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

Abstract

The present invention provides a gasification reduction device for co-producing yellow phosphorus and synthesis gas, which includes a phosphorus coal gasification reduction unit and a quenching unit, wherein the phosphorus coal gasification reduction unit is connected to the quenching unit in upper and lower directions, wherein the phosphorus coal gasification reduction unit: realizes the gasification reduction reaction of each material in the phosphorus coal gasification reduction unit to obtain phosphorus-containing furnace gas; the quenching 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. The present invention also provides a method for co-producing yellow phosphorus and synthesis gas using the gasification reduction device. The present invention is a technology with high energy utilization, optimized process, energy saving and environmental protection, and lower cost.

Description

Technical Field

[0001] The invention relates to the field of chemical industry, and in particular to a gasification reduction device and method for co-producing yellow phosphorus and synthesis gas. Background Art

[0002] 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 phosphides, and an important raw material for the preparation of fine phosphates and fine organic phosphorus chemicals. Currently, there are only two methods for industrial production of yellow phosphorus: blast furnace phosphorus production and electric furnace phosphorus production.

[0003] The process of blast furnace phosphorus production is to use lump phosphate rock as raw material, silica as flux, coke and anthracite as reducing agent and fuel, which are added into the blast furnace in a certain proportion and sequence. In the furnace, the coke is burned with the help of hot air to provide heat, and the remaining coke undergoes chemical reduction reaction with the molten phosphate rock under high temperature conditions. The furnace gas escapes from the top of the blast furnace and is obtained through dust removal equipment and condensation refining device to obtain phosphorus products.

[0004] There are two unsolved problems in the blast furnace method of phosphorus production: First, the reduction rate is low. Although the data of the pilot plant carried out in foreign countries in the 1930s showed that the residual phosphorus in the slag could reach as low as 1.5% (P2O5 content), corresponding to a phosphorus reduction rate of more than 90%, the actual reduction rate achieved by the domestic test device was as high as 73.9%. Second, the economy is poor. The main reason why the blast furnace method of phosphorus production technology in foreign countries in the last century was that the power resources were relatively tight at that time, the electricity price 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 the market. The electric furnace method produces yellow phosphorus by adding a mixed charge of phosphate ore, silica and coke into the electric furnace, converting 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, washed, refined and separated to obtain the finished phosphorus. However, the electric furnace method has high energy consumption, heavy pollution, cannot achieve long-term continuous production, and requires high-grade phosphate ore. The current yellow phosphorus production technology can no longer meet the new requirements of low-carbon and environmental protection.

[0005] Coal gasification refers to the process in which solid fuels such as coal, coke, and semi-coke react with a gasifying agent under high temperature, normal pressure, or pressurized conditions to convert them into gas products and a small amount of residue. The coal gasification process can be used to produce fuel gas, which can be used as industrial gas and city gas, and can also be used to produce synthesis gas, which can be used as a raw material for synthetic ammonia, synthetic methanol, and synthetic liquid fuels.

[0006] CN103897737A discloses a method for phosphorus refining and co-producing synthesis gas in an all-oxygen vertical furnace and a device for phosphorus refining and co-producing synthesis gas. The device continues the smelting idea of ​​phosphorus production by blast furnace method, wherein the all-oxygen vertical furnace includes a preheating zone, a reaction zone, a combustion zone, a furnace, a charging port, a gas outlet, a sealing port and a slag outlet. In specific operation, apatite carbon pellets are mixed with fuel coal to obtain a furnace charge, the furnace charge is added from the charging port at the top of the vertical furnace, and pure oxygen and water vapor are introduced from the tuyere at the bottom of the vertical furnace; the high-temperature flue gas generated by the combustion of fuel coal at the bottom of the vertical furnace countercurrently heats the descending furnace charge; in the middle of the vertical furnace, the reducing agent carbon in the apatite carbon pellets reduces the phosphorus pentoxide in the apatite to elemental phosphorus, and at the same time, the fuel coal undergoes a gasification reaction, and the generated phosphorus-containing coal gas is discharged from the coal gas outlet at the top of the vertical furnace. However, the configuration of the reaction zone in the vertical furnace is relatively simple, resulting in the heat generated by the coal gasification reaction not being efficiently utilized, and there is no detailed description of the slag discharge method of the vertical furnace. Smooth slag discharge is a key factor affecting the normal operation of the vertical furnace.

[0007] Therefore, a gasification reduction device for co-producing yellow phosphorus and synthesis gas with high energy utilization, optimized process, energy saving and environmental protection, and lower cost is developed. Summary of the invention

[0008] In order to solve the above-mentioned defects, the present invention provides a gasification reduction device for co-producing yellow phosphorus and synthesis gas.

[0009] The technical solution of the present invention is as follows:

[0010] A gasification reduction device for co-producing yellow phosphorus and synthesis gas, comprising a phosphorus coal gasification reduction unit and a quenching unit, wherein the phosphorus coal gasification reduction unit is connected to the quenching unit in vertical communication;

[0011] The phosphorus coal gasification and reduction unit: realizes the gasification and reduction reaction of each material in the phosphorus coal gasification and reduction unit to obtain phosphorus-containing furnace gas;

[0012] The quenching unit is used to cool the slag formed in the process of phosphorus coal gasification reduction reaction into a solid state and discharge it.

[0013] Furthermore, the phosphorus coal gasification reduction unit comprises a feed inlet, a reaction chamber and a slag pool which are arranged in sequence from top to bottom;

[0014] The feed inlet is located above the reaction chamber and is used to provide solid materials for the phosphorus coal gasification reduction reaction;

[0015] A gas inlet is provided at the lower side of the reaction chamber to provide gas materials for the phosphorus coal gasification reduction reaction;

[0016] A gas outlet is provided on the upper side of the reaction chamber for conducting out the phosphorus-containing furnace gas;

[0017] The slag pool is located directly below the reaction chamber and is used to receive the slag formed in the phosphorus coal gasification reduction reaction and discharge it to the quenching unit located below the slag pool.

[0018] Furthermore, the solid material includes phosphate pellets and raw coal and / or coke, wherein the phosphate pellets can be made by crushing, grinding and mixing phosphate ore, anthracite and silica in a certain proportion.

[0019] Furthermore, the gas material includes oxygen and water vapor, and the ratio of oxygen to 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.

[0020] Furthermore, the air inlet may include a plurality of gasifier nozzles, which are located above the slag pool and are evenly arranged circumferentially at an angle of 0 to 30° with the horizontal plane, so that the gas material is sprayed into the reaction chamber at a high speed through the gasifier nozzles to react with the raw coal and / or coke for gasification, thereby forming local high temperature inside the reaction chamber and adjusting the reduction reaction temperature of the phosphate pellets.

[0021] Furthermore, at least one coal material layer and at least one phosphorus material layer may be provided in the reaction chamber, wherein the coal material layer includes raw coal and / or coke, and the phosphorus material layer includes phosphorus pellets. The coal material layer and the phosphorus material layer may be arranged in an intermittent manner, and the coal material layer located at the bottom of the reaction chamber contacts with oxygen at the bottom of the reaction chamber, and burns to generate high-temperature furnace gas that flows upward; as the high-temperature furnace gas flows upward, the materials in the upper phosphorus material layer are fully mixed and contacted, so that the phosphate ore in the phosphorus pellets 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 is fully utilized to directly provide reduction reaction heat for the phosphorus pellets above, thereby reducing the heat loss of the furnace gas and achieving a higher heat utilization rate.

[0022] Furthermore, in order to achieve the maximum energy utilization rate, the material layer heights of the coal layer and the phosphorus layer should be set extremely cleverly. If the material layer height is too low, it will lead to insufficient reaction, waste of raw materials and low product yield. If the material layer height is too high, the mixing of materials during the reaction will be insufficient, the fluidity and contact efficiency of the materials in the reaction chamber will be insufficient, and the best reaction state cannot be guaranteed, resulting in a huge waste of cost and energy. Therefore, based on the high-temperature heat generated by the gasification reaction of the lower coal layer being equal to the required heat for the reduction reaction of the upper phosphorus layer, the mass of phosphorus pellets and raw coal and / or coke is calculated through heat balance, and then the material volume is calculated based on the bulk density of the phosphorus pellets and the materials in the coal layer, and then the appropriate material layer height ratio is obtained. The appropriate material layer height ratio of the phosphorus layer and the coal layer should be set as follows:

[0023]

[0024]

[0025] Where: H1——height of phosphorus layer consumed per hour, in m;

[0026] H2——height of coal layer consumed per hour, in m;

[0027] Q——The heat required to produce unit mass of yellow phosphorus, in J / kg;

[0028] q——The heat released by the reaction of unit mass of raw coal and / or coke with oxygen, in J / kg;

[0029] M——the mass of yellow phosphorus product, in kg;

[0030] a——Carbon content in raw coal and / or coke, %;

[0031] b——Conversion rate of carbon in raw coal and / or coke, %;

[0032] ρ——Bulk density of raw coal and / or coke, in kg / m 3 ;

[0033] d – the diameter of the reaction chamber, in m.

[0034] Furthermore, the phosphorus coal gasification reduction unit also includes a feed conduit and a manhole;

[0035] The feed conduit is located directly below the feed port and is used to vertically guide the solid material into the gasification chamber to prevent a small amount of solid material from entering the manhole or the gas outlet, thereby reducing mechanical scouring and abrasion of the inner wall of the phosphorus coal gasification reduction unit;

[0036] The manhole is located on the upper side of the reaction chamber and is used to enter the reaction chamber during maintenance.

[0037] Furthermore, the phosphorus coal gasification reduction unit also includes a phosphorus coal gasification reduction unit shell, which can adopt a water jacket structure or a coil water-cooled wall structure and be lined with refractory material to protect the shell from overheating, and the water in the water jacket or the coil water-cooled wall structure can absorb the heat generated by the coal gasification reaction to generate steam for heat recovery.

