CN115337775A - Complex iron desulfurizer - Google Patents
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Abstract
The invention discloses a complex iron desulfurizer, and relates to the technical field of desulfurization. The desulfurizer adopts soluble ferric salt or soluble ferrous salt as an iron source, fulvic acid and salt thereof, sodium alginate, iminodisuccinic acid and salt thereof as a complexing agent, and soluble nitrite as a catalyst. The complex iron desulfurizer provided by the invention has the advantages of wide raw material source range, low price and suitability for large-scale production, and meanwhile, the complex iron desulfurizer can be applied to hydrogen sulfide-containing gases such as natural gas, coke oven gas and the like. Meanwhile, the raw materials adopted by the desulfurizer of the invention, except ferric salt or ferrous salt as an iron source, the rest sodium alginate and iminodisuccinic acid can be naturally degraded, the harm to the environment is extremely low, and fulvic acid belongs to a widely used plant fertilizer additive, has a promoting effect on the growth of plants and has a positive effect on the maintenance of soil fertility, so the desulfurizer of the invention belongs to an environment-friendly desulfurizer.
Description
Technical Field
The invention relates to the technical field of desulfurization, in particular to a complex iron desulfurizer.
Background
Hydrogen sulfide, a flammable acidic gas under standard conditions, is colorless, smells like eggs at low concentrations, smells like sulfur at very low concentrations, and is extremely toxic (LC 50= 444ppm-to-500ppm). The aqueous solution is hydrogen sulfuric acid. Can be dissolved in water, is easy to dissolve in alcohols, petroleum solvents and crude oil, and belongs to one of eight odor pollutants for limiting emission.
The chemical raw material gas produced by using coal, coke, natural gas and petroleum as raw material contains H with different concentrations 2 S gas, high concentration H 2 The existence of S not only pollutes the environment, corrodes pipeline equipment and influences the quality of chemical products, but also can cause the poisoning and inactivation of the catalyst in the subsequent process production, and simultaneously, hydrogen sulfide is easy to poison people even under the condition of low dosage; meanwhile, after hydrogen sulfide is oxidized and combusted, pollutants such as sulfur dioxide and the like can be generated, and sulfur dioxide is a main pollutant for air pollution and can easily cause acid rain. Thus H 2 The technique of S removal is highly appreciated. Among the desulfurization methods, wet desulfurization is a method that can effectively remove sulfides and has a relatively low cost, and thus is a common method in industrial production at present.
Chinese patent CN1621133A discloses an absorption liquid for gas desulfurization and application thereof, wherein nano iron oxide is used as a catalyst for converting hydrogen sulfide into elemental sulfur, and chelated iron and light are used as a cocatalyst, although the nano iron oxide can promote hydrogen sulfide to generate elemental sulfur, the whole reaction process needs light participation and is difficult to apply under the conditions of no light and weak light; meanwhile, the nano iron oxide is solid, and is easy to adsorb in the process of converting sulfur simple substance into sulfur particles, so that the loss amount of the nano iron oxide is large; meanwhile, when the nano iron oxide is used as a catalyst, the nano iron oxide has defects, so that the catalytic efficiency is low and the desulfurization speed is low.
Chinese patent CN 103752163B discloses a composite desulfurization slurry, which is prepared by using soluble iron salt and iron oxyhydroxide as iron sources, alcohol amine, amino carboxylate or hydroxyl carboxylate as complexing agents, and adding a settling agent such as polyethylene glycol dimethyl ether and the like, a biological inhibitor such as dodecyl dimethyl benzyl ammonium chloride and the like, and a stabilizer such as sorbitol and the like.
Chinese patent CN 110559831A discloses a complex iron desulfurizer which adopts ferric trichloride as an iron source, EDTA as a complexing agent, maltose as a stabilizer and polyethylene glycol ether as a modifier to prepare the desulfurizer with high reaction speed, high desulfurization rate and low byproduct salt generation amount.
