CN111394133A - A gasification reduction device and method for co-production of yellow phosphorus and synthesis gas - Google Patents

Abstract

The invention provides a gasification reduction device for co-producing yellow phosphorus and synthesis gas, which comprises a phosphorus coal gasification reduction unit and a chilling unit, wherein the phosphorus coal gasification reduction unit is communicated with the chilling unit from top to bottom, and the phosphorus coal gasification reduction unit: the gasification reduction reaction of all materials in the phosphorus coal gasification reduction unit is realized to obtain phosphorus-containing furnace gas; the quench unit: used for cooling slag formed in the process of the coal gasification reduction reaction of the phosphorus to be solid and discharging the solid. The invention also provides a method for co-producing yellow phosphorus and synthesis gas by using the gasification reduction device. The invention is a technology with high energy utilization rate, optimized process, energy conservation, environmental protection and lower cost.

Description

A gasification reduction device and method for co-production of yellow phosphorus and synthesis gas

technical field

The invention relates to the field of chemical industry, in particular to a gasification reduction device and method for co-producing yellow phosphorus and synthesis gas.

Background technique

Yellow phosphorus is one of the important basic chemical raw materials. It is an important parent raw material for the production of thermal phosphoric acid and phosphide, and it is also an important raw material for the preparation of fine phosphate and fine organic phosphorus chemicals. At present, there are only two methods for industrialized production of yellow phosphorus: phosphorus production by blast furnace method and phosphorus production by electric furnace method.

The process of making phosphorus by blast furnace method is to use massive phosphate rock as raw material, silica as flux, coke and anthracite as reducing agent and fuel, which are added to the blast furnace in a certain proportion and order. In the furnace, the coke is burned to provide heat with the help of hot air. At the same time, the remaining coke undergoes a chemical reduction reaction with the molten phosphate rock under high temperature conditions. The furnace gas escapes from the top of the blast furnace, and the phosphorus product is obtained through the dust removal equipment and the condensation refining device.

There are two unsolved problems in the production of phosphorus by blast furnace method: First, the reduction rate is low. Although the data shows that the residual phosphorus in the slag can reach 1.5% (P ₂ O ₅ content) at a minimum, and the corresponding phosphorus reduction rate is more than 90%, the domestic test device actually achieves The highest reduction rate was 73.9%. Second, the economy is poor. The main reason for the development of the blast furnace method for phosphorus production in foreign countries in the last century was that the power resources were relatively tight, the price of electricity was relatively high, and the price of coke was relatively cheap. With the development of the power generation industry, the power supply is abundant and the electricity price is reduced. Compared with the electric furnace method, the blast furnace method has no cost advantage, and the blast furnace method has gradually lost its market. The production of yellow phosphorus by the electric furnace method is to add the mixed charge of phosphate rock, silica and coke into the electric furnace, and convert the electric energy into heat energy to melt it to produce a chemical reduction reaction, so that the phosphorus in it is sublimated, and the phosphorus-containing furnace gas is condensed and washed. Refined and separated to obtain finished phosphorus. However, the electric furnace method has high energy consumption and heavy pollution, cannot achieve long-term continuous production, and requires high grade of phosphate rock. The current production technology of yellow phosphorus can no longer meet the new requirements of current low-carbon environmental protection.

Coal gasification refers to the process in which solid fuels such as coal or coke and semi-coke react with gasification agents under high temperature, normal pressure or pressurized conditions, and are converted into gaseous products and a small amount of residues. The coal gasification process can be used to produce fuel gas, as industrial gas and city gas, and also to produce syngas, as a feedstock for synthetic ammonia, synthetic methanol, and synthetic liquid fuels.

CN103897737A discloses a method for smelting phosphorus and co-producing synthesis gas in an all-oxygen shaft furnace and a device for smelting phosphorus and co-producing synthesis gas. The device continues the smelting idea of producing phosphorus by blast furnace method, wherein the all-oxygen shaft furnace includes a preheating zone, a Reaction zone, combustion zone, hearth, feeding port, gas outlet, sealing and slag outlet. During the specific operation, the apatite plus carbon pellets are mixed with the fuel coal to obtain the charge, the charge is added from the charging port at the top of the shaft furnace, and pure oxygen and water vapor are introduced from the tuyere at the lower part of the shaft furnace; The high-temperature flue gas countercurrently heats the descending charge; in the middle of the shaft furnace, the reducing agent carbon in the apatite and carbon pellets reduces the phosphorus pentoxide in the apatite to elemental phosphorus, and the fuel coal undergoes a gasification reaction to generate Phosphorus-containing gas is discharged from the gas outlet at the top of the shaft furnace. However, the configuration of the reaction zone in the shaft furnace is relatively simple, so that the heat generated by the coal gasification reaction is not efficiently utilized, and the slagging method of the shaft furnace is not described in detail. The smooth discharge of the slag will affect the normal operation of the shaft furnace. key factor.

Therefore, a gasification reduction device for co-production of yellow phosphorus and synthesis gas with high energy utilization, process optimization, energy saving and environmental protection, and lower cost was developed.

SUMMARY OF THE INVENTION

In order to solve the above defects, the present invention provides a gasification reduction device for co-producing yellow phosphorus and synthesis gas.

The technical scheme of the present invention is as follows:

A gasification reduction device for co-producing yellow phosphorus and synthesis gas, comprising a phosphorus coal gasification reduction unit and a chilling unit, wherein the phosphorus coal gasification reduction unit is connected up and down with the chilling unit;

The phosphorus coal gasification reduction unit: realize the gasification reduction reaction of each material in the phosphorus coal gasification reduction unit to obtain phosphorus-containing furnace gas;

The chilling unit is used to cool the slag formed in the process of the phosphorus coal gasification reduction reaction into a solid state and discharge it.

Further, the phosphorus coal gasification and reduction unit includes a feed inlet, a reaction chamber and a slag pool arranged in sequence from top to bottom;

the feed port, located above the reaction chamber, is used to provide solid material for the phosphine coal gasification reduction reaction;

An air inlet is provided under the side of the reaction chamber to provide gas material for the phosphorus coal gasification reduction reaction;

An air outlet is provided on the upper side of the reaction chamber for exporting the phosphorus-containing furnace gas;

The slag pool, located just below the reaction chamber, is used to receive the slag formed in the phosphine coal gasification reduction reaction and discharge it to the chilling unit located below the slag pool.

Further, the solid material includes phosphorus pellets and raw coal and/or coke, wherein the phosphorus pellets can be prepared by crushing, grinding and mixing phosphate rock, anthracite and silica in a certain proportion. .

Further, the gas material includes oxygen and water vapor, and the ratio of oxygen and water vapor can be controlled to be 1.05-1.1 Nm ³ /kg, which is beneficial to the stable operation of the gasification reduction device.

Further, the air inlet may include a plurality of gasification agent nozzles, the plurality of gasification agent nozzles are located above the slag pool, and are evenly arranged in the circumferential direction at an included angle of 0 to 30° with the horizontal plane , so that the gas material is injected into the reaction chamber at high speed through the gasification agent nozzle to carry out coal gasification reaction with raw coal and/or coke, so that a local high temperature is formed inside the reaction chamber, and the phosphorus ball can be adjusted at the same time. The reduction reaction temperature of the group.

Further, at least one layer of coal material layer and at least one layer of phosphorus material layer may be arranged in the reaction chamber, the coal material layer includes raw coal and/or coke, and the phosphorus material layer includes phosphorus pellets, so The coal material layer and the phosphorus material layer can be arranged in a spaced manner, and the coal material layer located in the lower part of the reaction chamber is in contact with oxygen at the bottom of the reaction chamber, and burns to generate high-temperature furnace gas to flow upward; The gas flows upward, and the materials of the phosphorus material layer above are fully mixed and contacted, so that the phosphate rock in the phosphorus pellet is reduced to elemental phosphorus. Therefore, by arranging the coal material layer and the phosphorus material layer in layers in the reaction chamber, the high-temperature furnace gas generated by the coal gasification reaction below can be fully utilized to directly provide the reduction reaction heat for the phosphorus pellets above, reducing the furnace The heat loss of the gas can be achieved to achieve a higher heat utilization rate.

Further, in order to achieve maximum energy utilization, the heights of the coal layers and the phosphorus layers should be set extremely skillfully, and if the height of the layers is too low, it will lead to insufficient reaction, waste of raw materials and product yield. Low defect, the material layer height is too high, the mixing of materials in the reaction process will be insufficient, the fluidity and contact efficiency of materials in the reaction chamber will be insufficient, and the best reaction state cannot be guaranteed, resulting in great cost and energy. waste. Therefore, according to the high temperature heat generated by the gasification reaction of the lower coal layer is equal to the required heat of the reduction reaction of the upper phosphorus layer, the mass of the phosphorus pellets and raw coal and/or coke is calculated through the heat balance, and then according to the phosphorus pellets The bulk density of the pellets and the material in the coal bed is used to calculate the material volume, and then the appropriate bed height ratio is obtained. The appropriate bed height ratio of the phosphorus bed and the coal bed should be set as follows:

Among them: H ₁ ——the height of phosphorus material layer consumed per hour, the unit is m;

H ₂ ——the height of coal seam consumed per hour, the unit is m;

Q——The heat required to produce yellow phosphorus per unit mass product, the unit is J/kg;

q——The heat released by the reaction of raw coal and/or coke with oxygen per unit mass, in J/kg;

M——the mass of the yellow phosphorus of the product, the unit is kg;

a——carbon content in raw coal and/or coke, %;

b——the conversion rate of carbon in raw coal and/or coke, %;

ρ——Bulk density of raw coal and/or coke, in kg/m ³ ;

d—the diameter of the reaction chamber, in m.

Further, the phosphorus coal gasification reduction unit also includes a feed conduit and a manhole;

The feed conduit, located just below the feed port, is used to vertically introduce the solid material into the gasification chamber, preventing a small amount of solid material from entering the manhole or the air outlet, thereby reducing Mechanical scouring and abrasion of the inner wall of the phosphorus coal gasification reduction unit;

The manhole is located above the side of the reaction chamber, and is used to enter the reaction chamber during maintenance.

Further, the phosphorus coal gasification reduction unit further includes a phosphorus coal gasification reduction unit casing, the casing can adopt a water jacket structure or a coil water wall structure, and is lined with refractory materials to protect the casing from overheating, In addition, the water in the water jacket or the water cooling wall structure of the coil can absorb the heat generated by the coal gasification reaction to generate steam for realizing heat recovery.

