CN116731743A - Method for reducing sulfur content of petroleum coke in residual oil thermal conversion process - Google Patents
Method for reducing sulfur content of petroleum coke in residual oil thermal conversion process Download PDFInfo
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- CN116731743A CN116731743A CN202310792396.7A CN202310792396A CN116731743A CN 116731743 A CN116731743 A CN 116731743A CN 202310792396 A CN202310792396 A CN 202310792396A CN 116731743 A CN116731743 A CN 116731743A
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- coking
- oil
- polyethylene glycol
- auxiliary agent
- residual oil
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- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 76
- 239000011593 sulfur Substances 0.000 title claims abstract description 76
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 69
- 239000002006 petroleum coke Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000008569 process Effects 0.000 title claims abstract description 16
- 238000004939 coking Methods 0.000 claims abstract description 157
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 77
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 47
- 230000023556 desulfurization Effects 0.000 claims abstract description 47
- 238000012546 transfer Methods 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 28
- 239000004353 Polyethylene glycol 8000 Substances 0.000 claims description 28
- 229920001223 polyethylene glycol Polymers 0.000 claims description 28
- 229940093429 polyethylene glycol 6000 Drugs 0.000 claims description 28
- 229940085678 polyethylene glycol 8000 Drugs 0.000 claims description 28
- 235000019446 polyethylene glycol 8000 Nutrition 0.000 claims description 28
- 229910052684 Cerium Inorganic materials 0.000 claims description 25
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 25
- 230000035484 reaction time Effects 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 239000002283 diesel fuel Substances 0.000 claims description 18
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052721 tungsten Inorganic materials 0.000 claims description 14
- 239000010937 tungsten Substances 0.000 claims description 14
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- -1 VIB metals Chemical class 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 claims 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims 1
- 239000005642 Oleic acid Substances 0.000 claims 1
- 150000001450 anions Chemical class 0.000 claims 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000000571 coke Substances 0.000 description 25
- 239000007789 gas Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 19
- 238000012360 testing method Methods 0.000 description 18
- 239000011737 fluorine Substances 0.000 description 17
- 229910052731 fluorine Inorganic materials 0.000 description 17
- 238000000926 separation method Methods 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000002910 rare earth metals Chemical group 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004227 thermal cracking Methods 0.000 description 4
- 230000003111 delayed effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
Classifications
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- 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
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1077—Vacuum residues
-
- 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
-
- 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
- C10G2300/70—Catalyst aspects
-
- 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
- C10G2300/80—Additives
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a method for reducing the sulfur content of petroleum coke in the thermal conversion process of residual oil, which is used for reducing the sulfur content of petroleum coke in the coking process of residual oil. The method comprises the steps of uniformly mixing residual oil and a sulfur transfer agent, then sending the mixture into a coking device, and carrying out coking reaction to obtain low-sulfur petroleum coke, wherein the sulfur transfer agent comprises a mixture of an oil-soluble metal catalyst, an oil-soluble metal catalytic auxiliary agent and a desulfurization auxiliary agent.
Description
Technical Field
The invention relates to the technical field of residual oil raw material treatment, in particular to a method for reducing sulfur content of petroleum coke in a residual oil thermal conversion process.
Background
CN104946294B discloses an improved delayed coking process, in which a coking raw material is mixed with a hydrogenation catalytic distillate to obtain a mixed oil; the mixed oil is subjected to viscosity reduction-coking or direct coking to obtain coking gas, coking liquid and coke. By adding the hydrogenation catalytic distillate, the free radical thermal cracking and condensation reaction is terminated, the coking liquid yield is increased, and the coke yield is reduced.
CN110079354a discloses a method for preparing low sulfur petroleum coke by pretreating delayed coking raw materials, cavitation oxidation treatment is carried out on the delayed coking raw materials by adopting an oxidant-catalyst, and then viscosity reduction treatment is carried out, so that S element in the raw materials is converted into gas, the sulfur content of petroleum coke produced in the coking process is reduced, and the low sulfur petroleum coke is prepared.
US4919793a discloses an improved coking method, which comprises the steps of adding a thermal cracking tube in front of a heating furnace, sending gas with high hydrogen content into the thermal cracking tube, carrying out hydro-upgrading on residual oil raw materials in front of the coking heating furnace in the thermal cracking tube, improving the liquid yield of coking products, and reducing the coke and gas yields.
The prior process for reducing the sulfur content of petroleum coke in the thermal conversion process of residual oil is improved, so that the technical problem of high cost is generally existed.
Disclosure of Invention
The invention aims to solve the technical problem of how to reduce the sulfur content of petroleum coke in the thermal conversion process of residual oil at low cost.
The invention provides a method for reducing sulfur content of petroleum coke in a residual oil thermal conversion process, which comprises the following steps: mixing a proper amount of residual oil and a sulfur transfer agent, putting the mixture into a coking reaction device, and carrying out coking reaction to obtain the low-sulfur petroleum coke and oil-gas mixture, wherein the sulfur transfer agent is a mixture of an oil-soluble metal catalyst, an oil-soluble metal catalyst auxiliary agent and a desulfurization auxiliary agent, the mass fraction of the oil-soluble metal catalyst is 0.01-1%, the mass fraction of the oil-soluble metal catalyst auxiliary agent is 0.01-1%, and the mass fraction of the sulfur transfer agent is 5-20% based on the weight of the vacuum residual oil.
In the invention, the residual oil raw oil is one of atmospheric residual oil, vacuum residual oil and visbreaking oil;
in the invention, the desulfurization auxiliary agent comprises three kinds of decalin, tetrahydronaphthalene, polyethylene glycol 6000, polyethylene glycol 8000, polyethylene glycol 10000, palmitic acid and stearic acid; preferably polyethylene glycol 6000, polyethylene glycol 8000, polyethylene glycol 10000; the composition of the desulfurization auxiliary agent is polyethylene glycol 6000 based on the total amount of the desulfurization auxiliary agent: polyethylene glycol 8000: polyethylene glycol 10000=0.1 to 10:0.1 to 10:0.1 to 10.
In the invention, the metal element in the oil-soluble metal catalyst is selected from VIII group metal and VIB group metal, including iron, cobalt, nickel, molybdenum and tungsten; in order to lower the sulfur content of petroleum coke generated in the coking process, the VIII group metal and the VIB group metal in the catalyst are preferably nickel and tungsten.
In the present invention, the metal element in the oil-soluble metal catalyst promoter is selected from rare earth metals including cerium, scandium, preferably cerium.
In the invention, the carrier of the oil-soluble metal catalyst is alumina, and the carrier is modified by adopting the auxiliary agent containing boron, fluorine and phosphorus, and the content of the modified auxiliary agent is 0.5-5% based on the mass of the alumina. The modifying auxiliary agent is preferably fluorine, and the content is preferably 1-3%;
in the present invention, the reaction conditions for the coking reaction are: the reaction temperature is 400-500 ℃, the reaction time is 0.5-4 h, and the preferable reaction conditions are as follows: the reaction temperature is 450-500 ℃ and the reaction time is 1-3 h.
The laboratory evaluation method of the sulfur transfer agent selected by the invention comprises the following steps:
the evaluation method of the sulfur transfer agent is as follows: adding proper amount of sulfur transfer agent into the residual oil, heating and stirring until the auxiliary agent and the residual oil are mixed uniformly, closing the electric heating sleeve, pouring into a coking device while the electric heating sleeve is hot, and adding N 2 The device was continuously vented to replace the air in the device, 3 successive replacements. And then setting the reaction temperature, turning on a heating switch, starting timing when the temperature is stable, turning off heating after the reaction time is reached, and ending the reaction. After the device is completely cooled to room temperature, the device is opened, and the coke in the device is taken out. And (3) taking a proper amount of coke, putting the coke into a sulfur detector for sulfur content test, comparing the sulfur content of the coke generated by the coking reaction without adding the sulfur transfer agent, and evaluating the effect of the sulfur transfer agent according to the change of the sulfur content.
Technical innovation of the invention
The invention discloses a method for reducing the sulfur content of petroleum coke in the thermal conversion process of residual oil, which is characterized in that the residual oil, an oil-soluble metal catalyst auxiliary agent and a desulfurization auxiliary agent are mixed uniformly and then fed into a coking device, so that the sulfur content of petroleum coke generated in the coking process can be obviously reduced. The oil-soluble metal catalyst auxiliary agent selects rare earth elements, and the rare earth elements contain 4f orbitals which are not full of electrons from the aspect of an electron layer structure, so that lone pair electrons of S atoms are easily transferred to rare earth metals, the bond energy of C-S is reduced, and sulfur elements and the rare earth metals form metal-sulfur bonds to be removed. On the other hand, the catalyst carrier is modified by the fluorine-containing reagent, so that the acidity of the carrier can be improved by fluorine ions, the cracking capacity of the catalyst is improved, the hydrogenolysis activity of C-S bonds is improved, and the sulfur transfer can be efficiently promoted in the coking process.
Detailed Description
Embodiments of the invention will now be described in detail and with clarity, but with the description of only some, but not all embodiments of the invention.
The basic physical properties of the residual oil feedstock used in the examples and comparative examples are shown in table 1.
TABLE 1
Example 1
The sulfur transfer agent 1 is a nickel catalyst and cerium catalyst auxiliary agent combined desulfurization auxiliary agent polyethylene glycol 6000/polyethylene glycol 8000/polyethylene glycol 10000, the desulfurization auxiliary agent proportion is 10% of the residual oil mass, the residual oil raw oil and the sulfur transfer agent 1 are mixed and then added into a coking device, and the coking device is heated to the coking temperature for reaction, wherein the reaction conditions are as follows: the reaction temperature was 500℃and the reaction time was 3 hours. And (3) the generated petroleum coke is left at the bottom of the coking device, coking gas, coking gasoline and diesel oil and coking wax oil are obtained through coking gas-oil separation, and sulfur content test is carried out on the obtained coke.
The mass fraction of the nickel catalyst is 0.5% based on the mass of the residual oil; the mass fraction of the cerium-type catalyst auxiliary agent is 0.5%; desulfurization auxiliary agent composition: polyethylene glycol 6000: polyethylene glycol 8000: polyethylene glycol 10000=1: 1.3:1.
example 2
The sulfur transfer agent 2 is a fluorine modified nickel catalyst and cerium catalyst auxiliary agent combined desulfurization auxiliary agent polyethylene glycol 6000/polyethylene glycol 8000/polyethylene glycol 10000, the proportion of the desulfurization auxiliary agent is 10% of the residual oil mass, the residual oil raw oil and the sulfur transfer agent 2 are mixed and then added into a coking device, and the coking device is heated to the coking temperature for reaction, wherein the reaction conditions are as follows: the reaction temperature was 500℃and the reaction time was 3 hours. And (3) the generated petroleum coke is left at the bottom of the coking device, coking gas, coking gasoline and diesel oil and coking wax oil are obtained through coking gas-oil separation, and sulfur content test is carried out on the obtained coke.
The mass fraction of the nickel catalyst is 0.5% based on the mass of the residual oil; the mass fraction of the cerium-type catalyst auxiliary agent is 0.5%; taking the mass of the alumina carrier as a reference, the mass fraction of fluorine in the modified carrier is 1%, and the desulfurization auxiliary agent comprises the following components: polyethylene glycol 6000: polyethylene glycol 8000: polyethylene glycol 10000=1: 1.3:1.
example 3
The sulfur transfer agent 3 is tungsten catalyst and cerium catalyst auxiliary agent combined desulfurization auxiliary agent polyethylene glycol 6000/polyethylene glycol 8000/polyethylene glycol 10000, the desulfurization auxiliary agent proportion is 10% of the residual oil mass, the residual oil raw oil and the sulfur transfer agent 3 are mixed and then added into a coking device, and the reaction is carried out after heating to the coking temperature, wherein the reaction conditions are as follows: the reaction temperature was 500℃and the reaction time was 3 hours. And (3) the generated petroleum coke is left at the bottom of the coking device, coking gas, coking gasoline and diesel oil and coking wax oil are obtained through coking gas-oil separation, and sulfur content test is carried out on the obtained coke.
Based on the mass of residual oil, the mass fraction of the tungsten catalyst is 0.5%, the mass fraction of the cerium catalyst auxiliary agent is 0.5%, and the desulfurization auxiliary agent comprises: polyethylene glycol 6000: polyethylene glycol 8000: polyethylene glycol 10000=1: 1.3:1.
example 4
The sulfur transfer agent 4 is a tungsten catalyst modified by fluorine and a cerium catalyst auxiliary agent combined with a desulfurization auxiliary agent polyethylene glycol 6000/polyethylene glycol 8000/polyethylene glycol 10000, the proportion of the desulfurization auxiliary agent is 10% of the residual oil mass, the residual oil raw oil and the sulfur transfer agent 4 are mixed and then added into a coking device, and the coking device is heated to the coking temperature for reaction under the following reaction conditions: the reaction temperature was 500℃and the reaction time was 3 hours. And (3) the generated petroleum coke is left at the bottom of the coking device, coking gas, coking gasoline and diesel oil and coking wax oil are obtained through coking gas-oil separation, and sulfur content test is carried out on the obtained coke.
Taking the mass of residual oil as a reference, the mass fraction of the tungsten catalyst is 0.5%, the mass fraction of the cerium catalyst auxiliary agent is 0.5%, and the mass fraction of fluorine in the modified carrier is 1% by taking the mass of the alumina carrier as a reference; desulfurization auxiliary agent composition: polyethylene glycol 6000: polyethylene glycol 8000: polyethylene glycol 10000=1: 1.3:1.
example 5
The sulfur transfer agent 5 is a nickel catalyst and cerium catalyst auxiliary agent combined desulfurization auxiliary agent polyethylene glycol 6000/polyethylene glycol 8000/polyethylene glycol 10000, the desulfurization auxiliary agent proportion is 20% of the residual oil mass, the residual oil raw oil and the sulfur transfer agent 5 are mixed and then added into a coking device, and the reaction is carried out after heating to the coking temperature, wherein the reaction conditions are as follows: the reaction temperature was 500℃and the reaction time was 3 hours. And (3) the generated petroleum coke is left at the bottom of the coking device, coking gas, coking gasoline and diesel oil and coking wax oil are obtained through coking gas-oil separation, and sulfur content test is carried out on the obtained coke.
The mass fraction of the nickel catalyst is 0.5% based on the mass of the residual oil; the mass fraction of the cerium catalyst auxiliary agent is 0.5%, and the desulfurization auxiliary agent comprises the following components: polyethylene glycol 6000: polyethylene glycol 8000: polyethylene glycol 10000=1: 1.3:1.
example 6
The sulfur transfer agent 6 is a fluorine modified nickel catalyst and cerium catalyst auxiliary agent combined desulfurization auxiliary agent polyethylene glycol 6000/polyethylene glycol 8000/polyethylene glycol 10000, the proportion of the desulfurization auxiliary agent is 20% of the residual oil mass, the residual oil raw oil and the sulfur transfer agent 6 are mixed and then added into a coking device, and the coking device is heated to the coking temperature for reaction, wherein the reaction conditions are as follows: the reaction temperature was 500℃and the reaction time was 3 hours. And (3) the generated petroleum coke is left at the bottom of the coking device, coking gas, coking gasoline and diesel oil and coking wax oil are obtained through coking gas-oil separation, and sulfur content test is carried out on the obtained coke.
The mass fraction of the nickel catalyst is 0.5% based on the mass of the residual oil; the mass fraction of the cerium catalyst auxiliary agent is 0.5%, and the mass fraction of fluorine in the modified carrier is 1% based on the mass of the alumina carrier; desulfurization auxiliary agent composition: polyethylene glycol 6000: polyethylene glycol 8000: polyethylene glycol 10000=1: 1.3:1.
example 7
The sulfur transfer agent 7 is tungsten catalyst and cerium catalyst auxiliary agent combined desulfurization auxiliary agent polyethylene glycol 6000/polyethylene glycol 8000/polyethylene glycol 10000, the desulfurization auxiliary agent proportion is 20% of the residual oil mass, the residual oil raw oil and the sulfur transfer agent 7 are mixed and then added into a coking device, and the reaction is carried out after heating to the coking temperature, wherein the reaction conditions are as follows: the reaction temperature was 500℃and the reaction time was 3 hours. And (3) the generated petroleum coke is left at the bottom of the coking device, coking gas, coking gasoline and diesel oil and coking wax oil are obtained through coking gas-oil separation, and sulfur content test is carried out on the obtained coke.
Based on the mass of residual oil, the mass fraction of the tungsten catalyst is 0.5%, the mass fraction of the cerium catalyst auxiliary agent is 0.5%, and the desulfurization auxiliary agent comprises: polyethylene glycol 6000: polyethylene glycol 8000: polyethylene glycol 10000=1: 1.3:1.
example 8
The sulfur transfer agent 8 is a tungsten catalyst modified by fluorine and a cerium catalyst auxiliary agent combined with a desulfurization auxiliary agent polyethylene glycol 6000/polyethylene glycol 8000/polyethylene glycol 10000, the proportion of the desulfurization auxiliary agent is 20% of the residual oil mass, the residual oil raw oil and the sulfur transfer agent 8 are mixed and then added into a coking device, and the coking device is heated to the coking temperature for reaction under the following reaction conditions: the reaction temperature was 500℃and the reaction time was 3 hours. And (3) the generated petroleum coke is left at the bottom of the coking device, coking gas, coking gasoline and diesel oil and coking wax oil are obtained through coking gas-oil separation, and sulfur content test is carried out on the obtained coke.
Taking the mass of residual oil as a reference, the mass fraction of the tungsten catalyst is 0.5%, the mass fraction of the cerium catalyst auxiliary agent is 0.5%, and the mass fraction of fluorine in the modified carrier is 1% by taking the mass of the alumina carrier as a reference; desulfurization auxiliary agent composition: polyethylene glycol 6000: polyethylene glycol 8000: polyethylene glycol 10000=1: 1.3:1.
example 9
Mixing residual oil raw oil with a desulfurization auxiliary agent polyethylene glycol 6000/polyethylene glycol 8000/polyethylene glycol 10000 (the proportion of the desulfurization auxiliary agent is 20% of the residual oil mass), adding into a coking device, heating to a coking temperature, and reacting under the following reaction conditions: the reaction time was 3h at 500 ℃. And (3) the generated petroleum coke is left at the bottom of the coking device, coking gas, coking gasoline and diesel oil and coking wax oil are obtained through coking gas-oil separation, and sulfur content test is carried out on the obtained coke.
Desulfurization auxiliary agent composition: polyethylene glycol 6000: polyethylene glycol 8000: polyethylene glycol 10000=1: 1.3:1.
comparative example 1
Directly adding residual oil raw oil into a coking device, heating to coking temperature, and reacting under the following reaction conditions: the reaction temperature was 500℃and the reaction time was 3 hours. And (3) the generated petroleum coke is left at the bottom of the coking device, coking gas, coking gasoline and diesel oil and coking wax oil are obtained through coking gas-oil separation, and sulfur content test is carried out on the obtained coke.
Comparative example 2
The residual oil raw oil, the nickel catalyst and the cerium catalyst auxiliary agent are mixed and added into a coking device, and the reaction is carried out after heating to the coking temperature, wherein the reaction conditions are as follows: the reaction time was 3h at 500 ℃. And (3) the generated petroleum coke is left at the bottom of the coking device, coking gas, coking gasoline and diesel oil and coking wax oil are obtained through coking gas-oil separation, and sulfur content test is carried out on the obtained coke.
The mass fraction of the nickel catalyst is 0.5% based on the mass of the residual oil; the mass fraction of the cerium-type catalyst promoter is 0.5%.
Comparative example 3
Mixing residual oil raw oil, fluorine modified nickel catalyst and cerium catalyst auxiliary agent, adding into a coking device, heating to coking temperature, and reacting under the following reaction conditions: the reaction time was 3h at 500 ℃. And (3) the generated petroleum coke is left at the bottom of the coking device, coking gas, coking gasoline and diesel oil and coking wax oil are obtained through coking gas-oil separation, and sulfur content test is carried out on the obtained coke.
The mass fraction of the nickel catalyst is 0.5% based on the mass of the residual oil; the mass fraction of the cerium-type catalyst promoter is 0.5%. The mass fraction of fluorine in the modified carrier is 1% based on the mass of the alumina carrier.
Comparative example 4
The residual oil raw oil, the tungsten catalyst and the cerium catalyst auxiliary agent are mixed and added into a coking device, and the reaction is carried out after the heating to the coking temperature, wherein the reaction conditions are as follows: the reaction time was 3h at 500 ℃. And (3) the generated petroleum coke is left at the bottom of the coking device, coking gas, coking gasoline and diesel oil and coking wax oil are obtained through coking gas-oil separation, and sulfur content test is carried out on the obtained coke.
Based on the mass of residual oil, the mass fraction of the tungsten catalyst is 0.5%, and the mass fraction of the cerium catalyst auxiliary agent is 0.5%.
Comparative example 5
The residual oil raw oil, the fluorine modified tungsten catalyst and the cerium catalyst auxiliary agent are mixed and added into a coking device, and the reaction is carried out after the mixture is heated to the coking temperature, wherein the reaction conditions are as follows: the reaction time was 3h at 500 ℃. And (3) the generated petroleum coke is left at the bottom of the coking device, coking gas, coking gasoline and diesel oil and coking wax oil are obtained through coking gas-oil separation, and sulfur content test is carried out on the obtained coke.
Based on the mass of residual oil, the mass fraction of the tungsten catalyst is 0.5%, and the mass fraction of the cerium catalyst auxiliary agent is 0.5%. The mass fraction of fluorine in the modified carrier is 1% based on the mass of the alumina carrier.
Comparative example 6
Mixing residual oil raw oil with a desulfurization auxiliary agent polyethylene glycol 6000/polyethylene glycol 8000/polyethylene glycol 10000 (the proportion of the desulfurization auxiliary agent is 10% of the residual oil mass), adding into a coking device, heating to a coking temperature, and reacting under the following reaction conditions: the reaction time was 3h at 500 ℃. And (3) the generated petroleum coke is left at the bottom of the coking device, coking gas, coking gasoline and diesel oil and coking wax oil are obtained through coking gas-oil separation, and sulfur content test is carried out on the obtained coke.
Desulfurization auxiliary agent composition: polyethylene glycol 6000: polyethylene glycol 8000: polyethylene glycol 10000=1: 1.3:1.
comparative example 7
The residual oil raw oil and the desulfurization auxiliary agent decalin (the desulfurization auxiliary agent proportion is 20% of the residual oil mass) are mixed and added into a coking device, and the reaction is carried out after heating to the coking temperature, wherein the reaction conditions are as follows: the reaction time was 3h at 500 ℃. And (3) the generated petroleum coke is left at the bottom of the coking device, coking gas, coking gasoline and diesel oil and coking wax oil are obtained through coking gas-oil separation, and sulfur content test is carried out on the obtained coke.
Comparative example 8
The residual oil raw oil and the desulfurization auxiliary agent stearic acid (the desulfurization auxiliary agent proportion is 20% of the residual oil mass) are mixed and added into a coking device, and the reaction is carried out after heating to the coking temperature, wherein the reaction conditions are as follows: the reaction time was 3h at 500 ℃. And (3) the generated petroleum coke is left at the bottom of the coking device, coking gas, coking gasoline and diesel oil and coking wax oil are obtained through coking gas-oil separation, and sulfur content test is carried out on the obtained coke.
TABLE 2
| Examples numbering | Sulfur content of petroleum coke, wt% |
| Example 1 | 2.62％ |
| Example 2 | 2.18％ |
| Example 3 | 2.74％ |
| Example 4 | 2.26％ |
| Example 5 | 2.41％ |
| Example 6 | 2.03％ |
| Example 7 | 2.51％ |
| Example 8 | 2.10％ |
| Example 9 | 3.23％ |
| Comparative example 1 | 4.87％ |
| Comparative example 2 | 4.81％ |
| Comparative example 3 | 4.80％ |
| Comparative example 4 | 4.82％ |
| Comparative example 5 | 4.81％ |
| Comparative example 6 | 3.36％ |
| Comparative example 7 | 3.62％ |
| Comparative example 8 | 3.78％ |
Comparative analysis
As can be seen from the data in Table 2, the sulfur content of the petroleum coke obtained by the coking reaction with the addition of the sulfur transfer agent in all examples was less than 3wt%. The selected oil-soluble metal catalyst auxiliary agent contains rare earth metal, and because of the specificity of the electron layer structure, the oil-soluble metal catalyst auxiliary agent easily attracts lone pair electrons on sulfur atoms, so that the lone pair electrons are biased to metal, the bond energy of carbon-sulfur bonds is weakened, and meanwhile, the carrier is modified on the basis of the basic nickel/cerium catalyst, and the fluorine-containing reagent is added for modification, thereby improving the carrier Al 2 O 3 The acidity of the nickel/cerium catalyst is enhanced, the reactivity of the hydrogenolysis of the C-S bond is improved, the isoelectric point of the carrier is reduced, more active centers of hydrodesulfurization are generated, and the activity of the catalyst is improved. Meanwhile, macromolecular polymeric alcohol substances such as polyethylene glycol 6000/polyethylene glycol 8000/polyethylene glycol 10000 are added, chain scission decomposition is carried out in the thermal reaction process, the macromolecular polymeric alcohol substances are decomposed into polyalcohol substances, H free radicals are supplied to a reaction system, the H free radicals attack C-S bonds to accelerate bond scission, and meanwhile, the macromolecular polymeric alcohol substances are combined with the broken C-S bonds to generate H 2 S, the S is removed from the reaction system in a gas form, and compared with the conventional desulfurization auxiliary agent decalin and stearic acid, the thermal reaction process of the desulfurization auxiliary agent compounded by adding polyethylene glycol 6000/polyethylene glycol 8000/polyethylene glycol 10000 can be seen from examples 7 and 8 in the table, and the sulfur content of the produced petroleum coke is lower. From the tables of example 6, example 8 and comparative examples 7, comparative examples 1 and 3, it can be seen that the sulfur content of the coke produced by modifying the catalyst and adding the macromolecular polymeric alcohol material is significantly reduced, and sulfur transfer during coking is achieved.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (7)
1. A method for reducing the sulfur content of petroleum coke in a residuum thermal conversion process, characterized in that the method for reducing the sulfur content of petroleum coke is accomplished by adding a residuum sulfur transfer agent, the method comprising: the residual oil, the oil-soluble metal catalyst auxiliary agent and the desulfurization auxiliary agent are mixed uniformly and then sent into a coking device, and coking gas, coking gasoline and diesel oil, coking wax oil and low-sulfur petroleum coke are obtained after coking reaction of the residual oil.
2. The method of claim 1, wherein the residuum feed oil is one of atmospheric residuum, vacuum residuum, visbroken oil.
3. The method according to claim 1, wherein the metal cations in the oil-soluble metal catalyst comprise iron, cobalt, nickel, molybdenum and tungsten, the metal cations are selected from group VIII metals and group VIB metals, the anions are selected from naphthenic acid and oleic acid, and the mass fraction of the catalyst is 0.01% -1% based on the mass of the residue.
4. The method according to claim 1, wherein the metal in the oil-soluble metal catalyst promoter comprises cerium and scandium, and the mass fraction of the catalyst is 0.01% -1% based on the mass of the residual oil.
5. The method according to claim 1, wherein the desulfurization aid comprises three of decalin, tetrahydronaphthalene, polyethylene glycol 6000, polyethylene glycol 8000, polyethylene glycol 10000, palmitic acid and stearic acid, preferably polyethylene glycol 6000, polyethylene glycol 8000 and polyethylene glycol 10000, and the mass fraction of the desulfurization aid is 5% -25%, preferably 10% -20% based on the weight of the residual oil raw material oil.
6. The method according to claim 1, wherein the composition of the desulfurization aid is polyethylene glycol 6000, based on the total amount of desulfurization aids: polyethylene glycol 8000: polyethylene glycol 10000=0.1 to 10:0.1 to 10:1.
7. the method of claim 1, wherein the coking reaction conditions are: the reaction temperature is 400-500 ℃, the reaction time is 0.5-4 h, and the preferable reaction conditions are as follows: the reaction temperature is 450-500 ℃ and the reaction time is 1-3 h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4399024A (en) * | 1980-11-27 | 1983-08-16 | Daikyo Oil Company Ltd. | Method for treating petroleum heavy oil |
| US5158668A (en) * | 1988-10-13 | 1992-10-27 | Conoco Inc. | Preparation of recarburizer coke |
| JPH05329376A (en) * | 1992-06-01 | 1993-12-14 | Idemitsu Kosan Co Ltd | Catalyst for hydrogenation and hydrogenation of heavy oil using the same |
| CN112442391A (en) * | 2019-08-28 | 2021-03-05 | 中国石油化工股份有限公司 | Preparation method of low-sulfur petroleum coke |
| CN112442390A (en) * | 2019-08-28 | 2021-03-05 | 中国石油化工股份有限公司 | Method for preparing low-sulfur petroleum coke from residual oil |
-
2023
- 2023-06-30 CN CN202310792396.7A patent/CN116731743A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4399024A (en) * | 1980-11-27 | 1983-08-16 | Daikyo Oil Company Ltd. | Method for treating petroleum heavy oil |
| US5158668A (en) * | 1988-10-13 | 1992-10-27 | Conoco Inc. | Preparation of recarburizer coke |
| JPH05329376A (en) * | 1992-06-01 | 1993-12-14 | Idemitsu Kosan Co Ltd | Catalyst for hydrogenation and hydrogenation of heavy oil using the same |
| CN112442391A (en) * | 2019-08-28 | 2021-03-05 | 中国石油化工股份有限公司 | Preparation method of low-sulfur petroleum coke |
| CN112442390A (en) * | 2019-08-28 | 2021-03-05 | 中国石油化工股份有限公司 | Method for preparing low-sulfur petroleum coke from residual oil |
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