Chinese patent CN 107029537A discloses a complex iron desulfurizer for liquefied petroleum gas desulfurization and a preparation method thereof, the components of the complex iron desulfurizer comprise water-soluble ferrite, inorganic base, water-soluble manganese salt, an organic complexing agent, water, piperazine and an organic solvent, wherein the organic complexing agent is ethylenediamine tetraacetic acid, hydroxyethyl ethylene diamine triacetic acid and the like. The desulfurizer can simultaneously remove hydrogen sulfide and mercaptan.
Chinese patent CN106925103A discloses a complex iron desulfurizer for hydrogen sulfide removal by wet oxidation and a preparation method thereof, wherein a water-soluble iron salt and a water-soluble cobalt salt are used as desulfurization catalysts, ethylene diamine tetraacetic acid, hydroxyethyl ethylene diamine triacetic acid, nitrilotriacetic acid and the like are used as complexing agents, and piperazine and polyethylene glycol are also included.
However, the above-mentioned desulfurizing agent has problems that the regeneration speed of the desulfurization rich solution is slow, and in addition, more non-environment-friendly raw materials are added, which results in higher difficulty in treating the desulfurization solution in the subsequent process.
Disclosure of Invention
Aiming at the defects of the existing desulfurizer, the invention provides a complex iron desulfurizer which has better environmental protection performance, and the used raw materials except metal ions can be naturally degraded. And the regeneration speed is high.
The technical scheme of the invention is as follows: the complex iron desulfurizer comprises a mixture A and a material B, wherein the mixture A comprises the following substances in parts by weight:
the mass ratio of the iminodisuccinic acid and the salt thereof to the fulvic acid and the salt thereof is 1;
the material B is 5-10 parts of water-soluble nitrite. For the mixture A and the material B, the mixture A and the material B should be added according to the proportion when in use, namely the initial proportion of the mixture A and the material B is what, and the adding proportion of the mixture A and the material B when in use is what.
In the invention, the soluble ferric salt and the soluble ferrous salt are used for providing an iron source catalyst for the desulfurization process, and the soluble ferrous salt can be converted into the soluble ferric salt: fe 2+ +O 2 →Fe 3+ And in the actual desulfurization process, after the ferric ions absorb hydrogen sulfide and are converted into ferrous ions, in order to promote the regeneration of the ferrous ions, a certain amount of gas is usually blown into a regeneration tower to promote the regeneration of the ferrous ions: fe 2+ +O 2 →Fe 3+ . Therefore, even if the catalyst required in the use process of the invention is actually soluble ferric salt, the soluble ferrous salt can still be used for providing the iron source catalyst, and only when ferrous ions are used as the iron source catalyst, oxygen needs to be introduced before use, and then the gas to be desulfurized needs to be introduced.
The adopted fulvic acid and the salt thereof, sodium alginate, iminodisuccinic acid and the salt thereof have certain complexing effect on iron ions, and the fulvic acid, the salt thereof, the sodium alginate, the iminodisuccinic acid and the salt thereof all belong to environment-friendly complexing agents: fulvic acid is a common plant fertilizer, has a certain stabilizing effect on the fertilizer, and reduces the fertility loss of soil; the sodium alginate, the iminodisuccinic acid and the salt thereof have good biodegradability, and the degraded product has no harm to the environment.
Meanwhile, the fulvic acid adopted in the invention belongs to a generic term of organic acids, and generally comprises mineral source fulvic acid and biochemical fulvic acid, wherein the mineral source fulvic acid has a single structure, and the biochemical fulvic acid has complex components, but both the mineral source fulvic acid and the biochemical fulvic acid can be applied to the invention, and the effects are basically the same. And as fulvic acid is mostly used for agricultural fertilizers at present, the cost is lower.
One embodiment of the present invention is that the soluble ferric salt is at least one of ferric chloride, ferric nitrate and ferric sulfate; the soluble ferrous salt is at least one of ferrous chloride, ferrous sulfate and ferrous nitrate.
In principle, any soluble iron salt or soluble ferrous salt can be used in the present invention, but the above-mentioned soluble iron salt or soluble ferrous salt is preferable from the viewpoint of availability and cost. These salts are iron sources for the desulfurizing agent of the present invention, and therefore, anions thereof have no influence on the effects of the present invention.
