CN111203240B - Catalyst loading method and system, pulverized coal adding method and coal catalytic gasification system - Google Patents

Abstract

The invention provides a catalyst loading method and system, a pulverized coal adding method and a coal catalytic gasification system. The catalyst loading method includes: S1, providing chemical concentrated brine, and separating the chemical concentrated brine into NaCl-rich solution and _Na2SO4 -rich solution; S2, _{respectively concentrating and/or concentrating the NaCl-rich solution and Na2SO4 - rich} solution Or crystallize, and form NaCl loading agent and Na ₂ SO ₄ loading agent respectively; S3, provide coal powder, mix NaCl loading agent and Na ₂ SO ₄ loading agent with coal powder in a predetermined ratio to complete NaCl loading agent and Na ₂ Loading of _SO4 loading agent on pulverized coal. Through the separation and concentration of chemical concentrated brine, the concentration and ratio of ions in the NaCl loading agent and Na ₂ SO ₄ loading agent can be relatively stable, which is convenient for controlling the ratio of mixing with coal powder, thereby improving the catalytic effect and ensuring stability catalytic effect.

Description

Catalyst loading method and system, pulverized coal addition method and coal catalytic gasification system

technical field

The invention relates to the field of coal catalytic gasification, in particular to a catalyst loading method and system, a coal powder adding method and a coal catalytic gasification system.

Background technique

Coal catalytic gasification is a process in which coal and water vapor directly react to generate methane-rich gas under the action of a catalyst. In this process, the role of the catalyst is to promote the water-coal reaction and methanation reaction, so as to achieve the purpose of increasing the carbon conversion rate and methane yield per unit time. In the research of coal catalytic gasification catalysts, there are mainly three systems of alkali metals, alkaline earth metals and transition metals.

Chemical concentrated brine has a certain catalytic effect on coal catalytic gasification. In the prior art, chemical concentrated brine is also used as a catalyst for coal catalytic gasification. Chemical concentrated brine is the product of chemical desalinated water system, circulating water system, recycled water treatment system and boiler system. The solution is rich in Na ⁺ , Cl ^- , NO ₃ ^- and SO ₄ ^2- . At present, the commonly used concentrated brine treatment processes include electrodialysis and reverse osmosis, etc. These treatment processes not only have the disadvantages of large equipment investment, high treatment cost, and poor economy, but also the high-concentration brine produced cannot be effectively disposed of, resulting in waste of resources and environmental pollution. and other shortcomings.

In the prior art, the concentrated brine is directly loaded on the coal, therefore, the concentrations of Na ⁺ , Cl ^- , NO ₃ ^- and SO ₄ ^2- in the concentrated brine are all low, and when directly loaded on the coal in proportion, not only will A large amount of clear water will be generated, which will increase the load of the subsequent dryer, and will also stick to the inner wall of the dryer, making the dryer unable to operate stably for a long time, and the catalytic activity will be reduced due to the difficulty in controlling the concentration ratio of each ion in the concentrated brine , the catalytic efficiency is low, so that the concentrated brine cannot be effectively utilized.

Therefore, there are still many problems in the application of concentrated brine in coal catalytic gasification, and new improvements to existing coal catalytic gasification methods are urgently needed.

Contents of the invention

The purpose of the present invention is to provide a catalyst loading method and system, coal powder adding method and coal catalytic gasification system to solve the problem of poor catalytic effect of industrial concentrated brine in coal catalytic gasification in the prior art.

In order to achieve the above object, the present invention firstly provides a catalyst loading method, which is used to load the catalyst on the pulverized coal. The catalyst adopts chemical concentrated brine, and the catalyst loading method comprises the following steps:

S1, providing chemical concentrated brine, and separating the chemical concentrated brine into NaCl-rich solution and Na ₂ SO ₄ -rich solution;

S2, respectively concentrating and/or crystallizing the NaCl-rich solution and the Na ₂ SO ₄ -rich solution, and forming a NaCl loading agent and a Na ₂ SO ₄ loading agent, respectively;

S3, providing coal powder, mixing NaCl loading agent and Na ₂ SO ₄ loading agent with the coal powder in a predetermined ratio, so as to complete the loading of NaCl loading agent and Na ₂ SO ₄ loading agent on the coal powder.

Optionally, in the S1, a reverse osmosis membrane is used to separate the chemical brine into a NaCl-rich solution and a Na ₂ SO ₄ -rich solution.

Optionally, the S2 includes concentrating and _{crystallizing} the NaCl-rich solution and _{the Na2SO4} -rich solution respectively, the NaCl loading agent includes NaCl crystalline salt and NaCl salt solution, and the _Na2SO4 loading agent includes _Na2 SO ₄ crystalline salt and Na ₂ SO ₄ salt solution.

Optionally, the NaCl salt solution and the Na ₂ SO ₄ salt solution are input into a solid-liquid mixer according to a predetermined ratio, and mixed with coal powder in the solid-liquid mixer;

The NaCl crystalline salt and Na ₂ SO ₄ crystalline salt are input into a powder mixer in a predetermined ratio, and mixed with coal powder in the powder mixer.

