CN116064079B - Start-up method of diesel hydrogenation device - Google Patents
Start-up method of diesel hydrogenation device Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 49
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 105
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- 239000003054 catalyst Substances 0.000 claims abstract description 92
- 238000004073 vulcanization Methods 0.000 claims abstract description 86
- 239000007789 gas Substances 0.000 claims abstract description 29
- 238000002347 injection Methods 0.000 claims abstract description 23
- 239000007924 injection Substances 0.000 claims abstract description 23
- 238000011049 filling Methods 0.000 claims abstract description 16
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 46
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 45
- 229910052717 sulfur Inorganic materials 0.000 claims description 26
- 239000011593 sulfur Substances 0.000 claims description 26
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 claims description 22
- 238000013461 design Methods 0.000 claims description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 238000012545 processing Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention discloses a startup method of a diesel hydrogenation device. The method comprises the following steps: after finishing catalyst filling, air tightness checking and building a circulating hydrogen system for the diesel hydrogenation device, controlling the volume flow rate of circulating hydrogen per hour to be 200-1000 times of the total catalyst filling volume, injecting CO gas into the inlet of a reaction zone of the diesel hydrogenation device, wherein the volume injection rate of CO is 10-30% of the volume flow rate of the circulating hydrogen, increasing the inlet temperature of the reaction zone to 180-260 ℃, stopping injecting CO gas when the volume fraction of CO 2 in the circulating hydrogen is 10-40%, then sequentially carrying out hydrogen replacement on the gas in the device, vulcanizing the catalyst, and introducing raw oil into normal production after vulcanization is finished. The method of the invention adopts a start-up method of firstly reducing and then vulcanizing the catalyst in the diesel hydrogenation device, thereby realizing the aims of improving the stability of the catalyst and prolonging the running period of the device.
Description
Technical Field
The invention relates to the technical field of diesel hydrogenation, in particular to a startup method of a diesel hydrogenation device.
Background
In the 21 st century, under the great trend of increasingly severe environmental protection and sanitary safety requirements, petroleum products closely related to human production and life show a development trend of innocuity and cleanliness, and the adoption of hydrogenation technology to reduce impurities in crude oil to safe allowable values is critical. The hydrogenation technology has the advantages of clean and environment-friendly production process, high yield of main products, good quality and the like, and is widely reported and applied.
The diesel hydrogenation technology has the characteristics of good product quality and strong raw material adaptability. However, when a diesel hydrogenation device processes low-sulfur high-nitrogen raw materials, the catalyst reacts at high temperature for a long time, so that the problem of sulfur loss is easy to occur, the stability is poor, the problem of short device operation period seriously affects the economic benefit of enterprises, and sustainable high-efficiency development is not facilitated. Because the start-up method of diesel oil also affects the stability of the catalyst, it is necessary to develop a start-up method for improving the catalyst stability for a diesel oil hydrogenation device to meet the processing requirements of low-sulfur and high-nitrogen raw materials.
There are many reports about the start-up method of the diesel hydrogenation device, but there are few reports about the start-up method for improving the stability of the diesel hydrogenation device.
CN111068794a discloses an ex-situ presulfiding method of hydrogenation catalyst, which comprises uniformly mixing a vulcanizing agent with an oxidation state catalyst, then heat-treating, hydrogen-treating, loading excessive hydrocarbon oil, and vulcanizing in the device only by heating. The method can save the vulcanizing time of the device, but is easy to generate the risk of temperature runaway, and the problem of catalyst activity reduction caused by sulfur loss cannot be avoided.
CN103357449a discloses a catalyst sulfiding method for diesel hydrotreating process. The method is suitable for treating the high-sulfur diesel hydrogenation device, an oxidation state diesel hydrogenation catalyst is filled in a reactor of the diesel hydrogenation device, and hydrogen sulfide-containing gas discharged by the circulating hydrogen sulfide removal device of the treating high-sulfur diesel hydrogenation device is introduced into the diesel hydrogenation device by adjusting the hydrogen sulfide content of the circulating hydrogen sulfide removal device to vulcanize the catalyst of the diesel hydrogenation device. The method has complex process flow, difficult control of the concentration of the hydrogen sulfide and high operation difficulty.
