CN111974363A - Organic sulfur removal adsorbent, preparation method and test equipment - Google Patents

Organic sulfur removal adsorbent, preparation method and test equipment Download PDF

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Publication number
CN111974363A
CN111974363A CN202010807592.3A CN202010807592A CN111974363A CN 111974363 A CN111974363 A CN 111974363A CN 202010807592 A CN202010807592 A CN 202010807592A CN 111974363 A CN111974363 A CN 111974363A
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Prior art keywords
adsorbent
organic sulfur
polyamide
amine
drying
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CN202010807592.3A
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Chinese (zh)
Inventor
杨绪甲
朱道平
周志斌
余勇
毛松柏
陈小花
陈园园
宋丽
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • 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
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/324—Inorganic material layers containing free carbon, e.g. activated carbon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • C10L3/103—Sulfur containing contaminants
    • 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
    • B01D2257/306—Organic sulfur compounds, e.g. mercaptans

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

Abstract

The invention provides a high-efficiency organic sulfur adsorbent, which is used for removing organic sulfur in natural gas. The adsorbent consists of a polyamide-amine dendritic compound and porous active carbon. The preparation method of the adsorbent comprises the steps of preparing a solution with the concentration of more than 30% of a polyamide-amine dendritic compound, and then soaking a certain amount of porous active carbon into the prepared solution of the polyamide-amine dendritic compound, wherein the soaking temperature is controlled below 75 ℃. After a certain period of soaking balance, taking out the porous active carbon and drying, wherein the drying temperature is not higher than 130 ℃. And after drying, evaporating and escaping water in the impregnated porous activated carbon to obtain a finished adsorbent. The invention also provides test equipment for removing organic sulfur by the adsorbent, which comprises a raw material gas tank and an adsorption tank which are connected in series, wherein the adsorption tank is filled with the adsorbent. The invention has the following remarkable characteristics: high organic sulfur adsorption and removal efficiency, strong stability and the like, and meets the removal requirement of organic sulfur in natural gas.

Description

Organic sulfur removal adsorbent, preparation method and test equipment
Technical Field
The invention belongs to the field of gas purification, and particularly relates to an organic sulfur removal adsorbent, a preparation method and test equipment.
Background
Dendrimers are a class of novel macromolecules with a three-dimensional molecular structure, high degree of treeing and order. The molecular structure of the dendritic compound can be accurately controlled through molecular design, a large number of terminal functional groups capable of being modified or loaded exist outside the molecule, a hydrophobic cavity capable of wrapping the small molecular compound exists inside the molecule, and the wrapped small molecular compound can be released under certain conditions. The dendritic compound has great application prospect in the aspects of nano materials, drug release, gene transfer, catalyst carriers and the like. Polyamide-polyamide-amine (PAMAM) is a dendritic compound which is deeply researched, has the characteristics of good thermal stability, water solubility, special viscosity, surface tension and the like besides the common characteristics of the dendritic compound, and shows good application in the fields of wastewater treatment, oil exploitation, gas purification and separation and the like.
CN103509193A and CN103509193B research the preparation of the polyamidoamine dendrimer, and the 1-5 generation polyamidoamine dendrimer with high yield and high purity can be prepared by taking ethylenediamine and methyl acrylate as raw materials and carrying out Michael addition reaction and optimizing the proportion and conditions of the preparation process.
In natural gas purification processes, other than, for example, CO2、H2Besides the removal of acid gases such as S, a large amount of impurity components such as carbonyl sulfide, mercaptan and other organic sulfur compounds need to be removed. At present, the most widely used formula type alcohol amine solvent has better removal capability to acid gas in natural gas, and has certain removal effect to the removal of a small amount of organic sulfur components through formula adjustment. However, the treatment effect of natural gas containing high content of organic sulfur is not ideal, and the gas treated by alcohol amine solvent still contains high organic sulfur impurities, and the residual organic sulfur such as mercaptan and carbonyl sulfur still need to be removed by alkali washing, catalytic oxidation or catalytic hydrolysis.
Disclosure of Invention
1. The technical problem to be solved is as follows:
in the process of purifying natural gas, the most widely applied formula type alcohol amine solvent is adopted, but the treatment effect is not ideal when natural gas containing high content of organic sulfur is treated, gas treated by the alcohol amine solvent still contains high organic sulfur impurities, and residual organic sulfur such as mercaptan and carbonyl sulfur still need to be removed through alkali washing, catalytic oxidation or catalytic hydrolysis.
2. The technical scheme is as follows:
in order to solve the above problems, the present invention provides an organic sulfur removal adsorbent, which is composed of a polyamidoamine dendrimer and porous activated carbon.
The selected polyamide-amine dendritic compound can be one or two or more than two of 1-5 generation single products, wherein the purity of the single generation product is more than 99.5 percent by mass.
The selected porous activated carbon is of a sheet structure.
The invention also provides a preparation method of the organic sulfur removal adsorbent, which comprises the following steps: step S01: preparing a polyamide-amine dendritic compound solution, and then soaking a certain amount of porous active carbon into the prepared polyamide-amine dendritic compound solution; step S02: and after a certain period of soaking balance, taking out the porous activated carbon, drying, and evaporating and escaping water in the soaked porous activated carbon after drying to obtain the finished adsorbent.
The concentration of the polyamide-amine dendrimer solution is more than 30% by mass.
The temperature during the impregnation process is controlled below 75 ℃.
The drying temperature required by drying after the impregnation is controlled below 130 ℃.
The invention also provides test equipment for removing organic sulfur by the adsorbent, which comprises a raw material gas tank and an adsorption tank which are connected in series, wherein the adsorption tank is filled with the adsorbent.
The adsorption tank is internally filled with three parts, the upper part and the lower part are filled with ceramic balls, and the adsorbent is filled in the middle.
3. Has the advantages that:
the organic sulfur removal adsorbent provided by the invention has the characteristics of high organic sulfur adsorption and removal efficiency, strong stability and the like, and meets the removal requirement of organic sulfur in natural gas.
Drawings
FIG. 1 is a flow chart of the adsorbent production.
Fig. 2 is a flow chart of an experimental process for removing organic sulfur by an adsorbent.
Detailed Description
The invention is explained in detail below with reference to the figures and examples.
The invention provides an organic sulfur removal adsorbent, which consists of a polyamide-amine dendritic compound and porous activated carbon.
The preparation method of the organic sulfur removal adsorbent, as shown in fig. 2, includes the steps of S01: preparing a polyamide-amine dendritic compound solution, and then soaking a certain amount of porous active carbon into the prepared polyamide-amine dendritic compound solution; step S02: and after a certain period of soaking balance, taking out the porous activated carbon, drying, and evaporating and escaping water in the soaked porous activated carbon after drying to obtain the finished adsorbent.
The test for the removal of organic sulfur by the adsorbent,
preparation of the adsorbent: taking 500g of a single 5-generation polyamide-amine (PAMAM) dendrimer, adding water to prepare 1L of a polyamide-amine (PAMAM) dendrimer aqueous solution, wherein the concentration of the polyamide-amine dendrimer aqueous solution is more than 30% by mass, taking 0.5L of flake activated carbon with the specification size of 2mm multiplied by 0.5mm, introducing 0.5L of activated carbon into the prepared solution for immersion treatment, placing the activated carbon in a water bath with the temperature of below 75 ℃ in the immersion process, keeping the temperature for 1 hour, taking out the immersed activated carbon, placing the activated carbon in an oven for drying, and drying the activated carbon at the temperature of below 130 ℃ for 1 hour. And taking out after drying for later use.
Preparing raw material gas of organic sulfur, wherein organic sulfur components in the raw material gas are shown in table 1, and the balance is nitrogen.
Figure BDA0002629717080000031
As shown in fig. 2, the prepared raw material gas is charged into a raw material gas tank 1, an adsorbent is filled in an adsorption tank 2, three parts of the adsorbent are fully filled in the adsorbent tank, ceramic balls are filled in the upper part and the lower part, and the prepared adsorbent is arranged in the middle. The results of the examples are shown in Table 2.
Table 2 results of implementation of adsorbent organic sulfur removal
Figure BDA0002629717080000032
As can be seen from Table 2, the adsorption rate of the adsorbent of the invention for carbonyl sulfide reaches 95%, the adsorption rate for methyl mercaptan reaches 94%, and the adsorption rate for ethyl mercaptan reaches 95%.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (9)

