CN112225182B - System and method for preparing acid by utilizing industrial sulfur-containing waste - Google Patents

System and method for preparing acid by utilizing industrial sulfur-containing waste Download PDF

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Publication number
CN112225182B
CN112225182B CN202011118643.8A CN202011118643A CN112225182B CN 112225182 B CN112225182 B CN 112225182B CN 202011118643 A CN202011118643 A CN 202011118643A CN 112225182 B CN112225182 B CN 112225182B
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sulfur
outlet
dryer
containing waste
inlet
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CN112225182A (en
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赵传军
项裕桥
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Ningbo Fareasttech Catalyst Engineering Co ltd
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Ningbo Fareasttech Catalyst Engineering Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/48—Sulfur dioxide; Sulfurous acid
    • C01B17/50—Preparation of sulfur dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/24—Sulfates of ammonium

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Treating Waste Gases (AREA)

Abstract

The invention relates to an acid making system utilizing industrial sulfur-containing waste, which comprises a pretreatment unit, wherein the pretreatment unit comprises a sulfur pulp preparation unit and a dryer; the sulfur pulp preparation unit prepares industrial sulfur-containing waste into mixed waste liquid, prepares sulfur pulp through filtration and homogenization, and sends the sulfur pulp into the dryer for treatment; the dryer comprises a cylinder body and a rotating shaft, wherein a heating medium is introduced into at least the cylinder body or the rotating shaft, and the rotating shaft can be driven to rotate so as to stir sulfur slurry in the cylinder body. The acid making system disclosed by the invention is used for treating the sulfur-containing waste before drying to remove substances which can not be incinerated and converted into SO 2, SO that sulfur slurry with uniform components is prepared, and the reduction of incineration residues and the improvement of SO 2 conversion efficiency are facilitated.

Description

System and method for preparing acid by utilizing industrial sulfur-containing waste
Technical Field
The invention relates to the technical field of desulfurization waste treatment, in particular to an acid making system and an acid making method by utilizing industrial sulfur-containing waste.
Background
In the fields of chemical industry, metallurgy, coking, power plants, etc., wet desulfurization processes (e.g., HPF desulfurization processes) are widely used for desulfurization. The process produces a large amount of sulfur-containing waste, such as in a coke-oven plant, a large amount of sulfur sludge, sulfur paste, sulfur-containing foam or sulfur-containing slurry, and these various state waste materials mainly consist of sulfur, ammonium thiosulfate, ammonium thiocyanate, benzene and a small amount of tar, although the composition varies somewhat depending on the industry, and we refer to these various state waste materials as sulfur-containing waste in the present invention. Such sulfur-containing waste has low sulfur-containing purity and poor quality and is hardly sold, and therefore, it is necessary to produce acid from the existing sulfur foam and desulfurization waste liquid. The desulfurization waste liquid acid production is mainly divided into two types of dry acid production and wet acid production, and the dry acid production produces a small amount of dilute acid, which is favored.
In the current dry pretreatment process of preparing acid by a dry method, sulfur-containing waste is directly dried and then burned, although energy consumption and working procedures are saved, because the composition of the sulfur-containing waste is complex, the sulfur-containing waste is directly dried and burned without treatment, other impurities which cannot be burned and converted into SO 2 in the sulfur-containing waste enter burning equipment together, burning residues are increased, and the residues can wrap sulfur-containing substances, SO that on one hand, the equipment operation and maintenance are not facilitated, and on the other hand, the SO 2 conversion efficiency is also not facilitated.
In addition, the generated tail gas is directly discharged in the existing drying pretreatment process, so that the defects of poor on-site operation environment, serious dust discharge, peculiar smell, corrosion and incapability of meeting the environmental protection requirement are easily caused.
Therefore, the continuous research and development of a novel acid making system by utilizing industrial sulfur-containing waste has important significance.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a novel acid making system utilizing industrial sulfur-containing waste, wherein the acid making system is used for treating the sulfur-containing waste before drying to remove substances which can not be incinerated and converted into SO 2, and the sulfur slurry obtained after treatment is beneficial to reducing incineration residues and improving SO 2 conversion efficiency.
In order to solve the technical problems, the basic conception of the technical scheme adopted by the invention is as follows:
an acid making system utilizing industrial sulfur-containing waste, comprising a pretreatment unit comprising a sulfur slurry preparation unit and a dryer;
the sulfur pulp preparation unit prepares industrial sulfur-containing waste into mixed waste liquid, filters and homogenizes the mixed waste liquid to prepare sulfur pulp, and sends the sulfur pulp into the dryer for treatment;
The dryer comprises a cylinder body and a rotating shaft, wherein a heating medium is introduced into at least the cylinder body or the rotating shaft, and the rotating shaft can be driven to rotate so as to stir sulfur slurry in the cylinder body.
As one embodiment, the sulfur pulp preparation unit comprises a mixed waste liquid preparation device, a filtering device and a homogenizing device; the mixed waste liquid preparation device is used for preparing the sulfur-containing waste into mixed waste liquid, and the outlet of the mixed waste liquid preparation device is connected with the inlet of the filtering device so as to treat the mixed waste liquid to obtain intermediate sulfur liquid; and an intermediate sulfur liquid outlet of the filtering device is connected with an inlet of the homogenizing device so as to treat the intermediate sulfur liquid to obtain sulfur slurry.
Further, as an embodiment, the sulfur pulp preparation unit further comprises a sulfur pulp tank, a sulfur pulp outlet of the homogenizing device is connected with an inlet of the sulfur pulp tank, and an outlet of the sulfur pulp tank is connected with the dryer.
As an implementation mode, an intermediate tank is further arranged between the filtering device and the homogenizing device, an intermediate sulfur liquid outlet of the filtering device is connected with an inlet of the intermediate tank, and an outlet of the intermediate tank is connected with an inlet of the homogenizing device so as to treat the intermediate sulfur liquid to obtain sulfur slurry.
As one embodiment, the outlet of the mixed waste liquid preparation device is connected with the inlet of the filtering device through a delivery pump; or the outlet of the mixed waste liquid preparation device is directly connected with the inlet of the filtering device up and down through a pipeline, and the mixed waste liquid is flowed to the inlet of the filtering device by means of the difference of positions.
As one embodiment, the filtration device comprises a membrane filtration device provided with an intermediate sulfur liquid outlet, a regeneration liquid outlet and a filtrate outlet; the intermediate sulfur liquid outlet is connected with the inlet of the intermediate tank, the regenerated liquid outlet is connected with the mixed waste liquid preparation device, the filtrate outlet is connected with the filtrate tank, and the outlet of the filtrate tank is connected with a circulating cooling unit in the acid making system or an external coking desulfurization system.
Further, as an embodiment, the filtration device includes a plurality of membrane filtration devices arranged in parallel.
Further, as an embodiment, the membrane filtration device is a microporous filter.
Further, as an embodiment, the homogenizing device comprises a colloid mill.
Further, as an embodiment, the homogenizing device comprises a plurality of colloid mills arranged in series.
As one embodiment, at least one of the mixed waste liquid preparing device, the intermediate tank and the sulfur slurry tank is provided with a stirring element and a heating element.
As an embodiment, the heating element comprises a heating conduit into which a heating medium is fed, more preferably from the dryer.
As one embodiment, the outlet of the sulfur slurry tank enters the feed inlet of the dryer through a hopper and a screw feeder; or the outlet of the sulfur slurry tank is directly connected with the feed inlet of the dryer up and down through a pipeline and naturally subsides to the feed inlet of the dryer by means of gravity; or the outlet of the sulfur slurry tank is connected with the feed inlet of the dryer through a delivery pump.
As one implementation mode, the cylinder body is provided with a hollow inner cavity for containing sulfur slurry, sealing end covers are arranged at two ends of the cylinder body, the rotating shaft penetrates out of the sealing end covers at two ends of the cylinder body, and a sealing structure is arranged between the rotating shaft and the sealing end covers.
Further, as an embodiment, the sealing structure is a dynamic sealing ring.
As an implementation mode, the top end of the cylinder body is connected with a cylinder cover, and a viewing mirror is arranged on the side wall of the cylinder cover.
As an implementation mode, the dryer further comprises a motor and a driving device, one end of the rotating shaft, which is close to the feeding hole of the dryer, is connected with the driving device, and the driving device is connected with the motor.
As one implementation mode, the rotary shaft is provided with a plurality of blades, and the blades are uniformly arranged along the axial direction of the rotary shaft at intervals and form a structure capable of pushing the sulfur pulp to move towards the discharge hole of the dryer with the periphery of the rotary shaft.
As an embodiment, the blade has a hollow inner cavity, and the inner cavity of the blade is communicated with the inner cavity of the rotating shaft.
As one embodiment, two ends of the rotating shaft are respectively provided with a first inlet and a first outlet; the side wall of the cylinder is provided with a plurality of second inlets and second outlets, the second inlets and the second outlets are arranged along the axial direction of the cylinder, the side wall of the cylinder is provided with a plurality of air cavities along the axial direction, the air cavities are hollow and independently sealed cavities, and each air cavity is respectively communicated with the corresponding second inlet and second outlet; the second inlet and the first inlet are communicated with a main pipeline, and the main pipeline is filled with heating medium.
Further, as an embodiment, the second inlet is integrated and connected in parallel with the first inlet and in communication with the main pipe.
Further, as an implementation mode, the feed inlet of the dryer is communicated with an air inlet, the outer side of the air inlet is sequentially connected with a heater and a filter, and a third inlet of the heater is communicated with the main pipeline.
Further, as an embodiment, the second inlet and the second outlet are respectively disposed at the top and the bottom of the cylinder.
As one embodiment, the rotation shaft includes a first rotation shaft and a second rotation shaft disposed in parallel along the axial direction of the cylinder, and the rotation directions of the first rotation shaft and the second rotation shaft are opposite.
Further, as an embodiment, the blades on the first rotating shaft and the blades on the second rotating shaft are staggered; the blades comprise fan-shaped blade surfaces distributed along the circumferential direction of the rotating shaft, and the radian of each fan-shaped blade surface is not larger than that of a semicircle of the rotating shaft.
As one implementation mode, the end part of the blade for stirring the sulfur slurry is provided with a scraping structure, and the scraping structure is arranged along the axial extension of the rotating shaft and can be contacted with the inner wall of the cylinder body.
As an implementation mode, the preprocessing unit further comprises a processor, a temperature sensor and a pressure sensor, wherein the temperature sensor and the pressure sensor are positioned in the cylinder body, the temperature sensor and the pressure sensor are respectively connected with the processor, and the processor is respectively and electrically connected with the motor and the induced air fan.
As one embodiment, the acid making system further comprises:
the fluidized bed furnace is used for burning the sulfur-containing waste dried by the dryer to generate a process gas containing sulfur dioxide;
The waste heat boiler comprises an air inlet tower, an air outlet tower and a sealing plate, wherein the air inlet tower is communicated with the air outlet tower, the air inlet tower and the air outlet tower are in sealing connection with the sealing plate, an air inlet is formed in the side wall of the air inlet tower, and an air outlet is formed in the side wall of the air outlet tower; the side walls of the air inlet tower and the air outlet tower and the sealing plate are respectively provided with a hollow clamping cavity, cooling water is introduced into the hollow clamping cavities of the side walls of the air inlet tower and the air outlet tower and is mutually communicated, the cooling water in the side walls is converged into the sealing plate, and the sealing plate is provided with a steam outlet; the air inlet of the air inlet tower is filled with process air, and the steam outlet is communicated with the main pipeline; the top of the air inlet tower and the top of the air outlet tower are provided with bottom plates with downward concave structures, the sealing plates are provided with drainage plates which extend vertically and downward and extend downwards into the concave structures of the bottom plates, the drainage plates and the bottom plates are respectively provided with hollow inner cavities, the inner cavities of the drainage plates are communicated with the inner cavities of the sealing plates, and the inner cavities of the bottom plates are respectively communicated with the inner cavities of the side walls of the air inlet tower and the air outlet tower; the dust leakage hole is formed in the downward concave structure of the bottom plate, the valve device is arranged at the dust leakage hole and is in a normally closed state, and the valve device is changed into an openable state by means of accumulated dust weight.
Further, as an implementation manner, the bottom plate is in a shape of a V or a U.
As an embodiment, the pretreatment unit further comprises an exhaust gas scrubbing recovery system;
the tail gas washing and recycling system comprises a water washing device, an acid washing device and a tail gas washing device;
The washing device is used for washing and cooling tail gas discharged by the dryer, the air inlet end of the washing device is connected with the tail gas discharge port, and a part of washing mixed liquid generated by tail gas washing is supplied to the feed inlet of the dryer after being filtered; the acid washing device is connected with an air outlet of the water washing device and is used for neutralizing ammonia in tail gas after water washing to generate ammonium sulfate mother liquor; the tail gas washing device is connected with the gas outlet of the pickling device and used for washing and cooling the pickled tail gas.
As one embodiment, the ammonium sulfate mother liquor outlet of the pickling device is connected with one or two of an ammonium sulfate production device or a pretreatment evaporation concentration system, the ammonium sulfate production device is used for preparing the ammonium sulfate mother liquor into an ammonium sulfate product, and the outlet of the pretreatment evaporation concentration system is connected with the dryer.
Further, as an implementation mode, the water washing device is a water washing tower, and the water washing tower is provided with a cooling water inlet and a water washing circulating pump branch; the water washing circulating pump branch comprises a first path communicated with the internal circulation of the water washing tower and a second path connected to a feed inlet of the dryer through a filtering bypass system; the filter bypass system comprises a filter, and an outlet of the filter is connected with a feed inlet of the dryer; the pickling device is a pickling tower, the pickling tower is provided with a dilute acid branch and a pickling circulating pump branch, the dilute acid branch is connected with dilute acid supply equipment, and the pickling circulating pump branch comprises a third path communicated with the internal circulation of the pickling tower and a fourth path connected with an ammonium sulfate mother liquor tank through an ammonium sulfate mother liquor bypass.
Further, as an embodiment, the dilute acid supply device is a dynamic wave scrubber used in the system for producing H 2SO4.
Further, as an implementation mode, the air outlet of the pickling device is connected to the tail gas washing device through an induced draft fan.
The invention also provides an acid making method by utilizing the industrial sulfur-containing waste, which comprises a pretreatment process, wherein the pretreatment process comprises the following steps:
sulfur pulp preparation: preparing industrial sulfur-containing waste into mixed waste liquid, and then filtering and homogenizing to prepare sulfur slurry;
The drying process comprises the following steps: and (3) delivering the sulfur pulp obtained in the sulfur pulp preparation step into a dryer, and heating and drying the sulfur pulp by using a heating medium.
As an embodiment, the sulfur pulp preparation step further comprises a water content adjustment process, and the water content adjustment process is at least arranged in one or more steps of preparing the mixed waste liquid, preparing the intermediate sulfur liquid through filtering the mixed waste liquid or preparing the sulfur pulp through the intermediate sulfur liquid.
Further, as an embodiment, the acid making method further includes a tail gas washing and recovering process, and the tail gas washing and recovering process includes:
Step S11: washing and cooling tail gas discharged by the dryer to form a washing mixed solution, and conveying a part of the washing mixed solution into the dryer for recycling;
step S12: the tail gas after washing and cooling enters an acid washing tower, acid washing is carried out by acid liquor, ammonium sulfate mother liquor with a certain concentration is generated, and the ammonium sulfate mother liquor is used for preparing an ammonium sulfate finished product;
Step S13: and (3) enabling the tail gas after pickling to enter a tail gas washing device for washing and cooling, and discharging the washed tail gas into the atmosphere.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a sulfur-containing waste acid making system of the present invention;
FIG. 2 is a schematic diagram of a sulfur slurry preparation unit;
FIG. 3 is a schematic diagram of a dryer;
FIG. 4 is a schematic view of a waste heat boiler;
FIG. 5 is a cross-sectional view of a cartridge;
FIG. 6 is a cross-sectional view A-A as shown in FIG. 5;
FIG. 7 is a side cross-sectional view of another cartridge;
FIG. 8 is a cross-sectional view B-B as shown in FIG. 7;
The drawing is marked: a 10-sulfur slurry preparation unit; 101-a mixed waste liquid preparation device; 102-a filtration device; 103-an intermediate tank; 104-an intermediate tank; 105-sulfur slurry tank; a cylinder; 12-rotating shaft; 13-bearing seats; 14-a first inlet; 15-a first outlet; 16-a feed inlet; 17-a discharge hole; 18-an exhaust outlet; 19-a water scrubber; 20-an acid washing tower; 21-a tail gas washing tower; 22-a water washing circulating pump branch; 23-cooling water inlet; a 24-filtration bypass system; 25-dilute acid branch; 26-an acid washing circulating pump branch; a 27-ammonium sulfate mother liquor bypass; 28-induced draft fan; 29-a circulation wash pump branch; 30-overflow outlet; 31-a discharge port; 32-an electric motor; 33-driving means; 34-leaf; 35-a second inlet; 36-a second outlet; 37-air cavity; 38-a main pipeline; 39-an air inlet; 40-; a heater 41-filter; 42-viewing mirror; 43-an air inlet tower; 44-an outlet tower; 45-closing plate; 46-air inlet; 47-outlet; 48-steam outlet; 49- "V" -shaped bottom plate; 50-drainage plates; 51-ash leakage holes; 52-a third inlet; 53-valve means; 54-cylinder cover; 60-coat; 61-inner sleeve; 62-spacer bush; 63-a baffle; 64-a first elongated hole; 65-a second elongated hole; 66-scraping structure; 121-a first rotation axis; 122-a second axis of rotation.
Detailed Description
The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides an acid making system utilizing industrial sulfur-containing waste, which comprises a pretreatment unit, referring to fig. 1, wherein the pretreatment unit comprises a sulfur pulp preparation unit 10 and a dryer; the sulfur pulp preparation unit 10 prepares industrial sulfur-containing waste into mixed waste liquid, prepares sulfur pulp through filtration and homogenization, and sends the sulfur pulp into the dryer for treatment; the dryer comprises a cylinder 11 and a rotating shaft 12, wherein a heating medium is introduced into at least the cylinder 11 or the rotating shaft 12, and the rotating shaft 12 can be driven to rotate so as to stir sulfur slurry in the cylinder 11.
The industrial sulfur-containing waste may be sulfur-containing waste generated by coal chemical industry enterprises, including but not limited to sulfur-containing waste generated by desulfurization processes using wet desulfurization processes (e.g., HPF desulfurization processes), such as in coking plants, which produce a large amount of sulfur mud, sulfur paste, sulfur foam, or sulfur mud, and these different state waste mainly consist of sulfur, ammonium thiosulfate, ammonium thiocyanate, benzene, and small amounts of tar, although the composition may vary somewhat depending on the industry, we refer to these different state waste as sulfur-containing waste in this invention.
As an embodiment, the sulfur slurry preparation unit 10 adopts the structure shown in fig. 2, and the sulfur slurry preparation unit 10 includes a mixed waste liquid preparation device 101, a filtration device 102, a homogenization device 104, and a sulfur slurry tank 105. The mixed waste liquid preparation device 101 is used for preparing the sulfur-containing waste into mixed waste liquid, and an outlet of the mixed waste liquid preparation device 101 is connected with an inlet of the filtering device 102 so as to treat the mixed waste liquid to obtain intermediate sulfur liquid (i.e. a substance obtained by filtering the mixed waste liquid). The intermediate sulfur liquid outlet of the filtering device 102 is connected with the inlet of the homogenizing device 104 to process the intermediate sulfur liquid to obtain sulfur slurry (i.e. the material obtained by homogenizing the intermediate sulfur liquid can directly enter a dryer for processing).
As a preferred mode, the sulfur slurry outlet of the homogenizing device 104 is connected with the inlet of the sulfur slurry tank 105, and the outlet of the sulfur slurry tank 105 is connected with the dryer.
Of course, the sulfur slurry outlet of the homogenizing apparatus 104 may also be connected to the dryer by other similar means, for example, the sulfur slurry outlet of the homogenizing apparatus 104 may be directly connected to the dryer by a pipe.
The components which can not be incinerated and converted into SO 2 in the sulfur slurry prepared by the sulfur slurry preparation unit 10 are obviously reduced, a large amount of residues are avoided from being generated in the incinerator, the probability of shutdown cleaning or maintenance is reduced, and the production efficiency of the whole acid preparation system is improved and the service life of equipment is prolonged. In particular, the efficiency of converting sulfur slurry into SO 2 -containing process gas is improved, and the sulfuric acid yield is obviously increased.
Further, as another embodiment, an intermediate tank 103 is further arranged between the filtering device 102 and the homogenizing device 104, the intermediate sulfur liquid outlet of the filtering device 102 is connected with the inlet of the intermediate tank 103, and the outlet of the intermediate tank 103 is connected with the inlet of the homogenizing device 104, so as to process the intermediate sulfur liquid to obtain sulfur slurry.
The arrangement of the middle groove 103 is convenient for flexibly adjusting the acid making rate of the system according to the operation condition of the acid making system, reduces the probability of unexpected stopping of the acid making system, and is beneficial to keeping the operation continuity of the acid making system.
As an example, the outlet of the mixed waste liquid preparing apparatus 101 is connected to the inlet of the filtering apparatus 102 by a transfer pump. Or the outlet of the mixed waste liquid preparation device 101 is directly connected with the inlet of the filtering device 102 up and down through a pipeline, and naturally flows to the inlet of the filtering device 102 by means of the level difference.
Specifically, as an example, the filtration device 102 includes a plurality of microporous filters arranged in parallel, the microporous filters being provided with an intermediate sulfur liquid outlet, a regenerated liquid outlet, and a filtrate outlet. The intermediate sulfur liquid outlet is connected with the inlet of the intermediate tank 103, the regenerated liquid outlet is connected with the mixed waste liquid preparation device 101, and the filtrate outlet is connected with a filtrate tank (not shown in the figure). The outlet of the filtrate tank is connected with a circulating cooling unit inside the acid making system or connected with an external coking desulfurization system, so that filtrate obtained by separation can be used as a cooling medium inside the acid making system, and the filtrate tank can be used as the cooling medium of the external coking desulfurization system in the condition that the coking desulfurization system is arranged on a factory, thereby remarkably reducing industrial water, saving water resources and reducing industrial cost.
The homogenizing device 104 comprises a plurality of colloid mills which are sequentially connected in series, so that the prepared sulfur slurry can be dispersed more uniformly, the sulfur slurry can be dried sufficiently in a dryer to obtain powdery sulfur with uniform particles, and the sulfur slurry can be further converted into process gas containing S0 2 more efficiently.
Stirring elements and heating elements are arranged in the mixed waste liquid preparation device 101, the middle tank 103 and the sulfur slurry tank 105. The heating element comprises a heating pipeline, a heating medium is introduced into the heating pipeline, and the heating medium is from the dryer. The outlet of the sulfur slurry tank 105 enters the feed inlet of the dryer through a hopper and a screw feeder. Or the outlet of the sulfur slurry tank 105 is directly connected with the feed inlet of the dryer up and down through a pipeline and naturally subsides to the feed inlet of the dryer by means of gravity.
The heating element can utilize a heating medium from a dryer so as to adjust the water content of the mixed waste liquid, the intermediate sulfur liquid or the sulfur slurry to a proper range in a corresponding process section, and is beneficial to obtaining granular sulfur-containing materials with uniform particles and good dispersibility after being dried by the dryer, thereby being beneficial to full incineration and conversion and reducing energy consumption under the condition of improving the utilization rate of the materials.
The heating temperature and heating time of the heating element are controlled, the water content of the intermediate sulfur liquid in the intermediate tank 103 is controlled to be 35-45wt%, and the water content of the sulfur slurry in the sulfur slurry tank 105 is controlled to be 40-55wt%.
Further, as a preferred embodiment of the present invention, referring to fig. 1, the pretreatment unit further includes an exhaust gas washing recovery system. The tail gas washing and recycling system comprises a water washing device, an acid washing device and a tail gas washing device which are sequentially connected; the water washing device is used for washing and cooling tail gas discharged by the dryer, the air inlet end of the water washing device is connected with the tail gas discharge port 18, and a part of water washing mixed liquid generated by tail gas washing is supplied to the feed inlet of the dryer after being filtered; the acid washing device is connected with an air outlet of the water washing device and is used for neutralizing ammonia in tail gas after water washing to generate ammonium sulfate mother liquor; the tail gas washing device is connected with the gas outlet of the pickling device and used for washing and cooling the pickled tail gas.
As an example, the water scrubber is a water scrubber 19, the acid scrubber is an acid scrubber 20, and the tail gas scrubber is a tail gas scrubber 21.
As an embodiment, the sulfur slurry to be treated enters the feed inlet 16 of the dryer through a hopper and a screw feeder, or the sulfur slurry to be treated is directly connected up and down through a pipeline and naturally subsides to the feed inlet 16 of the dryer by means of gravity.
As an implementation manner, the cylinder 11 is provided with a hollow cavity capable of containing sulfur-containing waste, two ends of the cylinder 11 are provided with sealing end covers, the rotating shaft 12 penetrates out of the sealing end covers at the two ends, a movable sealing ring is arranged between the rotating shaft 12 and the sealing end covers, and the rotating shaft 12 is rotatably connected with bearing seats 13 at two sides.
The rotary shaft 12 is provided with a hollow inner cavity, two ends of the rotary shaft 12 are respectively provided with a first inlet 14 and a first outlet 15, two ends of the cylinder 11 are respectively provided with a feed inlet 16 and a discharge outlet 17, the feed inlet 16 is positioned at the top of the cylinder 11 and is close to one side of the first inlet 14, the discharge outlet 17 is positioned at the bottom of the cylinder 11, the top of the cylinder 11 is provided with a tail gas discharge outlet 18, the tail gas discharge outlet 18 and the discharge outlet 17 are positioned at the same side of the cylinder 11 and are close to one side of the first outlet 15, and the first inlet 14 is filled with a heating medium.
As an embodiment, the tail gas washing and recovering system comprises a water washing tower 19, an acid washing tower 20 and a tail gas washing tower 21 which are connected in sequence; the air inlet end of the water scrubber 19 is connected with the tail gas discharge port 18, and the water scrubber 19 is connected with a water scrubber circulating pump branch 22 and a cooling water inlet 23.
The water wash circulation pump leg 22 comprises a first leg in communication with the internal circulation of the water wash column 19, a second leg connected to the feed inlet of the dryer via a filter bypass system 24. The filter bypass system 24 includes a filter with an outlet connected to the feed inlet of the dryer.
By the arrangement, part of the water washing mixed liquid can be continuously used for circularly washing tail gas to sufficiently carry out tail gas purification, and the other part of the water washing mixed liquid is used as raw material liquid for preparing sulfur paste, so that the material cyclic utilization in the system is realized, the discharged waste liquid is reduced, the acid production yield is improved, and the environment is protected.
As a preferred embodiment, the ammonium sulfate mother liquor outlet of the pickling tower 20 is connected to one or both of an ammonium sulfate production device for producing the ammonium sulfate mother liquor into an ammonium sulfate product or a pretreatment evaporation concentration system, and the outlet of the pretreatment evaporation concentration system is connected to the dryer.
As an embodiment, the pickling tower 20 is provided with a dilute acid branch 25 and a pickling circulation pump branch 26 in a connecting way, and the dilute acid branch 25 is connected with a dilute acid supply device.
As one way, the dilute acid supply means may be a kinetic wave scrubber used in an acid making system, the dilute acid branch 25 being used to convey dilute acid liquid from the kinetic wave scrubber used in the acid making system to the pickling tower 20. An induced draft fan 28 is connected between the pickling tower 20 and the tail gas washing tower 21, the tail gas washing tower 21 is provided with a cooling water inlet 23, a circulating washing pump branch 29, an overflow outlet 30 and a discharge port 31, and the discharge port is arranged on the top of the tail gas washing tower 21.
The pickling circulation pump leg 26 comprises a third path in communication with the internal circulation of the pickling tower 20, a fourth path connected to the ammonium sulphate mother liquor tank via an ammonium sulphate mother liquor bypass 27.
By the arrangement, part of the pickling mixed liquor can be continuously used for circularly washing tail gas to sufficiently carry out tail gas purification, and the other part of the pickling mixed liquor is used as raw material liquor for preparing ammonium sulfate, so that the full utilization of materials is realized, the types of products are increased, the economic income is improved, and the discharged waste liquid is less and is more green and environment-friendly.
For a better understanding of the present invention, an exemplary workflow of the present invention utilizing an industrial sulfur-containing waste acid making system is described in detail below:
Industrial sulfur-containing waste including, but not limited to, sulfur paste, foamed sulfur, concentrated salt, and the like from a coke oven plant is fed into the mixed waste liquid preparation apparatus 101, and mixed with stirring sufficiently while evaporating water by means of a heating element, to prepare a mixed waste liquid having a certain water content. And then pumping the mixed waste liquid into two microporous filters arranged in parallel, filtering to remove impurities, enabling intermediate sulfur liquid obtained by filtering through the microporous filters to enter an intermediate tank 103 from an intermediate sulfur liquid outlet arranged below the intermediate sulfur liquid to be stored, simultaneously performing secondary evaporation of water, adjusting the water content of the intermediate sulfur liquid, sequentially entering a primary colloid mill and a secondary colloid mill which are arranged in series, performing primary homogenization and secondary homogenization, and then entering a sulfur slurry tank 105 to perform tertiary evaporation of water to obtain sulfur slurry with the water content suitable for entering a dryer for drying treatment.
The microporous filter is also provided with a regeneration liquid outlet which is connected with the mixed waste liquid preparation device 101, and the regeneration liquid is used as part of raw materials for preparing the mixed waste liquid for recycling, so that the waste liquid discharge is reduced, and the material utilization rate is improved. Meanwhile, a filtrate outlet is further formed in the microporous filter, the filtrate outlet is connected with a filtrate tank, and the outlet of the filtrate tank is connected with a circulating cooling unit in the acid making system or an external coking desulfurization system to serve as cooling medium, so that additional use of cooling water is reduced, and water resources are saved.
The sulfur pulp obtained by the sulfur pulp preparation unit 10 enters the feed inlet of the dryer, and the specific entering mode can adopt any one or a combination of the following modes: the outlet of the sulfur slurry tank 105 enters the feed inlet of the dryer through a hopper and a screw feeder; or the outlet of the sulfur slurry tank 105 is directly connected with the feed inlet of the dryer up and down through a pipeline and naturally subsides to the feed inlet of the dryer by means of gravity; or the outlet of the sulfur slurry tank 105 is connected with the feed inlet of the dryer through a delivery pump.
After the sulfur slurry enters the cylinder 11 of the dryer, the discharge port is gradually conveyed by the rotation of the rotating shaft 12, and in the process of conveying the sulfur slurry to the discharge port, the cylinder 11 or the rotating shaft 12 or the cylinder 11 and the rotating shaft 12 are filled with heating medium, so that the sulfur slurry can be heated and dried into powdery sulfur powder.
The heating medium can be steam, and the dried sulfur pulp discharged from the discharge port is sent to the storage bin through a closed conveying system. The material particles are smaller after being dried by the dryer, and part of particles are carried out along with gas from the tail gas discharge port, and meanwhile, the material contains ammonia, so that the material is directly discharged from the tail gas discharge port after evaporation to cause pollution. The gas discharged from the exhaust gas discharge port is collectively referred to as exhaust gas in the present invention.
The tail gas discharged from the dryer is washed and cooled by a water washing tower 19, one part of the water washing mixed liquid in the water washing tower 19 is filtered and separated by solid particles and then is used as an acid making raw material to be returned to a feed inlet of the dryer, and the other part of the water washing mixed liquid is used as a circulating washing liquid to sufficiently wash the tail gas in a circulating way.