One embodiment of the present invention is that the mixture a further includes a base, which makes the pH of the mixture a not less than 8.
For the complex iron desulfurizer, the complex iron desulfurizer can normally work under an alkaline condition, namely, under the condition that the pH value is more than 8, so that the pH value needs to be adjusted by adding alkali, but the pH value is adjusted usually under the desulfurization condition, so that the pH value can be adjusted even if the alkali is not added into the desulfurizer.
Preferably, the alkali is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
In one embodiment of the present invention, the iminodisuccinic acid or a salt thereof is one of iminodisuccinic acid and tetrasodium iminodisuccinate, and the water-soluble nitrite is sodium nitrite, potassium nitrite, or nitrous acid.
For iminodisuccinic acid, although it has a good complexing property, its solubility is relatively low, and therefore, in many cases, a salt of iminodisuccinic acid, such as tetrasodium iminodisuccinate, is generally used as a complexing agent. Of course, the water in the desulfurization solution may be adjusted to be alkaline in advance, and then the iminodisuccinic acid may be added, so that the iminodisuccinic acid is converted into a salt under the alkaline condition, and the solubility is increased.
For water soluble nitrites, it has two effects in the present invention: one is that nitrite ions can be used as a catalyst for converting hydrogen sulfide into sulfur, the combination of nitrite ions and sulfate ions can play a role in catalyzing the regeneration of ferrous ions, the ferrous ions can be rapidly regenerated under the action of oxygen, and a certain amount of sulfate can be generated in the desulfurization solution when complex iron is used for desulfurization; secondly, nitrite ions in the desulfurization solution can also promote the conversion of hydrogen sulfide into sulfur particles. Meanwhile, because the water solubility of the nitrite is better, solid phase nitrite and aqueous solution of the nitrite can be adopted.
In one embodiment of the present invention, the desulfurizing agent further comprises a corrosion inhibitor, wherein the corrosion inhibitor is a corrosion inhibitor commonly used in the art, such as an antimony-based corrosion inhibitor, a molybdenum-based corrosion inhibitor, and the like, and the addition amount of the corrosion inhibitor is the same as that of the conventional desulfurizing agent, such as 1 to 2 parts by weight.
One embodiment of the invention is that the invention also comprises 0.1-0.5 part of polyethylene glycol ether, usually polyethylene glycol dimethyl ether is selected, the price is cheap, and the acquisition difficulty is low. The polyethylene glycol ether can promote the aggregation and growth of the sulfur particles, the larger the addition of the polyethylene glycol ether is, the larger the sulfur particles are, and the smaller the addition is, the smaller the sulfur particles are. For different desulfurization processes, the addition amount of the polyglycol ether is different, for example, for a sulfur floating type desulfurization process (namely sulfur foam generation), the addition amount of the polyglycol ether should be less, for a sulfur sinking type desulfurization process, the addition amount of the polyglycol ether should be more, but the addition amount of the polyglycol ether should not be too large, and when the addition amount of the polyglycol ether is more than 0.5 part, the sulfur particle size is too large, the deposition speed is faster, and the sulfur blockage phenomenon is easily generated on a pipeline.
Further, the desulfurizer comprises a mixture A and a material B, wherein the mixture A comprises the following substances in parts by weight:
the mass ratio of the iminodisuccinic acid and the salt thereof to the fulvic acid and the salt thereof is 1;
the material B is 5-10 parts of water-soluble nitrite, and when the raw materials are in the range, the finally obtained desulfurizer has a better effect.
The invention has the following beneficial effects:
1. the complex iron desulfurizer provided by the invention has the advantages of wide source range of raw materials, low price and suitability for large-scale production, the mainly adopted raw materials such as fulvic acid and salt thereof belong to conventional agricultural products, the sodium alginate belongs to conventional industrial or food additives, and the yield is high and the price is low; even if the source of the iminodisuccinate is slightly narrow, the iminodisuccinate still belongs to a more conventional industrial product, and the iminodisuccinate has simple preparation method and lower price; meanwhile, the complex iron desulfurizer can be applied to coke oven gas desulfurization.
2. The desulfurizer of the invention has higher sulfur capacity and high regeneration speed, thus not only having good desulfurization effect, but also having less generation amount of final secondary salt and further reducing the discharge amount of waste liquid, thereby further reducing the production cost;
3. the adopted raw materials, except the iron source, other materials such as sodium alginate and iminodisuccinic acid can be naturally degraded, the harm to the environment is extremely low, and the fulvic acid belongs to a widely used plant fertilizer additive, has a promoting effect on the growth of plants and has a positive effect on the maintenance of soil fertility; and iron ions basically have no influence on the environment, so that the desulfurizer provided by the invention belongs to an environment-friendly desulfurizer on the whole and cannot influence the environment.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below with reference to embodiments of the present invention, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, each raw material was purchased from a conventional source unless otherwise specified;
in the following examples, the operations are all conventional in the art unless otherwise specified.
In the following examples, the amount of hydrate of iron salt was measured to remove crystal water.
In the following examples, mineral-derived fulvic acid was purchased from shandong yushuo chemical company ltd, and biochemical fulvic acid was purchased from jinan sea reputation chemical company ltd.
In the following examples, the polyglycol ether used was polyglycol dimethyl ether having an average molecular weight of about 500.
In the following examples, the minimum sulfur capacity of the desulfurizing agent was measured by the following method: placing 1000ml of mixture A of desulfurizer in a long-neck glass container, adding material B, wherein the volume of desulfurizer is at least two fifths of that of glass container, and making the concentration of hydrogen sulfide be 5g/m 3 The natural gas is injected into the glass container at a speed of 0.1L/min through a gas distribution head arranged at the bottom of the glass container, an opening is formed in the upper end of the glass container, the outlet hydrogen sulfide is detected through a hydrogen sulfide detector, the detection is performed once per minute until the outlet hydrogen sulfide can be detected, the ventilation time is recorded, the pH of the desulfurization liquid in the glass container is detected through the pH during the test, and the pH of the desulfurizer is maintained at the initial pH in the experimental process through the mode of adding a sodium carbonate solution. The minimum sulfur capacity is calculated by the following formula:
in the formula, C min Is the minimum sulfur capacity, g/L; c is hydrogen sulfide concentration, g/m 3 (ii) a v is hydrogen sulfide flow rate, L/min; t is the aeration time when hydrogen sulfide is detected, min; v is the volume of the desulfurizing agent, L.
In the following examples, the regeneration rate of the desulfurizing agent was measured by the following method: and (3) continuously introducing hydrogen sulfide into the residual liquid after the minimum sulfur capacity of the desulfurizer is measured, and stopping introducing the hydrogen sulfide when the desulfurization liquid is completely black and the difference between the amount of the outlet hydrogen sulfide and the amount of the inlet hydrogen sulfide is within 10%. And (3) placing a gas distribution head of an outlet pipe of the small blower in the glass container until the foam quantity in the glass container is reduced, the desulfurization liquid turns to wine red and more sulfur appears in the container, completely regenerating the desulfurizer at the moment, and recording the ventilation time as the regeneration time.
Example 1
Taking 1L of water, adding 55g of biochemical fulvic acid, 55g of iminodisuccinic acid tetrasodium and 33g of sodium alginate, dissolving the materials, adding 32g of ferric chloride hexahydrate, stirring the mixture to dissolve the ferric chloride, adding 0.2g of polyethylene glycol ether to dissolve the polyethylene glycol ether, adding sodium hydroxide to adjust the pH value to 9 after the ferric chloride is dissolved to obtain a mixture A1, taking 6g of sodium nitrite, preparing the sodium nitrite into a 20% aqueous solution serving as a material B1, and combining the A1 and the B1 to obtain the desulfurizer L-1.
The minimum sulfur capacity was measured to be 5.2g/L, the regeneration time was 9min, and it was observed that the sulfur particles were small and most of the sulfur particles adhered to the air bubbles during the regeneration.