[0038] Furthermore, the slag pool may be an inverted cone structure, the upper part is used to receive the slag from the reaction chamber, and the lower part is provided with a slag outlet, which is connected to the quenching unit for discharging the slag. The outer wall of the slag pool is a metal casting, the inner wall is a refractory material, and a cooling water pipe is provided between the outer wall and the inner wall. The temperature of the cooling water pipe can be 30-60°C, and the inlet and outlet temperature difference can be 10-20°C. Through the cooling treatment of the cooling water pipe, part of the slag can form a layer of solid slag attached to the inner wall at the inner wall boundary of the slag pool, so that a layer of solid slag formed between the cooling water pipe and the slag can maintain dynamic balance and protect the outer wall metal casting. Specifically, the diameter of the slag outlet can be 30-70mm, the metal casting is a pure copper casting, and the refractory material is a refractory brick.

[0039] Furthermore, the quenching unit includes a portion located below the phosphorus coal gasification reduction unit and connected to the phosphorus coal gasification reduction unit via a flange, and the slag outlet passes through the flange and directly connects to the quenching unit, so that the slag is discharged to the quenching unit.

[0040] Further, the quenching unit comprises a combustion chamber and a quenching chamber from top to bottom;

[0041] 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 fume cooling coil;

[0042] The annular gas passage is used to pass a mixture of fuel and air into the annular burner;

[0043] The annular burner is used to spray the mixed gas toward the slag outlet;

[0044] The ignition gun is used to ignite the mixed gas ejected from the annular burner, and in the combustion state, to perform secondary gasification on the slag at the slag outlet, thereby keeping the slag outlet always in an unblocked state;

[0045] The fume hood is used to form a gasification space, and the fume generated by the secondary gasification is sealed in the fume hood through the liquid sealing effect of the quenching water below;

[0046] The flue gas cooling coil is connected to the top of the flue gas hood and is used to discharge the flue gas generated by the secondary gasification out of the quenching unit. Specifically, the flue gas cooling coil also includes an exhaust inlet and an exhaust outlet, the exhaust inlet can be built into the flue gas hood, and the exhaust outlet is arranged outside the quenching unit.

[0047] Furthermore, the quenching chamber is located below the combustion chamber and is filled with quenching water. A solid slag outlet is provided at the bottom of the quenching chamber for cooling and discharging the slag that is not completely burned by secondary gasification, and also for cooling the flue gas in the flue gas cooling coil. Specifically, the temperature of the quenching water can be 50-60°C.

[0048] Furthermore, when the phosphine coal gasification reduction unit is working normally, 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 pressure is increased to a balance between the pressure conditions in the slag collecting component and the pressure conditions in the quenching unit, the solid slag outlet is opened, and the solid slag falls into the slag collecting component due to gravity, and then the solid slag outlet is closed to continue with subsequent operations.

[0049] Furthermore, cooling water is installed inside the slag collecting assembly to prevent the quenching water in the quenching chamber from falling into the slag collecting assembly.

[0050] Furthermore, the quenching unit also includes a quenching unit shell, which is not provided with a water jacket and refractory material.

[0051] The present invention also provides a method for co-producing yellow phosphorus and synthesis gas by using the aforementioned gasification reduction device for co-producing yellow phosphorus and synthesis gas, the method comprising a phosphorus coal gasification reduction reaction process and a slag discharge process;

[0052] The phosphorus coal gasification reduction reaction process comprises the following steps:

[0053] A1: crushing and grinding phosphate rock, anthracite and silica and mixing them in a mass ratio of phosphate rock: anthracite: silica of (30-80): (10-30): (10-20) to prepare the phosphate pellets, and then feeding the prepared phosphate pellets and the raw coal and / or coke into the reaction chamber through the feed inlet, wherein the phosphate pellets are placed on the phosphorus material layer, and the raw coal and / or coke are placed on the coal material layer;

[0054] A2: Water vapor and high-purity oxygen are introduced into the reaction chamber through the air inlet, respectively, and the coal layer located at the bottom of the reaction chamber contacts with oxygen at the bottom of the reaction chamber and burns to generate high-temperature furnace gas that flows upward;

[0055] A3: As the furnace gas flows upward, it drives the overall heat flow and circulation inside the reaction chamber, and at the same time promotes the full mixing and contact of the materials in the reaction chamber. The pressure in the reaction chamber is 1-10MPa and the temperature is 1200-1600℃. The phosphate ore in the phosphate pellets is reduced to elemental phosphorus, and the phosphorus-containing furnace gas generated during the reaction is discharged from the gas outlet.

