CN113117762A - Hydrocracking catalyst pretreatment method - Google Patents
Hydrocracking catalyst pretreatment method Download PDFInfo
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- CN113117762A CN113117762A CN201911417752.7A CN201911417752A CN113117762A CN 113117762 A CN113117762 A CN 113117762A CN 201911417752 A CN201911417752 A CN 201911417752A CN 113117762 A CN113117762 A CN 113117762A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 162
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 141
- 238000002203 pretreatment Methods 0.000 title claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 57
- 238000004073 vulcanization Methods 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 230000003647 oxidation Effects 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 76
- 238000000034 method Methods 0.000 claims description 61
- 239000007789 gas Substances 0.000 claims description 47
- 239000001257 hydrogen Substances 0.000 claims description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 38
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 37
- 229910052717 sulfur Inorganic materials 0.000 claims description 36
- 239000011593 sulfur Substances 0.000 claims description 36
- 230000008569 process Effects 0.000 claims description 31
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 17
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical group [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 17
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 14
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 6
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 5
- 239000012159 carrier gas Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 238000002161 passivation Methods 0.000 abstract description 21
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 25
- 206010037544 Purging Diseases 0.000 description 21
- 238000010926 purge Methods 0.000 description 21
- 238000002347 injection Methods 0.000 description 18
- 239000007924 injection Substances 0.000 description 18
- 230000000694 effects Effects 0.000 description 15
- 229910021529 ammonia Inorganic materials 0.000 description 12
- 238000005336 cracking Methods 0.000 description 10
- 238000011160 research Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 230000000630 rising effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000005987 sulfurization reaction Methods 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 1
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229940100684 pentylamine Drugs 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J33/00—Protection of catalysts, e.g. by coating
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
-
- 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
- C10G2300/705—Passivation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a pretreatment method of a hydrocracking catalyst, which comprises the steps of mixing an oxidation state hydrocracking catalyst with a pretreatment agent, then carrying out treatment in the presence of a first gas, stopping introducing the first gas after the treatment is finished, simultaneously switching to introducing a second gas for treatment, adjusting the temperature to 80-150 ℃ after the treatment is finished, stopping introducing the second gas, switching to introducing the first gas for treatment for a period of time, and obtaining the pretreated hydrocracking catalyst after the treatment is finished. The pretreatment method can synchronously finish the vulcanization and passivation of the catalyst in the preparation process of the hydrocracking catalyst, and can effectively shorten the time required by the startup, the raw material switching and the stable production working condition of the hydrocracking device.
Description
Technical Field
The invention belongs to the technical field of hydrocracking, and particularly relates to a hydrocracking catalyst pretreatment method.
Background
With the adjustment of international energy structure and the optimization of the process of a refinery enterprise, the hydrocracking process flow becomes an oil, chemical and fiber regulator because of the advantages of wide raw material source, excellent quality of cracked products, flexible operation, high liquid product yield and the like, the number of hydrocracking devices increases year by year, and the research on the hydrocracking process is paid extensive attention.
The hydrocracking device can be generally divided into a refining reaction part and a cracking reaction part, wherein the refining catalyst and the cracking catalyst are required to be vulcanized into a vulcanization state to exert activity, a vulcanizing agent is injected into a reactor for vulcanization in the conventional start-up process, the vulcanization process is not easy to control and influences the activity of the catalyst, a sulfur injection pump, a sulfur storage tank and other equipment are required, and the vulcanization time is long and influences the start-up period. At present, the true vulcanization type hydrogenation catalyst is also used in the industry to solve the problems caused by the vulcanization process in the start-up process, but the true vulcanization technology cannot solve the problems caused by the passivation operation in the start-up process of the hydrocracking unit. The cracking catalyst is a catalyst containing a molecular sieve, has strong hydrocracking activity, and the initial activity of the catalyst after activation is often high, so that the cracking catalyst can react violently if the catalyst is not inhibited, a large amount of reaction heat is released to further improve the cracking activity, the reaction is not controlled, the temperature of a catalyst bed layer is increased, potential safety hazards are caused, the activity of the catalyst is seriously influenced, and the stable operation of a device is seriously influenced. Therefore, the start-up process of the conventional hydrocracking unit is obviously different from that of other hydrocracking units, and the conventional hydrocracking unit needs certain passivation treatment on the cracking catalyst after the start-up of the unit for vulcanization operation. The prior hydrocracking catalyst passivation operation in the industry can be divided into two categories of ammonia injection passivation and aging treatment, and the application is wide but the obvious defects exist.