Example 2
Taking 1L of water, adding 55g of mineral source fulvic acid, 55g of tetrasodium iminodisuccinate and 33g of sodium alginate, dissolving the mineral source fulvic acid, adding 30g of ferric chloride hexahydrate, stirring to dissolve the ferric chloride, adding 0.2g of polyethylene glycol ether, dissolving the polyethylene glycol ether, adding sodium hydroxide to adjust the pH value to 9 after dissolving to obtain a mixture A2, taking 6g of sodium nitrite as a material B2, and combining the A2 and the B2 to obtain the desulfurizer L-2.
The minimum sulfur capacity was measured to be 5.5g/L, the regeneration time was 10min, and it was observed that the sulfur particles were small and most of the sulfur particles adhered to the air bubbles during the regeneration.
Example 3
Taking 1L of water, adding 48g of biochemical fulvic acid, 45g of iminodisuccinic acid tetrasodium and 27g of sodium alginate for dissolving, then adding 26g of ferric chloride hexahydrate for stirring for dissolving, adding 0.45g of polyethylene glycol ether for dissolving, adding sodium hydroxide for adjusting the pH value to 10 after dissolving to obtain a mixture A3, taking 9g of sodium nitrite as a material B3, and combining the A3 and the B3 to obtain the desulfurizer L-3.
The minimum sulfur capacity was measured to be 4.9g/L, the regeneration time was 11min, it was observed during the regeneration that the sulfur particles were large and settled to the bottom of the vessel after 10min after the aeration was stopped.
Example 4
Taking 1L of water, adding 55g of biochemical fulvic acid, 55g of iminodisuccinic acid tetrasodium and 33g of sodium alginate, dissolving, adding 32g of ferric chloride hexahydrate, stirring to dissolve, adding 0.2g of polyethylene glycol ether, dissolving, adding sodium hydroxide, adjusting the pH value to 9 to obtain a mixture A4, taking 6g of sodium nitrite, preparing an aqueous solution with the concentration of 20% as a material B4, and combining the A4 and the B4 to obtain the desulfurizer L-4.
The minimum sulfur capacity was measured to be 4.9g/L, the regeneration time was 10min, and it was observed that the sulfur particles were small and most of the sulfur particles adhered to the air bubbles during the regeneration.
Example 5
Taking 1L of water, adding 75g of biochemical fulvic acid, 50g of iminodisuccinic acid tetrasodium and 40g of sodium alginate, dissolving, adding 40g of ferric chloride hexahydrate, stirring to dissolve, adding 0.2g of polyethylene glycol ether, dissolving, adding sodium hydroxide, adjusting the pH value to 8.5 to obtain a mixture A5, taking 9g of sodium nitrite, preparing an aqueous solution with the concentration of 20% as a material B5, and combining the A5 and the B5 to obtain the desulfurizer L-5.
The minimum sulfur capacity was measured to be 5.3g/L, the regeneration time was 12min, and it was observed that the sulfur particles were small and most of the sulfur particles adhered to the air bubbles during the regeneration.
Example 6
Taking 1L of water, adding 55g of biochemical fulvic acid, 55g of tetrasodium iminodisuccinate and 33g of sodium alginate, dissolving the materials, adding 32g of ferric chloride hexahydrate, stirring the mixture to dissolve the ferric chloride hexahydrate, adding 0.2g of polyethylene glycol ether, dissolving the polyethylene glycol ether to obtain a mixture A6, taking 6g of sodium nitrite, preparing an aqueous solution with the concentration of 20% as a material B6, and combining the A6 and the B6 to obtain the desulfurizer L-6.
The minimum sulfur capacity was measured to be 5.2g/L, the regeneration time was 9min, it was observed that the sulfur particles were small and most of the sulfur particles adhered to the air bubbles during the regeneration, but since the pH was not adjusted by the desulfurizing liquid, a relatively large amount of alkaline solution was added to maintain the pH during the measurement of the minimum sulfur capacity.
Example 7
Taking 1L of water, adding 55g of biochemical fulvic acid, 55g of iminodisuccinic acid tetrasodium and 33g of sodium alginate, dissolving, adding 32g of ferric chloride hexahydrate, stirring to dissolve, adding 0.2g of polyethylene glycol ether and 1.5g of sodium molybdate, dissolving, adding sodium hydroxide after dissolving, adjusting the pH value to 9 to obtain a mixture A7, taking 6g of sodium nitrite, preparing an aqueous solution with the concentration of 20% as a material B7, and combining the A7 and the B7 to obtain the desulfurizer L-7.
The minimum sulfur capacity was measured to be 5.3g/L, the regeneration time was 10min, and it was observed that the sulfur particles were small and most of the sulfur particles adhered to the air bubbles during the regeneration.
Comparative example 1 (without nitrite)
Taking 1L of water, adding 55g of biochemical fulvic acid, 55g of iminodisuccinic acid tetrasodium and 33g of sodium alginate, dissolving, adding 32g of ferric chloride hexahydrate, stirring to dissolve, adding 0.2g of polyethylene glycol ether, dissolving, adding sodium hydroxide, and adjusting the pH value to 9 to obtain the desulfurizer D-1.
The minimum sulfur capacity was measured to be 4.2g/L, the regeneration time was 18min, and it was observed that the sulfur particles were small and most of the sulfur particles were attached to the air bubbles during the regeneration.
Comparative example 2
Taking 1L of water, adding 55g of tetrasodium iminodisuccinate and 33g of sodium alginate for dissolving, then adding 58g of ferric chloride hexahydrate for stirring for dissolving, adding 0.2g of polyethylene glycol ether for dissolving, adding sodium hydroxide for adjusting the pH value to 9 after dissolving to obtain a mixture A9, taking 6g of sodium nitrite and preparing into an aqueous solution with the concentration of 20% as a material B9, and combining the A9 and the B9 to obtain a desulfurizer D-2.
The minimum sulfur capacity was measured to be 3.7g/L, the regeneration time was 16min, and it was observed that the sulfur particles were small and most of the sulfur particles adhered to the air bubbles during the regeneration.
To further illustrate the effect of the desulfurization agent of the present invention, the desulfurization agent in the above examples was subjected to a performance test.
1. High temperature desulfurization of desulfurization agent
Diluting the above desulfurizing agent by 50 times with hydrogen sulfide content of 5-12g/m in certain coking plant in Shandong province 3 The content of hydrogen sulfide in the well site of the coke oven gas and the natural gas of Sichuan is 20-23g/m 3 Wherein the coke oven gas has an average sulfur content of about 10g/m 3 . In the desulfurization process, the gas treatment amount is 5m 3 H, volume of doctor solution is 0.5m 3 The temperature is about 10 ℃ to 35 ℃.
The experimental device comprises an absorption tower, a regeneration tower, a foam storage tank, a bag filter, a circulating pump, a regeneration fan and the like. Wherein, the absorption tower is the place that absorbs the sulphur, the regeneration tower is the place that produces the sulphur foam and carry out regeneration to the desulfurizer simultaneously, in the regeneration process, the sulphur foam of production gets into bag filter and filters, it makes the doctor solution regeneration to blow the air through the regeneration fan simultaneously, doctor solution after the regeneration passes through the circulating pump and gets into the absorption tower, in the regeneration process, the sulphur foam of production gets into in the defoaming jar, when the sulphur foam of treating the defoaming jar has a certain amount, adopt bag filter to filter in order to obtain sulphur. The structure of the whole desulfurization device is conventional in the art, and therefore, the detailed description thereof is omitted.
In the experimental process, 100g of the desulfurizing agent in the embodiment (the mixture A and the material B are added in equal proportion, wherein the material B is in a solid-bending amount) is added in every 5kg of sulfur output, and meanwhile, the pH of the desulfurizing liquid is kept at about 8.5 by adding alkali liquor. The operation conditions were the same, and since the number of the experimental devices was limited, only the desulfurizing agents L-1, D-1 and D-2 were selected to conduct the experiment, the hydrogen sulfide content in the exhaust port (i.e., the hydrogen sulfide content in the purified gas) was measured during the experiment, and no waste liquid was discharged to the outside during the entire test, and the final experimental results are shown in tables 3 and 4.
TABLE 1 Coke oven gas desulfurization experiment
TABLE 2 desulfurization of natural gas
Note: "-" indicates that the outlet hydrogen sulfide concentration exceeded 200ppm and that no subsequent experiments were performed.
