CN117050775A - Desulfurization method for high-sulfur inferior heavy oil - Google Patents
Desulfurization method for high-sulfur inferior heavy oil Download PDFInfo
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- CN117050775A CN117050775A CN202310986089.2A CN202310986089A CN117050775A CN 117050775 A CN117050775 A CN 117050775A CN 202310986089 A CN202310986089 A CN 202310986089A CN 117050775 A CN117050775 A CN 117050775A
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- China
- Prior art keywords
- product
- heavy oil
- sulfur
- inferior heavy
- iron
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 27
- 230000023556 desulfurization Effects 0.000 title claims abstract description 27
- 239000000295 fuel oil Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000011593 sulfur Substances 0.000 title claims abstract description 22
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000047 product Substances 0.000 claims abstract description 29
- 239000000945 filler Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- 239000000446 fuel Substances 0.000 claims abstract description 5
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- 239000012071 phase Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000008188 pellet Substances 0.000 claims 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 abstract description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 2
- 239000010779 crude oil Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000003009 desulfurizing effect Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/04—Metals, or metals deposited on a carrier
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The invention discloses a desulfurization method of high-sulfur inferior heavy oil, which comprises the following steps: (1) The inferior heavy oil in the raw material tank is pumped to a filler reactor through a raw material pump, and sulfur-containing compounds in the inferior heavy oil react with iron filler at a certain temperature, pressure and airspeed; (2) The reaction product enters a gas-liquid separator for gas-liquid separation, the gas-phase product is sent to be used as boiler fuel, the liquid-phase product is divided into two paths, one path is pumped to a product tank through the product pump, and the other path is pumped and circulated through the product pump and sent to the inlet of a raw material pump to be mixed with fresh raw materials. The invention pertinently reacts sulfur-containing compounds in inferior heavy oil with filler iron, inactive sulfide is decomposed into active sulfide at high temperature, mercaptan and the like in the active sulfide react with iron to generate ferrous sulfide and corresponding hydrocarbons, hydrogen sulfide reacts with iron to generate ferrous sulfide and hydrogen, and elemental sulfur reacts with iron to generate ferrous sulfide. The invention does not consume hydrogen, does not use catalyst, has mild reaction condition, simple process and low cost.
Description
Technical Field
The invention relates to an oil product desulfurization method, in particular to a desulfurization method for high-sulfur inferior heavy oil.
Background
Currently, the world crude oil property is changed towards the trend of emphasis and inferior quality, and the heavy and inferior crude oil resources are huge in reserve and are important resources which can be processed and utilized in the future. Besides heavy and inferior crude oil resources, the atmospheric residue obtained by atmospheric and vacuum distillation of crude oil, slurry obtained by a catalytic cracking device, heavy ethylene tar obtained by an ethylene cracking device and the like are also important inferior heavy oil resources with huge yield. The inferior heavy oil has extremely complex composition, high density, viscosity and carbon residue value, contains a large amount of non-hydrocarbon inferior components such as colloid, asphaltene and the like, has high content of hetero atoms such as sulfur, nitrogen, metal and the like, and has become a great difficult problem facing the current oil refining industry in storage, transportation, processing and utilization. The high sulfur content of the inferior residuum easily causes catalyst poisoning in the processing process, and seriously affects the product quality, thereby bringing a plurality of technical problems for heavy oil lightening and clean production. In addition, when inferior heavy oil is used as fuel oil for ships, there is a strict limitation on sulfur content thereof in order to prevent emission pollution from being caused to the ships. Therefore, the sulfur content of the inferior heavy oil must be reduced to an allowable range before comprehensive utilization.
The traditional inferior heavy oil desulfurization method mainly comprises hydrodesulfurization, oxidative desulfurization, adsorption desulfurization, biological desulfurization and the like. At present, hydrodesulfurization is still a mainstream technology, sulfur-containing compounds in inferior heavy oil can be converted into substances such as hydrogen sulfide which are easy to remove, the desulfurization efficiency is high, hydrogen is consumed, and the pressure condition is severe due to the fact that the catalyst is relied on. Compared with hydrodesulfurization, the oxidative desulfurization is characterized by no hydrogen consumption and milder reaction conditions, and the oxidative desulfurization is still in the basic research stage at present, so that more problems need to be solved from industrialization. The adsorption desulfurization is to selectively adsorb sulfur-containing compounds through the adsorbent, and has the characteristics of simple operation, high desulfurization efficiency, strong regeneration performance of the adsorbent and the like, but the adsorbent is unstable at high temperature, and the adsorption substances mainly comprise mercaptan and thioether. Biological desulfurization is carried out at ambient temperature and pressure by utilizing microorganisms without using complex and toxic chemicals, but the desulfurization time is long, and the microorganisms generally have the problems of activity, selectivity, service life and the like.
Therefore, the above-mentioned inferior heavy oil desulfurization methods all have various limitations, and the available methods are limited mainly by hydrodesulfurization, and a new desulfurization method with low cost, low energy consumption and simple process is needed.
Disclosure of Invention
The invention aims to provide a high-sulfur inferior heavy oil desulfurization method to solve the technical problems mentioned in the background art.
In order to achieve the above purpose, the present invention provides the following technical solutions: the desulfurizing process of low quality heavy oil includes the following two steps:
(1) The inferior heavy oil in the raw material tank is pumped to a filler reactor through a raw material pump, and the sulfur-containing compound in the inferior heavy oil reacts with the iron filler to obtain a reaction product at a certain reaction temperature, reaction pressure and mass airspeed;
(2) The reaction product enters a gas-liquid separator for gas-liquid separation, the gas-phase product is sent to be used as boiler fuel, the liquid-phase product is divided into two paths, one path is pumped to a product tank through the product pump, and the other path is pumped and circulated through the product pump and sent to the inlet of a raw material pump to be mixed with fresh raw materials.
Preferably, in the step (1), the filler used in the filler reactor is one of an iron net, an iron chain, an iron sheet and an iron particle.
Preferably, in the step (1), the reaction temperature is 200-400 ℃, the reaction pressure is 0.5-2 MPa, and the mass airspeed is 1-10 h -1 。
Preferably, in the step (2), the circulation ratio of the beating circulation is 0-5.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention starts from the corrosion mechanism of high-sulfur inferior heavy oil to refinery devices and pipelines, the sulfur-containing compounds in the inferior heavy oil react with filler iron in a targeted manner, the inactive sulfide is decomposed into active sulfide at high temperature, mercaptan and the like in the active sulfide react with iron to generate ferrous sulfide and corresponding hydrocarbons, hydrogen sulfide reacts with iron to generate ferrous sulfide and hydrogen, and elemental sulfur reacts with iron to generate ferrous sulfide. Compared with the traditional hydrodesulfurization process, the method disclosed by the invention does not consume hydrogen, does not use a catalyst, and is mild in reaction condition, simple in process and low in cost.
2. The method has flexible circulation ratio setting, can not be circulated, and can be flexibly set according to the desulfurization rate or the treatment capacity requirement condition.
Drawings
FIG. 1 is a flow chart of the process for desulfurizing inferior heavy oil.
Detailed Description
The present invention is further illustrated by the following examples, but the present invention is not limited thereto.
Example 1: the desulfurizing process of atmospheric residuum includes the following steps:
(1) The atmospheric residuum (sulfur content is 3.3%) in the raw material tank is pumped into a filler reactor (iron chain is used as filler), the reaction temperature is 350 ℃, the pressure is 1MPa, and the mass airspeed is 3h -1 Reacting the sulfur-containing compounds in the atmospheric residuum with the filler;
(2) The reaction product enters a gas-liquid separator to carry out gas-liquid separation, the gas-phase product is sent to be used as boiler fuel, the liquid-phase product is divided into two paths, one path is sent to a product tank through a product pump, the other path is sent to a raw material pump inlet through a product pump circulation to be mixed with fresh raw materials, the circulation ratio is 2, and the product desulfurization rate reaches 86.3%.
Example 2: the desulfurization method of the catalytic slurry oil comprises the following specific steps:
(1) The catalytic slurry oil (sulfur content is 1.2%) in the raw material tank is pumped into a filler reactor (iron chain is used as filler), the reaction temperature is 380 ℃, the pressure is 1MPa, and the mass airspeed is 3h -1 Reacting the sulfur-containing compound in the catalytic slurry with the filler;
(2) The reaction product enters a gas-liquid separator to carry out gas-liquid separation, the gas-phase product is sent to be used as boiler fuel, the liquid-phase product is divided into two paths, one path is sent to a product tank through a product pump, the other path is sent to a raw material pump inlet through a product pump circulation to be mixed with fresh raw materials, the circulation ratio is 3, and the product desulfurization rate reaches 82.6%.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention, but not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (4)
1. The desulfurization method of the high-sulfur inferior heavy oil is characterized by comprising the following steps of:
(1) The inferior heavy oil in the raw material tank is pumped to a filler reactor through a raw material pump, and the sulfur-containing compound in the inferior heavy oil reacts with the iron filler to obtain a reaction product at a certain reaction temperature, reaction pressure and mass airspeed;
(2) The reaction product enters a gas-liquid separator for gas-liquid separation, the gas-phase product is sent to be used as boiler fuel, the liquid-phase product is divided into two paths, one path is pumped to a product tank through the product pump, and the other path is pumped and circulated through the product pump and sent to the inlet of a raw material pump to be mixed with fresh raw materials.
2. The desulfurization method according to claim 1, wherein in the step (1), the filler used in the filler reactor is one of a net, a chain, a sheet, and a pellet.
3. The desulfurization method according to claim 1, wherein in the step (1), the reaction temperature is 200 to 400 ℃, the reaction pressure is 0.5 to 2mpa, and the mass space velocity is 1 to 10 hours -1 。
4. The desulfurization method according to claim 1, wherein in the step (2), the circulation ratio of the recycle is 0 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310986089.2A CN117050775A (en) | 2023-08-07 | 2023-08-07 | Desulfurization method for high-sulfur inferior heavy oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310986089.2A CN117050775A (en) | 2023-08-07 | 2023-08-07 | Desulfurization method for high-sulfur inferior heavy oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117050775A true CN117050775A (en) | 2023-11-14 |
Family
ID=88663761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310986089.2A Pending CN117050775A (en) | 2023-08-07 | 2023-08-07 | Desulfurization method for high-sulfur inferior heavy oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117050775A (en) |
-
2023
- 2023-08-07 CN CN202310986089.2A patent/CN117050775A/en active Pending
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