CN111644127A - Production system and production process for preparing nitrohumic acid through oxidative degradation - Google Patents

Production system and production process for preparing nitrohumic acid through oxidative degradation Download PDF

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Publication number
CN111644127A
CN111644127A CN202010643132.1A CN202010643132A CN111644127A CN 111644127 A CN111644127 A CN 111644127A CN 202010643132 A CN202010643132 A CN 202010643132A CN 111644127 A CN111644127 A CN 111644127A
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gas
outlet
liquid
inlet
curing
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Inventor
孙彬
刘子静
冯梦喜
冯莉杰
孙好文
毛彦君
郭振军
刘海飞
许美玲
马晶
任麒帆
李洋
张会平
刘平
刘艳婷
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Xinjiang Black Ecological Polytron Technologies Inc
Henan Black Ecological Technology Co ltd
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Xinjiang Black Ecological Polytron Technologies Inc
Henan Black Ecological Technology Co ltd
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Priority to CN202010643132.1A priority Critical patent/CN111644127A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D45/00—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces
    • B01D45/12—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by centrifugal forces
    • B01D45/16—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by centrifugal forces generated by the winding course of the gas stream, the centrifugal forces being generated solely or partly by mechanical means, e.g. fixed swirl vanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/02—Particle separators, e.g. dust precipitators, having hollow filters made of flexible material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D50/00—Combinations of methods or devices for separating particles from gases or vapours
    • B01D50/20—Combinations of devices covered by groups B01D45/00 and B01D46/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75—Multi-step processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/0066—Stirrers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/20—Stationary reactors having moving elements inside in the form of helices, e.g. screw reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/02—Feed or outlet devices; Feed or outlet control devices for feeding measured, i.e. prescribed quantities of reagents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1836—Heating and cooling the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1872—Details of the fluidised bed reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B01D2251/106—Peroxides

Abstract

The invention relates to a production system and a production process for preparing nitrohumic acid by oxidative degradation; the system comprises: at least one nitro humic acid preparation unit for preparing nitro humic acid; at least one curing unit which is connected with the nitrohumic acid preparation unit and is used for curing reaction of the nitrohumic acid; a gas-phase outlet at the top of the nitrohumic acid preparation unit is respectively connected with the gas-phase circulating absorption unit and the liquid-phase circulating utilization unit through a gas-liquid mixing unit; the circulating outlet of the gas-phase circulating absorption unit is connected with the gas-liquid mixing unit, and the liquid-phase outlet of the liquid-phase circulating utilization unit is connected with the nitrohumic acid preparation unit; the method has the advantages of reasonable equipment design, tight connection, easy operation of the process, realization of zero emission, safety and controllability of flue gas and dust, effective reduction of the use amount of nitric acid, reduction of production cost and improvement of product quality.

Description

Production system and production process for preparing nitrohumic acid through oxidative degradation
Technical Field
The invention relates to the technical field of nitrohumic acid production, in particular to a production system and a production process for preparing nitrohumic acid by oxidative degradation.
Background
Nitrohumic acid (NHA) is a complex aromatic macromolecular polycarboxylic acid system containing carboxyl, phenolic hydroxyl, quinonyl and nitro generated after low-rank coal is oxidized and degraded by nitric acid, is closer to soil humic acid in composition, and has higher chemical and biological activity and excellent colloid property.
In the prior art, nitrohumic acid is mainly produced by nitric acid oxidation degradation, nitric acid can be reduced into a plurality of gas components in the oxidation process to generate a large amount of yellow smoke, the main components of the yellow smoke are nitric oxides such as nitric oxide, nitrogen dioxide and the like, the serious harm is caused to the human health and the surrounding environment, and the consumption of the nitric acid is huge. In the prior art, in the production process of nitrohumic acid, coal plate knots on the inner wall of a reactor are difficult to treat, and coal parts are unreacted and easily block an outlet; meanwhile, a large amount of yellow smoke generated after the raw material coal and the nitric acid are mixed cannot be treated in time or is not treated completely, so that the environmental pollution is great; the concentration of nitric acid is gradually reduced in the later stage of the reaction, the coal oxidation degradation degree is poor, and the product quality is poor; for NO in various industries and all walks of life according to relevant requirements of environmental protection departments in 2011XThe total emission reduction is strictly regulated. Thereby reducing nitrogen and oxygenThe pollution of chemical substances and the reduction of the consumption of nitric acid are increasingly important in the production of humic acid. At present, the most common treatment of nitrogen oxides is waste gas tower spraying and liquid caustic soda treatment, and the method has the effect of liquid caustic soda treatment when the concentration of flue gas (mainly NO) is not high, but when the concentration of the flue gas (NO) is relatively high, the treatment effect is poor because NO is insoluble in alkali, the content of NO in the discharged waste gas is high, and secondary pollution of waste water is generated.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a production system and a production process for preparing nitrohumic acid by oxidative degradation, which solve the defects of air pollution and high nitric acid consumption caused by the fact that flue gas cannot be treated in time.
In order to achieve the purpose, the invention adopts the technical scheme that:
a production system for preparing nitro humic acid by oxidative degradation, which comprises: at least one nitro humic acid preparation unit for preparing nitro humic acid; at least one curing unit which is connected with the nitrohumic acid preparation unit and is used for curing reaction of the nitrohumic acid; a gas-phase outlet at the top of the nitrohumic acid preparation unit is respectively connected with the gas-phase circulating absorption unit and the liquid-phase circulating utilization unit through a gas-liquid mixing unit; and a circulating outlet of the gas-phase circulating absorption unit is connected with the gas-liquid mixing unit, and a liquid-phase outlet of the liquid-phase circulating utilization unit is connected with the nitrohumic acid preparation unit.
Preferably, the nitrohumic acid preparation unit includes spiral shell belt reation kettle, and spiral shell belt reation kettle top is equipped with tail gas entry, raw materials coal import, nitric acid spray thrower inlet pipe way, spray thrower inlet pipe way and exhanst gas outlet, and spiral shell belt reation kettle's inside is equipped with the spiral shell belt agitator, and the lower part of spiral shell belt reation kettle is equipped with the material outlet pipeline that links to each other with curing reaction unit.
Preferably, the raw material coal inlet is connected with the raw material coal feeding bin through a first fully-closed weighing feeder, and a raw material coal disperser is arranged between the raw material coal inlet and the first fully-closed weighing feeder; the liquid inlet pipeline of the nitric acid sprayer is connected with the nitric acid storage tank through a Venturi flowmeter.
Preferably, the gas-liquid mixing unit comprises a flue gas pipeline connected with a flue gas outlet, the flue gas pipeline is connected with a gas phase inlet of the spiral mixer, and an atomization inlet of the spiral mixer is connected with the hydrogen peroxide solution storage tank through an atomizer; the mixed fluid outlet of the spiral mixer is connected with the cyclone separator; and a liquid outlet of the cyclone separator is connected with the liquid phase recycling unit, and a gas outlet of the cyclone separator is connected with the gas phase circulating absorption unit.
Preferably, the gas phase circulation absorption unit comprises an oxygen absorption tower, a feed gas inlet at the middle lower part of the oxygen absorption tower is connected with a gas outlet of the cyclone separator, and a liquid phase outlet at the bottom of the oxygen absorption tower is connected with HNO in the liquid phase circulation utilization unit3-H2O2The solution storage tank is connected, the catalytic oxidation layer is arranged in the middle of the oxygen absorption tower, the top of the catalytic oxidation layer is provided with a hydrogen peroxide sprayer connected with a hydrogen peroxide solution pipeline, and a tail gas outlet at the top of the oxygen absorption tower is provided with a tail gas draught fan; the catalytic oxidation layer is a plurality of layers of plate-type Fenton catalyst wire meshes.
Preferably, the liquid phase recycling unit comprises HNO3-H2O2Solution storage tank, HNO3-H2O2The solution storage tank is connected with a liquid phase outlet at the bottom of the oxygen absorption tower through a second tee joint, and the third end of the second tee joint is connected with a liquid outlet of the cyclone separator; HNO3-H2O2The liquid outlet of the solution storage tank is connected with the liquid inlet pipeline of the sprayer through a liquid level control valve and a centrifugal pump.
Preferably, the curing unit comprises a fluidized curing bin, the top of the fluidized curing bin is provided with a nitrohumic acid inlet and a flue gas outlet which are connected with a material outlet pipeline, the inner lower part of the fluidized curing bin is provided with a fluidized bed with a vibrator, the tail end of the fluidized bed is provided with a finished product outlet, and the finished product outlet is connected with a product packaging system through a second totally-enclosed weighing feeder; the lower part of the front end of the fluidized bed is provided with a drying and curing part, and the lower part of the tail end of the fluidized bed is provided with a cooling part; and an inlet valve is arranged on the material outlet pipeline.
Preferably, the fluidized curing bin corresponding to the bottom of the fluidized bed is internally divided into a drying curing cavity and a cooling cavity; a baffle is arranged between the drying and curing cavity and the cooling cavity; the drying and curing part comprises a first air blower which is connected with a heating gas inlet at the bottom of the drying and curing cavity through a heat exchanger; the cooling portion comprises a second air blower, and the second air blower is connected with a cooling gas inlet at the bottom of the cooling cavity.
Preferably, the flue gas outlet is connected with a bag type dust collector, a gas phase outlet at the top of the bag type dust collector is connected with a tail gas inlet of the spiral-belt type reaction kettle, and a solid outlet at the bottom of the bag type dust collector is connected with the second totally-enclosed weighing feeder.
The invention also provides a production process of the production system for preparing the nitro humic acid by oxidative degradation, which comprises the following steps:
step 1: raw material coal is weighed by a raw material coal feeding bin and a first totally enclosed weighing feeder and then enters a spiral belt type reaction kettle through a raw material coal disperser and a raw material coal inlet, and nitric acid in a nitric acid storage tank is metered by a Venturi flowmeter and then enters the spiral belt type reaction kettle through a nitric acid sprayer; simultaneously starting a helical ribbon stirrer; the helical ribbon stirrer can not only enable the materials to fully generate oxidative degradation reaction and prevent the materials from being bonded with the inner wall of the helical ribbon reaction kettle, but also enable the materials to move towards a material outlet pipeline; the concentration of nitric acid in the nitric acid storage tank is 30% -60%, and the mass ratio of raw coal to nitric acid in the spiral-ribbon reaction kettle is 1-10: 1;
step 2: after the materials in the helical ribbon type reaction kettle are fully reacted, opening an inlet valve, and allowing the materials subjected to oxidative degradation to enter the top of a fluidized bed in a fluidized curing bin through a material outlet pipeline; the vibrator is started to control the advancing speed of the materials and enable the materials to be cured uniformly; simultaneously starting a first air blower of the drying and curing part and a second air blower of the cooling part;
air introduced by the first air blower is heated by the heat exchanger and then is heated by the heating gas inlet and the drying curing cavity to the front end of the fluidized bed and the material subjected to oxidative degradation at the front end of the fluidized bed, and in the heating process, the material subjected to oxidative degradation is cured at the curing temperature and water in the material subjected to oxidative degradation can be taken away; the heating gas keeps the temperature of the material after oxidative degradation at 80-90 ℃;
air introduced by the second air blower enters the cooling cavity through the cooling gas inlet to cool the tail end of the fluidized bed and the material subjected to oxidative degradation at the tail end of the fluidized bed; the air cools the cured material to 35-45 ℃, and then the cured material is conveyed into a product packaging system through a finished product outlet and a second totally-enclosed weighing feeder for packaging;
and step 3: flue gas generated in the curing process in the fluidized curing bin and air blown by the first air blower and the second air blower in the step 2 enter the bag type dust collector through a flue gas outlet for gas-solid separation, and a powder product after the gas-solid separation enters a product packaging system through a solid outlet at the bottom of the bag type dust collector and the second totally-enclosed weighing feeder for packaging; gas after gas-solid separation enters the helical ribbon type reaction kettle through a tail gas inlet of the helical ribbon type reaction kettle and is absorbed in the subsequent oxidation degradation reaction process;
and 4, step 4: in the oxidation degradation reaction process of the coal and the nitric acid in the helical ribbon type reaction kettle in the step 1, the nitric acid is reduced to generate NOXFlue gas; NOXThe flue gas enters the spiral mixer through the flue gas outlet, the flue gas pipeline and the gas phase inlet of the spiral mixer; said NOXThe temperature of the flue gas is: 80-100 ℃;
and 5: the hydrogen peroxide solution with the concentration of 15-30% in the hydrogen peroxide solution storage tank is atomized by the atomizer and then enters the spiral mixer from the atomization inlet of the spiral mixer and NO in the step 4XThe flue gas is fully mixed in a spiral mixing chamber in a spiral mixer;
said NOXThe low-valence nitrogen oxide in the flue gas is preliminarily oxidized and absorbed by the atomized hydrogen peroxide in the mixing chamber to generate HNO3-H2O2Small liquid drops;
the reaction process is as follows: NO + NO2+2H2O2= 2HNO3+H2O; hydrogen peroxide is in an excess state;
step 6: in the step 5, the gas-liquid mixture after the full mixing reaction in the spiral mixing chamber enters a cyclone separator through a mixed fluid outlet of the spiral mixer for gas-liquid separation;
the liquid phase after gas-liquid separation enters HNO through the liquid outlet of the cyclone separator and the third end of the second tee joint3-H2O2A solution storage tank;
gas phase after gas-liquid separation enters the oxygen absorption tower through a feed gas inlet at the middle lower part of the oxygen absorption tower; the hydrogen peroxide solution in the hydrogen peroxide solution pipeline is sprayed to the plurality of layers of plate-type Fenton catalyst metal wire nets through the hydrogen peroxide sprayer, gas phase after gas-liquid separation contacts the hydrogen peroxide solution from bottom to top and hydrogen peroxide liquid drops on the plurality of layers of plate-type Fenton catalyst metal wire nets are further oxidized and absorbed to generate HNO3-H2O2A solution; the gas which has been subjected to the two-stage oxidation absorption and reaches the standard is discharged outside through a tail gas induced draft fan; the HNO3-H2O2The solution enters HNO through a second tee joint3-H2O2A solution storage tank; the gas phase after the gas-liquid separation is nitrogen oxide which is not completely absorbed; the concentration of the hydrogen peroxide solution in the hydrogen peroxide solution pipeline is 15-30%;
and 7: HNO3-H2O2HNO in solution storage tank3-H2O2The flow of the solution is regulated by a liquid level control valve, and the solution is pressurized and conveyed into a liquid inlet pipeline of a sprayer by a centrifugal pump to carry out oxidative degradation on the raw material coal of the spiral belt type reaction kettle so as to realize the recycling of nitrogen oxide flue gas and save the using amount of nitric acid;
and 8: the oxygen absorption towers in the step 6 are arranged in series, and liquid phase outlets at the bottoms of the oxygen absorption towers are respectively connected with HNO in the liquid phase recycling unit3-H2O2The solution storage tanks are connected, the hydrogen peroxide solution pipelines 22 are respectively connected with hydrogen peroxide sprayers in the oxygen absorption towers, and a tail gas draught fan is arranged at a tail gas outlet at the top of the last oxygen absorption tower 19; two adjacent oxygen absorption towers, the top tail gas outlet and the back tail gas outlet of the front oxygen absorption towerThe middle lower part of the oxygen absorption tower is connected with a raw material gas inlet.
According to the production system and the production process for preparing nitrohumic acid through oxidative degradation, the problem of difficult treatment of coal plate knots on the inner wall of the reactor in the production process of the nitrohumic acid can be effectively solved by arranging the spiral-belt type reaction kettle and the spiral-belt type stirrer; the fluidized curing bin is arranged, so that the problems of incomplete curing reaction, heat preservation during curing, cooling after curing, secondary pollution of nitrogen oxides generated in the curing process and large dust of products are effectively solved; through setting up the hydrogen peroxide spray thrower and spray hydrogen peroxide solution to oxygen in inhaling the tower and can effectively absorb the nitrogen oxide flue gas that is difficult to handle in the humic acid production process of nitryl to inhale tower two-stage nitrogen oxide processing apparatus through setting up helical mixing ware and oxygen, make nitrogen oxide by the oxidation absorption completely, tail gas reaches outer row standard, and can be with the HNO who obtains3-H2O2The solution returns to the helical ribbon type reaction kettle for reuse, so as to achieve the purposes of effectively reducing the consumption of nitric acid and saving the cost; the hydrogen peroxide solution adopted by the invention can also enhance the oxidability of nitric acid, improve the oxidation efficiency of the nitric acid, ensure that the raw material coal is oxidized and degraded more thoroughly, and improve the quality of products; the method has the advantages of reasonable equipment design, easy operation of the process, realization of zero emission of flue gas and dust, safety and controllability, effective reduction of the use amount of nitric acid, reduction of production cost and improvement of product quality.
Drawings
FIG. 1 is a schematic structural diagram of the present invention.
In the figure:
1. a raw material coal feeding bin; 2. a first totally enclosed weighing feeder; 3. A raw material coal disperser; 4. A raw material coal inlet; 5. a helical ribbon type reaction kettle; 6. a nitric acid sprayer; 7. a ribbon blender; 8. a material outlet pipe; 9. a flue gas outlet; 10. a tail gas inlet; 11. a sprayer; 12. A venturi flow meter; 13. a nitric acid storage tank; 14. a flue gas duct; 15. a screw mixer; 16. an atomizer; 17. a hydrogen peroxide solution storage tank; 18. a cyclone separator; 19. an oxygen absorption tower; 20 a tail gas draught fan; 21. a catalytic oxidation layer; 22.a hydrogen peroxide solution conduit; 23. a hydrogen peroxide sprayer; 24. a middle and lower raw material gas inlet; 25. a second tee joint; 26. HNO3-H2O2A solution storage tank; 27. a liquid level control valve; 28. a centrifugal pump; 29. an inlet valve; 30. a fluidization curing bin; 31. a fluidized bed; 32. a first blower; 33. a heat exchanger; 34. a heated gas inlet; 35. a vibrator; 36. a cooling gas inlet; 37. a second blower; 38. a finished product outlet; 39. a flue gas outlet; 40. a bag type dust collector; 41. a baffle plate; 42. a second totally enclosed weighing feeder; 43. a product packaging system.
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 of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1: the invention relates to a production system and a production process for preparing nitrohumic acid by oxidative degradation, wherein the system comprises: at least one nitro humic acid preparation unit for preparing nitro humic acid; at least one curing unit which is connected with the nitrohumic acid preparation unit and is used for curing reaction of the nitrohumic acid; a gas-phase outlet at the top of the nitrohumic acid preparation unit is respectively connected with the gas-phase circulating absorption unit and the liquid-phase circulating utilization unit through a gas-liquid mixing unit; and a circulating outlet of the gas-phase circulating absorption unit is connected with the gas-liquid mixing unit, and a liquid-phase outlet of the liquid-phase circulating utilization unit is connected with the nitrohumic acid preparation unit. According to the invention, the nitrohumic acid preparation unit is arranged to prepare the nitrohumic acid, the product can be cured, cooled, metered and packaged through the curing unit and the product packaging unit, meanwhile, the gas-liquid mixing unit and the gas-phase circulating absorption unit are added to realize complete oxidation and absorption of flue gas, and the absorbed flue gas and liquid phase enter the nitrohumic acid preparation unit through the liquid-phase circulating utilization unit to carry out oxidation reaction on the raw material coal, so that the consumption of nitric acid can be saved, the raw material coal can be more thoroughly oxidized and degraded, and the quality of the product can be improved.
Further, the nitro humic acid preparation unit comprises a spiral shell type reaction kettle 5, a tail gas inlet 10, a raw material coal inlet 4, a nitric acid sprayer 6 liquid inlet pipeline, a sprayer 11 liquid inlet pipeline and a flue gas outlet 9 are arranged at the top of the spiral shell type reaction kettle 5, a spiral shell type stirrer 7 is arranged inside the spiral shell type reaction kettle 5, and a material outlet pipeline 8 connected with the curing reaction unit is arranged at the lower part of the spiral shell type reaction kettle 5. According to the invention, the spiral-belt type reaction kettle 5 is used as a reactor, and the spiral-belt type stirrer 7 is used in the spiral-belt type reaction kettle 5, so that the problem of coal hardening of the inner wall of the reactor in the production process of nitrohumic acid can be effectively avoided, and a foundation is laid for subsequent maintenance; further, the nitric acid sprayer 6 and the sprayer 11 are arranged in the invention, so that the raw material coal can be fully contacted with the nitric acid solution; can realize effectively retrieving and recycling the flue gas through exhanst gas outlet 9, can retrieve and recycle the nitrogen oxide tail gas that produces in fluidization curing storehouse 30 through setting up tail gas entry 10.
Further, the raw material coal inlet 4 is connected with the raw material coal feeding bin 1 through a first fully-enclosed weighing feeder 2, and a raw material coal disperser 3 is arranged between the raw material coal inlet 4 and the first fully-enclosed weighing feeder 2; the liquid inlet pipeline of the nitric acid sprayer 6 is connected with a nitric acid storage tank 13 through a Venturi flowmeter 12. First totally enclosed batcher 2 of weighing is totally closed and inside is equipped with the metering device that can automatic measure and adjust the feed rate, not only prevents that the dust diffusion can also carry out the accuracy measurement to raw materials coal to reach the mesh that makes raw materials coal and nitric acid fully react. The raw material coal obtained in the invention can enter the spiral belt type reaction kettle 5 in a dispersing way through the raw material coal disperser 3 so as to improve the oxidative degradation efficiency of the raw material coal.
Further, the gas-liquid mixing unit comprises a flue gas pipeline 14 connected with the flue gas outlet 9, the flue gas pipeline 14 is connected with a gas phase inlet of a spiral mixer 15, and an atomization inlet of the spiral mixer 15 is connected with a hydrogen peroxide solution storage tank 17 through an atomizer 16; the mixed fluid outlet of the spiral mixer 15 is connected with the cyclone separator 18; the liquid outlet of the cyclone separator 18 is connected with the liquid phase recycling unit, and the gas outlet of the cyclone separator 18 is connected with the gas phase recycling absorption unit. According to the invention, the spiral mixer 15 is arranged to realize the sufficient mixing of the flue gas and the hydrogen peroxide solution, so that the purpose of sufficiently absorbing the nitrogen oxides in the flue gas is realized.
Further, the gas phase circulation absorption unit comprises an oxygen absorption tower 19, a feed gas inlet 24 at the middle lower part of the oxygen absorption tower 19 is connected with a gas outlet of the cyclone separator 18, and a liquid phase outlet at the bottom of the oxygen absorption tower 19 is connected with HNO in the liquid phase circulation utilization unit3-H2O2The solution storage tank 26 is connected, the catalytic oxidation layer 21 is arranged in the middle of the oxygen absorption tower 19, the top of the catalytic oxidation layer 21 is provided with a hydrogen peroxide sprayer 23 connected with a hydrogen peroxide solution pipeline 22, and a tail gas draught fan 20 is arranged at a tail gas outlet at the top of the oxygen absorption tower 19; the catalytic oxidation layer 21 is a plurality of layers of plate-type Fenton catalyst wire meshes. The invention can realize the purpose of further absorbing the nitrogen oxide in the residual flue gas by arranging the oxygen absorption tower 19 so as to achieve the purpose of completely oxidizing and absorbing the flue gas; the aim of environmental friendliness is achieved by completely absorbing the flue gas, and meanwhile, the liquid phase absorbed with the flue gas can oxidize and degrade the raw material coal, so that the aims of saving nitric acid and improving the product quality are achieved; the gas phase circulation absorption unit can comprise a plurality of oxygen absorption towers 19 which are arranged in series so as to achieve the purposes of fully absorbing nitrogen oxides and discharging tail gas which reaches the standard.
Further, the liquid phase recycling unit comprises HNO3-H2O2 Solution storage tank 26, HNO3-H2O2The solution storage tank 26 is connected with a liquid phase outlet at the bottom of the oxygen absorption tower 19 through a second tee 25, and a third end of the second tee 25 is connected with a liquid outlet of the cyclone separator 18; HNO3-H2O2The solution outlet of the solution storage tank 26 is connected to the inlet pipe of the sprayer 11 through a level control valve 27 and a centrifugal pump 28. HNO described in the invention3-H2O2 Solution storageThe tank 26 is used for recovering a flue gas liquid phase produced in the oxygen absorption tower 19 and the cyclone separator 18, and the liquid phase enters the helical ribbon type reaction kettle 5 to achieve the purpose of recycling; the level control valve 27 is used for controlling HNO3-H2O2The level and flow of the solution storage tank 26, preferably ensuring HNO3-H2O2The solution tank 26 has a level no less than one-fourth of the total level.
Further, the curing unit comprises a fluidized curing bin 30, the top of the fluidized curing bin 30 is provided with a nitro humic acid inlet and a flue gas outlet 39 which are connected with the material outlet pipeline 8, the inner lower part of the fluidized curing bin 30 is provided with a fluidized bed 31 with a vibrator 35, the tail end of the fluidized bed 31 is provided with a finished product outlet 38, and the finished product outlet 38 is connected with a product packaging system 43 through a second totally-enclosed weighing feeder 42; a drying and curing part is arranged at the lower part of the front end of the fluidized bed 31, and a cooling part is arranged at the lower part of the tail end of the fluidized bed 31; an inlet valve 29 is arranged on the material outlet pipeline 8. The fluidized curing bin 30 corresponding to the bottom of the fluidized bed 31 is internally divided into a drying curing cavity and a cooling cavity; a baffle plate 41 is arranged between the drying and curing cavity and the cooling and cooling cavity; the drying and curing part comprises a first air blower 32, and the first air blower 32 is connected with a heating gas inlet 34 at the bottom of the drying and curing cavity through a heat exchanger 33; the cooling part comprises a second blower 37, and the second blower 37 is connected with a cooling gas inlet 36 at the bottom of the cooling cavity. The flue gas outlet 39 is connected with a bag type dust collector 40, a gas phase outlet at the top of the bag type dust collector 40 is connected with the tail gas inlet 10 of the spiral belt type reaction kettle 5, and a solid outlet at the bottom of the bag type dust collector 40 is connected with a second totally-enclosed weighing feeder 42. The flue gas outlet 39 in the invention can discharge nitrogen oxide gas generated in the curing process, thereby preventing secondary pollution; the bottom of the fluidized curing bin 30 is provided with a vibrator 35 and a fluidized bed 31 capable of adjusting residence time, and is also provided with a drying curing part and a cooling part, the middle of the drying curing part and the cooling part are separated by a baffle 41, and a finished product outlet 38 is arranged. The product of preliminary oxidation gets into fluidization curing storehouse 30 through material outlet pipe 8 and cures, the temperature of fluidization curing storehouse 30 reaction part is controlled through the hot-air after preheating, the cooling part temperature is controlled through the cold gas, make the temperature of each part in fluidization curing storehouse 30 remain the optimum range all the time, can ensure the product fully to react on the one hand, the other side can make the product directly dry, direct cooling, save material stoving and natural cooling process, the nitro humic acid finished product that the reaction finishes obtains exports 38 through the finished product. Flue gas generated in the material curing process in the fluidized curing bin 30 and air blown from the lower part enter the bag-type dust collector 40 through the flue gas outlet 39, and powdery products carried in the flue gas are separated out by the bag-type dust collector 40 and pass through a solid outlet at the bottom of the bag-type dust collector 40 and the second totally-enclosed weighing feeder 42 to achieve the purpose of recycling; the flue gas after dust removal enters the helical-ribbon type reaction kettle 5 through the gas phase outlet at the top of the bag type dust collector 40 and the tail gas inlet 10 of the helical-ribbon type reaction kettle 5, so that the secondary pollution caused by nitrogen oxides in the flue gas can be prevented, and the flue gas can be recycled.
The invention also provides a production process of the production system for preparing the nitro humic acid by oxidative degradation, which comprises the following steps:
step 1: raw material coal is weighed by a raw material coal feeding bin 1 and a first totally enclosed weighing feeder 2 and then enters a spiral belt type reaction kettle 5 through a raw material coal disperser 3 and a raw material coal inlet 4, and nitric acid in a nitric acid storage tank 13 is metered by a Venturi flowmeter 12 and then enters the spiral belt type reaction kettle 5 through a nitric acid sprayer 6; simultaneously starting the helical ribbon type stirrer 7; the helical ribbon stirrer 7 not only can fully perform oxidative degradation reaction on the materials and prevent the materials from being bonded with the inner wall of the helical ribbon reaction kettle 5, but also can move the materials to the material outlet pipeline 8; the concentration of nitric acid in the nitric acid storage tank 13 is 30% -60%, and the mass ratio of raw coal to nitric acid in the spiral-ribbon reaction kettle 5 is 1-10: 1;
step 2: after the materials in the helical ribbon type reaction kettle 5 are fully reacted, the inlet valve 29 is opened, and the materials after oxidative degradation enter the top of the fluidized bed 31 in the fluidized curing bin 30 through the material outlet pipeline 8; the vibrator 35 is started to control the advancing speed of the materials and enable the materials to be cured uniformly; simultaneously starting a first air blower 32 of the drying and curing part and a second air blower 37 of the cooling and cooling part;
air introduced by the first air blower 32 is heated by the heat exchanger 33, and then the front end of the fluidized bed 31 and the oxidatively degraded material at the front end of the fluidized bed 31 are heated by the heating gas inlet 34 and the drying and curing cavity, so that the oxidatively degraded material is cured at the curing temperature in the heating process and can take away moisture in the oxidatively degraded material; the heating gas keeps the temperature of the material after oxidative degradation at 80-90 ℃;
air introduced by the second air blower 37 enters the cooling cavity through the cooling gas inlet 36 to cool the tail end of the fluidized bed 31 and the material subjected to oxidative degradation at the tail end of the fluidized bed 31; the air cools the cured material to 35-45 ℃, and then the cured material is sent into a product packaging system 43 through a finished product outlet 38 and a second totally enclosed weighing feeder 42 for packaging;
and step 3: flue gas generated in the curing process in the fluidized curing bin 30 in the step 2 and air blown by the first air blower 32 and the second air blower 37 enter the bag type dust collector 40 through the flue gas outlet 39 for gas-solid separation, and a powder product after the gas-solid separation enters the product packaging system 43 through the solid outlet at the bottom of the bag type dust collector 40 and the second totally enclosed weighing feeder 42 for packaging; gas after gas-solid separation enters the helical ribbon type reaction kettle 5 through a tail gas inlet 10 of the helical ribbon type reaction kettle 5 to be absorbed in the subsequent oxidation degradation reaction process;
and 4, step 4: in the oxidation degradation reaction process of the coal and the nitric acid in the helical ribbon type reaction kettle 5 in the step 1, the nitric acid is reduced to generate NOXFlue gas; NOXThe flue gas enters the spiral mixer 15 through the flue gas outlet 9, the flue gas pipeline 14 and the gas phase inlet of the spiral mixer 15; said NOXThe temperature of the flue gas is: 80-100 ℃;
and 5: the hydrogen peroxide solution with the concentration of 15% -30% in the hydrogen peroxide solution storage tank 17 is atomized by the atomizer 16 and then enters the spiral mixer 15 from the atomization inlet of the spiral mixer 15 and NO in the step 4XThe flue gas is fully mixed in a spiral mixing chamber in a spiral mixer 15;
said NOXAtomized peroxygen of low-valence nitrogen oxide in flue gasThe hydrogen hydride is primarily oxidized and absorbed in the mixing chamber to generate HNO3-H2O2Small liquid drops;
the reaction process is as follows: NO + NO2+2H2O2= 2HNO3+H2O; hydrogen peroxide is in an excess state;
step 6: in the step 5, the gas-liquid mixture after the full mixing reaction in the spiral mixing chamber enters a cyclone separator 18 through a mixed fluid outlet of a spiral mixer 15 for gas-liquid separation;
the liquid phase after gas-liquid separation enters HNO through the liquid outlet of the cyclone separator 18 and the third end of the second tee joint 253-H2O2The solution storage tank 26;
the gas phase after gas-liquid separation enters the oxygen absorption tower 19 through a feed gas inlet 24 at the middle lower part of the oxygen absorption tower 19; the hydrogen peroxide solution in the hydrogen peroxide solution pipeline 22 is sprayed to the plurality of layers of plate-type Fenton catalyst metal wire nets through the hydrogen peroxide sprayer 23, gas phase after gas-liquid separation contacts the hydrogen peroxide solution from bottom to top and hydrogen peroxide liquid drops on the plurality of layers of plate-type Fenton catalyst metal wire nets are further oxidized and absorbed to generate HNO3-H2O2A solution; the gas which has been subjected to the two-stage oxidation absorption and reaches the standard is discharged out through a tail gas induced draft fan 20; the HNO3-H2O2The solution enters the HNO through the second tee 253-H2O2The solution storage tank 26; the gas phase after the gas-liquid separation is nitrogen oxide which is not completely absorbed; the concentration of the hydrogen peroxide solution in the hydrogen peroxide solution pipeline 22 is 15-30%;
and 7: HNO3-H2O2HNO in solution storage tank 263-H2O2The flow of the solution is regulated by a liquid level control valve 27, and the solution is pressurized and conveyed into a liquid inlet pipeline of a sprayer 11 by a centrifugal pump 28 to carry out oxidative degradation on the raw material coal of the spiral-belt type reaction kettle 5, so that the recycling of nitrogen oxide flue gas is realized, and the using amount of nitric acid is saved;
and 8: the oxygen absorption towers 19 in the step 6 are arranged in series, and liquid phase outlets at the bottoms of the oxygen absorption towers 19Recycle HNO in the unit with the liquid phase respectively3-H2O2The solution storage tank 26 is connected, the hydrogen peroxide solution pipeline 22 is respectively connected with the hydrogen peroxide sprayers 23 in the oxygen absorption towers 19, and a tail gas draught fan 20 is arranged at a tail gas outlet at the top of the last oxygen absorption tower 19; two adjacent oxygen absorption towers 19, the top tail gas outlet of the front oxygen absorption tower 19 is connected with the middle lower feed gas inlet 24 of the rear oxygen absorption tower 19.
The present invention will now be further illustrated with reference to examples in order to explain the present invention in more detail. The specific embodiment is as follows:
example 1
A production system for preparing nitro humic acid by oxidative degradation, which comprises: at least one nitro humic acid preparation unit for preparing nitro humic acid; at least one curing unit which is connected with the nitrohumic acid preparation unit and is used for curing reaction of the nitrohumic acid; a gas-phase outlet at the top of the nitrohumic acid preparation unit is respectively connected with the gas-phase circulating absorption unit and the liquid-phase circulating utilization unit through a gas-liquid mixing unit; and a circulating outlet of the gas-phase circulating absorption unit is connected with the gas-liquid mixing unit, and a liquid-phase outlet of the liquid-phase circulating utilization unit is connected with the nitrohumic acid preparation unit. The nitrohumic acid preparation unit comprises a spiral-ribbon type reaction kettle 5, wherein a tail gas inlet 10, a raw material coal inlet 4, a nitric acid sprayer 6 liquid inlet pipeline, a sprayer 11 liquid inlet pipeline and a flue gas outlet 9 are arranged at the top of the spiral-ribbon type reaction kettle 5, a spiral-ribbon type stirrer 7 is arranged inside the spiral-ribbon type reaction kettle 5, and a material outlet pipeline 8 connected with a curing reaction unit is arranged at the lower part of the spiral-ribbon type reaction kettle 5. The raw material coal inlet 4 is connected with the raw material coal feeding bin 1 through the first fully-closed weighing feeder 2, and a raw material coal disperser 3 is arranged between the raw material coal inlet 4 and the first fully-closed weighing feeder 2; the liquid inlet pipeline of the nitric acid sprayer 6 is connected with a nitric acid storage tank 13 through a Venturi flowmeter 12. The gas-liquid mixing unit comprises a flue gas pipeline 14 connected with the flue gas outlet 9, the flue gas pipeline 14 is connected with a gas phase inlet of a spiral mixer 15, and an atomization inlet of the spiral mixer 15 is connected with a hydrogen peroxide solution storage tank 17 through an atomizer 16; mixed fluid outlet of the helical mixer 15The port is connected to a cyclone separator 18; the liquid outlet of the cyclone separator 18 is connected with the liquid phase recycling unit, and the gas outlet of the cyclone separator 18 is connected with the gas phase recycling absorption unit. The gas phase circulation absorption unit comprises an oxygen absorption tower 19, a feed gas inlet 24 at the middle lower part of the oxygen absorption tower 19 is connected with a gas outlet of the cyclone separator 18, and a liquid phase outlet at the bottom of the oxygen absorption tower 19 is connected with HNO in the liquid phase circulation utilization unit3-H2O2The solution storage tank 26 is connected, the catalytic oxidation layer 21 is arranged in the middle of the oxygen absorption tower 19, the top of the catalytic oxidation layer 21 is provided with a hydrogen peroxide sprayer 23 connected with a hydrogen peroxide solution pipeline 22, and a tail gas draught fan 20 is arranged at a tail gas outlet at the top of the oxygen absorption tower 19; the catalytic oxidation layer 21 is a plurality of layers of plate-type Fenton catalyst wire meshes. The liquid phase recycling unit comprises HNO3-H2O2 Solution storage tank 26, HNO3-H2O2The solution storage tank 26 is connected with a liquid phase outlet at the bottom of the oxygen absorption tower 19 through a second tee 25, and a third end of the second tee 25 is connected with a liquid outlet of the cyclone separator 18; HNO3-H2O2The solution outlet of the solution storage tank 26 is connected to the inlet pipe of the sprayer 11 through a level control valve 27 and a centrifugal pump 28. The curing unit comprises a fluidized curing bin 30, the top of the fluidized curing bin 30 is provided with a nitro humic acid inlet and a flue gas outlet 39 which are connected with the material outlet pipeline 8, the inner lower part of the fluidized curing bin 30 is provided with a fluidized bed 31 with a vibrator 35, the tail end of the fluidized bed 31 is provided with a finished product outlet 38, and the finished product outlet 38 is connected with a product packaging system 43 through a second totally-enclosed weighing feeder 42; a drying and curing part is arranged at the lower part of the front end of the fluidized bed 31, and a cooling part is arranged at the lower part of the tail end of the fluidized bed 31; an inlet valve 29 is arranged on the material outlet pipeline 8. The fluidized curing bin 30 corresponding to the bottom of the fluidized bed 31 is internally divided into a drying curing cavity and a cooling cavity; a baffle plate 41 is arranged between the drying and curing cavity and the cooling and cooling cavity; the drying and curing part comprises a first air blower 32, and the first air blower 32 is connected with a heating gas inlet 34 at the bottom of the drying and curing cavity through a heat exchanger 33; the cooling part comprises a second blower 37, and the second blower 37 is connected with a cooling gas inlet 36 at the bottom of the cooling cavity. The flue gas outlet39 is connected with a bag type dust collector 40, a gas phase outlet at the top of the bag type dust collector 40 is connected with a tail gas inlet 10 of the spiral belt type reaction kettle 5, and a solid outlet at the bottom of the bag type dust collector 40 is connected with a second totally-enclosed weighing feeder 42.
