CN1362289A - Pre-sulfurizing process of hydrogenation catalyst - Google Patents
Pre-sulfurizing process of hydrogenation catalyst Download PDFInfo
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Abstract
In the front of traditional reactor one or several hydrogen sulfide formation reactors are added, in the reactor the solid inorganic sulfur or other sulfur-bearing substance capable of producing hydrogen sulfide is held, and is the presence of hydrogen gas and under the conditions of proper temp. and proper dpressure said material can be reacted to obtain the hydrogen sulfide. The hydrogen sulfide can be used for presulfurizing hydrogenation catalyst, the sulfurization process can be implemented by traditional method.
Description
The present invention relates to a kind of method for pre-sulphuration of hydrogenation catalyst.
Hydrogenation catalyst all exists with the oxidation state of VIB and VIII family metal (as W, Mo, Co, Ni etc.) element mostly.Big quantity research and facts have proved that when metal only existed with sulphided state in the catalyzer, the activity of hydrogenation catalyst just can obtain best performance, so catalyzer all must vulcanize before use.By sulfuration, can make the activity of such catalysts metal component become sulphided state, thereby improve activity of such catalysts and stability by oxidation state.
At present, to reach the activatory technology by sulfuration widely-used in petroleum refining industry for hydrotreating catalyst.This technology process experimental study decades and industrial practice have obtained updating and are perfect, and industrial vulcanization process commonly used has dry method sulfuration and wet method sulfuration two big classes at present.The dry method sulfuration is in the presence of hydrogen, directly uses certain density hydrogen sulfide or inject CS in recycle hydrogen
2Or other organic sulfide carries out the gas phase sulfuration; The wet method sulfuration is to adopt the vulcanized oil that contains sulfide to vulcanize under liquid phase or semi-liquid phase state, it again can be in two kinds of situation, a kind of is that the sulphur of sulfuration usefulness is to rely on the outside sulfide that adds to vulcanize, as mercaptan and other organic sulfide etc., another kind is to rely on the sulfide of petroleum fractions self to vulcanize.But no matter taking which kind of vulcanization process, its principle all is in the presence of hydrogen, the sulphur in vulcanizing agent or the vulcanized oil is changed into hydrogen sulfide, with active metal oxide reaction in hydrogen sulfide that generates and the catalyzer, make it be converted into the sulphided state of metal again.
US4177136 discloses with elementary sulfur the hydrotreatment process that hydrogenation catalyst carries out prevulcanized, with elementary sulfur catalyzer is carried out prevulcanized.This method shortcoming is that solid element sulphur changes into hydrogen sulfide at a lower temperature fully, but catalyzer can not vulcanize fully at low temperatures, can not supply with the enough sulphur of catalyzer during high temperature, the feed speed that is hydrogen sulfide can not be controlled exactly, make that the cure efficiency of catalyzer is poor, the catalyzer sulfurization rate is low.
CN1082591A discloses a kind of processing hydrocarbons catalyst vulcanization method, and this method adds vulcanizing agent by solvent, and all or part of a kind of component or the similar components that contains alkene and alkene cut (for example plant oil) of this solvent.The shortcoming of this method is that the chain olefinic constituent that adds in addition in the solvent is difficult to obtain in the refinery, and when sulfuration easily on hydrotreating catalyst polymerization coking influence activity of such catalysts, it is long also to exist curing time in this patent simultaneously, need to prepare a large amount of vulcanized oil and vulcanizing agent, defectives such as sulfuration cost height.
Purpose of the present invention overcomes above shortcoming exactly, proposes a kind of vulcanization process that is suitable for hydrogenation catalyst.Make may command hydrogen sulfide growing amount in the sulfidation, the generation that makes hydrogen sulfide and catalyzer drying, sulfuration carry out simultaneously, shorten the catalyst vulcanization time, reduce vulcanized oil, vulcanizing agent consumption, improve the cure efficiency of catalyzer.
Technical scheme of the present invention is as follows:
Before traditional hydrogenator, add one or more hydrogen sulfide generate reactors, the close S-contained substance that loads mutually in the hydrogen sulfide generate reactor, in the presence of hydrogen, S-contained substance is changed into hydrogen sulfide, use the hydrogen sulfide that is generated that hydrogenation catalyst is carried out prevulcanized.
