CN103100447B - Startup sulfuration method of hydrogenation unit - Google Patents
Startup sulfuration method of hydrogenation unit Download PDFInfo
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- CN103100447B CN103100447B CN201110352452.2A CN201110352452A CN103100447B CN 103100447 B CN103100447 B CN 103100447B CN 201110352452 A CN201110352452 A CN 201110352452A CN 103100447 B CN103100447 B CN 103100447B
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Abstract
The invention relates to a startup sulfuration method of a hydrogenation unit. According to the invention, startup oil is introduced at a low temperature, a part of recycle gas is heated by using a heating furnace, then a vulcanizing agent is introduced, and hydrogen sulfide is obtained after decomposition of the vulcanizing agent; then recycle gas rich in hydrogen sulfide is mixed with a second part of recycle gas, mixed gas is mixed with the startup oil, and an obtained mixture passes through a catalyst bed; heating is continued after hydrogen sulfide thoroughly penetrates the catalyst bed of a reactor, and injection amount of the vulcanizing agent is adjusted according to requirements on the content of hydrogen sulfide; when the catalyst bed reaches a certain temperature, injection of the startup oil is stopped, and subsequent sulfuration of a catalyst is finished by using dry sulfuration; and temperature is decreased after sulfuration is finished, the startup oil is introduced again for wetting of the catalyst bed, heating is carried out, and raw oil is introduced instead. Compared with the prior art, the method provided by the invention enables performance of the catalyst to be effectively brought into play and realizes safe and smooth startup.
Description
Technical field
The invention belongs to the processing method of oil Refining Technologies, particularly relate to a kind of vulcanization process of hydrogenation catalyst of hydrogenation plant use.
Background technology
Along with the protection to environment; environmental regulation increasingly stringent in global range, this just needs to produce a large amount of clean light clean fuels, and hydrogen addition technology is the effective means of cleaning products; therefore hydrogenation plant has become the standard configuration of oil plant, and the hydrogenation plant in oil refining enterprise is on the increase.
In hydrogen addition technology, the catalyst that uses is bifunctional catalyst, its Hydrogenation comes from metal, metal is divided into two kinds of noble metal and base metals conventionally, and base metal mainly comprises VI B HeⅧ family metal (as Mo, W, Ni and Co etc.) element, in commodity hydrogenation catalyst, these metals normally exist with the form of oxidation state.Because the Hydrogenation of oxidation state metal and metallic atom is very low, only be translated into sulphided state and just there is higher Hydrogenation, therefore in order to make the performance of hydrogenation catalyst reach best, need to catalyst, vulcanize (sometimes also claiming presulfurization) before use.
US4177136 discloses the hydrotreatment process of hydrogenation catalyst being vulcanized with elementary sulfur, with elementary sulfur, catalyst is vulcanized.The method shortcoming is that solid element sulphur is all converted into hydrogen sulfide at a lower temperature, but catalyst can not vulcanize completely at low temperatures, during high temperature, can not supply with the enough sulphur of catalyst, the feed speed of hydrogen sulfide can not be controlled accurately, makes the cure efficiency of catalyst poor.
CN1082591A discloses a kind of processing hydrocarbons catalyst vulcanization method, and the 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.Its shortcoming makes the chain olefinic constituent separately adding in solvent be difficult to obtain in refinery, and when sulfuration easy polymerization coking on hydrotreating catalyst, affect the activity of catalyst.
CN1362289A discloses a kind of vulcanization process of hydrogenation catalyst, and the method by arranging one or more hydrogen sulfide generators of the sulphur-containing substances such as troilite or elemental sulfur that loaded for the sulfuration of catalyst before hydrogenation reactor.Its shortcoming is to need to build separately a reactor, need to purify hydrogen sulfide gas, needs the make-up hydrogen compressor of hydrogen sulfide corrosion resistant, and sulphur iron ore also needs subsequent treatment simultaneously.
Catalyst vulcanization method has liquid phase sulfuration and gas phase to vulcanize two kinds.Liquid phase sulfuration also claims wet method sulfuration, sulfidation is used sulfuration base oil and vulcanizing agent, because the initial activity of catalyst when the high temperature is high, catalyst before complete cure with vulcanize base oil and do not react, thereby weakened the performance of catalyst, conventionally vulcanized finishing temperature low compared with gas phase sulfuration.Gas phase sulfuration also claims dry method sulfuration, sulfidation is only used vulcanizing agent, because not reacting with hydrocarbon molecules in sulfidation, and can at higher temperature, carry out catalyst vulcanization, but in catalyst vulcanization process, two important indicators of vulcanizing system are temperature and concentration of hydrogen sulfide, but in actual mechanical process, these two important indicators are not with operator, to adjust arbitrarily, particularly at initial stage of sulfidation.For example; at the initial stage of sulfidation; catalyst is at lower temperature; just need certain density hydrogen sulfide; or use liquid that catalyst protection is got up to prevent to be difficult to full cure after some component reduction or decomposition again, but now, because temperature is lower; the vulcanizing agent of introducing can not be converted into hydrogen sulfide, therefore can cause catalyst performance not give full play to.