The invention also provides a production process of the production system for preparing the nitro humic acid by oxidative degradation, which comprises the following steps:
step 1: raw material coal is weighed by a raw material coal feeding bin 1 and a first totally enclosed weighing feeder 2 and then enters a spiral belt type reaction kettle 5 through a raw material coal disperser 3 and a raw material coal inlet 4, and nitric acid in a nitric acid storage tank 13 is metered by a Venturi flowmeter 12 and then enters the spiral belt type reaction kettle 5 through a nitric acid sprayer 6; simultaneously starting the helical ribbon type stirrer 7; the helical ribbon stirrer 7 not only can fully perform oxidative degradation reaction on the materials and prevent the materials from being bonded with the inner wall of the helical ribbon reaction kettle 5, but also can move the materials to the material outlet pipeline 8; the concentration of nitric acid in the nitric acid storage tank 13 is 30%, and the mass ratio of the raw coal to the nitric acid in the spiral-ribbon reaction kettle 5 is 1: 1;
step 2: after the materials in the helical ribbon type reaction kettle 5 are fully reacted, the inlet valve 29 is opened, and the materials after oxidative degradation enter the top of the fluidized bed 31 in the fluidized curing bin 30 through the material outlet pipeline 8; the vibrator 35 is started to control the advancing speed of the materials and enable the materials to be cured uniformly; simultaneously starting a first air blower 32 of the drying and curing part and a second air blower 37 of the cooling and cooling part;
air introduced by the first air blower 32 is heated by the heat exchanger 33, and then the front end of the fluidized bed 31 and the oxidatively degraded material at the front end of the fluidized bed 31 are heated by the heating gas inlet 34 and the drying and curing cavity, so that the oxidatively degraded material is cured at the curing temperature in the heating process and can take away moisture in the oxidatively degraded material; the heating gas keeps the temperature of the material after oxidative degradation at 80 ℃;
air introduced by the second air blower 37 enters the cooling cavity through the cooling gas inlet 36 to cool the tail end of the fluidized bed 31 and the material subjected to oxidative degradation at the tail end of the fluidized bed 31; the air cools the cured material to 45 ℃, and then the cured material is sent into a product packaging system 43 for packaging through a finished product outlet 38 and a second totally enclosed weighing feeder 42;
and step 3: flue gas generated in the curing process in the fluidized curing bin 30 in the step 2 and air blown by the first air blower 32 and the second air blower 37 enter the bag type dust collector 40 through the flue gas outlet 39 for gas-solid separation, and a powder product after the gas-solid separation enters the product packaging system 43 through the solid outlet at the bottom of the bag type dust collector 40 and the second totally enclosed weighing feeder 42 for packaging; gas after gas-solid separation enters the helical ribbon type reaction kettle 5 through a tail gas inlet 10 of the helical ribbon type reaction kettle 5 to be absorbed in the subsequent oxidation degradation reaction process;
and 4, step 4: in the oxidation degradation reaction process of the coal and the nitric acid in the helical ribbon type reaction kettle 5 in the step 1, the nitric acid is reduced to generate NOXFlue gas; NOXThe flue gas enters the spiral mixer 15 through the flue gas outlet 9, the flue gas pipeline 14 and the gas phase inlet of the spiral mixer 15; said NOXThe temperature of the flue gas is: 80 ℃;
and 5: the hydrogen peroxide solution with the concentration of 15 percent in the hydrogen peroxide solution storage tank 17 is atomized by the atomizer 16 and then enters the spiral mixer 15 from the atomization inlet of the spiral mixer 15 and NO in the step 4XThe flue gas is fully mixed in a spiral mixing chamber in a spiral mixer 15;
said NOXThe low-valence nitrogen oxide in the flue gas is preliminarily oxidized and absorbed by the atomized hydrogen peroxide in the mixing chamber to generate HNO3-H2O2Small liquid drops;
the reaction process is as follows: NO + NO2+2H2O2= 2HNO3+H2O; hydrogen peroxide is in an excess state;
step 6: in the step 5, the gas-liquid mixture after the full mixing reaction in the spiral mixing chamber enters a cyclone separator 18 through a mixed fluid outlet of a spiral mixer 15 for gas-liquid separation;
the liquid phase after gas-liquid separation enters HNO through the liquid outlet of the cyclone separator 18 and the third end of the second tee joint 253-H2O2The solution storage tank 26;
the gas phase after gas-liquid separation enters the oxygen absorption tower 19 through a feed gas inlet 24 at the middle lower part of the oxygen absorption tower 19; the hydrogen peroxide solution in the hydrogen peroxide solution pipeline 22 is sprayed to the plurality of layers of plate-type Fenton catalyst metal wire nets through the hydrogen peroxide sprayer 23, gas phase after gas-liquid separation contacts the hydrogen peroxide solution from bottom to top and hydrogen peroxide liquid drops on the plurality of layers of plate-type Fenton catalyst metal wire nets are further oxidized and absorbed to generate HNO3-H2O2A solution; the gas which has been subjected to the two-stage oxidation absorption and reaches the standard is discharged out through a tail gas induced draft fan 20; the HNO3-H2O2The solution enters the HNO through the second tee 253-H2O2The solution storage tank 26; the gas phase after the gas-liquid separation is nitrogen oxide which is not completely absorbed; the concentration of the hydrogen peroxide solution in the hydrogen peroxide solution pipeline 22 is 15%;
and 7: HNO3-H2O2HNO in solution storage tank 263-H2O2The flow of the solution is regulated by a liquid level control valve 27, and the solution is pressurized and conveyed into a liquid inlet pipeline of a sprayer 11 by a centrifugal pump 28 to carry out oxidative degradation on the raw material coal of the spiral-belt type reaction kettle 5, so that the recycling of nitrogen oxide flue gas is realized, and the using amount of nitric acid is saved;
and 8: the oxygen absorption towers 19 in the step 6 are arranged in parallel, and liquid phase outlets at the bottoms of the oxygen absorption towers 19 are respectively connected with HNO in the liquid phase recycling unit3-H2O2The solution storage tank 26 is connected, the hydrogen peroxide solution pipeline 22 is respectively connected with the hydrogen peroxide sprayers 23 in the oxygen absorption towers 19, and a tail gas draught fan 20 is arranged at a tail gas outlet at the top of the last oxygen absorption tower 19; two adjacent oxygen absorption towers 19, the top tail gas outlet of the front oxygen absorption tower 19 is connected with the middle lower feed gas inlet 24 of the rear oxygen absorption tower 19.
Example 2
A production system for preparing nitro humic acid by oxidative degradation, which comprises: at least one nitro humic acid preparation unit for preparing nitro humic acid; at least one and nitro humic acidThe preparation units are connected with each other and are used for carrying out a curing reaction on the nitrohumic acid; a gas-phase outlet at the top of the nitrohumic acid preparation unit is respectively connected with the gas-phase circulating absorption unit and the liquid-phase circulating utilization unit through a gas-liquid mixing unit; and a circulating outlet of the gas-phase circulating absorption unit is connected with the gas-liquid mixing unit, and a liquid-phase outlet of the liquid-phase circulating utilization unit is connected with the nitrohumic acid preparation unit. The nitrohumic acid preparation unit comprises a spiral-ribbon type reaction kettle 5, wherein a tail gas inlet 10, a raw material coal inlet 4, a nitric acid sprayer 6 liquid inlet pipeline, a sprayer 11 liquid inlet pipeline and a flue gas outlet 9 are arranged at the top of the spiral-ribbon type reaction kettle 5, a spiral-ribbon type stirrer 7 is arranged inside the spiral-ribbon type reaction kettle 5, and a material outlet pipeline 8 connected with a curing reaction unit is arranged at the lower part of the spiral-ribbon type reaction kettle 5. The raw material coal inlet 4 is connected with the raw material coal feeding bin 1 through the first fully-closed weighing feeder 2, and a raw material coal disperser 3 is arranged between the raw material coal inlet 4 and the first fully-closed weighing feeder 2; the liquid inlet pipeline of the nitric acid sprayer 6 is connected with a nitric acid storage tank 13 through a Venturi flowmeter 12. The gas-liquid mixing unit comprises a flue gas pipeline 14 connected with the flue gas outlet 9, the flue gas pipeline 14 is connected with a gas phase inlet of a spiral mixer 15, and an atomization inlet of the spiral mixer 15 is connected with a hydrogen peroxide solution storage tank 17 through an atomizer 16; the mixed fluid outlet of the spiral mixer 15 is connected with the cyclone separator 18; the liquid outlet of the cyclone separator 18 is connected with the liquid phase recycling unit, and the gas outlet of the cyclone separator 18 is connected with the gas phase recycling absorption unit. The gas phase circulation absorption unit comprises an oxygen absorption tower 19, a feed gas inlet 24 at the middle lower part of the oxygen absorption tower 19 is connected with a gas outlet of the cyclone separator 18, and a liquid phase outlet at the bottom of the oxygen absorption tower 19 is connected with HNO in the liquid phase circulation utilization unit3-H2O2The solution storage tank 26 is connected, the catalytic oxidation layer 21 is arranged in the middle of the oxygen absorption tower 19, the top of the catalytic oxidation layer 21 is provided with a hydrogen peroxide sprayer 23 connected with a hydrogen peroxide solution pipeline 22, and a tail gas draught fan 20 is arranged at a tail gas outlet at the top of the oxygen absorption tower 19; the catalytic oxidation layer 21 is a plurality of layers of plate-type Fenton catalyst wire meshes. The liquid phase recycling unit comprises HNO3-H2O2Solution tank 26, HNO3-H2O2The solution storage tank 26 is connected with a liquid phase outlet at the bottom of the oxygen absorption tower 19 through a second tee 25, and a third end of the second tee 25 is connected with a liquid outlet of the cyclone separator 18; HNO3-H2O2The solution outlet of the solution storage tank 26 is connected to the inlet pipe of the sprayer 11 through a level control valve 27 and a centrifugal pump 28. The curing unit comprises a fluidized curing bin 30, the top of the fluidized curing bin 30 is provided with a nitro humic acid inlet and a flue gas outlet 39 which are connected with the material outlet pipeline 8, the inner lower part of the fluidized curing bin 30 is provided with a fluidized bed 31 with a vibrator 35, the tail end of the fluidized bed 31 is provided with a finished product outlet 38, and the finished product outlet 38 is connected with a product packaging system 43 through a second totally-enclosed weighing feeder 42; a drying and curing part is arranged at the lower part of the front end of the fluidized bed 31, and a cooling part is arranged at the lower part of the tail end of the fluidized bed 31; an inlet valve 29 is arranged on the material outlet pipeline 8. The fluidized curing bin 30 corresponding to the bottom of the fluidized bed 31 is internally divided into a drying curing cavity and a cooling cavity; a baffle plate 41 is arranged between the drying and curing cavity and the cooling and cooling cavity; the drying and curing part comprises a first air blower 32, and the first air blower 32 is connected with a heating gas inlet 34 at the bottom of the drying and curing cavity through a heat exchanger 33; the cooling part comprises a second blower 37, and the second blower 37 is connected with a cooling gas inlet 36 at the bottom of the cooling cavity. The flue gas outlet 39 is connected with a bag type dust collector 40, a gas phase outlet at the top of the bag type dust collector 40 is connected with the tail gas inlet 10 of the spiral belt type reaction kettle 5, and a solid outlet at the bottom of the bag type dust collector 40 is connected with a second totally-enclosed weighing feeder 42.
The invention also provides a production process of the production system for preparing the nitro humic acid by oxidative degradation, which comprises the following steps:
step 1: raw material coal is weighed by a raw material coal feeding bin 1 and a first totally enclosed weighing feeder 2 and then enters a spiral belt type reaction kettle 5 through a raw material coal disperser 3 and a raw material coal inlet 4, and nitric acid in a nitric acid storage tank 13 is metered by a Venturi flowmeter 12 and then enters the spiral belt type reaction kettle 5 through a nitric acid sprayer 6; simultaneously starting the helical ribbon type stirrer 7; the helical ribbon stirrer 7 not only can fully perform oxidative degradation reaction on the materials and prevent the materials from being bonded with the inner wall of the helical ribbon reaction kettle 5, but also can move the materials to the material outlet pipeline 8; the concentration of nitric acid in the nitric acid storage tank 13 is 60%, and the mass ratio of the raw coal to the nitric acid in the spiral-ribbon reaction kettle 5 is 10: 1;
step 2: after the materials in the helical ribbon type reaction kettle 5 are fully reacted, the inlet valve 29 is opened, and the materials after oxidative degradation enter the top of the fluidized bed 31 in the fluidized curing bin 30 through the material outlet pipeline 8; the vibrator 35 is started to control the advancing speed of the materials and enable the materials to be cured uniformly; simultaneously starting a first air blower 32 of the drying and curing part and a second air blower 37 of the cooling and cooling part;
air introduced by the first air blower 32 is heated by the heat exchanger 33, and then the front end of the fluidized bed 31 and the oxidatively degraded material at the front end of the fluidized bed 31 are heated by the heating gas inlet 34 and the drying and curing cavity, so that the oxidatively degraded material is cured at the curing temperature in the heating process and can take away moisture in the oxidatively degraded material; the heating gas keeps the temperature of the material after oxidative degradation at 90 ℃;
air introduced by the second air blower 37 enters the cooling cavity through the cooling gas inlet 36 to cool the tail end of the fluidized bed 31 and the material subjected to oxidative degradation at the tail end of the fluidized bed 31; the air cools the cured material to 45 ℃, and then the cured material is sent into a product packaging system 43 for packaging through a finished product outlet 38 and a second totally enclosed weighing feeder 42;
and step 3: flue gas generated in the curing process in the fluidized curing bin 30 in the step 2 and air blown by the first air blower 32 and the second air blower 37 enter the bag type dust collector 40 through the flue gas outlet 39 for gas-solid separation, and a powder product after the gas-solid separation enters the product packaging system 43 through the solid outlet at the bottom of the bag type dust collector 40 and the second totally enclosed weighing feeder 42 for packaging; gas after gas-solid separation enters the helical ribbon type reaction kettle 5 through a tail gas inlet 10 of the helical ribbon type reaction kettle 5 to be absorbed in the subsequent oxidation degradation reaction process;
and 4, step 4: in the oxidation degradation reaction process of the coal and the nitric acid in the helical ribbon type reaction kettle 5 in the step 1, the nitric acid is reduced to generate NOXFlue gas; NOXThe flue gas enters the spiral mixer 15 through the flue gas outlet 9, the flue gas pipeline 14 and the gas phase inlet of the spiral mixer 15; said NOXThe temperature of the flue gas is: 80-100 ℃;
and 5: the hydrogen peroxide solution with the concentration of 30 percent in the hydrogen peroxide solution storage tank 17 is atomized by the atomizer 16 and then enters the spiral mixer 15 from the atomization inlet of the spiral mixer 15 and NO in the step 4XThe flue gas is fully mixed in a spiral mixing chamber in a spiral mixer 15;
said NOXThe low-valence nitrogen oxide in the flue gas is preliminarily oxidized and absorbed by the atomized hydrogen peroxide in the mixing chamber to generate HNO3-H2O2Small liquid drops;
the reaction process is as follows: NO + NO2+2H2O2= 2HNO3+H2O; hydrogen peroxide is in an excess state;
step 6: in the step 5, the gas-liquid mixture after the full mixing reaction in the spiral mixing chamber enters a cyclone separator 18 through a mixed fluid outlet of a spiral mixer 15 for gas-liquid separation;
the liquid phase after gas-liquid separation enters HNO through the liquid outlet of the cyclone separator 18 and the third end of the second tee joint 253-H2O2The solution storage tank 26;
the gas phase after gas-liquid separation enters the oxygen absorption tower 19 through a feed gas inlet 24 at the middle lower part of the oxygen absorption tower 19; the hydrogen peroxide solution in the hydrogen peroxide solution pipeline 22 is sprayed to the plurality of layers of plate-type Fenton catalyst metal wire nets through the hydrogen peroxide sprayer 23, gas phase after gas-liquid separation contacts the hydrogen peroxide solution from bottom to top and hydrogen peroxide liquid drops on the plurality of layers of plate-type Fenton catalyst metal wire nets are further oxidized and absorbed to generate HNO3-H2O2A solution; the gas which has been subjected to the two-stage oxidation absorption and reaches the standard is discharged out through a tail gas induced draft fan 20; the HNO3-H2O2The solution enters the HNO through the second tee 253-H2O2The solution storage tank 26; the gas phase after the gas-liquid separation is nitrogen oxide which is not completely absorbed; the above-mentionedThe concentration of the hydrogen peroxide solution in the hydrogen peroxide solution pipe 22 is 30%;
and 7: HNO3-H2O2HNO in solution storage tank 263-H2O2The flow of the solution is regulated by a liquid level control valve 27, and the solution is pressurized and conveyed into a liquid inlet pipeline of a sprayer 11 by a centrifugal pump 28 to carry out oxidative degradation on the raw material coal of the spiral-belt type reaction kettle 5, so that the recycling of nitrogen oxide flue gas is realized, and the using amount of nitric acid is saved;
and 8: the oxygen absorption towers 19 in the step 6 are arranged in parallel, and liquid phase outlets at the bottoms of the oxygen absorption towers 19 are respectively connected with HNO in the liquid phase recycling unit3-H2O2The solution storage tank 26 is connected, the hydrogen peroxide solution pipeline 22 is respectively connected with the hydrogen peroxide sprayers 23 in the oxygen absorption towers 19, and a tail gas draught fan 20 is arranged at a tail gas outlet at the top of the last oxygen absorption tower 19; two adjacent oxygen absorption towers 19, the top tail gas outlet of the front oxygen absorption tower 19 is connected with the middle lower feed gas inlet 24 of the rear oxygen absorption tower 19.
Example 3
A production system for preparing nitro humic acid by oxidative degradation, which comprises: at least one nitro humic acid preparation unit for preparing nitro humic acid; at least one curing unit which is connected with the nitrohumic acid preparation unit and is used for curing reaction of the nitrohumic acid; a gas-phase outlet at the top of the nitrohumic acid preparation unit is respectively connected with the gas-phase circulating absorption unit and the liquid-phase circulating utilization unit through a gas-liquid mixing unit; and a circulating outlet of the gas-phase circulating absorption unit is connected with the gas-liquid mixing unit, and a liquid-phase outlet of the liquid-phase circulating utilization unit is connected with the nitrohumic acid preparation unit. The nitrohumic acid preparation unit comprises a spiral-ribbon type reaction kettle 5, wherein a tail gas inlet 10, a raw material coal inlet 4, a nitric acid sprayer 6 liquid inlet pipeline, a sprayer 11 liquid inlet pipeline and a flue gas outlet 9 are arranged at the top of the spiral-ribbon type reaction kettle 5, a spiral-ribbon type stirrer 7 is arranged inside the spiral-ribbon type reaction kettle 5, and a material outlet pipeline 8 connected with a curing reaction unit is arranged at the lower part of the spiral-ribbon type reaction kettle 5. The raw material coal inlet 4 is connected with a first totally-enclosed weighing feeder2 is connected with a raw material coal feeding bin 1, and a raw material coal disperser 3 is arranged between a raw material coal inlet 4 and the first totally enclosed weighing feeder 2; the liquid inlet pipeline of the nitric acid sprayer 6 is connected with a nitric acid storage tank 13 through a Venturi flowmeter 12. The gas-liquid mixing unit comprises a flue gas pipeline 14 connected with the flue gas outlet 9, the flue gas pipeline 14 is connected with a gas phase inlet of a spiral mixer 15, and an atomization inlet of the spiral mixer 15 is connected with a hydrogen peroxide solution storage tank 17 through an atomizer 16; the mixed fluid outlet of the spiral mixer 15 is connected with the cyclone separator 18; the liquid outlet of the cyclone separator 18 is connected with the liquid phase recycling unit, and the gas outlet of the cyclone separator 18 is connected with the gas phase recycling absorption unit. The gas phase circulation absorption unit comprises an oxygen absorption tower 19, a feed gas inlet 24 at the middle lower part of the oxygen absorption tower 19 is connected with a gas outlet of the cyclone separator 18, and a liquid phase outlet at the bottom of the oxygen absorption tower 19 is connected with HNO in the liquid phase circulation utilization unit3-H2O2The solution storage tank 26 is connected, the catalytic oxidation layer 21 is arranged in the middle of the oxygen absorption tower 19, the top of the catalytic oxidation layer 21 is provided with a hydrogen peroxide sprayer 23 connected with a hydrogen peroxide solution pipeline 22, and a tail gas draught fan 20 is arranged at a tail gas outlet at the top of the oxygen absorption tower 19; the catalytic oxidation layer 21 is a plurality of layers of plate-type Fenton catalyst wire meshes. The liquid phase recycling unit comprises HNO3-H2O2 Solution storage tank 26, HNO3-H2O2The solution storage tank 26 is connected with a liquid phase outlet at the bottom of the oxygen absorption tower 19 through a second tee 25, and a third end of the second tee 25 is connected with a liquid outlet of the cyclone separator 18; HNO3-H2O2The solution outlet of the solution storage tank 26 is connected to the inlet pipe of the sprayer 11 through a level control valve 27 and a centrifugal pump 28. The curing unit comprises a fluidized curing bin 30, the top of the fluidized curing bin 30 is provided with a nitro humic acid inlet and a flue gas outlet 39 which are connected with the material outlet pipeline 8, the inner lower part of the fluidized curing bin 30 is provided with a fluidized bed 31 with a vibrator 35, the tail end of the fluidized bed 31 is provided with a finished product outlet 38, and the finished product outlet 38 is connected with a product packaging system 43 through a second totally-enclosed weighing feeder 42; a drying and curing part is arranged at the lower part of the front end of the fluidized bed 31, and a cooling part is arranged at the lower part of the tail end of the fluidized bed 31; the material outletThe inlet pipe 8 is provided with an inlet valve 29. The fluidized curing bin 30 corresponding to the bottom of the fluidized bed 31 is internally divided into a drying curing cavity and a cooling cavity; a baffle plate 41 is arranged between the drying and curing cavity and the cooling and cooling cavity; the drying and curing part comprises a first air blower 32, and the first air blower 32 is connected with a heating gas inlet 34 at the bottom of the drying and curing cavity through a heat exchanger 33; the cooling part comprises a second blower 37, and the second blower 37 is connected with a cooling gas inlet 36 at the bottom of the cooling cavity. The flue gas outlet 39 is connected with a bag type dust collector 40, a gas phase outlet at the top of the bag type dust collector 40 is connected with the tail gas inlet 10 of the spiral belt type reaction kettle 5, and a solid outlet at the bottom of the bag type dust collector 40 is connected with a second totally-enclosed weighing feeder 42.