Optionally, the mixing environment in the solid-liquid mixer is: temperature 60°C-150°C, pressure 0.05MPa-1.0MPa, inert gas atmosphere.

Optionally, the method of inputting the NaCl crystalline salt and Na ₂ SO ₄ crystalline salt into a powder mixer in a predetermined ratio includes: first inputting the NaCl crystalline salt and Na ₂ SO ₄ crystalline salt into a crystalline salt melting system in a predetermined ratio Perform high-temperature melting to form molten salt, then pulverize the molten salt, and input the pulverized molten salt into a powder mixer to mix with coal powder.

Another aspect of the present invention provides a method for adding pulverized coal, which is used for adding pulverized coal loaded with a catalyst into a gasifier, and the pulverized coal loaded with a catalyst is loaded by the catalyst loading method of the present invention; the pulverized coal adding method include:

The pulverized coal mixed in the solid-liquid mixer is first dried and then input into the gasifier;

The pulverized coal mixed in the powder mixer is input into the solid-liquid mixer, and after being mixed in the solid-liquid mixer, it is sent to the gasifier after drying, or, the pulverized coal mixed in the powder mixer directly into the gasifier.

Another aspect of the present invention also provides a catalyst loading system, which is used to load a catalyst on coal powder. The catalyst is chemical concentrated brine. The catalyst loading system includes a separation device, a salt concentration and crystallization system, and a mixing device connected in sequence;

The separation device is used to separate the chemical concentrated brine into NaCl-rich solution and _{Na2SO4 -} rich solution;

The salt concentration and _{crystallization} system is used to concentrate and/or crystallize the NaCl-rich solution and the _Na2SO4 -rich solution respectively, and form the NaCl loading agent and _{the Na2SO4} loading agent respectively;

The mixing device is used for mixing the NaCl loading agent and the Na ₂ SO ₄ loading agent with the coal powder in a predetermined ratio.

Optionally, the separation device is a reverse osmosis membrane device,

The salt concentration and crystallization system includes a NaCl concentration device, a NaCl crystallization device, a _Na2SO4 concentration device and a _Na2SO4 crystallization device; _the NaCl concentration device is connected to the _NaCl crystallization device, and _{the Na2SO4 concentration} The device is connected to the Na ₂ SO ₄ crystallization device, and the NaCl concentration device, NaCl crystallization device, Na ₂ SO ₄ concentration device and Na ₂ SO ₄ crystallization device are all connected to the mixing device.

Optionally, the mixing device includes a solid-liquid mixer and a powder mixer, the NaCl concentration device and the _Na2SO4 concentration device are both connected to the solid _- liquid mixer, the NaCl crystallization device and the The Na ₂ SO ₄ crystallization devices are all connected to the powder mixer.

Optionally, the mixing device also includes a crystallization salt melting system and a crusher, the NaCl crystallization device and the _Na2SO4 crystallization device are both connected to the _{crystallization} salt melting system, and the crystallization salt melting system is connected to the The crusher is connected, and the crusher is connected with the powder mixer.

Optionally, the crusher or the powder mixer is connected with the solid-liquid mixer.

The present invention further provides a coal catalytic gasification system, including: a gasifier, a dryer, and the catalyst loading system provided by the present invention;

Both the dryer and the gasifier are in communication with the mixing device, and the dryer is in communication with the gasifier.

Through the separation and concentration of chemical brine, the concentration and ratio of ions in NaCl loading agent and Na ₂ SO ₄ loading agent can be relatively stable, which is convenient to control the ratio of mixing with coal powder, so that the catalytic effect can be improved and the stability can be guaranteed. catalytic effect.

Description of drawings

Fig. 1 is a flow chart of catalyst loading method in one embodiment of the present invention;

Fig. 2 is a schematic diagram of the catalyst loading system in an embodiment of the present invention;

Fig. 3 is the schematic diagram of catalyst loading system in another embodiment of the present invention;

Fig. 4 is a schematic diagram of a coal catalytic gasification system in an embodiment of the present invention;

Fig. 5 is a schematic diagram of a coal catalytic gasification system in another embodiment of the present invention.

Detailed ways

In order to more clearly understand the above objects, features and advantages of the present invention, the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the described embodiments are some, not all, embodiments of the present invention. The specific embodiments described here are only used to explain the present invention, but not to limit the present invention. All other embodiments obtained by those skilled in the art based on the described embodiments of the present invention belong to the protection scope of the present invention.

