CN105597516B - Magnetic iron oxide desulfurizer and preparation method thereof - Google Patents
Magnetic iron oxide desulfurizer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a magnetic ferric oxide desulfurizer and a preparation method thereof, wherein the preparation method comprises the following steps: s1, uniformly mixing the iron oxyhydroxide, the adhesive and the auxiliary agent to obtain a mixture I, wherein the auxiliary agent is fly ash and/or volcanic ash; s2, uniformly mixing the mixture I, a peptizing agent and water to obtain a mixture II; s3, forming and drying the mixture II; and S4, roasting the dried molded product to obtain the magnetic iron oxide desulfurizer. The prepared magnetic iron oxide desulfurizer has a porous structure and high mechanical strength, can be fully contacted with sulfur-containing gas, and improves the desulfurization efficiency. The desulfurizing agent can be used for desulfurization under the working conditions of normal temperature to medium temperature, normal pressure to high pressure, high hydrogen sulfide content, high water vapor content and different raw material gases, the strength of the desulfurizing agent is not reduced in the desulfurization process, the phenomenon of mud hardening is avoided, and the high desulfurization activity is maintained all the time.
Description
Technical Field
The invention belongs to the technical field of desulfurizer preparation, and particularly relates to a magnetic iron oxide desulfurizer and a preparation method thereof.
Background
With the rapid development of national economy of China, the consumption of natural gas, oilfield associated gas, synthesis gas, coal bed gas, methane, coke oven gas and the like which are important energy and chemical raw materials is continuously increased, but the raw materials contain trace sulfide, so that the environment is greatly polluted, equipment is corroded, subsequent catalyst poisoning is caused, and the subsequent catalyst poisoning needs to be removed and purified.
At home and abroad, gas desulfurization and purification are divided into wet desulfurization and dry desulfurization. Wet desulfurization is mostly used for removing a large amount of sulfides, and dry desulfurization is mostly used for fine desulfurization and has higher purification degree for both inorganic sulfur and organic sulfur. The main methods for dry desulfurization include an iron oxide method, a zinc oxide method and an activated carbon method. The active carbon desulfurizer is a disposable product and has the problems of low sulfur capacity and oxygen supplementation during desulfurization; although the desulfurization precision of the zinc oxide desulfurizer is high, the sulfur capacity is low and the price is high; the ferric oxyhydroxide has high desulfurization speed and high sulfur capacity, and the used ferric oxyhydroxide can be regenerated in an oxidation mode, so that the ferric oxyhydroxide can be recycled.
However, the iron oxyhydroxide serving as a desulfurizing agent also has some problems, for example, the iron oxyhydroxide is only suitable for use at normal temperature and cannot be used at high temperature, so that the application range of the iron oxyhydroxide is limited; furthermore, it has low mechanical strength and is not suitable for use under high pressure.
The use of magnetic iron oxides Fe has also been reported in the prior art21.333O32As desulfurizing agents, for example: chinese patent document CN101585557A discloses a method for preparing magnetic iron oxide and a magnetic iron oxide desulfurizer prepared by the same, wherein the magnetic iron oxide Fe21.333O32The preparation method comprises the following steps: 1) mixing solid soluble ferrous salt and solid hydroxide according to the molar ratio of iron to hydroxyl being 1:2-1: 3; 2) completing reaction of the mixture obtained in the step 1) through kneading, wherein the temperature of the material is controlled not to exceed 70 ℃ in the kneading process; 3) airing the reaction product obtained in the step 2) in the air; 4) washing the material obtained in the step 3) with water and filtering; 5) naturally drying or baking the solid obtained in the step 4); 6) roasting the product obtained in the step 5) at the temperature of 150 ℃ and 500 ℃.
The preparation process of the magnetic iron oxide generates no waste liquid and is environment-friendly, but the finally prepared magnetic iron oxide Fe21.333O32Is not beneficial to the subsequent molding treatment, and has low mechanical strength and weak anti-extrusion capability. The desulfurization process is easy to crush, the use is influenced, and the recycling is not favorable. In the steps 2) -4), iron oxyhydroxide is generated after the kneading reaction; in the step 5), the hydroxyl ferric oxide is roasted again to obtain magnetic ferric oxide Fe21.333O32However, the obtained structure is compact, the full contact of sulfur-containing gas with the sulfur-containing gas is not facilitated, and the desulfurization efficiency is low.