The service temperature of described hydrogen sulfide generate reactor is 80-200 ℃, is 90-180 ℃ preferably, and best is 100-160 ℃; Working pressure is 0.1-18.0MPa, is 5-16MPa preferably, and that best is 10-16MPa; Hydrogen gas rate is 50-5000 a times of catalyzer cumulative volume.
Said S-contained substance can be any solid-state sulfocompound, is preferably sulfurous iron ore and elemental sulfur.Sulfurous iron ore refers to can enrichment become a kind of general term of the iron sulfide mineral of industrial mineral deposit, mainly refers to pyrite, white pyrite and pyrrhotite; Elemental sulfur refers to virgin sulfur and reclaims sulphur that virgin sulfur refers to be present in natural natural sulphur, also claims rhombic sulfur; Reclaim sulphur and refer to the sulphur that from Sweet natural gas, oil, coal and other sulfur-bearing resource, obtains as by-product recovery.Preferred inorganic sulphide is to reclaim sulphur.The add-on of solid-state vulcanizing agent is the 5%-40w% of catalyzer total amount, is 15-30w% preferably.
The temperature rise rate of described hydrogen sulfide generate reactor also is a key parameter, and temperature rise rate is generally 1-10 ℃/h, is 1-8 ℃/h preferably, and that best is 1-5 ℃/h.
Be the concise and to the point description of example reaction process of the present invention so that single hydrogen sulfide generate reactor to be set below.
Fig. 1 is a kind of implementation and operation general flow chart that single hydrogen sulfide generate reactor is set.Wherein A is a head tank, B is the hydrogen sulfide generate reactor, C is a hydrogenator, D is a high-temperature high-pressure separator, E is the cryogenic high pressure separator, 101,104 is hydrogen gas lines, 102 is hydrogen sulfide generate reactor concentration of hydrogen sulfide thief hatch, 103 draw pipeline for hydrogen sulfide, and 105 is feed line, and 106 generate oily outfall pipeline for reaction, 107 isolate the heavy hydrocarbon outfall pipeline for high-temperature high-pressure separator, 108 for high-temperature high-pressure separator after separating lighter hydrocarbons and be rich in the pipeline that stink damp removes the cryogenic high pressure separator, 109 be light constituent hydrocarbon recovery line, 110 is the hydrogen sulfide circulation line after washing.Concrete operating process is: hydrogen is injected among the hydrogen sulfide generate reactor B by hydrogen gas lines 101 reacts, the hydrogen sulfide that is generated is drawn pipeline 103 by hydrogen sulfide and is drawn, and mix with raw material from head tank A, add new hydrogen that 104 hydrogen gas lines are replenished and enter among the hydrogenator C by feed line 105 hydrogenation catalyst is carried out prevulcanized from the recycle hydrogen of 110 pipelines.
The operating temperature of strict control hydrogen sulfide generate reactor in the sulfidation, to satisfy hydrogenation catalyst required concentration of hydrogen sulfide of when sulfuration, if concentration of hydrogen sulfide is on the low side, improve the operating temperature of hydrogen sulfide generate reactor, concentration of hydrogen sulfide is higher, can keep or reduce the operating temperature of hydrogen sulfide generate reactor.
Vulcanization process of the present invention can be controlled the hydrogen sulfide growing amount, generation and catalyst drying, the sulfuration of hydrogen sulfide are carried out simultaneously, shorten the catalyst vulcanization time, reduce sulfurized oil, vulcanizing agent consumption, reduced and vulcanized cost, improved the cure efficiency of catalyst.
Further describe technical scheme of the present invention below in conjunction with example:
Comparative example 1
On the pilot plant that three reactors are arranged, adopt the complete series hydrotreating catalyst of Fushun Petrochemical Research Institute's exploitation to carry out dry method sulfuration test.Wherein, the filling situation of each anticatalyzer is: one instead loads CEN-2, CEN-4, FZC-16, CEN-5, CEN-6 from top to bottom, filling ratio (V) is: 1: 1.5: 2.2: 2.4: 13, two instead load ZTS01 and ZTS02 from top to bottom, filling ratio (V) is: 7.5: 1, three anti-filling ZTN01, the filling ratio (V) of three reactors is 45: 20: 35.Above-mentioned CEN-2, CEN-4, FZC-16, CEN-5, CEN-6 catalyzer are to be produced by Fushun Petrochemical Research Institute pilot scale base, and ZTS01, ZTS02 and ZTN01 are produced by first fertilizer plant of Qilu Petrochemical company.The standard operation condition of device is: reaction pressure 15.7MPa, hydrogen-oil ratio are 758 (v/v), volume space velocity 0.2h during liquid
-1
Install airtight qualified after, with hydrogen device is raised to normal working pressure, the temperature rise rate with 20 ℃/h is raised to 180 ℃ with each anti-temperature then.Behind each anti-temperature-stable, start compressor and set up normal hydrogen recycle, inject dithiocarbonic anhydride from first reactor inlet and penetrate whole beds until hydrogen sulfide, annotating sulphur speed is 10ml/h.
