阅读说明：本技术 一种铁锰脱硫剂固体废弃物的资源化方法 (Recycling method of ferro-manganese desulfurizer solid waste ) 是由 王巍 杨鹏 宋尉源 杨皓 于 2021-10-09 设计创作，主要内容包括：本发明是铁锰氧化物脱硫剂固体废弃物的资源化方法,其特征在于：脱硫固体废弃物成分为FeS、MnS,将其磨粉后放入含有1～10%的稀硫酸和0.01～1%的硫酸矾混合溶液的反应器1中,再向反应器1中通入高温反应气和空气(或氧气)进行循环鼓泡,其中固液摩尔比为0.01～0.1:1,气液摩尔比为0.01～0.1:1,反应停留时间为2小时。分离反应器1得到的固体、液体、气体：固体脱水加热到480℃以上分离得到二氧化硅粉末为产品1,硫蒸气送入循环气催化反应器2；液体进行分步结晶得到Fe-(2)(SO-(4))-(3)、MnSO-(4),循环液体回到反应器1中；气体和添加的氧气一起进入循环气催化反应器2,循环气催化反应器2将硫蒸气、H-(2)S、SO-(2)都转化为三氧化硫后通入反应器1被水溶液吸收。(The invention relates to a resource method of solid waste of a ferro-manganese oxide desulfurizer, which is characterized by comprising the following steps: the desulfurization solid waste components are FeS and MnS, the powder is ground and then put into a reactor 1 containing a mixed solution of 1-10% of dilute sulfuric acid and 0.01-1% of vitriol, and high-temperature reaction gas and air (or oxygen) are introduced into the reactor 1 for circular bubbling, wherein the molar ratio of solid to liquid is 0.01-0.1: 1, the molar ratio of gas to liquid is 0.01-0.1: 1, and the reaction retention time is 2 hours. Solid, liquid, gas obtained in the separation reactor 1: dehydrating the solid, heating to above 480 ℃, separating to obtain silicon dioxide powder as a product 1, and sending sulfur vapor into a circulating gas catalytic reactor 2; the liquid is crystallized step by step to obtain Fe 2 (SO 4 ) 3 、MnSO 4 The circulating liquid is returned to the reactor 1; the gas and the added oxygen enter a circulating gas catalytic reactor 2 together, and the circulating gas catalytic reactor 2 mixes sulfur vapor and H 2 S、SO 2 All converted into sulfur trioxide and then are introduced into the reactor 1 to be absorbed by the aqueous solution.)

1. A method for recycling solid wastes of a ferro-manganese desulfurizer is characterized in that the waste desulfurizer is ground into powder and is placed into a reactor 1 containing 1-10% of dilute sulfuric acid and 0.01-1% of vanadium sulfate solution, the solid-liquid molar ratio is 0.01-0.1: 1, high-temperature reaction gas and air or oxygen are introduced for circular bubbling, and the gas-liquid molar ratio is 0.01-0.1: 1; after staying for 2 hours, separating liquid, solid and gas; feeding the gas into a circulating gas catalytic reactor 2 at the temperature of 360-800 ℃ for 0.1-2 hours, and feeding the reaction gas into the reactor 1; dehydrating the solid, heating to over 480 ℃ to obtain gaseous sulfur, sending the gaseous sulfur into a circulating gas catalytic reactor 2, taking the rest silicon dioxide powder as a product 1 for sale, and sending sulfur dioxide flue gas generated by combustion back to the reactor 1; and (3) crystallizing and separating the manganese sulfate as a product 2, using the ferric sulfate as a product 3 for sale, and returning the crystallized liquid to the reactor 1, thereby continuously treating the solid waste of the iron-manganese oxide desulfurizer.

2. The method for recycling solid wastes of iron and manganese desulfurizer as claimed in claim 1, wherein the catalyst of the recycle gas catalytic reactor 2 is a composite catalyst of iron oxide, vanadium oxide and manganese oxide.

Technical Field

The invention relates to the fields of chemical industry, energy conservation and environmental protection, and discloses a method for realizing sulfur resource circulation, pollution-free and consumption-free by natural gas desulfurization waste.

Background

For a long time, dry desulfurization is widely applied because of the advantages of simple process, no problem of sewage and waste acid treatment, low energy consumption and the like, and natural gas is treated by dry desulfurization and simultaneously generates a great amount of waste desulfurizer, which gradually becomes a new solid pollution source and needs to be subjected to harmless treatment.

