CN111889063B - BiOCl adsorbent, preparation method and application thereof in room temperature desulfurization - Google Patents

BiOCl adsorbent, preparation method and application thereof in room temperature desulfurization Download PDF

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CN111889063B
CN111889063B CN202010905722.7A CN202010905722A CN111889063B CN 111889063 B CN111889063 B CN 111889063B CN 202010905722 A CN202010905722 A CN 202010905722A CN 111889063 B CN111889063 B CN 111889063B
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biocl
adsorbent
room temperature
preparation
desulfurization
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CN111889063A (en
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王心晨
阳灿
杨浩
吴伟霆
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Fuzhou University
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Fuzhou University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0259—Compounds of N, P, As, Sb, Bi
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0288—Halides of compounds other than those provided for in B01J20/046
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a simple preparation BiOCl adsorbent with room temperature desulfurization effect and a preparation method and application thereof, belongs to the technical field of material preparation and adsorption desulfurization, and is a method for synthesizing BiOCl materials with different crystal face compositions in one step by using a solvothermal method. The adsorbent can realize excellent hydrogen sulfide gas adsorption performance at room temperature. The invention has simple process and low cost, can be produced in large scale, meets the actual production requirement and has larger application potential.

Description

BiOCl adsorbent, preparation method and application thereof in room temperature desulfurization
Technical Field
The invention belongs to the technical field of material preparation and adsorption desulfurization, and particularly relates to a BiOCl adsorbent, a preparation method and application thereof in room-temperature desulfurization.
Background
Hydrogen sulfide (H)2S) gas widely exists in industrial tail gas of coal, natural gas, petroleum and the like and sewage of agriculture and cities, and is a main substance causing catalyst poisoning, equipment corrosion and acid rain formation. How to remove H from raw gas or tail gas2S is an important issue. Catalytic combustion, condensation and acid gas treatment are widely used for H removal2And S. In these processes, development of efficient, economical and stable adsorbents is an urgent necessity. Zeolites, activated carbon, clays, alumina and metal oxides are the most commonly used adsorbents in desulfurization. Among them, transition metal oxides such as iron-based catalysts, zinc-based catalysts, vanadium-based catalysts, etc. are preferred because of their low cost,Easy preparation and excellent performance are generally considered. In particular, iron-based sorbents have been identified for H removal2Commercial catalyst for S, in terms of desulfurization, Fe-Fe2O3And Fe-Fe2O3All showed satisfactory activity. In addition, iron species can improve the desulfurization ability of other oxides as an additive. However, the d orbital of the transition metal atom is easily bonded to the p orbital of S to form a strong metal-S bond, which results in easy poisoning during desulfurization of the transition metal oxide. Therefore, the development of main group metal sorbents is a potential desulfurization solution.
Bismuth oxide (Bi) has been reported2O3) Has desulfurization activity, but the activity is very limited. Bismuth oxychloride (BiOCl) is a well known important member of bismuth-containing compounds and it exhibits excellent activity in a number of important chemical reactions. However, the use of BiOCl materials for desulfurization is very limited. Therefore, the development of a BiOCl adsorbent which is easy to prepare, low in cost and high in efficiency is of great significance.
Disclosure of Invention
The invention aims to provide a preparation method and application of a non-transition metal-based compound for room-temperature hydrogen sulfide gas adsorption.
The main group metal bismuth-based compound BiOCl prepared by the invention can realize high-efficiency adsorption of hydrogen sulfide gas at room temperature. Compared with pure metal oxide, the composite material has better performance and sulfur resistance. The invention has simple process, low cost and high efficiency, meets the actual production requirement and has wider application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
a BiOCl adsorbent is prepared by a simple one-step solvothermal method, and is in a sheet structure. The adsorbent is a main group metal-based adsorbent, and BiOCl materials with different crystal face compositions can be synthesized by changing the components of a solvent.
The preparation method of the BiOCl adsorbent specifically comprises the following steps:
