CN111822058B - Pre-sulfurizing process of hydrogenation catalyst - Google Patents
Pre-sulfurizing process of hydrogenation catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 239000005416 organic matter Substances 0.000 claims abstract description 11
- 238000004073 vulcanization Methods 0.000 claims abstract description 11
- 238000009736 wetting Methods 0.000 claims abstract description 9
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- -1 boron ester organic compound Chemical class 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims abstract description 3
- 150000007513 acids Chemical class 0.000 claims abstract description 3
- 150000001298 alcohols Chemical group 0.000 claims abstract description 3
- 150000002170 ethers Chemical class 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 12
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 12
- 238000005987 sulfurization reaction Methods 0.000 claims description 11
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 10
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 claims description 8
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 claims description 8
- 239000005711 Benzoic acid Substances 0.000 claims description 6
- 235000010233 benzoic acid Nutrition 0.000 claims description 6
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003350 kerosene Substances 0.000 claims description 6
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000002283 diesel fuel Substances 0.000 claims description 5
- 239000003502 gasoline Substances 0.000 claims description 5
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 claims description 4
- 229960003424 phenylacetic acid Drugs 0.000 claims description 4
- 239000003279 phenylacetic acid Substances 0.000 claims description 4
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 4
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 3
- HQRWWHIETAKIMO-UHFFFAOYSA-N 1-phenylbutan-1-ol Chemical compound CCCC(O)C1=CC=CC=C1 HQRWWHIETAKIMO-UHFFFAOYSA-N 0.000 claims description 2
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 claims description 2
- 229940126062 Compound A Drugs 0.000 claims description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropanol Chemical compound CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 claims description 2
- 229950009195 phenylpropanol Drugs 0.000 claims description 2
- 150000003577 thiophenes Chemical class 0.000 claims description 2
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 claims description 2
- LTEHWCSSIHAVOQ-UHFFFAOYSA-N tripropyl borate Chemical compound CCCOB(OCCC)OCCC LTEHWCSSIHAVOQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 20
- 239000007789 gas Substances 0.000 abstract description 12
- 238000010438 heat treatment Methods 0.000 abstract description 12
- 239000003921 oil Substances 0.000 description 57
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011160 research Methods 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- YAVVGPBYBUYPSR-UHFFFAOYSA-N benzene;oxygen Chemical compound [O].C1=CC=CC=C1 YAVVGPBYBUYPSR-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a presulfurization method of a hydrogenation catalyst, which comprises the following steps: (1) Filling an oxidation state hydrogenation catalyst in the reactor and confirming that the gas tightness is qualified; (2) adopting hydrogen to boost pressure; (3) Introducing vulcanized oil containing a vulcanizing agent and an additive into the reactor, and wetting a catalyst bed layer; the additive is a mixture of A and B, wherein A is a boron ester organic compound, B is an organic matter containing a benzene ring substituent, and the organic matter is alcohols, ethers or acids; (4) Adjusting the temperature of the catalyst bed layer to 120-180 ℃, after the hydrogen sulfide penetrates through the catalyst bed layer, heating the temperature of the catalyst bed layer to 180-240 ℃, and keeping the temperature for 4-16 hours; then raising the temperature of the catalyst bed to 250-330 ℃, and keeping the temperature for 4-16 hours; (5) And after vulcanization is finished, adjusting the process conditions of the system to reaction conditions, and switching the raw oil for normal operation. By adopting the presulfurization method provided by the invention, the hydrogenation catalyst has higher activity after being vulcanized.
Description
Technical Field
The invention relates to a presulfurization method of a hydrogenation catalyst, which is particularly suitable for presulfurization of hydrotreating, hydro-upgrading and hydrocracking catalysts.
Background
The hydrogenation catalyst comprises hydrotreating, hydro-upgrading and hydrocracking catalysts. Usually, the metal component of the hydrogenation catalyst is non-noble metal, and the VIB group metal and/or VIII group metal are used as active component, the VIB group metal is Mo and W, and the VIII group metal is Co and Ni. Before the non-noble metal catalyst is used, a presulfurization process needs to be completed, namely, the oxidation state active metal is reduced into a sulfuration state active matter, and then the catalyst has higher activity. Therefore, presulfiding has a significant effect on the performance of the catalyst and is an important process step prior to catalyst application.
CN201110321357 discloses a hydrofining catalyst sulfurizing method. According to the method, hydrogen sulfide and a vulcanizing agent are introduced into the system at a higher temperature, so that the low-temperature independent vulcanization of Co and/or Ni can be avoided, and Mo and/or W and Co and/or Ni are simultaneously vulcanized to form a high-activity Mo (W) -Co (Ni) -S active phase under the condition of higher temperature and the presence of hydrogen sulfide, and the deep hydrodesulfurization activity of the catalyst is improved.
CN201010222027 discloses a startup sulfuration method for hydrogenation catalysts. The method introduces the vulcanizing oil with a wetting temperature lower than that of the conventional vulcanizing temperature, and the requirement is less than 120 ℃. The catalyst start-up sulfuration method is beneficial to the catalyst to form more second-class hydrogenation active centers and is beneficial to improving the service performance of the catalyst.
CN201210408349 discloses a sulfurization method of a hydrodesulfurization catalyst. In the process of sulfurizing the hydrodesulfurization catalyst, the sulfurization is carried out firstly at a higher pressure and a lower temperature and then at a lower pressure and a higher temperature. The method of the invention can form more CoMoS phases and make the CoMoS phases more dispersed, generate more sulfur vacancies and form more desulfurization centers, thereby improving the hydrodesulfurization activity of the catalyst.
Said invention patent is characterized by that it utilizes the change of technological parameter of sulfurizing process to raise the activity of hydrogenation catalyst.
CN1165600 discloses a sulfiding method relating to a hydrocarbon feedstock hydroprocessing catalyst. According to the inventive method, a small amount of at least one phthalate is added to the sulfiding agent used to sulfide the catalyst. The catalyst thus sulphided proved to be more active than the conventional sulphided catalyst.
CN200410050714 discloses a method for presulfurizing a hydrogenation catalyst, which comprises contacting a sulfur oil containing an additive and a vulcanizing agent with a hydrogenation catalyst in a conventional oxidation state under presulfurization conditions in an atmosphere containing hydrogen gas for presulfurizing. The prevulcanisation conditions used were: the temperature is 100-400 ℃, the contact time is 0.1-24 h, the hydrogen partial pressure is 0.1-15 MPa, and the liquid hourly space velocity is 0.1h -1 ～10h -1 The volume ratio of hydrogen to oil is 50-2000. The method pre-sulfurizes the hydrogenation catalyst, and can obviously improve the activity of the catalyst.
With the implementation of increasingly strict national standards for automotive fuel oil, the activity requirement of hydrogenation catalysts is higher and higher, and it is necessary to research more advanced and effective methods to improve the pre-sulfurization effect of the catalysts, so as to improve the activity of the catalysts.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a presulfurization method of a hydrogenation catalyst. By adopting the presulfurization method provided by the invention, the hydrogenation catalyst has higher activity after being vulcanized.
The presulfurization method of the hydrogenation catalyst comprises the following steps:
(1) Filling an oxidation state hydrogenation catalyst in the reactor and confirming that the gas tightness is qualified;
(2) Starting a circulating compressor, and boosting pressure by adopting hydrogen;
(3) Introducing vulcanized oil containing a vulcanizing agent and an additive into the reactor, and wetting a catalyst bed layer; the additive is a mixture of A and B, wherein A is a boron ester organic compound, B is an organic matter containing a benzene ring substituent, and the organic matter is alcohols, ethers or acids;
(4) Adjusting the temperature of the catalyst bed layer to 120-180 ℃, after the hydrogen sulfide penetrates through the catalyst bed layer, heating the temperature of the catalyst bed layer to 180-240 ℃, and keeping the temperature for 4-16 hours; then raising the temperature of the catalyst bed to 250-330 ℃, and keeping the temperature for 4-16 hours;
(5) After the vulcanization is finished, the technological conditions of the system are adjusted to the reaction conditions, and the raw oil is switched to carry out normal operation.
In the method, the hydrogen is pure hydrogen, reformed hydrogen and the like commonly used in industry, and the purity is 75 to 100 percent, preferably 80 to 100 percent. The vulcanising oils and vulcanising agents used are well known in the art. The vulcanized oil can be one or more of straight-run gasoline, straight-run kerosene, refined gasoline, refined kerosene, first-line diesel oil, long second-line diesel oil and the like, and preferably one or more of straight-run kerosene, refined kerosene or first-line diesel oil. The vulcanizing agent is one or more of hydrogen sulfide, carbon disulfide, mercaptan, dimethyl disulfide, dimethyl sulfide or thiophene compounds, and the like, and preferably, the carbon disulfide, the dimethyl disulfide or the dimethyl sulfide. The sulfur content in the vulcanized oil is 0.2 to 10wt%, and preferably 0.5 to 3wt%.
In the method, the addition amount of the boron ester organic compound A is 0.05 to 10 percent of the weight of the vulcanized oil, preferably 0.1 to 5 percent; the addition amount of the organic matter containing the benzene ring substituent in the B is 0.05-10%, preferably 0.3-8% of the weight of the vulcanized oil. The mass ratio of A to B is 0.1 to 5, preferably 0.15 to 3, and more preferably 0.5 to 2.
In the method of the invention, the organic compounds of the borate esters are one or more of trimethyl borate, triethyl borate, tripropyl borate and tributyl borate, and trimethyl borate and/or triethyl borate are preferred. The organic matter containing the benzene ring substituent in the B is one or more of benzyl alcohol, phenethyl alcohol, anisole, phenetole, phenylpropanol, phenylbutanol, benzoic acid, phenylacetic acid or phenylpropanoic acid, preferably one or more of benzyl alcohol, phenethyl alcohol, anisole, phenetole, benzoic acid or phenylacetic acid.
In the method of the invention, the liquid hourly volume space velocity of the vulcanized oil is generally 0.1-10 h -1 The hydrogen-oil volume ratio in the vulcanization process is usually 50 to 1000, preferably 200 to 600.
In the method of the invention, in the step (4) in the process of constant temperature vulcanization at 180-240 ℃, the concentration of hydrogen sulfide in hydrogen is generally controlled to be 1000-20000 mu L/L; in the process of constant temperature vulcanization at 250-330 ℃, the concentration of hydrogen sulfide in hydrogen is generally controlled to be 5000-30000 mu L/L.
The conditions for the end of the vulcanization described in step (5) in the process of the invention are also well known to the person skilled in the art. For example, the common conditions for ending the sulfuration are that the concentration of the hydrogen sulfide in the circulating hydrogen at least reaches 10000 muL/L and does not drop, the liquid level of the high water separation is not increased, and the injection amount of the vulcanizing agent reaches the theoretical sulfur demand.
By adopting the hydrogenation catalyst presulfurization method, researches show that the organic borate compounds and the benzene oxygen-containing organic compounds which are taken as polar molecules are matched with each other and can be adsorbed on the surface of the active metal of the catalyst, so that the common sulfuration of the active metals Co/Ni and Mo/W is promoted, the excessive agglomeration of the metal in the sulfuration process is avoided, and the dispersion degree of the active metal components of the catalyst is improved. Meanwhile, the boron element in the borate is taken as an electron pair acceptor and adsorbed on the surface of the catalyst, so that the overall acidity of the catalyst is improved, and the vulcanization reaction of the oxidation state metal is promoted, thereby improving the hydrogenation activity of the catalyst.
Drawings
FIG. 1 is a TEM spectrum of the catalyst of example 4 after sulfiding.
Fig. 2 is a TEM spectrum of the catalyst of comparative example 3 after sulfiding.
Detailed Description
The following examples further illustrate the present invention and the effects thereof, but are not intended to limit the present invention.
In the embodiment and the comparative example of the invention, a hydrogenation catalyst FHUDS-5 (developed by the Fushun petrochemical research institute and produced by the Fushun division company of the Chinese petrochemical catalyst) is selected. The catalyst takes alumina as a carrier and Co-Mo metal as an active component, and the active metal accounts for 25 percent of the oxide. The specific surface area of the catalyst is 210 m 2 Per g, pore volume of 0.39 cm 3 (iv) g. The vulcanizate and basestock properties are shown in Table 1.
Table 1 properties of the sulfurized oils and the raw stock oils.
Comparative example 1
The conventional sulfurization conditions of common hydrogenation catalysts are adopted. 100mL of catalyst FHUDS-5 is filled into a small reactor, the airtightness is qualified, the hydrogen partial pressure is adjusted to be 6.4MPa, the catalyst FHUDS is pumped into a vulcanized oil wetting bed layer, the temperature is increased by 20 ℃/h, vulcanized oil is started to be fed when the temperature is increased to 140 ℃, and the vulcanized oil contains 2wt% of CS 2 Straight-run gasoline, with the conditions that the hydrogen-oil ratio is 350:1, the hourly space velocity of the vulcanized oil is 2.0h -1 And keeping the temperature constant for 3 hours. After the constant temperature is over, H 2 And (3) continuously heating the S gas to 230 ℃ at a speed of 20 ℃/h after the S gas penetrates through the bed layer, keeping the temperature for 6h, continuously heating to 330 ℃ at a speed of 20 ℃/h after the constant temperature is finished, and keeping the temperature for 8h. And after the constant temperature is finished, raw oil is switched according to the operation, and the process conditions are as follows: the system pressure is 6.4MPa, and the liquid hourly volume space velocity is 2.0h -1 The hydrogen-oil ratio is 400, and after the reactor is stably operated for 48 hours at 365 ℃, a finished oil sample is collected for analysis, and the catalyst activity is shown in Table 2.
Example 1
100mL of catalyst FHUDS-5 is filled into a small-sized reactor, the airtightness is qualified, the hydrogen partial pressure is adjusted to be 6.4MPa, the catalyst FHUDS is pumped into a vulcanized oil wetting bed layer, the temperature is increased by 20 ℃/h, vulcanized oil containing a vulcanizing agent and an additive is started to be added when the temperature is increased to 140 ℃, wherein the vulcanized oil contains 2wt% of CS 2 0.3wt% trimethyl borate and 0.5wt% benzyl alcohol, provided that the hydrogen to oil ratio is 350:1, the hourly space velocity of the vulcanized oil is 2.0h -1 And keeping the temperature constant for 3 hours. After the constant temperature is over, H 2 And (3) continuously heating the S gas to 230 ℃ at a speed of 20 ℃/h after the S gas penetrates through the bed layer, keeping the temperature for 6h, continuously heating to 330 ℃ at a speed of 20 ℃/h after the constant temperature is finished, and keeping the temperature for 8h. And after the constant temperature is finished, raw oil is switched according to the operation, and the process conditions are as follows: the system pressure is 6.4MPa, and the liquid hourly volume space velocity is 2.0h -1 The hydrogen-oil ratio is 400, and after the reactor is stably operated for 48 hours at 365 ℃, a finished oil sample is collected for analysis, and the catalyst activity is shown in Table 2.
Example 2
100mL of catalyst FHUDS-5 is filled into a small-sized reactor, the airtightness is qualified, the hydrogen partial pressure is adjusted to be 6.4MPa, the catalyst FHUDS is pumped into a vulcanized oil wetting bed layer, the temperature is increased by 20 ℃/h, vulcanized oil containing a vulcanizing agent and an additive is started to be added when the temperature is increased to 140 ℃, wherein the vulcanized oil contains 2wt% of CS 2 0.8wt% triethyl borate and 0.8wt% anisole, provided that the hydrogen to oil ratio is 350:1, the hourly space velocity of the vulcanized oil is 2.0h -1 And keeping the temperature constant for 3 hours. After the constant temperature is over, H 2 And (3) continuously heating the S gas to 220 ℃ at a speed of 20 ℃/h after the S gas penetrates through the bed layer, keeping the temperature for 6h, continuously heating to 330 ℃ at a speed of 20 ℃/h after the constant temperature is finished, and keeping the temperature for 8h. And after the constant temperature is finished, raw oil is switched according to the operation, and the process conditions are as follows: the system pressure is 6.4MPa, and the liquid hourly volume space velocity is 2.0h -1 The hydrogen-oil ratio is 400, and after the reactor is stably operated for 48 hours at 365 ℃, a finished oil sample is collected for analysis, and the catalyst activity is shown in Table 2.
Example 3
100mL of catalyst FHUDS-5 is put into a small reactor, the airtightness is qualified, the hydrogen partial pressure is adjusted to be 6.4MPa, the catalyst FHUDS-5 is pumped into a vulcanized oil wetting bed layer, the temperature is raised by 20 ℃/h, vulcanizing agent and additive vulcanized oil are added when the temperature is raised to 140 ℃, wherein the vulcanized oil contains 2wt% of CS 2 2.5wt% triethyl borate and 2.0wt% phenethyl alcohol, provided that the hydrogen-to-oil ratio is 350:1, the hourly space velocity of the vulcanized oil is 2.0h -1 And keeping the temperature constant for 3 hours. After the constant temperature is over, H 2 And (3) continuously heating the S gas to 220 ℃ at a speed of 20 ℃/h after the S gas penetrates through the bed layer, keeping the temperature for 6h, continuously heating to 330 ℃ at a speed of 20 ℃/h after the constant temperature is finished, and keeping the temperature for 8h. And after the constant temperature is finished, raw oil is switched according to the operation, and the process conditions are as follows: the system pressure is 6.4MPa, and the liquid hourly volume airspeed is 2.0h -1 The hydrogen-oil ratio is 400, and after the reactor is stably operated for 48 hours at 365 ℃, a finished oil sample is collected for analysis, and the catalyst activity is shown in Table 2.
Example 4
100mL of catalyst FHUDS-5 is put into a small reactor, the airtightness is qualified, the hydrogen partial pressure is adjusted to be 6.4MPa, the catalyst FHUDS-5 is pumped into a vulcanized oil wetting bed layer, the temperature is raised at 20 ℃/h, vulcanizing agent and additive vulcanized oil are added when the temperature is raised to 140 ℃, wherein the vulcanized oil contains 2wt% of CS 2 4.0wt% triethyl borate and 6.0wt% benzoic acid, provided that the hydrogen to oil ratio is 350:1, the hourly space velocity of the vulcanized oil is 2.0h -1 And keeping the temperature constant for 3 hours. After the constant temperature is over, H 2 And (3) continuously heating the S gas to 220 ℃ at a speed of 20 ℃/h after the S gas penetrates through the bed layer, keeping the temperature for 6h, continuously heating to 330 ℃ at a speed of 20 ℃/h after the constant temperature is finished, and keeping the temperature for 8h. And after the constant temperature is finished, raw oil is switched according to the operation, and the process conditions are as follows: the system pressure is 6.4MPa, and the liquid hourly volume airspeed is 2.0h -1 The hydrogen-oil ratio is 400, and after the reactor is stably operated for 48 hours at 365 ℃, a finished oil sample is collected for analysis, and the catalyst activity is shown in Table 2.
Comparative example 2
The protocol of example 2 was followed, but no anisole was added to the sulfurized oil.
Comparative example 3
The protocol of example 4 was followed except that triethyl borate was not added to the sulfide oil.
Comparative example 4
The protocol of example 4 was followed except that the percentage of triethyl borate and benzoic acid was changed to 4.0wt% and 0.6 wt%.
Table 2 refined oil properties.
As can be seen from fig. 1 and 2, the active components of the catalyst after sulfidation by the process of the present invention are more dispersed. As can be seen from Table 2, the catalyst activity was better with the start-up method provided by the present invention.
Claims (10)
1. The presulfurization method of hydrogenation catalyst is characterized by comprising the following steps: (1) Filling an oxidation state hydrogenation catalyst in the reactor and confirming that the air tightness is qualified; (2) starting the circulating compressor, and boosting the pressure by adopting hydrogen; (3) Introducing vulcanized oil containing a vulcanizing agent and an additive into the reactor, and wetting a catalyst bed layer; the additive is a mixture of A and B, wherein A is a boron ester organic compound, B is an organic matter containing a benzene ring substituent, and the organic matter is alcohols, ethers or acids; (4) Adjusting the temperature of the catalyst bed layer to be increased to 120-180 ℃, after the hydrogen sulfide penetrates through the catalyst bed layer, increasing the temperature of the catalyst bed layer to 180-240 ℃, and keeping the temperature for 4-16 hours; then raising the temperature of the catalyst bed to 250-330 ℃, and keeping the temperature for 4-16 hours; (5) After the vulcanization is finished, the technological conditions of the system are adjusted to the reaction conditions, and the raw oil is switched to carry out normal operation.
2. The method of claim 1, wherein: the vulcanized oil is one or more of straight-run gasoline, straight-run kerosene, refined gasoline, refined kerosene, normal first-line diesel oil or normal second-line diesel oil; the vulcanizing agent is one or more of hydrogen sulfide, carbon disulfide, mercaptan, dimethyl disulfide, dimethyl sulfide or thiophene compounds; the sulfur content in the vulcanized oil is 0.2 to 10wt%.
3. The method of claim 1, wherein: the addition amount of the boron ester organic compound A is 0.05-10% of the weight of the vulcanized oil.
4. The method of claim 1, wherein: the addition amount of the organic matter containing the benzene ring substituent in the B is 0.05-10% of the weight of the vulcanized oil.
5. The method of claim 1, wherein: the mass ratio of A to B is 0.1 to 5.
6. The method of claim 1, wherein: the borate organic compound is one or more of trimethyl borate, triethyl borate, tripropyl borate or tributyl borate.
7. The method of claim 1, wherein: the organic matter containing the benzene ring substituent is one or more of benzyl alcohol, phenethyl alcohol, anisole, phenetole, phenylpropanol, phenylbutanol, benzoic acid, phenylacetic acid or phenylpropionic acid.
8. The method of claim 1, wherein: the organic matter containing the benzene ring substituent is one or more of benzyl alcohol, phenethyl alcohol, anisole, phenetole, benzoic acid or phenylacetic acid.
9. The method of claim 1, wherein: the liquid hourly volume space velocity of the vulcanized oil is 0.1-10 h -1 The volume ratio of hydrogen to oil in the sulfurization process is 50-1000.
10. The method of claim 1, wherein: in the step (4), the concentration of hydrogen sulfide in hydrogen is controlled to be 1000-20000 mu L/L in the process of constant temperature vulcanization at 180-240 ℃; in the process of constant temperature vulcanization at 250-330 ℃, the concentration of hydrogen sulfide in hydrogen is controlled to be 5000-30000 mu L/L.
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Effective date of registration: 20231113 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |