CN114426895B - Method for removing sulfide in liquefied gas - Google Patents
Method for removing sulfide in liquefied gas Download PDFInfo
- Publication number
- CN114426895B CN114426895B CN202011183011.XA CN202011183011A CN114426895B CN 114426895 B CN114426895 B CN 114426895B CN 202011183011 A CN202011183011 A CN 202011183011A CN 114426895 B CN114426895 B CN 114426895B
- Authority
- CN
- China
- Prior art keywords
- desulfurization
- gas
- adsorbent
- regenerated
- liquefied gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C10L3/12—Liquefied petroleum gas
-
- 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
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
Abstract
The present disclosure relates to a method for removing sulfides in liquefied gas, which uses a passivated regenerative desulfurization adsorbent to perform adsorptive desulfurization treatment on the liquefied gas, and because the activity of the passivated regenerative desulfurization adsorbent is low, the method can effectively prevent unsaturated olefins in the liquefied gas from being converted into saturated alkanes during the desulfurization treatment, which can at least partially improve the yield of the unsaturated olefins in the liquefied gas.
Description
Technical Field
The disclosure relates to the technical field of petrochemical industry, in particular to a method for removing sulfides in liquefied gas.
Background
Liquefied petroleum gas contains a large amount of sulfides, which are mainly in the forms of hydrogen sulfide, mercaptans, sulfides and the like. With the development of petrochemical technology and the increasing perfection of relevant environmental regulations, the removal of sulfides in liquefied petroleum gas has become an important content in the technical field of petrochemical industry.
In the related art, the sulfur compounds in the liquefied gas are adsorbed and removed by using a desulfurization adsorbent in the presence of hydrogen.
However, in the above method, a part of olefins in the liquefied gas may react with hydrogen to form saturated alkanes, which may decrease the yield of olefins in the liquefied gas.
Disclosure of Invention
The purpose of the present disclosure is to solve the problem of the reduction of olefin yield in the existing methods for removing sulfides in liquefied gas, and to provide a method for removing sulfides in liquefied gas.
In order to achieve the above object, the present disclosure provides a method for removing sulfides from a liquefied gas, the method comprising the steps of:
s1, in a fast bed desulfurization reactor, contacting a passivated regenerative desulfurization adsorbent with liquefied gas and gas containing hydrogen to perform adsorption desulfurization reaction to obtain a reacted material;
s2, carrying out gas-solid separation on the reacted material to obtain a desulfurized oil gas material and a to-be-generated desulfurization adsorbent;
the method further comprises a step S3 of converting the spent desulfurization adsorbent into the passivated regenerated desulfurization adsorbent by one or two of the following methods, and returning the passivated regenerated desulfurization adsorbent to the step S1:
the method I comprises the following steps: transferring the to-be-regenerated desulfurization adsorbent into a fluidized bed regenerator, sequentially carrying out complete coke-burning regeneration and inert gas purging to obtain a regenerated desulfurization adsorbent, then contacting the regenerated desulfurization adsorbent with gasoline in a part below the height of the given position of the extension range of the fast bed desulfurization reactor, passivating to obtain a passivated regenerated desulfurization adsorbent, and contacting the passivated regenerated desulfurization adsorbent with liquefied gas and gas containing hydrogen in a part above the height of the given position of the extension range of the fast bed desulfurization reactor to carry out adsorption desulfurization reaction;
the second method comprises the following steps: transferring the to-be-regenerated desulfurization adsorbent into a fluidized bed regenerator, sequentially carrying out incomplete coke-burning regeneration and inert gas purging to obtain a semi-regenerated desulfurization adsorbent, then conveying the semi-regenerated desulfurization adsorbent serving as a passivated regenerated desulfurization adsorbent into the fast bed desulfurization reactor, and contacting with liquefied gas and gas containing hydrogen to carry out adsorption desulfurization reaction.
Optionally, in the fast bed desulfurization reactor, the conditions of the adsorptive desulfurization reaction include: the temperature is 200-550 ℃, the pressure is 0.1-3MPa, and the weight hourly space velocity of the liquefied gas is 0.1-50h -1 The weight ratio of hydrogen to liquefied gas is 1:100-5000;
preferably, in the fast bed desulfurization reactor, the conditions of the adsorption desulfurization reaction include: the temperature is 350-500 ℃, the pressure is 0.5-1.5MPa, and the weight hourly space velocity of the liquefied gas is 1-10h -1 The weight ratio of hydrogen to liquefied gas is 1:500-2000.
Alternatively, in the first mode, the height of the position where the extension is given in the fast bed desulfurization reactor is 20 to 90 percent, preferably 40 to 70 percent of the total height of the fast bed desulfurization reactor.
Optionally, in the first mode, the weight hourly space velocity of the gasoline is 0.1-50h -1 Preferably 1-20h -1 (ii) a The weight ratio of the regenerated desulfurization adsorbent to the gasoline is 2-20:1, preferably 5 to 10:1.
optionally, in the second mode, the weight ratio of the semi-regenerative desulfurization adsorbent to the liquefied gas is 2-50:1, preferably 10 to 20:1.
optionally, the gasoline is catalytic cracking crude gasoline and/or stabilized gasoline, and the carbon number of the gasoline is C5-C12; the sulfur content in the gasoline is more than 10 mug/g;
the liquefied gas is a gas which is produced by a catalytic cracking device, is not subjected to absorption stabilization and has a carbon number less than C4, or a gas which is produced by a catalytic cracking device, is subjected to absorption stabilization and has a carbon number of C3-C4; the sulfur content in the liquefied gas is more than 10 mu g/g;
the gas containing hydrogen is hydrogen and/or refinery gas containing hydrogen; preferably, the refinery-related gas containing hydrogen has a sulphur content of greater than 10 μ g/g.