This embodiment provides a catalyst loading method for loading catalyst on coal powder. The catalyst uses chemical concentrated brine, which can be used for desalinated water system drainage, circulating water system drainage, recycled water treatment system drainage and boiler A combination of one or more of the system drainage, in which the main ion concentration Na ⁺ ≥ 100mg/L, Cl ^- ≥ 50mg/L, NO ₃ ^- ≥ 20mg/L, SO ₄ ^2- ≥ 50mg/L, using concentrated Coupling catalysis of alkali metal salts NaCl, NaNO ₃ and Na ₂ SO ₄ in brine as a catalyst for catalytic gasification of coal. The concentration and ratio of each ion in this chemical concentrated brine are unstable. In order to maximize the catalytic effect of the chemical concentrated brine, this embodiment provides a catalyst loading method. Refer to Figures 1 and 2. The catalyst loading method includes The following steps:

S1, providing chemical concentrated brine, and separating the chemical concentrated brine into NaCl-rich solution and Na ₂ SO ₄ -rich solution;

S2, respectively concentrating and/or crystallizing the NaCl-rich solution and the Na ₂ SO ₄ -rich solution, and forming a NaCl loading agent and a Na ₂ SO ₄ loading agent, respectively;

S3, providing coal powder, mixing NaCl loading agent and Na ₂ SO ₄ loading agent with the coal powder in a predetermined ratio, so as to complete the loading of NaCl loading agent and Na ₂ SO ₄ loading agent on the coal powder.

In S2, only the NaCl-enriched solution and the _{Na2SO4 -} enriched solution may be concentrated, or crystallized after the concentration is completed, all crystallized, or partially crystallized. The concentration and ratio of each ion in the concentrated solution is relatively stable, so that it can be combined with coal powder according to the predetermined ratio, so that the catalytic effect is the best. It can be seen that through the separation and concentration of chemical brine, the concentration and ratio of ions in the NaCl loading agent and Na ₂ SO ₄ loading agent can be relatively stable, which is convenient for controlling the ratio of mixing with coal powder, thereby improving the catalytic effect. Moreover, a stable catalytic effect can be guaranteed.

In the S1, the reverse osmosis membrane can be used to separate the chemical concentrated brine into a NaCl-rich solution and a Na ₂ SO ₄ -rich solution. The purpose of _the above-mentioned reverse osmosis membrane is to separate the main components NaCl and _Na2SO4 in the chemical brine, and then use them separately. Main ion concentration of NaCl-rich solution at the outlet of reverse osmosis membrane: Na ⁺ ≥200mg/L, Cl ^- ≥200mg/L, SO ₄ ^2- ≤10mg/L, main ion concentration of Na ₂ SO ₄ -rich solution Na ⁺ ≥200mg/L L, SO ₄ ^2- ≥200mg/L, Cl- ^≤10mg /L.

Wherein, the concentrated NaCl-rich solution is NaCl salt solution, and the concentrated _Na2SO4 -rich solution is _Na2SO4 salt solution. If in S2, _the partially concentrated NaCl-rich solution and _{Na2SO4 -} rich _solution are crystallization, the NaCl loading agent includes NaCl crystal salt and NaCl salt solution, and the Na ₂ SO ₄ loading agent includes Na ₂ SO ₄ crystal salt and Na ₂ SO ₄ salt solution.

In one embodiment, the main ion concentration of the above-mentioned NaCl salt solution is Na ⁺ ≥ 10000 mg/L, Cl ⁻ ≥ 10000 mg/L, NO ₃ ⁻ ≥ 1000 mg/L, SO ₄ ²⁻ ≤ 1000 mg/L. The mass percentage of NaCl in the NaCl crystalline salt accounts for more than 95% (other components are NaNO ₃ , Na ₂ SO ₄ , etc.).

The main ion concentration of the above-mentioned Na ₂ SO ₄ salt solution is Na ⁺ ≥ 10000mg/L, SO ₄ ^2- ≥ 20000 mg/L, NO ₃ ⁻ ≥ 1000 mg/L, Cl ⁻ ≤ 1000 mg/L. The mass percentage of Na ₂ SO ₄ in the Na ₂ SO ₄ crystalline salt accounts for more than 95% (other components are NaNO ₃ , NaCl, etc.).

In a specific embodiment, the NaCl salt solution and Na ₂ SO ₄ salt solution are input into a solid-liquid mixer in a predetermined ratio, and mixed with coal powder in the solid-liquid mixer; the NaCl crystalline salt and Na The ₂ SO ₄ crystalline salt is input into the powder mixer according to a predetermined ratio, and mixed with coal powder in the powder mixer. Wherein, the mixing environment in the solid-liquid mixer is: temperature 60°C-150°C, pressure 0.05MPa-1.0MPa, inert gas atmosphere. In the powder mixer, since there is no liquid, it can be mixed at normal temperature and pressure.

Due to the high concentration of NaCl salt solution and Na ₂ SO ₄ salt solution, they have high viscosity and poor fluidity at room temperature. When loaded at room temperature, coal powder particles will be bonded and agglomeration will occur, which cannot ensure the uniformity of catalyst loading. sex. Compared with the normal temperature and pressure loading technology, the high temperature pressurized loading can accelerate the high temperature flow characteristics of the salt solution molecules in the loading process, and in the high pressure air flow, it is more conducive to the catalyst (here refers to the NaCl salt solution and Na ₂ SO ₄ salt solution) diffuses into the micropores of the coal to make the load uniform. The above-mentioned load temperature is preferably 60-120°C, and the pressure is preferably 0.05-0.5MPa. In order to make full use of the residual temperature of the concentrated brine and save energy consumption, the above-mentioned load temperature is preferably 60-90°C, and the pressure is preferably 0.05-0.3MPa . The inert gas is _N2 or _CO2 atmosphere.