The invention also provides a production process of the production system for preparing the nitro humic acid by oxidative degradation, which comprises the following steps:
step 1: raw material coal is weighed by a raw material coal feeding bin 1 and a first totally enclosed weighing feeder 2 and then enters a spiral belt type reaction kettle 5 through a raw material coal disperser 3 and a raw material coal inlet 4, and nitric acid in a nitric acid storage tank 13 is metered by a Venturi flowmeter 12 and then enters the spiral belt type reaction kettle 5 through a nitric acid sprayer 6; simultaneously starting the helical ribbon type stirrer 7; the helical ribbon stirrer 7 not only can fully perform oxidative degradation reaction on the materials and prevent the materials from being bonded with the inner wall of the helical ribbon reaction kettle 5, but also can move the materials to the material outlet pipeline 8; the concentration of nitric acid in the nitric acid storage tank 13 is 45%, and the mass ratio of the raw coal to the nitric acid in the spiral-ribbon reaction kettle 5 is 5.5: 1;
step 2: after the materials in the helical ribbon type reaction kettle 5 are fully reacted, the inlet valve 29 is opened, and the materials after oxidative degradation enter the top of the fluidized bed 31 in the fluidized curing bin 30 through the material outlet pipeline 8; the vibrator 35 is started to control the advancing speed of the materials and enable the materials to be cured uniformly; simultaneously starting a first air blower 32 of the drying and curing part and a second air blower 37 of the cooling and cooling part;
air introduced by the first air blower 32 is heated by the heat exchanger 33, and then the front end of the fluidized bed 31 and the oxidatively degraded material at the front end of the fluidized bed 31 are heated by the heating gas inlet 34 and the drying and curing cavity, so that the oxidatively degraded material is cured at the curing temperature in the heating process and can take away moisture in the oxidatively degraded material; the heating gas keeps the temperature of the material after oxidative degradation at 85 ℃;
air introduced by the second air blower 37 enters the cooling cavity through the cooling gas inlet 36 to cool the tail end of the fluidized bed 31 and the material subjected to oxidative degradation at the tail end of the fluidized bed 31; the air cools the cured material to 40 ℃, and then the cured material is sent into a product packaging system 43 for packaging through a finished product outlet 38 and a second totally enclosed weighing feeder 42;
and step 3: flue gas generated in the curing process in the fluidized curing bin 30 in the step 2 and air blown by the first air blower 32 and the second air blower 37 enter the bag type dust collector 40 through the flue gas outlet 39 for gas-solid separation, and a powder product after the gas-solid separation enters the product packaging system 43 through the solid outlet at the bottom of the bag type dust collector 40 and the second totally enclosed weighing feeder 42 for packaging; gas after gas-solid separation enters the helical ribbon type reaction kettle 5 through a tail gas inlet 10 of the helical ribbon type reaction kettle 5 to be absorbed in the subsequent oxidation degradation reaction process;
and 4, step 4: in the oxidation degradation reaction process of the coal and the nitric acid in the helical ribbon type reaction kettle 5 in the step 1, the nitric acid is reduced to generate NOXFlue gas; NOXThe flue gas enters the spiral mixer 15 through the flue gas outlet 9, the flue gas pipeline 14 and the gas phase inlet of the spiral mixer 15; said NOXThe temperature of the flue gas is: 90 ℃;
and 5: the hydrogen peroxide solution with the concentration of 22.5 percent in the hydrogen peroxide solution storage tank 17 is atomized by the atomizer 16 and then enters the spiral mixer 15 from the atomization inlet of the spiral mixer 15 and NO in the step 4XThe flue gas is fully mixed in a spiral mixing chamber in a spiral mixer 15;
said NOXThe low-valence nitrogen oxide in the flue gas is preliminarily oxidized and absorbed by the atomized hydrogen peroxide in the mixing chamber to generate HNO3-H2O2Small liquid drops;
the reaction process is as follows: NO + NO2+2H2O2= 2HNO3+H2O; hydrogen peroxide is in an excess state;
step 6: in the step 5, the gas-liquid mixture after the full mixing reaction in the spiral mixing chamber enters a cyclone separator 18 through a mixed fluid outlet of a spiral mixer 15 for gas-liquid separation;
the liquid phase after gas-liquid separation enters HNO through the liquid outlet of the cyclone separator 18 and the third end of the second tee joint 253-H2O2The solution storage tank 26;
the gas phase after gas-liquid separation enters the oxygen absorption tower 19 through a feed gas inlet 24 at the middle lower part of the oxygen absorption tower 19; the hydrogen peroxide solution in the hydrogen peroxide solution pipeline 22 is sprayed to the plurality of layers of plate-type Fenton catalyst metal wire nets through the hydrogen peroxide sprayer 23, gas phase after gas-liquid separation contacts the hydrogen peroxide solution from bottom to top and hydrogen peroxide liquid drops on the plurality of layers of plate-type Fenton catalyst metal wire nets are further oxidized and absorbed to generate HNO3-H2O2A solution; the gas which has been subjected to the two-stage oxidation absorption and reaches the standard is discharged out through a tail gas induced draft fan 20; the HNO3-H2O2The solution enters the HNO through the second tee 253-H2O2The solution storage tank 26; the gas phase after the gas-liquid separation is nitrogen oxide which is not completely absorbed; the concentration of the hydrogen peroxide solution in the hydrogen peroxide solution pipeline 22 is 22.5%;
and 7: HNO3-H2O2HNO in solution storage tank 263-H2O2The flow of the solution is regulated by a liquid level control valve 27, and the solution is pressurized and conveyed into a liquid inlet pipeline of a sprayer 11 by a centrifugal pump 28 to carry out oxidative degradation on the raw material coal of the spiral-belt type reaction kettle 5, so that the recycling of nitrogen oxide flue gas is realized, and the using amount of nitric acid is saved;
and 8: the oxygen absorption towers 19 in the step 6 are arranged in parallel, and liquid phase outlets at the bottoms of the oxygen absorption towers 19 are respectively connected with HNO in the liquid phase recycling unit3-H2O2The solution storage tank 26 is connected, the hydrogen peroxide solution pipelines 22 are respectively connected with hydrogen peroxide sprayers 23 in the oxygen absorption towers 19, and mostA tail gas draught fan 20 is arranged at a tail gas outlet at the top of the last oxygen absorption tower 19; two adjacent oxygen absorption towers 19, the top tail gas outlet of the front oxygen absorption tower 19 is connected with the middle lower feed gas inlet 24 of the rear oxygen absorption tower 19.
The invention does not use oxygen or liquid caustic soda and other forms in the process of absorbing the flue gas, so the operation process is safe and reliable and has high absorptivity, and the absorptivity of the hydrogen peroxide solution in the invention can reach more than 95 percent; the method has the characteristics of reasonable equipment design, easy operation of the process, realization of safe and environment-friendly emission of flue gas, effective reduction of the use amount of nitric acid, and improvement of product quality by reducing the production cost.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art through specific situations.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. The utility model provides a production system of oxidative degradation preparation nitro humic acid which characterized in that: the system comprises:
at least one nitro humic acid preparation unit for preparing nitro humic acid;
at least one curing unit which is connected with the nitrohumic acid preparation unit and is used for curing reaction of the nitrohumic acid;
a gas-phase outlet at the top of the nitrohumic acid preparation unit is respectively connected with the gas-phase circulating absorption unit and the liquid-phase circulating utilization unit through a gas-liquid mixing unit;
and a circulating outlet of the gas-phase circulating absorption unit is connected with the gas-liquid mixing unit, and a liquid-phase outlet of the liquid-phase circulating utilization unit is connected with the nitrohumic acid preparation unit.
2. The production system for preparing nitrohumic acid by oxidative degradation according to claim 1, wherein: the nitrohumic acid preparation unit comprises a spiral-ribbon type reaction kettle (5), a tail gas inlet (10), a raw material coal inlet (4), a nitric acid sprayer (6) liquid inlet pipeline, a sprayer (11) liquid inlet pipeline and a flue gas outlet (9) are arranged at the top of the spiral-ribbon type reaction kettle (5), a spiral-ribbon type stirrer (7) is arranged inside the spiral-ribbon type reaction kettle (5), and a material outlet pipeline (8) connected with a curing reaction unit is arranged at the lower part of the spiral-ribbon type reaction kettle (5).
3. The production system for preparing nitrohumic acid by oxidative degradation according to claim 2, characterized in that: the raw material coal inlet (4) is connected with the raw material coal feeding bin (1) through a first fully-closed weighing feeder (2), and a raw material coal disperser (3) is arranged between the raw material coal inlet (4) and the first fully-closed weighing feeder (2); the liquid inlet pipeline of the nitric acid sprayer (6) is connected with a nitric acid storage tank (13) through a Venturi flowmeter (12).
4. The production system for preparing nitrohumic acid by oxidative degradation according to claim 2, characterized in that: the gas-liquid mixing unit comprises a flue gas pipeline (14) connected with a flue gas outlet (9), the flue gas pipeline (14) is connected with a gas phase inlet of a spiral mixer (15), and an atomization inlet of the spiral mixer (15) is connected with a hydrogen peroxide solution storage tank (17) through an atomizer (16); the mixed fluid outlet of the spiral mixer (15) is connected with the cyclone separator (18); the liquid outlet of the cyclone separator (18) is connected with the liquid phase recycling unit, and the gas outlet of the cyclone separator (18) is connected with the gas phase recycling absorption unit.
