Gasification reduction device for co-production of yellow phosphorus and synthesis gas

Abstract

The utility model provides a gasification reduction device for co-production of yellow phosphorus and synthesis gas. The gasification reduction device comprises a phosphocoal gasification reduction unit and a chilling unit which are communicated up and down, the phosphocoal gasification reduction unit comprises a reduction chamber, a slag pool, a gasification chamber and a pulverized coal nozzle, and the gasification chamber and the reduction chamber are independently arranged and are communicated at a certain angle; the technical problems that an existing yellow phosphorus and synthesis gas co-production device is low in energy utilization rate, the phosphorite reduction reaction is incomplete, and especially the reduction rate of middle-low-grade phosphorite is low are solved.

Description

Technical Field

[0001] The utility model relates to the field of phosphorus chemical industry, in particular to a gasification reduction device 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 is also an important raw material for the preparation of fine phosphates and fine organic phosphorus chemicals. my country's phosphate reserves rank second in the world, but compared with other phosphorus-producing countries, my country has fewer rich phosphate ores and more poor ores. The average grade of my country's phosphate ore is about 17%, far lower than Morocco (33%) and the United States (30%). The reserves of rich ores with a grade greater than 30% are only 360 million tons, less than 10% of the total reserves, all distributed in Hubei, Yunnan, Guizhou, and Sichuan. In addition, my country has more difficult-to-select ores and fewer easy-to-select ores. Sedimentary phosphorus block rock accounts for about 85% of my country's reserves, and most of them are medium- and low-grade ores. Except for a few rich ores that can be directly used as raw materials for the production of high-concentration phosphate fertilizers, most of them need to be processed before they can be used. At present, the only technologies for industrial production of yellow phosphorus and phosphoric acid are the electric furnace method and the sulfuric acid method. Both require the use of high-grade block phosphate ores with a grade of more than 25%, and cannot use medium- and low-grade phosphate ores and a large amount of phosphate powder.

[0003] CN116656397A discloses a phosphorus coal gasification reaction device and method, and a system for co-producing yellow phosphorus and synthesis gas. The phosphorus coal gasification reaction device includes a reactor and a gas-solid separation unit. The furnace cavity of the reactor is provided with a reaction chamber and a slag chamber located in the upper and lower directions and connected. The reaction chamber is used for the phosphorus coal gasification reduction reaction. The slag chamber is used to receive the slag falling from the reaction chamber and form a slag layer. The upper part of the reactor is provided with a gas outlet for discharging phosphorus-containing furnace gas to the outside; the discharge port of the gas-solid separation unit is connected with the return port of the slag chamber to transport the solid material separated by the gas-solid separation unit back to the slag chamber. However, this technology has the defects of high investment cost, complex equipment, high difficulty in process control, high oxygen consumption, etc., especially the problem that the pulverized coal reacts preferentially with oxygen, resulting in the loss of carbon in the phosphate ore and the inability to reduce it.

[0004] In the prior art, the reaction rate of pulverized coal and oxygen is greater than the rate of phosphate ore reduction reaction, which often leads to a low phosphate ore reduction rate. Therefore, it is an urgent problem to improve the existing problems of low energy utilization, difficult process control, complex equipment, and low phosphate ore reduction rate. Utility Model Content

[0005] In order to solve the above defects, the utility model provides a gasification reduction device for co-producing yellow phosphorus and synthesis gas. The gasification reduction device solves the technical problems of low energy utilization rate, incomplete phosphate ore reduction reaction, and low reduction rate of medium and low-grade phosphate ore in existing co-producing yellow phosphorus and synthesis gas devices by independently arranging a gasification chamber and a reduction chamber and connecting the gasification chamber and the reduction chamber at a certain angle.

[0006] The technical solution of the utility model is as follows:

[0007] A gasification reduction device for co-producing yellow phosphorus and synthesis gas, comprising a phosphorus coal gasification reduction unit and a quenching unit connected up and down, wherein the phosphorus coal gasification reduction unit is used to carry out a phosphate ore reduction reaction and a coal gasification reaction to obtain phosphorus-containing furnace gas, and the quenching unit is used to quench the slag from the phosphorus coal gasification reduction unit with water to reduce the temperature and discharge it;

[0008] The phosphorus coal gasification reduction unit comprises a reduction chamber, a slag pool, a gasification chamber and a pulverized coal nozzle.

[0009] Wherein, the reduction chamber and the slag pool are connected to each other from top to bottom;

[0010] The reduction chamber is used for generating phosphorus vapor by a phosphate ore reduction reaction;

[0011] The slag pool is used to receive the slag formed in the phosphate ore reduction reaction and the coal gasification reaction and discharge it to the quenching unit located below the slag pool;

[0012] The gasification chamber is connected to the lower side of the reduction chamber and is used for coal gasification reaction to obtain synthesis gas, thereby providing heat for the phosphate ore reduction reaction;

[0013] The pulverized coal nozzle is disposed at the top of the gasification chamber and is used to feed pulverized coal and oxygen into the gasification chamber.

[0014] Furthermore, a phosphorus-containing furnace gas outlet is provided on the upper side of the reduction chamber for conducting the phosphorus-containing furnace gas out.