the method specifically comprises the following steps:
1) adding absolute ethyl alcohol and sodium hydroxide into deionized water;
2) adding bismuth chloride into the mixed solution of the step 1), and stirring for 30 minutes;
3) transferring the mixed solution obtained in the step 2) to a reaction kettle for high-temperature reaction;
4) after the reaction kettle is cooled to room temperature, centrifuging, washing and collecting a sample.
Further, the volume ratio of the absolute ethyl alcohol to the deionized water is 5: 60 or 35: 30 or 60: 5; the molar ratio of sodium hydroxide to bismuth chloride was 1 to 0.5.
Further, the high-temperature reaction in the step 3) is specifically as follows: the reaction was carried out at 160 ℃ for 24 hours.
Further, the following preparation conditions are preferred:
1) anhydrous ethanol (35 mL) and sodium hydroxide (0.400 g) were added to 30mL of deionized water;
2) adding bismuth chloride (1.577 g) into the mixed solution of the above 1), and stirring for 30 minutes;
3) transferring the mixed solution in the step 2) to a polytetrafluoroethylene reaction kettle for reaction at 160 ℃ for 24 hours;
4) after the reaction kettle is cooled to room temperature, centrifuging, washing and collecting a sample.
The main group metal bismuth-based catalyst prepared by the invention has controllable different crystal face proportions, and the adsorbent can realize the effect of removing hydrogen sulfide gas at room temperature.
The invention has the following remarkable advantages:
(1) the invention provides a method for preparing a BiOCl desulfurization adsorbent by a simple solvothermal method, which is simple and easy to operate.
(2) The main group metal bismuth-based adsorbing material BiOCl can realize the efficient hydrogen sulfide gas adsorption effect at room temperature.
(3) The whole process is simple and easy to control, low in energy consumption, high in yield and low in cost, meets the actual production requirement, and is favorable for large-scale popularization.
Drawings
FIG. 1 is an XRD pattern of a BiOCl material prepared;
FIG. 2 is an SEM image of a synthesized BiOCl material (a is BiOCl-60, b is BiOCl-35, and c is BiOCl-5);
FIG. 3 shows that the BiOCl adsorbent obtained in examples 1-3 has a space velocity of 3000 ml.g in a mixed gas containing 5000 ppm hydrogen sulfide and 2500 ppm oxygen-1•h-1The adsorption performance of hydrogen sulfide gas at the flow rate of (1).
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
1) Anhydrous ethanol (35 mL) and sodium hydroxide (0.400 g) were added to 30mL of deionized water;
2) adding bismuth chloride (1.577 g) into the mixed solution of the above 1), and stirring for 30 minutes;
3) transferring the mixed solution obtained in the step 2) to a stainless steel reactor of a polytetrafluoroethylene reaction kettle to react for 24 hours at 160 ℃;
4) after the reaction kettle is cooled to room temperature, centrifuging, washing and collecting a sample BiOCl-35.
Example 2
1) Absolute ethanol (5 mL) and sodium hydroxide (0.400 g) were added to 60mL deionized water;
2) adding bismuth chloride (1.577 g) into the mixed solution of the above 1), and stirring for 30 minutes;
3) transferring the mixed solution obtained in the step 2) to a stainless steel reactor of a polytetrafluoroethylene reaction kettle to react for 24 hours at 160 ℃;
4) and after the reaction kettle is cooled to room temperature, centrifuging, washing and collecting a sample BiOCl-5.
Example 3
1) Absolute ethanol (60 mL) and sodium hydroxide (0.400 g) were added to 5mL of deionized water;
2) adding bismuth chloride (1.577 g) into the mixed solution of the above 1), and stirring for 30 minutes;
3) transferring the mixed solution obtained in the step 2) to a stainless steel reactor of a polytetrafluoroethylene reaction kettle to react for 24 hours at 160 ℃;
4) after the reaction kettle is cooled to room temperature, centrifuging, washing and collecting a sample BiOCl-60.
Fig. 1 is an XRD (X-ray diffraction) pattern of the prepared BiOCl material, and the proportion of each crystal face of BiOCl can be controlled by changing the content of ethanol in the precursor solvent, thereby growing towards a specific morphology.
Figure 2 is an SEM (scanning electron microscope) picture of the synthesized BiOCl material showing that the synthesized BiOCl material is sheet-like in structure, and that varying the composition of the solvent in the precursor can vary the size and thickness of the BiOCl sheet.
FIG. 3 shows that the BiOCl adsorbent obtained in examples 1-3 has a space velocity of 3000 ml.g in a mixed gas containing 5000 ppm hydrogen sulfide and 2500 ppm oxygen-1•h-1The adsorption performance of hydrogen sulfide gas at the flow rate of (1). From the figure, we can see that when the precursor solvent contains 35mL of absolute ethanol, the synthesized BiOCl has the best adsorption performance on hydrogen sulfide, and the breakthrough time of the hydrogen sulfide can reach 5.5 hours.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (3)

1. The application of the BiOCl adsorbent in room temperature adsorption of hydrogen sulfide gas is characterized in that: bismuth chloride is used as a precursor, and the BiOCl adsorbent is synthesized in one step through solvothermal method, and the specific preparation method comprises the following steps:
1) adding absolute ethyl alcohol and sodium hydroxide into deionized water;
2) adding bismuth chloride into the mixed solution of the step 1), and stirring for 30 minutes;
3) transferring the mixed solution obtained in the step 2) to a reaction kettle for high-temperature reaction;
4) after the reaction kettle is cooled to room temperature, centrifuging, washing and collecting a sample.
2. Use according to claim 1, characterized in that: the volume ratio of the absolute ethyl alcohol to the deionized water is 5: 60 or 35: 30 or 60: 5; the molar ratio of sodium hydroxide to bismuth chloride was 1 to 0.5.
3. Use according to claim 1, characterized in that: the high-temperature reaction in the step 3) is specifically as follows: the reaction was carried out at 160 ℃ for 24 hours.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102512949A (en) * 2011-12-22 2012-06-27 中山大学 Method for treating exhaust gases by utilizing wet polyphase visible light catalytic oxidation
CN104014352A (en) * 2014-05-14 2014-09-03 太原理工大学 Multivariate controllable synthesis method of BiOCl photocatalyst
CN105457662A (en) * 2015-12-24 2016-04-06 江苏大学 3D ball-flower-structured BiOCl-ZnFe2O4 composite photocatalysis material and preparation method thereof
CN107866238A (en) * 2017-11-28 2018-04-03 江苏师范大学 A kind of BiOCl TiO2/Sb2S3The preparation method of composite photo-catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102512949A (en) * 2011-12-22 2012-06-27 中山大学 Method for treating exhaust gases by utilizing wet polyphase visible light catalytic oxidation
CN104014352A (en) * 2014-05-14 2014-09-03 太原理工大学 Multivariate controllable synthesis method of BiOCl photocatalyst
CN105457662A (en) * 2015-12-24 2016-04-06 江苏大学 3D ball-flower-structured BiOCl-ZnFe2O4 composite photocatalysis material and preparation method thereof
CN107866238A (en) * 2017-11-28 2018-04-03 江苏师范大学 A kind of BiOCl TiO2/Sb2S3The preparation method of composite photo-catalyst

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Microwave Synthesis of Hierarchical BiOCl Microspheres as a Green Adsorbent for the pH Dependent Adsorption of Methylene Blue;Xiao Xin等;《Journal of Nanoscience and Nanotechnology》;20161201;第16卷;摘要 *
The Inhibitory Effect of Bismuth Oxychloride in Halithosis Caused by Volatile Sulfur Compounds;Wang Pao-Li等;《Journal of Hard Tissue Biology》;20120731;第21卷;全文 *

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