[0056] The slag removal process comprises the following steps:

[0057] S1: When the phosphorus coal gasification reduction unit is operating normally, the ignition gun ignites the mixed gas of fuel and air sprayed from the annular burner. In the combustion state, the slag at the slag outlet is secondary gasified. The flue gas generated by the secondary gasification is sealed in the gasification space formed by the flue gas hood and the quenching water and discharged from the quenching unit through the flue gas cooling coil. By controlling the amount of mixed gas introduced into the annular burner, the pressure P1 in the flue gas hood is kept greater than the pressure P2 in the slag pool by a difference of 5-15Kpa, where P1-P2=ρ 渣料 g(h0-h), where h0 is the height of the slag pool and h is the height of the slag, thereby preventing the slag in the slag pool from falling into the quenching unit;

[0058] S2: As the amount of slag in the slag pool increases, the pressure difference P1-P2 between the fume hood and the slag pool gradually decreases. When the pressure difference is lower than 5Kpa, the mixed gas is stopped from being introduced into the annular burner. The slag that is not completely burned by the secondary gasification is discharged through the slag outlet and falls into the quenching water for cooling to form solid slag, which is then discharged through the solid slag outlet. After the slag discharge process is completed, steps S1 and S2 are repeated.

[0059] Furthermore, in A1, the phosphate pellet preparation process includes: grinding phosphate ore, anthracite and silica into fine powder of 60-100 mesh, mixing them evenly in a weight ratio of phosphate ore: anthracite: silica = 13:4:3, adding any one or more binders selected from refractory cement, sodium humate, peridot, water glass, and bentonite, and pressing them into pellets with a particle size of 10-30 mm, and after drying, making phosphate pellets with a compressive strength of 1800N / piece.

[0060] Further, in A2 and A3, the chemical reaction formula in the reaction chamber is as follows:

[0061] (1) Coal gasification reaction:

[0062] C+O2=CO2

[0063] 2C+O2=2CO

[0064] C+CO2=2CO

[0065] C+H2O=H2+CO

[0066] C+2H2O=2H2+CO2

[0067] CO+H2O=H2+CO2

[0068] The temperature of the high-temperature furnace gas produced is 1400-1600°C;

[0069] (2) Reduction reaction of phosphorus pellets: The reaction begins in the temperature range of 1152-1177°C. When the temperature reaches about 1227°C, the reaction is almost complete. The reaction formula is:

[0070] Ca3(PO4)2+5C+3SiO2=3CaSiO2+5CO+P2

[0071] When the temperature reaches above 1352℃, the reaction equation is:

[0072] Ca3(PO4)2+5C=3CaO+5CO+P2

[0073] The reduction reaction can proceed spontaneously, and the reaction equilibrium direction tends to the direction of generating P2, so that the yield of the yellow phosphorus product of the present invention (more than 95%) is much higher than the existing yellow phosphorus production technology (no more than 90%).

[0074] 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;

[0075] When the phosphorus coal gasification reduction unit operates normally, before the slag produced by the phosphorus coal gasification reduction reaction falls into the slag pool, the amount of mixed gas introduced into the annular burner is controlled so that the pressure difference between the fume hood and the slag pool is P1-P2=ρ 渣料 gh0, where h0 is the height of the slag pool;

[0076] As the amount of slag in the slag pool increases, the pressure difference between the fume hood and the slag pool is P1-P2=ρ 渣料 g(h0-h), gradually decreases, and when the slag pool is full of slag, the pressure difference P1-P2= is 0; generally, when the pressure difference drops below 5kPa, stop introducing the mixed gas into the flue gas burner to prepare for slag discharge.

[0077] The technical solution provided by the present invention may include the following beneficial effects:

[0078] 1. The gasification reduction device for co-producing yellow phosphorus and synthesis gas of the present invention connects the phosphorus coal gasification reduction unit and the quenching unit up and down into one body, and the slag formed during the phosphorus coal gasification reduction reaction is intermittently discharged into the quenching unit for cooling treatment, which promotes the continuous and stable operation of the entire gasification reduction device and is also beneficial to the environmentally friendly green discharge of the slag.

[0079] 2. In the present invention, a slag pool and a quenching unit are used together to cool and discharge the slag, wherein the slag formed during the gasification and reduction reaction of the phosphine coal is discharged into a slag pool provided with cooling water, and the slag at the slag outlet is secondary gasified by the annular burner in the quenching unit, thereby solving the problem in the prior art that the slag outlet is easily blocked by the slag, and ensuring the reliability and stability of the gasification and reduction device.

[0080] 3. The quenching unit of the present invention is further provided with components such as a fume hood and a fume cooling coil, so that the fume generated by the secondary gasification of the slag is sealed in the fume hood, and then discharged to the outside of the gasification reduction device after cooling, so as to realize the independent discharge of gaseous and solid wastes in the quenching unit; in addition, the provision of the fume hood can prevent the slag from splashing onto the inner wall of the quenching unit when burning, and provide a certain diversion space for the slag to fall onto the quenching 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 quenching unit, which is more conducive to the safe operation of the entire device;

[0081] 4. The phosphorus coal gasification reduction unit of the present invention combines the advantages of high gasification efficiency and high gasification intensity of pressurized coal gasification and the advantages of direct treatment of medium and low-grade phosphate ore by blast furnace phosphorus production to achieve the co-production of yellow phosphorus and synthesis gas.

