order to achieve the above object, the present invention provides a fluidized bed reactor, comprising:

[0012] The reactor body is provided with a gas material inlet, a gas material outlet, a purge gas inlet and a nozzle, wherein the nozzle is arranged at the top of the reactor body;

[0013] baffles, including at least one upper baffle and at least one lower baffle, wherein the upper baffle is disposed on the top of the reactor body, and the lower baffle is disposed on the bottom of the reactor body;

[0014] At least one resistor is disposed on the baffle.

[0015] The fluidized bed reactor described in the present invention is characterized in that the upper baffle is vertically arranged at the top of the reactor body, and there is a distance between the upper baffle and the bottom of the reactor body; the lower baffle is vertically arranged at the bottom of the reactor body, and there is a distance between the lower baffle and the top of the reactor body.

[0016] The fluidized bed reactor described in the present invention, wherein the baffles include a plurality of upper baffles and a plurality of lower baffles, and the upper baffles and the lower baffles are alternately arranged; and / or the baffles are parallel to each other; and / or the length of the upper baffles is greater than or equal to 1 / 2 of the longitudinal length of the reactor body, and the length of the lower baffles is greater than or equal to 1 / 2 of the longitudinal length of the reactor body.

[0017] In the fluidized bed reactor of the present invention, the resistor is disposed on the upper baffle plate, and / or each upper baffle plate is provided with one resistor.

[0018] A heating device is arranged on the lower baffle.

[0019] The fluidized bed reactor described in the present invention, wherein the reactor body is also provided with a sprayer, which is arranged at the top of the reactor body; the gas material inlet is arranged at the upper part of the reactor body, the gas material outlet is arranged at the lower part of the reactor body, and the purge gas inlet is arranged at the bottom of the reactor body.

[0020] In order to achieve the above object, the present invention also provides a system for adsorbing arsenic compounds, comprising:

[0021] The fluidized bed reactor described above;

[0022] an acid washing reactor, connected to the gas material outlet of the fluidized bed reactor;

[0023] A gas collecting device is connected to the pickling reactor.

[0024] The system for adsorbing arsenic compounds of the present invention further comprises a material buffer device connected to the fluidized bed reactor to transport the gas to be adsorbed to the fluidized bed reactor.

[0025] The system for adsorbing arsenic compounds described in the present invention, wherein the gas collecting device includes an inlet, which is connected to the pickling reactor; the gas collecting device includes a first outlet, a second outlet and a third outlet, the first outlet is connected to the material buffer device, the second outlet is connected to the subsequent reaction unit, and the third outlet is connected to the combustion unit.

[0026] In the system for adsorbing arsenic compounds of the present invention, a heat exchange device is provided in the gas collecting device to perform heat exchange on the gas in the gas collecting device.

[0027] Beneficial effects of the present invention:

[0028] (1) The present invention uses a fluidized bed as a reactor, which has high heat transfer efficiency, uniform temperature in the bed, and solid particles can be circulated and transported internally. The fluidization effect can eliminate internal diffusion resistance and fully exert the adsorption efficiency of the adsorbent.

[0029] (2) The fluidized bed reactor of the present invention is provided with baffles and resistors, which can disperse the gas raw materials into micron-sized bubbles through the action of microcurrent to fill the reactor, thereby increasing the gas-liquid-solid three-phase contact area and prolonging the residence time of the bubbles in the reactor, thereby strengthening the mass transfer in the reaction and improving the adsorption efficiency.

[0030] (3) The fluidized bed of the present invention is provided with a sprayer and has an online backwashing function, which can realize online elution, drying and regeneration of the adsorbent, with a elution rate of more than 98%, saving production costs and being safe and environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 FIG. 1 is a schematic diagram of a system for adsorbing arsenic compounds according to an embodiment of the present invention.