The prior art saves the sulfuration time when in startup, or utilizes the ex-situ pre-sulfuration, or improves the sulfuration method of the high-sulfur diesel, but the problems that the hydrogenation device cannot stably operate for a long period due to low mass concentration of hydrogen sulfide and poor stability of the catalyst in the low-sulfur diesel hydrogenation device are not solved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a startup method of a diesel hydrogenation device. The start-up method of the invention can achieve the aims of improving the stability of the catalyst and prolonging the running period of the device.
The invention provides a startup method of a diesel hydrogenation device, which comprises the following steps: after finishing catalyst filling, air tightness checking and building a circulating hydrogen system for the diesel hydrogenation device, controlling the volume flow rate of circulating hydrogen per hour to be 200-1000 times of the total catalyst filling volume, injecting CO gas into the inlet of a reaction zone of the diesel hydrogenation device, wherein the volume injection rate of CO is 10-30% of the volume flow rate of the circulating hydrogen, increasing the inlet temperature of the reaction zone to 180-260 ℃, stopping injecting CO gas when the volume fraction of CO 2 in the circulating hydrogen is 10-40%, then sequentially carrying out hydrogen replacement on the gas in the device, vulcanizing the catalyst, and introducing raw oil into normal production after vulcanization is finished.
Further, the volume injection rate of CO is 10% -30% of the volume flow of the circulating hydrogen, wherein the volume injection rate of CO and the volume flow of the circulating hydrogen are 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 gas tightness check and the establishment of the circulating hydrogen system, the high partial pressure is controlled to be the design pressure, and is generally: 4.0-12.0 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 the gas in the system is replaced by an inlet introduction device of the reaction zone until the volume fraction of the hydrogen in the circulating hydrogen reaches 95% -99%, so that the hydrogen replacement is completed.
Further, in the hydrogen substitution, the inlet temperature of the reaction zone can be reduced to 140-175 ℃.
Further, wet vulcanization or dry vulcanization, preferably dry vulcanization, may be employed in the vulcanization process.
Further, the dry vulcanization comprises a first vulcanization stage and a second vulcanization stage, wherein the first vulcanization stage is to raise the inlet temperature of the reaction zone to a first constant temperature, namely 220-240 ℃ at a speed of no more than 10 ℃/h, preferably 3-10 ℃/h, and then to carry out constant temperature vulcanization for 2-12 hours at the first constant temperature, and the mass concentration of hydrogen sulfide in the circulating hydrogen is controlled to be maintained at 1000-8000 ppm in the first vulcanization stage; the second vulcanization stage is to raise the inlet temperature of the reaction zone to a second constant temperature of 340-380 ℃ at a speed of no more than 10 ℃/h, preferably 2-10 ℃/h, and then to carry out constant temperature vulcanization for no less than 2h, preferably 2-8 h at the second constant temperature, wherein the mass concentration of hydrogen sulfide in the circulating hydrogen is controlled to be 8000-20000 ppm.
Further, the dry vulcanization is carried out, a vulcanizing agent is gradually injected into the diesel hydrogenation device before entering the first vulcanization stage, the temperature of the catalyst bed layer of the reaction zone is gradually increased and controlled to be not more than 230 ℃ until hydrogen sulfide penetrates through the catalyst bed layer; preferably, the conditions under which the hydrogen sulphide penetrates the whole catalyst bed are as follows: the mass concentration of hydrogen sulfide in the recycle hydrogen is 1000ppm or more, and more preferably 1000 to 8000ppm.
Further, the specific operation of introducing the raw oil is as follows: the inlet temperature of the reaction zone is reduced to 290-320 ℃, 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% of the design processing load, and the reaction temperature is adjusted until the diesel oil product is qualified.
Further, the catalyst comprises a hydrofinishing catalyst. The hydrofining catalyst comprises a hydrogenation active metal component, a carrier and a binder. The hydrogenation active metal comprises at least one of group VIB metal (such as tungsten and/or molybdenum) and group VIII metal (such as nickel and/or cobalt); the carrier comprises at least one of alumina, silica and amorphous silica-alumina; the binder is alumina and/or silica. Based on the weight of the catalyst, the content of the VIB group metal oxide is 25% -45%, preferably 28% -35%, and the content of the VIII group metal oxide is 3% -12%, preferably 4% -9%. Hydrofining catalysts can be prepared according to existing methods, and industrial catalysts such as FHUDS-5, FHUDS-6, FHUDS-7, FHUDS-8, 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 diesel oil, the initial distillation point of the raw oil is 50-110 ℃, the final distillation point is 310-380 ℃, the sulfur mass content is less than 5000ppm, and the nitrogen mass content is 500-2000 ppm.
Further, the reaction conditions at the time of transfer to normal production are as follows:
the reaction pressure is 4.0-12.0 MPa, the reaction temperature is 220-390 ℃, the liquid hourly space velocity is 0.2-6.0 h -1, preferably, the reaction pressure is 6.0-10.0 MPa, the reaction temperature is 340-380 ℃, and the liquid hourly space velocity is 0.5-2.0 h -1.
Further, after the raw oil is mixed with hydrogen, desulfurization, denitrification and dearomatization reaction are carried out with a catalyst in a hydrofining reaction zone, and the obtained hydrofining effluent is subjected to a separation system to obtain a diesel product.
Compared with the prior art, the invention has the following beneficial effects:
(1) In the starting process, the hydrofining catalyst is reduced moderately, then vulcanized, and part of the hexacoordinated active metal with high hydrogenation activity but poor stability is reduced to four coordinated active metals with good stability by flexibly adjusting the vulcanization atmosphere, temperature and time in the starting process, and the vulcanizing degree of the stable metal of the catalyst can be obviously improved by improving the vulcanization end temperature, so that the method is suitable for low-sulfur diesel raw materials, prolongs the running period of the device, reduces the hydrogen consumption when meeting the requirement of product quality, and can save energy and reduce consumption.
(2) The start-up method of the invention adopts CO gas as reducing gas, and can stably reduce the active metal in the catalyst at low temperature, thereby converting the active metal with high hydrogenation activity in the catalyst into the active metal with high stability.
(3) The starting process related by the 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.
In the examples and comparative examples of the present invention, when the mass concentration of hydrogen sulfide in the circulating hydrogen was 1000ppm or more at the time of sulfiding, it was considered that the hydrogen sulfide had penetrated the catalyst bed.
The raw oil related to the following examples and comparative examples is low sulfur diesel oil, the properties of the raw oil are shown in Table 1, the main physical indexes of various catalysts are shown in Table 2, FHUDS-5 hydrofining catalysts are filled in the refining reactors in the examples and comparative examples, the main evaluation conditions are shown in Table 3, the evaluation effects of the examples are shown in Table 4, and the evaluation effects of the comparative examples are shown in Table 5.
Example 1
After the catalyst filling, the air tightness checking and the establishment of a circulating hydrogen system are completed on the diesel hydrogenation device, the high partial pressure is controlled to be the design pressure (7.5 MPa), the volume flow rate of circulating hydrogen per hour is controlled to be 200 times of the total catalyst filling volume, CO gas is injected into the inlet of the reaction zone, the volume injection rate of CO is 12% of the volume flow rate of the circulating hydrogen, the temperature of the inlet of the reaction zone is increased to 200 ℃, and the CO gas injection is stopped when the volume fraction of CO 2 in the circulating hydrogen is 15%.
And reducing the inlet temperature of the reaction zone to 145 ℃, starting to introduce new hydrogen into the circulating hydrogen, introducing the diesel hydrogenation device into the reaction zone to perform gas replacement, and completing hydrogen replacement when the volume fraction of the hydrogen in the circulating hydrogen reaches 96%.
Starting a sulfur injection pump, gradually injecting a vulcanizing agent DMDS from an inlet of a reaction zone, gradually heating and controlling the temperature of a catalyst bed layer of the reaction zone to be not more than 230 ℃ until hydrogen sulfide penetrates through the catalyst bed layer, then entering a first vulcanization stage, lifting the temperature of the inlet of the reaction zone to 230 ℃ at a speed of 6 ℃/h, and then carrying out first constant-temperature vulcanization for 6 hours at 230 ℃, wherein the mass concentration of hydrogen sulfide in circulating hydrogen is controlled to be maintained at 2000-3000 ppm.
After the first constant temperature vulcanization is finished, the second vulcanization stage is carried out, the inlet temperature of the reaction zone is stably increased to 360 ℃ at the speed of 8 ℃/h, and then the second constant temperature vulcanization is carried out for 6h at 360 ℃. And controlling the mass concentration of hydrogen sulfide in the circulating hydrogen to be 8000-10000 ppm.
After the vulcanization is completed, the temperature at the inlet of the reaction zone is reduced to 310 ℃, the introduction of the raw oil is started, and the initial introduction amount is 40% 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 the catalyst filling, the air tightness checking and the establishment of a circulating hydrogen system are completed on the diesel hydrogenation device, the high partial pressure is controlled to be the design pressure (7.5 MPa), the volume flow rate of circulating hydrogen per hour is controlled to be 600 times of the total catalyst filling volume, CO gas is injected into the inlet of the reaction zone, the volume injection rate of CO is 28 percent of the volume flow rate of the circulating hydrogen, the inlet temperature of the reaction zone is increased to 250 ℃, and the CO gas injection is stopped when the volume fraction of CO 2 in the circulating hydrogen is 38 percent.
And reducing the inlet temperature of the reaction zone to 150 ℃, starting to introduce new hydrogen into the circulating hydrogen, introducing the diesel hydrogenation device into the reaction zone to perform gas replacement, and completing hydrogen replacement when the volume fraction of the hydrogen in the circulating hydrogen reaches 96%.
Starting a sulfur injection pump, gradually injecting a vulcanizing agent DMDS from an inlet of a reaction zone, gradually heating and controlling the temperature of a catalyst bed layer of the reaction zone to be not more than 230 ℃ until hydrogen sulfide penetrates through the catalyst bed layer, then entering a first vulcanization stage, lifting the temperature of the inlet of the reaction zone to 230 ℃ at a speed of 8 ℃/h, and then carrying out first constant-temperature vulcanization for 7h at 230 ℃, wherein the mass concentration of hydrogen sulfide in circulating hydrogen is controlled to be maintained at 2000-3000 ppm.
After the first constant temperature vulcanization is finished, the second vulcanization stage is carried out, the inlet temperature of the reaction zone is smoothly raised to 370 ℃ at a speed of 5 ℃/h, and then the second constant temperature vulcanization is carried out for 7h at 370 ℃. During the period, the mass concentration of the hydrogen sulfide in the circulating hydrogen is controlled to be maintained between 10000 and 12000ppm.
After the vulcanization is completed, the inlet temperature of the reaction zone is reduced to 320 ℃, the introduction of the raw oil is started, and the initial introduction amount is 30% 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 zone temperature was adjusted and the production of the product and the long period evaluation of the catalyst were performed according to the conditions in table 3.
Example 3
After the catalyst filling, the air tightness checking and the establishment of a circulating hydrogen system are completed on the diesel hydrogenation device, the high partial pressure is controlled to be the design pressure (7.5 MPa), the volume flow rate of circulating hydrogen per hour is controlled to be 1000 times of the total catalyst filling volume, CO gas is injected into the inlet of the reaction zone, the volume injection rate of CO is 20% of the volume flow rate of the circulating hydrogen, the temperature of the inlet of the reaction zone is increased to 210 ℃, and the CO gas injection is stopped when the volume fraction of CO 2 in the circulating hydrogen is 30%.
And reducing the inlet temperature of the reaction zone to 160 ℃, starting to introduce new hydrogen into the circulating hydrogen, introducing the diesel hydrogenation device into the reaction zone for gas replacement, and completing hydrogen replacement when the volume fraction of the hydrogen in the circulating hydrogen reaches 96%.
Starting a sulfur injection pump, gradually injecting a vulcanizing agent DMDS from an inlet of a reaction zone, gradually heating and controlling the temperature of a catalyst bed layer of the reaction zone to be not more than 230 ℃ until hydrogen sulfide penetrates through the catalyst bed layer, then entering a first vulcanization stage, lifting the temperature of the inlet of the reaction zone to 230 ℃ at a speed of 4 ℃/h, and then carrying out first constant-temperature vulcanization for 8 hours at 230 ℃, wherein the mass concentration of hydrogen sulfide in circulating hydrogen is controlled to be maintained at 2000-4000 ppm.
After the first constant temperature vulcanization is finished, the second vulcanization stage is carried out, the inlet temperature of the reaction zone is stably increased to 380 ℃ at the speed of 7 ℃/h, and then the second constant temperature vulcanization is carried out for 8 hours at 380 ℃. During the period, the mass concentration of the hydrogen sulfide in the circulating hydrogen is controlled to be maintained between 10000 and 12000ppm.
After the vulcanization is completed, the inlet temperature of the reaction zone is reduced to 290 ℃, the raw oil is started 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 zone temperature was adjusted and the production of the product and the long period evaluation of the catalyst were performed according to the conditions in table 3.
Example 4
After the catalyst filling, the air tightness checking and the establishment of a circulating hydrogen system are completed on the diesel hydrogenation device, the high partial pressure is controlled to be the design pressure (7.5 MPa), the volume flow rate of circulating hydrogen per hour is controlled to be 900 times of the total catalyst filling volume, CO gas is injected into the inlet of the reaction zone, the volume injection rate of CO is 18% of the volume flow rate of the circulating hydrogen, the temperature of the inlet of the reaction zone is increased to 230 ℃, and the CO gas injection is stopped when the volume fraction of CO 2 in the circulating hydrogen is 15%.
And reducing the inlet temperature of the reaction zone to 160 ℃, starting to introduce new hydrogen into the circulating hydrogen, introducing the diesel hydrogenation device into the reaction zone to perform gas replacement, and completing hydrogen replacement when the volume fraction of the hydrogen in the circulating hydrogen reaches 98%.
Starting a sulfur injection pump, gradually injecting a vulcanizing agent DMDS from an inlet of a reaction zone, gradually heating and controlling the temperature of a catalyst bed layer of the reaction zone to be not more than 230 ℃ until hydrogen sulfide penetrates through the catalyst bed layer, then entering a first vulcanization stage, lifting the temperature of the inlet of the reaction zone to 240 ℃ at a speed of 6 ℃/h, and then carrying out first constant-temperature vulcanization for 8 hours at 240 ℃, wherein the mass concentration of hydrogen sulfide in circulating hydrogen is controlled to be maintained at 3000-5000 ppm.
After the first constant temperature vulcanization is finished, the second vulcanization stage is carried out, the inlet temperature of the reaction zone is stably increased to 350 ℃ at the speed of 8 ℃/h, and then the second constant temperature vulcanization is carried out for 6h at 350 ℃. During the period, the mass concentration of the hydrogen sulfide in the circulating hydrogen is controlled to be 18000-20000 ppm.
After the vulcanization is completed, the temperature at the inlet of the reaction zone is reduced to 310 ℃, the introduction of the raw oil is started, and the initial introduction amount is 30% of the design processing load. After stabilization, the feed amount of the raw oil was adjusted to 75% of the design process load. Subsequently, the reaction zone temperature was adjusted and the production of the product and the long period evaluation of the catalyst were performed according to the conditions in table 3.
Comparative example 1
After the catalyst loading, the air tightness check and the establishment of a circulating hydrogen system are completed on the diesel hydrogenation device, the high partial pressure is controlled to be the design pressure (7.5 MPa), and the volume flow rate of the circulating hydrogen per hour is controlled to be 200 times of the total catalyst loading volume.
Controlling the temperature of the inlet of the reaction zone to 145 ℃, starting a sulfur injection pump, gradually injecting a vulcanizing agent DMDS from the inlet of the reaction zone, gradually heating and controlling the temperature of the catalyst bed layer of the reaction zone to be not more than 230 ℃, until hydrogen sulfide penetrates through the catalyst bed layer, then entering a first vulcanization stage, lifting the temperature of the inlet of the reaction zone to 230 ℃ at a speed of 6 ℃/h, then carrying out first constant temperature vulcanization for 6h at 230 ℃, and controlling the mass concentration of hydrogen sulfide in circulating hydrogen to be maintained at 2000-3000 ppm during the period.
After the first constant temperature vulcanization is finished, the second vulcanization stage is carried out, the inlet temperature of the reaction zone is stably increased to 360 ℃ at the speed of 8 ℃/h, and then the second constant temperature vulcanization is carried out for 6h at 360 ℃. And controlling the mass concentration of hydrogen sulfide in the circulating hydrogen to be 8000-10000 ppm.
After the vulcanization is completed, the temperature at the inlet of the reaction zone is reduced to 310 ℃, the introduction of the raw oil is started, and the initial introduction amount is 40% 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.
Comparative example 2
After the catalyst loading, the air tightness check and the establishment of a circulating hydrogen system are completed on the diesel hydrogenation device, the high partial pressure is controlled to be the design pressure (7.5 MPa), and the volume flow rate of the circulating hydrogen per hour is controlled to be 600 times of the total catalyst loading volume.
Controlling the temperature of the inlet of the reaction zone to 150 ℃, starting a sulfur injection pump, gradually injecting a vulcanizing agent DMDS from the inlet of the reaction zone, gradually heating and controlling the temperature of the catalyst bed layer of the reaction zone to be not more than 230 ℃, until hydrogen sulfide penetrates through the catalyst bed layer, then entering a first vulcanization stage, lifting the temperature of the inlet of the reaction zone to 230 ℃ at a speed of 8 ℃/h, then carrying out first constant temperature vulcanization for 7h at 230 ℃, and controlling the mass concentration of hydrogen sulfide in circulating hydrogen to be maintained at 2000-3000 ppm during the period.
After the first constant temperature vulcanization is finished, the second vulcanization stage is carried out, the inlet temperature of the reaction zone is smoothly raised to 370 ℃ at a speed of 5 ℃/h, and then the second constant temperature vulcanization is carried out for 7h at 370 ℃. During the period, the mass concentration of the hydrogen sulfide in the circulating hydrogen is controlled to be maintained between 10000 and 12000ppm.
After the vulcanization is completed, the inlet temperature of the reaction zone is reduced to 320 ℃, the introduction of the raw oil is started, and the initial introduction amount is 30% 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 zone temperature was adjusted and the production of the product and the long period evaluation of the catalyst were performed according to the conditions in table 3.
Comparative example 3
After the catalyst loading, the air tightness checking and the establishment of a circulating hydrogen system are completed on the diesel hydrogenation device, the high partial pressure is controlled to be the design pressure (7.5 MPa), and the volume flow rate of the circulating hydrogen per hour is controlled to be 900 times of the total catalyst loading volume. Controlling the inlet temperature of the reaction zone to 270 ℃, and reducing the inlet temperature of the refining reaction zone to 160 ℃ by volume counting when the water quantity separated in the high-pressure separator is 5% of the catalyst loading.
Starting a sulfur injection pump, gradually injecting a vulcanizing agent DMDS from an inlet of a reaction zone, gradually heating and controlling the temperature of a catalyst bed layer of the reaction zone to be not more than 230 ℃ until hydrogen sulfide penetrates through the catalyst bed layer, then entering a first vulcanization stage, lifting the temperature of the inlet of the reaction zone to 240 ℃ at a speed of 6 ℃/h, and then carrying out first constant-temperature vulcanization for 8 hours at 240 ℃, wherein the mass concentration of hydrogen sulfide in circulating hydrogen is controlled to be maintained at 3000-5000 ppm.
After the first constant temperature vulcanization is finished, the second vulcanization stage is carried out, the inlet temperature of the reaction zone is stably increased to 350 ℃ at the speed of 8 ℃/h, and then the second constant temperature vulcanization is carried out for 6h at 350 ℃. During the period, the mass concentration of the hydrogen sulfide in the circulating hydrogen is controlled to be 18000-20000 ppm.
After the vulcanization is completed, the temperature at the inlet of the reaction zone is reduced to 310 ℃, the introduction of the raw oil is started, and the initial introduction amount is 30% of the design processing load. After stabilization, the feed amount of the raw oil was adjusted to 75% of the design process load. Subsequently, the reaction zone temperature was adjusted and the production of the product and the long period evaluation of the catalyst were performed according to the conditions in table 3.
Comparative example 4
After the catalyst filling, the air tightness checking and the establishment of a circulating hydrogen system are completed on the diesel hydrogenation device, the high partial pressure is controlled to be the design pressure (7.5 MPa), the volume flow rate of circulating hydrogen per hour is controlled to be 1000 times of the total catalyst filling volume, CO gas is injected into the inlet of the reaction zone, the volume injection rate of CO is 60 percent of the volume flow rate of the circulating hydrogen, the temperature of the inlet of the reaction zone is increased to 210 ℃, and the CO gas injection is stopped when the volume fraction of CO 2 in the circulating hydrogen is 30 percent.
And reducing the inlet temperature of the reaction zone to 160 ℃, starting to introduce new hydrogen into the circulating hydrogen, introducing the diesel hydrogenation device into the reaction zone for gas replacement, and completing hydrogen replacement when the volume fraction of the hydrogen in the circulating hydrogen reaches 96%.
Starting a sulfur injection pump, gradually injecting a vulcanizing agent DMDS from an inlet of a reaction zone, gradually heating and controlling the temperature of a catalyst bed layer of the reaction zone to be not more than 230 ℃ until hydrogen sulfide penetrates through the catalyst bed layer, then entering a first vulcanization stage, lifting the temperature of the inlet of the reaction zone to 230 ℃ at a speed of 4 ℃/h, and then carrying out first constant-temperature vulcanization for 8 hours at 230 ℃, wherein the mass concentration of hydrogen sulfide in circulating hydrogen is controlled to be maintained at 2000-4000 ppm.
After the first constant temperature vulcanization is finished, the second vulcanization stage is carried out, the inlet temperature of the reaction zone is stably increased to 380 ℃ at the speed of 7 ℃/h, and then the second constant temperature vulcanization is carried out for 8 hours at 380 ℃. During the period, the mass concentration of the hydrogen sulfide in the circulating hydrogen is controlled to be maintained between 10000 and 12000ppm.
After the vulcanization is completed, the inlet temperature of the reaction zone is reduced to 290 ℃, the raw oil is started 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 zone temperature was adjusted and the production of the product and the long period evaluation of the catalyst were performed according to the conditions in table 3.
TABLE 1 oil Properties of raw materials
| Raw oil name | Low sulfur diesel |
| Density (20 ℃), g.cm -3 (GB/T1884) | 0.7918 |
| Distillation range, DEG C (ASTM D1160) | |
| IBP/10％ | 190/200 |
| 30％/50％ | 235/258 |
| 70％/90％ | 277/299 |
| 95％/EBP | 325/335 |
| Sulfur content, m% | 0.41 |
| Nitrogen content, m% | 0.15 |
TABLE 2 Industrial catalyst
| Industrial agent | FHUDS-5 |
| Physical and chemical Properties | |
| Pore size/nm | 2～8nm |
| Pore volume/mL.g -1 | ≥0.25 |
| Specific surface area/m 2·g-1 | ≥150 |
| Shape and shape | Clover with three leaves |
| Packing pile ratio, g/cm 3 | 0.79 |
Table 3 evaluation conditions
| High partial pressure, MPa | 7.5 |
| Refined liquid hourly space velocity, h -1 | 1.0 |
| Sulfur content of diesel oil, ppm | 10 |
| 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% | 0.86 | 0.82 | 0.87 | 0.88 |
| Refining catalyst deactivation rate, DEG C/d | 0.05 | 0.04 | 0.05 | 0.03 |
| Refining the average reaction temperature of 2500 hours at DEG C | 368 | 366 | 368 | 364 |
Table 5 comparative test results
| Project | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Hydrogen consumption, wt% | 0.92 | 0.94 | 0.97 | 0.98 |
| Refining catalyst deactivation rate, DEG C/d | 0.08 | 0.07 | 0.11 | 0.10 |
| Refining the average reaction temperature of 2500 hours at DEG C | 375 | 374 | 379 | 377 |
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 same sulfur content in diesel oil, and the device has long operation period.
Claims (13)
1. A startup method of a diesel hydrogenation device, comprising: after finishing catalyst filling, air tightness checking and building a circulating hydrogen system for the diesel hydrogenation device, controlling the volume flow rate of circulating hydrogen per hour to be 200-1000 times of the total catalyst filling volume, injecting CO gas into the inlet of a reaction zone of the diesel hydrogenation device, wherein the volume injection rate of CO is 10% -30% of the volume flow rate of the circulating hydrogen, increasing the temperature of the inlet of the reaction zone to 180-260 ℃, stopping injecting CO gas when the volume fraction of CO 2 in the circulating hydrogen is 10% -40%, then sequentially carrying out hydrogen replacement on the gas in the device, vulcanizing the catalyst, and introducing raw oil into 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 inlet temperature of a reaction zone to a first constant temperature, namely 220-240 ℃ at a speed of no more than 10 ℃/h, then to carry out constant temperature vulcanization for 2-12 hours at the first constant temperature, and the mass concentration of hydrogen sulfide in circulating hydrogen is controlled to be maintained at 1000-800 ppm in the first vulcanization stage; and in the second vulcanization stage, the inlet temperature of the reaction zone is increased to a second constant temperature of 340-380 ℃ at a speed of not more than 10 ℃/h, then the constant temperature vulcanization is carried out for 2h at the second constant temperature, and the mass concentration of the hydrogen sulfide in the circulating hydrogen is controlled to be 8000-20000 ppm in the second vulcanization stage.
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 hydrogen gas is replaced by reducing the inlet temperature of the reaction zone to 140-175 ℃.
4. The start-up method according to claim 1, wherein in the dry vulcanization, the first vulcanization stage is to raise the inlet temperature of the reaction zone to a first constant temperature of 220-240 ℃ at a speed of 3-10 ℃/h, then to carry out constant temperature vulcanization for 2-12 hours at the first constant temperature, and the first vulcanization stage is to control the mass concentration of hydrogen sulfide in the circulating hydrogen to be maintained at 1000-8000 ppm; and in the second vulcanization stage, the inlet temperature of the reaction zone is increased to a second constant temperature of 340-380 ℃ at a speed of 2-10 ℃/h, then constant temperature vulcanization is carried out for 2-8 h at the second constant temperature, and the mass concentration of hydrogen sulfide in the circulating hydrogen is controlled to be 8000-20000 ppm in the second vulcanization stage.
5. The start-up process of claim 4, wherein the dry sulfiding is performed by gradually injecting sulfiding agent into the diesel hydrogenation unit prior to entering the first sulfiding stage, gradually increasing the temperature and controlling the temperature of the catalyst bed in the reaction zone to not more than 230 ℃ until hydrogen sulfide penetrates the catalyst bed.
6. The start-up process of claim 5, wherein the hydrogen sulfide penetrates the entire catalyst bed under the following conditions: the mass concentration of hydrogen sulfide in the circulating hydrogen is more than 1000 ppm.
7. The start-up process of claim 5, wherein the hydrogen sulfide penetrates the entire catalyst bed under the following conditions: the mass concentration of hydrogen sulfide in the circulating hydrogen is 1000-8000 ppm.
8. The start-up method according to claim 4, wherein the hydrofining catalyst used for the diesel hydrogenation has a content of 25% -45% calculated by the group VIB metal oxide and a content of 3% -12% calculated by the group VIII metal oxide based on the weight of the catalyst.
9. The start-up method according to claim 8, wherein the hydrofining catalyst used for diesel hydrogenation has a content of 28% -35% calculated by group VIB metal oxide and a content of 4% -9% calculated by group VIII metal oxide based on the weight of the catalyst.
10. The method according to claim 1 or 5, 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 is selected from low-sulfur diesel, the raw oil has an initial distillation point of 50-110 ℃, a final distillation point of 310-380 ℃, a sulfur mass content of 5000ppm or less, and a nitrogen mass content of 500-2000 ppm.
12. The starting method according to claim 1, wherein the specific operation of introducing the raw oil is: and reducing the inlet temperature of the reaction zone to 290-320 ℃, starting to introduce the raw oil, wherein the initial introduction amount is 20-40% of the design processing load, adjusting the raw oil feeding amount to 60-100% of the design processing load after stabilizing, and adjusting the reaction temperature until the diesel oil product is qualified.
13. The start-up method according to claim 1, wherein the reaction conditions at the time of the normal production are as follows: the reaction pressure is 4.0-12.0 MPa, the reaction temperature is 220-390 ℃, and the liquid hourly space velocity is 0.2-6.0 h -1.
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| CN202111280348.7A CN116064079B (en) | 2021-10-29 | Start-up method of diesel hydrogenation device |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1412277A (en) * | 1972-10-16 | 1975-11-05 | British Petroleum Co | Treatment of platinum group metal reforming catalysts |
| DE19928670B4 (en) * | 1998-06-25 | 2013-03-07 | IFP Energies Nouvelles | Catalyst sulfurization process by reduction followed by sulfurization |
| CN107446616A (en) * | 2016-05-30 | 2017-12-08 | 中国石油化工股份有限公司 | One kind is hydrocracked start-up method |
| CN109777472A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | One kind plus hydrogen start-up method |
| CN112295575A (en) * | 2019-07-30 | 2021-02-02 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst and start-up method of hydrogenation device |
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1412277A (en) * | 1972-10-16 | 1975-11-05 | British Petroleum Co | Treatment of platinum group metal reforming catalysts |
| DE19928670B4 (en) * | 1998-06-25 | 2013-03-07 | IFP Energies Nouvelles | Catalyst sulfurization process by reduction followed by sulfurization |
| CN107446616A (en) * | 2016-05-30 | 2017-12-08 | 中国石油化工股份有限公司 | One kind is hydrocracked start-up method |
| CN109777472A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | One kind plus hydrogen start-up method |
| CN112295575A (en) * | 2019-07-30 | 2021-02-02 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst and start-up method of hydrogenation device |
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