Hydrogen sulfide penetrates back constant temperature sulfuration 8 hours concentration of hydrogen sulfide in recycle hydrogen and reaches 1.5v%.With the temperature rise rate of 5 ℃/h each instead is raised to 320 ℃ then, in the temperature-rise period in the Control Circulation hydrogen concentration of hydrogen sulfide scope at 2.0-3.5v%.Temperature is raised to back constant temperature sulfuration 8h.In the thermostatic process in the Control Circulation hydrogen concentration of hydrogen sulfide more than 2.0v%.
Dry method sulfurized test-results is listed in table 1.
Table 1: dry method sulfurized performance and test-results
| Catalyzer dry method sulfuration implementation process: | |||||
| Stage | Heat-up rate, ℃/h | Holding time, h | ?CS 2Injection rate, ml | Concentration of hydrogen sulfide in the recycle hydrogen, v% | |
| Room temperature-180 ℃ is stable | ????20 | ????14 | ????- | ?????- | |
| Annotating sulphur-hydrogen sulfide penetrates | ????0 | ????10 | ????100 | ????0-0.1 | |
| 180 ℃ of constant temperature | ????0 | ????8 | ????80 | ????0.1-1.8 | |
| 180℃-320℃ | ????7 | ????20 | ????280 | ????1.5-2.6 | |
| 320 ℃ of constant temperature | ????0 | ????8 | ????80 | ????2.0-4.0 | |
| Add up to | ????60 | ????400 | |||
| Dry method sulfuration test-results: | |||||
| The actual filling of catalyzer total amount, ml | ????????????????????800 | ||||
| Theoretical sulfur content, the g of needing of catalyzer | ????????????????????54.80 | ||||
| Vulcanizing agent injects total amount, g | ????????????????????400 | ||||
| Catalyzer sulfurization rate when sulfuration finishes, % | ????????????????????58.65 | ||||
| Sulfuration total time, h | ????????????????????60 | ||||
Comparative example 2
On the pilot plant that three reactors are arranged, adopt the complete series catalyst for hydrotreatment of residual oil of Fushun Petrochemical Research Institute's exploitation to carry out wet method sulfuration test.The catalyst loading scheme is with comparative example 1.
As vulcanized oil, the main character of vulcanized oil sees Table 2 with Saudi Arabia's atmosphere 3rd side cut in the wet method sulfuration.Vulcanizing agent adopts dithiocarbonic anhydride.Described vulcanizing agent add-on in elemental sulfur, satisfies that sulphur content is 2.0w% in the vulcanized oil according to the sulphur content in the vulcanized oil.
Install airtight qualified after, with hydrogen device is raised to normal working pressure, the temperature rise rate with 15 ℃/h is raised to 180 ℃ with each anti-temperature then.Behind each anti-temperature-stable, start compressor and set up normal hydrogen recycle.
The vulcanized oil that will contain vulcanizing agent is wetting until beds with 40% design loading (55g/h) introduction beds.After wetting feed loading carried the design loading (110g/h) to 80%, the temperature rise rate with 5 ℃/h rises to 230 ℃ with each anti-temperature simultaneously, and 230 ℃ of constant temperature sulfurations penetrate whole beds until hydrogen sulfide, continue constant temperature sulfuration 4 hours.Temperature rise rate with 5 ℃/h rises to 320 ℃ with each anti-temperature then, in the temperature-rise period in the Control Circulation hydrogen concentration of hydrogen sulfide more than 0.5v%.The constant temperature sulfuration finished until sulfuration after each anti-temperature was raised to 320 ℃.In the thermostatic process in the Control Circulation hydrogen concentration of hydrogen sulfide more than 2.0v%.