[0032] Wherein, the reference numerals are:

[0033] 1 Material buffer device

[0034] 2 Fluidized bed reactor

[0035] 3 Pickling reactor

[0036] 4 Gas collecting device

[0037] 5 Baffle

[0038] 6 Resistors

[0039] 7 Gas Disperser

[0040] 8 Heat exchanger

[0041] 9 Sprinkler

[0042] 10 Spray liquid inlet

[0043] 11 Material inlet

[0044] 12 Sample collection port

[0045] 13 Purge gas inlet

[0046] 14 Gas material outlet

[0047] 15 Acid addition port

[0048] 16 Sample collection port

[0049] 17 Acid Drain

[0050] 18 Make-up gas inlet

[0051] 19 Entrance

[0052] 20 Make-up gas inlet

[0053] 21 Nozzle

[0054] 22 Discharge port

[0055] 23 Exit 1

[0056] 24 feeding ports

[0057] 25 Second Exit

[0058] 26 Exit 3 DETAILED DESCRIPTION

[0059] The technical scheme of the present invention is described in detail below. The following implementation modes are implemented on the premise of the technical scheme of the present invention, and a detailed implementation process is given. However, the protection scope of the present invention is not limited to the following implementation modes. The structures or experimental methods of specific conditions are not specified in the following implementation modes, and generally conventional conditions are followed.

[0060] The present invention provides a fluidized bed reactor for adsorbing arsenic compounds in a mixed gas, such as arsenic oxide, arsenic hydride, etc. More specifically, the fluidized bed reactor of the present invention is used for adsorbing and removing arsenic compounds in octanol synthesis gas and arsenic compounds in the exhaust gas of octanol low-pressure carbonyl synthesis.

[0061] like Figure 1 As shown, the fluidized bed reactor 2 of the present invention includes a reactor body, a baffle 5 and at least one resistor 6.

[0062] The present invention does not impose any particular limitation on the shape of the reactor body, for example, it may be a cylindrical or rectangular structure. Furthermore, the bottom of the reactor body may be configured to resemble an inverted cone or an inverted square pyramid, and the top of the reactor body may be configured to resemble an arc, a trapezoid, etc., which are not particularly limited by the present invention.

[0063] The reactor body is provided with a gas material inlet 11, a gas material outlet 14 and a purge gas inlet 13. The gas material inlet 11 is used for the arsenic compound-containing gas to enter the fluidized bed reactor 2, and the gas material inlet 11 is, for example, arranged at the upper part of the reactor body; the gas material outlet 14 is used for the adsorbed gas to flow out of the fluidized bed reactor 2, and the gas material outlet 14 is, for example, arranged at the upper part of the reactor body. The purge gas inlet 13 is used for the purge gas to enter the fluidized bed reactor 2, and the purge gas inlet 13 is, for example, arranged at the bottom of the reactor body. In the present invention, being arranged at the top generally refers to being arranged on the top surface of the device; being arranged at the bottom generally refers to being arranged on the bottom surface of the device; the upper part includes not only the top surface, but also the part of the side surface of the device close to the top surface; the lower part includes not only the bottom surface, but also the part of the side surface of the device close to the bottom surface.

[0064] In one embodiment, a gas disperser 7 is further provided in the fluidized bed reactor 2 of the present invention. Specifically, the gas disperser 7 is provided at the bottom of the fluidized bed reactor body, and more specifically, the gas disperser 7 is provided near the purge gas inlet 13. The purge gas enters the gas disperser 7 through the purge gas inlet 13. The gas disperser 7 is provided with micropores, and the diameter of the micropores is 1 μm to 10 mm, which can make the gas dispersed evenly and effectively, and sprayed out through the disperser micropores to form micro bubbles, which are evenly diffused to the fluidized bed reactor, increase the contact area between the purge gas and the adsorbent, and improve the purge efficiency.

