阅读说明：本技术 一种原位强化耐火炉衬抗盐侵蚀性能的方法 (Method for strengthening salt corrosion resistance of refractory lining in situ ) 是由 韩桂洪 刘兵兵 黄艳芳 曹亦俊 王智骁 于 2021-04-28 设计创作，主要内容包括：本发明公开了一种原位强化增强耐火炉衬抗盐侵蚀性能的方法,该方法是将氧化铬和/或氧化锆粉末分散至化工高盐废液中,得到悬浮液；所述悬浮液喷洒至焚烧炉的耐火炉内衬上部,并沿耐火炉内衬向下流动,在焚烧炉内工作温度条件下,悬浮液中的溶剂与有机物不断挥发和分解,而氧化铬和/或氧化锆及盐类与耐火炉内衬发生反应,在耐火炉内衬表面形成抗侵蚀致密层,从而减小无机溶液对炉衬的渗透侵蚀,同时包含氧化铬/氧化锆的涂层可以提高有机废液燃烧过程的热传导性能,提高燃烧效率,该方法特别适用于有机废液焚烧行业焚烧炉炉衬的延寿,降低成产成本。(The invention discloses a method for enhancing the salt corrosion resistance of a refractory lining by in-situ reinforcement, which comprises the steps of dispersing chromium oxide and/or zirconium oxide powder into chemical high-salt waste liquid to obtain suspension; the suspension is sprayed to the upper part of the lining of the refractory furnace of the incinerator and flows downwards along the lining of the refractory furnace, under the condition of the working temperature in the incinerator, a solvent and organic matters in the suspension are volatilized and decomposed continuously, and chromium oxide and/or zirconium oxide and salts react with the lining of the refractory furnace to form an anti-erosion compact layer on the surface of the lining of the refractory furnace, so that the osmotic erosion of an inorganic solution to the lining is reduced, meanwhile, a coating containing chromium oxide/zirconium oxide can improve the heat conduction performance in the combustion process of organic waste liquid and improve the combustion efficiency, and the method is particularly suitable for prolonging the service life of the lining of the incinerator in the organic waste liquid incineration industry and reducing the production cost.)

1. A method for enhancing the salt erosion resistance of a refractory lining by in-situ reinforcement is characterized by comprising the following steps: dispersing chromium oxide and/or zirconium oxide powder into chemical high-salt waste liquid to obtain suspension; the suspension is sprayed to the upper part of the lining of the refractory furnace of the incinerator and flows downwards along the lining of the refractory furnace, under the condition of the working temperature in the incinerator, the solvent and organic matters in the suspension are volatilized and decomposed continuously, and the chromium oxide and/or zirconium oxide and salts react with the lining of the refractory furnace to form an anti-erosion compact layer on the surface of the lining of the refractory furnace.

2. The method for enhancing the salt corrosion resistance of the refractory lining by in-situ strengthening according to claim 1, wherein the method comprises the following steps: the particle size of the chromium oxide and/or zirconium oxide powder satisfies 100 nm-100 μm.

3. The method for enhancing the salt erosion resistance of the refractory lining by in-situ strengthening according to claim 1 or 2, wherein: the concentration of the chromium oxide and/or zirconium oxide powder in the suspension is not less than 5g/L, and the content of organic matters is not less than 40%.

4. The method for enhancing the salt corrosion resistance of the refractory lining by in-situ strengthening according to claim 1, wherein the method comprises the following steps: the suspension is sprayed to the upper part of a refractory furnace lining of an incinerator through a high-pressure nozzle, the aperture of the high-pressure nozzle is 0.1-0.3 mm, and the working pressure is 20-70 kg/cm²。

5. The method for enhancing the salt corrosion resistance of the refractory lining by in-situ strengthening according to claim 1, wherein the method comprises the following steps: the working temperature of the incinerator is 900-1350 ℃.

6. The method for strengthening the salt corrosion resistance of the refractory lining in situ according to claim 1, wherein the method comprises the following steps: the incinerator is a rotary furnace, a shaft furnace or a fluidized bed incinerator.

7. The method for strengthening the salt corrosion resistance of the refractory lining in situ according to claim 1, wherein the method comprises the following steps: the refractory lining is made of at least one of corundum, mullite, magnesia refractory material, forsterite type and magnesia-alumina spinel type refractory material.