Optionally, the desulfurization sorbent comprises a support and an active component supported on the support; the carrier contains zinc oxide of 10-90 wt%, alumina of 5-30 wt% and silica of 5-85 wt% based on the total weight of the carrier; the active component accounts for 5-30 wt% of the total weight of the desulfurization adsorbent; the active component is one or more oxides selected from cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin and vanadium.
Alternatively, in the first mode, the conditions for complete coke-burning regeneration include: the temperature is 200-800 ℃, the pressure is 0.1-3.0 MPa, the gas linear speed of air is 0.1-2.0 m/s, and the using amount of the air ensures that the carbon content in the regenerative desulfurization adsorbent is 0.01-1.0 wt%;
preferably, the conditions for complete char regeneration include: the temperature is 400-600 ℃, the pressure is 0.5-1.5MPa, and the amount of air is 0.1-0.5 wt% of carbon in the regenerated desulfurization adsorbent.
Alternatively, in the second mode, the conditions for the incomplete coke-burning regeneration include: the temperature is 200-800 ℃, the pressure is 0.1-3.0 MPa, the gas linear speed of air is 0.1-2.0 m/s, and the using amount of the air ensures that the carbon content in the semi-regenerative desulfurization adsorbent is 0.01-2.0 wt%;
preferably, the conditions for incomplete coke-burning regeneration include: the temperature is 400-600 ℃, the pressure is 0.5-1.5MPa, and the amount of air is used to ensure that the carbon content in the semi-regenerative desulfurization adsorbent is 1.0-1.5 wt%.
Optionally, the inert gas used for inert gas purging is steam, nitrogen or a mixture thereof;
in the first mode, the regenerated desulfurization adsorbent is directly introduced from the fluidized bed regenerator into the fast bed desulfurization reactor without being reduced to be contacted with gasoline for passivation;
in the second embodiment, the semi-regenerated desulfurization adsorbent is directly introduced from the fluidized bed regenerator into the fast bed desulfurization reactor without being reduced, and is contacted with a liquefied gas and a gas containing hydrogen to perform an adsorption desulfurization reaction.
Through the technical scheme, the passivated regenerative desulfurization adsorbent is used for carrying out adsorption desulfurization treatment on the liquefied gas, and the activity of the passivated regenerative desulfurization adsorbent is low, so that the method disclosed by the invention can effectively prevent unsaturated olefins in the liquefied gas from being converted into saturated alkanes during desulfurization treatment, and the yield of the unsaturated olefins in the liquefied gas can be at least partially improved.
Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure, but do not constitute a limitation of the disclosure. In the drawings:
fig. 1 schematically illustrates an apparatus to which a method according to an embodiment of the present disclosure is applied.
Description of the reference numerals
1. Gasoline 2 liquefied gas
3. 4 conveying pipe of fast bed desulfurization reactor
5. Cyclone separator 6 oil gas material
7. Control valve for 8 spent chemical in chemical storage tank
9. Fluidized bed regenerator 10 main air pipeline
12. Regenerant control valve 13 lifts the media
14. Gas containing hydrogen
Detailed Description
The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
Fig. 1 schematically illustrates an apparatus to which a method according to an embodiment of the present disclosure is applied. It should be noted that fig. 1 is only an example of an apparatus to which the method of the embodiment of the present disclosure may be applied to help those skilled in the art understand the technical content of the present disclosure, and does not mean that the method of the embodiment of the present disclosure may not be applied to other devices, apparatuses, environments or scenarios. As shown in fig. 1, the apparatus comprises a fast bed desulfurization reactor 3, a cyclone 5, and a fluidized bed regenerator 9.
One of the modes of operation of the device shown in fig. 1 is as follows: (1) In a fast bed desulfurization reactor 3, under the action of a lifting medium 13, a passivated regenerative desulfurization adsorbent is contacted with liquefied gas 2 and gas 14 containing hydrogen to carry out adsorption desulfurization reaction, so as to obtain a reacted material; (2) The reacted material is led into a cyclone separator 5 through a conveying pipe 4 for gas-solid separation to obtain a desulfurized oil gas material 6 and a to-be-generated desulfurization adsorbent; (3) introducing the adsorbent to be desulfurized into an agent storage tank 7 for storage; (4) Closing the regenerant control valve 12, and opening the spent agent control valve 8 to enable the spent desulfurization adsorbent to enter the fluidized bed regenerator 9; (5) Introducing air into the fluidized bed regenerator 9 through a main air pipeline 10, carrying out complete coke-burning regeneration, and introducing inert gas through the main air pipeline 10 for purging to obtain a regenerated desulfurization adsorbent; (6) Opening a regenerant control valve 12, introducing the regenerated desulfurization adsorbent into a fast bed desulfurization reactor 3, contacting with gasoline 1 for passivation to obtain a passivated regenerated desulfurization adsorbent, then contacting the passivated regenerated desulfurization adsorbent with liquefied gas 2 and gas 14 containing hydrogen to continue adsorption desulfurization reaction.