Further, the slag pool may be an inverted conical structure, the upper part is used to receive the slag from the reaction chamber, and the lower part is provided with a slag outlet, and the slag outlet is communicated with the chilling unit for to discharge the slag. The outer wall of the molten slag pool is a metal casting, the inner wall is a refractory material, and a cooling water pipe is arranged between the outer wall and the inner wall. The temperature of the cooling water pipe can be 30-60°C, and the temperature difference between the inlet and outlet can be 10-20°C. Through the cooling treatment of the cooling water pipe, part of the molten slag can form a layer of solid slag on the inner wall boundary of the molten slag pool. The material adheres to the inner wall, so that a layer of solid slag formed between the cooling water pipe and the molten slag maintains dynamic balance and can protect the outer wall metal casting. Specifically, the diameter of the slag outlet may be 30-70 mm, the metal casting is a pure copper casting, and the refractory material is a refractory brick.

Further, the chilling unit comprises a unit located below the phosphorous coal gasification and reduction unit, connected to the phosphorous coal gasification and reduction unit through a flange, and the slag outlet passes through the flange directly to the chilling unit, so that the The slag is discharged to the chill unit.

Further, the chilling unit includes a combustion chamber and a chilling chamber from top to bottom;

The upper part of the combustion chamber is provided with an annular air passage, an annular burner located on the annular air passage, an ignition gun, a fume hood and a flue gas cooling coil;

The annular air passage is used for introducing the mixed gas of fuel and air into the annular burner;

the annular burner is used for spraying the mixed gas to the slag outlet;

The ignition gun is used for igniting the mixed gas sprayed from the annular burner, and in the combustion state, the slag material at the slag outlet is re-gasified, so as to keep the slag outlet Always in an unblocked state;

The fume hood is used to form a gasification space, and the flue gas generated by the secondary gasification is sealed in the fume hood through the liquid sealing effect of the chilled water below;

The flue gas cooling coil is connected above the flue gas hood, and is used for discharging the flue gas generated by the secondary gasification out of the chilling unit. Specifically, the flue gas cooling coil further includes an exhaust inlet and an exhaust outlet, the exhaust inlet can be built in the fume hood, and the exhaust outlet is provided outside the chilling unit.

Further, the chilling chamber is located below the combustion chamber, and is equipped with chilled water, and the bottom of the chilling chamber is provided with a solid slag outlet for cooling and discharging the incompletely burnt off secondary gasification. The slag is also used to cool the flue gas in the flue gas cooling coil. Specifically, the temperature of the chilled water may be 50-60°C.

Further, when the phosphorus coal gasification and reduction unit is in normal operation, the solid slag outlet is in a closed state; when the amount of solid slag reaches the discharge standard, the slag collecting component is connected to the solid slag outlet, and the slag outlet is When the pressure condition in the slag collecting assembly and the pressure condition in the chilling unit reach equilibrium, the solid slag outlet is opened, and the solid slag falls into the slag collecting assembly based on the action of gravity, and then The solid slag outlet is closed, and subsequent operations are continued.

Further, cooling water is installed inside the slag collecting assembly to prevent the chilled water in the chilling chamber from falling into the slag collecting assembly.

Further, the chilling unit further includes a chilling unit casing without a water jacket and refractory material.

The present invention also provides a method for co-producing yellow phosphorus and synthesis gas by utilizing the aforementioned gasification reduction device for co-producing yellow phosphorus and synthesis gas, and the method includes a phosphorus coal gasification reduction reaction process and a slag removal process;

Described phosphatic coal gasification reduction reaction process comprises the following steps:

A1: The phosphate rock, anthracite and silica are crushed, pulverized and mixed according to the mass ratio of phosphate rock:anthracite:silica as (30-80):(10-30):(10-20). Phosphorus pellets, and then the prepared phosphorus pellets and the raw material coal and/or coke are respectively fed into the reaction chamber through the feed port, wherein the phosphorus pellets are placed in the reaction chamber. On the phosphorus material layer, the raw coal and/or coke are placed on the coal material layer;

A2: The water vapor and high-purity oxygen are respectively introduced into the reaction chamber through the air inlet, and the coal layer located in the lower part of the reaction chamber is contacted with oxygen at the bottom of the reaction chamber, and produced by combustion High temperature furnace gas flows upward;

A3: With the upward flow of furnace gas, the overall heat flow and circulation inside the reaction chamber is driven, and at the same time, the materials in the reaction chamber are fully mixed and contacted. The pressure in the reaction chamber is 1-10MPa, and the temperature is 1200 -1600°C, the phosphate rock in the phosphorus pellets is reduced to elemental phosphorus, and the phosphorus-containing furnace gas generated during the reaction is discharged from the gas outlet.