8. The method for strengthening the salt corrosion resistance of the refractory lining in situ according to claim 1, wherein the method comprises the following steps: the mass content of the chromium oxide and/or the zirconium oxide in the anti-erosion compact layer is more than 70%, and the thickness is controlled to be 100 nm-5 mm.

Technical Field

The invention relates to a method for in-situ strengthening of salt erosion resistance of a refractory lining, in particular to a method for improving the erosion resistance of the refractory lining by forming a compact erosion resistant layer on the surface of a refractory lining material in situ by using chromium oxide or zirconium oxide, and belongs to the technical field of service life prolonging of the refractory lining.

Background

The high-salt organic wastewater refers to wastewater with the total salt content of more than 1 percent and organic matters and the total dissolved solids of more than 3.5 percent. High-salinity wastewater generated in China each year exceeds 3 billion cubic meters, the generated amount accounts for about 5 percent of the total wastewater amount, the high-salinity wastewater still increases at a speed of 2 percent each year, and the main source of the high-salinity wastewater is the high-salinity wastewater generated in the production processes of petrochemical industry, coal chemical industry, medicine, printing and dyeing and the like. In addition to containing a large amount of free inorganic ions, the wastewater usually contains a large amount of organic components, such as polycyclic aromatic hydrocarbon compounds, halogenated hydrocarbon compounds, phenol and formaldehyde compounds. The waste water has complex components, toxicity, peculiar smell and poor biodegradability, and if the waste water is not properly treated, the discharged waste water can seriously damage soil ecology to poison crops; polluting rivers and underground water resources and causing the potential safety hazard of drinking water.

In industrial treatment, waste liquid which has high toxic concentration and is difficult to be biochemically degraded is generally treated by adopting an incineration method in the prior art. The incineration process is to completely decompose organic matters in the salt-containing waste liquid into carbon dioxide and water, and discharge residual salt in a molten state at high temperature, thereby realizing safe disposal of the high-salt-containing waste liquid. The incineration method is the most effective means of the high-temperature deep oxidation method and is most easy to realize industrialization. Incineration is the ultimate scheme of industrial waste treatment, and the waste that can be handled is various, and waste gas, waste liquid containing salt etc. can be handled simultaneously. High-temperature oxidation incineration is carried out, and the destruction removal rate of organic matters reaches more than 99.99 percent.

At present, the lining of a high-salt organic waste liquid incinerator is mainly made of corundum-mullite refractory materials, frequent replacement of the refractory lining of the waste liquid incinerator is a main factor influencing the efficiency of waste liquid incineration at high temperature, the large-area falling of the refractory lining of the incinerator can cause rapid temperature rise inside and outside the incinerator body to cause safety interlocking protection parking, so that waste liquid cannot be incinerated, unplanned parking and environmental protection accidents are caused, and economic loss and social influence cannot be estimated.

Aiming at the problems, part of enterprises adopt a chromium-zirconium corundum composite spinel material with excellent corrosion resistance to replace a common refractory material, the corrosion of waste liquid is reduced due to high content of chromium oxide and zirconium oxide and high volume density of the chromium-zirconium corundum composite spinel material, but the preparation of the chromium-zirconium corundum composite spinel material needs 5 steps of proportioning, mixing and grinding, forming, drying and sintering, each step is time-consuming and labor-consuming, the sintering temperature in the sintering process reaches more than 1600 ℃, only chromium and zirconium on the surface layer play a role in the salt corrosion resistance process, and the chromium-zirconium corundum composite spinel in the refractory material only plays a role in structural support. Due to the high price of raw materials and the complex and high-requirement process technology, the cost is extremely high, so that the industrial production is only used by a few enterprises, and the economic benefit is low.

Disclosure of Invention

Aiming at the problems of poor salt corrosion resistance, easy damage and falling and the like of corundum-mullite material as a refractory lining of an incinerator in the prior art, and the difficulties and problems of complex production process, high cost, low economic benefit and the like of the chrome-zirconium-corundum composite spinel material, the invention aims to provide a method for enhancing the corrosion resistance of an original lining by forming a corrosion-resistant compact layer on the surface of the refractory lining of the incinerator by using chromium oxide/chromium oxide and chemical high-salt waste liquid as raw materials through an in-situ strengthening technology under the condition of normal working conditions, the method uses a small amount of high-value raw materials such as chromium oxide/zirconium oxide and the like, has simple process, can be realized under the normal working conditions, and simultaneously consumes organic waste liquid, thereby solving the technical problems of poor salt corrosion resistance, easy damage and falling of materials such as corundum-mullite and the like, and solving the problem of complex process of the chromium oxide/zirconium oxide material, high cost and the like.