Another way of working the device shown in fig. 1 is as follows: (1) In a fast bed desulfurization reactor 3, under the action of a lifting medium 13, a passivated regenerative desulfurization adsorbent is contacted with liquefied gas 2 and gas 14 containing hydrogen to carry out adsorption desulfurization reaction, so as to obtain a reacted material; (2) The reacted materials are guided into a cyclone separator 5 through a conveying pipe 4 for gas-solid separation to obtain desulfurized oil gas materials 6 and a to-be-regenerated desulfurization adsorbent; (3) introducing the spent desulfurization adsorbent into an agent storage tank 7 for storage; (4) Closing the regenerant control valve 12 and opening the spent regenerant control valve 8 to enable the spent desulfurization adsorbent to enter the fluidized bed regenerator 9; (5) Introducing air into a fluidized bed regenerator 9 through a main air pipeline 10, performing incomplete coke-burning regeneration, and introducing inert gas through the main air pipeline 10 for purging to obtain a semi-regenerated desulfurization adsorbent; (6) The regenerant control valve 12 is opened, the obtained semi-regenerative desulfurization adsorbent is introduced into the fast bed desulfurization reactor 3, and the semi-regenerative desulfurization adsorbent is used as a passivated regenerative desulfurization adsorbent, and is brought into contact with the liquefied gas 2 and the gas 14 containing hydrogen to continue the adsorption desulfurization reaction.
A first aspect of the present disclosure provides a method of removing sulfides from a liquefied gas, the method comprising the steps of: s1, in a fast bed desulfurization reactor, contacting a passivated regenerative desulfurization adsorbent with liquefied gas and gas containing hydrogen to perform adsorption desulfurization reaction to obtain a reacted material; s2, carrying out gas-solid separation on the reacted material to obtain a desulfurized oil gas material and a to-be-generated desulfurization adsorbent; the method further comprises a step S3 of converting the spent desulfurization adsorbent into the passivated regenerated desulfurization adsorbent by one or two of the following methods, and returning the passivated regenerated desulfurization adsorbent to the step S1:
the first method is as follows: transferring the to-be-regenerated desulfurization adsorbent into a fluidized bed regenerator, sequentially carrying out complete coke-burning regeneration and inert gas purging to obtain a regenerated desulfurization adsorbent, then contacting the regenerated desulfurization adsorbent with gasoline in a part below the height of the given position of the extension range of the fast bed desulfurization reactor, passivating to obtain a passivated regenerated desulfurization adsorbent, and contacting the passivated regenerated desulfurization adsorbent with liquefied gas and gas containing hydrogen in a part above the height of the given position of the extension range of the fast bed desulfurization reactor to carry out adsorption desulfurization reaction;
the second method comprises the following steps: transferring the to-be-regenerated desulfurization adsorbent into a fluidized bed regenerator, sequentially carrying out incomplete coke-burning regeneration and inert gas purging to obtain a semi-regenerated desulfurization adsorbent, then conveying the semi-regenerated desulfurization adsorbent serving as a passivated regenerated desulfurization adsorbent into the fast bed desulfurization reactor, and contacting with liquefied gas and gas containing hydrogen to carry out adsorption desulfurization reaction.
In the disclosed embodiment, specifically, step S1 further includes a step of mixing the liquefied gas and the gas containing hydrogen with an atomizing medium before contacting the passivated regenerative desulfurization adsorbent with the liquefied gas and the gas containing hydrogen; in addition, the passivated regenerated desulfurization sorbent is contacted with a liquefied gas and a hydrogen-containing gas under the action of a lifting medium. The atomizing medium and the lifting medium can be, for example, water vapor, nitrogen, or a mixture of the two.
In the embodiment of the present disclosure, the passivated regenerative desulfurization adsorbent is used to perform the adsorptive desulfurization treatment on the liquefied gas, and due to the lower activity of the passivated regenerative desulfurization adsorbent, the embodiment of the present disclosure can effectively prevent the unsaturated olefin (which may be, for example, a C2-C4 olefin, and is preferably propylene) in the liquefied gas from being converted into a saturated alkane (which may be, for example, a C2-C4 alkane, and is preferably propane) during the desulfurization treatment, which can at least partially increase the yield of the unsaturated olefin in the liquefied gas.
In addition, in the first mode, the regenerated desulfurization adsorbent is passivated by using gasoline, at least part of sulfides in the gasoline can be removed, the yield of olefins in the gasoline is improved, and the octane number of the gasoline is improved. The embodiment of the disclosure realizes the cyclic regeneration and utilization of the desulfurization adsorbent, and has high efficiency and good effect of removing sulfides in the liquefied gas, and no waste such as caustic sludge is generated in the desulfurization process.
According to the present disclosure, the conditions of the adsorptive desulfurization reaction may vary within a certain range, for example, in the fast bed desulfurization reactor, the conditions of the adsorptive desulfurization reaction may include: the temperature is 200-550 ℃, the pressure is 0.1-3MPa, and the weight hourly space velocity of the liquefied gas is 0.1-50h -1 The weight ratio of hydrogen to liquefied gas is 1:100-5000.
Preferably, in the fast bed desulfurization reactor, the conditions of the adsorption desulfurization reaction may include: the temperature is 350-500 ℃, the pressure is 0.5-1.5MPa, and the weight hourly space velocity of the liquefied gas is 1-10h -1 The weight ratio of hydrogen to liquefied gas is 1:500-2000. Under the preferred conditions, the disclosed embodiments can further avoid the unsaturated olefins in the liquefied gas from being converted into saturated alkanes, which is beneficial to further improve the yield of the unsaturated olefins in the liquefied gas.