The slagging process includes the following steps:

S1: When the phosphorus coal gasification and reduction unit is in normal operation, the ignition gun ignites the mixed gas of fuel and air ejected from the annular burner, and in the combustion state, the slag material at the slag outlet is ignited. Carry out secondary gasification, and the flue gas produced by secondary gasification is sealed in the gasification space formed by the flue gas hood and the chilled water, and is discharged from the chilled unit through the flue gas cooling coil. Control the amount of mixed gas introduced into the annular burner, and keep the pressure P1 in the fume hood greater than the pressure P2 in the slag pool. The difference is 5-15Kpa, where P1-P2=ρ _slag g ( h ₀ -h), h ₀ is the height of the slag pool, and h is the height of the slag material, so as to prevent the slag material in the slag pool from falling into the chilling unit;

S2: As the slag material received in the slag pool increases, the pressure difference P1-P2 between the fume hood and the slag pool gradually decreases, and when the pressure difference is lower than 5Kpa, stop the The annular burner is fed with mixed gas, and the slag that is not completely burned out by the secondary gasification is discharged through the slag outlet, and falls into the chilled water for cooling to form a solid slag, which passes through the solid slag. The outlet is discharged, and after the slag discharge process is completed, steps S1 and S2 are repeated.

Further, in A1, the preparation process of the phosphorus pellets includes: grinding phosphate rock, anthracite and silica into 60-100 mesh fine powder, and mixing them according to the weight ratio of phosphate rock:anthracite:silica=13:4:3 Evenly, add any one or more binders among refractory cement, sodium humate, peridot, water glass, bentonite and press into pellets with a particle size of 10-30mm, and after drying, the compressive strength is 1800N/ Phosphorus pellets.

Further, in A2 and A3, the chemical reaction formula in the reaction chamber is as follows:

(1) Coal gasification reaction:

C+O ₂ =CO ₂

2C+O ₂ =2CO

C+CO ₂ =2CO

C+H ₂ O=H ₂ +CO

C+2H ₂ O=2H ₂ +CO ₂

CO+H ₂ O=H ₂ +CO ₂

Wherein, the temperature of the generated high-temperature furnace gas is 1400-1600 °C;

(2) Reduction reaction of phosphorus pellets: The reaction starts in the temperature range of 1152-1177 °C. When the temperature reaches about 1227 °C, the reaction is almost complete. The reaction formula is:

Ca ₃ (PO ₄ ) ₂ +5C+3SiO ₂ =3CaSiO ₂ +5CO+P ₂

When the temperature reaches above 1352°C, the reaction formula is:

Ca ₃ (PO ₄ ) ₂ +5C=3CaO+5CO+P ₂

The reduction reaction can proceed spontaneously, and the reaction equilibrium direction tends to the direction of generating P2, so that the yellow phosphorus yield (above 95% ₎ of the product of the present invention is much higher than the existing yellow phosphorus production technology (not more than 90%).

Further, in S1 and S2, the pressure difference P1-P2 between the fume hood and the slag pool can be determined by monitoring the pressure gauges of the slag pool and the fume hood;

When the phosphorus coal gasification reduction unit is in normal operation, before the slag produced by the phosphorus coal gasification reduction reaction falls into the slag pool, the amount of the mixed gas introduced into the annular burner is controlled to make the flue gas hood and the The pressure difference of the slag pool P1-P2=ρslag _material gh ₀ , where h ₀ is the height of the slag pool;

As the amount of slag received in the slag pool increases, the pressure difference between the fume hood and the slag pool, P1-P2=ρ _slag g(h ₀ -h), gradually decreases. When the slag pool is full of slag, the pressure difference value P1-P2= is 0; in general, when the pressure difference value drops below 5kPa, stop feeding the mixed gas to the flue gas burner and prepare for slag discharge .

The technical scheme provided by the present invention can include the following beneficial effects:

1. The gasification reduction device for co-production of yellow phosphorus and synthesis gas of the present invention integrates the phosphorus coal gasification reduction unit and the chilling unit up and down, and discharges the slag formed in the process of the phosphorus coal gasification reduction reaction to the cooling unit intermittently. The cooling treatment is carried out in the cooling unit, which promotes the continuous and stable operation of the entire gasification reduction unit, and is also conducive to the environmental protection and green discharge of the slag.

2. In the present invention, the slag pool and the chilling unit are used together to cool the slag material, and the slag formed in the phosphorus coal gasification reduction reaction process is discharged into the slag pool provided with cooling water, And the annular burner in the chilling unit is used to carry out secondary gasification of the slag material at the slag outlet at the same time, which solves the problem that the slag material easily blocks the slag outlet in the prior art, and ensures the reliability and reliability of the gasification reduction device. stability.

3. The chilling unit of the present invention is further provided with components such as a flue gas hood and a flue gas cooling coil, and the flue gas generated by the secondary gasification of the slag is sealed in the flue gas hood, and then discharged to the gasification after cooling. Outside the reduction device, the independent discharge of gas and solid waste in the chilling unit is realized; in addition, the setting of the fume hood can prevent the slag from splashing on the inner wall of the chilling unit when burning, and provide a certain guide for the slag falling to the chilled water. At the same time, the exhaust inlet can be built into the fume hood to reduce the surface stress on the inner wall of the chilling unit, which is more conducive to the safe operation of the entire device;

4. The phosphorus coal gasification reduction unit of the present invention combines the advantages of high gasification efficiency and high gasification strength of pressurized coal gasification and the advantages of blast furnace phosphorus production to directly treat low-grade phosphate rock, and realizes the combination of yellow phosphorus and synthesis gas. Produce.