[0082] 5. The phosphorus coal gasification reduction unit of the present invention is provided with a phosphorus material layer and a coal material layer in layers, and the high-temperature furnace gas generated by the pressurized gasification reaction of the lower coal material layer is fully utilized to directly provide heat for the reduction reaction of the upper phosphorus material layer, thereby reducing the heat loss of the furnace gas. Compared with the all-oxygen vertical 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 more than 95%.

[0083] It is to be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0084] 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.

[0085] FIG1 is a schematic diagram of the structure of a gasification reduction device for co-producing yellow phosphorus and synthesis gas according to an exemplary embodiment, wherein FIG1(a) is a schematic diagram of the overall structure, and FIG1(b) is a schematic diagram of a partial enlargement;

[0086] Figure 2 It is a schematic structural diagram of a slag pool according to an exemplary embodiment.

[0087] The reference numerals are as follows:

[0088] 1——Phosphorus coal gasification reduction unit,

[0089] 11 - Reaction Chamber

[0090] 12——Feed port

[0091] 13 - Air Inlet

[0092] 14——Air outlet

[0093] 15 - Slag pool

[0094] 151——Slag outlet

[0095] 152——Outer wall of slag pool

[0096] 153——Cooling water pipe

[0097] 154——Inner wall of slag pool

[0098] 16 - Feed duct

[0099] 17 - Manhole

[0100] 18——Phosphorus coal gasification reduction unit shell

[0101] 19——Refractory materials

[0102] 2 - Chiller unit

[0103] 21——Circular airway

[0104] 211——Annular burner

[0105] 22——Quenching water level

[0106] 23 - Firing gun

[0107] 24——Solid slag outlet

[0108] 25——Fume hood

[0109] 26——Flue gas cooling coil

[0110] 261——Exhaust inlet

[0111] 262——Exhaust outlet

[0112] 27——Quenching chamber unit housing

[0113] 3—Flange DETAILED DESCRIPTION

[0114] The following description and accompanying drawings fully illustrate specific embodiments of the present invention so that those skilled in the art can practice them. The examples represent possible variations only. Unless explicitly required, separate components and functions are optional, and the order of operations can vary. Parts and features of some embodiments may be included in or replace parts and features of other embodiments. The scope of the embodiments of the present invention includes the entire scope of the claims, and all available equivalents of the claims. In this article, each embodiment may be represented individually or generally by the term "invention", which is only for convenience, and if more than one invention is in fact disclosed, it is not intended to automatically limit the scope of the application to any single invention or inventive concept. In this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, without requiring or implying any actual relationship or order between these entities or operations. Moreover, the term "include", "comprise" or any other variant thereof is intended to cover non-exclusive inclusion, so that the process, method or device including a series of elements includes not only those elements, but also other elements that are not explicitly listed. The various embodiments are described in a progressive manner herein, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the various embodiments can be referred to each other. As for the structures, products, etc. disclosed in the embodiments, since they correspond to the parts disclosed in the embodiments, the description is relatively simple, and the relevant parts can be referred to the description of the method part.

[0115] The present invention will be further described below in conjunction with the accompanying drawings and embodiments:

[0116] As shown in Fig. 1(a) and Fig. 1(b), a gasification reduction device for co-producing yellow phosphorus and synthesis gas comprises a phosphorus coal gasification reduction unit 1 and a quenching unit 2, wherein the phosphorus coal gasification reduction unit 1 and the quenching unit 2 are connected to each other through a flange 3. 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 quenching unit 2 is mainly used to cool the slag formed in the process of phosphorus coal gasification reduction reaction into a solid state and discharge it.

[0117] The phosphorus coal gasification reduction unit 1 comprises 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 housing 18 and a refractory material 19;

[0118] The feed inlet 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;

[0119] The air inlet 13 is located at the lower side of the reaction chamber 11 and above the slag pool 15, and is used to provide gas materials, namely oxygen and water vapor, for the phosphorus coal gasification reduction reaction. The air inlet 13 includes a plurality of gasifying agent nozzles arranged circumferentially at an angle of 20° to the horizontal plane, and is used to spray the gas materials into the reaction chamber 11 through the gasifying agent nozzles at high speed to react with the raw coal for coal gasification, so that a local high temperature is formed inside the reaction chamber 11, and at the same time, the reduction reaction temperature of the phosphorus pellets can be adjusted;

[0120] The gas outlet 14 is located on the upper side of the reaction chamber 11 and is used to discharge the phosphorus-containing furnace gas;

[0121] The slag pool 15 is located directly below the reaction chamber 11 and is an inverted cone-shaped structure. The upper portion is used to receive the slag from the reaction chamber 11, and the lower portion is provided with a slag outlet 151. The slag outlet 151 passes through the flange 3 and directly connects to the quenching unit 2, and is used to discharge the slag into the quenching unit 2.

[0122] At least one coal material layer 111 and at least one phosphorus material layer 112 are arranged in the reaction chamber 11. The coal material layer 111 includes raw coal and / or coke, and the phosphorus material layer 112 includes phosphorus pellets. The coal material layer 111 and the phosphorus material layer 112 are arranged in layers in an intermittent manner, and the material layer height ratio of the coal material layer 111 and the phosphorus material layer 112 is H1 / H2=1.4. When the phosphorus coal gasification reduction reaction is carried out, the coal material layer 111 located at the lower part of the reaction chamber 11 contacts with oxygen at the bottom of the reaction chamber 11, burns and generates high-temperature furnace gas flowing upward. As the high-temperature furnace gas flows upward, the materials in the upper phosphorus material layer 112 are fully mixed and contacted, so that the phosphate ore in the phosphorus pellets is reduced to elemental phosphorus.

[0123] The feed conduit 16 is located directly below the feed port 12 and is used to vertically guide solid materials into the gasification chamber 11 to prevent a small amount of solid materials from entering the manhole 17 or the gas outlet 14, thereby reducing the mechanical scouring and abrasion of the inner wall of the phosphorus coal gasification reduction unit 1; the manhole 17 is located on the upper side of the reaction chamber and is used to enter the reaction chamber 11 during maintenance;

[0124] The shell 18 of the phosphorus coal gasification reduction unit can adopt a water jacket structure or a coil water-cooled wall structure, and is lined with refractory material 19 to reduce the heat radiation from the reaction chamber 11 from the inside to the outside, protect the shell 18 from overheating, and at the same time generate steam to achieve heat recovery.

[0125] The quenching unit 2 is located below the phosphorus coal gasification reduction unit 1 and is connected to the phosphorus coal gasification reduction unit 1 through a flange 3, and includes a combustion chamber, a quenching chamber and a quenching unit housing 27;

[0126] The combustion chamber includes an annular gas passage 21, an annular burner 211 located on the annular gas passage, an ignition gun 23, a solid slag outlet 24, a fume hood 25 and a fume cooling coil 26;

[0127] The annular gas channel 21 is located below the slag outlet 151 and is used to pass a mixture of natural gas and air into the annular burner 211. The annular gas channel 21 is an annular multi-channel metal component, and air holes are evenly arranged inside the annular channel.

[0128] The annular burner 211 is used to inject a mixture of natural gas and air into the slag outlet 151;

[0129] The ignition gun 23 is located below the annular gas channel 21 and is used to ignite the mixed gas ejected from the annular burner 211. In the combustion state, the slag at the slag outlet 151 is secondary gasified, thereby keeping the slag outlet 151 in an unblocked state at all times.

[0130] The fume hood 25 is used to form a gasification space, and the fume generated by the secondary gasification is sealed in the fume hood 25 through the liquid sealing effect of the quenching water 22 below;

[0131] The flue gas cooling coil 26 is used to discharge the flue gas generated by the secondary gasification out of the quenching unit, and includes an exhaust inlet 261 and an exhaust outlet 262, wherein the exhaust inlet is connected to the top of the flue gas hood 25, and the exhaust outlet is arranged outside the quenching unit 2;

[0132] The quenching chamber is located below the combustion chamber and is filled with quenching water 22. A solid slag outlet 24 is provided at the bottom of the quenching chamber for discharging the slag that is not completely burned by the secondary gasification and for cooling the flue gas in the flue gas cooling coil 26. The temperature of the quenching water can be 50-60°C.

[0133] When the phosphorus coal gasification reduction unit 1 is operating normally, the solid slag outlet 24 is in a closed state; when the amount of solid slag reaches the discharge standard, the slag collecting component (not shown in the figure) is connected to the solid slag outlet 24, and the temperature and pressure are increased until the pressure conditions in the slag collecting component and the pressure conditions in the quenching unit are balanced, and then the solid slag outlet 24 is opened, and the solid slag falls into the slag collecting component due to gravity, and then the solid slag outlet 24 is closed, and subsequent operations are continued, wherein the slag collecting component is filled with cooling water to prevent the quenching water 22 in the quenching chamber from falling into the slag collecting component;

[0134] The quenching unit housing is not provided with a water jacket and refractory material.

[0135] like Figure 2 As shown, the slag pool 15 is an inverted cone structure with a height of h0 = 667 mm. A slag outlet 151 is provided at the bottom. The slag outlet 151 is connected to the quenching unit for discharging slag. The density of the slag is 2500 kg / m 3The diameter of the slag outlet 151 is 50 mm, 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 of the cooling water pipe 153 is 30-60°C, and the inlet and outlet temperature difference 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 at the inner wall boundary 154 of the slag pool 15 and adhere to the inner wall 154. In this way, 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.