According to the present disclosure, the height of the extension setting position in the rapid bed desulfurization reactor may vary within a certain range, for example, in the first mode, the height of the extension setting position in the rapid bed desulfurization reactor may be 20 to 90% of the total height of the rapid bed desulfurization reactor, preferably 40 to 70%. At the above preferred height, not only the passivation degree of the regenerated desulfurization adsorbent is appropriate, but also the passivated regenerated desulfurization adsorbent can be in full contact with the liquefied gas and the gas containing hydrogen, which is beneficial to fully performing the adsorption desulfurization reaction, and can effectively remove the sulfide in the liquefied gas.
According to the disclosure, in the first mode, the weight hourly space velocity of the gasoline can be 0.1-50h -1 Preferably 1-20h -1 (ii) a The weight ratio of the regenerated desulfurization adsorbent to the gasoline can be 2-20:1,preferably 5 to 10:1.
according to the disclosure, in the second mode, the weight ratio of the semi-regenerative desulfurization adsorbent to the liquefied gas may be 2 to 50:1, preferably 10 to 20:1.
according to the present disclosure, the kinds of the gasoline and the liquefied gas may be selected within a certain range, for example, the gasoline may be a catalytically cracked naphtha, and/or a stabilized gasoline, and the carbon number of the gasoline may be C5 to C12; the sulfur content in the gasoline may be greater than 10 μ g/g; the liquefied gas can be gas which is produced by a catalytic cracking device and has no absorption stability and has carbon number less than C4, or gas which is produced by a catalytic cracking device and has carbon number of C3-C4 and has absorption stability; the sulphur content in the liquefied gas may be greater than 10 μ g/g; the hydrogen-containing gas can be hydrogen and/or refinery gas containing hydrogen; preferably, the refinery-related gas containing hydrogen has a sulphur content of greater than 10 μ g/g.
In the embodiment of the disclosure, the refinery gas containing hydrogen is used as the gas containing hydrogen, so that at least part of sulfides in the refinery gas can be removed, and the residual hydrogen in the refinery gas is fully utilized, thereby being beneficial to saving production resources and reducing production cost.
Optionally, the desulfurization sorbent comprises a support and an active component supported on the support; the carrier contains zinc oxide of 10-90 wt%, alumina of 5-30 wt% and silica of 5-85 wt% based on the total weight of the carrier; the active component accounts for 5-30 wt% of the total weight of the desulfurization adsorbent; the active component is one or more oxides selected from cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin and vanadium.
Alternatively, in the first mode, the conditions for complete coke-burning regeneration may include: the temperature is 200-800 ℃, the pressure is 0.1-3.0 MPa, the gas linear speed of air is 0.1-2.0 m/s, and the using amount of the air ensures that the carbon content in the regenerative desulfurization adsorbent is 0.01-1.0 wt%; preferably, the conditions for complete char regeneration may include: the temperature is 400-600 ℃, the pressure is 0.5-1.5MPa, and the amount of air is used to ensure that the carbon content in the regenerated desulfurization adsorbent is 0.1-0.5 wt%.
Alternatively, in the second mode, the conditions for the incomplete coke-burning regeneration may include: the temperature is 200-800 ℃, the pressure is 0.1-3.0 MPa, the gas linear speed of air is 0.1-2.0 m/s, and the using amount of the air ensures that the carbon content in the semi-regenerative desulfurization adsorbent is 0.01-2.0 wt%; preferably, the conditions for incomplete coke-burning regeneration may include: the temperature is 400-600 ℃, the pressure is 0.5-1.5MPa, and the amount of air is used to ensure that the carbon content in the semi-regenerative desulfurization adsorbent is 1.0-1.5 wt%.
Alternatively, the inert gas used for inert gas purging may be water vapor, nitrogen, or a mixture thereof; in the first mode, the regenerated desulfurization adsorbent can be directly introduced from the fluidized bed regenerator to the fast bed desulfurization reactor without reduction to contact with gasoline for passivation; in the second embodiment, the semi-regenerated desulfurization adsorbent may be directly introduced from the fluidized bed regenerator into the fast bed desulfurization reactor without reduction, and may be contacted with a liquefied gas and a gas containing hydrogen to perform an adsorption desulfurization reaction.
The present disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby.
The desulfurization adsorbent involved in the examples and comparative examples of the present disclosure was FCAS-20 adsorbent, produced by the institute of petrochemical science and technology of china, and its chemical composition and physicochemical properties are shown in table 1.
TABLE 1
The gasolines referred to in the examples and comparative examples of the present disclosure are catalytic gasolines, which are derived from the division of the petrochemical Yanshan in China, and the compositions and physicochemical properties thereof are shown in Table 2.
TABLE 2
The liquefied gases involved in the examples and comparative examples of the present disclosure are catalytically cracked liquefied gases, which are sourced from the chinese petrochemical yanshan division, and the compositions and physicochemical properties thereof are shown in table 3.
TABLE 3
The fast bed desulfurization reactors according to the examples and comparative examples of the present disclosure were hollow cylinders having a height of 2.6 m and a diameter of 39 mm, the upper portions of which were communicated with a storage tank through a 2.4 m long transfer pipe, and the height of the extension thereof was set to 1.3 m.