[0065] In one embodiment, the reactor body of the present invention is further provided with a spray liquid inlet 10 and a sprayer 9, the spray liquid inlet 10 is, for example, provided at the top of the reactor body, the sprayer 9 is provided in the fluidized bed reactor 2 and located at the top of the reactor body, and the sprayer 9 is communicated with the spray liquid inlet 10, so that the spray liquid can enter the sprayer 9 through the spray liquid inlet 10, and then spray into the fluidized bed reactor 2. The present invention can elute the adsorbent by spraying the spray liquid, realize online elution, drying, and regeneration of the adsorbent, save production costs, and be safe and environmentally friendly.

[0066] In one embodiment, the reactor body of the present invention is further provided with a nozzle 21, which is located in the fluidized bed reactor 2 and at the top of the reactor body, and is used to add liquid materials, such as acid liquid for adsorption mixed with the adsorbent and acid liquid for adsorbent regeneration. In another embodiment, the nozzle 21 is located on the top surface of the reactor body, the top surface is a plane, and the angle between the nozzle 21 and the top surface is 45° to 90°, preferably 60° to 90°.

[0067] In one embodiment, a sample collection port 12 is further provided at the bottom of the reactor body of the present invention for collecting adsorbent to measure the arsenic content in the adsorbent, that is, the adsorption amount of arsenic.

[0068] In the present invention, the baffle 5 is arranged in the fluidized bed reactor 2, including at least one upper baffle and at least one lower baffle, the upper baffle is arranged at the top of the reactor body, and the lower baffle is arranged at the bottom of the reactor body. The present invention does not specifically limit the number of upper baffles and lower baffles, for example, the number of upper baffles is 2, 3, 4, 5, and the number of lower baffles is 1, 2, 3, 4. The present invention does not specifically limit the structure of the upper baffle and the lower baffle, and the upper baffle and the lower baffle are, for example, plate-like structures. The plate-like structure side of the upper baffle is connected to the top of the reactor body, and can also be an integral design, that is, the upper baffle is vertically arranged at the top of the reactor body; the plate-like structure side of the lower baffle is connected to the bottom of the reactor body, and can also be an integral design, that is, the lower baffle is vertically arranged at the bottom of the reactor body.

[0069] The vertical length of the baffle of the present invention is smaller than the height of the fluidized bed reactor 2, that is, there is a distance between the upper baffle and the bottom of the reactor body, and there is a distance between the lower baffle and the top of the reactor body. The present invention does not specifically limit this distance and can be adjusted as needed.

[0070] The baffles 5 of the present invention include a plurality of upper baffles and a plurality of lower baffles, and the upper baffles and the lower baffles are arranged alternately. In one embodiment, the baffles 5 of the present invention are arranged in parallel, and the distances between the baffles 5 are equal. In another embodiment, the length of the upper baffle of the present invention is greater than or equal to 1 / 2 of the longitudinal length of the reactor body, and the length of the lower baffle is greater than or equal to 1 / 2 of the longitudinal length of the reactor body, so that the flow can be better guided and the residence time of the gas in the reactor can be increased.

[0071] The fluidized bed reactor 2 of the present invention is also provided with at least one resistor 6, which is located on the baffle 5. In one embodiment, the resistor 6 of the present invention is only located on the upper baffle. In another embodiment, each upper baffle is provided with a resistor. The resistor is connected to a power supply. In this way, when the resistor is heated, the resistor can release a microcurrent, which can disperse the gas raw material into micron-sized small bubbles that fill the reactor, increase the gas-liquid-solid three-phase contact area, and prolong the residence time of the bubbles in the reactor, thereby strengthening the mass transfer in the reaction and improving the adsorption efficiency.

[0072] The present invention does not specifically limit the resistor 6. In one embodiment, the microcurrent formed on the resistor 6 is 1 to 50 mA / m 2 .

[0073] In one embodiment, a heating device is installed on the lower baffle of the present invention for drying and regenerating the adsorbent, and the heating temperature is set to 100°C to 500°C.

[0074] The fluidized bed reactor 2 of the present invention is filled with adsorbent, more specifically, may be filled with a multi-layer modified adsorption material bed, and the top of the reactor body is, for example, detachable, so that it can be used for filling and replacing the adsorbent.