As can be seen from tables 1 and 2, the outlet hydrogen sulfide can still be maintained within a normal range under the condition that the desulfurizing agent L-1 is operated for a long time; comparing L-1 and D-1, it can be known that D1 does not contain sodium nitrite, so that the regeneration speed is slow, the byproducts are more and more, and the final desulfurization effect is poor; comparing L-1 and D-2, it can be seen that D2 lacks one of the materials, resulting in a lower sulfur capacity and a lower desulfurization effect. In fact, when the desulfurizer D-1 runs for 44 days and the desulfurizer D-2 runs for 31 days in the process of coke oven gas desulfurization, the daily sulfur output is lower than 0.5kg, which indicates that a large amount of sulfur is converted into byproducts; when the desulfurizer D-1 runs for 60 days and the desulfurizer D-2 runs for 55 days during natural gas desulfurization, the daily sulfur output is lower than 0.5kg, which indicates that a large amount of sulfur is converted into byproducts.
As will be appreciated by those skilled in the art, since coke oven gas contains a large amount of impurities, such as coal tar, hydrocyanic acid, dust, etc., even if the sulfur content of natural gas is relatively high, the normal operation time is relatively low when operating in coke oven gas, which is the same as that of large-scale desulfurization, and further, the above experiment can provide support for actual large-scale production.
2. Amount of by-product salt formed
The test desulfurization solutions in table 1 were used, and the secondary salt content of each desulfurization solution was measured at regular intervals, and the final measurement results are shown in table 3.
TABLE 3 amount of variation of secondary salt in desulfurization process
As can be seen from Table 3, the desulfurizing agent prepared in example 1 has a low amount of the secondary salt formed, and even when it is operated for 180 days, it has a low content of the secondary salt, and thus it can satisfy the actual desulfurization requirement. Even if the whole system is expanded to the actual production scale, the generation amount of the secondary salt is increased probably due to the change of the environment, but compared with the desulfurization by an alcohol amine method and a PDS desulfurization method in the prior art, the generation amount of the secondary salt is still low, so that the emission amount of the final waste liquid is relatively low, the pressure of the subsequent salt extraction process is relatively low, and the environment is protected.
Although the present invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the present invention.
Claims (8)
1. The complex iron desulfurizer is characterized by comprising a mixture A and a material B, wherein the mixture A comprises the following substances in parts by weight:
iminodisuccinic acid and salts thereof
The mass ratio of the iminodisuccinic acid and the salt thereof to the fulvic acid and the salt thereof is 1;
the material B is 5-10 parts of water-soluble nitrite.
2. The desulfurizing agent according to claim 1, wherein said soluble iron salt is at least one of ferric chloride, ferric nitrate and ferric sulfate; the soluble ferrous salt is at least one of ferrous chloride, ferrous sulfate and ferrous nitrate.
3. The desulfurization agent of claim 1, wherein the mixture A further comprises a base, wherein the base is such that the pH of the mixture A is not less than 8.
4. The desulfurizing agent according to claim 3, wherein said base is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate.
5. The desulfurizing agent according to claim 1, wherein said iminodisuccinic acid and salts thereof are one of iminodisuccinic acid and tetrasodium iminodisuccinate, and said water-soluble nitrite is sodium nitrite, potassium nitrite, nitrous acid.
6. The desulfurization agent of claim 1, further comprising a corrosion inhibitor.
7. The desulfurizing agent according to claim 1, wherein the desulfurizing agent further comprises 0.1-0.5 parts of polyethylene glycol ether.
8. The desulfurizing agent according to any one of claims 1 to 7, comprising a mixture A and a material B, wherein the mixture A comprises the following substances in parts by weight:
iminodisuccinic acid and salts thereof
The mass ratio of the iminodisuccinic acid and the salt thereof to the fulvic acid and the salt thereof is 1;
the material B is 5-10 parts of water-soluble nitrite.
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| CN116474532A (en) * | 2023-06-20 | 2023-07-25 | 明硕环境科技集团股份有限公司 | High-activity complex iron desulfurizing agent and preparation method thereof |
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