5. The production system for preparing nitrohumic acid by oxidative degradation according to claim 1 or 4, wherein: the gas phase circulation absorption unit comprises an oxygen absorption tower (19), a feed gas inlet (24) at the middle lower part of the oxygen absorption tower (19) is connected with a gas outlet of the cyclone separator (18), and a liquid phase outlet at the bottom of the oxygen absorption tower (19) is connected with HNO in the liquid phase circulation utilization unit3-H2O2The solution storage tank (26) is connected, the catalytic oxidation layer (21) is arranged in the middle of the oxygen absorption tower (19), the top of the catalytic oxidation layer (21) is provided with a hydrogen peroxide sprayer (23) connected with a hydrogen peroxide solution pipeline (22), and a tail gas outlet at the top of the oxygen absorption tower (19) is provided with a tail gas draught fan (20);
the catalytic oxidation layer (21) is a plurality of layers of plate-type Fenton catalyst wire meshes.
6. The production system for preparing nitrohumic acid by oxidative degradation according to claim 1 or 4, wherein: the liquid phase recycling unit comprises HNO3-H2O2Solution storage tank (26), HNO3-H2O2The solution storage tank (26) is connected with a liquid phase outlet at the bottom of the oxygen absorption tower (19) through a second tee joint (25), and a third end of the second tee joint (25) is connected with a liquid outlet of the cyclone separator (18); HNO3-H2O2The liquid outlet of the solution storage tank (26) is connected with the liquid inlet pipeline of the sprayer (11) through a liquid level control valve (27) and a centrifugal pump (28).
7. The production system for preparing nitrohumic acid by oxidative degradation according to claim 1, wherein: the curing unit comprises a fluidized curing bin (30), a nitro humic acid inlet and a smoke outlet (39) which are connected with a material outlet pipeline (8) are arranged at the top of the fluidized curing bin (30), a fluidized bed (31) with a vibrator (35) is arranged at the inner lower part of the fluidized curing bin (30), a finished product outlet (38) is arranged at the tail end of the fluidized bed (31), and the finished product outlet (38) is connected with a product packaging system (43) through a second totally-enclosed weighing feeder (42);
a drying and curing part is arranged at the lower part of the front end of the fluidized bed (31), and a cooling part is arranged at the lower part of the tail end of the fluidized bed (31);
an inlet valve (29) is arranged on the material outlet pipeline (8).
8. The production system for preparing nitrohumic acid by oxidative degradation according to claim 7, wherein: the fluidized curing bin (30) corresponding to the bottom of the fluidized bed (31) is internally divided into a drying curing cavity and a cooling cavity; a baffle (41) is arranged between the drying and curing cavity and the cooling and cooling cavity;
the drying and curing part comprises a first air blower (32), and the first air blower (32) is connected with a heating gas inlet (34) at the bottom of the drying and curing cavity through a heat exchanger (33);
the cooling part comprises a second blower (37), and the second blower (37) is connected with a cooling gas inlet (36) at the bottom of the cooling cavity.
9. The production system for preparing nitrohumic acid by oxidative degradation according to claim 7, wherein: the flue gas outlet (39) is connected with the bag type dust collector (40), a gas phase outlet at the top of the bag type dust collector (40) is connected with a tail gas inlet (10) of the spiral belt type reaction kettle (5), and a solid outlet at the bottom of the bag type dust collector (40) is connected with the second totally-enclosed weighing feeder (42).
10. A production process of the production system for preparing nitro humic acid by oxidative degradation according to claims 1 to 9, which is characterized in that: the production process comprises the following steps:
step 1: raw material coal is weighed by a raw material coal feeding bin (1) and a first totally enclosed weighing feeder (2) and then enters a spiral belt type reaction kettle (5) through a raw material coal disperser (3) and a raw material coal inlet (4), and nitric acid in a nitric acid storage tank (13) is metered by a Venturi flowmeter (12) and then enters the spiral belt type reaction kettle (5) through a nitric acid sprayer (6); simultaneously starting the helical ribbon stirrer (7); the helical ribbon stirrer (7) can not only make the materials fully generate oxidative degradation reaction and prevent the materials from being bonded with the inner wall of the helical ribbon reaction kettle (5), but also can make the materials move to the material outlet pipeline (8); the concentration of nitric acid in the nitric acid storage tank (13) is 30% -60%, and the mass ratio of raw coal to nitric acid in the spiral-belt type reaction kettle (5) is 1-10: 1;
step 2: after the materials in the helical ribbon type reaction kettle (5) fully react, opening an inlet valve (29), and feeding the materials after oxidative degradation into the top of a fluidized bed (31) in a fluidized curing bin (30) through a material outlet pipeline (8); the vibrator (35) is started to control the advancing speed of the materials and enable the materials to be uniformly cured; simultaneously starting a first air blower (32) of the drying and curing part and a second air blower (37) of the cooling and cooling part;
air introduced by a first air blower (32) is heated by a heat exchanger (33) and then is heated by a heating gas inlet (34) and a drying curing cavity to the front end of the fluidized bed (31) and the oxidatively degraded material at the front end of the fluidized bed (31), and in the heating process, the oxidatively degraded material is cured at a curing temperature and can take away moisture in the oxidatively degraded material; the heating gas keeps the temperature of the material after oxidative degradation at 80-90 ℃;
air introduced by a second air blower (37) enters the cooling cavity through a cooling gas inlet (36) to cool the tail end of the fluidized bed (31) and the material subjected to oxidative degradation at the tail end of the fluidized bed (31); the air cools the cured materials to 35-45 ℃, and then the cured materials are conveyed into a product packaging system (43) for packaging through a finished product outlet (38) and a second totally-enclosed weighing feeder (42);
and step 3: flue gas generated in the curing process in the fluidized curing bin (30) in the step 2 and air blown by the first air blower (32) and the second air blower (37) enter the bag type dust collector (40) through a flue gas outlet (39) for gas-solid separation, and a powder product after the gas-solid separation enters a product packaging system (43) through a solid outlet at the bottom of the bag type dust collector (40) and the second totally-enclosed weighing feeder (42) for packaging; gas after gas-solid separation enters the helical ribbon type reaction kettle (5) through a tail gas inlet (10) of the helical ribbon type reaction kettle (5) and is absorbed in the subsequent oxidation degradation reaction process;
and 4, step 4: in the process of carrying out oxidative degradation reaction on coal and nitric acid in the helical ribbon type reaction kettle (5) in the step 1, nitric acid is reduced to generate NOXFlue gas; NOXThe flue gas enters the spiral mixer (15) through the flue gas outlet (9), the flue gas pipeline (14) and a gas phase inlet of the spiral mixer (15); said NOXThe temperature of the flue gas is: 80-100 ℃;
and 5: hydrogen peroxide solution with the concentration of 15% -30% in the hydrogen peroxide solution storage tank (17) is atomized by the atomizer (16) and then enters the spiral mixer (15) from the atomization inlet of the spiral mixer (15) to react with NO in the step 4XThe flue gas is fully mixed in a spiral mixing chamber in a spiral mixer (15);
said NOXThe low-valence nitrogen oxide in the flue gas is preliminarily oxidized and absorbed by the atomized hydrogen peroxide in the mixing chamber to generate HNO3-H2O2Small liquid drops;
the reaction process is as follows: NO + NO2+2H2O2= 2HNO3+H2O; hydrogen peroxide is in an excess state;
step 6: in the step 5, the gas-liquid mixture after the full mixing reaction in the spiral mixing chamber enters a cyclone separator (18) through a mixed fluid outlet of a spiral mixer (15) for gas-liquid separation;
the liquid phase after gas-liquid separation enters HNO through the liquid outlet of the cyclone separator (18) and the third end of the second tee joint (25)3-H2O2A solution storage tank (26);
the gas phase after gas-liquid separation enters through a feed gas inlet (24) at the middle lower part of the oxygen absorption tower (19)An oxygen intake tower (19); the hydrogen peroxide solution in the hydrogen peroxide solution pipeline (22) is sprayed to a plurality of layers of plate-type Fenton catalyst wire nets through a hydrogen peroxide sprayer (23), gas phase after gas-liquid separation contacts the hydrogen peroxide solution from bottom to top and hydrogen peroxide liquid drops on the plurality of layers of plate-type Fenton catalyst wire nets are further oxidized and absorbed to generate HNO3-H2O2A solution; the gas which has been subjected to the two-stage oxidation absorption and reaches the standard is discharged outside through a tail gas induced draft fan (20); the HNO3-H2O2The solution enters HNO through a second tee joint (25)3-H2O2A solution storage tank (26); the gas phase after the gas-liquid separation is nitrogen oxide which is not completely absorbed;
the concentration of the hydrogen peroxide solution in the hydrogen peroxide solution pipeline (22) is 15-30%;
and 7: HNO3-H2O2HNO in solution storage tank (26)3-H2O2The flow of the solution is regulated by a liquid level control valve (27), and the solution is pressurized and conveyed into a liquid inlet pipeline of a sprayer (11) by a centrifugal pump (28) to carry out oxidative degradation on the raw material coal of the spiral-belt type reaction kettle 5, so that the recycling of nitrogen oxide flue gas is realized, and the using amount of nitric acid is saved;
and 8: the oxygen absorption towers (19) in the step 6 are arranged in series, and liquid phase outlets at the bottoms of the oxygen absorption towers (19) are respectively connected with HNO in the liquid phase recycling unit3-H2O2A solution storage tank (26) is connected, a hydrogen peroxide solution pipeline (22) is respectively connected with hydrogen peroxide sprayers (23) in a plurality of oxygen absorption towers (19), and a tail gas draught fan (20) is arranged at a tail gas outlet at the top of the last oxygen absorption tower (19); two adjacent oxygen absorption towers (19), wherein the top tail gas outlet of the front oxygen absorption tower (19) is connected with the middle-lower feed gas inlet (24) of the rear oxygen absorption tower (19).
CN202010643132.1A 2020-07-06 2020-07-06 Production system and production process for preparing nitrohumic acid through oxidative degradation Pending CN111644127A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113145055A (en) * 2021-05-25 2021-07-23 河南七倍山实业有限公司 Equipment for producing humic acid
CN115072744A (en) * 2022-08-08 2022-09-20 山西小禹植物营养科技有限公司 Production process for by-products of sodium nitrate and sodium nitrite in production process of nitro humic acid

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113145055A (en) * 2021-05-25 2021-07-23 河南七倍山实业有限公司 Equipment for producing humic acid
CN115072744A (en) * 2022-08-08 2022-09-20 山西小禹植物营养科技有限公司 Production process for by-products of sodium nitrate and sodium nitrite in production process of nitro humic acid

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