CN116064077B - A method for starting up a wax oil hydrogenation unit - Google Patents
A method for starting up a wax oil hydrogenation unit Download PDFInfo
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- CN116064077B CN116064077B CN202111271812.6A CN202111271812A CN116064077B CN 116064077 B CN116064077 B CN 116064077B CN 202111271812 A CN202111271812 A CN 202111271812A CN 116064077 B CN116064077 B CN 116064077B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
- C10G45/06—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 containing nickel or cobalt metal, or compounds thereof
- C10G45/08—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 containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
- C10G45/12—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 containing crystalline alumino-silicates, e.g. molecular sieves
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明公开了一种蜡油加氢装置的开工方法。该方法是对蜡油加氢装置完成催化剂装填、气密性检查、循环氢系统的建立之后，控制循环氢每小时体积流量为总催化剂装填体积的100～800倍，向蜡油加氢装置的反应区入口注入NO气体，NO的体积注入速率为循环氢体积流量的10％～30％，将反应区入口温度提高至200～240℃，当循环氢中NO2体积分数为5％～30％时，停止注入NO气体，然后依次进行氢气置换、硫化，硫化完成后引入原料油正常生产。采用本发明开工方法对蜡油加氢装置进行开工，可以提高催化剂的稳定性，延长装置运转周期。The present invention discloses a start-up method for a wax oil hydrogenation device. The method is to control the hourly volume flow rate of circulating hydrogen to be 100 to 800 times of the total catalyst loading volume after the wax oil hydrogenation device completes catalyst loading, air tightness inspection, and establishment of a circulating hydrogen system, and inject NO gas into the inlet of the reaction zone of the wax oil hydrogenation device, and the volume injection rate of NO is 10% to 30% of the circulating hydrogen volume flow rate, and the inlet temperature of the reaction zone is increased to 200 to 240°C. When the volume fraction of NO2 in the circulating hydrogen is 5% to 30%, the injection of NO gas is stopped, and then hydrogen replacement and sulfurization are carried out in sequence, and after the sulfurization is completed, raw oil is introduced for normal production. The start-up method of the present invention is used to start the wax oil hydrogenation device, which can improve the stability of the catalyst and extend the operation cycle of the device.
Description
Technical Field
The invention relates to the technical field of wax oil hydrogenation, in particular to a starting method of a wax oil hydrogenation device.
Background
Wax oil hydroprocessing technology began to be applied in the seventies of the last century, with the primary objective of meeting environmental regulations for the production of low sulfur fuel oils and for the reduction of FCC unit regenerator sulfide emissions. In recent years, it has been recognized that nitrogen and aromatics in FCC feed are key factors affecting the benefits of FCC units, and reducing the nitrogen and aromatics content of the feedstock can increase the gasoline yield of the unit, improve catalyst stability, extend the operating cycle of the unit, and increase the benefits of the enterprise.
At present, more than ten sets of wax oil hydrotreating industrial devices are running in China, and the technology used is mainly provided by two academies of FRIPP and RIPP of the inferior middle petrochemical industry. Although wax oil hydrotreating technology can meet the production requirements of enterprises to a certain extent, the wax oil hydrotreating main catalyst technology and the technological level completely reach the level of the foreign similar technology, in recent years, along with obvious heavy and inferior trend of crude oil, environmental protection regulations become stricter and oil quality upgrading is accelerated, and in the production process, the defects and problems existing in the process and the catalyst are gradually revealed and need to be solved. The Chinese wax oil composition is most obvious from foreign countries and is characterized by low sulfur and high nitrogen. When the wax oil hydrogenation device processes the raw oil for a long time, the catalyst is easy to lose sulfur, and the stability of the catalyst and the running period of the device are seriously affected.
There are many reports about the startup method of the wax oil hydrogenation device, but there are few reports about the startup method for improving the stability of the wax oil hydrogenation device.
CN112742427a discloses a method for starting hydrogenation catalyst, which comprises the steps of mixing hydrogenation catalyst carrier with thiomolybdate and/or thiotungstate solution, nickel salt and/or cobalt salt solution respectively, drying to obtain intermediate hydrogenation catalyst, mixing sulfuration agent with the intermediate hydrogenation catalyst uniformly, adding phosphorus-containing substance, drying material to obtain presulfiding catalyst, loading the presulfiding catalyst into hydrogenation reactor, and starting. The method can solve the problems of high initial activity and poor safety of the catalyst.
CN111068795A discloses an ex-situ presulfiding method of hydrogenation catalysts, which comprises uniformly mixing a sulfiding agent with an oxidation state hydrogenation catalyst, then performing heat treatment, and further supplementing sulfiding by adopting a material containing hydrogen sulfide. And loading excessive hydrocarbon oil on the intermediate material after hydrogen sulfide vulcanization to obtain the deeply vulcanized pre-vulcanized catalyst. The method can effectively shorten the vulcanization start-up time. .
In the prior art, when the hydrogenation device is started, the outside pre-vulcanization is utilized to save the vulcanization time, and the vulcanized hydrogenation catalyst is directly developed, but the problems that the hydrogenation device cannot stably operate for a long period due to low concentration of hydrogen sulfide and poor stability of the catalyst in the low-sulfur wax oil hydrogenation device are not solved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a starting method of a wax oil hydrogenation device. The starting method of the invention can improve the stability of the catalyst and prolong the running period of the device.
The invention provides a starting method of a wax oil hydrogenation device, which comprises the steps of after finishing catalyst filling, air tightness checking and establishment of a circulating hydrogen system for the wax oil hydrogenation device, controlling the volume flow of circulating hydrogen per hour to be 100-800 times of the total catalyst filling volume, injecting NO gas into an inlet of a reaction zone of the wax oil hydrogenation device, wherein the volume injection rate of NO is 10-30% of the volume flow of the circulating hydrogen, increasing the inlet temperature of the reaction zone to 200-240 ℃, stopping injecting the NO gas when the volume fraction of NO 2 in the circulating hydrogen is 5-30%, then sequentially carrying out hydrogen replacement and vulcanization, and introducing raw oil for normal production after the vulcanization is finished.
Further, the volume injection rate of the NO is 10% -30% of the volume flow of the circulating hydrogen, wherein the volume injection rate of the NO and the volume flow of the circulating hydrogen are both calculated in hours.
Further, the process of the airtight inspection and the establishment of the recycle hydrogen system is performed using a method conventional in the art, and there is no particular limitation in the present invention. After the air tightness check and the establishment of the circulating hydrogen system, the high partial pressure is controlled to be the design pressure, and is generally 5.0-10.0 MPa.
Further, the hydrogen replacement is completed when the volume fraction of hydrogen in the circulating hydrogen is adjusted to be 95% -99%. The hydrogen replacement process can introduce new hydrogen into the circulating hydrogen, and introduce a wax oil hydrogenation device at the inlet of the reaction zone to replace the gas in the system until the hydrogen volume fraction in the circulating hydrogen reaches 95% -99%, so as to complete the hydrogen replacement.
Further, the inlet temperature of the reaction zone may be reduced to 150 to 170 ℃ prior to hydrogen replacement, and then hydrogen replacement may be performed.
Further, the vulcanization process employs wet vulcanization or dry vulcanization, preferably dry vulcanization.
Further, the dry vulcanization comprises a first vulcanization stage and a second vulcanization stage, wherein the first vulcanization stage is to raise the temperature of the inlet of the reaction zone to a first constant temperature of 230-250 ℃ at a temperature rise rate of no more than 10 ℃ per hour, preferably 3-10 ℃ per hour, then keep the temperature of the reaction zone at the first constant temperature for 4-10 hours, the first vulcanization stage is to control the mass concentration of hydrogen sulfide in the circulating hydrogen to be 1000-5000 ppm, and the second vulcanization stage is to raise the temperature of the reaction zone to a second constant temperature of 350-390 ℃ at a temperature rise rate of no more than 10 ℃ per hour, preferably 3-10 ℃ per hour, the mass concentration of hydrogen sulfide in the circulating hydrogen is controlled to be 5000-10000 ppm during the temperature rise, then keep the temperature of the reaction zone at the second constant temperature for 2-6 hours, and the mass concentration of hydrogen sulfide in the circulating hydrogen is controlled to be 10000-20000 ppm during the second constant temperature.
Further, before entering the first vulcanization stage, the vulcanizing agent is gradually injected into the wax oil hydrogenation device, the temperature of the catalyst bed layer in the reaction zone is gradually increased and controlled to be not more than 230 ℃ until the hydrogen sulfide penetrates through the whole catalyst bed layer, and preferably, the condition that the hydrogen sulfide penetrates through the whole catalyst bed layer is as follows, the mass concentration of the hydrogen sulfide in the circulating hydrogen reaches more than 1000ppm, and more preferably, 1000-10000 pm.
Further, the catalyst comprises a hydrofinishing catalyst. The reaction zone is filled with hydrofining catalyst. The hydrofining catalyst comprises a hydrogenation active metal component, a carrier and a binder. The hydrogenation active metal comprises at least one of a VIB group metal (such as tungsten and/or molybdenum) and a VIII group metal (such as nickel and/or cobalt), the carrier comprises at least one of alumina, silica and amorphous silica-alumina, and the binder is alumina and/or silica. Based on the weight of the catalyst, the content of the VIB group metal oxide is 15% -35%, preferably 18% -30%, and the content of the VIII group metal oxide is 2% -10%, preferably 4% -8%. Hydrofining catalysts can be prepared according to existing methods, and industrial catalysts such as FF-34, FF-24, FF-14, FF-66, etc. developed by Dalian petrochemical institute can also be used.
Further, the vulcanizing agent is a vulcanizing agent commonly used in industry and/or an environment-friendly vulcanizing agent. The industrially used vulcanizing agent is at least one of dimethyl disulfide (DMDS), carbon disulfide (CS 2) and the like.
Further, the raw oil is selected from low-sulfur wax oil, the initial distillation point of the raw oil is 300-400 ℃, the final distillation point is 550-650 ℃, the sulfur mass content is less than 5000ppm, and the nitrogen mass content is 1500-4000 ppm.
Further, the specific operation of introducing the raw oil is that the inlet temperature of a reaction zone is reduced to 280-320 ℃, the raw oil starts to be introduced, the initial introduction amount is 20-40% of the design processing load, and after the raw oil is stabilized, the feeding amount of the raw oil is adjusted to 60-100%. And (3) adjusting the reaction temperature until the quality of the wax oil product is qualified.
Further, at the time of the normal production, the reaction conditions are as follows:
The reaction pressure is 5.0-10.0 MPa, the reaction temperature is 280-410 ℃, the volume space velocity of hydrofining solution is 0.5-6.0 h -1, preferably, the reaction pressure is 6.0-8.0 MPa, the reaction temperature is 340-400 ℃, and the volume space velocity of hydrofining solution is 0.6-2.0 h -1.
Further, after the raw oil is mixed with hydrogen, the raw oil contacts with a catalyst in a hydrofining reaction zone to carry out desulfurization, denitrification and dearomatization, and the obtained hydrofining effluent is subjected to a separation system to obtain a wax oil product.
Compared with the prior art, the invention has the following beneficial effects:
(1) Before the wax oil hydrogenation catalyst is vulcanized, NO gas is used as reducing gas, the catalyst is moderately reduced, acting force between metal and a carrier is improved, part of hexacoordinated active metal with high hydrogenation activity but poor stability in the catalyst is reduced to four coordinated active metals with good stability, and then the aim of high-degree vulcanization of the catalyst is finally realized by improving the vulcanization end temperature, so that the sulfur loss resistance of the catalyst is improved, and the running period of the device is prolonged.
(2) The starting process related by the starting method is simple and controllable, the risk of temperature runaway does not occur, and the product adjustment time is short.
Detailed Description
The working method provided by the invention will be further described below with reference to examples to compare the effects and advantages of the working method of the invention, but the invention is not limited thereby.
In the present invention, unless otherwise specified, percentages refer to mass fractions.
The raw oil of the following examples and comparative examples is low sulfur wax oil, the properties of the raw oil are shown in Table 1, the main physical properties of each catalyst are shown in Table 2, the refining reactor of examples and comparative examples is filled with FF-34 hydrofining catalyst, the main evaluation conditions are shown in Table 3, the evaluation effect ratio of examples is shown in Table 4, and the evaluation effect ratio of comparative examples is shown in Table 5.
Example 1
After finishing catalyst filling, air tightness checking and building a circulating hydrogen system for the wax oil hydrogenation device, controlling the high partial pressure to be the design pressure (7 MPa), controlling the volume flow rate of circulating hydrogen per hour to be 400 times of the total catalyst filling volume, injecting NO gas into an inlet of a reaction zone, wherein the volume injection rate of NO is 10% of the volume flow rate of the circulating hydrogen, increasing the inlet temperature of the reaction zone to 200 ℃, stopping introducing the NO gas when the volume fraction of NO 2 in the circulating hydrogen is 15%, and reducing the inlet temperature of the reaction zone to 170 ℃.
And introducing new hydrogen into the circulating hydrogen, introducing a wax oil hydrogenation device from a reaction zone, replacing gas in a reaction system, and completing hydrogen replacement when the volume fraction of hydrogen in the circulating hydrogen reaches 98%.
Starting a sulfur injection pump, gradually injecting a vulcanizing agent DMDS into the reaction zone, gradually heating and controlling the temperature of a catalyst bed layer of the reaction zone to be not more than 230 ℃, until the mass concentration of hydrogen sulfide in circulating hydrogen is maintained to be more than 1000ppm, penetrating the hydrogen sulfide into the catalyst bed layer, then entering a first vulcanization stage, lifting the inlet temperature of the reaction zone to be 230 ℃ at a speed of 5 ℃ per hour, and vulcanizing at a constant temperature for 8 hours, wherein the mass concentration of hydrogen sulfide in the circulating hydrogen is controlled to be maintained to be 2000-3000 ppm.
After finishing the constant temperature of 230 ℃, entering a second vulcanization stage, and stably lifting the inlet temperature of the reaction zone to 360 ℃ at a speed of 5 ℃ per hour, wherein the concentration of hydrogen sulfide is controlled to be 5000-10000 ppm. And (3) carrying out constant-temperature vulcanization for 5 hours at the temperature of 360 ℃, and controlling the concentration of hydrogen sulfide in the circulating hydrogen to be 10000-15000 ppm during the constant-temperature vulcanization.
After the constant temperature of 360 ℃ is finished, the inlet temperature of the reaction zone is reduced to 300 ℃, the raw oil starts to be introduced, and the initial introduction amount is 30% of the design processing load. After stabilization, the feed amount of the raw oil was adjusted to 80% of the design process load. Subsequently, the reaction temperature was adjusted, and the production of the product and the long-period evaluation of the catalyst were performed in accordance with the conditions in table 3.
Example 2
After finishing catalyst filling, air tightness checking and establishment of a circulating hydrogen system for the wax oil hydrogenation device, controlling the high partial pressure to be the design pressure (7 MPa), controlling the volume flow rate of circulating hydrogen per hour to be 600 times of the total catalyst filling volume, injecting NO gas into an inlet of a reaction zone, wherein the volume injection rate of NO is 15% of the volume flow rate of the circulating hydrogen, increasing the inlet temperature of the reaction zone to 210 ℃, stopping introducing the NO gas when the volume fraction of NO 2 in the circulating hydrogen is 20%, and reducing the inlet temperature of the reaction zone to 170 ℃.
And introducing new hydrogen into the circulating hydrogen, introducing a wax oil hydrogenation device from a reaction zone, replacing gas in a reaction system, and completing hydrogen replacement when the volume fraction of hydrogen in the circulating hydrogen reaches 97%.
Starting a sulfur injection pump, gradually injecting a vulcanizing agent DMDS into the reaction zone, gradually heating and controlling the temperature of a catalyst bed layer of the reaction zone to be not more than 230 ℃, until the mass concentration of hydrogen sulfide in circulating hydrogen is maintained to be more than 1000ppm, penetrating the catalyst bed layer, lifting the inlet temperature of the reaction zone to 250 ℃ at a speed of 5 ℃ per hour, vulcanizing for 10 hours at a constant temperature, and controlling the concentration of hydrogen sulfide in the circulating hydrogen to be maintained to 4000-5000 ppm.
After the constant temperature of 250 ℃ is over, the second vulcanization stage is carried out, the inlet temperature of the reaction zone is stably increased to 360 ℃ at the speed of 8 ℃ per hour, and the concentration of hydrogen sulfide is controlled to be 6000-8000 ppm. And (3) vulcanizing at the constant temperature of 360 ℃ for 3 hours, and controlling the concentration of hydrogen sulfide in the circulating hydrogen to be 13000-15000 ppm during the constant temperature vulcanizing.
After the constant temperature of 360 ℃ is finished, the inlet temperature of the reaction zone is reduced to 320 ℃, the raw oil starts to be introduced, and the initial introduction amount is 35% of the design processing load. After stabilization, the feed amount of the raw oil was adjusted to 70% of the design process load. Subsequently, the reaction temperature was adjusted, and the production of the product and the long-period evaluation of the catalyst were performed in accordance with the conditions in table 3.
Example 3
After the wax oil hydrogenation device is filled with the catalyst, checked for air tightness and built up in a circulating hydrogen system, the high partial pressure is controlled to be the design pressure (7 MPa), the volume flow rate of the circulating hydrogen per hour is controlled to be 800 times of the total catalyst filling volume, NO gas is injected into the inlet of the reaction zone, and the volume injection rate of the NO gas is 30% of the volume flow rate of the circulating hydrogen. The reaction zone inlet temperature was increased to 200 ℃. When the volume fraction of NO 2 in the circulating hydrogen is 30%, the NO gas is stopped, and the inlet temperature of the reaction zone is reduced to 150 ℃.
And introducing new hydrogen into the circulating hydrogen, introducing a wax oil hydrogenation device from a reaction zone, replacing gas in a reaction system, and completing hydrogen replacement when the volume fraction of hydrogen in the circulating hydrogen reaches 98%.
Starting a sulfur injection pump, gradually injecting a vulcanizing agent DMDS into the reaction zone, gradually heating and controlling the temperature of a catalyst bed layer of the reaction zone to be not more than 230 ℃, until the mass concentration of hydrogen sulfide in circulating hydrogen is maintained to be more than 2000ppm, penetrating the hydrogen sulfide into the catalyst bed layer, then entering a first vulcanization stage, lifting the inlet temperature of the reaction zone to 240 ℃ at a speed of 7 ℃ per hour, and vulcanizing at a constant temperature for 8 hours, wherein the concentration of hydrogen sulfide in the circulating hydrogen is controlled to be maintained to 3000-4000 ppm.
After finishing the constant temperature of 240 ℃, entering a second vulcanization stage, and stably lifting the inlet temperature of the reaction zone to 360 ℃ at the speed of 8 ℃ per hour, wherein the concentration of hydrogen sulfide is controlled to be 7000-9000 ppm. And (3) carrying out constant-temperature vulcanization for 4 hours at the temperature of 360 ℃, and controlling the concentration of hydrogen sulfide in the circulating hydrogen to be 12000-14000 ppm during the constant-temperature vulcanization.
After the constant temperature of 360 ℃ is finished, the inlet temperature of the reaction zone is reduced to 310 ℃, the raw oil is started to be introduced, and the initial introduction amount is 40% of the design processing load. After stabilization, the feed amount of the raw oil was adjusted to 95% of the design process load. Subsequently, the reaction temperature was adjusted, and the production of the product and the long-period evaluation of the catalyst were performed in accordance with the conditions in table 3.
Example 4
After the wax oil hydrogenation device is filled with the catalyst, checked for air tightness and built up in a circulating hydrogen system, the high partial pressure is controlled to be the design pressure (7 MPa), the volume flow rate of circulating hydrogen per hour is controlled to be 500 times of the total catalyst filling volume, NO gas is injected into the inlet of the reaction zone, and the volume injection rate of NO is 15% of the volume flow rate of the circulating hydrogen. The reaction zone inlet temperature was increased to 210 ℃. When the volume fraction of NO 2 in the circulating hydrogen is 15%, the NO gas is stopped, and the inlet temperature of the reaction zone is reduced to 160 ℃.
And introducing new hydrogen into the circulating hydrogen, introducing a wax oil hydrogenation device from a reaction zone, replacing gas in a reaction system, and completing hydrogen replacement when the volume fraction of the hydrogen in the circulating hydrogen reaches 99%.
Starting a sulfur injection pump, gradually injecting a vulcanizing agent DMDS into the reaction zone, gradually heating and controlling the temperature of a catalyst bed layer of the reaction zone to be not more than 230 ℃, until the mass concentration of hydrogen sulfide in circulating hydrogen is maintained to be more than 3000ppm, penetrating the hydrogen sulfide into the catalyst bed layer, then entering a first vulcanization stage, lifting the inlet temperature of the reaction zone to 235 ℃ at a speed of 7 ℃ per hour, and vulcanizing at a constant temperature for 10 hours, wherein the concentration of hydrogen sulfide in the circulating hydrogen is controlled to be maintained to 3000-4000 ppm.
After finishing the constant temperature of 235 ℃, entering a second vulcanization stage, and stably lifting the inlet temperature of the reaction zone to 390 ℃ at the speed of 9 ℃ per hour, wherein the concentration of hydrogen sulfide is controlled to be 8000-10000 ppm. And (3) carrying out constant-temperature vulcanization for 6 hours at 390 ℃, and controlling the concentration of hydrogen sulfide in circulating hydrogen to be 14000-15000 ppm during the constant-temperature vulcanization.
After the constant temperature of 390 ℃ is finished, the inlet temperature of the reaction zone is reduced to 310 ℃, the raw oil starts to be introduced, and the initial introduction amount is 25% of the design processing load. After stabilization, the feed amount of the raw oil was adjusted to 95% of the design process load. Subsequently, the reaction temperature was adjusted, and the production of the product and the long-period evaluation of the catalyst were performed in accordance with the conditions in table 3.
Comparative example 1
After the wax oil hydrogenation device is filled with the catalyst, the air tightness is checked, and a circulating hydrogen system is established, the high partial pressure is controlled to be the design pressure (7 MPa), the volume flow rate of circulating hydrogen per hour is controlled to be 400 times of the total catalyst filling volume, and the inlet temperature of a reaction zone is controlled to be 170 ℃.
Gradually injecting a vulcanizing agent DMDS into the reaction zone through a high-pressure sulfur injection pump, gradually heating and controlling the temperature of a catalyst bed layer of the reaction zone to be not more than 230 ℃ until the mass concentration of hydrogen sulfide in circulating hydrogen is maintained to be more than 1000ppm, enabling the hydrogen sulfide to penetrate through the catalyst bed layer, then entering a first vulcanization stage, lifting the inlet temperature of the reaction zone to be 230 ℃ at a speed of 5 ℃ per hour, vulcanizing for 8 hours at a constant temperature, and controlling the concentration of the hydrogen sulfide in the circulating hydrogen to be maintained to be 2000-3000 ppm during constant temperature.
After the constant temperature of 230 ℃ is over, the inlet temperature of the reaction zone is stably increased to 360 ℃ at the speed of 5 ℃ per hour, and the concentration of hydrogen sulfide is controlled to be 5000-10000 ppm. And (3) carrying out constant-temperature vulcanization for 5 hours at the temperature of 360 ℃, and controlling the concentration of hydrogen sulfide in the circulating hydrogen to be 10000-15000 ppm during the constant-temperature vulcanization.
After the constant temperature of 360 ℃ is finished, the inlet temperature of the reaction zone is reduced to 300 ℃, the raw oil starts to be introduced, and the initial introduction amount is 30% of load. After stabilization, the feed amount of the raw oil was adjusted to 80% load. Subsequently, the reaction temperature was adjusted, and the production of the product and the long-period evaluation of the catalyst were performed in accordance with the conditions in table 3.
Comparative example 2
After the completion of catalyst loading, air tightness inspection and establishment of a circulating hydrogen system for the wax oil hydrogenation device, the high partial pressure is controlled to be the design pressure (7 MPa), and the volume flow rate of circulating hydrogen per hour is controlled to be 400 times of the total catalyst loading volume. The zone inlet temperature was increased to 270 ℃. When the volume of water produced by the high-pressure separator is 10% of the catalyst loading, the inlet temperature of the reaction zone is reduced to 170 ℃ by volume timing.
Gradually injecting a vulcanizing agent DMDS into the reaction zone through a high-pressure sulfur injection pump, gradually heating and controlling the temperature of a catalyst bed layer of the reaction zone to be not more than 230 ℃ until the mass concentration of hydrogen sulfide in circulating hydrogen is maintained to be more than 1000ppm, enabling the hydrogen sulfide to penetrate through the catalyst bed layer, then entering a first vulcanization stage, lifting the inlet temperature of the reaction zone to be 230 ℃ at a speed of 5 ℃ per hour, vulcanizing for 8 hours at a constant temperature, and controlling the concentration of the hydrogen sulfide in the circulating hydrogen to be maintained to be 2000-3000 ppm during constant temperature.
After the constant temperature of 230 ℃ is over, the inlet temperature of the reaction zone is stably increased to 360 ℃ at the speed of 5 ℃ per hour, and the concentration of hydrogen sulfide is controlled to be 5000-10000 ppm. And (3) carrying out constant-temperature vulcanization for 5 hours at the temperature of 360 ℃, and controlling the concentration of hydrogen sulfide in the circulating hydrogen to be 10000-15000 ppm during the constant-temperature vulcanization.
After the constant temperature of 360 ℃ is finished, the inlet temperature of the reaction zone is reduced to 300 ℃, the raw oil starts to be introduced, and the initial introduction amount is 30% of load. After stabilization, the feed amount of the raw oil was adjusted to 80% load. Subsequently, the reaction temperature was adjusted, and the production of the product and the long-period evaluation of the catalyst were performed in accordance with the conditions in table 3.
Comparative example 3
After the completion of catalyst loading, air tightness inspection and establishment of a circulating hydrogen system for the wax oil hydrogenation device, the high partial pressure is controlled to be the design pressure (7 MPa), and the volume flow rate of circulating hydrogen per hour is controlled to be 1000 times of the total catalyst loading volume. The reaction zone inlet temperature was increased to 280 ℃. When the volume of water produced by the high-pressure separator is 20% of the catalyst loading, the inlet temperature of the reaction zone is reduced to 170 ℃ by volume timing.
Gradually injecting a vulcanizing agent DMDS into the reaction zone by a high-pressure sulfur injection pump, gradually heating and controlling the temperature of a catalyst bed layer of the reaction zone to be not more than 230 ℃ until the mass concentration of hydrogen sulfide in circulating hydrogen is maintained to be more than 1000ppm, enabling the hydrogen sulfide to penetrate through the catalyst bed layer, then entering a first vulcanization stage, lifting the inlet temperature of the reaction zone to be 230 ℃ at a speed of 5 ℃ per hour, vulcanizing for 8 hours at a constant temperature, and controlling the concentration of the hydrogen sulfide in the circulating hydrogen to be maintained to be 2000-3000 ppm during constant temperature.
After the constant temperature of 230 ℃ is over, the inlet temperature of the reaction zone is stably increased to 360 ℃ at the speed of 5 ℃ per hour, and the concentration of hydrogen sulfide is controlled to be 5000-10000 ppm. And (3) carrying out constant-temperature vulcanization for 5 hours at the temperature of 360 ℃, and controlling the concentration of hydrogen sulfide in the circulating hydrogen to be 10000-15000 ppm during the constant-temperature vulcanization.
After the constant temperature of 360 ℃ is finished, the inlet temperature of the reaction zone is reduced to 300 ℃, the raw oil starts to be introduced, and the initial introduction amount is 30% of load. After stabilization, the feed amount of the raw oil was adjusted to 80% load. Subsequently, the reaction temperature was adjusted, and the production of the product and the long-period evaluation of the catalyst were performed in accordance with the conditions in table 3.
Comparative example 4
After the wax oil hydrogenation device is filled with the catalyst, checked in air tightness and built in a circulating hydrogen system, the high partial pressure is controlled to be the design pressure (7 MPa), the volume flow rate of the circulating hydrogen per hour is controlled to be 600 times of the total catalyst filling volume, NO gas is injected into the inlet of the corresponding area, and the volume injection rate of the NO is 15% of the volume flow rate of the circulating hydrogen. The zone inlet temperature was increased to 210 ℃. When the volume fraction of NO 2 in the circulating hydrogen is 2%, the NO gas is stopped, and the inlet temperature of the reaction zone is reduced to 170 ℃.
And introducing new hydrogen into the circulating hydrogen, introducing a wax oil hydrogenation device from a reaction zone, replacing gas in a reaction system, and completing hydrogen replacement when the volume fraction of hydrogen in the circulating hydrogen reaches 97%.
Gradually injecting a vulcanizing agent DMDS into the reaction zone through a high-pressure sulfur injection pump, gradually heating and controlling the temperature of a catalyst bed layer of the reaction zone to be not more than 230 ℃ until the mass concentration of hydrogen sulfide in circulating hydrogen is maintained to be more than 1000ppm, enabling the hydrogen sulfide to penetrate through the catalyst bed layer, then entering a first vulcanization stage, lifting the inlet temperature of the reaction zone to be 250 ℃ at a speed of 5 ℃ per hour, vulcanizing for 10 hours at a constant temperature, and controlling the concentration of the hydrogen sulfide in the circulating hydrogen to be maintained to 4000-5000 ppm during constant temperature vulcanization.
After the constant temperature of 250 ℃ is over, the inlet temperature of the reaction zone is stably increased to 360 ℃ at the speed of 8 ℃ per hour, and the concentration of hydrogen sulfide is controlled to be 6000-8000 ppm. And (3) vulcanizing at the constant temperature of 360 ℃ for 3 hours, and controlling the concentration of hydrogen sulfide in the circulating hydrogen to be 13000-15000 ppm during the constant temperature vulcanizing.
After the constant temperature of 360 ℃ is finished, the inlet temperature of the reaction zone is reduced to 320 ℃, the raw oil starts to be introduced, and the initial introduction amount is 35% of load. After stabilization, the feed amount of the raw oil was adjusted to 70% load. Subsequently, the reaction temperature was adjusted, and the production of the product and the long-period evaluation of the catalyst were performed in accordance with the conditions in table 3.
TABLE 1 oil Properties of raw materials
| Raw oil name | Low sulfur wax oil |
| Density (20 ℃), g.cm -3 (GB/T1884) | 0.9235 |
| Distillation range, C (ASTM D1160) | |
| IBP/10% | 350/371 |
| 30%/50% | 401/425 |
| 70%/90 | 483/525 |
| 95%/EBP | 539/568 |
| Sulfur content, ppm | 4500 |
| Nitrogen content, ppm | 2000 |
TABLE 2 Industrial catalyst
| Industrial agent | FF-34 |
| Physical and chemical Properties | |
| Pore size/nm | 2~10nm |
| Pore volume/mL.g -1 | ≥0.35 |
| Specific surface area/m 2·g-1 | ≥120 |
| Shape and shape | Clover with three leaves |
| Packing pile ratio, g/cm 3 | 0.75 |
Table 3 evaluation conditions
| High partial pressure, MPa | 7.0 |
| Refined liquid hourly space velocity, h -1 | 1.0 |
| Sulfur content of wax oil, ppm | ~2500 |
| Hydrofining inlet hydrogen-oil volume ratio | 400:1 |
| Run time, h | 2500 |
Table 4 example test results
| Project | Example 1 | Example 2 | Example 3 | Example 4 |
| Hydrogen consumption, wt% | 0.90 | 0.92 | 0.95 | 0.93 |
| Refined catalyst deactivation rate, °c/d | 0.04 | 0.06 | 0.05 | 0.08 |
| 2500H refining average reaction temperature, °C | 380 | 382 | 381 | 384 |
Table 5 comparative test results
| Project | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Hydrogen consumption, wt% | 1.09 | 1.03 | 1.06 | 1.00 |
| Refined catalyst deactivation rate, °c/d | 0.19 | 0.15 | 0.16 | 0.12 |
| 2500H refining average reaction temperature, °C | 397 | 393 | 395 | 388 |
From the above examples and comparative examples, it can be seen that the start-up method of the present invention has low hydrogen consumption and slow catalyst deactivation rate under the condition of controlling the sulfur content of the same wax oil.
Claims (14)
1. The method comprises the steps of after finishing catalyst filling, air tightness checking and establishment of a circulating hydrogen system for the wax oil hydrogenation device, controlling the volume flow rate of circulating hydrogen per hour to be 100-800 times of the total catalyst filling volume, injecting NO gas into a reaction zone inlet of the wax oil hydrogenation device, wherein the volume injection rate of NO is 10-30% of the volume flow rate of the circulating hydrogen, increasing the inlet temperature of the reaction zone to 200-240 ℃, stopping injecting NO gas when the volume fraction of NO 2 -30% in the circulating hydrogen, then sequentially carrying out hydrogen replacement and vulcanization, and introducing raw oil for normal production after vulcanization is finished;
The vulcanization adopts dry vulcanization, the dry vulcanization comprises a first vulcanization stage and a second vulcanization stage, wherein the first vulcanization stage is to raise the temperature of an inlet of a reaction zone to a first constant temperature of 230-250 ℃ at a heating rate of no more than 10 ℃ per hour, then keep the temperature constant for 4-10 hours at the first constant temperature, the first vulcanization stage is to control the mass concentration of hydrogen sulfide in circulating hydrogen to be maintained at 1000-5000 ppm, the second vulcanization stage is to raise the temperature of an inlet of the reaction zone to a second constant temperature of 350-390 ℃ at a heating rate of no more than 10 ℃ per hour, then control the mass concentration of hydrogen sulfide in the circulating hydrogen to reach 5000-10000 ppm at the second constant temperature, and then keep the mass concentration of hydrogen sulfide in the circulating hydrogen to reach 10000-20000 ppm at the second constant temperature.
2. The start-up method of claim 1, wherein the hydrogen replacement is completed when the volume fraction of hydrogen in the recycle hydrogen is adjusted to 95% -99%.
3. The start-up method according to claim 1 or 2, wherein the inlet temperature of the reaction zone is reduced to 150 to 170 ℃ before hydrogen substitution, and then hydrogen substitution is performed.
4. The start-up method according to claim 1, wherein in the dry vulcanization, the first vulcanization stage is to raise the temperature of the inlet of the reaction zone to a first constant temperature of 230-250 ℃ at a temperature of 3-10 ℃ per hour, then to maintain the temperature at the first constant temperature for 4-10 hours, the first vulcanization stage is to control the mass concentration of hydrogen sulfide in the circulating hydrogen to be 1000-5000 ppm, and the second vulcanization stage is to raise the temperature of the inlet of the reaction zone to a second constant temperature of 350-390 ℃ at a temperature of 3-10 ℃ per hour, and then to control the mass concentration of hydrogen sulfide in the circulating hydrogen to 5000-10000 ppm during the temperature raising period, then to maintain the temperature at the second constant temperature for 2-6 hours, and the mass concentration of hydrogen sulfide in the circulating hydrogen to 10000-20000 ppm during the second constant temperature period.
5. The start-up method according to claim 4, wherein the dry vulcanization is performed by gradually injecting a vulcanizing agent into the wax oil hydrogenation device before entering the first vulcanization stage, gradually heating up and controlling the temperature of the catalyst bed in the reaction zone to be not more than 230 ℃ until hydrogen sulfide penetrates through the whole catalyst bed.
6. A start-up process according to claim 5, wherein the hydrogen sulphide penetrates the entire catalyst bed under conditions such that the mass concentration of hydrogen sulphide in the recycle hydrogen reaches more than 1000ppm.
7. The start-up method of claim 6, wherein the hydrogen sulfide penetrates through the whole catalyst bed under the condition that the mass concentration of the hydrogen sulfide in the circulating hydrogen reaches 1000-10000 pm.
8. The method according to claim 4, wherein the reaction zone is filled with a hydrofining catalyst, the hydrofining catalyst comprises 15% -35% of a group VIB metal oxide and 2% -10% of a group VIII metal oxide based on the weight of the catalyst.
9. The start-up method according to claim 8, wherein the hydrofining catalyst is 18% -30% in terms of group VIB metal oxide and 4% -8% in terms of group VIII metal oxide based on the weight of the catalyst.
10. The method according to claim 1 or 4, wherein the vulcanizing agent used for vulcanization is at least one of dimethyl disulfide and carbon disulfide.
11. The start-up method according to claim 1, wherein the raw oil has an initial distillation point of 300 to 400 ℃, a final distillation point of 550 to 650 ℃, a sulfur content of 5000ppm or less, and a nitrogen content of 1500 to 4000ppm by mass.
12. The starting method according to claim 1, wherein the specific operation of introducing the raw oil is that the inlet temperature of the reaction zone is reduced to 280-320 ℃, the raw oil is introduced, the initial introduction amount is 20-40% of the design processing load, after the raw oil is stabilized, the raw oil feeding amount is adjusted to 60-100%, and the reaction temperature is adjusted until the quality of wax oil products is qualified.
13. The method according to claim 1, wherein the reaction conditions are as follows, the reaction pressure is 5.0-10.0 MPa, the reaction temperature is 280-410 ℃, and the volume space velocity of the hydrofining solution is 0.5-6.0 h -1.
14. The method according to claim 13, wherein the reaction conditions are such that the reaction pressure is 6.0-8.0 MPa, the reaction temperature is 340-400 ℃, and the volume space velocity of the hydrofining solution is 0.6-2.0 h -1 during normal production.
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