In order to avoid the separation of powder particles NaCl and Na ₂ SO ₄ during the catalytic gasification process, the crystalline salt was formed into a NaCl-Na ₂ SO ₄ composite low-temperature eutectic catalyst system before being mixed with coal powder, and loaded as a whole into Coal powder, improve its catalytic activity. Specifically, the method of inputting the NaCl crystalline salt and Na ₂ SO ₄ crystalline salt into the powder mixer according to a predetermined ratio includes: first inputting the NaCl crystalline salt and Na ₂ SO ₄ crystalline salt into a crystalline salt melting system according to a predetermined ratio. It is melted at high temperature to form molten salt, and then the molten salt is pulverized, and the pulverized molten salt is input into a powder mixer and mixed with coal powder. The melting point of pure NaCl is 801°C, and the melting point of pure Na ₂ SO ₄ is 884°C, both of which are relatively high. In order to form a composite low-temperature eutectic catalyst system of NaCl-Na ₂ SO ₄ in the process lower than the gasification temperature, it has It can better promote the catalytic effect of coal.

The crystalline salt melting system mentioned above can be a high-temperature furnace or a molten bed. The melting temperature of the crystalline salt is 400-800°C, preferably 500-700°C, more preferably 600-650°C. The mass ratio of crystalline NaCl and Na ₂ SO ₄ in the crystalline salt melting system as described above is 25:75-35:65, more preferably 30:70.

In order to make the NaCl-Na ₂ SO ₄ composite low-temperature eutectic catalyst fully contact with pulverized coal during the gasification process without separation, the particle size of the NaCl-Na ₂ SO ₄ composite low-temperature eutectic catalyst after crushing as described above (that is, the particle size of the molten salt) is consistent with the particle size range of coal powder, that is, the particle size is less than or equal to 5mm, and 2-5mm is less than 10%.

The mass ratio of NaCl salt solution and _Na2SO4 salt solution in the above-mentioned solid-liquid _mixer is preferably 15:85-55:45 (converted into the mass _of pure NaCl and _Na2SO4 in the solution), more preferably 20:80-40:60, for example: the mass ratio of NaCl salt solution and Na ₂ SO ₄ salt solution can be 25:75, 28:72, 30:70, 35:65, etc. The _mass ratio of NaCl crystalline salt and _Na2SO4 crystalline salt after crystallization in the powder mixer as described above is 15:85-55:45, which can be 25:75, 30:70, 35:65, 38: 62 etc.

The amount of NaCl salt solution and Na ₂ SO ₄ salt solution input to the solid-liquid mixer depends on the moisture content of the crushed coal. In order not to produce clear water when loading and to make the load uniform, if the moisture content of the coal is greater than 20%, the NaCl salt solution input into the solid-liquid mixer accounts for 0-50% of the total NaCl salt solution after concentration, and the input solid The mass ratio of the Na ₂ SO ₄ salt solution in the liquid mixer to the total concentrated Na ₂ SO ₄ salt solution is 0-50%. If the moisture content of the coal is lower than 20%, the mass ratio of the input solid-liquid mixer NaCl salt solution to the concentrated NaCl salt solution is _50-100 %, and the input solid-liquid mixer _Na2SO4 salt solution accounts for the total concentrated NaCl salt solution. The mass ratio of Na ₂ SO ₄ salt solution is 50-100%.

In a specific embodiment, the mass ratio of the concentrated liquid in the solid-liquid mixer (i.e. NaCl salt solution and Na ₂ SO ₄ salt solution, containing NaCl, NaNO ₃ , Na ₂ SO ₄ ) to the mass of pulverized coal is 1 :100-20:100, preferably 1:100-10:100, if the ratio of the concentrated solution is too large, the content of fluxing alkali metal sodium in the coal ash after gasification will be relatively large, which will easily lead to gasification furnace contact slag, making it difficult for the entire system to operate continuously and stably.

The mass ratio of the sum of NaCl crystalline salt and Na ₂ SO ₄ crystalline salt in the above powder mixer to the mass ratio of coal powder is 1:100-20:100, preferably 1:100-10:100.

In this embodiment, the pulverized coal after crushing is pulverized coal with a particle size of ≤5mm, of which 2-5mm≤10%. Scattered, and it is difficult for the catalyst to enter the inner pore surface of the coal, which will lead to uneven loading of the catalyst solution and affect the gasification efficiency. At the same time, due to the local loading of too much catalyst on the coal particles, the coal ash will melt, causing the gasifier Blocking slag.

