CN112158861A - Production system of low chlorine potassium sulfate - Google Patents
Production system of low chlorine potassium sulfate Download PDFInfo
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- CN112158861A CN112158861A CN202010411038.3A CN202010411038A CN112158861A CN 112158861 A CN112158861 A CN 112158861A CN 202010411038 A CN202010411038 A CN 202010411038A CN 112158861 A CN112158861 A CN 112158861A
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- mannheim furnace
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- potassium sulfate
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 69
- WCXFGIOTWOPDMG-UHFFFAOYSA-L S(=O)(=O)([O-])[O-].[K+].[Cl+] Chemical compound S(=O)(=O)([O-])[O-].[K+].[Cl+] WCXFGIOTWOPDMG-UHFFFAOYSA-L 0.000 title claims description 5
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 57
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 56
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 48
- 239000000460 chlorine Substances 0.000 claims abstract description 41
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 41
- 238000002156 mixing Methods 0.000 claims abstract description 37
- 238000012216 screening Methods 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 111
- 239000007789 gas Substances 0.000 claims description 60
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 24
- 239000003546 flue gas Substances 0.000 claims description 24
- 238000011084 recovery Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 12
- 238000006386 neutralization reaction Methods 0.000 claims description 10
- 230000003472 neutralizing effect Effects 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 5
- 238000002485 combustion reaction Methods 0.000 claims description 4
- 239000003595 mist Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000010276 construction Methods 0.000 abstract description 3
- 238000010924 continuous production Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 64
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 24
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 17
- 239000002245 particle Substances 0.000 description 14
- 239000003345 natural gas Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 239000001103 potassium chloride Substances 0.000 description 9
- 235000011164 potassium chloride Nutrition 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 chlorine ions Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/02—Preparation of sulfates from alkali metal salts and sulfuric acid or bisulfates; Preparation of bisulfates
Abstract
The invention discloses a production system of low-chlorine potassium sulfate, which comprises a first Mannheim furnace, a first screening device, a first crushing device, a mixing device and a second Mannheim furnace, wherein a potassium sulfate product in the first Mannheim furnace enters the first screening device for screening, screened oversize products enter the first crushing device, the crushed oversize products are mixed with concentrated sulfuric acid in the mixing device, and the mixture enters the second Mannheim furnace for heating reaction to obtain the low-chlorine potassium sulfate. According to the invention, the corresponding devices are connected in sequence, oversize materials in the discharge of the first Mannheim furnace are further processed, so that raw materials are reacted more fully, the continuous production of low-chlorine potassium sulfate is realized, the oversize materials are reacted in the second Mannheim furnace, the existing production devices can be fully utilized for manufacturers adopting the Mannheim method to produce potassium sulfate, the construction of a production system can be completed only by changing a material conveying mode on the basis of the existing production devices, and the cost and investment are saved.
Description
Technical Field
The invention belongs to the technical field of inorganic chemical industry, and particularly relates to a production system of low-chlorine potassium sulfate.
Background
In the prior art, potassium sulfate is produced industrially by the Mannheim method, in which potassium chloride and concentrated sulfuric acid are used as raw materials and continuously fed into a Mannheim furnace according to a certain proportion to react to produce potassium sulfate. The specific reaction process comprises the following two steps:
KCl+H2SO4→KHSO4+HCl
KCl+KHSO4→K2SO4+HCl
the above two reactions are heterogeneous reactions, and are affected by factors such as uneven heating in the reaction process, and the potassium bisulfate generated in the first reaction is often coated on the surface of potassium chloride, which hinders the further reaction and causes the chlorine content in the product to be higher. For potassium sulfate produced by a Mannheim furnace, when the potassium sulfate just comes out of the furnace and a neutralizer is not added, the chlorine content is 1.5 percent, and the sulfuric acid content is generally 3 percent; when the chlorine content is 1.0%, the sulfuric acid content is generally 4.5%. Caking of the solid starting material during the reaction results in a greater proportion of potassium chloride being coated, resulting in a higher chlorine content in the final product. Thus, for the potassium sulfate product produced by the Mannheim process, less potassium chloride may be coated in the smaller size particles, the chlorine content is relatively low, and the chlorine content is generally higher in the larger size particles. If the low-chlorine potassium sulfate product needs to be produced, the discharged material of potassium sulfate produced by the Mannheim method needs to be screened, undersize products with smaller particle sizes can be directly collected, and oversize products with larger particle sizes also need to be further treated, so that the chlorine content in the oversize products is reduced to be below the standard.