5. In the phosphorus coal gasification and reduction unit of the present invention, a phosphorus material layer and a coal material layer are arranged in layers and intervals, and the high temperature furnace gas generated by the pressurized gasification reaction of the lower coal material layer is fully utilized to directly provide the reduction reaction heat for the upper phosphorus material layer. , reduce the heat loss of furnace gas. Compared with the all-oxygen shaft furnace in the prior art, the heat utilization rate of the phosphorus coal gasification reduction unit of the present invention can be as high as 80% to 85%, and the yellow phosphorus yield can be as high as 95% or more.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention.

Description of drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description serve to explain the principles of the invention.

1 is a schematic structural diagram of a gasification reduction device for co-producing yellow phosphorus and synthesis gas according to an exemplary embodiment, wherein FIG. 1( a ) is a schematic diagram of the overall structure, and FIG. 1( b ) is a schematic diagram of a partial enlarged ;

Fig. 2 is a schematic structural diagram of a slag pool according to an exemplary embodiment.

The reference numbers are as follows:

1—Phosphorus coal gasification reduction unit,

11 - Reaction Chamber

12 - feed inlet

13 - air intake

14 - air outlet

15 - Slag pool

151 - Slag outlet

152 - The outer wall of the slag pool

153 - cooling water pipe

154 - The inner wall of the slag pool

16 - Feed conduit

17 - Manhole

18 - shell of phosphorus coal gasification reduction unit

19 - Refractory

2 - Chilled Chamber Unit

21 - Circular airway

211 - ring burner

22 - Chilled water level

23 - Pointing Gun

24 - solid slag outlet

25 - fume hood

26 - flue gas cooling coil

261 - exhaust inlet

262 - exhaust outlet

27 - Chill Chamber Unit Housing

3—Flange

Detailed ways

The following description and drawings sufficiently illustrate specific embodiments of the invention to enable those skilled in the art to practice them. The examples represent only possible variations. Unless expressly required, individual components and functions are optional and the order of operations may vary. Portions and features of some embodiments may be included in or substituted for those of other embodiments. The scope of embodiments of the invention includes the full scope of the claims, along with all available equivalents of the claims. Various embodiments may be referred to herein by the term "invention," individually or collectively, for convenience only, and are not intended to automatically limit the scope of this application to any if more than one invention is in fact disclosed. A single invention or inventive concept. Herein, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation and do not require or imply any actual relationship between these entities or operations or order. Moreover, the terms "comprising", "comprising" or any other variation thereof are intended to encompass a non-exclusive inclusion such that a process, method or device comprising a list of elements includes not only those elements, but also others not expressly listed elements. The various embodiments herein are described in a progressive manner, and each embodiment focuses on the differences from other embodiments, and the same and similar parts between the various embodiments may be referred to each other. For the structures, products, etc. disclosed in the embodiments, since they correspond to the parts disclosed in the embodiments, the descriptions are relatively simple, and the related parts can be referred to the descriptions in the method part.

Below in conjunction with accompanying drawing and embodiment, the present invention will be further described:

As shown in Figure 1(a) and Figure 1(b), a gasification reduction device for co-production of yellow phosphorus and synthesis gas includes a phosphorus coal gasification reduction unit 1 and a chilling unit 2, and a phosphorus coal gasification reduction unit 1 It is integrated with the chilling unit 2 through the flange 3 up and down. Among them, the coal gasification reduction unit 1 is mainly used to realize the gasification reduction reaction of phosphorus pellets, raw coal and/or coke, oxygen and water vapor to obtain phosphorus-containing furnace gas; the chilling unit 2 is mainly used to gasify the phosphorus coal The slag formed during the reduction reaction is cooled to a solid state and discharged.

The phosphorus coal gasification reduction unit 1 includes a reaction chamber 11 , a feed port 12 , an air inlet 13 , an air outlet 14 , a slag pool 15 , a feed conduit 16 , a manhole 17 , a phosphorus coal gasification reduction unit shell 18 and a refractory material 19 ;

Wherein, the feeding port 12 is located directly above the reaction chamber 11, and is used to provide solid materials, namely phosphorus pellets and raw coal, for the phosphorus coal gasification reduction reaction;

The air inlet 13 is located below the side of the reaction chamber 11 and above the slag pool 15, and is used to provide gas materials, ie, oxygen and water vapor, for the phosphine coal gasification reduction reaction. °The gasification agent nozzles arranged in the circumferential direction are used to inject gas materials into the reaction chamber 11 at high speed through the gasification agent nozzles to carry out coal gasification reaction with the raw coal, so that a local high temperature is formed inside the reaction chamber 11, and at the same time, phosphorus can be adjusted. The reduction reaction temperature of the pellet;

The gas outlet 14 is located above the side of the reaction chamber 11, and is used to export the phosphorus-containing furnace gas;

The slag pool 15 is located directly below the reaction chamber 11 and has an inverted conical structure. The upper part is used to receive the slag from the reaction chamber 11, and the lower part is provided with a slag outlet 151. Unit 2, for discharging slag to chilling unit 2;

The reaction chamber 11 is provided with at least one layer of coal layer 111 and at least one layer of phosphorus layer 112, the coal layer 111 includes raw coal and/or coke, the phosphorus layer 112 includes phosphorus pellets, the coal layer 111 and phosphorus The material layers 112 are arranged in layers in a spaced manner, and the height ratio of the coal material layers 111 and the phosphorus material layers 112 is H ₁ /H ₂ =1.4; The coal layer 111 is in contact with oxygen at the bottom of the reaction chamber 11, and the high-temperature furnace gas is generated by combustion to flow upward. With the upward flow of the high-temperature furnace gas, the materials in the upper phosphorus layer 112 are fully mixed and contacted, so that the phosphorus in the phosphorus pellets The ore is reduced to elemental phosphorus;

The feeding conduit 16 is located directly below the feeding port 12, and is used to vertically introduce the solid material into the gasification chamber 11 to prevent a small amount of solid material from entering the manhole 17 or the gas outlet 14, thereby reducing the amount of phosphate coal gasification and reducing the inner wall of the reduction unit 1. The manhole 17 is located above the side of the reaction chamber, and is used to enter the reaction chamber 11 during maintenance;

The shell 18 of the phosphorus coal gasification reduction unit can adopt a water jacket structure or a coil water wall structure, and is lined with a refractory material 19 to reduce the heat radiation from the inside to the outside of the reaction chamber 11, protect the shell 18 from overheating, and can generate steam at the same time , to achieve heat recovery.

The chilling unit 2 is located below the phosphorous coal gasification and reduction unit 1, and is connected to the phosphorous coal gasification and reduction unit 1 through the flange 3, including a combustion chamber, a chilling chamber and a chilling unit shell 27;

The combustion chamber includes an annular air passage 21, an annular burner 211 located on the annular air passage, an ignition gun 23, a solid slag outlet 24, a flue gas hood 25 and a flue gas cooling coil 26;

The annular air passage 21 is located below the slag outlet 151, and is used for feeding the mixed gas of natural gas and air to the annular burner 211. The annular air passage 21 is an annular multi-channel metal component, and the inner side of the annular passage is evenly arranged with air holes;

The annular burner 211 is used to inject the mixed gas of natural gas and air into the slag outlet 151;

The ignition gun 23 is located below the annular air passage 21, and is used to ignite the mixed gas sprayed from the annular burner 211. In the combustion state, the slag material at the slag outlet 151 is re-gasified, thereby maintaining the slag outlet. 151 is always in an unblocked state;

The fume hood 25 is used to form a gasification space, and the flue gas generated by the secondary gasification is sealed in the fume hood 25 through the liquid sealing effect of the chilled water 22 below;

The flue gas cooling coil 26 is used to discharge the flue gas produced by the secondary gasification out of the chilling unit, and includes an exhaust gas inlet 261 and an exhaust gas outlet 262. The exhaust gas inlet is connected to the top of the fume hood 25, and the exhaust gas The outlet is located outside the chilling unit 2;

The chilling chamber is located below the combustion chamber, and is equipped with chilled water 22. The bottom of the chilling chamber is provided with a solid slag outlet 24, which is used to discharge the slag that has not been completely burned by the secondary gasification. The flue gas in the flue gas cooling coil 26 is cooled, and the temperature of the chilled water can be 50-60°C;

When the phosphorus coal gasification and reduction unit 1 is in normal operation, the solid slag outlet 24 is in a closed state; when the amount of solid slag reaches the discharge standard, the slag collecting assembly (not shown in the figure) is connected to the solid slag outlet 24, When the temperature is raised and the pressure is increased until the pressure conditions in the slag collecting assembly and the pressure conditions in the chilling unit reach a balance, the solid slag material outlet 24 is opened, and the solid slag material falls into the slag collecting assembly based on the action of gravity, and then the solid slag material is discharged into the slag collecting assembly. The material outlet 24 is closed, and subsequent operations are continued, wherein cooling water is installed inside the slag collecting assembly to prevent the chilled water 22 in the chilling chamber from falling into the slag collecting assembly;

The chilling unit shell is not provided with water jacket and refractory material.

As shown in FIG. 2 , the slag pool 15 has an inverted conical structure with a height h ₀ =667mm, and a slag outlet 151 is provided at the lower part. The slag outlet 151 is communicated with the chilling unit for discharging slag. The diameter ^of the slag outlet 151 is 50mm, the outer wall of the slag pool 15 is a pure steel casting 152, the inner wall is a refractory brick 154, and a cooling water pipe 153 is arranged between the outer wall 152 and the inner wall 154. The temperature is 30-60°C, and the temperature difference between the inlet and outlet is 10-20°C. Through the cooling treatment of the cooling water pipe 153, part of the slag can form a layer of solid slag on the inner wall boundary 154 of the molten slag pool 15 and adhere to the inner wall 154, so that A layer of solid slag is formed between the cooling water pipe 153 and the slag to maintain dynamic balance and protect the pure steel casting of the outer wall 152 .