[0075] The present invention does not particularly limit the adsorbent. In a preferred embodiment, the preparation method of the adsorbent of the present invention comprises:

[0076] The adsorbent carrier is soaked and washed with deionized water to remove floating dust and other impurities, and then dried at low temperature to remove the adsorbed water on the surface of the carrier to form particles. The weighed modifier is added to the pretreated adsorbent carrier to obtain the adsorbent under certain conditions.

[0077] In one embodiment, the adsorbent carrier is mainly selected from activated carbon, activated alumina, etc., and the molecular sieve can be zeolite and commercial molecular sieve.

[0078] The modifiers are mainly copper-based, lead-based, zinc-based, palladium-based, single metal compounds, bimetallic oxides or polymetallic oxides.

[0079] In one embodiment, the filling ratio of the filler, that is, the ratio of the space occupied by the filler, is 0.6 to 0.9 in consideration of the filler flow and the total container volume inside the fluidized bed reactor 2 of the present invention to achieve the best mixing effect.

[0080] In one embodiment, the liquid material that enters the fluidized bed reactor 2 through the nozzle 9 and acts with the adsorbent to adsorb arsenic compounds is a weak acid solution. The weak acid solution can be hydrochloric acid or nitric acid with a mass concentration of 0.01% to 0.5%.

[0081] In one embodiment, the flow rate of the gas material entering the material inlet 11 of the fluidized bed reactor 2 of the present invention is 0.5m 3 / s~1.5m 3 / s, preferably 1.0m 3 / s~1.5m 3 / s, the residence time of the gas material in the fluidized bed reactor 2 is 30s-200s, preferably 30s-160s, and the adsorption reaction temperature is 30°C-85°C, preferably 30°C-70°C.

[0082] The present invention also provides a system for adsorbing arsenic compounds, which includes, in addition to the above-mentioned fluidized bed reactor 2, a pickling reactor 3 and a gas collecting device 4.

[0083] The structure of the fluidized bed reactor 2 has been described in detail above and will not be repeated here.

[0084] The acid washing reactor 3 is connected to the gas material outlet 14 of the fluidized bed reactor 2 so as to transport the gas material preliminarily dearsenified to the acid washing reactor 3 for further dearsenification treatment.

[0085] The present invention does not particularly limit the shape of the pickling reactor 3. In one embodiment, the pickling reactor 3 is a columnar structure. The pickling reactor 3 is provided with a feed port 24, a discharge port 22, an acid solution addition port 15, a sample collection port 16, an acid solution discharge port 17, and a supplementary gas inlet 18. The feed port 24 is connected to the gas material outlet 14 of the fluidized bed reactor 2. The sample collection port 16 is used to collect the strong oxidant solution in the pickling reactor 3 to determine the arsenic content in the strong oxidant solution, that is, the amount of arsenic adsorption. The acid solution addition port 15 is used to add a strong oxidant solution to the pickling reactor 3, the acid solution discharge port 17 is used to discharge the strong oxidant solution after arsenic adsorption from the pickling reactor 3, and the supplementary gas inlet 18 is used to pass the waste gas discharged from other sections of the device, abnormal conditions, or other device waste gas into the pickling reactor 3 for centralized treatment.

[0086] In one embodiment of the present invention, the strong oxidant solution in the pickling reactor 3 can be a combination of one or more of a permanganate solution, a dichromate solution, and a hypochlorite solution with a hydrogen peroxide solution. The strong oxidant solution system can be acidic, neutral or alkaline, with a concentration of 0.001mol / L to 0.2mol / L in an acidic system, 0.001mol / L to 0.2mol / L in a neutral system, and 0.001mol / L to 0.2mol / L under alkaline conditions, wherein the oxidant solution system refers to a permanganate solution, a dichromate solution, and a hypochlorite solution. The mass concentration of the hydrogen peroxide solution is 1% to 30%.