[0015] Furthermore, a phosphorus ball feed port is arranged at the top of the reduction chamber, and a phosphorus ball rectifying cylinder is arranged directly below the phosphorus ball feed port for guiding the phosphorus balls into the reduction chamber and preventing the phosphorus balls from falling into the pipe of the phosphorus-containing furnace gas outlet.

[0016] Furthermore, the inner side of the reduction chamber is provided with a refractory material, the outer side is a steel pressure vessel shell, and a water jacket is provided between the steel pressure vessel shell and the refractory material to cool the furnace wall temperature of the reduction chamber. The water in the water jacket circulates in a bottom-in and top-out flow direction.

[0017] Furthermore, the refractory material includes but is not limited to corundum and silicon carbide.

[0018] Furthermore, the gasification chamber is connected to the reduction chamber via a flange, and an angle between the gasification chamber and the reduction chamber is 10-90°, preferably 50-80°, and more preferably 60-70°.

[0019] Furthermore, the gasification chamber is provided as one or more, preferably 2 or 4, which are arranged at intervals along the circumference of the furnace body of the reduction chamber.

[0020] Furthermore, a cooling water inlet is provided at the lower side of the vaporization chamber, and a cooling water outlet is provided at the upper side of the vaporization chamber. The cooling water inlet and the cooling water outlet are respectively connected to the inlet and outlet of the water-cooled wall coil inside the vaporization chamber.

[0021] Furthermore, the outer side of the gasification chamber is a steel pressure vessel shell, and the inner side is a silicon carbide refractory layer.

[0022] Furthermore, the pulverized coal nozzle is connected to the gasification chamber via a flange.

[0023] Furthermore, the slag pool is an inverted cone structure, and the upper part is used to receive the slag from the reduction chamber and the gasification chamber; the lower part is provided with a slag outlet, the diameter of the slag outlet is 30-200mm, and the slag outlet is connected to the quenching unit for discharging the slag into the quenching unit.

[0024] Furthermore, an annular burner is provided below the slag outlet, wherein the diameter of the annular burner is 100-300 mm and is used to spray combustion gas toward the slag outlet to maintain the outlet temperature and prevent the slag from solidifying.

[0025] Furthermore, the quenching unit includes a quenching chamber, a quenching water inlet flange is provided on the side of the quenching chamber, a slag discharge port is provided at the bottom of the quenching chamber, the interior of the quenching chamber is filled with quenching water, and the quenching water liquid level is controlled at 1 / 2 to 3 / 4.

[0026] The utility model provides a method for co-producing yellow phosphorus and synthesis gas by using the above-mentioned gasification reduction device, the method comprising:

[0027] A coal gasification reaction is carried out in the gasification chamber to obtain synthesis gas, and the synthesis gas is contacted and heat-exchanged with the phosphorus balls in the reduction chamber in a countercurrent manner, so that a phosphate ore reduction reaction occurs in the reduction chamber to obtain phosphorus vapor;

[0028] The phosphorus steam and the synthesis gas after heat exchange are discharged from the upper side of the reduction chamber as phosphorus-containing furnace gas, and the slag formed in the phosphate ore reduction reaction and the coal gasification reaction is discharged into the quenching unit through the slag pool located below the reduction chamber.

[0029] Furthermore, oxygen with an oxygen content of ≥99.6% and pulverized coal with a particle size of ≤90μm (moisture content ≤2wt%) are sprayed into the gasification chamber from a pulverized coal nozzle located at the top of the gasification chamber to generate a coal gasification reaction, and the generated high-temperature synthesis gas of 1500-1700°C and molten coarse slag enter the reduction chamber together. As the high-temperature synthesis gas flows upward, it fully contacts the phosphorus balls in the reduction chamber in reverse, so that the phosphate ore in the phosphorus ball pellets is reduced to elemental phosphorus, and is discharged through the phosphorus-containing furnace gas outlet together with the synthesis gas after heat exchange. Therefore, the utility model makes full use of the high-temperature synthesis gas generated by the coal gasification reaction to directly provide reduction reaction heat for the upper phosphorus balls in the reduction chamber, reduce the heat loss of the synthesis gas, and achieve a higher heat utilization rate.

[0030] Furthermore, the water volume of the water-cooled wall coil inside the gasification chamber is set according to the cooling water outlet temperature, and the cooling water outlet temperature is usually required to be lower than the saturated steam temperature corresponding to the pressure. The pressure of the water-cooled wall coil inside the gasification chamber of the utility model is slightly higher than the furnace chamber pressure of the gasification chamber, and the flow rate and outlet temperature of the water entering the water-cooled wall coil can be obtained by heat exchange calculation based on the furnace chamber pressure of the gasification chamber. Furthermore, the furnace chamber pressure of the gasification chamber is 0.1-10MPa, and the furnace chamber temperature is 1500-1700℃.

[0031] Furthermore, the furnace pressure of the reduction chamber is 0.1-10 MPa, and the furnace temperature is 1300-1500° C. The equation for the phosphate ore reduction reaction occurring in the reduction chamber is as follows:

[0032] 4Ca5(PO4)3F(s)+30C(s)+21SiO2(s)=6P2(g)+20CaSiO3(s)+SiF4(g)

[0033] Furthermore, the phosphate ball comprises phosphate rock, coal and silica; the mass ratio of the phosphate rock: coal: silica is 6:2:1. Specific preparation process: the phosphate rock, coal and silica are ground into 60 μm fine powder, organic and inorganic binders are added, and after being evenly mixed in a mass ratio of phosphate rock: coal: silica of 6:2:1, the phosphate ball is pressed. The inorganic binder comprises any one or more of refractory cement, sodium humate, peridot, water glass and bentonite.

[0034] Furthermore, the phosphorus-containing furnace gas is provided to downstream units such as methanol and synthetic ammonia for use after dust removal, cooling, phosphorus collection and purification.

[0035] The technical solution provided by the utility model may have the following beneficial effects:

[0036] 1) The setting of the gasification chamber of the utility model is conducive to the full reaction of pulverized coal and oxygen, and can avoid the direct injection of oxygen into the reduction chamber, which causes the phosphorus balls to lose carbon. Because the reaction rate of carbon and oxygen is greater than the reduction reaction rate of phosphorus balls and C, the yield of yellow phosphorus is reduced.

[0037] 2) The utility model is applicable to low-, medium- and high-grade phosphate ores, and effectively solves the problem that low-grade phosphate ores cannot be utilized.

[0038] 3) The utility model ingeniously utilizes the heat energy generated by the gasification of pulverized coal for the production of yellow phosphorus, thereby improving the utilization rate of gasification heat.

[0039] 4) The pressure in the reduction chamber of the utility model is 0.1-10MPa, and can reach up to 10MPa, which is higher than the pressure of the traditional gasification reduction device (usually as low as 4MPa). The high pressure can make the reduction reaction of phosphate ore faster, the density of phosphorus-containing furnace gas is large, and the residence time of elemental phosphorus and ash particles in the phosphorus-containing furnace gas in the reduction chamber is long, which can make the reduction reaction of phosphate ore more thorough, more suitable for the current large-scale high-pressure chemical industry requirements, and more convenient for subsequent product processing and use.

[0040] 5) Compared with electric furnace phosphorus production, the utility model produces a larger and more stable amount of tail gas, and produces more yellow phosphorus per unit time. When the furnace pressure of the reduction chamber is higher than that of the traditional electric furnace, the materials and synthesis gas put into the furnace chamber per unit time increase, so the amount of tail gas and yellow phosphorus produced is more, and the production capacity is higher. The utility model produces about 50,000 Nm of effective gas per ton of yellow phosphorus. 3 / h; the phosphorus content per unit volume of phosphorus-containing furnace gas in this utility model is 300g / m 3 , the carbon conversion rate of coal gasification is about 99%, and the conversion rate of phosphate rock is about 96%.

[0041] 6) Compared with the electric furnace method for phosphorus production, the utility model does not require workers to remove slag on site, is safer and more reliable, and effectively reduces pollution to the environment. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] The accompanying drawings herein are incorporated in and constitute a part of the specification, illustrate embodiments consistent with the present utility model, and together with the description, are used to explain the principles of the present utility model.

[0043] Figure 1 It is a schematic diagram of the structure of the gasification reduction device for co-producing yellow phosphorus and synthesis gas according to Examples 1-3 of the present utility model.

[0044] The reference numerals are as follows:

[0045] 1——Reduction chamber;

[0046] 2 – slag pool;

[0047] 3 – Gasification chamber;

[0048] 4 – pulverized coal nozzle;

[0049] 5——Phosphorus ball feeding port;

[0050] 6——Phosphorus ball rectifier tube;

[0051] 7——Cooling water inlet;

[0052] 8——Cooling water outlet;

[0053] 9 – slag outlet;

[0054] 10——annular burner;

[0055] 11 – chilling chamber;

[0056] 12——chilling water inlet;

[0057] 13——slag discharge port;

[0058] 14——Outlet of phosphorus-containing furnace gas. DETAILED DESCRIPTION

[0059] The following description and accompanying drawings fully illustrate the specific embodiments of the utility model 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 utility model 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 "utility model", which is only for convenience, and if more than one utility model is disclosed in fact, it is not intended to automatically limit the scope of the application to any single utility model or utility model concept. In this article, relational terms such as first and second 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.

[0060] The utility model is further described below in conjunction with the accompanying drawings and embodiments:

[0061] Example 1

[0062] Figure 1 A gasification reduction device for co-producing yellow phosphorus and synthesis gas, comprising a phosphorus coal gasification reduction unit and a quenching unit connected up and down, the phosphorus coal gasification reduction unit is used to carry out phosphate ore reduction reaction and coal gasification reaction to obtain phosphorus-containing furnace gas, and the quenching unit is used to quench the slag from the phosphorus coal gasification reduction unit with water to cool it down and discharge it;

[0063] The phosphorus coal gasification reduction unit comprises a reduction chamber 1, a slag pool 2, a gasification chamber 3 and a pulverized coal nozzle 4.