The start-up process of ammonia injection of the hydrocracking device generally comprises the steps of introducing start-up oil into the device at a low temperature, introducing a vulcanizing agent into the device when the temperature of a reaction system is increased to 180-200 ℃, starting an ammonia injection pump to inject a passivating agent (generally liquid ammonia) into a cracking reactor after the temperature is raised to a vulcanizing temperature and is kept constant for a period of time, and continuously raising the temperature and vulcanizing after ammonia penetrates. Significant disadvantages in this start-up scheme include: a special vulcanizing agent storage tank, a vulcanizing agent injection pump and a passivating agent injection pump are required to be arranged, so that the equipment investment is improved, and meanwhile, the ammonia injection operation is carried out under a high-pressure condition, so that the high requirement is provided for the ammonia injection pump, and the normal operation of a start-up link is often influenced by the failure of the ammonia injection equipment in the start-up process; on one hand, the vulcanizing agent and the passivating agent are injected on site, so that the operation difficulty is increased, and on the other hand, the environmental pollution is easily caused; meanwhile, the sulfuration and passivation effects are not easy to control, and the side reactions can only be carried out by detecting the concentration of hydrogen sulfide in the circulating hydrogen and the content of ammonia in high-acid-content water, so that the phenomena of low catalyst activity caused by insufficient sulfuration and temperature runaway of a catalyst bed layer caused by insufficient passivation often occur.
The hydrocracking start-up process of the aging treatment generally comprises the steps of introducing start-up oil into a device at a low temperature, introducing a vulcanizing agent into the device when the temperature of a reaction system is increased to 180-200 ℃, slowly increasing the temperature after the temperature is increased to a vulcanizing temperature and is kept constant for a period of time, and using enough long aging time to exceed the initial activity of the catalyst in the temperature increasing process. However, the start-up scheme of the aging treatment is easy to cause the situation that the temperature of the catalyst bed layer is not controlled, and the time for start-up is obviously longer than that for ammonia injection passivation start-up, thereby greatly influencing the economic benefit of enterprises.
The patent CN1074466A discloses a hydrocracking start-up method, wherein a hydrocracking catalyst carries 1-6% of nitrogen element, the nitrogen element is one or more of propylamine, butylamine and pentylamine, the start-up process comprises the steps of introducing low-nitrogen start-up oil, hydrogen and a vulcanizing agent into a device at low temperature, vulcanizing at constant temperature of 220-260 ℃, reducing the injection amount of the vulcanizing agent when the content of hydrogen sulfide in circulating hydrogen reaches 5000ppm, increasing the injection amount of the vulcanizing agent again when the temperature of a reactor is increased to 310-330 ℃, and increasing the reaction temperature to gradually cut in raw oil after constant-temperature vulcanization. According to the vulcanizing agent storage tank, passivation treatment is not needed in the starting process, a vulcanizing link is still needed, a container for storing a vulcanizing agent and a sulfur injection pump are needed to be arranged on the site, meanwhile, the hydrogen sulfide content in circulating hydrogen needs to be concerned all the time in the starting process, the sulfur injection rate and the temperature rise rate are adjusted, and the starting process is still more tedious and longer in time.
Patent 101003749a discloses a start-up scheme for an oxidized hydrocracking catalyst, which essentially utilizes the reducibility of hydrogen to reduce the oxidized hydrocracking catalyst to an intermediate state between a sulfided state and a fully reduced state, which is believed to retain high hydrogenation performance and strong sulfur resistance. However, the reduction degree of the method is not easy to control, the activity of the catalyst is greatly reduced once the catalyst is reduced to a complete reduction state, and meanwhile, the method does not consider the problem that the initial activity of the hydrocracking catalyst in industrial application is high and the temperature runaway of a catalyst bed layer is easy to occur, so that the method has low practical application value.
Patent CN102284299A discloses a sulfurization method and an application form of a hydrogenation catalyst, which can be summarized as an application form of sulfurization outside a reactor and activation inside the reactor, wherein a sulfurization gas is used for presulfurization outside the reactor, and an oxygen-containing passivation gas is used for passivation, but the passivation purpose performed here is to ensure the safety of the hydrogenation catalyst during transportation and filling, and passivation treatment is still required during the startup of a hydrocracking unit.
