CN111333037A - System and method for preparing high-purity hydrogen sulfide gas - Google Patents

System and method for preparing high-purity hydrogen sulfide gas Download PDF

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Publication number
CN111333037A
CN111333037A CN202010297230.4A CN202010297230A CN111333037A CN 111333037 A CN111333037 A CN 111333037A CN 202010297230 A CN202010297230 A CN 202010297230A CN 111333037 A CN111333037 A CN 111333037A
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hydrogen sulfide
activated carbon
adsorber
silica gel
purity
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CN111333037B (en
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赵毅
计燕秋
刘颖
冯凯
赵趫
王天源
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Dalian Kelide Optoelectronic Mat Co ltd
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Dalian Kelide Optoelectronic Mat Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/16—Hydrogen sulfides
    • C01B17/168—Purification
    • 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
    • B01D53/04—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 with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/80—Water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

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

Abstract

The invention discloses a system and a method for preparing hydrogen sulfide gas with 99.99 percent of purity, which can remove impurities such as propylene, water and the like which are difficult to remove by rectification from hydrogen sulfide with 99.5 percent of purity through the treatment of an adsorbent and a constant-temperature pressure swing adsorption technology, thereby obtaining high-purity liquid hydrogen sulfide with 99.99 percent of purity. The high-purity hydrogen sulfide is an important chemical raw material, is obtained by further purifying on the basis of industrial hydrogen sulfide, has the purity of over 99.99 percent, and is mainly applied to the industries of national defense chemical industry, electronic semiconductors and the like.

Description

System and method for preparing high-purity hydrogen sulfide gas
Technical Field
The invention relates to a gas purification system and a method, in particular to a preparation method of 4N (99.99%) purity hydrogen sulfide gas, which is simple in process operation, low in cost and capable of realizing industrial production.
Background
At present, hydrogen sulfide gas continues to play an important role in national defense chemical industry, electric discharge light and optical conductor, and is also rapidly developed in semiconductor industry and photovoltaic in recent years.
At present, a plurality of methods for producing and purifying hydrogen sulfide gas exist, and Chinese patent No. CN108392948A indicates that 99.5% hydrogen sulfide products are obtained by adsorbing methanol washing acid gas through 6-level pressure change and adopting different molecular sieves such as alumina, silica gel, zeolite, activated carbon and the like to adsorb gas phase impurities.
Chinese patent application No. CN201511001246.1 indicates that the product with content of more than 99% can be obtained by using methanol to wash acid gas as raw material and carrying out concentration, flash evaporation and rectification.
Chinese patent application No. CN201320831012.X shows that the methanol-washed acid gas can be subjected to flash evaporation, regeneration, concentration and rectification to obtain a product with the content of more than 99.5 percent.
At present, the domestic purification of hydrogen sulfide gas firstly cools acid gas, and the acid gas is introduced into a rectifying tower for rectification after passing through a precision filter to obtain a hydrogen sulfide product with the content of more than 99.5 percent. The rectification mainly utilizes the difference of the boiling points of various volatile substances for separation, but the boiling point of propylene is-47.4 ℃ and the boiling point of hydrogen sulfide is-60.4 ℃, so the rectification is difficult to separate, and the purity of the hydrogen sulfide gas obtained by the general rectification can only reach 99.5 percent.
Disclosure of Invention
The invention aims to further improve the quality of hydrogen sulfide products and provides a preparation system and a preparation method of 4N (99.99%) hydrogen sulfide gas, which are simple in process operation, low in cost and capable of realizing industrialization.
The technical scheme of the invention is that,
the invention provides a system for preparing 4N-purity hydrogen sulfide gas, which comprises the following components in sequential connection: industrial hydrogen sulfide steel cylinders, buffer tanks, flow meters, activated carbon adsorbers, silica gel adsorbers, and collection steel cylinders with cold sources;
the activated carbon adsorbers are 2 activated carbon adsorbers connected in series; the activated carbon adsorber contains acidified and oxidized fruit shell activated carbon;
the silica gel adsorber is 2 silica gel adsorbers connected in series.
And pipelines containing constant-temperature water are arranged outside the activated carbon adsorber and the silica gel adsorber.
The invention provides a method for preparing 4N-purity hydrogen sulfide gas, which adopts the system and comprises the steps of gasifying 99.5% liquid hydrogen sulfide, sequentially performing constant-temperature adsorption on the gasified liquid hydrogen sulfide by modified activated carbon and drying the gasified liquid hydrogen sulfide by silica gel, and collecting a product with the purity of 4N.
The acidification and oxidation treatment is to immerse DV-11 type coconut shell activated carbon into dilute nitric acid (mass fraction is 16-20%) for 2 hours, and then dry the activated carbon at 100-110 ℃.
Preferably, the adsorption pressure is 1.0 to 1.2MPa, preferably 1.1 to 1.2 MPa.
Preferably, the adsorption temperature is 10-30 ℃, and preferably 10-15 ℃. Higher pressures and lower temperatures result in increased amounts of exhaust gases. The cold source and the heat source are water, and the temperature is kept by a refrigerator or a mold temperature controller.
The regeneration method of the adsorber is a constant-temperature regeneration method, and the regeneration temperature is preferably 125-135 ℃, and more preferably 130-135 ℃. The regeneration pressure is normal pressure, and the regeneration time is preferably 4-6 h, more preferably 6 h.
According to the invention, acidified and modified shell activated carbon is used as an adsorbent, so that the adsorption quantity of conventional activated carbon to hydrogen sulfide is reduced, propylene in hydrogen sulfide gas can be deeply removed, and water in hydrogen sulfide is removed by using silica gel, so that the purity of the product reaches 4N level.
Drawings
FIG. 1 is a schematic diagram of the system for producing 4N-purity hydrogen sulfide gas according to the present invention;
in the figure, 1, industrial hydrogen sulfide steel cylinder; 2. a buffer tank; 3. a flow meter; 4. an activated carbon adsorber I; 5. an active carbon adsorber II; 6. a silica gel adsorber I; 7. a silica gel adsorber II; 8; a collecting steel cylinder with a cold source.
Detailed Description
DV-11 type coconut shell activated carbon is available from Kyoto Jindawei activated carbon technology Co.
Example 1
The invention will be further described in the following with reference to specific embodiments in conjunction with the accompanying drawings, see fig. 1: the high-purity hydrogen sulfide purifying equipment comprises an industrial hydrogen sulfide steel cylinder, a buffer tank, four adsorption beds (the four adsorption beds are connected into a multistage adsorption bed group which is connected in series through pipelines and valves), and pipelines containing constant-temperature water are arranged outside the adsorption beds.
The method specifically comprises the following steps: a system for preparing 4N hydrogen sulfide gas with purity comprises an industrial hydrogen sulfide steel cylinder, a buffer tank, a flowmeter, an activated carbon adsorber, a silica gel adsorber and a collection steel cylinder with a cold source which are connected in sequence;
the activated carbon adsorbers are 2 activated carbon adsorbers connected in series; the activated carbon adsorber contains acidified and oxidized fruit shell activated carbon;
the silica gel adsorber is 2 silica gel adsorbers connected in series.
According to the invention, gas impurities such as propylene and the like are removed by acidifying modified activated carbon, but hydrogen sulfide has unique physicochemical property and poor stability, and can generate strong adsorption heat after being adsorbed by activated carbon, which brings great difficulty to the purification of gas.
In the invention, the adsorption pressure of all adsorbers is preferably 1.0-1.2 MPa, more preferably 1.1-1.2 MPa, and the adsorption temperature is preferably 10-30 ℃, more preferably 10-15 ℃. But high pressures and low temperatures cause an increase in the amount of exhaust gases.
In the invention, the regeneration method of the adsorber is a constant-temperature regeneration method, and the regeneration temperature is preferably 125-135 ℃, and more preferably 130-135 ℃. The regeneration pressure is normal pressure, and the regeneration time is preferably 4-6 h, more preferably 6 h.
The embodiment is specifically described as follows, hydrogen sulfide gas enters through a buffer tank in sequence, and activated carbon is absorbedAn adsorber I4, an activated carbon adsorber II 5, a silica gel adsorber I6 and a silica gel adsorber II 7, wherein the flow of an adsorption bed in the adsorber is 0.5-1 m3The temperature of each adsorber is kept to be 25-30 ℃ by using temperature control water; to an adsorber pressure of 1.0 MPa. The regeneration temperature of the adsorber is 135 ℃, the pressure is normal pressure, and the regeneration time is 6 hours. And vacuumizing the adsorber after regeneration is finished.
The analysis result of the hydrogen sulfide raw material was H2O content 22.1ppm, gas phase analysis N2Content 2.7ppm, O2Content 0.6ppm, CO211.3ppm, 0.1ppm CO, 1.0ppm propane, 5.8ppm COS, C3H6Content 1655 ppm. Collecting the product by using a steel cylinder; the collected gas was analyzed by moisture meter H2O content 15.3ppm, N analysis by gas chromatography2Content 3.1ppm, O2Content 0.7ppm, CO28.3ppm, 0.1ppm CO, 0.3ppm propane, 4.5ppm COS, C3H6The content was 55.0 ppm.
Example 2
A system for preparing 4N hydrogen sulfide gas with purity comprises an industrial hydrogen sulfide steel cylinder, a buffer tank, a flowmeter, an activated carbon adsorber, a silica gel adsorber and a collection steel cylinder with a cold source which are connected in sequence;
the activated carbon adsorbers are 2 activated carbon adsorbers connected in series; the activated carbon adsorber contains acidified and oxidized fruit shell activated carbon; the acidification and oxidation treatment is to immerse DV-11 type coconut shell activated carbon into dilute nitric acid (mass fraction is 16-20%) for 2 hours, and then dry the activated carbon at 100-110 ℃.
The silica gel adsorber is 2 silica gel adsorbers connected in series.
The hydrogen sulfide gas enters an active carbon adsorber I4, an active carbon adsorber II 5, a silica gel adsorber I6 and a silica gel adsorber II 7 in sequence through a buffer tank, and the flow in the adsorbers is 0.5-1 m3The temperature of the adsorber is kept to be 10-15 ℃ by using temperature-controlled water; to an adsorber pressure of 1.2 MPa.
The hydrogen sulfide gas raw material is from Shandong Yifeng biochemical environmental protection limited company, and the product specification is 99.5%. H2O content 150ppm, N2Content 13.3ppm, O2Content 3.3ppm, CO29.3ppm, 0.1ppm CO, 0.2ppm propane, 4.7ppm COS, C3H6The content was 1600 ppm.
The collected gas was analyzed by moisture meter H2O content 15.3ppm, N analysis by gas chromatography2Content 3.3ppm, O2Content 0.9ppm, CO27.3ppm, 0.1ppm CO, 0.2ppm propane, 4.0ppm COS, C3H6The content was 35.0 ppm.