[0136] The present invention utilizes as shown in Figure 1 and Figure 2 The gasification reduction device implements a gasification reduction method for co-producing yellow phosphorus and synthesis gas, and the specific steps are as follows:

[0137] A1: Phosphorus coal gasification reduction reaction process: Phosphorus ore, anthracite and silica are crushed and ground into 80 mesh fine powder, and mixed evenly according to the mass ratio of phosphate ore: anthracite: silica of 13:4:3, and bentonite is added as a binder to press into phosphorus pellets with a particle size of 20 mm, and after drying, phosphorus pellets with a compressive strength of 1800N / piece are made. Then the prepared phosphorus pellets and raw coal are respectively fed into the reaction chamber 11 of the phosphorus coal gasification reduction unit 1 through the feed port 12, wherein the phosphorus pellets are placed on the phosphorus material layer 111, and the raw coal is placed on the coal material layer 112;

[0138] A2: Water vapor and high-purity oxygen (oxygen vapor ratio of 1.1Nm 3 / kg), are respectively introduced into the reaction chamber 11 through the air inlet 13, and the raw coal in the coal material layer 111 reacts with oxygen and water vapor to produce a high-temperature furnace gas of 1500°C, which flows upward;

[0139] A3: As the furnace gas flows upward, it drives the heat flow and circulation inside the reaction chamber 11 as a whole, and promotes the materials in the reaction chamber 11 to be fully mixed and contacted. The high-temperature furnace gas heats the adjacent upper phosphorus pellets to 1300°C, and maintains the reaction time for 30 minutes, so that the phosphorus pentoxide in the phosphorus pellets is reduced to elemental phosphorus. At this time, the pressure in the reaction chamber is about 4MPa and the temperature is about 1400°C. 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%.

[0140] The slag removal process is as follows:

[0141] S1: When the phosphorus coal gasification reduction unit 1 is operating normally, the ignition gun 23 ignites the mixed gas of fuel and air sprayed from the annular burner 211. In the combustion state, the slag at the slag outlet 151 is secondary gasified. The flue gas generated by the secondary gasification is sealed in the gasification space formed by the flue gas hood 25 and the quenching water 22, and is discharged from the quenching unit through the flue gas cooling coil 26. By controlling the amount of mixed gas introduced into the annular burner 211, the pressure P1 in the flue gas hood is kept greater than the pressure P2 in the slag pool. The difference P1-P2 is 5-16.3 kpa. At this time, the solid slag outlet is closed;

[0142] S2: As the amount of slag in the slag pool 15 increases, the pressure difference P1-P2 gradually decreases. When P1-P2 is lower than 5Kpa as monitored by the smoke hood and the slag pool pressure gauge, the mixed gas is stopped from being introduced into the annular burner 211, and the slag that is not completely burned by the secondary gasification is discharged through the slag outlet 151 and falls into the quenching water 22 to be cooled to form solid slag. When the amount of solid slag reaches the discharge standard, the slag collecting component is connected to the solid slag outlet 24, and the pressure is increased to a balance between the pressure condition in the slag collecting component and the pressure condition in the quenching unit 2, that is, 4Mpa, the solid slag outlet 24 is opened, and the solid slag falls into the slag collecting component filled with cooling water due to gravity, and then the solid slag outlet 24 is closed, and S1 and S2 are repeated.

[0143] The above description is only a preferred embodiment of the present invention and does not constitute any other form of limitation to the present invention. Any modification or equivalent change made based on the technical essence of the present invention still falls within the scope of protection required by the present invention.