[0064] The reduction chamber 1 and the slag pool 2 are connected to each other from top to bottom;

[0065] Reduction chamber 1 is used for the reduction reaction of phosphate ore to obtain phosphorus vapor;

[0066] The slag pool 2 is used to receive the slag formed in the phosphate ore reduction reaction and the coal gasification reaction and discharge it to the quenching unit located below the slag pool 2;

[0067] The gasification chamber 3 is connected to the side and lower part of the reduction chamber 1 to generate synthesis gas by coal gasification reaction, thereby providing heat for the phosphate ore reduction reaction;

[0068] The pulverized coal nozzle 4 is disposed at the top of the gasification chamber 3 and is used to feed pulverized coal and oxygen into the gasification chamber 3 .

[0069] A phosphorus-containing furnace gas outlet 14 is provided on the upper side of the reduction chamber 1 for conducting the phosphorus-containing furnace gas.

[0070] A phosphorus ball feed port 5 is arranged at the top of the reduction chamber 1, and a phosphorus ball rectifying cylinder 6 is arranged just below the phosphorus ball feed port 5 for guiding the phosphorus balls into the reduction chamber 1 and preventing the phosphorus balls from falling into the outlet pipe of the phosphorus-containing furnace gas 14.

[0071] The inner side of the reduction chamber 1 is covered with refractory materials, and the outer side is a steel pressure vessel shell. A water jacket is provided between the steel pressure vessel shell and the refractory materials to cool the furnace wall temperature of the reduction chamber 1 and protect the shell in a "slag against slag" manner. The water in the water jacket circulates in a bottom-in and top-out flow direction.

[0072] The angle α between the gasification chamber 3 and the reduction chamber 1 is 90°.

[0073] The number of gasification chambers 3 is 2 or 4, and they are arranged at intervals along the circumference of the furnace body of the reduction chamber 1.

[0074] A cooling water inlet 7 is provided at the lower side of the vaporization chamber 3 , and a cooling water outlet 8 is provided at the upper side of the vaporization chamber 3 . The cooling water inlet 7 and the cooling water outlet 8 are connected to the inlet and outlet of the water-cooled wall coil inside the vaporization chamber 3 , respectively.

[0075] The outer side of the gasification chamber 3 is a steel pressure vessel shell, and the inner side is a silicon carbide refractory layer.

[0076] The pulverized coal nozzle 4 is connected to the gasification chamber 3 via a flange.

[0077] The slag pool 2 is an inverted cone structure, and the upper part is used to receive the slag from the reduction chamber 1 and the gasification chamber 3; the lower part is provided with a slag outlet 9, the diameter of the slag outlet 9 is 30-200mm, and the slag outlet 9 is connected to the quenching unit for discharging the slag into the quenching unit.

[0078] An annular burner 10 is provided below the slag outlet 9. The diameter of the annular burner 10 is 100-300 mm and is used to spray combustion gas to the slag outlet to maintain the outlet temperature and prevent the slag from solidifying.

[0079] The quenching unit comprises a quenching chamber 11, a quenching water inlet 12 is arranged on the side of the quenching chamber 11, a slag discharge port 13 is arranged at the bottom of the quenching chamber 11, and the interior of the quenching chamber 11 is filled with quenching water, and the quenching water liquid level is controlled at 1 / 2 to 3 / 4.

[0080] When the gasification reduction device implements the process of co-producing yellow phosphorus and synthesis gas, the specific operation is as follows:

[0081] In the gasification chamber 3, coal gasification reaction is performed to obtain synthesis gas, and the synthesis gas is contacted and heat-exchanged with the phosphorus balls in the reduction chamber 1 in a countercurrent manner, so that a phosphate ore reduction reaction occurs in the reduction chamber 1 to obtain phosphorus vapor;

[0082] Phosphorus steam and the synthesis gas after heat exchange are discharged from the upper side of the reduction chamber 1 as phosphorus-containing furnace gas, and the slag formed in the phosphate ore reduction reaction and coal gasification reaction is discharged to the quenching unit through the slag pool 2 located below the reduction chamber 1.

[0083] Oxygen with an oxygen content of ≥99.6% and pulverized coal with a particle size of ≤90μm (moisture content ≤2wt%) are sprayed into the gasification chamber 3 from the pulverized coal nozzle 4 located at the top of the gasification chamber 3 to generate a coal gasification reaction, and the generated high-temperature synthesis gas of 1500-1700°C and molten coarse slag enter the reduction chamber 1. As the high-temperature synthesis gas flows upward, it fully contacts the phosphorus balls in the reduction chamber 1 in the reverse direction, so that the phosphate ore in the phosphorus ball pellets is reduced to elemental phosphorus, and is discharged through the phosphorus-containing furnace gas outlet 14 together with the synthesis gas after heat exchange.

[0084] The water volume of the water-cooled wall coil inside the vaporization chamber 3 is set according to the cooling water outlet temperature, and the cooling water outlet temperature is usually required to be lower than the saturated steam temperature corresponding to the pressure. The pressure of the water-cooled wall coil inside the vaporization chamber 3 of the utility model is slightly higher than the furnace pressure of the vaporization chamber 3. The flow rate and outlet temperature of the water entering the water-cooled wall coil can be obtained by heat exchange calculation based on the furnace pressure of the vaporization chamber. The cooling water inlet temperature of the water-cooled wall coil is 25°C, and the cooling water outlet temperature is 200°C.

[0085] The furnace pressure of the gasification chamber 3 is 4 MPa, and the furnace temperature is 1700°C.

[0086] The furnace chamber pressure of the reduction chamber 1 is 4 MPa, and the furnace chamber temperature is 1300-1500°C.

[0087] Phosphorus balls include phosphate rock, coal and silica; the mass ratio of phosphate rock: coal: silica is 6:2:1. Specific preparation process: grind phosphate rock, coal and silica into 60μm fine powder, add organic and inorganic binders, mix them evenly according to the mass ratio of phosphate rock: coal: silica of 6:2:1, and press them into phosphate balls. The inorganic binder includes any one or more of refractory cement, sodium humate, peridot, water glass and bentonite.

[0088] The phosphorus-containing furnace gas is dust-removed, cooled, phosphorus-collected and purified before being used by downstream methanol, synthetic ammonia and other units.

[0089] When the angle α between the gasification chamber 3 and the reduction chamber 1 is 90°, the diffusion angle is 14.5°, the jet depth is 0.19m, the conversion rate of phosphorus balls per unit time is 93.2%, and the carbon conversion rate of coal gasification is about 99%. The diffusion angle is the deflection angle of the airflow after entering the reduction chamber 1, and the jet depth is the depth of the airflow penetrating the material layer.

[0090] Example 2

[0091] Figure 1 A gasification reduction device for co-producing yellow phosphorus and synthesis gas, comprising a phosphorus coal gasification reduction unit and a quenching unit connected up and down, the phosphorus coal gasification reduction unit is used to carry out phosphate ore reduction reaction and coal gasification reaction to obtain phosphorus-containing furnace gas, and the quenching unit is used to quench the slag from the phosphorus coal gasification reduction unit with water to cool it down and discharge it;

[0092] The phosphorus coal gasification reduction unit comprises a reduction chamber 1, a slag pool 2, a gasification chamber 3 and a pulverized coal nozzle 4.

[0093] The reduction chamber 1 and the slag pool 2 are connected to each other from top to bottom;

[0094] Reduction chamber 1 is used for the reduction reaction of phosphate ore to obtain phosphorus vapor;

[0095] The slag pool 2 is used to receive the slag formed in the phosphate ore reduction reaction and the coal gasification reaction and discharge it to the quenching unit located below the slag pool 2;

[0096] The gasification chamber 3 is connected to the side and lower part of the reduction chamber 1 to generate synthesis gas by coal gasification reaction, thereby providing heat for the phosphate ore reduction reaction;

[0097] The pulverized coal nozzle 4 is disposed at the top of the gasification chamber 3 and is used to feed pulverized coal and oxygen into the gasification chamber 3 .

[0098] A phosphorus-containing furnace gas outlet 14 is provided on the upper side of the reduction chamber 1 for conducting the phosphorus-containing furnace gas.

[0099] A phosphorus ball feed port 5 is arranged at the top of the reduction chamber 1 , and a phosphorus ball rectifying cylinder 6 is arranged just below the phosphorus ball feed port 5 , which is used to guide the phosphorus balls into the reduction chamber 1 and prevent the phosphorus balls from falling into the pipe of the phosphorus-containing furnace gas outlet 14 .

[0100] The inner side of the reduction chamber 1 is covered with refractory materials, and the outer side is a steel pressure vessel shell. A water jacket is provided between the steel pressure vessel shell and the refractory materials to cool the furnace wall temperature of the reduction chamber 1 and protect the shell in a "slag against slag" manner. The water in the water jacket circulates in a bottom-in and top-out flow direction.

[0101] The angle α between the gasification chamber 3 and the reduction chamber 1 is 70°.

[0102] The number of gasification chambers 3 is 2 or 4, and they are arranged at intervals along the circumference of the furnace body of the reduction chamber 1.

[0103] A cooling water inlet 7 is provided at the lower side of the vaporization chamber 3 , and a cooling water outlet 8 is provided at the upper side of the vaporization chamber 3 . The cooling water inlet 7 and the cooling water outlet 8 are connected to the inlet and outlet of the water-cooled wall coil inside the vaporization chamber 3 , respectively.

[0104] The outer side of the gasification chamber 3 is a steel pressure vessel shell, and the inner side is a silicon carbide refractory layer.

[0105] The pulverized coal nozzle 4 is connected to the gasification chamber 3 via a flange.

[0106] The slag pool 2 is an inverted cone structure, and the upper part is used to receive the slag from the reduction chamber 1 and the gasification chamber 3; the lower part is provided with a slag outlet 9, the diameter of the slag outlet 9 is 30-200mm, and the slag outlet 9 is connected to the quenching unit for discharging the slag into the quenching unit.

[0107] An annular burner 10 is provided below the slag outlet 9. The diameter of the annular burner 10 is 100-300 mm and is used to spray combustion gas to the slag outlet to maintain the outlet temperature and prevent the slag from solidifying.

[0108] The quenching unit comprises a quenching chamber 11, a quenching water inlet 12 is arranged on the side of the quenching chamber 11, a slag discharge port 13 is arranged at the bottom of the quenching chamber 11, and the interior of the quenching chamber 11 is filled with quenching water, and the quenching water liquid level is controlled at 1 / 2 to 3 / 4.

[0109] When the gasification reduction device implements the process of co-producing yellow phosphorus and synthesis gas, the specific operation is as follows:

[0110] In the gasification chamber 3, coal gasification reaction is performed to obtain synthesis gas, and the synthesis gas is contacted and heat-exchanged with the phosphorus balls in the reduction chamber 1 in a countercurrent manner, so that a phosphate ore reduction reaction occurs in the reduction chamber 1 to obtain phosphorus vapor;

[0111] Phosphorus steam and the synthesis gas after heat exchange are discharged from the upper side of the reduction chamber 1 as phosphorus-containing furnace gas, and the slag formed in the phosphate ore reduction reaction and coal gasification reaction is discharged to the quenching unit through the slag pool 2 located below the reduction chamber 1.

[0112] Oxygen with an oxygen content of ≥99.6% and pulverized coal with a particle size of ≤90μm (moisture content ≤2wt%) are sprayed into the gasification chamber 3 from the pulverized coal nozzle 4 located at the top of the gasification chamber 3 to generate a coal gasification reaction, and the generated high-temperature synthesis gas of 1500-1700°C and molten coarse slag enter the reduction chamber 1. As the high-temperature synthesis gas flows upward, it fully contacts the phosphorus balls in the reduction chamber 1 in the reverse direction, so that the phosphate ore in the phosphorus ball pellets is reduced to elemental phosphorus, and is discharged through the phosphorus-containing furnace gas outlet 14 together with the synthesis gas after heat exchange.

[0113] The cooling water inlet temperature of the water-cooled wall coil is 25℃, and the cooling water outlet temperature is 200℃.

[0114] The furnace pressure of the gasification chamber 3 is 4 MPa, and the furnace temperature is 1700°C.

[0115] The furnace chamber pressure of the reduction chamber 1 is 4 MPa, and the furnace chamber temperature is 1300-1500°C.

[0116] Phosphorus balls include phosphate rock, coal and silica; the mass ratio of phosphate rock: coal: silica is 6:2:1. Specific preparation process: grind phosphate rock, coal and silica into 60μm fine powder, add organic and inorganic binders, mix them evenly according to the mass ratio of phosphate rock: coal: silica of 6:2:1, and press them into phosphate balls. The inorganic binder includes any one or more of refractory cement, sodium humate, peridot, water glass and bentonite.

[0117] The phosphorus-containing furnace gas is dust-removed, cooled, phosphorus-collected and purified before being used by downstream methanol, synthetic ammonia and other units.

[0118] When the angle α between the gasification chamber 3 and the reduction chamber 1 is 70°, the diffusion angle is 15.5°, the jet depth is 0.15 m, the conversion rate of phosphorus balls per unit time is 96.3%, and the carbon conversion rate of coal gasification is about 99%.

[0119] Example 3

[0120] Figure 1 A gasification reduction device for co-producing yellow phosphorus and synthesis gas, comprising a phosphorus coal gasification reduction unit and a quenching unit connected up and down, the phosphorus coal gasification reduction unit is used to carry out phosphate ore reduction reaction and coal gasification reaction to obtain phosphorus-containing furnace gas, and the quenching unit is used to quench the slag from the phosphorus coal gasification reduction unit with water to cool it down and discharge it;

[0121] The phosphorus coal gasification reduction unit comprises a reduction chamber 1, a slag pool 2, a gasification chamber 3 and a pulverized coal nozzle 4.

[0122] The reduction chamber 1 and the slag pool 2 are connected to each other from top to bottom;

[0123] Reduction chamber 1 is used for the reduction reaction of phosphate ore to obtain phosphorus vapor;

[0124] The slag pool 2 is used to receive the slag formed in the phosphate ore reduction reaction and the coal gasification reaction and discharge it to the quenching unit located below the slag pool 2;

[0125] The gasification chamber 3 is connected to the side and lower part of the reduction chamber 1 to generate synthesis gas by coal gasification reaction, thereby providing heat for the phosphate ore reduction reaction;

[0126] The pulverized coal nozzle 4 is disposed at the top of the gasification chamber 3 and is used to feed pulverized coal and oxygen into the gasification chamber 3 .

[0127] A phosphorus-containing furnace gas outlet 14 is provided on the upper side of the reduction chamber 1 for conducting the phosphorus-containing furnace gas.

[0128] A phosphorus ball feed port 5 is arranged at the top of the reduction chamber 1 , and a phosphorus ball rectifying cylinder 6 is arranged just below the phosphorus ball feed port 5 , which is used to guide the phosphorus balls into the reduction chamber 1 and prevent the phosphorus balls from falling into the pipe of the phosphorus-containing furnace gas outlet 14 .

[0129] The inner side of the reduction chamber 1 is covered with refractory materials, and the outer side is a steel pressure vessel shell. A water jacket is provided between the steel pressure vessel shell and the refractory materials to cool the furnace wall temperature of the reduction chamber 1 and protect the shell in a "slag against slag" manner. The water in the water jacket circulates in a bottom-in and top-out flow direction.