This embodiment also provides a method for adding pulverized coal, which is used to add pulverized coal loaded with a catalyst into the gasifier, and the pulverized coal loaded with a catalyst is loaded by the catalyst loading method provided in this embodiment; the method for adding pulverized coal includes :

The pulverized coal mixed in the solid-liquid mixer is first dried, and then input into the gasifier; the pulverized coal mixed in the powder mixer is first input into the solid-liquid mixer, and then After mixing, it is dried and input into the gasifier, or, the coal powder mixed in the powder mixer is directly input into the gasifier.

Because the moisture content of the pulverized coal mixed in the solid-liquid mixer is relatively high, it needs to be dried before being fed into the gasifier, while the pulverized coal in the powder mixer has a small moisture content, so it can be directly fed into the gasifier . If the moisture content in the pulverized coal is large, it is easy to cause caking or hardening, which is not conducive to the smooth coal feeding of the gasifier. The moisture content of the pulverized coal transported to the gasifier should be ≤15%, preferably ≤10%.

Referring to Fig. 2, this embodiment also provides a catalyst loading system, which is used to load a catalyst on the coal powder, the catalyst is a chemical brine, including a separation device, a salt concentration and crystallization system and a mixing device connected in sequence; The separation device is used to separate the chemical concentrated brine into a NaCl-rich solution and a Na ₂ SO _4- rich solution; the salt concentration and crystallization system is used to concentrate and/or crystallize the NaCl-rich solution and the Na ₂ SO ₄ -rich solution respectively, and The NaCl loading agent and the Na ₂ SO ₄ loading agent are formed respectively; the mixing device is used for mixing the NaCl loading agent and the Na ₂ SO ₄ loading agent with the coal powder in a predetermined ratio.

Specifically, the separation device is a reverse osmosis membrane device, and the reverse osmosis membrane device has a reverse osmosis membrane, which can effectively separate chemical concentrated brine. Those skilled in the art can also select other similar separation devices according to actual needs. The salt concentration and crystallization system includes a NaCl concentration device, a NaCl crystallization device, a _Na2SO4 concentration device and a _Na2SO4 crystallization device; _the NaCl concentration device is connected to the _NaCl crystallization device, and _{the Na2SO4 concentration} The device is connected to the Na ₂ SO ₄ crystallization device, and the NaCl concentration device, NaCl crystallization device, Na ₂ SO ₄ concentration device and Na ₂ SO ₄ crystallization device are all connected to the mixing device. The mixing device can mix pulverized coal and crystallized salt, and can also mix pulverized coal and salt solution.

Further, the mixing device includes a solid-liquid mixer and a powder mixer, the NaCl concentration device and _{the Na2SO4} concentration device are all connected to the solid-liquid mixer, the NaCl crystallization device and the Na The ₂ SO ₄ crystallization devices are all connected to the powder mixer.

Referring to Fig. 3, in a preferred embodiment, the mixing device also includes a crystallization salt melting system and a crusher, and the NaCl crystallization device and _{the Na2SO4} crystallization device are all connected to the crystallization salt melting system , the crystalline salt melting system is connected to the crusher, and the crusher is connected to the powder mixer. That is to say, the NaCl crystallization device and the Na ₂ SO ₄ crystallization device are sequentially connected to the powder mixer through a crystallization salt melting system and a crusher. The crystal salt melting system is used to melt two crystal salts to form molten salt, and the crusher is used to crush the molten salt so that it can be mixed with coal powder in a suitable size.

Wherein, the crusher or the powder mixer is connected with the solid-liquid mixer. That is to say, the molten salt can also be input into the solid-liquid mixer after being crushed by the crusher, and the coal powder loaded with catalyst in the powder mixer can also be input into the solid-liquid mixer.

This embodiment also provides a coal catalytic gasification system, referring to Figure 4 and Figure 5, the coal catalytic gasification system includes: a gasifier, a dryer, and a catalyst loading system provided in this embodiment; the dryer and the The gasification furnaces are all in communication with the mixing device, and the dryers are in communication with the gasification furnaces. Specifically, the dryer is connected to the solid-liquid mixer and the gasifier, and the powder mixer is connected to the gasifier.

The operating temperature of the aforementioned gasifier is 600-1000° C., the operating pressure is 1-4 MPa, and the mass ratio of water to coal is 0.6-1.5. In order to increase methane production, the gasifier can be operated at low temperature, high pressure and low water-to-coal ratio. The preferred temperature is 600-800°C, the operating pressure is 3-4MPa, and the water-to-coal mass ratio is 0.6-1.0.

In order to further verify the technical effect of the above technical solution, this embodiment provides the following examples and comparative examples and corresponding experimental data.

Comparative example 1

Take pulverized coal with a particle size of ≤5mm after crushing, 2-5mm accounting for 8%, without adding a catalyst, and gasify the raw coal in the gasifier. The gasification conditions are: temperature 800°C, operating pressure 3.5MPa, water coal quality Ratio 1.2, carbon conversion rate and methane yield after gasification are shown in Table 1.

