CN114470885B - Sulfur flocculation precipitant and preparation method and application thereof - Google Patents

Sulfur flocculation precipitant and preparation method and application thereof Download PDF

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CN114470885B
CN114470885B CN202210192341.8A CN202210192341A CN114470885B CN 114470885 B CN114470885 B CN 114470885B CN 202210192341 A CN202210192341 A CN 202210192341A CN 114470885 B CN114470885 B CN 114470885B
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sulfur
flocculation
precipitant
tween
desulfurization
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CN114470885A (en
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李金环
穆廷桢
朱红彬
邢建民
刘海丽
杨茂华
张硕琳
王伟健
傅莉
董金婷
张宁宁
张建
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China Petrochemical Corp
Sinopec Oilfield Service Corp
Sinopec Petroleum Engineering Corp
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Sinopec Oilfield Service Corp
Sinopec Petroleum Engineering Corp
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/48Sulfur compounds
    • B01D53/52Hydrogen sulfide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D21/00Separation of suspended solid particles from liquids by sedimentation
    • B01D21/01Separation of suspended solid particles from liquids by sedimentation using flocculating agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/73After-treatment of removed components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77Liquid phase processes
    • B01D53/78Liquid phase processes with gas-liquid contact
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/84Biological processes
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00Sulfur; Compounds thereof
    • C01B17/02Preparation of sulfur; Purification
    • C01B17/0205Separation of sulfur from liquids, e.g. by coalescence
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/95Specific microorganisms
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biomedical Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Molecular Biology (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

The invention relates to the technical field of desulfurization, and provides a sulfur flocculation precipitant, and a preparation method and application thereof. The sulfur flocculation precipitant provided by the invention comprises the following components in percentage by mass: 6-12% of glycolipid type biosurfactant, 0-1.5% of tween type surfactant, 0.1-1% of low carbon alcohol and the balance of water. The sulfur flocculation precipitant provided by the invention has good wettability and strong bridging effect, and the higher wettability can change the hydrophobicity of sulfur, so that the sulfur forms a wetting body and the adhesiveness is reduced; the better bridging effect can promote the wetted sulfur to quickly agglomerate to form hydrophilic large-particle sulfur, and accelerate the sedimentation of the sulfur, thereby effectively preventing the adhesion and blockage of the sulfur. The results of the examples show that the sulfur flocculation precipitant obtained by the invention can promote the rapid aggregation and precipitation of sulfur particles, the precipitation time is as low as 18 seconds, and the particle size of the generated sulfur particles is as high as 150 mu m.

Description

Sulfur flocculation precipitant and preparation method and application thereof
Technical Field
The invention relates to the technical field of desulfurization, in particular to a sulfur flocculation precipitant and a preparation method and application thereof.
Background
Wet alkaline desulfurization refers to a process in which an aqueous alkali solution is used to absorb hydrogen sulfide and directly convert the hydrogen sulfide into elemental sulfur. The particle size of sulfur particles generated in the desulfurization process is small, agglomeration and precipitation are difficult, so that the sulfur can float upwards to be mainly, the sulfur floats on the surface of the desulfurization liquid, a large amount of sulfur foam is easy to form, the production is influenced, meanwhile, the sulfur is easy to adhere to the pipe wall, the risk of pipe sulfur blockage is large, and equipment needs to be cleaned and overhauled frequently. Therefore, whether the sulfur can be timely treated becomes the key whether the process can continuously and stably run.
Patent CN112457895a provides a sulfur precipitant, which comprises N-acyl amino acid type surfactant, polyethylene glycol type nonionic surfactant, organosilicon surfactant, low carbon alcohol and water. The sulfur precipitant can promote the aggregation of sulfur to be reduced, thereby avoiding the occurrence of sulfur blockage to a certain extent. However, the sulfur precipitant still forms smaller sulfur particles, and the rate of sulfur precipitation needs to be further improved.
Disclosure of Invention
The invention aims to provide a sulfur flocculation precipitant, and a preparation method and application thereof. The sulfur flocculation precipitant provided by the invention can promote the rapid agglomeration of sulfur, and the formed sulfur aggregation particles have large particle size and higher precipitation speed, so that the adhesion and blockage of sulfur can be more effectively prevented.
In order to achieve the above object, the present invention provides the following technical solutions:
the sulfur flocculation precipitant comprises the following components in percentage by mass: 6-12% of glycolipid type biosurfactant, 0-1.5% of tween type surfactant, 0.1-1% of low carbon alcohol and the balance of water.
Preferably, the glycolipid type biosurfactant comprises one or more of rhamnolipids, sophorolipids, trehalose lipids and mannose lipids.
Preferably, the tween-type surfactant comprises one or more of tween-40, tween-60 and tween-80.
Preferably, the lower alcohol has 2 to 6 carbon atoms.
Preferably, the low carbon alcohol comprises one or more of ethylene glycol, ethanol, isopropanol and propanol.
The invention also provides a preparation method of the sulfur flocculation precipitant, which comprises the following steps:
mixing glycolipid type biosurfactant, tween type surfactant, low carbon alcohol and water to obtain sulfur flocculation precipitant.
Preferably, the mixing method is as follows: the glycolipid biosurfactant and water are mixed first, and then tween-type surfactant and low-carbon alcohol are added in sequence.
The invention also provides application of the sulfur flocculation precipitant in wet alkaline desulfurization or prepared by the preparation method in the scheme.
Preferably, the wet alkaline desulfurization comprises complex iron desulfurization or microbial desulfurization.
Preferably, the working pH value range of the sulfur flocculation precipitant is 7.0-11.0, and the working temperature range is 10-50 ℃.
The invention provides a sulfur flocculation precipitant, which comprises the following components in percentage by mass: 6-12% of glycolipid type biosurfactant, 0-1.5% of tween type surfactant, 0.1-1% of low carbon alcohol and the balance of water. In the present invention, glycolipid biosurfactants are a class of amphoteric compounds with surface activity produced by organisms such as animals, plants, microorganisms, etc., and have more remarkable properties of lowering surface tension and interfacial tension than chemical surfactants; the Tween surfactant is a nonionic surfactant with strong hydrophilicity, has stable performance and good wetting and foaming functions; and the low-carbon alcohol can further improve the surface activity of the system. The sulfur flocculation precipitant provided by the invention has better wettability and stronger bridging effect, and the higher wettability can change the hydrophobicity of sulfur, so that the sulfur forms a wetting body and the adhesiveness is reduced; the better bridging effect can promote the wetted sulfur to be quickly agglomerated to form sulfur particles with larger particle size, and the sedimentation speed of the sulfur is accelerated, so that the adhesion and blockage of the sulfur are effectively prevented.
The invention also provides a preparation method of the sulfur flocculation precipitant, which is simple in steps and easy to operate.
The invention also provides application of the sulfur flocculation precipitant in wet alkaline desulfurization. The sulfur flocculation precipitant provided by the invention has good aggregation precipitation performance on sulfur, can effectively reduce the generation of sulfur foam by applying the sulfur flocculation precipitant to a wet alkaline desulfurization process, ensures that sulfur microparticles are quickly aggregated and precipitated, effectively avoids the problems of floating up and blocking sulfur, and ensures the desulfurization efficiency and the stable operation of a system. The example results show that the sulfur flocculation precipitant obtained by the invention is applied to complex iron desulfurization, the precipitation time of sulfur is as low as 18s, and the particle size of the produced sulfur particles is as high as 150 mu m.
Drawings
FIG. 1 is a graph showing the particle size distribution of elemental sulfur at a sulfur flocculation precipitant concentration of 0 in example 1;
FIG. 2 is a graph showing the particle size distribution of elemental sulfur at a concentration of 8mg/L for the sulfur flocculation precipitant of example 1;
FIG. 3 is a graph showing the particle size distribution of elemental sulfur at a sulfur flocculation precipitant concentration of 16mg/L in example 1;
FIG. 4 is a graph showing the particle size distribution of elemental sulfur at a concentration of 24mg/L for the sulfur flocculation precipitant of example 1;
FIG. 5 is a graph showing the particle size distribution of elemental sulfur at a concentration of 32mg/L for the sulfur flocculation precipitant of example 1;
FIG. 6 is a graph showing the sedimentation effect of sulfur after the addition of the sulfur flocculation precipitant in example 1;
FIG. 7 is a photomicrograph of sulfur particles formed at sulfur flocculation precipitant concentrations of 0mg/L, 24mg/L and 32mg/L in example 1.
Detailed Description
The invention provides a sulfur flocculation precipitant, which comprises the following components in percentage by mass: 6-12% of glycolipid type biosurfactant, 0-1.5% of tween type surfactant, 0.1-1% of low carbon alcohol and the balance of water.
All the components described in the present invention are commercially available products unless otherwise specified.
The sulfur flocculation precipitant provided by the invention comprises 6-12% of glycolipid type biosurfactant, preferably 8-10%, and more preferably 8.5-9% by mass. In the present invention, the glycolipid type biosurfactant preferably includes one or more of rhamnolipids, sophorolipids, trehalose lipids and mannose lipids; in a specific embodiment of the invention, the glycolipid type biosurfactants are preferably rhamnolipids and sophorolipids.
The sulfur flocculation precipitant provided by the invention comprises 0-1.5% of Tween-type surfactant, preferably 0.5-1.3%, and more preferably 0.8-1.0% by mass. In the present invention, the tween-type surfactant is preferably one or more of tween-40, tween-60, tween-80, etc. In a specific embodiment of the present invention, the tween-type surfactant is preferably tween-80.
The sulfur flocculation precipitant provided by the invention comprises 0.1-1% of low carbon alcohol, preferably 0.2-0.8%, and more preferably 0.3-0.5% by mass. In the present invention, the carbon number of the lower alcohol is preferably 2 to 6; the lower alcohol preferably comprises one or more of ethylene glycol, ethanol, isopropanol and propanol.
In the invention, the sulfur flocculation precipitant also comprises the balance of water. The water is not particularly limited in the present invention, and water well known in the art may be used.
The invention also provides a preparation method of the sulfur flocculation precipitant, which comprises the following steps:
mixing glycolipid type biosurfactant, tween type surfactant, low carbon alcohol and water to obtain sulfur flocculation precipitant.
In the present invention, the mixing is preferably: the glycolipid biosurfactant and water are mixed first, and then tween-type surfactant and low-carbon alcohol are added in sequence.
The specific method of operation of the mixing is not particularly limited, and the components are uniformly mixed, such as stirring, by methods well known to those skilled in the art.
The invention also provides application of the sulfur flocculation precipitant in wet alkaline desulfurization.
In the present invention, the wet alkaline desulfurization preferably includes complex iron desulfurization or microbial desulfurization; the specific method of the application is preferably as follows: adding the sulfur flocculation precipitant into sulfur-containing desulfurization liquid to enable the sulfur to be aggregated and precipitated; in a specific embodiment of the invention, the desulfurization liquid is specifically a desulfurization liquid in a regeneration tower of a complex iron desulfurization device; in the present invention, the amount of the sulfur flocculation precipitant is preferably 0.5 to 2.0% by weight, more preferably 1.0 to 1.5% by weight, based on the weight of sulfur produced in the desulfurization system; the working pH value range of the sulfur flocculation precipitant is preferably 7.0-11.0, more preferably 8-10, and the working temperature range of the sulfur flocculation precipitant is preferably 10-50 ℃, more preferably 20-40 ℃.
The following is a detailed description of the present invention with reference to examples, but they should not be construed as limiting the scope of the invention.
Example 1
Preparing a sulfur flocculation precipitant: the sulfur flocculation precipitant is prepared from rhamnolipid, tween-80, isopropyl alcohol and water, and the preparation method comprises the following steps: mixing rhamnolipid with water, then successively adding tween-80 and isopropanol, and stirring uniformly to obtain the sulfur flocculation precipitant. The amounts of the individual components are shown in Table 1.
TABLE 1 sulphur flocculation precipitant composition and dosage
Application example 1
Taking the regenerated desulfurization liquid (the content of sulfur is 1.6g/L through measurement) in a regeneration tower of complex iron desulfurization equipment, then adding a certain amount of sulfur flocculation precipitants into the desulfurization liquid, wherein the dosage of the sulfur flocculation precipitants in the desulfurization liquid is controlled to be 0, 8mg/L, 16mg/L, 24mg/L and 32mg/L respectively, examining the influence of the sulfur flocculation precipitants on the size of sulfur particles, and measuring the particle size distribution of sulfur precipitates in each experimental group, wherein the obtained results are shown in figures 1-6, wherein figures 1-5 are respectively particle size distribution diagrams of elemental sulfur when the concentration of the sulfur flocculation precipitants is 0, 8mg/L, 16mg/L, 24mg/L and 32mg/L, and figure 6 is the influence of the dosage of the sulfur flocculation precipitants on the particle size distribution of elemental sulfur.
According to the figures 1-6, the sulfur flocculation precipitant is beneficial to the aggregation of elemental sulfur, sulfur particles with larger particle sizes can be formed, and the median value of the particle size of the sulfur particles is increased from 22 mu m to 150 mu m along with the increase of the dosage of the sulfur flocculation precipitant from 0 to 24mg/L, so that the sulfur can be aggregated rapidly, and the large-particle sulfur is easier to sink, thereby avoiding the temperature of floating and blocking the sulfur.
A photomicrograph of the corresponding sulfur particles obtained at 0mg/L, 24mg/L and 32mg/L of sulfur flocculation precipitant is shown in FIG. 7. As can be seen from FIG. 7, sulfur was in an adherent state with less particle size when the sulfur flocculation precipitant was not added, whereas the sulfur particle size produced was larger in the experimental group with the sulfur flocculation precipitant added.
The amounts of the sulfur flocculation precipitants in the desulfurizing liquid were controlled to 0, 8mg/L, 16mg/L, 24mg/L, 32mg/L, 40mg/L, 50mg/L, 60mg/L and 70mg/L, respectively, and the precipitation times of sulfur were recorded, and the obtained results are shown in Table 2.
TABLE 2 sulphur precipitation time vs. precipitant usage
The results in Table 2 show that as the amount of sulfur flocculation precipitant increases, the precipitation time of sulfur is gradually shortened, wherein when the amount of sulfur flocculation precipitant is 24mg/L, the precipitation time of sulfur is only 18s, the precipitation time is greatly shortened, and when the amount of sulfur flocculation precipitant continues to increase, the precipitation time of sulfur is slightly increased, but still the precipitation speed is faster than when no sulfur flocculation precipitant is added. As can be seen from the results in Table 2, the precipitation time of sulfur slightly increases as the amount of the precipitant increases from 24mg/L to 32mg/L, so that it can be determined that the optimum amount of the sulfur flocculation precipitant is 16 to 32mg/L.
Example 2
Preparing a sulfur flocculation precipitant: the sulfur flocculation precipitant is prepared by isopropanol, mannose ester, tween-60 and water, and the preparation method comprises the following steps: firstly, mixing mannose ester with water, then adding tween-60 and isopropanol successively, stirring to form uniform sulfur flocculation precipitant. The amounts of the individual components are shown in Table 3.
TABLE 3 sulphur flocculation precipitant composition and dosage
Composition of the composition Dosage of
Mannose lipid 90g
Tween-60 10g
Isopropyl alcohol 5g
Water and its preparation method 895g
Application example 2
Taking the regenerated desulfurization solution (the content of sulfur is 1.6g/L through measurement) in a regeneration tower of the complex iron desulfurization device, and then adding a certain amount of sulfur flocculation precipitant into the desulfurization solution, wherein the dosage of the sulfur flocculation precipitant in the desulfurization solution is controlled to be 0, 8mg/L, 16mg/L, 24mg/L, 32mg/L and 40mg/L respectively, and observing the relationship between the sedimentation time and the dosage of the sedimentation amount, wherein the obtained results are shown in Table 4.
TABLE 4 sulphur precipitation time vs. precipitant usage
As can be seen from the results in Table 4, similar to application example 1, as the amount of the sulfur flocculation precipitant increases, the precipitation time of sulfur decreases first and then increases slightly, but as a whole, the precipitation speed is faster than that of the experimental group without the sulfur flocculation precipitant, wherein the sulfur sedimentation time is shorter when the addition amount of the sulfur flocculation precipitant is 16 to 32mg/L.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (8)

1. The sulfur flocculation precipitant is characterized by comprising the following components in percentage by mass: 6-12% of glycolipid type biosurfactant, 0.5-1.5% of tween type surfactant, 0.1-1% of low carbon alcohol and the balance of water; the glycolipid type biosurfactant comprises one or more of rhamnolipid, sophorolipid, trehalose lipid and mannose lipid; the Tween-type surfactant comprises one or more of Tween-40, tween-60 and Tween-80.
2. The sulfur flocculation precipitant of claim 1, wherein the lower alcohol has 2 to 6 carbon atoms.
3. The sulfur flocculation precipitant of claim 1 or 2, wherein the lower alcohol comprises one or more of ethylene glycol, ethanol, isopropanol, and propanol.
4. A method for preparing the sulfur flocculation precipitant as claimed in any one of claims 1 to 3, comprising the steps of:
mixing glycolipid type biosurfactant, tween type surfactant, low carbon alcohol and water to obtain sulfur flocculation precipitant.
5. The method of claim 4, wherein the mixing is performed by: the glycolipid biosurfactant and water are mixed first, and then tween-type surfactant and low-carbon alcohol are added in sequence.
6. Use of the sulfur flocculation precipitant of any one of claims 1 to 3 or prepared by the preparation method of claim 4 or 5 in wet alkaline desulfurization.
7. The use according to claim 6, wherein the wet alkaline desulfurization comprises complex iron desulfurization or microbial desulfurization.
8. The use according to claim 6 or 7, wherein the sulphur flocculation precipitant has an operating pH in the range of 7.0 to 11.0 and an operating temperature in the range of 10 to 50 ℃.
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CN105084319A (en) * 2014-04-29 2015-11-25 北京化工大学 Separating agent for separating sulfur from sulfur-containing system and method for separating sulfur
CN105712494A (en) * 2016-04-14 2016-06-29 太原理工大学 Method for coagulation treatment of mining industry wastewater by means of microbial flocculant and surfactant
CN112457895A (en) * 2020-10-27 2021-03-09 中国石油化工集团有限公司 Sulfur precipitator, desulfurization system and application thereof

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