Disclosure of Invention
The invention aims to solve the problem of the prior art that the magnetic iron oxide Fe21.333O32The desulfurizer has insufficient contact with sulfur-containing gas and low mechanical strength, and further provides a preparation method of the magnetic iron oxide desulfurizer with a porous structure and high mechanical strength.
Therefore, the invention adopts the technical proposal that,
a preparation method of a magnetic iron oxide desulfurizer comprises the following steps:
s1, uniformly mixing the iron oxyhydroxide, the adhesive and the auxiliary agent to obtain a mixture I, wherein the auxiliary agent is fly ash and/or volcanic ash;
s2, uniformly mixing the mixture I, a peptizing agent and water to obtain a mixture II;
s3, forming and drying the mixture II;
and S4, roasting the dried molded product to obtain the magnetic iron oxide desulfurizer.
In the step S4, the roasting temperature is 200-450 ℃, and the roasting time is 0.5-12 h.
The binder comprises an inorganic binder and an organic binder; the inorganic adhesive is at least one of clay, alumina, pseudo-boehmite, diatomite and calcium hydroxide; the peptizing agent is at least one of nitric acid, hydrochloric acid, acetic acid, formic acid, citric acid, oxalic acid and tartaric acid.
Further, the inorganic binder is alumina and/or pseudo-boehmite.
In step S1, the iron oxyhydroxide is at least one of alpha-FeOOH, beta-FeOOH, gamma-FeOOH, delta-FeOOH, and amorphous FeOOH;
the organic adhesive is at least one of sesbania gum, guar gum, carboxymethyl cellulose, gum, pectin, seaweed plant gum and polyvinyl alcohol.
The mass ratio of the iron oxyhydroxide to the inorganic adhesive to the auxiliary to the peptizing agent to the organic adhesive is (50-95): (1-45): (1-50): (1-40): (1-40).
In both the step S1 and the step S2, the mixing step is performed in a mixing mill or a kneader.
In the step S1, the time of the mixing step is not less than 3min, preferably 3-45 min.
In the step S2, the time of the mixing step is not less than 5min, preferably 5 to 60 min.
The drying temperature in the drying step is-5-120 ℃, and the time is 0.5-24 h.
The invention also provides the magnetic iron oxide desulfurizer prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
1) according to the preparation method of the magnetic iron oxide desulfurizer, the fly ash and/or the volcanic ash are adopted, and the three-dimensional pore channel structure is built in the magnetic iron oxide desulfurizer, so that sulfur-containing gas can enter the desulfurizer through the channel, the magnetic iron oxide desulfurizer is fully contacted with the sulfur-containing gas, the sulfur-containing gas can be in contact reaction with main active ingredients in the desulfurizer, and the sulfur capacity of the desulfurizer is improved.
Meanwhile, inorganic adhesive, especially pseudo-boehmite and alumina are added, sol formed after the reaction of the pseudo-boehmite and the alumina and peptizing agent can be highly dispersed on the surface of the hydroxyl ferric oxide, and high-strength gamma-Al is obtained after high-temperature roasting2O3As a supporting framework of the magnetic iron oxide desulfurizer, the mechanical strength of the magnetic iron oxide desulfurizer is obviously improved.
2) According to the preparation method of the magnetic iron oxide desulfurizer, the applicant discovers through creative work that when the roasting temperature is 200-450 ℃ and the roasting time is 0.5-12 hours, the mechanical strength of the magnetic iron oxide desulfurizer can be enhanced, and meanwhile, iron oxyhydroxide can be converted into magnetic iron oxide. Meanwhile, the prepared magnetic iron oxide can be used at normal temperature and high temperature; when the magnetic iron oxide desulfurizer is used under normal pressure and high pressure, generally, a person skilled in the art thinks that the organic binder is incinerated or volatilized in the roasting treatment of the organic binder in the preparation process, so that the organic binder cannot play the role (such as forming role) of the organic binder, but the inventor finds that the organic binder can be completely volatilized by firstly forming and then roasting at the roasting temperature and time, so that the organic binder plays the forming role of the organic binder on the one hand, and on the other hand, the problems of low mechanical strength, poor water resistance and the like of the magnetic iron oxide desulfurizer caused by the existence of the organic binder in the magnetic iron oxide desulfurizer are avoided, and the technical bias is overcome. Meanwhile, under the temperature condition, the organic adhesive can be completely volatilized, so that holes can be generated, the contact area of the magnetic iron oxide desulfurizer and sulfur-containing gas is further increased, and the sulfur capacity is increased; the roasting temperature is optimal, the low temperature is avoided, the purposes of removing the organic adhesive and converting the hydroxyl ferric oxide into the magnetic ferric oxide cannot be achieved, and the problems of particle agglomeration, structure collapse, active ingredient volatilization and the like caused by high roasting temperature are avoided.
3) According to the preparation method of the magnetic iron oxide desulfurizer, the organic binder is completely volatilized by limiting the roasting temperature to be 200-450 ℃ and the roasting time to be 0.5-12 h, so that the magnetic iron oxide desulfurizer does not have a mud hardening phenomenon during desulfurization under the working condition of high water vapor content, and keeps high desulfurization activity all the time.
4) According to the preparation method of the magnetic iron oxide desulfurizer, the inorganic binder and the organic binder are added in the preparation process, so that the subsequent forming is facilitated, the roasting is combined, the organic binder is removed, the inorganic binder is converted into the support framework of the magnetic iron oxide desulfurizer, and the mechanical strength of the magnetic iron oxide desulfurizer is improved.
5) The magnetic iron oxide desulfurizer prepared by the preparation method of the embodiment of the invention has high sulfur capacity and high strength, and can be used for desulfurization under the working conditions of normal temperature to medium temperature, normal pressure to high pressure, high hydrogen sulfide content, high water vapor content and different raw material gases.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific embodiments. This invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the concept of the invention to those skilled in the art, and the present invention will only be defined by the appended claims.
The evaluation test methods of the sulfur capacity, the radial crushing resistance, the specific surface area, the pore volume and the water resistance of the magnetic iron oxide desulfurizer in the following examples and comparative examples are respectively as follows:
1) the method for testing the sulfur capacity comprises the following steps: 1g of a desulfurizing agent was charged into a desulfurizing device, and the content was measured at-5 to 45 ℃ under normal pressure, and 40000ppmH was fed to the inlet of the desulfurizing device2The gas of S is measured by a domestic WDL-94 trace sulfur analyzer to determine the H at the gas outlet of the desulfurization device2S content, as H in gas at gas outlet2When the S content reaches 1ppm, the air intake is stopped because of the H contained in the intake air2And S can corrode the measuring instrument, so that the gas volume V of the gas outlet is recorded, and the calculation is carried out according to the following formula to obtain the sulfur capacity of the desulfurizer.
2) Radial crush resistance test method: the radial crushing resistance is obtained by testing with a domestic ZOJ-II intelligent particle strength tester and testing and calculating according to HG/T2782 standard.
3) Specific surface area test method: the test was carried out using a V-Sorb 2800P specific surface area tester.
4) The pore volume test method comprises the following steps: the pore volume test was carried out using a 3H-2000PS2 model pore size tester manufactured by Behcet.
5) Evaluation test of water resistance: the magnetic iron oxide desulfurizing agents of different specifications in the examples and comparative examples were soaked in water for 15 days for observation.
Examples 1,
The embodiment provides a magnetic iron oxide desulfurizer and a preparation method thereof, wherein the preparation method comprises the following steps:
s1, placing 400g of alpha-FeOOH, 20g of alumina, 30g of fly ash and 10g of sesbania gum into a mixing mill, and mixing and milling for 5min to obtain a mixture I;
s2, adding 5g of acetic acid and 200g of water into the mixture I, continuing to mix and grind for 10min, and fully and uniformly kneading to obtain a mixture II;
s3, placing the mixture II into a screw rod extruder to be extruded into a strip-shaped molding object with the diameter of 4 x 2-10 mm;
s4, drying the strip-shaped forming object at-5 ℃ for 24h, and roasting the dried material at 200 ℃ for 6h to obtain the magnetic iron oxide desulfurizer, wherein the sulfur capacity of the desulfurizer is 47.6%, the radial crushing resistance is 96N/cm, and the specific surface area is 105m2The pore volume is 0.48 ml/g.
Through the evaluation test of water resistance, the strip-shaped magnetic iron oxide desulfurizer with the diameter of 4 multiplied by 2-10mm has good shape, no expansion, no crushing by hand and good strength.
The component of the magnetic iron oxide in the magnetic iron oxide desulfurizer is Fe through XRD test21.333O32。
Examples 2,
The embodiment provides a magnetic iron oxide desulfurizer and a preparation method thereof, wherein the preparation method comprises the following steps:
s1, placing 900g of beta-FeOOH, 100g of diatomite, 50g of volcanic ash and 100g of guar gum into a mixing mill, and mixing and milling for 30min to obtain a mixture I;
s2, adding 100g of nitric acid and 400g of water into the mixture I, continuing to mix and grind for 30min, and obtaining a mixture II after fully and uniformly kneading;
s3, placing the mixture II into a screw rod extruder to be extruded into a strip-shaped molding object with the diameter of 4 x 2-10 mm;
s4, drying the strip-shaped forming object at 120 ℃ for 3h, and roasting the dried material at 300 ℃ for 3h to obtain the magnetic iron oxide desulfurizer, wherein the sulfur capacity of the desulfurizer is 44.8 percent, the radial crushing resistance is 105N/cm, and the specific surface area is 95m2The pore volume is 0.45 ml/g.
Through the evaluation test of water resistance, the strip-shaped magnetic iron oxide desulfurizer with the diameter of 4 multiplied by 2-10mm has good shape, no expansion, no crushing by hand and good strength.
The magnetic iron oxide in the magnetic iron oxide desulfurizer is prepared from the following components by XRD testFe21.333O32。
Examples 3,
The embodiment provides a magnetic iron oxide desulfurizer and a preparation method thereof, wherein the preparation method comprises the following steps:
s1, placing 700g of gamma-FeOOH, 300g of pseudo-boehmite, 100g of fly ash and 200g of carboxymethyl cellulose into a mixing mill, and mixing and milling for 15min to obtain a mixture I;
s2, adding 150g of hydrochloric acid and 300g of water into the mixture I, continuously mixing and grinding for 20min, and fully and uniformly kneading to obtain a mixture II;
s3, placing the mixture II into a screw rod extruder to be extruded into a strip-shaped molding object with the diameter of 4 x 2-10 mm;
s4, drying the strip-shaped forming object at 100 ℃ for 10h, roasting the dried material at 400 ℃ for 12h to obtain the magnetic iron oxide desulfurizer, wherein the sulfur capacity of the desulfurizer is 43.7 percent, the radial crushing resistance is 96N/cm, and the specific surface area is 92m2The pore volume is 0.39 ml/g.
Through the evaluation test of water resistance, the strip-shaped magnetic iron oxide desulfurizer with the diameter of 4 multiplied by 2-10mm has good shape, no expansion, no crushing by hand and good strength.
The component of the magnetic iron oxide in the magnetic iron oxide desulfurizer is Fe through XRD test21.333O32。
Examples 4,
The embodiment provides a magnetic iron oxide desulfurizer and a preparation method thereof, wherein the preparation method comprises the following steps:
s1, placing 500g of delta-FeOOH, 200g of clay, 45g of volcanic ash and 10g of gum into a mixing mill, and mixing and milling for 10min to obtain a mixture I;
s2, adding 10g of citric acid and 250g of water into the mixture I, continuously mixing and grinding for 10min, and fully and uniformly kneading to obtain a mixture II;
s3, placing the mixture II into a screw rod extruder to be extruded into a strip-shaped molding object with the diameter of 4 x 2-10 mm;
s4, drying the strip-shaped forming object at-5 ℃ for 24h, and roasting the dried material at 400 ℃ for 12h to obtain magnetic oxygenThe iron melting desulfurizer is tested to have the sulfur capacity of 45.5 percent, the radial crushing resistance of 93N/cm and the specific surface area of 98m2The pore volume is 0.42 ml/g.
Through the evaluation test of water resistance, the strip-shaped magnetic iron oxide desulfurizer with the diameter of 4 multiplied by 2-10mm has good shape, no expansion, no crushing by hand and good strength.
The component of the magnetic iron oxide in the magnetic iron oxide desulfurizer is Fe through XRD test21.333O32。
Examples 5,
The embodiment provides a magnetic iron oxide desulfurizer and a preparation method thereof, wherein the preparation method comprises the following steps:
s1, placing 950g of amorphous iron oxyhydroxide, 150g of calcium hydroxide, 100g of fly ash and 200g of pectin into a mixing mill, and mixing and milling for 9min to obtain a mixture I;
s2, adding 400g of formic acid and 350g of water into the mixture I, continuing to mix and grind for 30min, and obtaining a mixture II after fully and uniformly kneading;
s3, placing the mixture II into a screw rod extruder to be extruded into a strip-shaped molding object with the diameter of 4 x 2-10 mm;
s4, drying the strip-shaped forming object at 80 ℃ for 3h, roasting the dried material at 400 ℃ for 12h to obtain the magnetic iron oxide desulfurizer, wherein the sulfur capacity of the desulfurizer is 48.3 percent, the radial crushing resistance is 92N/cm, and the specific surface area is 112m2The pore volume is 0.52 ml/g.
Through the evaluation test of water resistance, the strip-shaped magnetic iron oxide desulfurizer with the diameter of 4 multiplied by 2-10mm has good shape, no expansion, no crushing by hand and good strength.
The component of the magnetic iron oxide in the magnetic iron oxide desulfurizer is Fe through XRD test21.333O32。
Examples 6,
The embodiment provides a magnetic iron oxide desulfurizer and a preparation method thereof, wherein the preparation method comprises the following steps:
s1, placing 950g of amorphous iron oxyhydroxide, 150g of calcium hydroxide, 100g of fly ash and 400g of pectin into a mixing mill, and mixing and milling for 9min to obtain a mixture I;
s2, adding 200g of formic acid and 350g of water into the mixture I, continuing to mix and grind for 30min, and obtaining a mixture II after fully and uniformly kneading;
s3, placing the mixture II into a screw rod extruder to be extruded into a strip-shaped molding object with the diameter of 4 x 2-10 mm;
s4, drying the strip-shaped forming object at 80 ℃ for 3h, roasting the dried material at 400 ℃ for 12h to obtain the magnetic iron oxide desulfurizer, wherein the sulfur capacity of the desulfurizer is 48.0 percent, the radial crushing resistance is 91N/cm, and the specific surface area is 109m2The pore volume is 0.49 ml/g.
Through the evaluation test of water resistance, the strip-shaped magnetic iron oxide desulfurizer with the diameter of 4 multiplied by 2-10mm has good shape, no expansion, no crushing by hand and good strength.
The component of the magnetic iron oxide in the magnetic iron oxide desulfurizer is Fe through XRD test21.333O32。
Comparative examples 1,
The embodiment provides a magnetic iron oxide desulfurizer and a preparation method thereof, wherein the preparation method comprises the following steps:
s1, placing 400g of alpha-FeOOH, 20g of alumina and 10g of sesbania gum into a mixing mill, and mixing and milling for 5min to obtain a mixture I;
s2, adding 5g of acetic acid and 200g of water into the mixture I, continuing to mix and grind for 10min, and fully and uniformly kneading to obtain a mixture II;
s3, placing the mixture II into a screw rod extruder to be extruded into a strip-shaped molding object with the diameter of 4 x 2-10 mm;
s4, drying the strip-shaped forming object at-5 ℃ for 24h, roasting the dried material at 200 ℃ for 6h to obtain the magnetic iron oxide desulfurizer, wherein the sulfur capacity of the desulfurizer is 37.1 percent, the radial crushing resistance is 65N/cm, and the specific surface area is 76m2The pore volume is 0.25 ml/g.
Through the evaluation test of water resistance, the strip-shaped magnetic iron oxide desulfurizer with the diameter of 4 multiplied by 2-10mm has good shape, no expansion, no crushing by hand and good strength.
Comparative examples 2,
The embodiment provides an iron oxyhydroxide desulfurizer and a preparation method thereof, wherein the preparation method comprises the following steps:
s1, placing 900g of beta-FeOOH, 100g of diatomite, 50g of volcanic ash and 100g of guar gum into a mixing mill, and mixing and milling for 30min to obtain a mixture I;
s2, adding 100g of nitric acid and 400g of water into the mixture I, continuing to mix and grind for 30min, and obtaining a mixture II after fully and uniformly kneading;
s3, placing the mixture II into a screw rod extruder to be extruded into a strip-shaped molding object with the diameter of 4 x 2-10 mm;
s4, drying the strip-shaped forming object at 120 ℃ for 3h to obtain the desulfurizer, wherein the sulfur capacity of the desulfurizer is 36.2%, the radial crushing resistance is 42N/cm, and the specific surface area is 70m2The pore volume is 0.32 ml/g.
Through the evaluation test of water resistance, the strip-shaped desulfurizer with the diameter of 4 multiplied by 2-10mm is broken in shape, and the phenomena of expansion and pulverization appear.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (5)
1. A preparation method of a magnetic iron oxide desulfurizer comprises the following steps:
s1, uniformly mixing iron oxyhydroxide, an organic binder, an inorganic binder and an auxiliary agent to obtain a mixture I, wherein in the step S1, the mixing step lasts for 3-45min, the auxiliary agent is fly ash and/or volcanic ash, and the inorganic binder is at least one of clay, alumina, pseudo-boehmite, diatomite and calcium hydroxide;
s2, uniformly mixing the mixture I, a peptizing agent and water to obtain a mixture II, wherein in the step S2, the mixing step lasts for 5-60min, and the peptizing agent is at least one of nitric acid, hydrochloric acid, acetic acid, formic acid, citric acid, oxalic acid and tartaric acid;
the mass ratio of the iron oxyhydroxide to the inorganic adhesive to the auxiliary to the peptizing agent to the organic adhesive is (50-95): (1-45): (1-50): (1-40): (1-40);
s3, forming and drying the mixture II, wherein the drying temperature in the drying step is-5-120 ℃, and the drying time is 0.5-24 h;
s4, roasting the dried formed product at 200-450 ℃ for 0.5-12 h to obtain the magnetic iron oxide desulfurizer.
2. The method of claim 1, wherein: the inorganic binder is alumina and/or pseudo-boehmite.
3. The production method according to any one of claims 1 to 2, characterized in that: in step S1, the iron oxyhydroxide is at least one of alpha-FeOOH, beta-FeOOH, gamma-FeOOH, delta-FeOOH, and amorphous FeOOH;
the organic adhesive is at least one of sesbania gum, guar gum, carboxymethyl cellulose, gum, pectin, seaweed plant gum and polyvinyl alcohol.
4. The production method according to any one of claims 1 to 2, characterized in that: in both the step S1 and the step S2, the mixing step is performed in a mixing mill or a kneader.
5. A magnetic iron oxide desulfurizing agent prepared by the preparation method of any one of claims 1-4.
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| CN106732478A (en) * | 2016-12-07 | 2017-05-31 | 郑州丽福爱生物技术有限公司 | A kind of diatomite desulfurizing agent and its preparation method and application |
| CN110404538B (en) * | 2018-04-28 | 2022-07-19 | 北京三聚环保新材料股份有限公司 | Use of waste agents |
| CN110496590A (en) * | 2019-08-12 | 2019-11-26 | 江苏宇星工贸有限公司 | The production technology of ferric oxide desulfurizer |
| CN111111508A (en) * | 2019-12-30 | 2020-05-08 | 东营市海嘉化工有限公司 | Preparation system and method of iron oxyhydroxide desulfurizer |
| CN114471133B (en) * | 2022-02-25 | 2023-08-01 | 射洪科瑞沃环保技术有限公司 | Desulfurizing agent for preventing desulfurizing rich agent from forming hardening at low temperature and preparation method thereof |
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