Example 1
This example illustrates the process for removing sulfides from liquefied gases according to the present disclosure, comprising the following operations.
(1) In a fast bed desulfurization reactor, under the action of a lifting medium (water vapor), the regenerated desulfurization adsorbent which is completely burnt and regenerated is mixed with gasoline (catalytic gasoline, the sulfur content of the catalytic gasoline is 569 mug/g, and the weight hourly space velocity is 1.3h -1 ) And (3) carrying out contact at a height below a given position of a delay range, and passivating to obtain a passivated regenerated desulfurization adsorbent, wherein the weight ratio of the regenerated desulfurization adsorbent fully burnt to the catalytic gasoline is 8:1;
(2) Introducing liquefied gas (catalytic cracking liquefied gas) and refinery gas containing hydrogen at a given position of an extension distance of a rapid bed desulfurization reactor, contacting the liquefied gas (catalytic cracking liquefied gas) and the refinery gas containing hydrogen with a passivated regenerative desulfurization adsorbent to perform an adsorption desulfurization reaction to obtain a reacted material, wherein the conditions of the adsorption desulfurization reaction comprise: the temperature is 400 ℃, the pressure is 1.0MPa, and the weight hourly space velocity of the liquefied gas is 2.6h -1 The weight ratio of hydrogen to liquefied gas is 1:1000, parts by weight;
(3) Introducing the obtained reacted material into a cyclone separator through a conveying pipe, and performing gas-solid separation to obtain a desulfurized oil gas material and a to-be-regenerated desulfurization adsorbent;
(4) Transferring the obtained adsorbent to be regenerated into a fluidized bed regenerator, and sequentially performing complete scorching regeneration for 15min and inert gas (nitrogen) purging for 15min to obtain the regenerated adsorbent for complete scorching regeneration, wherein the complete scorching regeneration conditions comprise: the temperature is 530 ℃, the pressure is 1.0MPa, the gas linear speed of air is 1.0m/s, and the using amount of the air ensures that the carbon content in the regenerated desulfurization adsorbent for complete coke burning regeneration is 0.1 weight percent;
(5) And introducing the regenerated desulfurization adsorbent obtained by complete coke burning regeneration into a part below the height of a given position of the extension of the fast bed desulfurization reactor, and continuing to perform passivation and adsorption desulfurization reactions.
The oil and gas materials obtained after desulfurization in this example were subjected to physicochemical analysis, and the sulfur content, olefin content, and octane number thereof were measured, and the measurement results are shown in table 4.
Example 2
A process for the removal of sulfides from liquefied gases according to the procedure of example 1, except that: when in passivation, the airspeed of the gasoline is 0.7h -1 (ii) a The temperature of the adsorption desulfurization reaction is 430 ℃, the pressure is 2.0MPa, and the weight hourly space velocity of the liquefied gas is 1.4h -1 。
The oil and gas materials obtained after desulfurization in this example were subjected to physicochemical analysis, and the sulfur content, olefin content, and octane number thereof were measured, and the measurement results are shown in table 4.
Example 3
This example illustrates the process for removing sulfides from liquefied gases according to the present disclosure, comprising the following operations.
(1) The method comprises the steps of taking a semi-regenerative desulfurization adsorbent regenerated by incomplete burning as a passivated regenerative desulfurization adsorbent, contacting the passivated regenerative desulfurization adsorbent with liquefied gas (catalytic cracking liquefied gas) and refinery gas containing hydrogen in a fast bed desulfurization reactor under the action of a lifting medium (water vapor), and carrying out adsorption desulfurization reaction to obtain a reacted material, wherein the weight ratio of the semi-regenerative desulfurization adsorbent regenerated by incomplete burning to the liquefied gas is 16:1, suctionThe conditions of the desulfurization reaction include: the temperature is 400 ℃, the pressure is 1.0MPa, and the weight hourly space velocity of the liquefied gas is 2.6h -1 The weight ratio of hydrogen to liquefied gas is 1:1000, parts by weight;
(2) Introducing the obtained reacted material into a cyclone separator through a conveying pipe, and performing gas-solid separation to obtain a desulfurized oil gas material and a to-be-regenerated desulfurization adsorbent;
(3) Transferring the obtained adsorbent to be regenerated into a fluidized bed regenerator, and sequentially performing incomplete coke-burning regeneration for 8min and inert gas (nitrogen) purging for 15min to obtain a semi-regenerated adsorbent for incomplete coke-burning regeneration, wherein the incomplete coke-burning regeneration conditions comprise: the temperature is 530 ℃, the pressure is 1.0MPa, the gas linear speed of the air is 1.0m/s, and the using amount of the air ensures that the carbon content in the semi-regenerative desulfurization adsorbent is 1.0 weight percent;
(4) And (3) taking the obtained semi-regenerative desulfurization adsorbent regenerated by incomplete scorching as a passivated regenerative desulfurization adsorbent, introducing the passivated regenerative desulfurization adsorbent into a fast bed desulfurization reactor, contacting the passivated regenerative desulfurization adsorbent with liquefied gas and gas containing hydrogen, and continuing the adsorption desulfurization reaction.
The oil and gas materials obtained after desulfurization in this example were subjected to physicochemical analysis, and the sulfur content and olefin content thereof were measured, and the measurement results are shown in table 4.