[0087] The gas collecting device 4 of the present invention is connected to the pickling reactor 3. In one embodiment, the gas collecting device 4 is provided with an inlet 19, a first outlet 23, a second outlet 25, a third outlet 26 and a supplementary gas inlet 20. The inlet 19 is connected to the discharge port 22 of the pickling reactor 3 to transport the gas material after adsorption and arsenic removal to the gas collecting device 4. The gas entering the gas collecting device 4 through the supplementary gas inlet 20 can be arsenic-free synthetic gas from other devices, so that the gas can be collected and centrally processed.

[0088] In one embodiment, a heat exchanger 8 is provided in the gas collecting device 4 of the present invention, for performing heat exchange treatment on the gas material entering the gas collecting device 4 after arsenic removal by adsorption.

[0089] In one embodiment, the system for adsorbing arsenic compounds of the present invention further comprises a material buffer device 1, which is connected to a material inlet 11 of a fluidized bed reactor 2. Arsenic compound-containing gas is first input into the material buffer device 1 and then enters the fluidized bed reactor 2 for adsorption and arsenic removal.

[0090] In another embodiment, the first outlet 23 of the gas collecting device 4 is connected to the material buffer device 1 to circulate the gas material after heat exchange of the gas collecting device 4 back to the material buffer device 1. The second outlet 25 of the gas collecting device 4 can be connected to the subsequent reaction unit to transport the dearsenicized gas to the subsequent reaction unit; the third outlet 26 can be connected to the combustion unit to burn part of the exhaust gas.

[0091] In one embodiment, in a system for adsorbing arsenic compounds, control valves are provided at the material inlets and outlets of the material buffer device 1, the fluidized bed reactor 2, the pickling reactor 3 and the gas collecting device 4 to control the opening and closing of each inlet and outlet.

[0092] The system for adsorbing arsenic compounds of the present invention can adsorb arsenide in butyl octanol synthesis gas online, and solve the problem of arsenide pollution from synthesis gas and exhaust gas in butyl octanol workshop. The present invention effectively collects arsenide and performs analysis and detection by using micro-current internal circulation multi-electrode plate fluidized bed adsorption and chemical adsorption double combination absorption, and timely monitors the emission of arsenide at the production site. The method has a fast absorption speed and complete absorption, realizes the rapid monitoring of arsenide collection on site and analysis and detection, timely guides production, and ensures the smooth operation of the butyl octanol production process, etc., which plays an important role.

[0093] The fluidized bed reactor of the present invention enhances the mass transfer capacity through intermittent transmission of micro-current, the phase content and the circulation amount of solid particles can be controlled separately, the solution is fully oxygenated, the hydraulic retention time is shortened, and the adsorption effect is improved. At the same time, it also has an online backwashing function, and can realize the elution, drying and regeneration of the adsorbent online, with a elution rate of more than 98%, saving production costs, and being safe and environmentally friendly.

[0094] The following is an explanation of the operating method of the system for adsorbing arsenic compounds in one embodiment of the present invention. The present invention is not limited to the specific parameter values ​​involved in the following operating method. First, the preparation of the adsorbent in the fluidized bed reactor 2, weigh 500g of activated carbon and place it in an oven at 80°C for 3h. Weigh 24.0g of copper nitrate, add 2L of deionized water, put it in a beaker and stir it at room temperature to dissolve, add the prepared copper nitrate solution to the pretreated activated carbon, keep the speed at 220rpm, stir at room temperature for 24h, put it in an oven at 150°C for drying, and after the sample is cooled to room temperature, copper nitrate-modified activated carbon is obtained and placed in a fluidized bed reactor 2. Preparation of the pickling solution, take 15g of potassium permanganate powder and dissolve it in 3L 1mol / L H2SO4 and 50mL 30wt% H2O2 mixed solution, and place it in the pickling reactor 3.