Claims

1. A method for co-producing yellow phosphorus and synthesis gas using a gasification reduction device, characterized in that: The method comprises a phosphorus coal gasification reduction reaction process and a slag discharge process; The phosphorus coal gasification reduction reaction process comprises the following steps: A1: Phosphate ore, anthracite and silica are crushed, ground and mixed in a mass ratio of phosphate ore: anthracite: silica of (30-80): (10-30): (10-20) to form phosphorus pellets, and the prepared phosphorus pellets and raw coal and / or coke are respectively fed into a reaction chamber (11) through a feed port (12), wherein the phosphorus pellets are placed on a phosphorus material layer (112), and the raw coal and / or coke are placed on a coal material layer (111); A2: Water vapor and high-purity oxygen are introduced into the reaction chamber (11) through the air inlet (13), respectively, with an oxygen-to-gas ratio of 1.1 Nm 3 / kg, the coal layer (111) located at the bottom of the reaction chamber (11) contacts with oxygen at the bottom of the reaction chamber (11), burns and generates high-temperature furnace gas that flows upward; A3: As the furnace gas flows upward, it drives the heat flow and circulation inside the reaction chamber (11) as a whole, and at the same time promotes the full mixing and contact of the materials in the reaction chamber (11). The pressure in the reaction chamber (11) is 1-10 MPa and the temperature is 1200-1600° C. The phosphate ore 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 (14); The slag removal process comprises the following steps: S1: When the phosphorus coal gasification reduction unit is operating normally, the ignition gun (23) ignites the mixed gas of fuel and air ejected from the annular burner (211). In the combustion state, the slag at the slag outlet (151) is secondary gasified. The flue gas generated by the secondary gasification is sealed in the gasification space formed by the flue gas hood (25) and the quenching water (22) and discharged from the quenching unit through the flue gas cooling coil (26). By controlling the amount of the mixed gas introduced into the annular burner (211), the pressure P1 in the flue gas hood (25) is kept greater than the pressure P2 in the slag pool (15), and the difference P1-P2 is 5-16.3 Kpa. At this time, the solid slag outlet is in a closed state; S2: As the amount of slag in the slag pool (15) increases, the pressure difference P1-P2 between the fume hood (25) and the slag pool (15) gradually decreases. When the pressure difference is lower than 5 KPa, the mixed gas is stopped from being introduced into the annular burner (211). The slag that is not completely burned by secondary gasification is discharged through the slag outlet (151), falls into the quenching water (22) to be cooled to form solid slag, and then discharged through the solid slag outlet (24). After the slag discharge process is completed, steps S1 and S2 are repeated. The method uses a gasification reduction device for co-producing yellow phosphorus and synthesis gas, the gasification reduction device comprises a phosphorus coal gasification reduction unit and a quenching unit, the phosphorus coal gasification reduction unit is connected to the quenching unit in vertical communication; The phosphorus coal gasification and reduction unit: realizes the gasification and reduction reaction of each material in the phosphorus coal gasification and reduction unit to obtain phosphorus-containing furnace gas; The quenching unit is used to cool the slag formed during the phosphorus coal gasification reduction reaction into a solid state and discharge it; The phosphorus coal gasification reduction unit comprises a feed inlet (12), a reaction chamber (11) and a slag pool (15) which are arranged in sequence from top to bottom; The feed inlet (12) is located above the reaction chamber (11) and is used to provide solid materials for the phosphorus coal gasification reduction reaction; The reaction chamber (11) is provided with an air inlet (13) at the lower side thereof, for providing gaseous materials for the phosphorus coal gasification reduction reaction; A gas outlet (14) is provided on the upper side of the reaction chamber (11) for discharging the phosphorus-containing furnace gas; The slag pool (15) is located directly below the reaction chamber (11) and is used to receive slag formed in the phosphorus coal gasification reduction reaction and discharge it to the quenching unit located below the slag pool (15); The reaction chamber (11) is provided with at least one coal material layer (111) and at least one phosphorus material layer (112), wherein the coal material layer (111) and the phosphorus material layer (112) are arranged in an alternate manner, the coal material layer (111) comprises raw coal and / or coke, and the phosphorus material layer (112) comprises phosphorus pellets, wherein the material layer height ratio of the phosphorus material layer (112) to the coal material layer (111) is set as follows: Where: H1——height of phosphorus layer consumed per hour, in m; H2——height of coal layer consumed per hour, in m; Q——The heat required to produce unit mass of yellow phosphorus, in J / kg; q——The heat released by the reaction of unit mass of raw coal and / or coke with oxygen, in J / kg; M——the mass of yellow phosphorus product, in kg; a——Carbon content in raw coal and / or coke, %; b——Conversion rate of carbon in raw coal and / or coke, %; ρ——Bulk density of raw coal and / or coke, in kg / m 3 ; d——diameter of the reaction unit, in m; The quenching unit comprises a combustion chamber and a quenching chamber from top to bottom; The upper part of the combustion chamber is provided with an annular air passage (21), an annular burner (211) located on the annular air passage, an ignition gun (23), a fume hood (25) and a fume cooling coil (26); The annular gas passage (21) is used to pass a mixture of fuel and air into the annular burner (211); The annular burner (211) is used to spray the mixed gas toward the slag outlet (151); The ignition gun (23) is used to ignite the mixed gas ejected from the annular burner (211) and, in a combustion state, to perform secondary gasification on the slag at the slag outlet (151), thereby keeping the slag outlet (151) always in an unblocked state; The fume hood (25) is used to form a gasification space, and the fume generated by the secondary gasification is sealed in the fume hood (25) through the liquid sealing effect of the quenching water (22) below; The flue gas cooling coil (26) is connected to the top of the flue gas hood (25) and is used to discharge the flue gas generated by the secondary gasification out of the quenching unit.

2. The method according to claim 1, 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 port (12) and is used to vertically introduce the solid material into the reaction chamber (11).

3. The method according to claim 1, characterized in that: The slag pool (15) is an inverted cone-shaped structure, the upper part of which is used to receive the slag from the reaction chamber (11), and the lower part of which is provided with a slag outlet (151), wherein the slag outlet (151) is connected to the quenching unit and is used to discharge the slag.

4. The method according to claim 3, characterized in that The quenching unit is located below the phosphine coal gasification reduction unit and is connected to the phosphine coal gasification reduction unit via a flange. The slag outlet (151) passes through the flange and directly connects to the quenching unit, so that the slag is discharged to the quenching unit.

5. The method according to claim 4, characterized in that The quenching chamber is located below the combustion chamber and is filled with quenching water (22). A solid slag outlet (24) is provided at the bottom of the quenching chamber for cooling and discharging slag that is not completely burned in the secondary gasification, and is also used to cool the flue gas in the flue gas cooling coil (26).

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