In order to realize the technical purpose, the invention provides a method for enhancing the salt corrosion resistance of a refractory lining by in-situ reinforcement, which comprises the steps of dispersing chromium oxide and/or zirconium oxide powder into chemical high-salt waste liquid to obtain suspension; the suspension is sprayed to the upper part of the lining of the refractory furnace of the incinerator and flows downwards along the lining of the refractory furnace, under the condition of the working temperature in the incinerator, the solvent and organic matters in the suspension are volatilized and decomposed continuously, and the chromium oxide and/or zirconium oxide and salts react with the lining of the refractory furnace to form an anti-erosion compact layer on the surface of the lining of the refractory furnace.

According to the technical scheme, the chromium oxide and/or zirconium oxide material powder and the surface of the lining of the refractory furnace are subjected to in-situ reinforced reaction under the normal working condition, the proportion of the components of the chromium oxide and/or zirconium oxide powder and the temperature in the incinerator are strictly controlled, so that the chromium oxide and/or zirconium oxide and the surface layer of the refractory material are regulated and controlled to react to generate a compact anti-erosion layer, the zirconium oxide and the chromium oxide do not react with the refractory material under the normal condition, and how to fuse the chromium oxide and/or zirconium oxide powder into the pores of the refractory material and react to generate the compact anti-erosion layer is the key of the technical scheme. The key point of the technical scheme of the invention is that chemical high-salt waste liquid is used as a dispersing and reacting medium, on one hand, the chemical high-salt waste liquid can uniformly disperse zirconia and/or chromic oxide powder to form suspension liquid, so that the suspension liquid can be uniformly sprayed to the surface of a refractory material through high-pressure spraying, on the other hand, under the high temperature action in the incinerator, organic matters and solvents in the chemical high-salt waste liquid are decomposed and volatilized at high temperature, chromium oxide and/or zirconium oxide powder are/is melted into molten inorganic salt, has better fluidity and infiltration capacity, so that the zirconia and/or the chromic oxide can be fully infiltrated into the surface gaps of the refractory material, particularly under the activation action of high-temperature molten salt, the method is favorable for promoting the in-situ strengthening reaction of the chromium oxide and/or the zirconium oxide and the refractory material, and a coating with high density and salt erosion resistance is formed on the surface layer of the refractory material.

In the technical scheme of the invention, the chromium oxide and/or zirconium oxide micro powder is used as the material for in-situ reinforcement of the refractory material, mainly because the chromium oxide and/or zirconium oxide micro powder has stronger erosion resistance, and the chemical reaction of the contact surface of the chromium oxide and/or zirconium oxide and the refractory material can be realized under special conditions to form a compact erosion-resistant layer, so that the erosion of waste liquid to the refractory material is reduced.

Preferably, the particle size of the chromium oxide and/or zirconium oxide powder satisfies 100nm to 100 μm. In the preferable particle size range, the chromium oxide and zirconium oxide powder can form uniform suspension in the chemical high-salt waste liquid, the chromium oxide and/or zirconium oxide powder with smaller particle size is favorable for permeating holes and gaps on the surface of the refractory lining, and the chromium oxide and/or zirconium oxide powder with smaller particle size has high chemical reaction activity and is favorable for subsequent in-situ strengthening reaction with the refractory material.

As a preferable scheme, the concentration of the chromium oxide and/or zirconium oxide powder in the suspension is not lower than 5g/L, and the content of organic matters is not less than 40%. The thickness of the erosion-resistant compact layer and the degree of compaction can be controlled to some extent by controlling the concentration of chromium oxide and/or zirconium oxide powder in the suspension.

Preferably, the suspension is sprayed to the upper part of a refractory furnace lining of an incinerator through a high-pressure nozzle, the aperture of the high-pressure nozzle is 0.1-0.3 mm, and the working pressure is 20-70 kg/cm². Under preferred conditions, dispersion of the suspension on the surface of the refractory lining is facilitated.

As a preferable scheme, the working temperature of the incinerator is 900-1350 ℃. It is advantageous to enhance the reaction of the chromium oxide and/or zirconium oxide with the surface of the refractory lining under the preferred temperature conditions.

As a preferred embodiment, the incinerator is a rotary kiln, a shaft furnace or a fluidized bed incinerator.

Preferably, the refractory lining is made of at least one of corundum, mullite, magnesia-based refractory, forsterite-type and magnesium aluminate spinel-type refractory.

As a preferable scheme, the mass content of the chromium oxide and/or the zirconium oxide in the anti-erosion compact layer is more than 70%, and the thickness is controlled to be 100 nm-5 mm.

As a preferable scheme, the chemical high-salt waste liquid is subjected to filtration pretreatment, so that solid impurities with the particle size larger than 0.3mm are avoided.

The total salt content of the chemical high-salt waste liquid related by the invention is more than 1 wt%, and the total dissolved solid content of the organic matter is more than 3.5 wt%. Such as petrochemical wastewater, coal chemical wastewater, pharmaceutical wastewater, and printing and dyeing wastewater, the wastewater usually contains a large amount of organic components, such as polycyclic aromatic hydrocarbon compounds, halogenated hydrocarbon compounds, phenol and formaldehyde compounds, in addition to a large amount of free inorganic ions.

The atmosphere in the incinerator related to the invention is a conventional air atmosphere.

The purity of the chromium oxide and/or zirconium oxide powder related by the invention is more than 90%, and the chromium oxide and/or zirconium oxide powder can be common chemical raw materials in the market.

The invention provides a method for enhancing erosion resistance of a refractory lining by in-situ reinforcement, which comprises the following specific steps:

1) adding chromium oxide and/or zirconium oxide into chemical high-salt waste liquid, and uniformly stirring and mixing to obtain a suspension; wherein, the chromium oxide and/or zirconium oxide meet the requirement that the particle size is 100 nm-100 mu m, and the addition amount of the chromium oxide and/or zirconium oxide accounts for not less than 5g/L of the suspension;

2) spraying the suspension to the upper layer inside the refractory lining of the waste liquid incinerator through a high-pressure nozzle, wherein at high temperature, organic matters in the suspension are combusted and decomposed, a solvent is volatilized, inorganic salt and chromium oxide and/or zirconium oxide form a molten body which flows to the bottom of the furnace along the wall of the refractory lining, and in the process, the chromium oxide and/or zirconium oxide and the surface of the refractory lining are subjected to in-situ reinforcement at high temperature to form an anti-corrosion compact layer; wherein the temperature in the incinerator is 900-1350 ℃, the aperture of the high-pressure nozzle is 0.1-0.3 mm, and the working pressure is 20-70 kg/cm²。

Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:

according to the technical scheme, an anti-erosion compact layer can be formed on the surface of an original refractory material such as low-value corundum-mullite by an in-situ reinforced reaction by using a small amount of chromium oxide or zirconium oxide micro powder material with high value and excellent anti-erosion performance, the anti-erosion effect is not inferior to that of chromium-zirconium corundum composite spinel, the chromium and zirconium oxide introduced into the surface of the lining of the refractory furnace is beneficial to combustion and heat transfer of organic waste liquid, the combustion efficiency can be effectively improved, and the method has an absolute cost advantage compared with the prior art.

The technical scheme of the invention is applied to the traditional refractory material by taking the in-situ strengthening technology as a reference, and the chromium oxide or zirconium oxide micro powder with excellent erosion resistance is reacted with the refractory material to form the erosion-resistant compact layer under the condition of not influencing normal production.

Drawings

FIG. 1 is a schematic diagram of a corundum-mullite furnace lining corroded by chemical high-salt waste liquid; it can be seen from the figure that there is a crack gap between the eroded face and the original brick layer.

FIG. 2 is a schematic diagram of a corundum-mullite furnace lining corroded by chemical high-salt waste liquid added with chromium oxide or zirconium oxide micro powder, and it can be seen from the diagram that an anti-corrosion compact layer is formed in situ on the surface of the corundum-mullite furnace lining, and the corundum-mullite furnace lining is not cracked.

Detailed Description

The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.

The refractory lining referred to in the following examples is a corundum-mullite lining.

Example 1

Taking 1kg of chromium oxide powder with purity of 92% and particle size of 187nm as raw material, selecting 20L of waste liquid from production of phenol and acetone co-production, filtering until no solid impurities with particle size larger than 0.3mm exist, wherein the organic matter content of the waste liquid is 53%, uniformly stirring and mixing the chromium oxide powder and the waste liquid to be used as spraying liquid, and spraying the spraying liquid by 4 high-pressure nozzles (with pore size of 0.2mm and working pressure of 45 kg/cm) evenly distributed on the top of a furnace²) The mixture is sprayed into a vertical incinerator, the temperature of the incinerator is 1000-1300 ℃, and after the incinerator runs for 20 hours, a green anti-corrosion compact layer with the thickness of 1mm is covered on the surface of the refractory lining, and the reduction rate of the refractory lining is reduced to one tenth of the former.

Example 2

Using 1kg of zirconia powder with the purity of 93 percent and the grain diameter of 196nm as a raw material, selecting 20LBDO production waste liquid, filtering the waste liquid until no solid impurities with the grain diameter of more than 0.3mm exist, wherein the content of organic matters in the waste liquid is 55 percent, uniformly stirring and mixing the zirconia powder and the waste liquid to be used as spraying liquid, and spraying the spraying liquid by 4 high-pressure nozzles (with the pore diameter of 0.2mm and the working pressure of 45 kg/cm) which are uniformly distributed on the top of a furnace²) Spraying the mixture into a vertical incinerator at 1000-1300 deg.CAfter the furnace is operated for 20 hours, the surface of the refractory lining is covered with a white anti-corrosion dense layer with the thickness of 1.2mm, and the reduction rate of the refractory lining is reduced to one tenth of the former.

Example 3

Using 500g of zirconium oxide powder with the purity of 93 percent and the particle size of 196nm and 500g of chromium oxide powder with the purity of 92 percent and the particle size of 187nm as raw materials, selecting 20L of waste liquid generated in the production of phenol and acetone co-production to be filtered until no solid impurities with the particle size of more than 0.3mm exist, wherein the content of organic matters in the waste liquid is 54 percent, uniformly stirring and mixing the two kinds of powder and the waste liquid to be used as spraying liquid, and spraying the spraying liquid by 4 high-pressure nozzles (the pore diameter is 0.2mm, the working pressure is 45 kg/cm)²) The mixture is sprayed into a fluidized bed incinerator, the temperature of the incinerator is 900-1200 ℃, after the incinerator runs for 20 hours, a layer of cyan anti-corrosion dense layer with the thickness of 1.2mm is covered on the surface of the refractory lining, and the reduction rate of the refractory lining is reduced to one tenth of the former.

Comparative example 1

The grain size of the chromium oxide powder was increased to 113 μm in this comparative example.

Using 1kg of chromium oxide powder with the purity of 93 percent and the particle size of 113 mu m as a raw material, selecting 20L of waste liquid of phenol co-production acetone production, filtering the waste liquid until no solid impurities with the particle size of more than 0.3mm exist, wherein the organic matter content of the waste liquid is 54 percent, uniformly stirring and mixing the zirconium oxide powder and the waste liquid to be used as spraying liquid, and spraying the spraying liquid by 4 high-pressure nozzles (with the pore size of 0.2mm and the working pressure of 45 kg/cm) which are uniformly distributed on the top of a furnace²) The water is sprayed into a vertical incinerator, the temperature of the incinerator is 1000-1300 ℃, and after the incinerator runs for 20 hours, the surface of the refractory lining is seen to have light green, but a compact anti-erosion layer is not formed, and the thinning rate of the refractory lining is not obviously reduced.

Comparative example 2

The comparative example did not have the addition of the chromium/zirconium oxide additive.

Selecting 20L BDO production waste liquid, filtering to remove solid impurities with particle size larger than 0.3mm, wherein the organic matter content of the waste liquid is 54%, and directly passing through 4 high-pressure nozzles (with pore size of 0.2mm and working pressure of 45 kg/cm) uniformly distributed on the top of the furnace²) Spraying the mixture into a vertical incinerator at the temperatureAt the temperature of 1000-1300 ℃, after the incinerator runs for 20 hours, the contact surface of the refractory lining and the waste liquid is obviously corroded, a cracking gap exists between the corrosion surface and the original brick layer, and the high-salinity waste liquid seriously corrodes the refractory material.