In prior art, in hydrogenation catalyst sulfidation, only select wet method sulfuration or dry method sulfuration.In wet method when sulfuration, does not vulcanize catalyst activity completely when avoiding high temperature and is affected, and does not substantially carry out high temperature vulcanized process, and sulfidation is just through with under lower temperature conditions.During dry method sulfuration, when temperature is high, inject vulcanizing agent, cannot produce at a lower temperature hydrogen sulfide, there is not the sulfidation under low temperature in catalyst, for hydrogenation catalyst, can affect the performance of catalyst performance, particularly contain the catalyst of easy decomposition components, larger to the activity influence of catalyst.In addition, conventional hydrogenation catalyst sulfidation, when temperature is low, inject vulcanizing agent, vulcanizing agent does not decompose, not only do not reach catalyst needs the requirement of hydrogen sulfide atmosphere when low temperature, and along with the raising of temperature, vulcanizing agent decomposes in a large number and forms higher temperature wave, sulfidation to catalyst causes adverse influence, when serious, can cause because temperature rise is too high security incident.The present invention is by adopting wet method to vulcanize when the low temperature, and can keep certain density hydrogen sulfide atmosphere at low temperature, when being raised to uniform temperature, temperature stops introducing the oil that goes into operation, then adopt the method for dry method sulfuration to complete follow-up catalyst vulcanization process, can realize good catalyst vulcanization effect and vulcanize stably start-up process.The present invention is by being divided into recycle hydrogen high temperature and low temperature two parts, it is hydrogen sulfide that high-temperature part can make the effective hydrogenolysis of vulcanizing agent of injecting, then partly mix with low temperature, can obtain the hydrogen sulfide containing circulating air of lower temperature, during for hydrogenation catalyst sulfidation, guarantee to have the sulfidation of a low temperature, by the temperature of different circulating air and the injection rate of vulcanizing agent, can realize good catalyst vulcanization effect and vulcanize stably start-up process.
Summary of the invention
For the deficiencies in the prior art; in order to reach the quiet run of better catalyst vulcanization effect and sulfidation; the invention provides a kind of start-up vulcanization method of hydrogenation plant; can not lose in cryogenic vulcanization stage guard catalyst active component; and improve catalyst end of a period curing temperature; improve catalyst vulcanization effect, and then improve reactivity worth, realize quiet run simultaneously.
The start-up vulcanization method of hydrogenation plant of the present invention comprises the steps:
(a), when hydrogenation plant goes into operation sulfuration, the circulating air of hydrogenation plant is divided into two parts, i.e. first's circulating air and second portion circulating air;
(b) more than first's circulating air is heated to through heating furnace temperature that vulcanizing agent hydrogenolysis is hydrogen sulfide, vulcanizing agent is introduced before heating furnace or after heating furnace in this part circulating air;
(c) second portion circulating air is through the heating of heating furnace only, and mixes through heating furnace first's circulating air of introducing vulcanizing agent, and mixed gas enters in reactor the hydrogenation catalyst in reactor is vulcanized;
(d) reactor is introduced the oil that goes into operation, and stops introducing the oil that goes into operation after hydrogen sulfide penetrates after reactor, is warming up to 190～270 ℃;
(e) stop introducing and go into operation after oil, dry method conditions of vulcanization is adjusted the temperature of circulating air routinely, and the injection rate of vulcanizing agent and heating rate complete the sulfidation of catalyst.
In the inventive method step (a), the circulating air using when hydrogenation plant goes into operation is the gases at high pressure that are rich in hydrogen in start-up process, and hydrogen purity (volume) is not less than 50%, is preferably not less than 60%, is preferably not less than 75%.In step (a), the volume ratio of the first portions circulating air and second portion circulating air is generally 1:10～10:1, and concrete ratio can be according to using the hydrogenolysis temperature of vulcanizing agent and beds inlet temperature that hydrogen sulfide penetrates before hydrogenation catalyst bed to require to adjust.