[0130] The angle α between the gasification chamber 3 and the reduction chamber 1 is 60°.

[0131] The number of gasification chambers 3 is 2 or 4, and they are arranged at intervals along the circumference of the furnace body of the reduction chamber 1.

[0132] A cooling water inlet 7 is provided at the lower side of the vaporization chamber 3 , and a cooling water outlet 8 is provided at the upper side of the vaporization chamber 3 . The cooling water inlet 7 and the cooling water outlet 8 are connected to the inlet and outlet of the water-cooled wall coil inside the vaporization chamber 3 , respectively.

[0133] The outer side of the gasification chamber 3 is a steel pressure vessel shell, and the inner side is a silicon carbide refractory layer.

[0134] The pulverized coal nozzle 4 is connected to the gasification chamber 3 via a flange.

[0135] The slag pool 2 is an inverted cone structure, and the upper part is used to receive the slag from the reduction chamber 1 and the gasification chamber 3; the lower part is provided with a slag outlet 9, the diameter of the slag outlet 9 is 30-200mm, and the slag outlet 9 is connected to the quenching unit for discharging the slag into the quenching unit.

[0136] An annular burner 10 is provided below the slag outlet 9. The diameter of the annular burner 10 is 100-300 mm and is used to spray combustion gas to the slag outlet to maintain the outlet temperature and prevent the slag from solidifying.

[0137] The quenching unit comprises a quenching chamber 11, a quenching water inlet 12 is arranged on the side of the quenching chamber 11, a slag discharge port 13 is arranged at the bottom of the quenching chamber 11, and the interior of the quenching chamber 11 is filled with quenching water, and the quenching water liquid level is controlled at 1 / 2 to 3 / 4.

[0138] When the gasification reduction device implements the process of co-producing yellow phosphorus and synthesis gas, the specific operation is as follows:

[0139] In the gasification chamber 3, coal gasification reaction is performed to obtain synthesis gas, and the synthesis gas is contacted and heat-exchanged with the phosphorus balls in the reduction chamber 1 in a countercurrent manner, so that a phosphate ore reduction reaction occurs in the reduction chamber 1 to obtain phosphorus vapor;

[0140] Phosphorus steam and the synthesis gas after heat exchange are discharged from the upper side of the reduction chamber 1 as phosphorus-containing furnace gas, and the slag formed in the phosphate ore reduction reaction and coal gasification reaction is discharged to the quenching unit through the slag pool 2 located below the reduction chamber 1.

[0141] Oxygen with an oxygen content of ≥99.6% and pulverized coal with a particle size of ≤90μm (moisture content ≤2wt%) are sprayed into the gasification chamber 3 from the pulverized coal nozzle 4 located at the top of the gasification chamber 3 to generate a coal gasification reaction, and the generated high-temperature synthesis gas of 1500-1700°C and molten coarse slag enter the reduction chamber 1. As the high-temperature synthesis gas flows upward, it fully contacts the phosphorus balls in the reduction chamber 1 in the reverse direction, so that the phosphate ore in the phosphorus ball pellets is reduced to elemental phosphorus, and is discharged through the phosphorus-containing furnace gas outlet 14 together with the synthesis gas after heat exchange.

[0142] The water volume of the water-cooled wall coil inside the vaporization chamber 3 is set according to the cooling water outlet temperature, which is usually required to be lower than the saturated steam temperature corresponding to the pressure. The cooling water inlet temperature of the water-cooled wall coil is 25°C, and the cooling water outlet temperature is 200°C.

[0143] The furnace pressure of the gasification chamber 3 is 4 MPa, and the furnace temperature is 1700°C.

[0144] The furnace chamber pressure of the reduction chamber 1 is 4 MPa, and the furnace chamber temperature is 1300-1500°C.

[0145] Phosphorus balls include phosphate rock, coal and silica; the mass ratio of phosphate rock: coal: silica is 6:2:1. Specific preparation process: grind phosphate rock, coal and silica into 60μm fine powder, add organic and inorganic binders, mix them evenly according to the mass ratio of phosphate rock: coal: silica of 6:2:1, and press them into phosphate balls. The inorganic binder includes any one or more of refractory cement, sodium humate, peridot, water glass and bentonite.

[0146] The phosphorus-containing furnace gas is dust-removed, cooled, phosphorus-collected and purified before being used by downstream methanol, synthetic ammonia and other units.

[0147] When the angle α between the gasification chamber 3 and the reduction chamber 1 is 60°, the diffusion angle is 11.5°, the jet depth is 0.16m, and the conversion rate of phosphorus balls per unit time is 94.8%. The carbon conversion rate of coal gasification is about 99%.

[0148] From the results of Examples 1-3, it can be seen that the angles between the gasification chamber and the reduction chamber are different, and the angle and residence time of the high-temperature synthesis gas generated by the gasification chamber into the bottom of the reduction chamber are also different, which will affect the time that the phosphorus balls are exposed to the high-temperature synthesis gas. When the angle is 70°, the diffusion angle is the largest, the high-temperature zone of the reduction chamber covers the largest range, and it is easier to melt the phosphorus balls, which is beneficial to improve the reduction reaction efficiency of the phosphorus balls.