The present invention utilizes the gasification reduction device as shown in Figure 1 and Figure 2 to implement a gasification reduction method for co-producing yellow phosphorus and synthesis gas, and the specific steps are as follows:

A1: Phosphate coal gasification reduction reaction process: The phosphate rock, anthracite and silica are crushed and ground into 80 mesh fine powder, and the mass ratio of phosphate rock:anthracite:silica is 13:4:3, mix evenly, add bentonite As a binder, it is pressed into phosphorus pellets with a particle size of 20mm, and after drying, it is made into phosphorus pellets with a compressive strength of 1800N/piece. Then, the obtained phosphorus pellets and raw coal are respectively fed into the reaction chamber 11 of the phosphorus coal gasification reduction unit 1 through the feeding port 12, wherein the phosphorus pellets are placed on the phosphorus material layer 111, and the raw coal is placed on the phosphorus layer 111. on the coal bed 112;

A2: The water vapor and high-purity oxygen (oxygen-steam ratio is 1.1Nm ³ /kg) are respectively introduced into the reaction chamber 11 through the air inlet 13, and the raw coal located in the coal bed 111 is gasified with oxygen and water vapor. The reaction and combustion produce a high temperature furnace gas of 1500 °C to flow upward;

A3: With the upward flow of the furnace gas, the overall heat flow and circulation inside the reaction chamber 11 is driven, and at the same time, the materials in the reaction chamber 11 are fully mixed and contacted, and the high-temperature furnace gas heats the adjacent upper phosphorus pellets to 1300 ° C , keep the reaction time for 30 minutes, so that the phosphorus pentoxide in the phosphorus pellet is reduced to elemental phosphorus. At this time, the pressure in the reaction chamber is about 4 MPa and the temperature is about 1400° C., and the phosphorus-containing furnace gas generated during the reaction is discharged from the gas outlet 14 . The heat utilization rate is 85%, and the yellow phosphorus yield is 95%.

The slag removal process is as follows:

S1: When the phosphorus coal gasification and reduction unit 1 is in normal operation, the ignition gun 23 is ignited to ignite the mixture of fuel and air sprayed from the annular burner 211, and in the combustion state, the slag at the slag outlet 151 is subjected to secondary Gasification, the flue gas generated by the secondary gasification is sealed in the gasification space formed by the flue gas hood 25 and the chilled water 22, and is discharged from the chilling unit through the flue gas cooling coil 26, and is fed into the annular boiler through control. The amount of mixed gas in the nozzle 211 keeps the pressure P1 in the fume hood greater than the pressure P2 in the slag pool, and the difference P1-P2 is 5-16.3kpa. At this time, the solid slag outlet is in a closed state;

S2: As the slag material received in the slag pool 15 increases, the pressure difference P1-P2 gradually decreases. When the pressure gauge of the flue gas hood and the slag pool monitors that P1-P2 is lower than 5Kpa, stop feeding to the annular burner 211 The mixed gas is introduced, and the slag that has not been completely burned by the secondary gasification is discharged through the slag outlet 151 and falls into the chilled water 22 to be cooled to form a solid slag; when the amount of the solid slag reaches the discharge standard, the slag collecting component and the The solid slag outlet 24 is connected, and the pressure is increased until the pressure condition in the slag collecting component and the pressure condition in the chilling unit 2 reach a balance of 4Mpa, the solid slag outlet 24 is opened, and the solid slag material falls into the interior based on gravity In the slag collecting assembly equipped with cooling water, the solid slag outlet 24 is closed again, and S1 and S2 are continued to be repeated.

The above are only preferred embodiments of the present invention, and are not intended to limit the present invention in any other form, and any modifications or equivalent changes made according to the technical essence of the present invention still fall within the scope of protection of the present invention. .

Claims (9)

1. A gasification reduction device for co-producing yellow phosphorus and synthesis gas is characterized by comprising a phosphorus coal gasification reduction unit and a chilling unit, wherein the phosphorus coal gasification reduction unit is communicated with the chilling unit from top to bottom;

the phosphorus coal gasification reduction unit: the gasification reduction reaction of all materials in the phosphorus coal gasification reduction unit is realized to obtain phosphorus-containing furnace gas;

the quench unit: used for cooling slag formed in the process of the coal gasification reduction reaction of the phosphorus to be solid and discharging the solid.

2. A gasification reduction apparatus according to claim 1, wherein the phosphorus coal gasification reduction unit comprises a feed inlet (12), a reaction chamber (11) and a slag bath (15) arranged in sequence from top to bottom;

the feeding hole (12) is positioned above the reaction chamber (11) and is used for providing solid materials for the phosphorus coal gasification reduction reaction;

an air inlet (13) is formed in the lateral lower part of the reaction chamber (11) and is used for providing gas materials for the coal gasification reduction reaction of the phosphorus;

an air outlet (14) is arranged above the side of the reaction chamber (11) and used for leading out the phosphorus-containing furnace gas;

the slag pool (15) is located right below the reaction chamber (11) and used for receiving slag formed in the phosphorus coal gasification reduction reaction and discharging the slag to the chilling unit located below the slag pool (15).

3. A gasification reduction apparatus according to claim 2, characterized in that at least one coal layer (111) and at least one phosphorus layer (112) are provided in the reaction chamber (11), the coal layer (111) and the phosphorus layer (112) are arranged in a spaced-apart manner, the coal layer (111) comprises raw coal and/or coke, the phosphorus layer (112) comprises phosphorus pellet, wherein the layer height ratio of the phosphorus layer (112) and the coal layer (111) is set as follows:

wherein: h₁-the height of the phosphorus layer consumed per hour, in m;

H₂-the height of the coal bed consumed per hour in m;

q is the heat required for producing the yellow phosphorus product of unit mass, and the unit is J/kg;

q is the heat released by the reaction of unit mass of the raw material coal and/or coke and oxygen, and the unit is J/kg;

m is the mass of the product yellow phosphorus, and the unit is kg;

a-carbon content in the feed coal and/or coke,%;

b-conversion of carbon in feed coal and/or coke,%;

rho-bulk density of the feed coal and/or coke in kg/m³；

d-diameter of the reaction unit in m.

4. A gasification reduction apparatus according to claim 2, characterized in that the phosphorus coal gasification reduction unit further comprises a feed conduit (16);

the feed conduit (16) is located directly below the feed inlet (12) for vertically introducing the solid material into the reaction chamber (11).

5. A gasification reduction apparatus according to claim 2, wherein the slag bath (15) is of an inverted cone-shaped configuration, the upper portion being adapted to receive slag from the reaction chamber (11), and the lower portion being provided with a slag outlet (151), the slag outlet (151) being in communication with the quench unit for discharging the slag charge.

6. A gasification reduction apparatus according to claim 5, wherein the quench unit is located below the P-coal gasification reduction unit and connected thereto by a flange, and the slag outlet (151) leads directly to the quench unit through the flange, discharging the slag to the quench unit.

7. The gasification reduction apparatus of claim 6, wherein the quench unit comprises, from top to bottom, a combustion chamber and a quench chamber;

the upper part of the combustion chamber is provided with an annular air passage (21), an annular burner (211) positioned on the annular air passage, an ignition gun (23), a flue gas cover (25) and a flue gas cooling coil (26);

the annular air channel (21) is used for introducing mixed gas of fuel and air into the annular burner (211);

the annular burner (211) is used for spraying the mixed gas to the slag outlet (151);

the ignition gun (23) is used for igniting the mixed gas sprayed out by the annular burner (211), and performing secondary gasification on slag at the slag outlet (151) in a combustion state, so that the slag outlet (151) is kept in an unblocked state all the time;

the flue gas cover (25) is used for forming a gasification space, and flue gas generated by secondary gasification is sealed in the flue gas cover (25) through the liquid seal effect of the lower chilling water (22);

and the flue gas cooling coil (26) is connected above the flue gas hood (25) and is used for discharging flue gas generated by secondary gasification out of the chilling unit.

8. A gasification reduction apparatus according to claim 7, characterized in that the chilling chamber is located below the combustion chamber and contains chilling water (22) inside, and the bottom of the chilling chamber is provided with a solid slag outlet (24) for cooling and discharging the slag which is not completely burned in the secondary gasification and cooling the flue gas in the flue gas cooling coil (26).

9. A method for co-producing yellow phosphorus and synthesis gas by using the gasification reduction plant according to any one of claims 1 to 8, wherein the method comprises a phosphorus coal gasification reduction process and a slag discharge process;

the phosphorus coal gasification reduction reaction process comprises the following steps:

a1: crushing and grinding the phosphate ore, anthracite and silica into powder, and mixing the powder with the phosphate ore: anthracite coal: the mass ratio of silica is (30-80): (10-30): (10-20) mixing the phosphorus pellets to prepare phosphorus pellet pellets, and feeding the prepared phosphorus pellet pellets and the raw material coal and/or coke into the reaction chamber (11) through the feeding hole (12) respectively, wherein the phosphorus pellet is placed on the phosphorus layer (112), and the raw material coal and/or coke is placed on the coal layer (111);

a2: introducing water vapor and high-purity oxygen into the reaction chamber (11) through the air inlet (13), wherein the coal bed (111) positioned at the lower part of the reaction chamber (11) is contacted with the oxygen at the bottom of the reaction chamber (11) and is combusted to generate high-temperature furnace gas to flow upwards;

a3: the furnace gas flows upwards to drive the heat of the whole interior of the reaction chamber (11) to flow and circulate, and simultaneously promote the materials in the reaction chamber (11) to be fully mixed and contacted, the pressure in the reaction chamber (11) is 1-10MPa, the temperature is 1200-1600 ℃, phosphate ore in the phosphorus pellet is reduced into elemental phosphorus, and the phosphorus-containing furnace gas generated in the reaction process is discharged from the gas outlet (14);

the slag discharging process comprises the following steps:

s1: when the phosphorus coal gasification reduction unit normally operates, the ignition gun (23) ignites mixed gas of fuel and air sprayed by the annular burner (211), when the phosphorus coal gasification reduction unit is in a combustion state, slag at the slag outlet (151) is secondarily gasified, flue gas generated by secondary gasification is sealed in a gasification space formed by the flue gas cover (25) and the quenching water (22) and is discharged out of the chilling unit through the flue gas cooling coil (26), and the difference P1-P2 that the pressure P1 in the flue gas cover (25) is greater than the pressure P2 in the slag pool (15) is kept to be 5-20Kpa by controlling the amount of the mixed gas introduced into the annular burner (211), wherein P1-P2 ═ P_{Slag charge}g(h₀-h)，h₀The height h of the slag pool is the height of the slag charge, so that the slag charge in the slag pool (15) is prevented from falling into the chilling unit;

s2: with the increase of slag materials borne in the slag pool (15), the pressure difference P1-P2 between the flue gas cover (25) and the slag pool (15) is gradually reduced, when the pressure difference is lower than 5Kpa, mixed gas is stopped to be introduced into the annular burner (211), the slag materials which are not completely combusted in the secondary gasification are discharged through the slag outlet (151), fall into the quenching water (22) to be cooled to form solid slag materials, and then are discharged through the solid slag material outlet (24), and after the slag discharging process is finished, the steps S1 and S2 are repeated.

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