Example 4
A process for the removal of sulfides from liquefied gas according to the procedure of example 3, except that: the temperature of the adsorption desulfurization reaction is 430 ℃, the pressure is 2.0MPa, and the weight hourly space velocity of the liquefied gas is 1.3h -1 。
The oil and gas materials obtained after desulfurization in this example were subjected to physicochemical analysis, and the sulfur content and olefin content thereof were measured, and the measurement results are shown in table 4.
Comparative example 1
(1) At the bottom of the fast bed desulfurization reactor, under the action of a lifting medium (water vapor), the regenerated desulfurization adsorbent fully burnt and regenerated is mixed with gasoline (catalytic gasoline, the sulfur content of the catalytic gasoline is 569 mug/g, and the weight hourly space velocity is 1.3h -1 ) Contacting liquefied gas (catalytic cracking liquefied gas) with refinery gas containing hydrogen to perform adsorption desulfurization reaction to obtain the productThe weight ratio of the regenerated desulfurization adsorbent which is completely burnt and regenerated to the catalytic gasoline is 8: the conditions of the adsorption desulfurization reaction comprise: the temperature is 400 ℃, the pressure is 1.0MPa, and the weight hourly space velocity of the liquefied gas is 2.6h -1 The weight ratio of hydrogen to liquefied gas is 1:1000, parts by weight;
(2) Introducing the obtained reacted material into a cyclone separator through a conveying pipe, and performing gas-solid separation to obtain a desulfurized oil gas material and a to-be-regenerated desulfurization adsorbent;
(3) Transferring the obtained adsorbent to be regenerated into a fluidized bed regenerator, and sequentially carrying out complete scorching regeneration for 15min and inert gas (nitrogen) purging for 15min to obtain the regenerated adsorbent for complete scorching regeneration, wherein the conditions of complete scorching regeneration comprise: the temperature is 530 ℃, the pressure is 1.0MPa, the gas linear speed of air is 1.0m/s, and the using amount of the air ensures that the carbon content in the regenerated desulfurization adsorbent for complete coke burning regeneration is 0.1 weight percent;
(4) And (3) introducing the obtained regenerated desulfurization adsorbent into a fast bed desulfurization reactor, contacting the regenerated desulfurization adsorbent with gasoline, liquefied gas and gas containing hydrogen, and continuing to perform adsorption desulfurization reaction.
The oil gas material after desulfurization obtained in the comparative example was subjected to physical and chemical analysis, and the sulfur content, olefin content and octane number thereof were measured, and the measurement results are shown in table 4.
Comparative example 2
(1) At the bottom of the rapid bed desulfurization reactor, under the action of a lifting medium (water vapor), contacting a regenerated desulfurization adsorbent which is completely burnt and regenerated with liquefied gas (catalytic cracking liquefied gas) and refinery gas containing hydrogen to perform adsorption desulfurization reaction to obtain a reacted material, wherein the adsorption desulfurization reaction conditions comprise: the temperature is 400 ℃, the pressure is 1.0MPa, and the weight hourly space velocity of the liquefied gas is 2.6h -1 The weight ratio of hydrogen to liquefied gas is 1:1000, parts by weight;
(2) Introducing the obtained reacted material into a cyclone separator through a conveying pipe, and performing gas-solid separation to obtain a desulfurized oil gas material and a to-be-regenerated desulfurization adsorbent;
(3) Transferring the obtained adsorbent to be regenerated into a fluidized bed regenerator, and sequentially carrying out complete scorching regeneration for 15min and inert gas (nitrogen) purging for 15min to obtain the regenerated adsorbent for complete scorching regeneration, wherein the conditions of complete scorching regeneration comprise: the temperature is 530 ℃, the pressure is 1.0MPa, the gas linear speed of air is 1.0m/s, and the using amount of the air ensures that the carbon content in the regenerated desulfurization adsorbent for complete coke burning regeneration is 0.1 weight percent;
(4) And (3) introducing the regenerated desulfurization adsorbent which is completely burnt and regenerated into a fast bed desulfurization reactor, contacting the regenerated desulfurization adsorbent with liquefied gas and gas containing hydrogen, and continuing to perform adsorption desulfurization reaction.
The desulfurized oil and gas material obtained in the comparative example was subjected to physical and chemical analysis, and the sulfur content and olefin content were measured, with the results shown in table 4.
Comparative example 3
(1) In the fast bed desulfurization reactor, under the effect of promoting medium (vapor), contact inert quartz sand with gasoline, liquefied gas (catalytic cracking liquefied gas) and the refinery gas that contains hydrogen, adsorb desulfurization reaction, obtain the material after the reaction, wherein, adsorb desulfurization reaction's condition includes: the temperature is 400 ℃, the pressure is 1.0MPa, and the weight hourly space velocity of the liquefied gas is 2.6h -1 The mass ratio of the hydrogen to the liquefied gas is 1:1000, parts by weight;
(2) Introducing the obtained reacted material into a cyclone separator through a conveying pipe, and performing gas-solid separation to obtain a desulfurized oil gas material and inert quartz sand;
(3) And (3) introducing the inert quartz sand into the rapid bed desulfurization reactor, and continuing to perform adsorption desulfurization reaction.
The desulfurized oil and gas material obtained in the comparative example was subjected to physical and chemical analysis, and the sulfur content, olefin content and octane number thereof were measured, with the results shown in table 4.