Comparative example 2

Take the crushed coal powder with a particle size of ≤5mm, 2-5mm accounting for 8%, impregnate the 8% alkali metal potassium catalyst in a high-speed mixer under normal temperature and pressure, and then dry it in a dryer. After drying, the coal sample The moisture content of the raw coal is 5%, and the raw coal gasification is carried out in the gasifier. The gasification conditions are: temperature 800°C, operating pressure 3.5MPa, water-to-coal mass ratio 1.2, and the carbon conversion rate and methane yield after gasification are shown in Table 1. Show.

Comparative example 3

Take the pulverized coal with a particle size of ≤5mm after crushing and 2-5mm accounting for 8%, impregnate the industrial concentrated brine with a load of 8% in the high-speed mixer at normal temperature and pressure at normal temperature and pressure, and then dry it in the dryer. The moisture content of the dried coal sample is 5%, and the coal gasification with concentrated brine is carried out in the gasifier. The gasification conditions are: temperature 800°C, operating pressure 3.5MPa, water-to-coal mass ratio 1.2, carbon conversion rate after gasification and The methane yield is shown in Table 1. The concentration of each ion in the concentrated brine discharged from the desalinated water system is shown in Table 2.

Example 1

Take the industrial concentrated brine drained from the circulating water system, and first pass the industrial concentrated brine through the reverse osmosis membrane to separate the rich NaCl solution and the rich Na ₂ SO ₄ solution.

The NaCl-rich solution is concentrated, and after concentration, the 40% NaCl salt solution is crystallized, and the mass percentage of the NaCl crystalline salt after crystallization accounts for 96% of the total crystalline salt. The rich Na ₂ SO ₄ solution is concentrated, and after concentration, the 30% Na ₂ SO ₄ salt solution is crystallized, and the mass percentage of Na ₂ SO ₄ crystalline salt accounts for 95% of the total crystalline salt after crystallization.

The mass ratio of the NaCl salt solution input into the solid-liquid mixer to the total NaCl salt solution after concentration is 30%, and the _Na2SO4 salt solution input into _the solid _- liquid mixer accounts for the mass ratio of the concentrated _Na2SO4 salt solution 30%.

Take pulverized coal with particle size ≤ 5mm after crushing, 8% of 2-5mm, and 25% moisture, and load 8% concentrated high-concentration by impregnation in a solid-liquid mixer at 120°C, 0.5MPa, and _N2 atmosphere NaCl salt solution and Na ₂ SO ₄ salt solution, wherein, the mass ratio of pure NaCl and pure Na ₂ SO ₄ in NaCl salt solution and Na ₂ SO ₄ salt solution is 50:50, and then dried in a dryer, dried The moisture of the back coal sample is 6%.

NaCl crystalline salt and Na ₂ SO ₄ crystalline salt are mixed according to the mass ratio of 50:50 and mixed with the crushed coal powder according to the mass ratio of 8% in the powder mixer, and the coal sample after the powder mixer is mixed It is mixed with the coal sample dried by the dryer and then added to the gasifier. The coal gasification reaction is carried out in the gasifier. The reaction gasification conditions are: temperature 800 ° C, operating pressure 3.5 MPa, water-to-coal mass ratio 1.2, and the carbon conversion rate and methane yield after gasification are shown in Table 1.

Example 2

Differences from Example 1 include:

NaCl crystalline salt and Na ₂ SO ₄ crystalline salt are melted at a high temperature at 650°C in a high-temperature furnace according to the mass ratio of 50:50, and then the molten salt is broken into particles with a particle size of ≤5mm and 2-5mm accounting for 8% by a crusher , mixed with the crushed coal powder in a powder mixer at a mass ratio of 8%, and the coal sample mixed by the powder mixer and the coal sample dried by the dryer were mixed and added to the gasifier . The coal gasification loaded with concentrated brine is carried out in the gasifier. The carbon conversion rate and methane yield after gasification are shown in Table 1.

Example 3

Differences from Example 1 include:

The rich Na ₂ SO ₄ solution is concentrated, and after concentration, the 40% Na ₂ SO ₄ solution is crystallized, and the mass percentage of Na ₂ SO ₄ crystalline salt accounts for 95% of the total crystalline salt.

The mass ratio of the NaCl salt solution input into the solid-liquid mixer to the total NaCl salt solution after concentration is 60%, and the _Na2SO4 salt solution input into _the solid _- liquid mixer accounts for the mass ratio of the concentrated _Na2SO4 salt solution 60%.

Take the crushed coal powder with particle size ≤ 5mm, 2-5mm accounted for 8%, moisture content 25%, in solid-liquid mixer at 120°C, 0.5MPa, _N2 atmosphere, load 5% concentrated high concentration by impregnation NaCl salt solution and Na ₂ SO ₄ salt solution, wherein, the mass ratio of pure NaCl and pure Na ₂ SO ₄ in NaCl salt solution and Na ₂ SO ₄ salt solution is 30:70, and then dried in a dryer, dried The moisture of the back coal sample is 6%.

NaCl crystalline salt and Na ₂ SO ₄ crystalline salt are mixed according to the mass ratio of 30:70 and mixed with the crushed coal powder according to the mass ratio of 5% in the powder mixer, and the coal sample after the powder mixer is mixed It is mixed with the coal sample dried by the dryer and then added to the gasifier. The coal gasification reaction is carried out in the gasifier. The reaction gasification conditions are: temperature 700 ° C, operating pressure 2.0 MPa, water-to-coal mass ratio 0.8, and the carbon conversion rate and methane yield after gasification are shown in Table 1.

Example 4

Differences from Example 1 include:

The mass ratio of the NaCl salt solution input into the solid-liquid mixer to the total NaCl salt solution after concentration is 60%, and the _Na2SO4 salt solution input into _the solid _- liquid mixer accounts for the mass ratio of the concentrated _Na2SO4 salt solution 60%.

Take the pulverized coal whose particle size is ≤5mm after crushing, 2-5mm accounts for 8%, and the water content is 15%, and put it in a solid-liquid mixer at 70°C, 0.3MPa, and _a CO2 atmosphere to load 1% of the concentrated high-concentration NaCl salt solution and Na ₂ SO ₄ salt solution, wherein, the mass ratio of pure NaCl and pure Na ₂ SO ₄ in NaCl salt solution and Na ₂ SO ₄ salt solution is 30:70, and then dried in a dryer, dried The moisture of the back coal sample is 6%.

NaCl crystalline salt and Na ₂ SO ₄ crystalline salt are melted at a high temperature at 800°C in a high-temperature furnace according to the mass ratio of 30:70, and then the molten salt is broken into particles with a particle size of ≤5mm and 2-5mm accounting for 8% by a crusher , mixed with the crushed coal powder in a powder mixer according to the mass ratio of 1%, and the coal sample mixed by the powder mixer and the coal sample dried by the dryer were mixed and added to the gasifier . The coal gasification reaction is carried out in the gasifier. The reaction gasification conditions are: temperature 700 ° C, operating pressure 2.0 MPa, water-to-coal mass ratio 0.8, and the carbon conversion rate and methane yield after gasification are shown in Table 1.

Example 5

Differences from Example 1 include:

The NaCl-rich solution is concentrated, and after concentration, the 30% NaCl salt solution is crystallized, and the mass percentage of the NaCl crystalline salt after crystallization accounts for 96% of the total crystalline salt. The rich Na ₂ SO ₄ solution is concentrated, and after concentration, the 30% Na ₂ SO ₄ salt solution is crystallized, and the mass percentage of Na ₂ SO ₄ crystalline salt accounts for 95% of the total crystalline salt after crystallization.

The mass ratio of the NaCl salt solution input into the solid-liquid mixer to the total NaCl salt solution after concentration is 60%, and the _Na2SO4 salt solution input into _the solid _- liquid mixer accounts for the mass ratio of the concentrated _Na2SO4 salt solution 60%.

Take pulverized coal with particle size ≤ 5mm after crushing, 2-5mm accounted for 8%, moisture content 15%, in solid-liquid mixer at 150℃, 1.0MPa, _CO2 atmosphere, load 8% high concentration after concentration by impregnation NaCl salt solution and Na ₂ SO ₄ salt solution, wherein, the mass ratio of pure NaCl and pure Na ₂ SO ₄ in NaCl salt solution and Na ₂ SO ₄ salt solution is 55:45, and then dried in a dryer, dried The moisture of the back coal sample is 6%.

NaCl crystalline salt and Na ₂ SO ₄ crystalline salt are melted at a high temperature at 800°C in a high-temperature furnace according to the mass ratio of 30:70, and then the molten salt is broken into particles with a particle size of ≤5mm and 2-5mm accounting for 8% by a crusher , mixed with the crushed coal powder in a powder mixer according to the mass ratio of 1%, and the coal sample mixed by the powder mixer and the coal sample dried by the dryer were mixed and added to the gasifier . The coal gasification reaction is carried out in the gasifier. The reaction gasification conditions are: temperature 750 ° C, operating pressure 2.0 MPa, water-to-coal mass ratio 1.5, and the carbon conversion rate and methane yield after gasification are shown in Table 1.

Table 1 Gasification characteristic data

Table 2 Concentration data of various ions in concentrated brine

It can be seen from the test data of the above examples and comparative examples that the catalyst loading method of this embodiment is applied to the coal catalytic gasification reaction, which can effectively improve the methane recovery rate and carbon conversion rate, that is to say, the catalytic effect is improved; and The chemical brine can be rationally utilized, the comprehensive utilization efficiency of wastewater can be improved, economic investment can be reduced, and continuity, reliability, and environmental protection can be guaranteed.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: it can still be Modifications are made to the technical solutions described in the foregoing embodiments, or equivalent replacements are made to some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims (11)

1. a catalyst loading method, for loading catalyst on coal powder, described catalyst adopts chemical industry strong brine, it is characterized in that, described catalyst loading method comprises the following steps: S1, providing chemical concentrated brine, and separating the chemical concentrated brine into NaCl-rich solution and Na ₂ SO ₄ -rich solution; S2, respectively concentrating and crystallizing the NaCl-rich solution and the _{Na2SO4 -} rich solution, and forming a NaCl loading agent and _{a Na2SO4} loading agent, respectively; S3, providing coal powder, mixing NaCl loading agent and Na ₂ SO ₄ loading agent with coal powder in a predetermined ratio, so as to complete the loading of NaCl loading agent and Na ₂ SO ₄ loading agent on coal powder; The S2 includes concentrating and crystallizing the NaCl-rich solution and the _{Na2SO4 -} rich solution respectively, the NaCl loading agent includes NaCl crystalline salt and _NaCl salt solution, and _{the Na2SO4} loading agent includes _Na2SO4 crystalline salt and _Na2SO4 salt _solution ; The NaCl crystalline salt and the Na ₂ SO ₄ crystalline salt are input into a powder mixer according to a predetermined ratio, and the method includes: firstly, the NaCl crystalline salt and Na ₂ SO ₄ crystalline salt are input into a crystalline salt melting system according to a predetermined ratio. It is melted at high temperature to form molten salt, and then the molten salt is pulverized, and the pulverized molten salt is input into a powder mixer and mixed with coal powder. 2. The catalyst loading method according to claim 1, characterized in that, in said S1, reverse osmosis membrane is used to separate the concentrated chemical brine into NaCl-enriched solution and _{Na2SO4 -} enriched solution. 3. The catalyst loading method according to claim 1, characterized in that, the NaCl salt solution and _Na2SO4 salt solution are input into a solid-liquid mixer in a predetermined ratio, and mixed with _pulverized coal in the solid-liquid mixer mix; The NaCl crystalline salt and Na ₂ SO ₄ crystalline salt are input into a powder mixer in a predetermined ratio, and mixed with coal powder in the powder mixer. 4. The catalyst loading method according to claim 3, characterized in that the mixing environment in the solid-liquid mixer is: temperature 60°C-150°C, pressure 0.05MPa-1.0MPa, inert gas atmosphere. 5. A method for adding pulverized coal, which is used to add pulverized coal loaded with a catalyst in a gasifier, wherein the pulverized coal loaded with a catalyst is loaded by the catalyst loading method as claimed in claim 3 or 4; Described pulverized coal addition method comprises: The pulverized coal mixed in the solid-liquid mixer is first dried and then input into the gasifier; The pulverized coal mixed in the powder mixer is input into the solid-liquid mixer, and after being mixed in the solid-liquid mixer, it is sent to the gasifier after drying, or, the pulverized coal mixed in the powder mixer directly into the gasifier. 6. A catalyst loading system, adopting the catalyst loading method as claimed in any one of claims 1 to 4, to load the catalyst on the pulverized coal, the catalyst is chemical concentrated brine, it is characterized in that, comprises the separating device connected in sequence , salt concentration and crystallization system and mixing device; The separation device is used to separate the chemical concentrated brine into NaCl-rich solution and _{Na2SO4 -} rich solution; The salt concentration and crystallization system is used to concentrate and crystallize the NaCl-rich solution and the _{Na2SO4 -} rich solution respectively, and form the NaCl loading agent and _{the Na2SO4} loading agent respectively; The mixing device is used for mixing the NaCl loading agent and the Na ₂ SO ₄ loading agent with the coal powder in a predetermined ratio. 7. catalyst loading system as claimed in claim 6, is characterized in that, described separating device is reverse osmosis membrane device, The salt concentration and crystallization system includes a NaCl concentration device, a NaCl crystallization device, a _Na2SO4 concentration device and a _Na2SO4 crystallization device; _the NaCl concentration device is connected to the _NaCl crystallization device, and _{the Na2SO4 concentration} The device is connected to the Na ₂ SO ₄ crystallization device, and the NaCl concentration device, NaCl crystallization device, Na ₂ SO ₄ concentration device and Na ₂ SO ₄ crystallization device are all connected to the mixing device. 8. catalyst loading system as claimed in claim 7, is characterized in that, described mixing device comprises solid-liquid mixer and powder mixer, and described NaCl concentrating device and described Na ₂ SO ₄ concentrating device is all with described A solid-liquid mixer is connected, and both the NaCl crystallization device and the Na ₂ SO ₄ crystallization device are connected to the powder mixer. 9. catalyst loading system as claimed in claim 8, is characterized in that, described mixing device also comprises crystallization salt melting system and breaker, and described NaCl crystallization device and described Na ₂ SO ₄ crystallization device all with described crystallizer The salt melting system is connected, the crystal salt melting system is connected with the crusher, and the crusher is connected with the powder mixer. 10. The catalyst loading system according to claim 9, wherein the crusher is connected with the solid-liquid mixer; Or, the powder mixer is connected with the solid-liquid mixer. 11. A coal catalytic gasification system, characterized in that it comprises: a gasifier, a dryer, and the catalyst loading system according to any one of claims 6-10; Both the dryer and the gasifier are in communication with the mixing device, and the dryer is in communication with the gasifier.

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