[0095] First, dilute nitric acid with a mass concentration of 0.01% is sprayed into the reactor 2 through the sprayer 9. After the liquid material is fully mixed with the adsorbent in the reactor, the power supply of the resistor 6 is turned on to release a microcurrent, and then the arsenic compound gas is transported to the material buffer device 1, and then enters the fluidized bed reactor 2 through the material inlet 11. The microcurrent can disperse the gas raw material into micron-sized small bubbles that fill the reactor, increasing the gas-liquid-solid three-phase contact area. The flow rate of the arsenic compound gas is 1.2m / s, and it stays in the fluidized bed reactor 2 for 60S. After the arsenic compound gas fully reacts with the adsorbent, it enters the pickling reactor 3 for secondary arsenic removal. In the pickling reactor 3, the arsenic compound gas fully reacts with the pickling liquid to remove the arsenic compound. The gas after arsenic removal enters the gas collecting device 4 through the discharge port 22. After the gas collected by the gas collecting device 4 is cooled by the heat exchanger 8, part of the gas enters the subsequent reaction unit, part of the gas is discharged by combustion, and part of the gas is returned to the material buffer tank 1, and the arsenic removal treatment is circulated.

[0096] Among them, the arsenic-containing gas in the buffer device 1 is measured by silver diethyldithiocarbamate spectrophotometry, wherein the mass concentration of arsenic and its compounds is 482.41 μg / L; 5 g of adsorbent in the fluidized bed reactor 2 is collected through the sample collection port 12, dissolved with 5 wt% hydrochloric acid, and the arsenic content in the acid solution is determined by atomic fluorescence hydride generation after constant volume, and the arsenic determination result is 359.44 μg / L; 10 mL of pickling liquid in the pickling reactor 3 is collected through the sample collection port 16, treated with 5 wt% hydrochloric acid, and the arsenic content in the absorption liquid is determined by atomic fluorescence hydride generation, and the arsenic determination result is 120.56 μg / L. It can be seen that the total arsenic content in the recovered synthesis gas is 480.0 μg / L. The total arsenic recovery rate is 99.50%.

[0097] The present invention also provides an operating method of a system for adsorbing arsenic compounds in another embodiment:

[0098] First, the adsorbent in fluidized bed reactor 2 was prepared by weighing 500g of activated carbon and drying it in an oven at 80°C for 3h. Weigh 26.0g of copper chloride, add 2L of deionized water, put it in a beaker and stir it at room temperature to dissolve, add the prepared copper chloride solution to the pretreated activated carbon, keep the speed at 200rpm, stir it at room temperature for 24h, put it in an oven and dry it at 150°C, wait for the sample to cool to room temperature to obtain copper chloride-modified activated carbon, and place it in fluidized bed reactor 2. The pickling solution was prepared by taking 15g of potassium permanganate powder and dissolving it in 3L of 1mol / L H2SO4 and 50mL30wt% H2O2 mixed solution, and placing it in the pickling reactor 3.

[0099] First, dilute nitric acid with a mass concentration of 0.01% is sprayed into the reactor 2 through the sprayer 9. After the liquid material is fully mixed with the adsorbent in the reactor, the power supply of the resistor 6 is turned on to release a microcurrent, and then the arsenic compound gas is transported to the material buffer device 1, and then enters the fluidized bed reactor 2 through the material inlet 11. The microcurrent can disperse the gas raw material into micron-sized small bubbles that fill the reactor, increasing the gas-liquid-solid three-phase contact area. The flow rate of the arsenic compound gas is 1.2m / s, and it stays in the fluidized bed reactor 2 for 60S. After the arsenic compound gas fully reacts with the adsorbent, it enters the pickling reactor 3 for secondary arsenic removal. In the pickling reactor 3, the arsenic compound gas fully reacts with the pickling liquid to remove the arsenic compound. The gas after arsenic removal enters the gas collecting device 4 through the discharge port 22, and the excess gas collected by the gas collecting device 4 is cooled by the heat exchanger 8 and returned to the material buffer tank 1 for arsenic removal treatment.

[0100] The arsenic-containing gas in the buffer material was determined by silver diethyldithiocarbamate spectrophotometry, where the mass concentration of arsenic and its compounds was 511.56 μg / L. 5 g of adsorbent in the fluidized bed reactor 2 was collected through the sample collection port 12, dissolved with 5 wt% hydrochloric acid, and the arsenic content in the acid solution was determined by atomic fluorescence hydride generation after constant volume. The arsenic determination result was 381.04 μg / L. 10 mL of pickling solution in the pickling reactor 3 was collected through the sample collection port 16, treated with 5 wt% hydrochloric acid, and the arsenic content in the absorption liquid was determined by atomic fluorescence hydride generation. The arsenic determination result was 128.47 μg / L. It can be seen that the total arsenic content in the recovered synthesis gas is 509.51 μg / L. The total arsenic recovery rate is 99.6%.

[0101] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, technicians familiar with the field may make various corresponding changes and deformations based on the present invention, but these corresponding changes and deformations should all fall within the scope of protection of the claims of the present invention.

Claims

1. A fluidized bed reactor, characterized in that: include: The reactor body is provided with a gas material inlet, a gas material outlet, a purge gas inlet and a nozzle, wherein the nozzle is arranged at the top of the reactor body; baffles, including at least one upper baffle and at least one lower baffle, wherein the upper baffle is disposed on the top of the reactor body, and the lower baffle is disposed on the bottom of the reactor body; At least one resistor is disposed on the baffle.

2. The fluidized bed reactor according to claim 1, characterized in that The upper baffle is vertically arranged at the top of the reactor body, and there is a distance between the upper baffle and the bottom of the reactor body; the lower baffle is vertically arranged at the bottom of the reactor body, and there is a distance between the lower baffle and the top of the reactor body.

3. The fluidized bed reactor according to claim 1, characterized in that: The baffles include a plurality of upper baffles and a plurality of lower baffles, and the upper baffles and the lower baffles are alternately arranged; and / or the baffles are parallel to each other; and / or the length of the upper baffles is greater than or equal to 1 / 2 of the longitudinal length of the reactor body, and the length of the lower baffles is greater than or equal to 1 / 2 of the longitudinal length of the reactor body.

4. The fluidized bed reactor according to claim 1, characterized in that The resistor is disposed on the upper baffle, and / or each upper baffle is provided with a resistor, and / or a heating device is disposed on the lower baffle.

5. The fluidized bed reactor according to claim 1, characterized in that: The reactor body is also provided with a sprayer, which is arranged at the top of the reactor body; the gas material inlet is arranged at the upper part of the reactor body, the gas material outlet is arranged at the lower part of the reactor body, and the purge gas inlet is arranged at the bottom of the reactor body.

6. A system for adsorbing arsenic compounds, characterized in that: include: The fluidized bed reactor according to any one of claims 1 to 5; an acid washing reactor, connected to the gas material outlet of the fluidized bed reactor; A gas collecting device is connected to the pickling reactor.

7. The system for adsorbing arsenic compounds according to claim 6, characterized in that: The invention also comprises a material buffer device which is in communication with the fluidized bed reactor so as to transport the gas to be adsorbed to the fluidized bed reactor.

8. The system for adsorbing arsenic compounds according to claim 7, characterized in that: The gas collecting device includes an inlet, and the inlet is connected to the acid washing reactor.

9. The system for adsorbing arsenic compounds according to claim 6, characterized in that: The gas collecting device comprises a first outlet, a second outlet and a third outlet, the first outlet is communicated with the material buffer device, the second outlet is communicated with the subsequent reaction unit, and the third outlet is communicated with the combustion unit.

10. The system for adsorbing arsenic compounds according to claim 1, characterized in that: A heat exchange device is provided in the gas collecting device to exchange heat for the gas in the gas collecting device.

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