In the inventive method step (a), vulcanizing agent is the conventional vulcanizing agent using of hydrogenation process, is generally liquid sulfur-containing compound, requires hydrogenolysis temperature for higher than 140 ℃, is generally 150 ℃～400 ℃, concrete as CS
2, DMDS(dimethyl disulfide), SulfrZol
?54(C
8h
18s
4), diethyl disulfide, dipropyl disulfides etc. can be also transportations and store other safer polysulfide etc.
In the inventive method step (b), the first's circulating air temperature by heating furnace by surpass the hydrogenolysis temperature of use vulcanizing agent, need to be higher than used vulcanizing agent hydrogenolysis temperature more than 10 ℃, preferably higher than vulcanizing agent hydrogenolysis temperature more than 30 ℃.The sulfuration dosage of introducing in step (b) is that 500～6000 μ L/L determine by beds entrance hydrogen sulfide in gas phase content.
In the inventive method step (d), the oil that goes into operation using when hydrogenation plant goes into operation is the petroleum distillate that is rich in saturated hydrocarbons, as straight run boat coal, straight-run diesel oil etc., can be also the boat coal that obtains through deep hydrofinishing, diesel oil etc., or the boat coal that obtains of hydrocracking, diesel oil, tail oil etc.Requirement nitrogen content ≯ 200 μ the g/g in oil that goes into operation, preferably ≯ 100 μ g/g.The reactor inlet temperature that step (d) is introduced while going into operation oil is generally 50～150 ℃, the oil that goes into operation is also heated to relevant temperature, the oil that goes into operation can enter heating furnace jointly with circulating air, also can be without heating furnace, when reactor inlet temperature is higher, the oil that goes into operation need enter heating furnace heating, otherwise does not reach needed temperature.Step (d) hydrogen sulfide penetrates before reactor hydrogenation catalyst bed, and beds inlet temperature, lower than 160 ℃, is preferably 80 ℃～140 ℃.Hydrogen sulfide penetrates reactor catalyst bed, more than referring to that concentration of hydrogen sulfide in reactor outlet gas phase reaches 1000 μ L/L.When reactor bed inlet temperature is when being used the hydrogenolysis temperature of vulcanizing agent, two parts recycle hydrogen can be merged into normal recycle hydrogen, all by after heating furnace, then enter hydrogenation reactor.
In the inventive method, after step (d) hydrogen sulfide penetrates reactor catalyst bed, be warmed up to uniform temperature, target temperature, is generally 190～270 ℃, preferably 200～260 ℃.If target temperature is not less than 230 ℃, 230 ℃ of constant temperature 8～20 hours.Programming rate General Requirements is not more than 10 ℃/h.In step (d), control concentration 1000～7000 μ L/L of hydrogen sulfide in gas phase in reactor outlet.While going into operation liquid oily, volume space velocity is generally 1～8h
-1.
In the inventive method, step (e) stops introducing the sulfidation going into operation after oil and adopts this area conventional process and condition to carry out catalyst vulcanization, when keeping reactor outlet concentration of hydrogen sulfide to be 5000～30000 μ L/L, be warming up to 330～380 ℃, and at the temperature being finally raised to constant temperature at least 8 hours.
In the inventive method, the pressure of sulfidation can be operating pressure, also can be low compared with operating pressure, be preferably 50%～100% of design operation pressure, preferably 60%～100%.In sulfidation, between 225～235 ℃, generally need constant temperature 8～20 hours.
In this forwarding method, hydrogenation plant can be Naphtha hydrofining unit, gasoline hydrogenation device, kerosene hydrogenation device, diesel hydrotreating unit, Wax Oil Hydrogenation Unit, hydrocracking unit, residual hydrogenation equipment etc.Hydrogenation plant uses non-precious metal catalyst.
The specific embodiment
Method of the present invention is specific as follows: first a part for circulating air is passed through heating furnace, after reaching certain temperature (higher than the hydrogenolysis temperature of vulcanizing agent used), at furnace outlet, introduce vulcanizing agent, vulcanizing agent hydrogenolysis obtains hydrogen sulfide gas, then this part circulating air mixes with another part circulating air, after reaching the temperature requirement of expection, pass through beds, when low temperature, introduce the oil that goes into operation, continue to heat up and wait for that hydrogen sulfide penetrates beds, hydrogen sulfide is adjusted the injection rate of vulcanizing agent and the ratio of two parts hydrogen according to the requirement of hydrogen sulfide content after penetrating reactor, with ≯ 5 ℃/h speed, be warming up to 230 ℃ simultaneously, constant temperature sulfuration 8 hours, stop introducing the oil that goes into operation, then 3～6 ℃/h speed is warming up to 290 ℃, with 4～8 ℃/h speed, be warming up to 370 ℃ again, and at this temperature constant temperature 8 hours, complete the pre-vulcanization process of catalyst.After cooling, introduce the glossy moist catalysis bed that goes into operation, then heat up and swap-in feedstock oil.