Claims (7)

1. A system for preparing 4N-purity hydrogen sulfide gas comprises the following components connected in sequence: industrial hydrogen sulfide steel cylinders, buffer tanks, flow meters, activated carbon adsorbers, silica gel adsorbers, and collection steel cylinders with cold sources;
the activated carbon adsorbers are 2 activated carbon adsorbers connected in series; the activated carbon adsorber contains acidified and oxidized fruit shell activated carbon;
the silica gel adsorber is 2 silica gel adsorbers connected in series.
2. The system of claim 1, wherein: and pipelines containing constant-temperature water are arranged outside the activated carbon adsorber and the silica gel adsorber.
3. The system of claim 1, wherein: the acidification and oxidation treatment is to soak DV-11 type coconut shell activated carbon into dilute nitric acid with the mass fraction of 16-20% for 2 hours, and then to dry the activated carbon at the temperature of 100-110 ℃.
4. A method for preparing 4N-purity hydrogen sulfide gas is characterized by comprising the following steps: by using the system of any one of claims 1 to 3, the product with a purity of 4N can be collected after gasifying hydrogen sulfide and passing through an activated carbon adsorber and a silica gel adsorber in sequence for modified activated carbon adsorption and silica gel drying.
5. The method for producing 4N-purity hydrogen sulfide gas according to claim 4, characterized in that: the pressure of the gas passing through the activated carbon adsorber and the silica gel adsorber is 1.0-1.2 MPa, and the adsorption temperature is 10-30 ℃.
6. The method for producing 4N-purity hydrogen sulfide gas according to claim 4, wherein: the active carbon adsorption is a constant temperature adsorption method, and the active carbon regeneration method is a constant temperature regeneration method.
7. The method for producing 4N-purity hydrogen sulfide gas according to claim 6, wherein: the regeneration temperature is 125-135 ℃; the regeneration pressure is normal pressure, and the regeneration time is 4-6 h.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111689476A (en) * 2020-06-30 2020-09-22 太和气体（荆州）有限公司 Preparation process of high-purity hydrogen sulfide

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GB481850A (en) * 1936-08-24 1938-03-18 Carbo Norit Union Verwaltungs Process for extracting valuable substances from synthetic process gases
GB966404A (en) * 1961-03-17 1964-08-12 Metallgesellschaft Ag Process for separating hydrogen sulphide and carbon disulphide from impure air containing them
CN85104605A (en) * 1984-01-30 1986-12-10 环球油品公司 From gas, remove the method for oxysulfide
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GB481850A (en) * 1936-08-24 1938-03-18 Carbo Norit Union Verwaltungs Process for extracting valuable substances from synthetic process gases
GB966404A (en) * 1961-03-17 1964-08-12 Metallgesellschaft Ag Process for separating hydrogen sulphide and carbon disulphide from impure air containing them
CN85104605A (en) * 1984-01-30 1986-12-10 环球油品公司 From gas, remove the method for oxysulfide
CN101262926A (en) * 2005-08-08 2008-09-10 琳德股份有限公司 Method and apparatus for purifying a gas
CN101898071A (en) * 2009-05-25 2010-12-01 中国石油化工股份有限公司 Method for treating sulfur- and hydrocarbon-containing foul waste gas
CN103079682A (en) * 2010-07-15 2013-05-01 夸德罗吉动力系统公司 Integrated biogas cleaning system to remove water, siloxanes, sulfur, oxygen, chlorides and volatile organic compounds
CN102068967A (en) * 2010-12-14 2011-05-25 浙江大学 Supported polypropylene imine material and preparation method and application thereof
CN105967149A (en) * 2016-07-07 2016-09-28 云南煤业能源股份有限公司 Method for producing high-purity H2S from acid vapor
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CN212024774U (en) * 2020-04-15 2020-11-27 大连科利德光电子材料有限公司 System for preparing 4N-purity hydrogen sulfide gas

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111689476A (en) * 2020-06-30 2020-09-22 太和气体（荆州）有限公司 Preparation process of high-purity hydrogen sulfide
CN111689476B (en) * 2020-06-30 2021-09-14 太和气体（荆州）有限公司 Preparation process of high-purity hydrogen sulfide

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