1. An organic sulfur removal adsorbent, characterized in that: consists of polyamide-amine (PAMAM) dendritic compound and porous active carbon.
2. The organic sulfur removal adsorbent of claim 1, wherein: the selected polyamide-amine (PAMAM) dendritic compound can be one or two or more than two of 1-5 generation single products, wherein the purity of the single generation product is more than 99.5 percent by mass.
3. The organic sulfur removal adsorbent of claim 1, wherein: the selected porous activated carbon is of a sheet structure.
4. The method for preparing the organic sulfur removal adsorbent according to any one of claims 1 to 3, comprising the steps of: step S01: preparing a polyamide-amine (PAMAM) dendrimer solution, and then soaking a certain amount of porous activated carbon into the prepared polyamide-amine (PAMAM) dendrimer solution; step S02: and after a certain period of soaking balance, taking out the porous activated carbon, drying, and evaporating and escaping water in the soaked porous activated carbon after drying to obtain the finished adsorbent.
5. The method of claim 4, wherein: the concentration of the polyamide-amine (PAMAM) dendrimer solution is more than 30% by mass.
6. The method of claim 4, wherein: the temperature during the impregnation process is controlled below 75 ℃.
7. The method of claim 4, wherein: the drying temperature required by drying after the impregnation is controlled below 130 ℃.
8. A test apparatus for removing organic sulfur by using the adsorbent according to any one of claims 1 to 7, wherein: the device comprises a raw material gas tank (1) and an adsorption tank (2) which are connected in series, wherein the adsorption tank (2) is filled with an adsorbent.
9. The sorbent organosulfur removal test apparatus of claim 8, wherein: the adsorption tank (2) is internally filled with three parts, the upper part and the lower part are filled with ceramic balls, and the adsorbent is filled in the middle.
CN202010807592.3A 2020-08-12 2020-08-12 Organic sulfur removal adsorbent, preparation method and test equipment Pending CN111974363A (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005262023A (en) * 2004-03-16 2005-09-29 Aisin Seiki Co Ltd Aldehydes removal material
US20070000385A1 (en) * 2005-07-01 2007-01-04 Stouffer Mark R Adsorbents for removing H2S, other odor causing compounds, and acid gases from gas streams and methods for producing and using these adsorbents
CN102580473A (en) * 2012-03-20 2012-07-18 中国石油化工股份有限公司 Absorbent for selectively removing H2S and organic sulfur
CN103509193A (en) * 2012-06-30 2014-01-15 中国石油化工股份有限公司 Preparation method of polyamide-amine dendritic compound
US20150290575A1 (en) * 2014-04-09 2015-10-15 Jeffrey Todd Rothermel Methods and systems for purifying natural gases
CN105498720A (en) * 2014-10-14 2016-04-20 中国石油化工股份有限公司 Solid adsorbent for removing H2S, CO2, and organic sulfur from mixed gas
CN106693690A (en) * 2016-12-14 2017-05-24 山东迅达化工集团有限公司 Desulfurization purification process of natural gas
CN107510991A (en) * 2017-08-31 2017-12-26 无锡风正科技有限公司 A kind of purification of air environment-friendly type filtrate and preparation method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005262023A (en) * 2004-03-16 2005-09-29 Aisin Seiki Co Ltd Aldehydes removal material
US20070000385A1 (en) * 2005-07-01 2007-01-04 Stouffer Mark R Adsorbents for removing H2S, other odor causing compounds, and acid gases from gas streams and methods for producing and using these adsorbents
CN102580473A (en) * 2012-03-20 2012-07-18 中国石油化工股份有限公司 Absorbent for selectively removing H2S and organic sulfur
CN103509193A (en) * 2012-06-30 2014-01-15 中国石油化工股份有限公司 Preparation method of polyamide-amine dendritic compound
US20150290575A1 (en) * 2014-04-09 2015-10-15 Jeffrey Todd Rothermel Methods and systems for purifying natural gases
CN105498720A (en) * 2014-10-14 2016-04-20 中国石油化工股份有限公司 Solid adsorbent for removing H2S, CO2, and organic sulfur from mixed gas
CN106693690A (en) * 2016-12-14 2017-05-24 山东迅达化工集团有限公司 Desulfurization purification process of natural gas
CN107510991A (en) * 2017-08-31 2017-12-26 无锡风正科技有限公司 A kind of purification of air environment-friendly type filtrate and preparation method thereof

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