TABLE 4
As can be seen from table 4, the method disclosed by the present disclosure uses the passivated regenerative desulfurization adsorbent to perform the adsorption desulfurization treatment on the liquefied gas, and due to the lower activity of the passivated regenerative desulfurization adsorbent, the unsaturated olefins in the liquefied gas can be effectively prevented from being converted into saturated alkanes during the desulfurization treatment, which can at least partially improve the yield of the unsaturated olefins in the liquefied gas and the octane number of the catalytic gasoline.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (17)
1. A method for removing sulfides from a liquefied gas, the method comprising the steps of:
s1, in a fast bed desulfurization reactor, contacting a passivated regenerative desulfurization adsorbent with liquefied gas and gas containing hydrogen to perform adsorption desulfurization reaction to obtain a reacted material;
s2, carrying out gas-solid separation on the reacted material to obtain a desulfurized oil gas material and a to-be-generated desulfurization adsorbent;
the method further comprises a step S3 of converting the spent desulfurization adsorbent into the passivated regenerated desulfurization adsorbent by one or two of the following methods, and returning the passivated regenerated desulfurization adsorbent to the step S1:
the first method is as follows: transferring the to-be-regenerated desulfurization adsorbent into a fluidized bed regenerator, sequentially carrying out complete coke-burning regeneration and inert gas purging to obtain a regenerated desulfurization adsorbent, then contacting the regenerated desulfurization adsorbent with gasoline in a part below the height of the given position of the extension range of the fast bed desulfurization reactor, passivating to obtain a passivated regenerated desulfurization adsorbent, and contacting the passivated regenerated desulfurization adsorbent with liquefied gas and gas containing hydrogen in a part above the height of the given position of the extension range of the fast bed desulfurization reactor to carry out adsorption desulfurization reaction;
the second method comprises the following steps: transferring the to-be-regenerated desulfurization adsorbent into a fluidized bed regenerator, sequentially performing incomplete coke-burning regeneration and inert gas purging to obtain a semi-regenerated desulfurization adsorbent, and then conveying the semi-regenerated desulfurization adsorbent serving as a passivated regeneration desulfurization adsorbent into the fast bed desulfurization reactor to contact with liquefied gas and gas containing hydrogen to perform adsorption desulfurization reaction;
in the first mode, the regenerated desulfurization adsorbent is directly introduced into the fast bed desulfurization reactor from the fluidized bed regenerator without reduction to be contacted with gasoline for passivation;
in the second embodiment, the semi-regenerated desulfurization adsorbent is directly introduced from the fluidized bed regenerator into the fast bed desulfurization reactor without being reduced, and is contacted with a liquefied gas and a gas containing hydrogen to perform an adsorption desulfurization reaction.
2. The method of claim 1, wherein in the fast bed desulfurization reactor, the conditions of the adsorptive desulfurization reaction comprise: the temperature is 200-550 ℃, the pressure is 0.1-3MPa, and the weight hourly space velocity of the liquefied gas is 0.1-50h -1 The weight ratio of hydrogen to liquefied gas is 1:100-5000.
3. The method of claim 2, wherein in the fast bed desulfurization reactor, the conditions of the adsorptive desulfurization reaction comprise: the temperature is 350-500 deg.C, and the pressure is 0.5-1.5MPa, liquefied gas weight hourly space velocity of 1-10h -1 The weight ratio of hydrogen to liquefied gas is 1:500-2000.
4. The method of claim 1, wherein in the first mode, the height of the position of the extended range in the rapid bed desulfurization reactor is 20-90% of the total height of the rapid bed desulfurization reactor.
5. The method of claim 4, wherein in the first mode, the height of the position where the distance is extended in the fast bed desulfurization reactor is set to be 40-70% of the total height of the fast bed desulfurization reactor.
6. The method as claimed in claim 1 or 4, wherein in the first mode, the weight hourly space velocity of the gasoline is 0.1-50h -1 (ii) a The weight ratio of the regenerated desulfurization adsorbent to the gasoline is 2-20:1.
7. the method as claimed in claim 6, wherein in the first mode, the weight hourly space velocity of the gasoline is 1-20h -1 (ii) a The weight ratio of the regenerated desulfurization adsorbent to the gasoline is 5-10:1.
8. the method of claim 1, wherein in mode two, the weight ratio of the semi-regenerative desulfurization adsorbent to the liquefied gas is from 2 to 50:1.
9. the method of claim 8, wherein in mode two, the weight ratio of the semi-regenerative desulfurization adsorbent to the liquefied gas is 10-20:1.
10. the process according to claim 1, wherein the gasoline is a catalytically cracked naphtha, and/or a stabilized gasoline, the gasoline having a carbon number of C5-C12; the sulfur content in the gasoline is more than 10 mug/g;
the liquefied gas is a gas which is produced by a catalytic cracking device, is not subjected to absorption stabilization and has a carbon number less than C4, or a gas which is produced by a catalytic cracking device, is subjected to absorption stabilization and has a carbon number of C3-C4; the sulfur content in the liquefied gas is more than 10 mug/g;
the hydrogen-containing gas is hydrogen and/or refinery gas containing hydrogen.
11. The method of claim 10, wherein the hydrogen-containing refinery-related gas has a sulfur content greater than 10 μ g/g.
12. The method according to claim 1, wherein the desulfurization adsorbent comprises a carrier and an active component supported on the carrier; the carrier contains zinc oxide of 10-90 wt%, alumina of 5-30 wt% and silica of 5-85 wt% based on the total weight of the carrier; the active component accounts for 5-30 wt% of the total weight of the desulfurization adsorbent; the active component is one or more oxides selected from cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin and vanadium.
