CN109777476B - Safe start-up method of hydrocracking catalyst - Google Patents
Safe start-up method of hydrocracking catalyst Download PDFInfo
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- CN109777476B CN109777476B CN201711118999.XA CN201711118999A CN109777476B CN 109777476 B CN109777476 B CN 109777476B CN 201711118999 A CN201711118999 A CN 201711118999A CN 109777476 B CN109777476 B CN 109777476B
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- 238000000034 method Methods 0.000 title claims abstract description 126
- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 79
- 238000004073 vulcanization Methods 0.000 claims abstract description 57
- 239000002808 molecular sieve Substances 0.000 claims abstract description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 13
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 81
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 66
- 229910021529 ammonia Inorganic materials 0.000 abstract description 29
- 238000002347 injection Methods 0.000 abstract description 19
- 239000007924 injection Substances 0.000 abstract description 19
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000003921 oil Substances 0.000 description 59
- 238000002161 passivation Methods 0.000 description 25
- 230000000694 effects Effects 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 15
- 238000005336 cracking Methods 0.000 description 14
- 238000005984 hydrogenation reaction Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 10
- 230000000977 initiatory effect Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 150000004767 nitrides Chemical class 0.000 description 5
- 230000000087 stabilizing effect Effects 0.000 description 5
- 230000006378 damage Effects 0.000 description 4
- 238000005987 sulfurization reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011066 ex-situ storage Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 230000007420 reactivation Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
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- 230000003213 activating effect Effects 0.000 description 1
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- 230000009849 deactivation Effects 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- UYDPQDSKEDUNKV-UHFFFAOYSA-N phosphanylidynetungsten Chemical compound [W]#P UYDPQDSKEDUNKV-UHFFFAOYSA-N 0.000 description 1
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- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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Abstract
The invention discloses a safe startup method of a hydrocracking catalyst, which is characterized in that raw oil is introduced in the vulcanization process, the reaction temperature is adjusted after vulcanization is finished, and the hydrocracking reaction is carried out under the hydrocracking reaction condition when the light oil mass yield of less than 360 ℃ is constant to be 55-60%, wherein the hydrocracking catalyst contains 30-50% of molecular sieve by weight, and the molecular sieve comprises but is not limited to Y type or USY type. The method has the advantages of simple processes of start-up and raw material switching, stable operation and avoidance of consumption of the passivator in the start-up process and potential danger in the ammonia injection process.
Description
Technical Field
The invention relates to a safe start-up method of a hydrocracking catalyst, in particular to a safe start-up method of a hydrocracking catalyst without ammonia injection passivation.
Background
The hydrocracking process is a process for converting heavy distillate oil (VGO, CGO and DAO) into target products such as light oil, middle distillate oil and the like through hydrodesulfurization, hydrodenitrogenation, polycyclic aromatic hydrocarbon hydrosaturation and ring-opening cracking under the conditions of hydrogen presence, high temperature and high pressure and under the action of a catalyst. The hydrocracking catalysts currently produced industrially in China are basically of the oxidation type. The active metal components (Mo, Ni, Co, W) contained in the new catalyst or regenerated catalyst are all in oxidation state (MoO)3、NiO、CoO、WO3) Exist in the form of (1). Basic research and industrial application practices show that most of the active metal components of the hydrogenation catalyst have higher hydrogenation activity and activity stability in a vulcanized state, so that the processes of drying the catalyst, vulcanizing (passivating), changing feed oil and the like are generally included before the catalyst is used.
The hydrocracking catalyst containing molecular sieve has high hydrocracking activity after sulfurization, so that before the raw oil is switched, corresponding measures are taken to passivate the catalyst to inhibit the overhigh initial activity of the catalyst, prevent and avoid the temperature rise possibly occurring in the oil feeding process, and ensure the safety of the catalyst, equipment and human body. The injected anhydrous liquid ammonia is adsorbed by the catalyst after being decomposed, so that the initial activity of the catalyst can be effectively inhibited, ammonia adsorbed by acid centers of the catalyst can be gradually desorbed and lost along with the rise of the reaction temperature and the continuation of the running time, and the catalyst can recover the normal activity. The adopted passivant anhydrous liquid ammonia is a compressive liquefied toxic gas, is a colorless liquid under a certain pressure, has the characteristics of high pressure, flammability and explosiveness, and is generally transported and stored by steel cylinders, automobiles and train tankers. The industrial use of anhydrous liquid ammonia has certain dangerousness, has great harm to human bodies, and does not accord with the concept of safety, health and environmental protection.
Although the hydrocracking catalyst without the molecular sieve has weak cracking activity after being vulcanized, the catalyst can not be passivated, but raw oil is introduced and process parameters are frequently adjusted when the hydrocracking catalyst enters normal production due to the existence of initial activity of the catalyst, so that the operation fluctuation of an enterprise device is large, the risk is high, and the step of entering a stable state is complicated.
The hydrocracking device generally carries out the vulcanization start-up under the high-pressure environment, and in the prior art, the catalyst start-up can select two modes of injecting ammonia and not injecting ammonia, but the two modes have the advantages and disadvantages.
The typical process for injecting ammonia is generally: controlling the inlet temperature of the reactor at 160 ℃, introducing low-nitrogen oil into the reaction system, raising the inlet temperature of the reactor to 180 ℃, and injecting a vulcanizing agent into the reaction system. After the concentration of hydrogen sulfide in the circulating hydrogen reaches 0.1v%, the inlet temperature of the reactor is raised to 230 ℃, and the constant-temperature vulcanization is carried out for at least 8 h. And after 4 hours of constant-temperature vulcanization at 230 ℃, starting an ammonia injection pump, starting ammonia injection passivation, and starting injecting washing water in front of an air cooler after 2 hours of ammonia injection. After 2 hours of water injection, analysis of the ammonia content in the high-acid-content water was started. After the constant-temperature vulcanization at 230 ℃, the inlet temperature of the reactor is smoothly increased. When the ammonia content in the highly acidic water reached 0.1w%, the ammonia was considered to have penetrated. Before ammonia penetrates, the inlet temperature of a cracking catalyst bed is controlled to not more than 250 ℃, and the temperature rise of any bed is not more than 5 ℃. After ammonia penetrates through the reactor, the injection rate of anhydrous liquid ammonia is adjusted, the inlet temperature of the reactor is stably raised to 320 ℃, and the temperature is kept constant for 8 hours.
Typical processes for non-ammonia injection are generally: the reactor inlet temperature was controlled at 160 ℃. Introducing low-nitrogen oil into the reaction system, raising the temperature of the inlet of the reactor to 180 ℃, and injecting a vulcanizing agent into the reaction system. After the concentration of hydrogen sulfide in the circulating hydrogen reaches 0.1v%, the inlet temperature of the reactor is raised to 230 ℃, and the constant-temperature vulcanization is carried out for at least 8 h. After the constant-temperature vulcanization is finished, the inlet temperature of the reactor is stably increased. In the temperature raising process, when the temperature of the cracking catalyst bed layer rises to 5 ℃, the temperature raising is stopped, and the constant temperature is kept for 8 hours.
The passivant such as anhydrous liquid ammonia injected outside the device can make the start-up process stable and safe, but needs to use a pressure pump for conveying, which not only increases the one-time investment of the device and wastes the floor area, but also because the pump belongs to the equipment which is periodically and intermittently started, the fault occurs frequently and the start-up progress is influenced, meanwhile, the danger of the anhydrous liquid ammonia and the like are already described in the front, and the control difficulty is obvious; if the passivator injection outside the reactor is not carried out during the sulfurization of the cracking catalyst, the smooth safety of the start-up process is reduced, and the sulfurization process is shortened or terminated, which has great influence on the activity of the catalyst, thereby possibly influencing the long-period stable operation of the catalyst and greatly prolonging the time for the catalyst to enter a stable state.
Both CN101492613A and CN101492607A disclose a start-up method of hydrocracking process, which has certain safety and convenience, but still belongs to a method of injecting a certain passivation agent into a reaction system by using extra-reactor forced ammonia injection to inhibit the activity of the cracking agent, and the disadvantages existing in the above-mentioned ammonia injection in the prior art are bound to exist, which may bring about certain hidden danger and harm.
CN101003749A introduces a start-up method of an oxidation state hydrocracking catalyst, relates to a catalyst, and particularly relates to an oxidation state hydrocracking catalyst in an oil refining process. Provides a start-up method of an oxidation state hydrocracking catalyst without presulfurizing the catalyst under the condition of adopting the existing hydrocracking catalyst. In the process, a vulcanizing agent is not required to be added to pre-vulcanize the catalyst in an oxidation state, so that the problems caused by pre-vulcanization are avoided, and the partially reduced catalyst has higher hydrocracking activity. The hydrocracking start-up method does not need a passivator in the whole process, has the characteristics of safety, environmental protection and stable process, and is difficult to ensure the cracking activity and activity stability of an oxidation state and an elemental metal catalyst although the operation is simple and the process is easy.
CN103059961A and CN103059969A disclose a method for the start-up passivation of hydrocracking catalysts. High-nitrogen naphtha is introduced into the refining section in the catalyst passivation stage, and ammonia generated by hydrogenation of the high-nitrogen naphtha is used as a passivator to passivate a cracking agent, so that the aim of not using the passivator is fulfilled. Although the method can play a role in deactivating the initial activity of the cracking catalyst, other liquid components need to be additionally introduced, the control process is complicated, the effect is not easy to realize, and the purpose of reducing the start-up time is difficult to achieve.
CN103789023A introduces a startup method of a hydrocracking device. In the passivation step of the startup process of the hydrocracking device, the catalyst is passivated by introducing the nitrogen-containing distillate oil step by step, the nitrogen-containing distillate oil can replace anhydrous liquid ammonia, and the startup process is stable. There are still additional liquid components introduced, control is difficult to achieve, and the start-up process is lengthy.
CN102284299A and CN16029 1602999A relate to a method for presulfurizing a hydrogenation catalyst outside a hydrogenation reactor and activating the hydrogenation catalyst in the hydrogenation reactor, the passivation process of a vulcanizing agent of the catalyst is completed under a specific working condition outside the reactor, but introduced gas contains a toxic substance of the catalyst and is single, the passivation process of the catalyst cannot be completely completed, in addition, the adsorption and the excessive amount of the passivation gas are difficult to ensure in the transportation and vulcanization processes, and the shortage of the passivation gas is easily caused in the start-up process.
CN102921441A describes a method for preparing a tungsten phosphide catalyst, wherein nitrogen gas flow is introduced during the preparation process to passivate the catalyst, which has a passivation effect to some extent, but the passivation effect of inert gas is poor, and thus the method cannot be applied to the hydrocracking process.
CN104593051A and CN104593050A disclose a start-up method of a sulfidized hydrogenation catalyst, in which an oil film generated by an added chemical substance is used to passivate the exothermic process of the sulfidized hydrogenation catalyst, which can thoroughly solve the problem of heat control of sulfur release in the sulfidized hydrogenation process, but cannot be applied to the hydrocracking field, and the generated oil film can react or decompose during hydrocracking, and cannot perform passivation.
CN102310006A discloses a method for regenerating and presulfurizing a hydrogenation catalyst, which is mainly used for directly carrying out presulfurization and passivation treatment outside a reactor in the process of burning carbon by the deactivated hydrogenation catalyst. Although the process for preparing the ex-situ presulfurization catalyst is convenient and feasible and reduces the energy consumption, the passivation process still plays a certain role in inhibiting the heat release of the ex-situ presulfurization catalyst and cannot be applied to the field of hydrocracking.
CN104342200A discloses a selective hydrogenation method for reformate, which is characterized in that some "poison" is used to passivate active metals in the catalyst, and the method is not suitable for passivation of molecular sieves by hydrocracking process, although the effect is significant.
Disclosure of Invention
Aiming at the problems in the prior start-up technology, the invention provides a safe start-up method of a hydrocracking catalyst. The method has the advantages of simple processes of starting and switching raw materials, stable operation, avoiding the consumption of the passivator in the starting process and potential danger in the ammonia injection process, saving energy consumption, reducing the pollution of the passivator to the environment and the harm to the human body, and simultaneously inhibiting the overhigh initial activity and instability of the catalyst after the introduction of fresh feed in the conventional process, so that the starting vulcanization process is smoother and more convenient, and most risks and hidden dangers are avoided.
A safe start-up method of a hydrocracking catalyst is characterized in that raw oil is introduced in the vulcanization process, the reaction temperature is adjusted after vulcanization is finished, the hydrocracking reaction is carried out under the hydrocracking reaction condition when the light oil mass yield of 360 ℃ is kept to be 55-60%, and the hydrocracking catalyst contains 30-50% of molecular sieve in weight content, wherein the molecular sieve comprises but is not limited to Y type or USY type.
The hydrocracking start-up method comprises the steps of firstly introducing low-nitrogen oil, hydrogen and a vulcanizing agent into a hydrocracking device, then carrying out constant-temperature vulcanization on a hydrocracking catalyst at 210-240 ℃, raising the reaction temperature to 250-260 ℃ after the constant-temperature vulcanization is finished, introducing raw oil, raising the temperature to 320-330 ℃, continuing to vulcanize for 4-8 hours at a constant temperature, then finishing the vulcanization process, and controlling the content of hydrogen sulfide in circulating hydrogen to be 4000-8000 ppm during the constant-temperature vulcanization.
According to the hydrocracking start-up method, the hydrocracking catalyst contains 12-35 wt%, preferably 18-30 wt% of active metal oxide, the active metal comprises one or more of Wo, Mo, Co and Ni, and the hydrocracking catalyst can be selected from various conventional commercial catalysts, such as hydrocracking catalysts developed and developed by the Fushu petrochemical industry research institute (FRIPP), such as FC-12, FC-32, FC-76 and the like; it can also be prepared according to the common knowledge in the field, if necessary.
According to the hydrocracking start-up method, low-nitrogen oil is introduced into the reactor when the inlet temperature of the reactor is controlled to be 140-160 ℃, the inlet temperature of the reactor is increased to 180-200 ℃, a vulcanizing agent is injected into a reaction system, the inlet temperature of the reactor is increased to 210-240 ℃ after the concentration of hydrogen sulfide in circulating hydrogen reaches 0.1v%, and constant-temperature vulcanization is carried out for at least 8-12 hours.
In the hydrocracking start-up method, the raw material oil is vacuum wax oil, the final distillation point of the vacuum wax oil is generally 450-550 ℃, preferably 460-520 ℃, and the density is generally 0.92g/cm3Below, 0.91g/cm is preferable3Hereinafter, the nitrogen content is generally 0.1wt% or more, preferably 0.1 to 0.12wt%, and the sulfur content is not particularly limited. Can be selected from those obtained by processing middle east crude oilAny liquid-phase oil suitable as a raw material for a hydrocracking apparatus is within the applicable range, and the vacuum wax oil (VGO) may be one or more of iran VGO, sauter VGO and the like.
In the hydrocracking start-up method, preferably, after the completion of the vulcanization, the reaction temperature is adjusted so that the mass yield of light oil at <360 ℃ is constant in the order of 35 to 40%, 45 to 50%, and 55 to 60%, and the nitride is subjected to the stepwise analysis, so that the activity of the catalyst is stably and rapidly recovered.
The hydrocracking reaction conditions of the hydrocracking start-up method are that the operating pressure is 6.0-16.0 MPa, the volume ratio of hydrogen to oil is 300: 1-1500: 1, and the volume airspeed is 0.1-5.0 h-1(ii) a The preferred operating pressure is 8.0-15.0 MPa, and the volume ratio of hydrogen to oil is 800: 1-1000: 1.
Compared with the prior art, the invention greatly innovates the start-up process, generally needs an additional ammonia injection pump to carry out the passivation treatment of the catalyst in the existing start-up process of the hydrocracking catalyst containing the molecular sieve, thereby not only losing resources but also wasting time, if the passivation process is forcibly cancelled, the temperature point of the switching raw materials is certainly greatly advanced to avoid the temperature runaway or overtemperature of the catalyst due to the overhigh initial activity of the cracking catalyst, thus causing the catalyst poisoning to a certain extent, on the other hand, the activity of the catalyst is reduced due to insufficient vulcanization, which is not beneficial to the long-period stable production of the device. In order to make up for the defects of the prior art, the invention breaks through the inherent limitation of the startup process of the hydrocracking catalyst, the vacuum wax oil is directly introduced at a lower temperature, the catalyst is passivated by using the nitride in the wax oil, even if the catalyst enters a dormant state, in order to avoid permanent damage to the cracking activity of the catalyst caused by the introduction of the low-temperature nitride, the low-conversion rate 'reactivation' process of the catalyst is set in the temperature rising process, so that on one hand, the toxic nitride in the catalyst can be removed at a certain temperature, on the other hand, at a lower conversion depth, the catalyst shows that violent chemical reaction is not easy to occur, thereby reducing the deactivation rate of carbon deposition, simultaneously improving the removal speed of the toxic, fitting the chemical reaction to the startup process according to the requirements of the process, reforming and innovating the passivation of the catalyst, the start-up passivation process is upgraded, the characteristics of the physical properties of the raw materials can be fully utilized to obtain an ideal comprehensive processing effect, the vulcanization and passivation work of the catalyst can be completed on the basis of not influencing the activity of the catalyst, the consumption of an externally injected passivating agent is eliminated, not only can a large amount of manpower and material resources be saved, but also the pollution of the environment and the poison of the passivating agent to a human body are avoided, the operation difficulty and the danger are reduced, and the overall investment in the start-up process can be reduced.
In the process, the method directly introduces the hydrocracking vacuum wax oil raw material into the vulcanization process at low temperature, plays a role of passivation, can be directly applied to the wet process start-up process in a hydrocracking device, avoids the investment of ammonia injection equipment, performs catalyst reactivation according to requirements, stabilizes the activity of the catalyst, passivates the cracking catalyst by utilizing the existing flow of the device to the maximum extent, solves the problem of toxic substance emission or subsequent treatment work, achieves the aim of reasonable utilization of resources, and has the advantages of energy conservation, simple process flow, convenience in operation, environmental protection, low carbon and the like.
In addition, the method has good passivation effect on the catalyst, full vulcanization process, proper process conditions and simple selection of the passivating agent, can inhibit the initial activity of the catalyst to the maximum extent by using the nitride contained in the passivating agent, can further accelerate the initial activity stabilization process of the catalyst, avoids the embarrassing state of frequent adjustment after raw materials are introduced at the initial startup due to the initial activity of the catalyst, enables the startup process to be more refined and standardized, reduces the operation fluctuation and operation risk of enterprise devices, and enables the steps of enabling the catalyst to enter the stable state to be simpler and more stable.
Detailed Description
The following will further illustrate the operation and effect of the safe start-up method of a hydrocracking catalyst according to the present invention with reference to examples and comparative examples. The properties of the working oils and stock oils used in the following examples and comparative examples are shown in Table 1, in whichThe conversions mentioned all correspond to<The mass yield of the 360 ℃ fraction and the main physicochemical properties of the catalyst used are shown in Table 2, catalyst B was used only in example 5, and catalyst A was used in the remaining examples and comparative examples, wherein the nitrogen content in the working oil was less than 100. mu.g.g-1The straight-run diesel oil and the vulcanizing agent are dimethyl disulfide, the examples and the comparative examples generally comprise a hydrocracking pretreatment process, the process has no special requirements during the vulcanization, and the nitrogen content in the refined oil can be controlled to be lower than 30ppm (w), preferably lower than 20ppm (w) after the vulcanization is finished.
TABLE 1 Primary Properties of the crude oils and oils
TABLE 2 catalyst key Properties
Example 1
And starting the hydrocracking device according to the starting process of the conventional hydrocracking device, controlling the inlet temperature of the reactor to be 160 ℃, introducing low-nitrogen oil into the reaction system, increasing the inlet temperature of the reactor to 180 ℃, and injecting a vulcanizing agent into the reaction system. After the concentration of hydrogen sulfide in the circulating hydrogen reaches 0.1v%, the inlet temperature of the reactor is raised to 220 ℃, and the constant-temperature vulcanization is carried out for at least 8 h. Then heating to 250 ℃, introducing the raw oil, changing the raw oil into one-time process for continuous vulcanization, heating to 320 ℃ at the heating rate of 15 ℃/hour, keeping the temperature for 4 hours, and finishing the vulcanization. Then, the reaction temperature is firstly increased to 335 ℃, the temperature is adjusted, the conversion rate is controlled to be constant at 35 percent, and the stability is carried out for 2 days; continuously adjusting the reaction temperature, controlling the conversion rate to be constant at 50%, and stabilizing for 2 days; the reaction temperature was continuously adjusted, the conversion rate was controlled to be constant at 55%, and the reaction was stabilized for 2 days. And (5) finishing the revival process, and adjusting the process conditions to enter normal production. The operation conditions of the vulcanization process are that the operation pressure is 15MPa, the volume ratio of hydrogen to oil is 1000: 1, and the volume space velocity is 0.8 h < -1 >.
Example 2
And starting the hydrocracking device according to the starting process of the conventional hydrocracking device, controlling the inlet temperature of the reactor to be 160 ℃, introducing low-nitrogen oil into the reaction system, increasing the inlet temperature of the reactor to 180 ℃, and injecting a vulcanizing agent into the reaction system. After the concentration of hydrogen sulfide in the circulating hydrogen reaches 0.1v%, the inlet temperature of the reactor is raised to 240 ℃, and the constant-temperature vulcanization is carried out for at least 8 h. Then heating to 260 ℃ to introduce the raw oil, changing the raw oil into one-time process to continue vulcanization, heating to 330 ℃ at a heating rate of 15 ℃/h, keeping the temperature for 4 hours, and then finishing vulcanization. Then, the reaction temperature is firstly increased to 345 ℃, the temperature is adjusted, the conversion rate is controlled to be constant at 35 percent, and the stability is kept for 1 day; continuously adjusting the reaction temperature, controlling the conversion rate to be constant at 50%, and stabilizing for 2 days; the reaction temperature was continuously adjusted, the conversion rate was controlled to be constant at 55%, and the reaction was stabilized for 1 day. And (5) finishing the revival process, and adjusting the process conditions to enter normal production. The operation conditions of the vulcanization process are that the operation pressure is 15MPa, the volume ratio of hydrogen to oil is 1000: 1, and the volume space velocity is 0.8 h < -1 >.
Example 3
And starting the hydrocracking device according to the starting process of the conventional hydrocracking device, controlling the inlet temperature of the reactor to be 160 ℃, introducing low-nitrogen oil into the reaction system, increasing the inlet temperature of the reactor to 180 ℃, and injecting a vulcanizing agent into the reaction system. After the concentration of hydrogen sulfide in the circulating hydrogen reaches 0.1v%, the inlet temperature of the reactor is raised to 220 ℃, and the constant-temperature vulcanization is carried out for at least 8 h. Then heating to 250 ℃, introducing raw oil, changing the raw oil into one-time process for continuous vulcanization, heating to 320 ℃ at the heating rate of 15 ℃/hour, keeping the temperature for 8 hours, and finishing vulcanization. Then, firstly, the reaction temperature is increased to 340 ℃, the temperature is adjusted, the conversion rate is controlled to be constant to 40 percent, and the stability is carried out for 2 days; continuously adjusting the reaction temperature, controlling the conversion rate to be constant at 45%, and stabilizing for 2 days; the reaction temperature was continuously adjusted, the conversion rate was controlled to be constant at 60%, and the reaction was stabilized for 2 days. And (5) finishing the revival process, and adjusting the process conditions to enter normal production. The operation conditions of the vulcanization process are that the operation pressure is 15MPa, the volume ratio of hydrogen to oil is 1000: 1, and the volume space velocity is 0.8 h < -1 >.
Example 4
And starting the hydrocracking device according to the starting process of the conventional hydrocracking device, controlling the inlet temperature of the reactor to be 160 ℃, introducing low-nitrogen oil into the reaction system, increasing the inlet temperature of the reactor to 180 ℃, and injecting a vulcanizing agent into the reaction system. After the concentration of hydrogen sulfide in the circulating hydrogen reaches 0.1v%, the inlet temperature of the reactor is raised to 240 ℃, and the constant-temperature vulcanization is carried out for at least 8 h. Then heating to 260 ℃ to introduce the raw oil, changing the raw oil into one-time process to continue vulcanization, heating to 330 ℃ at a heating rate of 15 ℃/h, keeping the temperature for 8 hours, and then finishing vulcanization. Then, the reaction temperature is firstly increased to 345 ℃, the temperature is adjusted, the conversion rate is controlled to be constant to 40 percent, and the stability is carried out for 1 day; continuously adjusting the reaction temperature, controlling the conversion rate to be constant at 45%, and stabilizing for 2 days; the reaction temperature was continuously adjusted, the conversion rate was controlled to be constant at 60%, and the reaction was stabilized for 1 day. And (5) finishing the revival process, and adjusting the process conditions to enter normal production. The operation conditions of the vulcanization process are that the operation pressure is 15MPa, the volume ratio of hydrogen to oil is 1000: 1, and the volume space velocity is 0.8 h < -1 >.
Example 5
And starting the hydrocracking device according to the starting process of the conventional hydrocracking device, controlling the inlet temperature of the reactor to be 160 ℃, introducing low-nitrogen oil into the reaction system, increasing the inlet temperature of the reactor to 190 ℃, and injecting a vulcanizing agent into the reaction system. After the concentration of hydrogen sulfide in the circulating hydrogen reaches 0.1v%, the inlet temperature of the reactor is raised to 220 ℃, and the constant-temperature vulcanization is carried out for at least 12 h. Then heating to 250 ℃, introducing the raw oil, changing the raw oil into one-time process for continuous vulcanization, heating to 320 ℃ at the heating rate of 15 ℃/hour, keeping the temperature for 4 hours, and finishing the vulcanization. Then, the reaction temperature is increased to 340 ℃, the temperature is adjusted, the conversion rate is controlled to be constant to 40 percent, and the stability is kept for 1 day; continuously adjusting the reaction temperature, controlling the conversion rate to be constant at 45%, and stabilizing for 2 days; the reaction temperature was continuously adjusted, the conversion rate was controlled to be constant at 60%, and the reaction was stabilized for 1 day. And (5) finishing the revival process, and adjusting the process conditions to enter normal production. The operation conditions of the vulcanization process are that the operation pressure is 15MPa, the volume ratio of hydrogen to oil is 1000: 1, and the volume space velocity is 0.8 h < -1 >.
Comparative example 1
And starting the hydrocracking device according to the starting process of the conventional hydrocracking device, controlling the inlet temperature of the reactor to be 160 ℃, introducing low-nitrogen oil into the reaction system, increasing the inlet temperature of the reactor to 180 ℃, and injecting a vulcanizing agent into the reaction system. After the concentration of hydrogen sulfide in the circulating hydrogen reaches 0.1v%, the inlet temperature of the reactor is raised to 230 ℃, and the constant-temperature vulcanization is carried out for at least 8 h. And after 4 hours of constant-temperature vulcanization at 230 ℃, starting an ammonia injection pump, starting ammonia injection passivation, and starting injecting washing water in front of an air cooler after 2 hours of ammonia injection. After 2 hours of water injection, analysis of the ammonia content in the high-acid-content water was started. After the constant-temperature vulcanization at 230 ℃, the inlet temperature of the reactor is smoothly increased. When the ammonia content in the highly acidic water reached 0.1w%, the ammonia was considered to have penetrated. Before ammonia penetrates, the inlet temperature of a cracking catalyst bed is controlled to not more than 250 ℃, and the temperature rise of any bed is not more than 5 ℃. After ammonia penetrates through the reactor, the injection rate of anhydrous liquid ammonia is adjusted, the inlet temperature of the reactor is stably raised to 320 ℃, the temperature is kept constant for 8 hours, then the temperature is slowly raised, and raw oil is gradually switched to normal production.
Comparative example 2
The reactor inlet temperature was controlled at 160 ℃. Introducing low-nitrogen oil into the reaction system, raising the temperature of the inlet of the reactor to 180 ℃, and injecting a vulcanizing agent into the reaction system. After the concentration of hydrogen sulfide in the circulating hydrogen reaches 0.1v%, the inlet temperature of the reactor is raised to 230 ℃, and the constant-temperature vulcanization is carried out for at least 8 h. After the constant-temperature vulcanization is finished, the inlet temperature of the reactor is stably increased. In the temperature raising process, when the temperature rise of the cracking catalyst bed reaches 5 ℃, the temperature raising is stopped, the temperature is kept for 8 hours, then the temperature is slowly raised, and the raw oil is gradually switched to be transferred to normal production.
Comparing the effects of the above examples with those of the comparative examples, at the same conversion depth, the results are as follows:
the above embodiments and comparative examples can see that the method for starting up the power plant is characterized in that, on the basis of not affecting the sulfuration activity of the catalyst, aiming at some defects existing in the existing method for starting up the power plant, especially the problems occurring in the process of starting up the power plant, the existing process and material improvement of an enterprise are utilized to carry out passivation treatment, so that the consumption of the passivating agent in the process of starting up the power plant can be greatly saved, frequent adjustment steps in the process of starting up the power plant can be reduced, the potential safety hazard of poisoning of the passivating agent can be eliminated, the investment can be saved, and the method has great advantages in manpower and material resources.
Claims (8)
1. A safe start-up method of a hydrocracking catalyst is characterized by comprising the following steps: firstly, introducing the starting oil, hydrogen and a vulcanizing agent into a hydrocracking device: introducing starting oil into a reactor when the inlet temperature of the reactor is controlled to be 140-160 ℃, increasing the inlet temperature of the reactor to 180-200 ℃, injecting a vulcanizing agent into a reaction system, increasing the inlet temperature of the reactor to 210-240 ℃ after the concentration of hydrogen sulfide in circulating hydrogen reaches 0.1v%, then carrying out constant-temperature vulcanization on a hydrocracking catalyst for at least 8-12 h at 210-240 ℃, increasing the reaction temperature to 250-260 ℃ after the constant-temperature vulcanization is finished, introducing raw oil, increasing the temperature to 320-330 ℃, continuing the vulcanization for 4-8 h at constant temperature, finishing the vulcanization process, and controlling the content of hydrogen sulfide in the circulating hydrogen to be 4000-8000 ppm during the constant-temperature vulcanization; the raw oil is vacuum wax oil, and the nitrogen content is below 0.1 wt%;
and after the vulcanization is finished, adjusting the reaction temperature, and adjusting the hydrocracking reaction conditions to carry out the hydrocracking reaction when the mass yield of light oil at the temperature of less than 360 ℃ is constant to be 55-60%, wherein the hydrocracking catalyst contains 30-50% of molecular sieve by weight, and the molecular sieve comprises but is not limited to Y type or USY type.
2. The method of claim 1, wherein: the hydrocracking catalyst contains 12-35 wt% of active metal oxide, and the active metal is one or more of Wo, Mo, Co and Ni.
3. The method of claim 2, wherein: the hydrocracking catalyst contains 18-30 wt% of active metal oxide.
4. The method of claim 1, wherein: the final distillation point of the vacuum wax oil is 450-550 ℃, and the density of the vacuum wax oil is 0.92g/cm3The following.
5. The method of claim 1, wherein the first and second light sources are selected from the group consisting of,the method is characterized in that: the final distillation point of the vacuum wax oil is 460-520 ℃, and the density is 0.91g/cm3The nitrogen content is 0.1 to 0.12wt% or less.
6. The method of claim 1, wherein: after completion of the vulcanization, the reaction temperature is adjusted so that the mass yields of light oil at <360 ℃ are constant in the order of 35 to 40%, 45 to 50%, and 55 to 60%.
7. The method of claim 1, wherein: the hydrocracking reaction conditions are that the operating pressure is 6.0-16.0 MPa, the volume ratio of hydrogen to oil is 300: 1-1500: 1, and the volume airspeed is 0.1-5.0 h-1。
8. The method of claim 7, wherein: the hydrocracking reaction conditions are that the operating pressure is 8.0-15.0 MPa and the volume ratio of hydrogen to oil is 800: 1-1000: 1.
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| US6559092B1 (en) * | 1999-08-17 | 2003-05-06 | Europeenne De Retraitement De Catalyseurs Eurecat | Precarbonisation of a hydrotreatment catalyst |
| US7513990B2 (en) * | 2004-09-08 | 2009-04-07 | Institut Francais Du Petrole | Process for sulfurization of catalysts for hydrotreatment |
| CN103059937A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Startup method of hydrocracking device |
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| US6559092B1 (en) * | 1999-08-17 | 2003-05-06 | Europeenne De Retraitement De Catalyseurs Eurecat | Precarbonisation of a hydrotreatment catalyst |
| US7513990B2 (en) * | 2004-09-08 | 2009-04-07 | Institut Francais Du Petrole | Process for sulfurization of catalysts for hydrotreatment |
| CN103059937A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Startup method of hydrocracking device |
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