The waste desulfurizing agent contains a large amount of sulfide which is usually treated by a moistening method, a burning burying method, an acid washing method, a chemical inhibition method, an oxidizing agent method and the like. H is treated by burning method and acid washing method₂S，SO₂The generation of the fire-resistant coating has great harm to human bodies and the environment, and can cause potential safety hazards and cause accidents such as fire, explosion and the like while polluting the environment; the chemical inhibition method using sodium hydroxide is high in cost, and the use of other reducing agents to form solution or precipitate is another worthless waste; the neutralization process also uses lime to convert it to stable, harmless calcium sulfide for landfilling and is of no economic value. In summary, there is an urgent need in our country for a technical method for harmless treatment of desulfurizer solid waste while producing products with added value.

CN108796215B Zhudeqing and other announcements use a waste desulfurizer treatment method, and waste desulfurizer, iron ore powder, solid fuel, flux and return ore are mixed to obtain sintering mixture; adding water into the sintering mixture, mixing and granulating to obtain a granulating material; sintering the granulated material to obtain sintered ore and sintered flue gas; and discharging the sintering flue gas into the atmosphere after desulfurization and denitrification. The technology produces sinter from the waste desulfurizer and other raw materials for ironmaking, the mode of discharging sintering flue gas after desulfurization and denitrification has low economic value, and the conversion of sulfur in the waste desulfurizer into sulfur oxide is to transfer desulfurization treatment to a rear working section without solving the problem.

CN111607704A Lili et al disclose a process for treating waste desulfurizer, which comprises mixing waste desulfurizer with pyrolusite to obtain mixed solid, leaching the mixed solid with sulfuric acid to obtain leachate, adding carbonizing agent into the leachate for carbonization and crystallization, filtering after the carbonization and crystallization to obtain manganese carbonate, and completing manganeseIs a treatment process of waste desulfurizer. The method for leaching carbonized crystals by adopting sulfuric acid in the technology only aims at simply obtaining manganese carbonate and completely omits the leaching of H₂Contamination of S gas and technical economy.

CN103771346A Liu Shuhe et al announced a sulfur recovery method in waste desulfurizer, the waste desulfurizer is dried, then mixed with catalytic cracking diesel oil at 40-250 ℃, after 0.1-10 hours, the desulfurizer material and desulfurization liquid are obtained by solid-liquid separation, the liquid phase is cooled to 0-30 ℃, the elemental sulfur is recovered, and the desulfurization liquid can be recycled. The technology is to separate sulfur from solid and liquid to obtain sulfur, but the economic value of the sulfur is low.

In conclusion, it can be seen that the waste desulfurizing agent is digested to avoid the generation of H₂S、SO₂Pollution and new waste, and simultaneously, the production of products with higher value is a technical problem which is not solved at present.

Disclosure of Invention

The invention relates to a resource method of solid waste of a ferro-manganese oxide desulfurizer, which is characterized by comprising the following steps: the desulfurization solid waste components are FeS and MnS, the powder is ground and then put into a reactor 1 containing a mixed solution of 1-10% of dilute sulfuric acid and 0.01-1% of vitriol, and high-temperature reaction gas and air (or oxygen) are introduced into the reactor 1 for circular bubbling, wherein the molar ratio of solid to liquid is 0.01-0.1: 1, the molar ratio of gas to liquid is 0.01-0.1: 1, and the reaction retention time is 2 hours. Solid, liquid, gas obtained in the separation reactor 1: dehydrating the solid, heating to above 480 ℃, separating to obtain silicon dioxide powder as a product 1, and sending sulfur vapor into a circulating gas catalytic reactor 2; the liquid is crystallized step by step to obtain Fe₂(SO₄)₃、MnSO₄The circulating liquid is returned to the reactor 1; the gas and the added oxygen enter a circulating gas catalytic reactor 2 together, and the circulating gas catalytic reactor 2 mixes sulfur vapor and H₂S、SO₂All converted into sulfur trioxide and then are introduced into the reactor 1 to be absorbed by the aqueous solution.

Compared with the prior art, the invention has the advantages that:

(1) the invention provides a method for treating natural gas ferro-manganese waste desulfurizer, which has simple and reliable process and not only produces Fe₂(SO₄)₃、MnSO₄Valuable products such as the like reduce solid waste discharge, and new solid, liquid and gas wastes are not generated;

(2) the invention provides a method for treating natural gas waste iron and manganese desulfurizer, which can treat a large amount of natural gas waste desulfurizer, has low treatment cost, realizes complete conversion of waste into products, and achieves the purpose of sustainable development;

(3) the invention provides a method for treating natural gas ferro-manganese waste desulfurizer, which is used for treating H generated in the process of recycling the waste desulfurizer₂S、SO₂The sulfur trioxide is completely converted and then absorbed by water, thereby not only avoiding gas pollution, but also simplifying the process of preparing sulfuric acid by sulfur trioxide and then reacting with a waste desulfurizer;

(4) the invention provides a method for treating natural gas ferro-manganese waste desulfurizer, wherein the sulfur in the waste desulfurizer is finally MnSO₄And Fe₂(SO₄)₃The form of the sulfur is completely converted into a product, and the full-cycle resource utilization of the sulfur is realized.

Drawings

FIG. 1 is a process schematic flow chart of a method for recycling solid waste of a ferro-manganese oxide desulfurizer.

Detailed Description

Example 1: placing a mixed solution of 5% dilute sulfuric acid and 0.2% vanadium sulfate in a reactor 1, adding the waste ferro-manganese desulfurizer into the mixed solution, wherein the solid-liquid molar ratio is 0.08:1, and introducing a mixed gas of high-temperature reaction gas and air (or oxygen) for circular bubbling, and the gas-liquid molar ratio is 0.1: 1; the reaction is kept for 2 hours, and liquid, solid and gas are separated; the gas is sent into a high-temperature catalytic reactor 2, the reaction temperature is 500 ℃, the reaction time is 0.5 hour, and the reaction gas is sent into a reactor 1; dehydrating the solid, heating to over 480 ℃ to obtain gaseous sulfur, sending the gaseous sulfur into a circulating gas catalytic reactor 2, remaining silicon dioxide powder, and sending sulfur dioxide flue gas generated by combustion back to the reactor 1; and (3) crystallizing the liquid to separate manganese sulfate and ferric sulfate, and returning the crystallized liquid to the reactor 1.

Example 2: placing a mixed solution of 8% dilute sulfuric acid and 0.2% vanadium sulfate in a reactor 1, adding the waste ferro-manganese desulfurizer into the mixed solution, wherein the solid-liquid molar ratio is 0.06:1, and introducing a mixed gas of high-temperature reaction gas and air (or oxygen) for circular bubbling, and the gas-liquid molar ratio is 0.08: 1; the reaction is kept for 2 hours, and liquid, solid and gas are separated; the gas is sent into a high-temperature catalytic reactor 2, the reaction temperature is 500 ℃, the reaction time is 1 hour, and the reaction gas is sent into the reactor 1; dehydrating the solid, heating to over 480 ℃ to obtain gaseous sulfur, sending the gaseous sulfur into a circulating gas catalytic reactor 2, remaining silicon dioxide powder, and sending sulfur dioxide flue gas generated by combustion back to the reactor 1; and (3) crystallizing the liquid to separate manganese sulfate and ferric sulfate, and returning the crystallized liquid to the reactor 1.

Example 3: placing a mixed solution of 10% dilute sulfuric acid and 0.1% vanadium sulfate in a reactor 1, adding the waste ferro-manganese desulfurizer into the mixed solution, wherein the solid-liquid molar ratio is 0.1:1, and introducing a mixed gas of high-temperature reaction gas and air (or oxygen) for circular bubbling, and the gas-liquid molar ratio is 0.08: 1; the reaction is kept for 2 hours, and liquid, solid and gas are separated; the gas is sent into a high-temperature catalytic reactor 2, the reaction temperature is 500 ℃, the reaction time is 0.6 hour, and the reaction gas is sent into a reactor 1; dehydrating the solid, heating to over 480 ℃ to obtain gaseous sulfur, sending the gaseous sulfur into a circulating gas catalytic reactor 2, remaining silicon dioxide powder, and sending sulfur dioxide flue gas generated by combustion back to the reactor 1; and (3) crystallizing the liquid to separate manganese sulfate and ferric sulfate, and returning the crystallized liquid to the reactor 1.