[0149] Comparative Example

[0150] The difference between the gasification reduction device of the comparative example and the utility model is that the gasification chamber and the reduction chamber are integrated devices (such as the device described in the background technology CN116656397A or other prior art devices in which the coal gasification reaction and the phosphate ore reduction reaction are in the same reaction chamber) rather than being independently set. In the coal gasification reaction of the comparative example, pulverized coal combustion is used to provide heat. The integrated device of the gasification chamber and the reduction chamber will cause the phosphate ore to lose carbon and reduce the phosphate ore conversion rate; if lump coal combustion is used to provide heat, the carbon conversion rate is low, and the amount of syngas is 3000Nm 3 / h or so. In addition, the heat utilization rate of the integrated equipment is lower than that of the present invention.

[0151] However, the utility model sets up the gasification chamber separately, and can use pulverized coal gasification to provide heat, the carbon conversion rate can be as high as 99%, and the synthesis gas volume can reach 50000Nm 3 / h, the increase in the amount of synthesis gas can "dilute" harmful gases such as hydrogen fluoride and phosphine, reducing their corrosion to pipelines and equipment. In addition, the heat utilization rate of the gasification reduction device of the utility model can reach 90%.

[0152] The above is only a preferred embodiment of the present invention and does not constitute any other limitation on 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 gasification reduction device for co-producing yellow phosphorus and synthesis gas, characterized in that: It comprises a phosphorus coal gasification reduction unit and a quenching unit which are connected up and down, wherein the phosphorus coal gasification reduction unit is used for carrying out a phosphate ore reduction reaction and a coal gasification reaction to obtain phosphorus-containing furnace gas, and the quenching unit is used for quenching the slag from the phosphorus coal gasification reduction unit with water to cool it down and discharge it; The phosphorus coal gasification reduction unit comprises a reduction chamber (1), a slag pool (2), a gasification chamber (3) and a pulverized coal nozzle (4). The reduction chamber (1) and the slag pool (2) are connected to each other from top to bottom; The reduction chamber (1) is used to generate phosphorus vapor by a phosphate ore reduction reaction; The slag pool (2) is used to receive the slag formed in the phosphate ore reduction reaction and the coal gasification reaction and discharge it to the quenching unit located below the slag pool (2); The gasification chamber (3) is connected to the side and lower part of the reduction chamber (1) to generate synthesis gas through coal gasification reaction, thereby providing heat for the phosphate ore reduction reaction; The pulverized coal nozzle (4) is arranged at the top of the gasification chamber (3) and is used to feed pulverized coal and oxygen into the gasification chamber (3).

2. The gasification reduction device according to claim 1, characterized in that: A phosphorus-containing furnace gas outlet (14) is arranged on the upper side of the reduction chamber (1) for guiding out the phosphorus-containing furnace gas; a phosphorus ball feed port (5) is arranged on the top of the reduction chamber (1), and a phosphorus ball straightening cylinder (6) is arranged directly below the phosphorus ball feed port (5) for guiding the phosphorus balls into the reduction chamber (1) and preventing the phosphorus balls from falling into the pipe of the phosphorus-containing furnace gas outlet (14).

3. The gasification reduction device according to claim 1 or 2, characterized in that: The gasification chamber (3) is connected to the reduction chamber (1) via a flange, and an included angle α between the gasification chamber (3) and the reduction chamber (1) is 10-90°.

4. The gasification reduction device according to claim 3, characterized in that: The included angle between the gasification chamber (3) and the reduction chamber (1) is 60-70°.

5. The gasification reduction device according to claim 4, characterized in that: The gasification chambers (3) are arranged in two or four configurations and are spaced apart from each other along the circumference of the furnace body of the reduction chamber (1).

6. The gasification reduction device according to claim 5, characterized in that: A cooling water inlet (7) is provided at the lower side of the vaporization chamber (3), and a cooling water outlet (8) is provided at the upper side of the vaporization chamber. The cooling water inlet (7) and the cooling water outlet (8) are respectively connected to the inlet and outlet of the water-cooled wall coil inside the vaporization chamber (3).

7. The gasification reduction device according to claim 6, characterized in that: The outer side of the gasification chamber (3) is a steel pressure vessel shell, and the inner side is a silicon carbide refractory layer.

8. The gasification reduction device according to claim 1, characterized in that: The pulverized coal nozzle (4) is connected to the gasification chamber (3) via a flange.

9. The gasification reduction device according to claim 1, characterized in that: The slag pool (2) is an inverted cone-shaped structure, and the upper part is used to receive the slag from the reduction chamber (1) and the gasification chamber (3); the lower part is provided with a slag outlet (9), the diameter of the slag outlet (9) is 30-200mm, and the slag outlet (9) is connected to the quenching unit to discharge the slag into the quenching unit.

10. The gasification reduction device according to claim 1, characterized in that: The quenching unit comprises a quenching chamber (11), a quenching water inlet (12) flange is arranged on the side of the quenching chamber (11), a slag discharge port (13) is arranged at the bottom of the quenching chamber (11), and the interior of the quenching chamber (11) is filled with quenching water, and the quenching water liquid level is controlled at 1 / 2 to 3 / 4.

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