Wet method sulfurized test-results is listed in table 3.
Table 2: the critical nature of vulcanized oil
| Density (20 ℃), Kg/m 3 | 864.3 |
| ????S，ppm | 1.06 |
| ????N，ppm | 180 |
| Boiling range ASTM D-86, ℃ | |
| Initial boiling point | 214.1 |
| ????10％/30％ | 290.5/318.5 |
| ????50％/70％ | 333.1/349.6 |
| ????90％/95％ | 371.2/382.5 |
| Do | 390.0 |
Table 3: wet method sulfurized performance and test-results
| Catalyzer wet method sulfuration implementation process: | |||||
| Stage | Heat-up rate, ℃/h | Holding time, h | ??CS 2Injection rate, ml | The vulcanized oil injection rate, g | Concentration of hydrogen sulfide in the recycle hydrogen, v% |
| Room temperature-180 ℃ is stable | ????20 | ????14 | ?????- | ?????- | ??????- |
| ???180℃-230℃ | ????5 | ????10 | ????9.2 | ????825 | ??????- |
| 230 ℃ of constant temperature | ????0 | ????20 | ????26.1 | ????2200 | ?????0-0.1 |
| ???230℃-320℃ | ????5 | ????18 | ????23.0 | ????1980 | ?????0.6-2.0 |
| 320 ℃ of constant temperature | ????0 | ????12 | ????13.9 | ????1200 | ?????1.8-2.6 |
| Add up to | ????70 | ????72.2 | ????6205 | ||
| Wet method sulfuration test-results: | |||||
| The actual filling of catalyzer total amount, ml | ?????800 | ||||
| Theoretical sulfur content, the g of needing of catalyzer | ?????54.80 | ||||
| The vulcanized oil injection rate, g | ?????6205 | ||||
| The vulcanizing agent add-on, g | ?????72.2 | ||||
| Catalyzer sulfurization rate when sulfuration finishes, % | ?????81.75 | ||||
| Sulfuration total time, h | ?????70 | ||||
Embodiment 1
On the pilot plant that three reactors are arranged, the complete series catalyst for hydrotreatment of residual oil that adopts Fushun Petrochemical Research Institute to develop carries out the present invention and vulcanizes test.The catalyst loading scheme is with comparative example 1.The SULPHUR POWDER that the industry that accounts for catalyst weight 20% is generated is packed in the hydrogen sulfide generate reactor, and the hydrogen sulfide generate reactor adopts vertical reactor, and the flow hydrogen gas direction adopts from top to bottom and flows with other reactor; The same catalyzer of the filling method of SULPHUR POWDER.
Install airtight qualified after, with hydrogen device is raised to normal working pressure, the temperature rise rate with 20 ℃/h is raised to 180 ℃ with each anti-temperature then, simultaneously with 10 ℃/h hydrogen sulfide formation reaction actuator temperature is raised to 80 ℃.Behind the temperature-stable, start compressor and set up normal hydrogen recycle, continue with 5 ℃/h hydrogen sulfide formation reaction actuator temperature to penetrate whole beds until hydrogen sulfide to 110 ℃ of intensifications.
Carry out constant temperature sulfuration concentration of hydrogen sulfide in recycle hydrogen after hydrogen sulfide penetrates and reach 1.5v%.With the temperature rise rate of 5 ℃/h each instead is raised to 320 ℃ then, simultaneously with 5 ℃/h with hydrogen sulfide formation reaction actuator temperature to 160 ℃ of intensifications, in the temperature-rise period in the Control Circulation hydrogen concentration of hydrogen sulfide scope at 2.0-3.5v%, if concentration of hydrogen sulfide is higher, then should stop the intensification of hydrogen sulfide generate reactor, even can reduce the temperature of hydrogen sulfide generate reactor, rate of temperature fall should adopt 1 ℃/h; If concentration of hydrogen sulfide is on the low side, then should accelerate the temperature rise rate of hydrogen sulfide generate reactor, should adopt 8 ℃/h.
Temperature is raised to back constant temperature sulfuration 8h, in the thermostatic process in the Control Circulation hydrogen concentration of hydrogen sulfide more than 2.0v%.
The sulfurized test-results is listed in table 4.
Table 4: sulfurized performance of the present invention and test-results
| The catalyst vulcanization implementation process: | |||||
| Stage | Heat-up rate, ℃/h | The sulfuration holding time, h | Concentration of hydrogen sulfide in the recycle hydrogen, v% | ||
| ????A | ????B | ??A | ??B | ||
| Room temperature-80 ℃ is stable | Room temperature-180 ℃ is stable | ??10 | ??20 | ????14 | ?????- |
| Detect hydrogen sulfide 80-110 ℃ | Annotating sulphur-hydrogen sulfide penetrates | ??5 | ??5 | ????10 | ????0-0.1 |
| 110 ℃ of constant temperature | 180 ℃ of constant temperature | ??0 | ??0 | ????8 | ????0.1-1.8 |
| 110℃-160℃ | 180℃-320℃ | ?1-8 | ??5 | ????20 | ????1.5-2.6 |
| 160 ℃ of constant temperature | 320 ℃ of constant temperature | ??0 | ??0 | ????8 | ????2.0-4.0 |
| Add up to | ????60 | ||||
| The sulfuration test-results: | |
| The actual filling of catalyzer total amount, ml | ????800 |
| Theoretical sulfur content, the g of needing of catalyzer | ????54.80 |
| SULPHUR POWDER filling total amount, g | ????160 |
| Catalyzer sulfurization rate when sulfuration finishes, % | ????72.35 |
| Sulfuration total time, h | ????60 |
Embodiment 2
On the pilot plant that three reactors are arranged, the complete series catalyst for hydrotreatment of residual oil that adopts Fushun Petrochemical Research Institute to develop carries out the present invention and vulcanizes test.The catalyst loading scheme is with comparative example 1.The SULPHUR POWDER that the industry that accounts for catalyst weight 15% is generated is packed in the hydrogen sulfide generate reactor, and filling method is with embodiment 1.
Present embodiment still uses the used Saudi Arabia's atmosphere 3rd side cut of comparative example 2 as vulcanized oil, and the main character of vulcanized oil sees Table 2.
Install airtight qualified after, with hydrogen device is raised to normal working pressure, the temperature rise rate with 20 ℃/h is raised to 180 ℃ with each anti-temperature then, simultaneously with 10 ℃/h hydrogen sulfide formation reaction actuator temperature is raised to 80 ℃.Behind the temperature-stable, start compressor and set up normal hydrogen recycle, the vulcanized oil that will contain vulcanizing agent is wetting until beds with 40% design loading (55g/h) introduction beds.Continue simultaneously with 5 ℃/h hydrogen sulfide formation reaction actuator temperature to penetrate whole beds until hydrogen sulfide to 110 ℃ of intensifications.
After wetting feed loading carried design loading (110g/h) to 80%, temperature rise rate with 5 ℃/h rises to 230 ℃ with each anti-temperature simultaneously, 230 ℃ of constant temperature sulfurations penetrate whole beds until hydrogen sulfide, continue constant temperature sulfuration constant temperature sulfuration concentration of hydrogen sulfide in recycle hydrogen and reach 1.5v%.This process hydrogen sulfide generate reactor is at 110 ℃ of constant temperature.
Constant temperature finishes the back and with the temperature rise rate of 5 ℃/h each instead is raised to 320 ℃, simultaneously with 5 ℃/h with hydrogen sulfide formation reaction actuator temperature to 160 ℃ of intensifications, in the temperature-rise period in the Control Circulation hydrogen concentration of hydrogen sulfide scope at 2.0-3.5v%, if concentration of hydrogen sulfide is higher, then should stop to rise the temperature of hydrogen sulfide generate reactor, even can reduce the temperature of hydrogen sulfide generate reactor, rate of temperature fall should adopt 1 ℃/h; If concentration of hydrogen sulfide is on the low side, then should accelerate the temperature rise rate of hydrogen sulfide generate reactor, should adopt 8 ℃/h.
Temperature is raised to back constant temperature sulfuration 8h, in the thermostatic process in the Control Circulation hydrogen concentration of hydrogen sulfide more than 2.0v%.
The sulfurized test-results is listed in table 5.
Table 5: sulfurized performance of the present invention and test-results
| The catalyst vulcanization implementation process: | ||||||
| Stage | Speed heats up | The sulfuration holding time, h | The vulcanized oil consumption, g | H in the recycle hydrogen 2S concentration, | ||
| ????A | ????B | ??A | ??B | |||
| Room temperature-80 ℃ | Room temperature-180 ℃ | ??10 | ??20 | ????14 | ????- | ?????- |
| 80-110℃ | 180℃-230℃ | ??5 | ??5 | ????8 | ??700 | ???0-0.1 |
| 110 ℃ of constant temperature | 230 ℃ of constant temperature | ??0 | ??0 | ????10 | ??1100 | ???0.1-1.8 |
| 110℃-160℃ | 230℃-320℃ | ?1-8 | ??5 | ????18 | ??1980 | ???1.5-2.6 |
| 160 ℃ of constant temperature | 320 ℃ of constant temperature | ??0 | ??0 | ????10 | ??1000 | ???2.0-4.0 |
| Add up to | ????60 | ??4780 | ||||
| The sulfuration test-results: | ||||||
| The actual filling of catalyzer total amount, ml | ????800 | |||||
| Theoretical sulfur content, the g of needing of catalyzer | ????54.80 | |||||
| The vulcanized oil injection rate, g | ????4780 | |||||
| SULPHUR POWDER filling total amount, g | ????120 | |||||
| Catalyzer sulfurization rate when sulfuration finishes, % | ????83.46 | |||||
| Sulfuration total time, h | ????60 | |||||
Embodiment 3
Present embodiment is the comparing result of comparative example 1, comparative example 2 and embodiment 1.The vulcanization process comparing result is listed in table 6.
Table 6: sulfuration test comparing result
| Comparative example 1 | Comparative example 2 | Embodiment 1 | Embodiment 2 | |
| The vulcanized oil injection rate, g | ?0 | ?6025 | ?0 | ?4780 |
| The vulcanizing agent add-on, g | ?400 | ?72.2 | ?0 | ?0 |
| The SULPHUR POWDER add-on, ml | ?0 | ?0 | ?160 | ?120 |
| Sulfuration total time, h | ?60 | ?70 | ?60 | ?60 |
| The catalyzer sulfurization rate, % | ?58.60 | ?81.25 | ?72.35 | ?83.46 |
Embodiment 4
After 2 sulfurations of comparative example 2, embodiment 1, embodiment finished, substep switched in 100% sand normal slag and tests, and the main character of normal slag is listed in following table 7 in the sand.The standard operation condition of device is: reaction pressure 15.7MPa, and 385 ℃ of temperature of reaction, hydrogen-oil ratio is 800 (v/v), volume space velocity 0.2h during liquid
-1Normal slag runs to 1000,3000 hours hydrogenated oil is carried out sampling analysis in sand, and test technology condition and test-results are listed in table 8.
Table 7: test raw material oil main character
| Density, Kg/m3 | ????981.6 |
| ????S，m％ | ????2.83 |
| ????N，m％ | ????0.28 |
| Carbon residue, m% | ????13.49 |
| ????(Ni+V)，ppm | ????118.8 |
| Four components, m% | |
| Stable hydrocarbon | ????37.1 |
| Aromatic hydrocarbon | ????40.5 |
| Colloid | ????19.2 |
| Bituminous matter | ????3.2 |
Table 8: test technology condition and test-results
| The test technology condition: | ||||||
| Reaction pressure, MPa | ????15.7 | |||||
| Temperature of reaction, ℃ | ????385 | |||||
| Hydrogen-oil ratio, v/v | ????800 | |||||
| Volume space velocity, h -1 | ????0.20 | |||||
| Runtime, h | ????1000 | ????3000 | ||||
| Test-results: | ||||||
| Embodiment | Comparative example 2 | Embodiment 1 | Embodiment 2 | Comparative example 2 | Embodiment 1 | Embodiment 2 |
| Desulfurization degree, % | ???91.2 | ???91.5 | ???92.6 | ???90.0 | ???90.4 | ???90.8 |
| Denitrification percent, % | ???57.0 | ???57.3 | ???57.8 | ???53.9 | ???54.5 | ???55.9 |
| Take off carbon yield, % | ???68.5 | ???69.4 | ???70.5 | ???67.3 | ???68.1 | ???68.8 |
| Demetalization (Ni+V) rate, % | ???89.1 | ???89.6 | ???90.5 | ???88.0 | ???88.6 | ???89.3 |
By table 8 as seen, stable with vulcanization process ratio of the present invention with traditional vulcanization process catalyst activity.
Claims (14)
1. the vulcanization process of a hydrotreating catalyst, it is characterized in that before traditional hydrogenator, adding one or more hydrogen sulfide generate reactors, in the hydrogen sulfide generate reactor, load S-contained substance, in the presence of hydrogen, S-contained substance is changed into hydrogen sulfide, use the hydrogen sulfide that is generated that hydrogenation catalyst is carried out prevulcanized.
2. according to the described vulcanization process of claim 1, the service temperature that it is characterized in that described hydrogen sulfide generate reactor is 80-200 ℃; Working pressure is 0.1-18.0MPa; Hydrogen gas rate is 50-5000 a times of catalyzer cumulative volume.
3. according to claim 1 or 2 described vulcanization process, the service temperature that it is characterized in that said hydrogen sulfide generate reactor is 90-180 ℃, and pressure is 5-16MPa.
4. according to claim 1 or 2 described vulcanization process, the service temperature that it is characterized in that said hydrogen sulfide generate reactor is 100-160 ℃, and working pressure is 10-16MPa.
5. according to the described vulcanization process of claim 1, it is characterized in that said S-contained substance is solid-state sulfocompound.
6. according to the described vulcanization process of claim 5, it is characterized in that said solid-state sulfocompound is sulfurous iron ore and/or elemental sulfur.
7. according to the described vulcanization process of claim 6, it is characterized in that said sulfurous iron ore refers to pyrite, white pyrite and pyrrhotite.
8. according to the described vulcanization process of claim 6, it is characterized in that said elemental sulfur refers to virgin sulfur or reclaims sulphur.
9. according to the described vulcanization process of claim 8, it is characterized in that said recovery sulphur refers to the sulphur that obtains as by-product recovery from Sweet natural gas, oil, coal and other sulfur-bearing resource.
10. according to the described vulcanization process of claim 1, the add-on that it is characterized in that said S-contained substance is the 5%-40w% of catalyzer total amount.
11. according to the described vulcanization process of claim 10, the add-on that it is characterized in that said S-contained substance is the 15%-30w% of catalyzer total amount.
12. according to the described vulcanization process of claim 1, the temperature rise rate that it is characterized in that said hydrogen sulfide generate reactor is 1-10 ℃/h.
13. according to the described vulcanization process of claim 12, the temperature rise rate that it is characterized in that said hydrogen sulfide generate reactor is 1-8 ℃/h.
14. according to the described vulcanization process of claim 12, the temperature rise rate that it is characterized in that said hydrogen sulfide generate reactor is 1-5 ℃/h.
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| CN102049318B (en) * | 2009-10-27 | 2012-12-26 | 中国石油化工股份有限公司 | Sulfidizing agent supply method for use in catalyst wet sulfidizing process |
| CN102909011A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Activation and sulfurization method for dehydrogenation catalyst |
| CN102942957A (en) * | 2012-10-30 | 2013-02-27 | 中国石油化工股份有限公司 | Presulfuration technology of hydrogenation unit |
| CN103100449A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Startup sulfuration method of liquid phase circulation hydrogenation unit |
| CN113426493A (en) * | 2021-06-11 | 2021-09-24 | 中科合成油技术有限公司 | Presulfurization method of coal liquefaction hydrogenation iron-based catalyst |
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2001
- 2001-01-05 CN CNB011060093A patent/CN1137788C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049318B (en) * | 2009-10-27 | 2012-12-26 | 中国石油化工股份有限公司 | Sulfidizing agent supply method for use in catalyst wet sulfidizing process |
| CN102909011A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Activation and sulfurization method for dehydrogenation catalyst |
| CN103100449A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Startup sulfuration method of liquid phase circulation hydrogenation unit |
| CN103100449B (en) * | 2011-11-10 | 2015-04-15 | 中国石油化工股份有限公司 | Startup sulfuration method of liquid phase circulation hydrogenation unit |
| CN102942957A (en) * | 2012-10-30 | 2013-02-27 | 中国石油化工股份有限公司 | Presulfuration technology of hydrogenation unit |
| CN102942957B (en) * | 2012-10-30 | 2014-10-08 | 中国石油化工股份有限公司 | Presulfuration technology of hydrogenation unit |
| CN113426493A (en) * | 2021-06-11 | 2021-09-24 | 中科合成油技术有限公司 | Presulfurization method of coal liquefaction hydrogenation iron-based catalyst |
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| CN1137788C (en) | 2004-02-11 |
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