The tail gas enters the pickling tower 20, ammonia in the tail gas is neutralized with dilute acid liquid to generate ammonium sulfate mother liquor, a part of the pickling mixed liquor is conveyed to an ammonium sulfate mother liquor tank for manufacturing an ammonium sulfate finished product for external sale, and the other part of the pickling mixed liquor is used for circularly washing the tail gas.
The tail gas after acid washing enters a tail gas washing tower 21 through an induced draft fan for further washing and cooling, and the tail gas after washing reaches the environmental protection requirement and is discharged into the atmosphere through a discharge port.
The induced draft fan is used between the pickling tower 20 and the tail gas washing tower 21, so that micro negative pressure can be formed in each device and pipeline to avoid powder particles escaping, and the energy consumption is obviously reduced. The sealing structure of the movable sealing ring is arranged between the sealing end cover of the dryer and the rotary shaft 12, so that leakage of powder particles is further avoided.
In the drying pretreatment process, the generated tail gas is washed and purified, meanwhile, the recycling of ammonia is further realized, the escape of ammonia is reduced, the ammonium sulfate mother liquor generated in the system is utilized to manufacture a product, the cost is low, and the economic benefit is improved.
The invention also realizes the recycling of solid particles, reduces the emission of dust, improves the field operation environment and is more environment-friendly.
One specific structure of the dryer of the present invention is further described below:
Referring to fig. 3 and 5-6, the dryer further includes a motor 32 and a driving device 33, wherein one end of the rotary shaft 12 near the feed inlet 16 is connected to the driving device 33, and the driving device 33 is connected to the motor 32. The rotating shaft 12 is provided with a plurality of blades 34, the blades 34 are uniformly arranged along the axial direction of the rotating shaft 12 at intervals, and a structure capable of pushing the sulfur pulp to move towards the discharge hole 17 of the dryer is formed with the periphery of the rotating shaft 12. The rotary shaft 12 is provided at both ends thereof with a first inlet 14 and a first outlet 15, respectively.
As a preferred mode, the top end of the cylinder 11 is connected with a cylinder cover 54, the side wall of the cylinder cover 54 is provided with a sight glass 42, further, the sight glass 42 can be arranged on two side walls of the cylinder cover 54 which incline inwards and upwards, thus being beneficial to operators to observe the dryness of materials in the cylinder, and the feeding amount of the materials can be adjusted according to the material condition in the cylinder, or the temperature in the cylinder can be adjusted by adjusting the steam amount, so that the drying process can be controlled stably.
The blades 34 have hollow cavities, and the cavities of the blades 34 communicate with the cavities of the rotating shaft 12. The side wall of the cylinder 11 is provided with a plurality of second inlets 35 and second outlets 36, the second inlets 35 and the second outlets 36 are arranged along the axial direction of the cylinder 11, the second inlets 35 and the second outlets 36 are respectively arranged at the top and the bottom of the cylinder 11, the side wall of the cylinder 11 is provided with a plurality of air cavities 37 along the axial direction, the air cavities 37 are hollow and are independent sealed cavities, and each air cavity 37 is respectively communicated with the corresponding second inlet 35 and second outlet 36; the second inlet 35 is connected with the first inlet 14 in parallel after being assembled and is communicated with a main pipeline 38, and the main pipeline 38 is filled with heating medium; the feeding port 16 of the dryer is communicated with an air inlet 39, the outer side of the air inlet 39 is sequentially connected with a heater 40 and a filter 41, and a third inlet 52 of the heater 40 is communicated with the main pipeline 38. The plurality of second outlets 36 may be integrated into a manifold for draining condensate that is formed after the heat is released from the steam.
The following is a specific structure of the cylinder 11:
the cylinder 11 can comprise an outer sleeve 60, a plurality of inner sleeves 61 and a plurality of spacer sleeves 62, the spacer sleeves 62 are uniformly arranged along the axial direction of the outer sleeve 60 at intervals, an independent sealed air cavity 37 is formed among each inner sleeve 61, each spacer sleeve 62 and the outer sleeve 60, the air cavities at the two ends are surrounded by end covers, a plurality of baffles 63 are uniformly arranged in each air cavity along the radial direction, the top end of each baffle 63 connected with the outer sleeve is provided with a first long hole 64, or the bottom end connected with the inner sleeve is provided with a second long hole 65, and the first long hole 64 and the second long hole 65 are arranged at intervals up and down; steam enters the air cavity from the third inlet 35 and can be separated into two paths to reach the third outlet 36 at the bottom in a tortuous path (for example, an S-shaped path), so that the steam can extend a travelling path and the residence time in the air cavity, and in addition, a heat insulation material can be arranged on the outer surface of the outer sleeve so as to promote the steam in the air cavity to heat the materials in the cylinder better, more fully and more uniformly; the third inlet 35 and the third outlet 36 are both provided on the outer sleeve 60.
As shown in fig. 7 to 8, another preferred embodiment of the barrel 11 in the present invention is:
the bottom of the cylinder 11 is semi-elliptic arc, and the bottom and the side wall are in arc transition, so that the phenomenon of stacking in the cylinder can be avoided; in addition, the two sides of the jacket 60 of the cylinder 11 are respectively provided with a second inlet 35, steam can be introduced, and after the materials in the cylinder are heated, condensed water is finally discharged from the second outlet 36 at the bottom of the cylinder 11.
In order to avoid material wall built-up in the cylinder body and improve the heating and drying efficiency of the material, the technical scheme of the invention is designed as follows:
the rotary shaft 12 includes a first rotary shaft 121 and a second rotary shaft 121 disposed in parallel along the axial direction of the cylinder 11
And a second rotation shaft 122, wherein the rotation directions of the first rotation shaft 121 and the second rotation shaft 122 are opposite.
The blades 34 on the first rotation shaft 121 and the blades 34 on the second rotation shaft 122 are staggered with each other. The vane 34 includes a fan-shaped vane surface distributed along the circumferential direction of the rotation shaft 12, and the arc of the fan-shaped vane surface is not greater than a semicircle of the rotation shaft 12.
The end of the blade 34 for stirring sulfur slurry is provided with a scraping structure 66, and the scraping structure 66 extends along the axial direction of the rotating shaft 12 and can be contacted with the inner wall of the cylinder 11.
The rotating shaft adopts double-shaft reverse rotation, so that the stirring efficiency of the rotating shaft on materials is improved, the heated area of the materials is increased while stirring is carried out, and the evaporation of water in the materials is facilitated; the scraping structure 66 scrapes the material accumulated at the bottom in the rotating process, so that the stirring efficiency is improved, and the radiant heat area is increased.
The pretreatment unit of the invention also comprises a processor, a temperature sensor and a pressure sensor, wherein the temperature sensor and the pressure sensor are positioned in the cylinder 11, the temperature sensor and the pressure sensor are respectively connected with the processor, and the processor is respectively and electrically connected with the motor 32 and the induced draft fan 28.
Further, the present invention provides an acid making system using industrial sulfur-containing waste, comprising:
The fluidized bed furnace is used for burning the sulfur slurry dried by the dryer to generate process gas containing sulfur dioxide;
The waste heat boiler is shown with reference to fig. 4, and comprises an air inlet tower 43, an air outlet tower 44 and a sealing plate 45, wherein the air inlet tower 43 is communicated with the air outlet tower 44, the air inlet tower 43 and the air outlet tower 44 are in sealing connection with the sealing plate 45, an air inlet 46 is arranged on the side wall of the air inlet tower 43, and an air outlet 47 is arranged on the side wall of the air outlet tower 44; the side walls of the air inlet tower 43 and the air outlet tower 44 and the sealing plate 45 are respectively provided with a hollow clamping cavity, cooling water is introduced into the hollow clamping cavities of the side walls of the air inlet tower 43 and the air outlet tower 44 and is mutually communicated, the cooling water in the side walls is converged into the sealing plate 45, and the sealing plate 45 is provided with a steam outlet 48; an air inlet 46 of the air inlet tower 43 is filled with process air, and a steam outlet 48 is communicated with the main pipeline 38; the top of the air inlet tower 43 and the top of the air outlet tower 44 are provided with a bottom plate 49 with a downward concave structure, the sealing plate 45 is provided with a drainage plate 50 which extends vertically and downward, the drainage plate 50 extends downwards into the concave structure of the bottom plate 49, the drainage plate 50 and the bottom plate 49 are respectively provided with a hollow inner cavity, the inner cavities of the drainage plate 50 are communicated with the inner cavities of the sealing plate 45, and the inner cavities of the bottom plate 49 are respectively communicated with the inner cavities of the side walls of the air inlet tower 43 and the air outlet tower 44;
The bottom plate 49 has a downwardly concave structure provided with a dust leakage hole 51, and the dust leakage hole 51 is provided with a valve device 53, the valve device 53 is normally closed, and the valve device 53 is changed to an openable state by means of the accumulated dust weight.
In particular embodiments, the bottom plate 49 may be in a "V" or "U" configuration.
The invention also relates to a method for preparing acid by utilizing the industrial sulfur-containing waste, which comprises a pretreatment process; the pretreatment process comprises the following steps:
sulfur pulp preparation: preparing industrial sulfur-containing waste into mixed waste liquid, and then filtering and homogenizing to prepare sulfur slurry;
The drying process comprises the following steps: the sulfur slurry obtained in the sulfur slurry preparation step is fed into the cylinder 11 of the dryer, and the sulfur slurry is heated and dried by a heating medium.
As an embodiment, the sulfur pulp preparation step further comprises a water content adjustment process, and the water content adjustment process is at least set in one or more steps of preparing mixed waste liquid, preparing intermediate sulfur liquid through filtering the mixed waste liquid or preparing sulfur pulp through the intermediate sulfur liquid.
In the step of preparing sulfur slurry, sulfur-containing waste is prepared into mixed waste liquid in a mixed waste liquid preparation device 101, an outlet of the mixed waste liquid preparation device 101 is connected with an inlet of a filtering device 102, and filtering treatment is performed in the filtering device 102 to obtain intermediate sulfur liquid; the middle sulfur liquid outlet of the filtering device 102 is connected with the inlet of the homogenizing device 104 to process the middle sulfur liquid to obtain sulfur slurry; the sulfur slurry outlet of the homogenizing device 104 is connected with the inlet of the sulfur slurry tank 105, and the water content of the sulfur slurry is evaporated and regulated in the sulfur slurry tank 105.
Further, the acid preparation method also comprises the following tail gas washing and recycling process steps:
Step S11: washing and cooling tail gas discharged by the dryer to form a washing mixed solution, and conveying a part of the washing mixed solution into the dryer for recycling;
step S12: the tail gas after washing and cooling enters an acid washing tower, acid washing is carried out by acid liquor, ammonium sulfate mother liquor with a certain concentration is generated, and the ammonium sulfate mother liquor is used for preparing an ammonium sulfate finished product;
Step S13: and (3) enabling the tail gas after pickling to enter a tail gas washing device for washing and cooling, and discharging the washed tail gas into the atmosphere.
As an embodiment, the drying process comprises the following steps: the sulfur-containing waste is put into a cylinder 11 of the dryer, a rotating shaft 12 of the dryer stirs and pushes the sulfur-containing material to move in the cylinder 11 from a feed inlet 16 to a discharge outlet 17, and meanwhile, a heating medium heats and dries the sulfur-containing waste, and the heating medium is at least arranged in the cylinder 11 or the rotating shaft 12.
As a preferred embodiment, the acid making method is based on the acid making system, and specifically adopts the following drying process steps:
The heating medium introduced by the main pipeline 38 enters the inner cavity of the rotary shaft 12 through the second inlet 35, one end of the rotary shaft 12, which is close to the feed inlet 16, is driven by a motor, the blades 34 stir and push the sulfur-containing material to move from the feed inlet 16 to the discharge outlet 17 in the barrel in the rotating process, and the heating medium in the inner cavity of the rotary shaft 12 flows into the inner cavity of the blades 34 to heat sulfur slurry; the heating medium introduced by the main pipeline 38 enters each air cavity on the side wall of the cylinder body through the second inlet 35 to heat and dry the sulfur slurry in the cylinder body 11; the heating medium introduced into the main pipeline 38 enters the heater through the third inlet 52, the filtered air enters the cylinder 11 through the air inlet after being heated, meanwhile, sulfur slurry enters the cylinder 11 through the feed inlet, and the heated air stirs, heats and dries the sulfur slurry in the cylinder 11 and dilutes the ammonia concentration in the cylinder 11.
As an embodiment, the pretreatment process further comprises the following steps:
The temperature sensor is used for detecting the working temperature in the cylinder and sending the detected temperature value to the processor, the processor receives the detected temperature value and processes the detected temperature value, and if the temperature is lower than a set threshold value, the processor sends a signal to the motor, adjusts the speed of the motor and controls the discharging speed;
the pressure sensor is used for detecting the working pressure in the cylinder body and sending the detected pressure value to the processor, the processor receives the detected pressure value and processes the detected pressure value, and if the pressure is higher than a set negative pressure threshold value, the processor sends a signal to the induced draft fan to adjust the speed of the induced draft fan.
As one embodiment, the acid making method of the present invention further comprises:
The incineration recovery process comprises the following steps: incinerating the granular solid sulfur powder obtained after drying by a dryer to generate a process gas containing sulfur dioxide;
The waste heat recovery process comprises the following steps:
The method comprises the steps that sulfur dioxide-containing process gas enters through an air inlet on the side wall of an air inlet tower, which is close to the top end, is guided by a drainage plate, ascends from top to bottom to enter an air outlet tower according to an S-shaped route, ascends from top to bottom to reach an air outlet according to an S-shaped route, and meanwhile, the residence time of the process gas in the air inlet tower and the air outlet tower is prolonged, the inner cavity of the drainage plate is communicated with cooling water in the inner cavity of a top sealing plate, the V-shaped bottom plates of the air inlet tower and the air outlet tower are communicated with the side wall, cooling water in the side wall is converged into the sealing plate, and the process gas and the cooling water perform more sufficient and uniform heat exchange; the cooling water is heated to become steam which escapes from the top end of the sealing plate and is conveyed to the main pipeline to be used as a heating medium of the dryer, so that the waste heat recovery of the process gas containing sulfur dioxide by the waste heat boiler is realized.
The sulfur foam was filtered using a filter that set up a blowback flow path. After the water content of the outlet of the filter is about 50%, the water enters a sulfur slurry tank and is uniformly stirred, the water enters a dryer through a sulfur slurry pump to be dried, because the water content is high, the required heat exchange area is large, the prior art adopts a two-stage dryer connected in series to be dried, the occupied area of the system is large, the energy consumption is high, and aiming at the problem, the applicant of the invention adopts the following technical scheme:
the pretreatment process also comprises the following steps:
The sulfur slurry to be pretreated comprises sulfur paste and mixed salt; the sulfur paste after centrifugal dehydration by a horizontal centrifuge and the mixed salt after concentration and crystallization enter a feed inlet of a dryer through a hopper and a screw feeder;
Or the sulfur paste after centrifugal dehydration by a horizontal centrifuge and the concentrated water-containing mixed salt concentrated solution are directly connected up and down by a pipeline and naturally settled to a feed inlet of a dryer by means of gravity.
After the improvement of the process steps, the requirement can be met by adopting a primary dryer, the total occupied area of an acid making system is reduced, the structure of the dryer is optimized, the steam consumption is reduced, and the energy is saved.
Compared with the prior art, the technical scheme has the following advantages:
1. The invention provides a sulfur pulp acid making system and a method thereof, which are used in the drying pretreatment process
The generated tail gas is washed and purified, and meanwhile, ammonia is recycled; the recycling of solid particles is realized, the escape of ammonia is reduced, the emission of dust is reduced, the field operation environment is improved, and the environmental protection requirement is met.
2. In the tail gas washing and recycling process, part of the tail gas discharged by the dryer is repeatedly washed by the washing tower, and part of the mixed liquid is used as washing liquid for circulating washing, and the other part of the mixed liquid is filtered by solid particles and then conveyed into the dryer for recycling, so that no solid waste is discharged and no secondary pollution is generated;
The tail gas after being washed and cooled by the water washing tower enters the acid washing tower, dilute acid liquid generated by the dynamic wave washing tower in the integral subsequent process step of the acid preparation method is conveyed to the acid washing tower, the dilute acid generated in the acid preparation process reacts with ammonia in the tail gas to generate ammonium sulfate, and ammonium sulfate mother liquor with certain concentration is formed through multiple times of circulating acid washing; the ammonium sulfate mother liquor can be conveyed to an original ammonium sulfate mother liquor tank in a factory together with the mother liquor treated by the final tail gas in the acid making process for mixed use to prepare an ammonium sulfate finished product; or firstly enter a desulfurizing liquid pretreatment evaporation concentration system for treatment, then enter a dryer together with sulfur paste, then enter a furnace for combustion and cracking as raw materials of preparation process gas, and the acid preparation system basically does not discharge dilute acid and salt-containing waste liquid, so that the waste emission is reduced, the environment is protected, the material utilization effect and the enterprise economic benefit are improved, and the desulfurizing liquid pretreatment evaporation concentration system is a green, environment-friendly, economic and efficient chemical production system.
3. The system and the method for preparing the acid by utilizing the sulfur pulp are beneficial to operators to observe the cylinder
The material drying degree in the cylinder can be adjusted according to the material condition in the cylinder, or the temperature in the cylinder can be adjusted by adjusting the steam quantity, so that the drying process can be controlled stably.
4. The system and the method for preparing the acid by utilizing the sulfur pulp provided by the invention can utilize the waste heat boiler pair
The process gas containing sulfur dioxide is subjected to waste heat recovery, cooling water is heated to steam, the steam is used as a heating medium of the dryer, and materials in the cylinder are heated better, more fully and more uniformly by the steam.
5. The invention provides a sulfur pulp acid making system and a method thereof, which are improved by the process steps,
The primary dryer can meet the requirements, the structure of the dryer is optimized, the steam consumption is reduced, and the energy is saved.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.

Claims (31)

1. An acid making system using industrial sulfur-containing waste, characterized by comprising a pretreatment unit comprising a sulfur slurry preparation unit (10) and a dryer; the sulfur pulp preparation unit (10) prepares industrial sulfur-containing waste into mixed waste liquid, filters and homogenizes the mixed waste liquid to prepare sulfur pulp, and sends the sulfur pulp into the dryer for treatment;
The dryer comprises a cylinder (11) and a rotating shaft (12), wherein a heating medium is introduced into at least the cylinder (11) or the rotating shaft (12), and the rotating shaft (12) can be driven to rotate so as to stir sulfur slurry in the cylinder (11);
The sulfur pulp preparation unit (10) comprises a mixed waste liquid preparation device (101) and a filtering device (102), an intermediate tank (103), a homogenizing device (104) and a sulfur pulp tank (105); the mixed waste liquid preparation device (101) is used for preparing sulfur-containing waste into mixed waste liquid, and an outlet of the mixed waste liquid preparation device (101) is connected with an inlet of the filtering device (102) so as to treat the mixed waste liquid to obtain intermediate sulfur liquid; the middle sulfur liquid outlet of the filtering device (102) is connected with the inlet of the middle tank (103), and the outlet of the middle tank (103) is connected with the inlet of the homogenizing device (104) so as to treat the middle sulfur liquid to obtain sulfur slurry; the sulfur slurry outlet of the homogenizing device (104) is connected with the inlet of the sulfur slurry tank (105), and the outlet of the sulfur slurry tank (105) is connected with the dryer;
The filtering device (102) comprises a membrane filtering device, wherein the membrane filtering device is provided with an intermediate sulfur liquid outlet, a regenerated liquid outlet and a filtrate outlet; the intermediate sulfur liquid outlet is connected with the inlet of the intermediate tank (103), the regenerated liquid outlet is connected with the mixed waste liquid preparation device (101), the filtrate outlet is connected with a filtrate tank, and the outlet of the filtrate tank is connected with a circulating cooling unit in the acid making system or an external coking desulfurization system;
At least one of the mixed waste liquid preparation device (101), the intermediate tank (103) and the sulfur slurry tank (105) is provided with a stirring element and a heating element; the heating element comprises a heating pipeline, a heating medium is introduced into the heating pipeline, and the heating medium is from the dryer.
2. The acid making system using industrial sulfur-containing waste according to claim 1, wherein an outlet of the mixed waste liquid preparing device (101) is connected with an inlet of the filtering device (102) through a transfer pump; or the outlet of the mixed waste liquid preparation device (101) is directly connected with the inlet of the filtering device (102) up and down through a pipeline, and the mixed waste liquid is flowed to the inlet of the filtering device (102) by means of the difference of positions.
3. The acid making system using industrial sulfur-containing waste as claimed in claim 2, wherein the filter device (102) comprises a plurality of membrane filter devices arranged in parallel.
4. The acid making system using industrial sulfur-containing waste as claimed in claim 3, wherein the membrane filtration device is a microporous filter.
5. The acid making system using industrial sulfur-containing waste according to claim 1, wherein the homogenizing device (104) comprises a colloid mill.
6. The acid making system using industrial sulfur-containing waste as claimed in claim 5, wherein said homogenizing means (104) comprises a plurality of colloid mills disposed in series.
7. The acid making system using industrial sulfur-containing waste according to claim 1, wherein the outlet of the sulfur slurry tank (105) enters the feed inlet of the dryer through a hopper and a screw feeder; or the outlet of the sulfur slurry tank (105) is directly connected with the feed inlet of the dryer up and down through a pipeline and naturally subsides to the feed inlet of the dryer by gravity; or the outlet of the sulfur slurry tank (105) is connected with the feed inlet of the dryer through a delivery pump.
8. The acid making system using industrial sulfur-containing waste according to any one of claims 1 to 7, wherein the cylinder (11) has a hollow inner cavity for containing sulfur slurry, sealing end covers are provided at both ends, the rotary shaft (12) penetrates out of the sealing end covers at both ends, and a sealing structure is provided between the rotary shaft (12) and the sealing end covers.
9. The acid making system using industrial sulfur-containing waste of claim 8, wherein the sealing structure is a dynamic sealing ring.
10. The acid making system using industrial sulfur-containing waste as claimed in claim 8, wherein a barrel cover (54) is connected to the top end of the barrel body (11), and a sight glass (42) is provided on the side wall of the barrel cover (54).
11. The acid making system using industrial sulfur-containing waste according to claim 8, wherein the dryer further comprises a motor (32) and a driving device (33), wherein one end of the rotary shaft (12) near the feed inlet (16) of the dryer is connected to the driving device (33), and the driving device (33) is connected to the motor (32).
12. The acid making system using industrial sulfur-containing waste as claimed in claim 11, wherein a plurality of blades (34) are provided on the rotary shaft (12), and the blades (34) are uniformly arranged along the axial direction of the rotary shaft (12) at intervals and form a structure with the periphery of the rotary shaft (12) for pushing sulfur pulp to move towards the discharge port (17) of the dryer.
13. The acid making system using industrial sulfur-containing waste as claimed in claim 12, wherein the blade (34) has a hollow inner cavity, and the inner cavity of the blade (34) communicates with the inner cavity of the rotary shaft (12).
14. The acid making system using industrial sulfur-containing waste according to claim 12, wherein both ends of the rotating shaft (12) are provided with a first inlet (14) and a first outlet (15), respectively; a plurality of second inlets (35) and second outlets (36) are formed in the side wall of the barrel (11), the second inlets (35) and the second outlets (36) are arranged along the axial direction of the barrel (11), a plurality of air cavities (37) are formed in the side wall of the barrel (11) along the axial direction, the air cavities (37) are hollow and independently sealed cavities, and each air cavity (37) is communicated with the corresponding second inlet (35) and second outlet (36); the second inlet (35) and the first inlet (14) are communicated with a main pipeline (38), and the main pipeline (38) is communicated with a heating medium.
15. The acid making system using industrial sulfur-containing waste as claimed in claim 14, wherein the second inlet (35) is connected in parallel with the first inlet (14) and is in communication with the main conduit (38) after integration.
16. The acid making system using industrial sulfur-containing waste as claimed in claim 14, wherein the feeding port (16) of the dryer is provided with an air inlet (39) in communication, the outside of the air inlet (39) is sequentially connected with a heater (40) and a filter (41), and a third inlet (52) of the heater (40) is communicated with the main pipeline (38).
17. The acid making system using industrial sulfur-containing waste according to claim 16, wherein the second inlet (35) and the second outlet (36) are provided at the top and bottom of the cylinder (11), respectively.
18. The acid making system using industrial sulfur-containing waste according to any one of claims 1 to 7, 9 to 17, wherein the rotary shaft (12) comprises a first rotary shaft (121) and a second rotary shaft (122) disposed in parallel along the axial direction of the cylinder (11), the rotary directions of the first rotary shaft (121) and the second rotary shaft (122) being opposite.
19. The acid making system using industrial sulfur-containing waste according to claim 18, wherein the blades (34) on the first rotation shaft (121) and the blades (34) on the second rotation shaft (122) are staggered with each other; the blades (34) include sector-shaped blade surfaces distributed in a circumferential direction of the rotary shaft (12), and the radian of the sector-shaped blade surfaces is not greater than a semicircle of the rotary shaft (12).
20. The acid making system using industrial sulfur-containing waste as claimed in claim 19, wherein the blade (34) is provided with a scraping structure (66) at an end portion for stirring sulfur slurry, and the scraping structure (66) is provided extending along an axial direction of the rotary shaft (12) and is capable of contacting with an inner wall of the cylinder (11).
21. The acid making system using industrial sulfur-containing waste as claimed in claim 1, wherein the pretreatment unit further comprises a processor, a temperature sensor and a pressure sensor, wherein the temperature sensor and the pressure sensor are positioned in the cylinder (11), the temperature sensor and the pressure sensor are respectively connected with the processor, and the processor is respectively electrically connected with the motor (32) and the induced draft fan (28).
22. The acid making system utilizing industrial sulfur waste as defined in any one of claims 1-7 wherein said acid making system further comprises:
the fluidized bed furnace is used for burning the sulfur-containing waste dried by the dryer to generate a process gas containing sulfur dioxide;
The waste heat boiler comprises an air inlet tower (43), an air outlet tower (44) and a sealing plate (45), wherein the air inlet tower (43) is communicated with the air outlet tower (44), the air inlet tower (43), the air outlet tower (44) are in sealing connection with the sealing plate (45), an air inlet (46) is formed in the side wall of the air inlet tower (43), and an air outlet (47) is formed in the side wall of the air outlet tower (44); the side walls of the air inlet tower (43) and the air outlet tower (44) and the sealing plate (45) are respectively provided with a hollow clamping cavity, cooling water is introduced into the hollow clamping cavities of the side walls of the air inlet tower (43) and the air outlet tower (44) and communicated with each other, the cooling water in the side walls is converged into the sealing plate (45), and the sealing plate (45) is provided with a steam outlet (48);
an air inlet (46) of the air inlet tower (43) is filled with process air, and the steam outlet (48) is communicated with the main pipeline (38);
The top of the air inlet tower (43) and the top of the air outlet tower (44) are provided with a bottom plate (49) with a downward concave structure, the sealing plate (45) is provided with a drainage plate (50) which extends vertically and downward, the drainage plate (50) extends downward into the concave structure of the bottom plate (49), the drainage plate (50) and the bottom plate (49) are respectively provided with a hollow inner cavity, the inner cavities of the drainage plate (50) are communicated with the inner cavities of the sealing plate (45), and the inner cavities of the bottom plate (49) are respectively communicated with the inner cavities of the side walls of the air inlet tower (43) and the air outlet tower (44);
The dust collector is characterized in that a dust leakage hole (51) is formed in the downward concave structure of the bottom plate (49), a valve device (53) is arranged at the dust leakage hole (51), the valve device (53) is in a normally closed state, and the valve device (53) is changed into an openable state according to the accumulated dust weight.
23. The acid making system using industrial sulfur-containing waste as claimed in claim 22, wherein the bottom plate (49) is in a "V" shape or a "U" shape.
24. The acid making system using industrial sulfur-containing waste of claim 22, wherein the pretreatment unit further comprises a tail gas scrubbing recovery system;
the tail gas washing and recycling system comprises a water washing device, an acid washing device and a tail gas washing device;
The washing device is used for washing and cooling tail gas discharged by the dryer, the air inlet end of the washing device is connected with a tail gas discharge port (18), and a part of washing mixed liquid generated by tail gas washing is supplied to the feed inlet of the dryer after being filtered;
the acid washing device is connected with an air outlet of the water washing device and is used for neutralizing ammonia in tail gas after water washing to generate ammonium sulfate mother liquor;
The tail gas washing device is connected with the gas outlet of the pickling device and used for washing and cooling the pickled tail gas.
25. The acid making system using industrial sulfur-containing waste according to claim 24, wherein an ammonium sulfate mother liquor outlet of the acid washing device is connected to one or both of an ammonium sulfate production device for producing an ammonium sulfate product from the ammonium sulfate mother liquor or a pretreatment evaporation concentration system, and an outlet of the pretreatment evaporation concentration system is connected to the dryer.
26. The acid making system using industrial sulfur-containing waste according to claim 24, wherein the water washing device is a water washing tower (19), the water washing tower (19) being provided with a cooling water inlet (23) and a water washing circulation pump branch (22);
The water wash circulation pump leg (22) comprises a first path in communication with the internal circulation of the water wash column (19), a second path connected to the feed inlet of the dryer via a filtration bypass system (24);
The filter bypass system (24) comprises a filter, the outlet of which is connected with the feed inlet of the dryer;
The pickling device is a pickling tower (20), the pickling tower (20) is provided with a dilute acid branch circuit (25) and a pickling circulating pump branch circuit (26), the dilute acid branch circuit (25) is connected with dilute acid supply equipment, and the pickling circulating pump branch circuit (26) comprises a third path communicated with the internal circulation of the pickling tower (20) and a fourth path connected with an ammonium sulfate mother liquor tank through an ammonium sulfate mother liquor bypass (27).
27. The acid making system using industrial sulfur-containing waste of claim 26, wherein the dilute acid supply device is a dynamic wave scrubber used in the H 2SO4 making system.
28. The acid making system using industrial sulfur-containing waste of claim 26, wherein the air outlet of the acid washing unit is connected to the tail gas washing unit via an induced draft fan (28).
29. A process for producing acid from industrial sulfur-containing waste, characterized in that the process for producing acid is carried out in the acid production system using industrial sulfur-containing waste according to any one of claims 1 to 26, comprising a pretreatment process comprising the steps of:
sulfur pulp preparation: preparing industrial sulfur-containing waste into mixed waste liquid, and then filtering and homogenizing to prepare sulfur slurry;
The drying process comprises the following steps: and (3) delivering the sulfur pulp obtained in the sulfur pulp preparation step into a dryer, and heating and drying the sulfur pulp by using a heating medium.
30. The method for producing acid by utilizing industrial sulfur-containing waste as claimed in claim 29, wherein the sulfur slurry preparing step further comprises a water content adjusting process, wherein the water content adjusting process is at least provided in one or more of the steps of preparing mixed waste liquid, preparing intermediate sulfur liquid by filtering the mixed waste liquid, or preparing sulfur slurry by the intermediate sulfur liquid.
31. The method for producing acid from industrial sulfur-containing waste according to claim 30, further comprising a tail gas washing and recovering process comprising:
Step S11: washing and cooling tail gas discharged by the dryer to form a washing mixed solution, and conveying a part of the washing mixed solution into the dryer for recycling;
step S12: the tail gas after washing and cooling enters an acid washing tower, acid washing is carried out by acid liquor, ammonium sulfate mother liquor with a certain concentration is generated, and the ammonium sulfate mother liquor is used for preparing an ammonium sulfate finished product;
Step S13: and (3) enabling the tail gas after pickling to enter a tail gas washing device for washing and cooling, and discharging the washed tail gas into the atmosphere.
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