Patent CN101417245A discloses a pretreatment method of hydrogenation catalyst, in which sulfur-containing substances such as elemental sulfur are loaded into the pore channels of the catalyst, and organic solvent is introduced to help regulate the interaction between sulfur and the active components of the catalyst, thereby reducing the exothermic degree of the catalyst during the start-up process. The method can cancel the operation of injecting a vulcanizing agent on site, reduce the operation difficulty, but still can not solve the problem that a cracking catalyst bed layer is easy to fly warm, and still needs to introduce a passivating agent for passivating the catalyst during start-up.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a pretreatment method of a hydrocracking catalyst. The pretreatment method can synchronously complete the vulcanization and passivation of the catalyst in the preparation process of the hydrocracking catalyst, can effectively shorten the time required by the startup, the raw material switching and the stable production working condition of the hydrocracking device, can effectively guarantee the vulcanization and passivation effects of the catalyst, does not need to inject a vulcanizing agent and a passivating agent in the startup process, greatly reduces the field operation difficulty, and effectively controls the pollution to the environment and the harm to the health of operators due to the use of the vulcanizing agent and the passivating agent.
The first aspect of the present invention provides a pretreatment method for a hydrocracking catalyst, which comprises the following steps:
(1) mixing an oxidation state hydrocracking catalyst with a pretreating agent, and then treating in the presence of a first gas, wherein the first gas is nitrogen and/or an inert gas;
(2) after the treatment in the step (1) is finished, stopping introducing the first gas, and simultaneously switching to introducing a second gas for treatment, wherein the second gas is a hydrogen-containing gas, the hydrogen-containing gas is a mixed gas of hydrogen, hydrogen and a carrier gas, and the carrier gas is nitrogen and/or an inert gas;
(3) and (3) after the treatment in the step (2) is finished, adjusting the temperature to 80-150 ℃, preferably 110-130 ℃, stopping introducing the second gas, switching to introducing the first gas for treatment for a period of time, and obtaining the pretreated hydrocracking catalyst after the treatment is finished, wherein the first gas is nitrogen and/or inert gas.
In the above method for pretreating a hydrocracking catalyst, the pretreating agent in the step (1) comprises a component A and a component B; the component A is an ammonium sulfide solution and/or an ammonium thiosulfate solution, preferably an ammonium sulfide and ammonium thiosulfate solution; the component B is sodium sulfide, specifically can be one or more of sodium sulfide solution, sodium thiosulfate, sodium polysulfide and sodium sulfate, and preferably is sodium sulfide solution. The addition amount of the component A is 40-120% of the theoretical sulfur demand of the hydrocracking catalyst, and preferably 60-90%. The addition amount of the component B is 10-50% of the theoretical sulfur demand of the hydrocracking catalyst, and preferably 20-40%.
In the above hydrocracking catalyst pretreatment method, the treatment conditions in step (1) are as follows: the pressure is 0.1-8.0 MPa, preferably 0.1-2.0 MPa, the temperature is 120-200 ℃, preferably 160-180 ℃, and the treatment time is 0.5-24 hours, preferably 4-10 hours.
In the above hydrocracking catalyst pretreatment method, the treatment conditions in step (2) are as follows: the pressure is 0.1-8.0 MPa, preferably 1.0-6.0 MPa; the temperature is 200-350 ℃, preferably 220-310 ℃, and the treatment time is 1-48 hours, preferably 10-16 hours; further preferably adopting a two-stage temperature programming mode, wherein the temperature of the first stage is 200-280 ℃, preferably 220-240 ℃, and the treatment is carried out for 0.5-24 hours, preferably 5-8 hours; the temperature of the second stage is 280-350 ℃, preferably 290-310 ℃, and the treatment is carried out for 0.5-24 hours, preferably 5-8 hours.
In the above pretreatment method of the hydrocracking catalyst, the hydrogen gas in the hydrogen-containing gas in the step (2) accounts for 50% to 100% by volume, preferably 65% to 85% by volume.
In the pretreatment method of the hydrocracking catalyst, the treatment time in the step (3) is 0.5 to 10 hours, preferably 2 to 8 hours.
In the pretreatment method of the hydrocracking catalyst, the volume of the pretreatment agent in the step (1) is 100-200% of the stacking volume of the hydrocracking catalyst, and preferably 120-150%.
In the above method for pretreating a hydrocracking catalyst, the hydrocracking catalyst in step (1) is a conventional hydrocracking catalyst in the art, and comprises a cracking component and a hydrogenation component, wherein the cracking component usually comprises amorphous silica-alumina and a molecular sieve; the hydrogenation component is one or more of non-noble metal elements in VI group, VII group or VIII group, preferably one or more of Co, Mo, Ni and W. Based on the weight of the catalyst, the content of the hydrogenation component is 10-40 wt% calculated by oxide. Specifically, the hydrocracking catalyst can be any commercial hydrocracking catalyst, different types of hydrocracking catalysts are selected according to different target products, light oil type hydrocracking catalysts can be selected for required naphtha, medium oil type hydrocracking catalysts can be selected for required middle distillate, and flexible hydrocracking catalysts can be selected for flexible production of naphtha and middle distillate. For example, commercial hydrocracking catalysts such as FC-34, FC-50, FC-52 and FC-76 developed by the Fushun petrochemical research institute (FRIPP) may be prepared according to conventional methods disclosed in the art as required.
The second aspect of the invention provides a hydrocracking catalyst treated by the pretreatment method.
In a third aspect, the present invention provides a method for starting up a hydrocracking apparatus, in which the pretreated hydrocracking catalyst is loaded, the method comprising: introducing starting oil and hydrogen into a hydrocracking device at 120-180 ℃, then heating to 200-250 ℃, treating for a period of time, then heating to 280-320 ℃ for continuous treatment, and finally cutting in raw oil at 330-340 ℃ for hydrocracking reaction.
In the method for starting up the hydrocracking device, the pretreated hydrocracking catalyst can be matched with any true vulcanization type hydrofining catalyst for use, the true vulcanization type hydrofining catalyst can be obtained by the method, and commercial true vulcanization type hydrofining catalysts sold in the market, such as true vulcanization type hydrofining catalysts developed and developed by Fucheng oil chemical industry institute (FRIPP) and petrochemical industry science institute (RIPP), and the like can be obtained.
Compared with the prior art, the pretreatment method of the hydrocracking catalyst has the following advantages:
the conventional hydrocracking catalyst has to undergo a vulcanization and passivation process in the process of starting operation, special sulfur injection and ammonia injection equipment needs to be additionally arranged during the vulcanization and passivation treatment, and the problems of long treatment time, difficult control of the vulcanization and passivation effect, easy temperature runaway of a catalyst bed layer, high difficulty in field operation, easy environmental pollution and the like exist at the same time. The pretreatment method of the hydrocracking catalyst provided by the invention uses pretreatmentThe agent treats the hydrocracking catalyst to generate H through sulfur and oxygen exchange under proper pretreatment conditions2S gas sulfurizes the active component of the catalyst via the generated NH3And the contained alkaline component is adsorbed on the acid site of the catalyst to realize the passivation of the hydrocracking catalyst, under the synergistic cooperation effect of the components in the pretreating agent, the problems in the prior art are solved, the hydrocracking catalyst can be vulcanized and passivated before being placed in a reactor, the operations of injecting a vulcanizing agent and a passivating agent on site are cancelled while the normal reaction activity of the catalyst is not influenced, the start-up process of a hydrocracking device is simplified to the maximum extent, the start-up time is greatly saved, and meanwhile, the harm of the vulcanizing agent and the passivating agent to workers and the environment is avoided.
Detailed Description
The following examples are given to further illustrate the action and effect of the process of the present invention, but the following examples are not intended to limit the process of the present invention.
The low-nitrogen start-up oil in the inventive examples and the comparative examples adopts straight-run diesel oil, the specific properties are shown in table 1, and the properties of the raw oil are also shown in table 1.
The catalysts involved in the examples and comparative examples of the present invention are commercial catalysts which have been developed by the institute of petrochemical industry, even though the research institute of petrochemical industry has been in force.
Example 1
The method is characterized in that the off-line pretreatment is carried out by taking a commercial hydrocracking catalyst FC-76 (developed and produced by Dalian (comforting) petrochemical research institute) as an object, and the specific pretreatment process is as follows:
(1) the FC-76 hydrocracking catalyst was placed in a pretreatment reactor and a pretreatment agent was introduced. The pretreating agent is a mixed solution of a component A (ammonium sulfide) and a component B (sodium sulfide). The addition amount of the ammonium sulfide is 80% of the theoretical sulfur demand of the hydrocracking catalyst, and the addition amount of the sodium sulfide is 30% of the theoretical sulfur demand of the hydrocracking catalyst. The volume of the pretreatment agent is 120% of the stacking volume of the hydrocracking catalyst, nitrogen is used for purging the pretreatment reactor, the system pressure is kept at 0.1MPa under the nitrogen atmosphere, meanwhile, the temperature of the pretreatment reactor is raised to 160 ℃, and the constant temperature treatment is carried out for 6 hours.
(2) And (2) introducing a mixed gas of hydrogen and nitrogen after the constant temperature treatment in the step (1) is finished, wherein the proportion of the hydrogen in the mixed gas is 60%, keeping the system pressure at 2.0MPa in the atmosphere of the mixed gas of the hydrogen and the nitrogen, simultaneously raising the temperature of the pretreatment reactor to 230 ℃, and carrying out constant temperature treatment for 8 hours.
(3) And (3) after the constant temperature in the step (2) is finished, the temperature of the pretreatment reactor is increased to 120 ℃, nitrogen is used for purging the pretreatment reactor, and purging treatment is carried out for 6 hours to obtain the target pretreatment type hydrocracking catalyst FCS 1-76.
Example 2
The method is characterized in that the off-line pretreatment is carried out by taking a commercial hydrocracking catalyst FC-46 (developed and produced by Dalian (comforting) petrochemical research institute) as an object, and the specific pretreatment process is as follows:
(1) the FC-46 hydrocracking catalyst was placed in a pretreatment reactor and a pretreatment agent was introduced. The pretreating agent is a mixed solution of a component A (ammonium thiosulfate) and a component B (sodium sulfide). The addition amount of the ammonium thiosulfate is 120 percent of the theoretical sulfur demand of the hydrocracking catalyst, and the addition amount of the sodium sulfide is 10 percent of the theoretical sulfur demand of the hydrocracking catalyst. The volume of the pretreatment agent is 150% of the stacking volume of the hydrocracking catalyst, nitrogen is used for purging the pretreatment reactor, the system pressure is kept at 1.0MPa under the nitrogen atmosphere, meanwhile, the temperature of the pretreatment reactor is raised to 200 ℃, and the constant temperature treatment is carried out for 16 hours.
(2) Introducing mixed gas of hydrogen and nitrogen after the constant temperature treatment in the step (1) is finished, wherein the proportion of the hydrogen in the mixed gas is 80%, keeping the system pressure at 4.0MPa in the atmosphere of the mixed gas of the hydrogen and the nitrogen, raising the temperature of the pretreatment reactor to 230 ℃, and carrying out constant temperature treatment for 2 hours; then the temperature of the pretreatment reactor was raised to 290 ℃ and the treatment was carried out at a constant temperature for 5 hours.
(3) And (3) after the constant temperature in the step (2) is finished, the temperature of the pretreatment reactor is reduced to 80 ℃, nitrogen is used for purging the pretreatment reactor, and purging treatment is carried out for 2 hours to obtain the target pretreatment type hydrocracking catalyst FCS 2-46.
Example 3
The method is characterized in that the off-line pretreatment is carried out by taking a commercial hydrocracking catalyst FC-76 (developed and produced by Dalian (comforting) petrochemical research institute) as an object, and the specific pretreatment process is as follows:
(1) the FC-76 hydrocracking catalyst was placed in a pretreatment reactor and a pretreatment agent was introduced. The pretreating agent is a mixed solution of a component A (ammonium sulfide and ammonium thiosulfate) and a component B (sodium sulfide). The addition amount of the component A is 70 percent of the theoretical sulfur demand of the hydrocracking catalyst (wherein the addition amount of ammonium sulfide is 40 percent of the theoretical sulfur demand of the hydrocracking catalyst, the addition amount of ammonium thiosulfate is 30 percent of the theoretical sulfur demand of the hydrocracking catalyst), and the addition amount of sodium sulfide is 50 percent of the theoretical sulfur demand of the hydrocracking catalyst. The volume of the pretreatment agent is 170% of the stacking volume of the hydrocracking catalyst, nitrogen is used for purging the pretreatment reactor, the system pressure is kept at 1.2MPa under the nitrogen atmosphere, meanwhile, the temperature of the pretreatment reactor is raised to 150 ℃, and the constant temperature treatment is carried out for 3 hours.
(2) Introducing mixed gas of hydrogen and nitrogen after the constant temperature treatment in the step (1) is finished, wherein the proportion of the hydrogen in the mixed gas is 75%, keeping the system pressure at 6.0MPa in the atmosphere of the mixed gas of the hydrogen and the nitrogen, raising the temperature of the pretreatment reactor to 200 ℃, and carrying out constant temperature treatment for 4 hours; the temperature of the pretreatment reactor was then raised to 340 ℃ and the treatment was maintained at constant temperature for 2 hours.
(3) And (3) after the constant temperature in the step (2) is finished, the temperature of the pretreatment reactor is reduced to 125 ℃, nitrogen is used for purging the pretreatment reactor, and purging treatment is carried out for 4 hours to obtain the target pretreatment type hydrocracking catalyst FCS 3-76.
Example 4
The method is characterized in that the off-line pretreatment is carried out by taking a commercial hydrocracking catalyst FC-76 (developed and produced by Dalian (comforting) petrochemical research institute) as an object, and the specific pretreatment process is as follows:
(1) the FC-76 hydrocracking catalyst was placed in a pretreatment reactor and a pretreatment agent was introduced. The pretreating agent is a mixed solution of a component A (ammonium sulfide and ammonium thiosulfate) and a component B (sodium sulfide). The addition amount of the component A is 60 percent of the theoretical sulfur demand of the hydrocracking catalyst (wherein the addition amount of ammonium sulfide is 50 percent of the theoretical sulfur demand of the hydrocracking catalyst, the addition amount of ammonium thiosulfate is 10 percent of the theoretical sulfur demand of the hydrocracking catalyst), and the addition amount of sodium sulfide is 45 percent of the theoretical sulfur demand of the hydrocracking catalyst. The volume of the pretreatment agent is 110% of the stacking volume of the hydrocracking catalyst, nitrogen is used for purging the pretreatment reactor, the system pressure is kept at 0.5MPa under the nitrogen atmosphere, meanwhile, the temperature of the pretreatment reactor is raised to 110 ℃, and the constant temperature treatment is carried out for 1.5 hours.
(2) Introducing mixed gas of hydrogen and nitrogen after the constant temperature treatment in the step (1) is finished, wherein the proportion of the hydrogen in the mixed gas is 55%, keeping the system pressure at 8.0MPa in the atmosphere of the mixed gas of the hydrogen and the nitrogen, firstly raising the temperature of the pretreatment reactor to 320 ℃, and carrying out constant temperature treatment for 12 hours.
(3) And (3) after the constant temperature in the step (2) is finished, the temperature of the pretreatment reactor is reduced to 112 ℃, nitrogen is used for purging the pretreatment reactor, and purging treatment is carried out for 2 hours to obtain the target pretreatment type hydrocracking catalyst FCS 4-76.
Example 5
The method is characterized in that the off-line pretreatment is carried out by taking a commercial hydrocracking catalyst FC-76 (developed and produced by Dalian (comforting) petrochemical research institute) as an object, and the specific pretreatment process is as follows:
(1) the FC-76 hydrocracking catalyst was placed in a pretreatment reactor and a pretreatment agent was introduced. The pretreating agent is a mixed solution of a component A (ammonium sulfide and ammonium thiosulfate) and a component B (sodium sulfide). The addition amount of the component A is 60 percent of the theoretical sulfur demand of the hydrocracking catalyst (wherein the addition amount of ammonium sulfide is 40 percent of the theoretical sulfur demand of the hydrocracking catalyst, the addition amount of ammonium thiosulfate is 20 percent of the theoretical sulfur demand of the hydrocracking catalyst), and the addition amount of sodium thiosulfate is 50 percent of the theoretical sulfur demand of the hydrocracking catalyst. The volume of the pretreatment agent is 170% of the stacking volume of the hydrocracking catalyst, nitrogen is used for purging the pretreatment reactor, the system pressure is kept at 1.2MPa under the nitrogen atmosphere, meanwhile, the temperature of the pretreatment reactor is raised to 150 ℃, and the constant temperature treatment is carried out for 3 hours.
(2) Introducing mixed gas of hydrogen and nitrogen after the constant temperature treatment in the step (1) is finished, wherein the proportion of the hydrogen in the mixed gas is 75%, keeping the system pressure at 6.0MPa in the atmosphere of the mixed gas of the hydrogen and the nitrogen, raising the temperature of the pretreatment reactor to 200 ℃, and carrying out constant temperature treatment for 8 hours; the temperature of the pretreatment reactor was then raised to 340 ℃ and the treatment was maintained at constant temperature for 3 hours.
(3) And (3) after the constant temperature in the step (2) is finished, the temperature of the pretreatment reactor is reduced to 125 ℃, nitrogen is used for purging the pretreatment reactor, and purging treatment is carried out for 4 hours to obtain the target pretreatment type hydrocracking catalyst FCS 5-76.
Comparative example 1
The method is characterized in that the off-line pretreatment is carried out by taking a commercial hydrocracking catalyst FC-76 (developed and produced by Dalian (comforting) petrochemical research institute) as an object, and the specific pretreatment process is as follows:
(1) the FC-76 hydrocracking catalyst was placed in a pretreatment reactor and a pretreatment agent was introduced. The pretreating agent is a mixed solution of the component A (ammonium sulfide and ammonium thiosulfate). The addition amount of the component A is 120 percent of the theoretical sulfur demand of the hydrocracking catalyst (wherein the addition amount of the ammonium sulfide is 80 percent of the theoretical sulfur demand of the hydrocracking catalyst, and the addition amount of the ammonium thiosulfate is 40 percent of the theoretical sulfur demand of the hydrocracking catalyst). The volume of the pretreating agent is 110% of the stacking volume of the hydrocracking catalyst, nitrogen is used for purging the pretreatment reactor, the system pressure is kept at 1.8MPa under the nitrogen atmosphere, meanwhile, the temperature of the pretreatment reactor is raised to 175 ℃, and the constant temperature treatment is carried out for 7 hours.
(2) Introducing mixed gas of hydrogen and nitrogen after the constant temperature treatment in the step (1) is finished, wherein the proportion of the hydrogen in the mixed gas is 78%, keeping the system pressure at 3.4MPa in the atmosphere of the mixed gas of the hydrogen and the nitrogen, raising the temperature of the pretreatment reactor to 235 ℃, and carrying out constant temperature treatment for 2 hours; the temperature of the pretreatment reactor was then raised to 335 ℃ and the treatment was maintained at constant temperature for 3 hours.
(3) And (3) after the constant temperature in the step (2) is finished, the temperature of the pretreatment reactor is reduced to 112 ℃, nitrogen is used for purging the pretreatment reactor, and purging treatment is carried out for 6 hours to obtain the target pretreatment type hydrocracking catalyst FCS 6-76.
Comparative example 2
The method is characterized in that the off-line pretreatment is carried out by taking a commercial hydrocracking catalyst FC-46 (developed and produced by Dalian (comforting) petrochemical research institute) as an object, and the specific pretreatment process is as follows:
(1) the FC-46 hydrocracking catalyst was placed in a pretreatment reactor and a pretreatment agent was introduced. The pretreating agent is a mixed solution of the component B (sodium sulfide and sodium thiosulfate). The addition amount of the component B is 100 percent of the theoretical sulfur demand of the hydrocracking catalyst (wherein the addition amount of the sodium sulfide is 80 percent of the theoretical sulfur demand of the hydrocracking catalyst, and the addition amount of the sodium thiosulfate is 20 percent of the theoretical sulfur demand of the hydrocracking catalyst). The volume of the pretreatment agent is 100% of the stacking volume of the hydrocracking catalyst, nitrogen is used for purging the pretreatment reactor, the system pressure is kept at 8.0MPa in the nitrogen atmosphere, meanwhile, the temperature of the pretreatment reactor is raised to 190 ℃, and the constant temperature treatment is carried out for 5 hours.
(2) Introducing mixed gas of hydrogen and nitrogen after the constant temperature treatment in the step (1) is finished, wherein the proportion of the hydrogen in the mixed gas is 95%, keeping the system pressure at 8.0MPa in the atmosphere of the mixed gas of the hydrogen and the nitrogen, raising the temperature of the pretreatment reactor to 250 ℃, and carrying out constant temperature treatment for 5 hours; the temperature of the pretreatment reactor was then raised to 325 ℃ and the treatment was carried out at constant temperature for 6 hours.
(3) And (3) after the constant temperature in the step (2) is finished, the temperature of the pretreatment reactor is reduced to 90 ℃, nitrogen is used for purging the pretreatment reactor, and purging treatment is carried out for 1 hour to obtain the target pretreatment type hydrocracking catalyst FCS 7-46.
And (3) start-up evaluation:
the start-up schemes for the 7 catalysts involved in examples 1-5 and comparative examples 1-2 were: the catalyst is used in combination with a true vulcanization type FF-66 hydrofining catalyst, low-nitrogen start oil and hydrogen are introduced into a hydrocracking device at 160 ℃, the temperature of a system is increased to 230 ℃ at a temperature rising speed of 15 ℃/hour, the hydrocracking catalyst is stabilized for 4-8 hours at 230 ℃, the temperature of the system is increased to 300 ℃ at a temperature rising speed of 10 ℃/hour, the system is stabilized for 2-8 hours, and the temperature of the system is increased to 330-340 ℃ at a temperature rising speed of 5 ℃/hour, and the raw oil is cut into for hydrocracking reaction.
Comparative example 3
The conventional FC-76 catalyst and a true vulcanization type FF-66 hydrofining catalyst are used in a combined mode, low-nitrogen start-up oil and hydrogen are introduced into a hydrocracking device at the temperature of 140 ℃, the system temperature is increased to 185 ℃ at the temperature rising speed of 20 ℃/hour, a sulfur injection pump is started to inject a vulcanizing agent DMDS into a reaction system, the system temperature is increased to 230 ℃ at the temperature rising speed of 10 ℃/hour, the temperature is kept constant at 230 ℃ for 8 hours, the concentration of the hydrogen sulfide in circulating hydrogen is kept between 0.1 and 0.5v%, an ammonia injection pump is started after the constant temperature of 230 ℃ is over, the temperature is increased to 290 ℃ at the speed of 8 ℃/hour after ammonia penetrates through the system temperature, the temperature is kept constant for 4 hours, the temperature is increased to 320 ℃ at the speed of 5 ℃/hour after the constant temperature is over, the temperature is kept for 6 hours, and the temperature is slowly increased to the.
TABLE 1 Start-Up straight run diesel and stock oil Primary Properties
TABLE 2 comparison of the working efficiency of the examples and comparative examples
As can be seen from the start-up conditions of the above examples and comparative examples, the hydrocracking catalyst treated by the method of the present invention has activity equivalent to that of the prior art, and the start-up period is significantly shortened, and the start-up time is saved by 30 hours. Meanwhile, the method of the invention has the following advantages: the vulcanizing agent and the passivating agent are not required to be injected on site, the operation difficulty and the environmental pollution during the start-up period are greatly reduced while the equipment investment is reduced, and the vulcanization and passivation degrees of the catalyst fully avoid the hidden troubles of poor catalyst activity, bed temperature runaway and the like caused by insufficient vulcanization and passivation during the processing period.
Claims (12)
1. A hydrocracking catalyst pretreatment process, said pretreatment process comprising the steps of:
(1) mixing an oxidation state hydrocracking catalyst with a pretreating agent, and then treating in the presence of a first gas, wherein the first gas is nitrogen and/or an inert gas, the pretreating agent comprises a component A and a component B, the component A is an ammonium sulfide solution and/or an ammonium thiosulfate solution, and the component B is a sodium sulfide;
(2) after the treatment in the step (1) is finished, stopping introducing the first gas, and simultaneously switching to introducing a second gas for treatment, wherein the second gas is a hydrogen-containing gas, the hydrogen-containing gas is a mixed gas of hydrogen, hydrogen and a carrier gas, and the carrier gas is nitrogen and/or an inert gas;
(3) and (3) after the treatment in the step (2) is finished, adjusting the temperature to 80-150 ℃, preferably 110-130 ℃, stopping introducing the second gas, switching to introducing the first gas for treatment for a period of time, and obtaining the pretreated hydrocracking catalyst after the treatment is finished, wherein the first gas is nitrogen and/or inert gas.
2. The method for pretreating a hydrocracking catalyst according to claim 1, wherein: the component A is ammonium sulfide and ammonium thiosulfate solution; the component B is one or more of sodium sulfide solution, sodium thiosulfate, sodium polysulfide and sodium sulfate, and preferably sodium sulfide solution.
3. The method for pretreating a hydrocracking catalyst according to claim 1, wherein: the addition amount of the component A is 40-120% of the theoretical sulfur demand of the hydrocracking catalyst, and preferably 60-90%.
4. The addition amount of the component B is 10-50% of the theoretical sulfur demand of the hydrocracking catalyst, and preferably 20-40%.
5. The method for pretreating a hydrocracking catalyst according to claim 1, wherein: the treatment conditions in the step (1) are as follows: the pressure is 0.1-8.0 MPa, preferably 0.1-2.0 MPa, the temperature is 120-200 ℃, preferably 160-180 ℃, and the treatment time is 0.5-24 hours, preferably 4-10 hours.
6. The method for pretreating a hydrocracking catalyst according to claim 1, wherein: the treatment conditions in the step (2) are as follows: the pressure is 0.1-8.0 MPa, preferably 1.0-6.0 MPa; the temperature is 200-350 ℃, preferably 220-310 ℃, and the treatment time is 1-48 hours, preferably 10-16 hours.
7. The method for pretreating a hydrocracking catalyst according to claim 1, wherein: a two-stage temperature programming mode is adopted in the step (2), wherein the temperature of the first stage is 200-280 ℃, preferably 220-240 ℃, and the treatment is carried out for 0.5-24 hours, preferably 5-8 hours; the temperature of the second stage is 280-350 ℃, preferably 290-310 ℃, and the treatment is carried out for 0.5-24 hours, preferably 5-8 hours.
8. The method for pretreating a hydrocracking catalyst according to claim 1, wherein: the treatment time in the step (3) is 0.5-10 hours, preferably 2-8 hours.
9. The method for pretreating a hydrocracking catalyst according to claim 1, wherein: the volume of the pretreating agent in the step (1) is 100-200% of the stacking volume of the hydrocracking catalyst, and preferably 120-150%.
10. A hydrocracking catalyst treated by the pretreatment method according to any one of claims 1 to 8.
11. A method for starting up a hydrocracking apparatus in which the hydrocracking catalyst according to claim 9 is packed, comprising: introducing starting oil and hydrogen into a hydrocracking device at 120-180 ℃, then heating to 200-250 ℃, treating for a period of time, then heating to 280-320 ℃ for continuous treatment, and finally cutting in raw oil at 330-340 ℃ for hydrocracking reaction.
12. The hydrocracking plant start-up method according to claim 10, characterized by: the pretreated hydrocracking catalyst is matched with any true vulcanization type hydrofining catalyst for use.
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