In the above production method, the following scheme is adopted in the conventional production method for treating oversize products. For the production of potassium sulfate product (K)2O is more than or equal to 52 percent), the product discharged from the furnace is screened, and the undersize product is collected as a low-chlorine potassium sulfate product (K)2O is more than or equal to 52 percent), and the separated large particles are returned to the common potassium sulfate product (K)2O is more than or equal to 50 percent) as a common potassium sulfate product (K)2O is more than or equal to 50 percent). The low-chlorine potassium sulfate product (K) is produced due to the factors of the price difference between the two products, the dosage difference of the medium-mixing agent caused by the large particles as the return material and the like2O is more than or equal to 52 percent) is less than or equal to 3 percent than the production cost of free acid and the chlorine content is low1.5% or less potassium sulfate product (K)2O.gtoreq.52%) higher. The cost increase per ton of product is calculated to be about 293 yuan. Meanwhile, 25000t of common potassium sulfate product (K) is produced every 1000t of low-chlorine potassium sulfate2O is more than or equal to 50 percent) to consume the generated oversize products, and reduce potassium sulfate products (K)2O is more than or equal to 52 percent) of the total weight of the raw materials.
The Chinese patent with application number 95108703.7 discloses a non-return process for preparing potassium sulfate by Mannheim furnace, which is characterized in that the return material of potassium sulfate is mixed with sulfuric acid, and then the mixture enters a reactor for heating reaction, the concentration of the sulfuric acid is 98 percent, the amount of the sulfuric acid is 80 to 110 percent of the theoretical amount of the reaction, the reaction is carried out at the temperature of 400 ℃ and 600 ℃, and after 0.3 to 4 hours, the reaction product is cooled and crushed to obtain a qualified finished product. However, in the scheme, a new reactor needs to be additionally arranged for production, so that the cost is increased.
The present invention has been made in view of this situation.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a production system which can fully utilize the prior equipment to produce low-chlorine potassium sulfate.
In order to solve the technical problems, the invention adopts the technical scheme that:
the utility model provides a production system of low chlorine potassium sulfate, includes first manheim stove, first screening plant, first breaker, mixing arrangement and second manheim stove, the potassium sulfate product in first manheim stove gets into first screening plant screening, and the oversize after the screening gets into first breaker, and kibbling oversize mixes with concentrated sulfuric acid in mixing arrangement, and the mixture gets into second manheim stove and carries out heating reaction, obtains low chlorine potassium sulfate.
In the scheme, the discharged material of the first Mannheim furnace is screened by the first screening device, oversize products with higher chlorine content are sent to the first crushing device to be crushed, the potassium chloride coated inside can be exposed, then the crushed material enters the mixing device to be mixed with concentrated sulfuric acid, and finally the crushed material enters the second Mannheim furnace to be heated and reacted, so that excessive chlorine ions in the oversize products are consumed, and the chlorine content in the produced potassium sulfate products is greatly reduced.
Furthermore, the first Mannheim furnaces comprise a plurality of first Mannheim furnaces, and the plurality of first Mannheim furnaces are connected to the same first screening device or are respectively connected with one first screening device; the multiple first screening devices are connected to the same first crushing device or respectively connected with one first crushing device;
preferably, the first Mannheim furnace comprises four first sieving devices, each first Mannheim furnace is connected with one first sieving device, and each first sieving device is connected with one first crushing device.
In the scheme, in the discharging of the first Mannheim furnace, the ratio of oversize products is smaller than that of undersize products, only the oversize products enter the second Mannheim furnace to carry out heating reaction, and the production capacity of the second Mannheim furnace can be fully utilized as far as possible by arranging a plurality of first Mannheim furnaces corresponding to one second Mannheim furnace. Generally, the oversize material ratio in the discharge of the first Mannheim furnace is about 20-25%, and preferably every four first Mannheim furnaces correspond to one second Mannheim furnace, so that the production capacity of the second Mannheim furnace can be fully utilized under the condition that the production capacities of the first and second Mannheim furnaces are close.
Further, a conveying device is arranged between the first crushing device and the mixing device, and the conveying device conveys the materials in the first crushing device to the mixing device;
preferably, the conveying device is a bucket elevator.
Further, the mixing device is provided with a stirring device and a spraying device, concentrated sulfuric acid enters the mixing device in a mist form through the spraying device and is mixed with oversize materials under the stirring of the stirring device.
In the scheme, the using amount of the concentrated sulfuric acid is smaller than that of the oversize product in the solid particle shape, the oversize product is sent into the mixing device, and the atomized concentrated sulfuric acid is sprayed into the mixing device, so that atomized liquid drops formed by the concentrated sulfuric acid can be wrapped on the surface of the solid particle, the atomized liquid drops and the solid particle are mixed more uniformly through stirring, and the subsequent reaction in the second Mannheim furnace is more fully performed.
Further, the combustion chamber of the first Mannheim furnace is provided with a flue gas outlet, the second Mannheim furnace is provided with a flue gas inlet, and the flue gas outlet of the first Mannheim furnace is communicated with the flue gas inlet of the second Mannheim furnace through a pipeline.
In the scheme, the mass ratio of oversize particles in the mixture fed into the second Mannheim furnace is more than 90%, the concentrated sulfuric acid is in a solid state after being mixed with the mixture, the potassium sulfate in the oversize particles accounts for a large proportion, the incompletely reacted potassium chloride and potassium bisulfate are relatively less, and the reaction can be completed without a large driving force, so that the reaction can be carried out at a slightly low temperature. The reaction temperature of the materials in the second Mannheim furnace is lower than the temperature of the flue gas tail gas generated in the production of potassium sulfate by the general Mannheim method, the flue gas tail gas of the first Mannheim furnace can be led to the second Mannheim furnace to provide heat for reaction, and the lacking energy is provided by newly added natural gas, so that the consumption of the natural gas can be greatly reduced, the energy is saved, and the production cost is saved. Meanwhile, when the potassium sulfate is produced by adopting the Mannheim method in the prior art, the raw material sulfuric acid is in a liquid state, so that the hearth of the Mannheim furnace can be corroded, acid leakage is easily caused, the flue gas is generally not introduced into the bottom of the furnace to reuse the heat energy in the flue gas, and in the production system, the material entering the second Mannheim furnace is in a solid state, liquid concentrated sulfuric acid does not exist, the corrosion phenomenon of the hearth does not exist, so that the flue gas can be introduced into the hearth to utilize the heat.
And further, the system also comprises a hydrochloric acid tail gas recovery system, and the hydrochloric acid tail gas outlets of the reaction chambers of the first Mannheim furnace and the second Mannheim furnace are communicated with the same hydrochloric acid tail gas recovery system.
In the scheme, a large amount of hydrogen chloride gas can be generated in the process of preparing the potassium sulfate by the Mannheim method, and hydrochloric acid gas in reaction tail gas can be collected by the hydrochloric acid tail gas recovery system to produce byproduct hydrochloric acid, so that the environmental pollution is avoided. Most of the mixed material fed into the second Mannheim furnace is potassium sulfate, the content of hydrochloric acid gas generated by further heating reaction in reaction tail gas is far less than that of hydrochloric acid in tail gas generated by the general Mannheim method, and the content of the hydrochloric acid gas is about 6% of that of the tail gas generated by the general Mannheim method for producing potassium sulfate. The same hydrochloric acid tail gas treatment system has enough treatment capacity to collect and treat a small amount of hydrochloric acid generated by the second Mannheim furnace while collecting and treating the hydrochloric acid tail gas of the first Mannheim furnace. The hydrochloric acid tail gas outlets of the reaction chambers of the first Mannheim furnace and the second Mannheim furnace are connected to the same hydrochloric acid tail gas recovery system, so that the tail gas recovery system does not need to be additionally arranged for the second Mannheim furnace, and the cost is saved.
Further, the system comprises a plurality of sets of hydrochloric acid tail gas recovery systems, and the hydrochloric acid tail gas outlets of the reaction chambers of the first Mannheim furnace and the second Mannheim furnace are respectively communicated with different hydrochloric acid tail gas recovery systems.
In the scheme, the hydrochloric acid content in the tail gas generated in the first Mannheim furnace and the tail gas generated in the second Mannheim furnace are different, and the hydrochloric acid tail gas outlets of the reaction chambers of the first Mannheim furnace and the second Mannheim furnace are respectively communicated with different hydrochloric acid tail gas recovery systems, so that the whole production system is easier to control.
And the discharging material of the second Mannheim furnace enters the second screening device for screening, the screened oversize material enters the second crushing device, and the crushed oversize material enters the first Mannheim furnace again for reaction.
In the above scheme, because the materials are mixed uniformly, the number of the agglomerates generated in the second Mannheim furnace is reduced greatly, and a small part of the agglomerates with higher chlorine content may be generated in abnormal conditions, so that the finished products with low chlorine content need to be screened from the discharge of the second Mannheim furnace. Through connecting the corresponding equipment in sequence, the agglomerated product is crushed and then returned to the first Mannheim furnace for re-reaction, so that chloride ions in the agglomerated product can be further consumed, low-chlorine potassium sulfate is generated, and the raw materials are fully utilized.
Further, a conveying device is arranged between the second screening device and the second crushing device, and screened oversize products are conveyed to the second crushing device; or a conveying device is arranged between the second crushing device and a feed inlet of the first Mannheim furnace, and the materials in the second crushing device are conveyed to the first Mannheim furnace;
preferably, the conveying device is a bucket elevator.
And further, a neutralization device is further included, and the discharge of the second Mannheim furnace enters the neutralization device to be mixed with a neutralizing agent.
In the scheme, in order to further react oversize materials, concentrated sulfuric acid is added into the materials in the mixing device for mixing, so that the acid content in the discharged material of the second Mannheim furnace is possibly higher, the discharged material is sent to the neutralizing device and then is mixed with the neutralizing agent, the acid content can be reduced to the requirements of customers or national standards, and meanwhile, the adding of the neutralizing agent plays a role in diluting, so that the chlorine content in the final product is further reduced.
After the technical scheme is adopted, compared with the prior art, the invention has the following beneficial effects.
According to the production system, the corresponding devices are connected in sequence, the discharged material of the first Mannheim furnace is screened, crushed, mixed with acid and then put into the second Mannheim furnace for further reaction, so that the raw materials are reacted more fully, the continuous production of low-chlorine potassium sulfate is realized, oversize materials are treated by the Mannheim furnace, the existing production devices can be fully utilized for manufacturers producing potassium sulfate by adopting the Mannheim method, the construction of the production system can be completed only by changing the material conveying mode on the basis of the existing production devices, and the cost investment is saved.
The production system is communicated through the pipeline, the tail gas of the flue gas of the first Mannheim furnace is communicated to the second Mannheim furnace to provide heat for reaction, the consumption of natural gas can be reduced, energy is saved, and the production cost is saved.
According to the production system, the hydrochloric acid tail gas generated by the reaction in the second Mannheim furnace and the hydrochloric acid tail gas generated by the reaction in the first Mannheim furnace are introduced into the same hydrochloric acid tail gas recovery system for treatment, so that the hydrochloric acid tail gas recovery system does not need to be additionally arranged for the second Mannheim furnace, and the production cost is saved.
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention, are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention without limiting the invention to the right. It is obvious that the drawings in the following description are only some embodiments, and that for a person skilled in the art, other drawings can be derived from them without inventive effort. In the drawings:
FIG. 1 is a schematic view of a low-chlorine potassium sulfate production system of the present invention.
In the figure: 1. a first Mannheim furnace; 2. a first crushing device; 3. a mixing device; 4. a second Mannheim furnace; 5. a bucket elevator; 6. and a cooling device.
It should be noted that the drawings and the description are not intended to limit the scope of the inventive concept in any way, but to illustrate it by a person skilled in the art with reference to specific embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and the following embodiments are used for illustrating the present invention and are not intended to limit the scope of the present invention.
Example one
As shown in fig. 1, the system for producing potassium hypochlorinate according to this embodiment includes a first mannheim furnace 1, a first sieving device, a first crushing device 2, a mixing device 3, and a second mannheim furnace 4. The potassium sulfate product in the first Mannheim furnace 1 enters a first screening device for screening, the screened oversize product enters a first crushing device 2, the crushed oversize product is mixed with concentrated sulfuric acid in a mixing device 3, and the mixture enters a second Mannheim furnace 4 for heating reaction to obtain the low-chlorine potassium sulfate.
The first Mannheim furnace 1 comprises four first Mannheim furnaces 1, each first Mannheim furnace 1 is respectively connected with a first screening device, each first screening device is connected with a first crushing device 2, and each first crushing device 2 is respectively communicated to the mixing device 3.
In another embodiment of this embodiment, four first mannheim kilns may be connected to the same first screening device, or each first mannheim kiln may be connected to one first screening device, and the four first screening devices may be connected to the same first crushing device.
A bucket elevator 5 is arranged between the first crushing device 2 and the mixing device 3, and is used for conveying crushed materials upwards, so that the materials can be conveniently and subsequently fed into the second Mannheim furnace 4. The second Mannheim furnace 4 is further connected with a cooling device 6 for cooling the discharge of the second Mannheim furnace 4, and then transferring the discharge to other equipment for subsequent processing into a marketable finished product.
The method for producing the low-chlorine potassium sulfate by adopting the production system comprises the following steps:
1) respectively feeding materials into No. 1 to No. 4 first Mannheim furnaces at the feeding speed of 1050kg/h of potassium chloride and 730kg/h of concentrated sulfuric acid, staying the raw materials at 470 ℃ for 1-2 hours, discharging the materials through a first screening device, collecting undersize products into qualified products, and conveying the oversize products to a first crushing device to be crushed into 16-mesh solid particles;
2) conveying the crushed oversize products to a mixing device through a bucket elevator, adding concentrated sulfuric acid into the mixing device, and uniformly mixing, wherein the adding amount of the concentrated sulfuric acid is (c + 2.5)% of the total mass of the oversize products, and c% of the total mass of the oversize products is the reaction theoretical using amount of the concentrated sulfuric acid;
3) conveying the mixed materials to a second Mannheim furnace, keeping the temperature in the reaction chamber at 470 ℃, and staying for 1-2 hours;
4) and (3) conveying the discharged material of the second Mannheim furnace to a cooling device for cooling to obtain a qualified product, and mixing the qualified product with the undersize material obtained in the step 1).
Wherein, the theoretical dosage of the reaction is the dosage of sulfuric acid which theoretically completely consumes chloride ions in oversize products and needs to be supplemented. Specifically, 0.5mol of sulfuric acid is theoretically required to consume it per 1mol of chloride ion. When the chlorine content in the oversize product is a% and the sulfuric acid content is b%, c% ((49 a/35.5-b)%).
In the embodiment, when the production system and the production method are adopted for producing the low-chlorine potassium sulfate, the yield of the first Mannheim furnace from No. 1 to No. 4 is 1288kg/h per machine, namely the yield of the production system is 5152kg/h, and oversize products account for about 20% of the total mass of the discharged materials of the first Mannheim furnace. Through determination, in the undersize products discharged from No. 1 to No. 4 first Mannheim furnace, the mass ratio of each component is as follows: 52.47% K2O，0.38％Cl，2.33％H2SO4(ii) a In the discharging of the second Mannheim furnace, the mass ratio of each component is as follows: 52.77% K2O，0.32％Cl，1.82％H2SO4(ii) a In the final product obtained after mixing, the mass ratio of each component is as follows: 52.53% K2O，0.34％Cl，2.23％H2SO4。
In the embodiment, the corresponding devices are connected in sequence, the discharged material of the first Mannheim furnace is screened, crushed, added with acid and mixed, and then put into the second Mannheim furnace for further reaction, so that the raw material reaction is more sufficient, and the continuous production of the low-chlorine potassium sulfate is realized; the oversize materials are treated by a Mannheim furnace, so that manufacturers adopting the Mannheim method to produce potassium sulfate can fully utilize the existing production equipment, and the construction of a production system can be completed only by changing a material conveying mode on the basis of the existing production equipment, thereby saving the cost and investment; the four first Mannheim furnaces are communicated with the second Mannheim furnace in parallel, so that the amount of materials entering the second Mannheim furnace is close to the feeding amount of each first Mannheim furnace, and the production capacity of the second Mannheim furnace can be fully utilized under the condition that the production capacities of the first and second Mannheim furnaces are close.
Example two
As shown in fig. 1, the present embodiment is further limited to the first embodiment, the mixing device 3 has a stirring device and a spraying device, and the concentrated sulfuric acid enters the mixing device 3 in the form of mist through the spraying device and is mixed with the oversize material under the stirring of the stirring device. Because the use amount of concentrated sulfuric acid is very little compared with the oversize material of solid particle shape, spout concentrated sulfuric acid into mixing arrangement 3 with the spraying form, can make the vaporific liquid drop parcel that the concentrated sulfuric acid formed on the solid particle surface, both mix more evenly after the stirring, be favorable to follow-up second manheim stove 4's reaction more abundant going on.
In this embodiment, adopt the mixing arrangement who has agitating unit and atomizer, spout concentrated sulfuric acid into the oversize thing with the spraying form in, the rethread stirring can make both mix more evenly.
EXAMPLE III
In this embodiment, which is a further limitation of the first embodiment, a flue gas outlet is formed in the combustion chamber of the first Mannheim furnace, a flue gas inlet is formed in the second Mannheim furnace, and the flue gas outlet of the first Mannheim furnace is communicated with the flue gas inlet of the second Mannheim furnace through a pipeline. In the prior art, when the potassium sulfate is produced by adopting the Mannheim method, the raw material sulfuric acid is in a liquid state, the hearth of the Mannheim furnace can be corroded, acid leakage is easily caused, generally, the flue gas is not introduced into the bottom of the furnace to reuse heat energy in the flue gas, in the embodiment, the concentrated sulfuric acid and oversize materials are mixed in a mixing device to form a solid state, and then the solid state enters a second Mannheim furnace, the liquid concentrated sulfuric acid does not exist, and the corrosion phenomenon of the furnace bottom does not exist, so that the high-temperature flue gas generated by a combustion chamber of the first Mannheim furnace can be introduced into the bottom of the second Mannheim furnace through pipeline communication, and the furnace bottom of the second Mannheim furnace is heated by adopting the high-temperature flue gas generated by the. The energy still lacking after the high-temperature flue gas is utilized is provided by the natural gas, so that the consumption of the natural gas can be greatly reduced, the energy is saved, and the production cost is saved.
Specifically, the smoke of the first Mannheim furnace is about 780 ℃, the smoke is led to the bottom of the second Mannheim furnace, the temperature is reduced to about 600 ℃ at the bottom of the second Mannheim furnace, and the available smoke flow is 310m3The heat energy which can be supplied to the second Mannheim furnace is 17737.19 kcal/h. The natural gas has a calorific value of 9000kcal/m3By using the first sea of MandarinThe smoke of the mu furnace can save the consumption of natural gas by 1.97m3/h。
Example four
In this embodiment, which is further defined in the first embodiment, the production system further includes a hydrochloric acid tail gas recovery system, a first hydrochloric acid tail gas outlet is formed in the reaction chamber of the first Mannheim furnace, a second hydrochloric acid tail gas outlet is formed in the reaction chamber of the second Mannheim furnace, and the first hydrochloric acid tail gas outlet and the second hydrochloric acid tail gas outlet are connected to the same hydrochloric acid tail gas recovery system.
Because the potassium sulfate prepared by adopting the Mannheim method can generate a large amount of hydrochloric acid gas, the hydrochloric acid gas is generally introduced into a hydrochloric acid tail gas recovery system and is connected with a hydrochloric acid tail gas outlet of a Mannheim furnace reaction chamber through a pipeline, and the generated hydrochloric acid gas is introduced into the hydrochloric acid tail gas recovery system for treatment or recovered for producing a byproduct hydrochloric acid. Most of the mixed material fed into the second Mannheim furnace is potassium sulfate, the content of hydrochloric acid gas generated by further heating reaction in reaction tail gas is far less than that of hydrochloric acid in tail gas generated by the general Mannheim method, and the content of the hydrochloric acid gas is about 6% of that of the tail gas generated by the general Mannheim method for producing potassium sulfate. Therefore, the same hydrochloric acid tail gas recovery system is enough for collecting and processing the hydrochloric acid tail gas generated in the first Mannheim furnace and the second Mannheim furnace.
In this embodiment, the second hydrochloric acid tail gas outlet and the first hydrochloric acid tail gas outlet are connected to the same hydrochloric acid tail gas recovery system, and the tail gas recovery system does not need to be separately added to the second Mannheim furnace, so that the cost is saved.
EXAMPLE five
The present embodiment is different from the fourth embodiment in that the hydrochloric acid off-gas recovery system includes multiple sets, and the first hydrochloric acid off-gas outlet and the second hydrochloric acid off-gas outlet are connected to different hydrochloric acid off-gas recovery systems.
In this embodiment, the contents of hydrochloric acid in the tail gas generated in the first Mannheim furnace and the second Mannheim furnace are different, and the hydrochloric acid tail gas outlets of the reaction chambers of the first Mannheim furnace and the second Mannheim furnace are respectively communicated with different hydrochloric acid tail gas recovery systems, so that the overall control of the production system is easier.
EXAMPLE six
This embodiment is further defined by the first embodiment, wherein the production system further includes a second screening device and a second crushing device, the discharge of the second mannheim furnace enters the second screening device for screening, the screened oversize product enters the second crushing device, and the crushed oversize product enters the first mannheim furnace again for reaction.
When the production system in the embodiment is adopted for potassium sulfate production, the materials entering the second Mannheim furnace are uniformly mixed, and the number of caking produced in the second Mannheim furnace is greatly reduced. In the event of an abnormality, it is possible to produce a very small portion of agglomerated products, which have a relatively high chlorine content and for which the chlorine content can be reduced by further refining and returned to the first Mannheim furnace for renewed reaction. Through setting up corresponding device and connecting in proper order, can sieve out the caking product in the second mannheim stove ejection of compact to will caking product is carried to the first mannheim stove after smashing and is reacted again.
Preferably, as shown in fig. 1, a bucket elevator 5 is provided between the discharge port of the second mannheim furnace 4 and the feed port of the first mannheim furnace 1. Specifically, the bucket elevator 5 is disposed between the second screening device and the second crushing device, or the bucket elevator 5 is disposed between the second crushing device and the feed inlet of the first Mannheim furnace 1. The agglomerated product in the discharge of the second Mannheim furnace 4 is conveyed upwards through the bucket elevator 5, so that the feeding into the first Mannheim furnace 1 is facilitated.
In this embodiment, through the discharge gate with the second mannheim stove with the feed inlet intercommunication of first mannheim stove to set gradually second screening plant and second breaker on the pipeline between the two, can sieve out caking product in the ejection of compact of second mannheim stove, and carry the caking product breakage to first mannheim stove and react the refining again, realized automatic processing and the returning charge of caking product, saved the hand labor power.
EXAMPLE six
This embodiment is further defined by the first embodiment, wherein the production system further comprises a neutralization device, and the discharge of the second Mannheim furnace enters the neutralization device to be mixed with a neutralizing agent. As the oversize material in the discharge of the first Mannheim furnace is mixed by adding concentrated sulfuric acid in the mixing device, the acid content in the discharge of the second Mannheim furnace is relatively high, and a neutralizer is also added into the reaction product for neutralization in order to reduce the acid content in the final product to the standard requirement. The acid content in the product can be reduced to the standard requirement by arranging a neutralization device, conveying the discharge of the second Mannheim furnace to the neutralization device, and adding a neutralizing agent into the neutralization device for mixing. Specifically, when the production system described in this example is used to perform production according to the production method described in example one, 3 to 8kg of soda ash is charged into the neutralization device every 1t of the output.
In the embodiment, the neutralizing agent is added for deacidification of the discharge of the second Mannheim furnace by arranging the neutralizing device, and meanwhile, the added neutralizing agent also plays a certain role in dilution, so that the chlorine content in the final product can be further reduced.
When the production cost of the potassium sulfate subchloride production by using the production system in the above embodiment is calculated, the amount of heat which can be supplied when the furnace bottom of the second Mannheim furnace is heated by using the flue gas off-gas of the first Mannheim furnace is 17737.19 kcal/h. Through calculation, the total reaction heat quantity is 226936kcal/h, the heat dissipation quantity of the second Mannheim furnace body is 51810kcal/h, and the heat quantity which needs to be supplemented to the second Mannheim furnace is 226936+ 51810-17737.19-261008.81 kcal/h. The natural gas has a calorific value of 9000kcal/m3Then the second Mannheim furnace is supplemented with 29m of natural gas3H is used as the reference value. The output of the first Mannheim furnace from No. 1 to No. 4 is 1288kg/h, which is equivalent to that the second Mannheim furnace needs to be supplemented with 5.63m for every ton of potassium sulfate product3To maintain the reaction in normal operation. The price of the natural gas in the market is 4 yuan/m3The cost increase due to the make-up of natural gas is 22.52 yuan/t.
The depreciation of the original equipment for producing the potassium sulfate of 1t is 73.72 yuan, the power cost except natural gas is 32.15 yuan, a second Mannheim furnace is additionally arranged to treat oversize products discharged from the first Mannheim furnace, and the two costs are increased to (73.72+32.15) × 5 ÷ 4 ÷ 132.34 yuan/t, namely the cost is increased to 26.47 yuan/t.
In conclusion, after the production system is built, the cost increase of each ton of low-chlorine potassium sulfate is only 22.52+ 26.47-48.99 yuan. If the annual output of the low-chlorine potassium sulfate product produced by the production system is 4 ten thousand tons, and the sale price of each ton of low-chlorine potassium sulfate product can be increased by 210 yuan, the profit can be increased by 640 ten thousand yuan each year.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A production system of low chlorine potassium sulfate which is characterized in that: the production system comprises a first Mannheim furnace, a first screening device, a first crushing device, a mixing device and a second Mannheim furnace, wherein a potassium sulfate product in the first Mannheim furnace enters the first screening device for screening, screened oversize products enter the first crushing device, the crushed oversize products are mixed with concentrated sulfuric acid in the mixing device, and the mixture enters the second Mannheim furnace for heating reaction to obtain the low-chlorine potassium sulfate.
2. The production system according to claim 1, wherein: the first Mannheim furnaces comprise a plurality of first Mannheim furnaces, and the plurality of first Mannheim furnaces are connected to the same first screening device or are respectively connected with one first screening device; the multiple first screening devices are connected to the same first crushing device or respectively connected with one first crushing device;
preferably, the first Mannheim furnace comprises four first sieving devices, each first Mannheim furnace is connected with one first sieving device, and each first sieving device is connected with one first crushing device.
3. The production system according to claim 1 or 2, wherein: a conveying device is arranged between the first crushing device and the mixing device and used for conveying the materials in the first crushing device to the mixing device;
preferably, the conveying device is a bucket elevator.
4. The production system according to any one of claims 1 to 3, wherein: the mixing device is provided with a stirring device and a spraying device, concentrated sulfuric acid enters the mixing device in a mist form through the spraying device and is mixed with oversize materials under the stirring of the stirring device.
5. The production system according to any one of claims 1 to 4, wherein: the combustion chamber of the first Mannheim furnace is provided with a flue gas outlet, the second Mannheim furnace is provided with a flue gas inlet, and the flue gas outlet of the first Mannheim furnace is communicated with the flue gas inlet of the second Mannheim furnace through a pipeline.
6. The production system according to any one of claims 1 to 5, wherein: the hydrochloric acid tail gas recovery system is further included, and the hydrochloric acid tail gas outlets of the reaction chambers of the first Mannheim furnace and the second Mannheim furnace are communicated with the same hydrochloric acid tail gas recovery system.
7. The production system according to any one of claims 1 to 5, wherein: the system is characterized by further comprising a plurality of sets of hydrochloric acid tail gas recovery systems, and the hydrochloric acid tail gas outlets of the reaction chambers of the first Mannheim furnace and the second Mannheim furnace are respectively communicated with different hydrochloric acid tail gas recovery systems.
8. The production system according to any one of claims 1 to 7, wherein: the discharging of the second Mannheim furnace enters the second screening device for screening, the screened oversize products enter the second crushing device, and the crushed oversize products enter the first Mannheim furnace again for reaction.
9. The production system according to claim 8, wherein: a conveying device is arranged between the second screening device and the second crushing device, and screened oversize products are conveyed to the second crushing device; or a conveying device is arranged between the second crushing device and a feed inlet of the first Mannheim furnace, and the materials in the second crushing device are conveyed to the first Mannheim furnace;
preferably, the conveying device is a bucket elevator.
10. The production system according to any one of claims 1 to 9, wherein: and the discharge of the second Mannheim furnace enters the neutralization device and is mixed with a neutralizing agent.
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Cited By (1)
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| CN113666338A (en) * | 2021-09-14 | 2021-11-19 | 齐齐哈尔市茂尔农业有限公司 | Production device, heat dissipation mechanism and process flow of potassium sulfate byproduct hydrochloric acid by Mannheim method |
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