13. The method of claim 1, wherein in mode one, the conditions for full char regeneration comprise: the temperature is 200-800 ℃, the pressure is 0.1-3.0 MPa, the gas linear speed of the air is 0.1-2.0 m/s, and the using amount of the air ensures that the carbon content in the regenerative desulfurization adsorbent is 0.01-1.0 wt%.
14. The method of claim 13, wherein the conditions for full char regeneration comprise: the temperature is 400-600 ℃, the pressure is 0.5-1.5MPa, and the amount of air is used to ensure that the carbon content in the regenerated desulfurization adsorbent is 0.1-0.5 wt%.
15. The method of claim 1, wherein in mode two, the conditions for incomplete char regeneration comprise: the temperature is 200-800 ℃, the pressure is 0.1-3.0 MPa, the gas linear speed of the air is 0.1-2.0 m/s, and the using amount of the air ensures that the carbon content in the semi-regenerative desulfurization adsorbent is 0.01-2.0 wt%.
16. The method of claim 15, wherein the conditions for incomplete char regeneration comprise: the temperature is 400-600 ℃, the pressure is 0.5-1.5MPa, and the amount of air is used to ensure that the carbon content in the semi-regenerative desulfurization adsorbent is 1.0-1.5 wt%.
17. The method of claim 1, wherein the inert gas used for inert gas purging is water vapor, nitrogen, or a mixture thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011183011.XA CN114426895B (en) | 2020-10-29 | 2020-10-29 | Method for removing sulfide in liquefied gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011183011.XA CN114426895B (en) | 2020-10-29 | 2020-10-29 | Method for removing sulfide in liquefied gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114426895A CN114426895A (en) | 2022-05-03 |
| CN114426895B true CN114426895B (en) | 2023-03-24 |
Family
ID=81308985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011183011.XA Active CN114426895B (en) | 2020-10-29 | 2020-10-29 | Method for removing sulfide in liquefied gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114426895B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1179019C (en) * | 2002-05-31 | 2004-12-08 | 中国石油化工股份有限公司 | Method for eatalyzing and transfering petroleum hydrocarbon compounds by using reactor with dual reacting regions |
| CN101921611B (en) * | 2009-06-12 | 2013-07-31 | 中国石油天然气股份有限公司 | Catalytic cracking method and system for reducing sulphur content of petrol |
| CN102191080B (en) * | 2010-03-11 | 2014-04-30 | 中国石油化工股份有限公司 | Method for lowering sulfur and olefin content in gasoline |
| CN103031143B (en) * | 2011-09-29 | 2014-12-31 | 中国石油化工股份有限公司 | Method for simultaneously removing sulfides in gasoline and liquefied gas through single reactor |
| CN107469798B (en) * | 2016-06-07 | 2020-12-04 | 中国石油化工股份有限公司 | Regeneration method of sulfur adsorbent |
-
2020
- 2020-10-29 CN CN202011183011.XA patent/CN114426895B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114426895A (en) | 2022-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6338794B1 (en) | Desulfurization with zinc titanate sorbents | |
| US2560433A (en) | Desulfurization of hydrocarbon oils | |
| US5928980A (en) | Attrition resistant catalysts and sorbents based on heavy metal poisoned FCC catalysts | |
| JP2004533492A (en) | Removal of sulfur compounds from hydrocarbon feed streams using a cobalt-containing adsorbent in a substantially hydrogen-free atmosphere | |
| JP4547922B2 (en) | Partially coked catalyst usable for hydrotreatment of fractions containing sulfur compounds and olefins | |
| CN103031143B (en) | Method for simultaneously removing sulfides in gasoline and liquefied gas through single reactor | |
| CN103031150B (en) | Double-reactor removes the method for gasoline and liquefied gas medium sulphide content simultaneously | |
| CN114426895B (en) | Method for removing sulfide in liquefied gas | |
| CN110337487A (en) | Oxidation sweetening and the sulfone management of oil distillate are carried out using FCC | |
| CN112745936B (en) | Desulfurization method for catalytic cracking light product, method and device for producing low-sulfur light oil product through catalytic cracking | |
| JP4767169B2 (en) | Nitrogen removal from olefinic naphtha feed streams to improve hydrodesulfurization selectivity for olefin saturation | |
| CN110249035A (en) | Oxidation sweetening and the sulfone management of oil distillate are carried out using FCC | |
| CN114426876B (en) | Conversion method of raw oil | |
| CN107469798B (en) | Regeneration method of sulfur adsorbent | |
| CN107159096A (en) | Adsorbing and desulfurizing catalytic cracking gasoline agent and preparation method and application | |
| CN104212476A (en) | Anti-vanadium auxiliary agent of heavy oil cracking catalyst or contact agent | |
| CN115216333A (en) | Deep desulfurization method for liquefied gas | |
| CN112745938B (en) | Catalytic cracking light product desulfurization and separation method | |
| CN114456833B (en) | Desulfurization method and device for catalytic cracking light products and method for producing low-sulfur light oil products | |
| CN107974290B (en) | A kind of vapour oil treatment process | |
| CN1286955C (en) | Method for decreasing sulfur content of hydrocarbon | |
| CN107974294B (en) | A kind of vapour oil treatment process | |
| CN111117695B (en) | Method for processing inferior heavy oil | |
| CN107974296B (en) | Gasoline treatment method | |
| CN107974289B (en) | A kind of processing method and system of gasoline |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |