Integrated device for preparing hydrogen sulfide through self-circulation drainage catalytic reduction

Abstract

The utility model relates to an integrated device for preparing hydrogen sulfide through self-circulation drainage catalytic reduction. The integrated device comprises a catalytic reduction section (1), a Venturi jet device and a product gas backflow unit (7), the catalytic reduction section (1) is provided with an SO2 reduction catalyst packing layer, raw material gas is sprayed into the device through a raw material gas inlet at a high speed at a subsonic flow speed, sulfide product gas obtained by catalytic reduction conversion of SO2 is partially refluxed by negative pressure generated under high-speed jet flow and flows out through an outlet (4) of the venturi type jet device, and the tail gas of the venturi type jet device is discharged through an outlet (5) of the venturi type jet device. And the mixed gas is fully mixed with raw material gas and then drained to the bottom of the catalytic reduction section (1), and high-concentration hydrogen sulfide product gas is prepared through efficient reduction conversion of SO2 under the action of a catalyst based on the reverse disproportionation reaction principle of sulfur. Compared with the prior art, operation energy consumption can be reduced, economic and environmental benefits are improved, and good application and popularization prospects are achieved.

Description

TECHNICAL FIELD

[0001] The utility model belongs to the field of environmental protection technology, more particularly to a self-circulation drainage catalytic reduction preparation hydrogen sulfide integrated device. BACKGROUND

[0002] Sulfidation method is a commonly used method for treating heavy metals in waste acid, the main measure is to add sodium sulfide, hydrogen sulfide, ferrous sulfide and other reagents to the acidic arsenic-containing waste liquid, but the addition of sodium sulfide and ferrous sulfide will introduce a large amount of sodium ions and ferrous ions into the solution, affecting the quality of recovered acid liquid and arsenic residue. In the process of treating heavy metals in waste acid by using flue gas sulfur dioxide to reduce H2S, direct arsenic removal by hydrogen sulfide can avoid the introduction of other cations, which is beneficial to the recovery of acid liquid. How to safely and economically produce H2S for the removal of heavy metals in smelting industry has become a research hotspot. Therefore, if a new device can be designed to reasonably use sulfur dioxide and natural gas to produce hydrogen sulfide, it will have good application prospect.

[0003] Patent CN103626134B discloses a hydrogen sulfide generator in hydrogen sulfide production, the hydrogen sulfide generation device in the invention uses sodium sulfide as raw material to produce hydrogen sulfide; patent CN212102450U discloses a microbial hydrogen sulfide generator for waste acid sulfidation precipitation, the hydrogen sulfide generation device in the invention uses microbial sulfate reduction method to produce hydrogen sulfide, but the above two devices cannot be heated, do not have a self-circulation system and also do not have a matched jet device. Patent CN110479026B discloses a method and system for in-situ preparation of hydrogen sulfide for treating arsenic-containing wastewater, the hydrogen sulfide production system in the invention uses activated carbon bed to absorb sulfur dioxide and then heats and leaches to collect the generated hydrogen sulfide, but the invention does not have a self-circulation system and a matched jet device, therefore, there are problems of low conversion efficiency, unstable operation, etc. UTILITY MODEL CONTENTS

[0004] The utility model aims at overcoming the defects of the prior art and provides a self-circulation drainage catalytic reduction preparation hydrogen sulfide integrated device, which has simple structure and does not produce waste liquid, and has high hydrogen sulfide preparation efficiency and stable and reliable operation.

[0005] The utility model discloses a purpose can be realized through following technical scheme: a kind of integrated device of self-circulation drainage catalytic reduction preparation hydrogen sulfide, including catalytic reduction section, venturi injection device and product gas backflow unit;The catalytic reduction section is equipped with SO2 reduction catalyst packing layer, and the product gas backflow unit is arranged in packing layer, and its bottom is communicated venturi injection device, and top is worn out catalytic reduction section, and is arranged sulfide product gas backflow port, and venturi injection backflow device side is communicated raw material gas inlet, and bottom is set venturi injection device outlet, and raw material gas is injected into device at subsonic speed high speed through raw material gas inlet, and the negative pressure generated under high-speed jet flow carries out partial backflow to sulfide product gas of SO2 catalytic reduction conversion, and flows out by venturi injection device outlet, and then after being mixed with raw material gas sufficiently, it is drained to the bottom of catalytic reduction section, based on the principle of sulfur reverse disproportionation reaction and under the action of catalyst, the efficient reduction conversion of SO2 is carried out to prepare high-concentration hydrogen sulfide product gas, and then can be used in subsequent polluted acid heavy metal purification treatment process.

[0006] Further, the SO2 reduction catalyst filled in the catalytic layer of the catalytic reduction section is commercial active γ-alumina, and the active γ-alumina is modified by hydrothermal, impregnation and other methods, and the modification components used include Ti / Zr, Co / Mo or Ni / Mo active metals, and the filling amount of the packing layer is determined according to the space velocity ratio, and the space velocity ratio is 200-1500 h -1 .

[0007] Further, the venturi injection backflow device is composed of a nozzle, a throat pipe and a diffusion port,

[0008] The nozzle aperture of the venturi injection device is 9-15 mm, the gas flow rate of the nozzle port is 200-300 m / s, reaching the subsonic level; the throat pipe diameter at the nozzle port is 15-20 mm, and the gas flow rate of the throat pipe is 70-100 m / s.

[0009] Further, the venturi injection device has a detachable sealing snap ring fixing module, which can be easily detached and pulled out during maintenance, and the nozzle can be replaced; at the same time, the nozzle can be fixed during operation, and the center of the nozzle and the throat pipe can be kept on the same concentric shaft, so that the venturi effect reaches the best.

[0010] Further, the venturi injection device includes a two-stage venturi injection device and a one-stage venturi injection device arranged vertically;

[0011] The raw material gas inlet comprises a first raw material gas inlet and a second raw material gas inlet, the second Venturi jet device is communicated with the first raw material gas inlet, the first Venturi jet device is communicated with the second raw material gas inlet, the top of the second Venturi jet device is communicated with the product gas backflow unit, and the bottom of the first Venturi jet device is communicated with the Venturi jet device outlet.

[0012] Further, the pressure drop generated by the product gas backflow unit under the jet action of the Venturi jet device is 1000-2500 Pa.

[0013] Further, the backflow ratio of the product gas backflow unit for introducing the reduced product sulfuration gas to the bottom of the catalytic reduction section by self-circulation is 1:10-1:3, that is, 10-33% of the reduced product mixed gas is backflowed, and the backflowed sulfuration gas induces the newly input raw material gas to be subjected to high-efficiency catalytic reduction reaction under the action of the catalyst.

[0014] Further, the raw material gas is a mixed gas of sulfur dioxide and methane gas.

[0015] Further, the packing layer of the catalytic reduction section is 4-6 layers, and the catalytic reduction reaction temperature is 500-700 DEG C.

[0016] Further, the main body material of the catalytic reduction section, the Venturi jet device and the product gas backflow unit is 304H or 310S stainless steel.

[0017] Compared with the prior art, the utility model has the following advantages and beneficial effects:

[0018] 1) the utility model discloses an integrated device, and the shell is a sealed shell, the product outlet is arranged at the top, the raw material gas inlet is arranged at the bottom, the catalytic layer is arranged in the middle of the shell interior, the product gas and the backflow area are arranged at the top of the catalytic layer, the raw material gas and the backflow gas mixing area are arranged at the bottom of the catalytic layer, the Venturi jet backflow device is arranged at the bottom of the catalytic layer, the raw material gas speed introduced by controlling the raw material gas inlet is combined with the Venturi jet backflow device, a powerful negative pressure is formed, the product gas part at the top is returned through the product gas backflow unit, is mixed with the raw material gas, and is sprayed from the bottom Venturi jet device outlet, a self-induction internal circulation process is formed, the sealing property is good, negative pressure production is realized, hydrogen sulfide leakage is prevented, and the safety is higher.

[0019] 2) the device is beneficial to reducing the heat loss through the internal circulation process, thereby reducing the energy consumption in the operation process, the catalyst bed layer stability is good, continuous operation is realized, and the device is beneficial to industrial practical application.

[0020] 3) The overall structure is simple and compact, economical and practical, and the hydrogen sulfide product gas is more conducive to the activation of the reactant material through the internal circulation process, thereby increasing the preparation efficiency of the hydrogen sulfide product gas, and the operation is stable and reliable, and has a good application prospect. Through the self-circulation drainage mode, the efficient reduction conversion of sulfur dioxide is promoted, and the conversion efficiency of SO2 can reach more than 97%, the operation energy consumption is reduced (the existing technology is generally 10 kW / Kg-H2S, and the present application can be reduced to less than 1 kW / Kg-H2S), the operation is stable and reliable (can be continuously operated for more than 2000h), the economic and environmental benefits are improved, and the application and popularization prospect is good.

[0021] 4) The device is used for preparing hydrogen sulfide, and has the advantages of simple method, easy operation, low production cost and suitability for enterprise scale production. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 The figure is a main reaction device structure schematic view of the utility model;

[0023] Marking in the figure:

[0024] 1 - catalytic reduction section, 2 - first raw material gas inlet, 3 - second raw material gas inlet, 4 - venturi type injection device outlet, 5 - first venturi type injection device, 6 - second venturi type injection device, 7 - product gas backflow unit, 8 - sulfide product gas backflow port, 9 - hydrogen sulfide product gas outlet. DETAILED DESCRIPTION

[0025] The utility model will be described in detail below in combination with the drawings and specific embodiments. The embodiment is implemented on the premise of the technical scheme of the utility model, and detailed implementation mode and specific operation process are given, but the protection scope of the utility model is not limited to the following examples.

[0026] It should be noted that: similar labels and letters represent similar items in the following drawings, so once an item is defined in one drawing, it does not need to be further defined and explained in subsequent drawings.

[0027] Some embodiments of the utility model will be described in detail below in combination with the drawings. In the case of no conflict, the following examples and features in the examples can be combined with each other.

[0028] In the following examples, if there is no special description of raw materials or processing technology, it means that they are all conventional commercially available raw materials or conventional processing technology in the art. If there is no special description of functional components or structures, it means that they are all conventional components or conventional structures adopted in the art to realize the corresponding functions.

[0029] As Figure 1As shown, an integrated device for preparing hydrogen sulfide by self-circulation flow catalytic reduction includes a shell, a catalytic reduction section 1, a Venturi injection device and a product gas reflux unit 7. The catalytic reduction section 1 is located at the middle position inside the shell, the top of the catalytic layer thereof is a product gas and reflux zone, and the bottom of the catalytic layer is a raw material gas and reflux gas mixing zone. The catalytic reduction section 1 is provided with a SO2 reduction catalyst packing layer, the product gas reflux unit 7 is arranged in the middle of the packing layer of the catalytic reduction section 1 and penetrates through the packing layer, the bottom thereof is communicated with the Venturi injection device, the top thereof is communicated with a hydrogen sulfide product gas outlet 9 through the catalytic reduction section 1, and a sulfide product gas reflux port 8 is arranged at the top of the product gas reflux unit 7.

[0030] The SO2 reduction catalyst filled in the catalytic layer of the catalytic reduction section (1) is a commercial active γ-alumina or a catalytic material modified by hydrothermal, impregnation or the like method. The modification components used include Ti / Zr, Co / Mo or Ni / Mo active metals. The filling amount of the packing layer is determined according to the space velocity ratio, and the space velocity ratio is 200-1500 h-1. -1 The packing layer of the catalytic reduction section 1 is 4-6 layers, and the catalytic reduction reaction temperature is 500-700℃.

[0031] The Venturi injection reflux device includes a primary Venturi injection device 5 and a secondary Venturi injection device 6, and both of the two-stage Venturi injection devices are composed of a throat pipe and a diffusion port. The secondary Venturi injection device 6 is communicated with the primary raw material gas inlet 2, the primary Venturi injection device 5 is communicated with the secondary raw material gas inlet 3, the secondary Venturi injection device 6 is located above the primary Venturi injection device 5, the top of the secondary Venturi injection device 6 is communicated with the product gas reflux unit 7, and the bottom of the primary Venturi injection device 5 is communicated with the Venturi injection device outlet 4. The nozzle diameter of the Venturi injection device is 9-15 mm, the gas flow rate of the nozzle is 200-300 m / s, reaching the subsonic level; the throat pipe diameter at the nozzle port is 15-20 mm, and the gas flow rate of the throat pipe is 70-100 m / s. The Venturi injection device has a detachable sealing snap ring fixing module, which can be easily detached and pulled out during maintenance to replace the nozzle. At the same time, the nozzle can be fixed during operation and kept on the same concentric shaft as the center of the throat pipe, so that the Venturi effect reaches the best.

[0032] The raw material gas is a mixed gas of sulfur dioxide and methane, and the mixed gas of sulfur dioxide and methane is injected into the reaction device at a subsonic flow rate at a high speed through the first raw material gas inlet 2 and the second raw material gas inlet 3. Under the high-speed jet flow, the negative pressure (the pressure drop is generally 1000-2500 Pa) generated can cause the sulfide product gas converted by the catalytic reduction of SO2 to partially backflow (that is, part of the product gas in the product gas backflow unit 7 at the top of the catalytic layer and in the product gas backflow area returns under the action of the negative pressure), and the backflow ratio is 1:10-1:3, and the backflow is discharged through the venturi injection device outlet 4, and then fully mixed with the raw material gas and introduced into the bottom of the packed layer of the catalytic reduction section 1. Based on the principle of the reverse disproportionation reaction of sulfur and under the action of the catalyst, the efficient reduction conversion of SO2 is carried out to prepare high-concentration hydrogen sulfide product gas, which can be used for subsequent heavy metal purification treatment of waste acid.

[0033] Compared with the prior art, the self-circulation drainage method can promote the efficient reduction conversion of sulfur dioxide, reduce the operation energy consumption, improve the economic and environmental benefits, and has good application and promotion prospect. The following will be described in detail through specific examples. The reduction catalyst used in the following examples is a commercial active alumina ball modified by impregnating cobalt molybdenum sulfide, wherein the active alumina is from Henan Jiezhiyuan Water Purification Material Co., Ltd., model number: JZY-HXYHL01, cobalt disulfide and molybdenum disulfide are dissolved in deionized water to prepare a solution with a concentration of 5%, and the molar ratio of Co and Mo is controlled to be 1:1, mixed, to obtain a mixed solution, then the mixed solution is impregnated on the commercial active alumina ball by the equal-volume impregnation method for 12 h, dried at 100℃ for 1 h, and then calcined at 550℃ for 2 h to obtain the reduction catalyst.

[0034] Example 1:

[0035] The device reliability test produces hydrogen sulfide by using the self-circulation drainage method, wherein the nozzle aperture of the venturi injection backflow device is 9 mm, and the gas flow rate of the nozzle aperture is about 280 m / s. The throat pipe diameter of the lower part of the nozzle aperture of the venturi injection backflow device is 18 mm, and the gas flow rate of the throat pipe is about 80 m / s. The reduction catalyst used is a commercial active alumina ball modified by impregnating cobalt molybdenum sulfide, and the diameter is 3 mm. The reduction zone temperature is 600℃. After operation, the hydrogen sulfide backflow amount is 10% of the output amount, the ratio of the inlet sulfur dioxide to methane is 4:3, and the total gas amount is about 65 m 3 / h. The concentration of the produced hydrogen sulfide is detected to be 45 vol%.

[0036] Example 2:

[0037] The self-circulation and drainage integrated device is used to produce hydrogen sulfide, the designed hydrogen sulfide production is 10kg / h, the catalytic pre-reduction catalyst is cobalt-molybdenum modified commercial active alumina catalyst (diameter 5mm), and the total space velocity is about 510h -1 -1. The inlet SO2 and CH4 ratio is 4:3, and the total gas volume is about 68m 3 / h. The reduction bed layer operating temperature is set to 650℃. The nozzle diameter of the Venturi jet backflow device is 9mm, and the nozzle port jet gas flow rate is about 300m / s. The nozzle port lower throat pipe diameter of the Venturi jet backflow device is 17mm, and the throat pipe gas flow rate is about 83m / s. The detected outlet hydrogen sulfide concentration is 53vol%.

[0038] Example 3:

[0039] The self-circulation and drainage integrated device is used to produce hydrogen sulfide, the designed hydrogen sulfide production is 25kg / h, the catalytic pre-reduction catalyst is nickel-molybdenum modified commercial active alumina catalyst (diameter 4mm), and the total space velocity is 600h -1 , and the inlet SO2 and CH4 ratio is 4:3. The reduction bed layer operating temperature is set to 680℃. The nozzle diameter of the Venturi jet backflow device is 9mm, and the nozzle port jet gas flow rate is about 300m / s. The nozzle port lower throat pipe diameter of the Venturi jet backflow device is 17mm, and the throat pipe gas flow rate is about 83m / s. The detected outlet hydrogen sulfide concentration is 55vol%, and the long-time operation is 2000h, the SO2 conversion efficiency loss is within 3%, and the hydrogen sulfide production operating energy consumption is basically maintained at 0.9-1.0kW / Kg-H2S.

[0040] The above description of the embodiments is for the convenience of the ordinary skilled in the art to understand and use the invention. Those skilled in the art can easily make various modifications to these embodiments, and apply the general principles described herein to other embodiments without creative labor. Therefore, the present application is not limited to the above embodiments, and the improvements and modifications made by those skilled in the art without departing from the scope of the present application should be within the scope of protection of the present application.

Claims

1. An integrated device for preparing hydrogen sulfide by self-circulating drainage catalytic reduction, characterized in that: The invention comprises a catalytic reduction section (1), a venturi-type injection device and a product gas reflux unit (7); the catalytic reduction section (1) is provided with an SO2 reduction catalyst packing layer, the product gas reflux unit (7) is arranged in the packing layer, the bottom of the catalytic reduction section is connected to the venturi-type injection device, the top passes through the catalytic reduction section (1), and a sulfide product gas reflux port (8) is provided, the side of the venturi-type injection reflux device is connected to the raw gas inlet, and the bottom is provided with a venturi-type injection device outlet (4).

2. The integrated device for preparing hydrogen sulfide by self-circulating drainage catalytic reduction according to claim 1, characterized in that: The catalytic layer of the catalytic reduction section (1) is filled with SO2 reduction catalyst, and the filling amount of the packing layer is determined according to the space velocity ratio, and the space velocity ratio is 200-1500h -1 .

3. The integrated device for preparing hydrogen sulfide by self-circulating drainage catalytic reduction according to claim 1, characterized in that: The Venturi-type jet reflux device is composed of a nozzle, a throat and a diffuser. The nozzle diameter of the Venturi injection device is 9-15mm, and the gas flow rate of the nozzle is 200-300m / s, reaching the subsonic level; the throat diameter at the nozzle is 15-20mm, and the gas flow rate of the throat is 70-100m / s.

4. The integrated device for preparing hydrogen sulfide by self-circulating drainage catalytic reduction according to claim 1, characterized in that: The Venturi-type injection device has a detachable sealing clamping ring fixing module, which keeps the nozzle fixed and kept on a concentric axis with the center of the throat.

5. An integrated device for preparing hydrogen sulfide by self-circulating drainage catalytic reduction according to claim 1, 3 or 4, characterized in that: The Venturi-type injection device comprises a secondary Venturi-type injection device (6) and a primary Venturi-type injection device (5) arranged above and below; The raw gas inlet includes a primary raw gas inlet (2) and a secondary raw gas inlet (3); the secondary venturi-type injection device (6) is connected to the primary raw gas inlet (2); the primary venturi-type injection device (5) is connected to the secondary raw gas inlet (3); the top of the secondary venturi-type injection device (6) is connected to the product gas reflux unit (7); and the bottom of the primary venturi-type injection device (5) is connected to the venturi-type injection device outlet (4).

6. The integrated device for preparing hydrogen sulfide by self-circulating drainage catalytic reduction according to claim 1, characterized in that: The pressure drop generated by the product gas reflux unit (7) under the jet action of the Venturi-type injection device is 1000-2500 Pa.

7. The integrated device for preparing hydrogen sulfide by self-circulating drainage catalytic reduction according to claim 1, characterized in that: The product gas reflux unit (7) guides the reduction product sulfide gas to the bottom of the catalytic reduction section (1) through self-circulation, with a reflux ratio of 1:10 to 1:

3.

8. The integrated device for preparing hydrogen sulfide by self-circulating drainage catalytic reduction according to claim 1, characterized in that: The raw gas is a mixture of sulfur dioxide and methane gas.

9. The integrated device for preparing hydrogen sulfide by self-circulating drainage catalytic reduction according to claim 1, characterized in that: The catalytic reduction section (1) has 4 to 6 filler layers.

10. The integrated device for preparing hydrogen sulfide by self-circulating drainage catalytic reduction according to claim 1, characterized in that: The main body materials of the catalytic reduction section (1), the Venturi-type injection device and the product gas reflow unit (7) are 304H or 310S stainless steel.

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