In the inventive method, above-mentioned steps (d), if target temperature is less than 230 ℃, is increased to target temperature with ≯ 10 ℃/h speed by the temperature of beds, then stops introducing the oil that goes into operation.If target temperature is greater than 230 ℃, with ≯ 10 ℃/h speed, the temperature of beds is increased to 230 ℃, and at least constant temperature sulfuration 8 hours at this temperature, control reactor outlet hydrogen sulfide in gas phase concentration 1000～7000 μ L/L around here, then ≯ 8 ℃/h speed is increased to target temperature by the temperature of beds.If target temperature is 230 ℃, with ≯ 10 ℃/h speed, the temperature of beds is increased to 230 ℃, and at least constant temperature sulfuration 8 hours at this temperature, can start at constant temperature, in thermostatic process, also can be after constant temperature finishes, to stop introducing the oil that goes into operation, but require the total time of constant temperature to be not less than 8 hours.
In the inventive method, above-mentioned steps (e) stops introducing the sulfidation going into operation after oil and adopts this area conventional process and condition to carry out catalyst vulcanization.Other technology contents of concrete hydrogenation plant start-up vulcanization method is well known to those skilled in the art, can specifically determine according to the type of device, as by suitable programming rate, progressively improves vulcanization reaction temperature, adjusts on demand concentration of hydrogen sulfide simultaneously.Common conditions of vulcanization is: the temperature of quoting if stop while going into operation oil is less than 230 ℃, with ≯ 8 ℃/h speed, the temperature of beds is increased to 230 ℃, and at least constant temperature sulfuration 8 hours at this temperature, control concentration of hydrogen sulfide 1000～7000 μ L/L around here, then ≯ 8 ℃/h speed is increased to 290 ℃ by the temperature of beds, control reactor outlet hydrogen sulfide in gas phase concentration 5000～12000 μ L/L around here, for reaction bed temperature being reached steadily and being to reach the requirement of controlling concentration of hydrogen sulfide in next stage circulating air, can consider at this temperature constant temperature 0.1～4 hour, with ≯ 15 ℃/h speed, the temperature of beds is increased to 330～380 ℃ again, and at the temperature being finally raised to constant temperature at least 8 hours, control during this period concentration 10000～30000 μ L/L of reactor outlet hydrogen sulfide in gas phase, complete above-mentioned steps, completed the pre-vulcanization process of catalyst.The temperature of quoting if stop while going into operation oil is greater than 230 ℃, with ≯ 8 ℃/h speed, the temperature of beds is increased to 290 ℃, control reactor outlet concentration of hydrogen sulfide 5000～12000 μ L/L around here, for reaction bed temperature being reached steadily and being to reach the requirement of controlling concentration of hydrogen sulfide in next stage circulating air, can consider at this temperature constant temperature 0.1～4 hour, with ≯ 15 ℃/h speed, the temperature of beds is increased to 330～380 ℃ again, and at the temperature being finally raised to constant temperature at least 8 hours, control during this period concentration 10000～30000 μ L/L of reactor outlet hydrogen sulfide, complete above-mentioned steps, completed the pre-vulcanization process of catalyst.The temperature of quoting if stop while going into operation oil is 230 ℃, need to be at this temperature at least constant temperature sulfuration 8 hours, reaching total total time of 230 ℃ of constant temperature, be not less than 8 hours, control reactor outlet hydrogen sulphide in the vapor phase concentration 1000～7000 μ L/L around here, then ≯ 8 ℃/h speed is increased to 290 ℃ by the temperature of beds, control concentration of hydrogen sulfide 5000～12000 μ L/L around here, for reaction bed temperature being reached steadily and being to reach the requirement of controlling concentration of hydrogen sulfide in next stage circulating air, can consider at this temperature constant temperature 0.1～4 hour, with ≯ 15 ℃/h speed, the temperature of beds is increased to 330～380 ℃ again, and at the temperature being finally raised to constant temperature at least 8 hours, control during this period concentration 10000～30000 μ L/L of hydrogen sulfide, complete above-mentioned steps, completed the pre-vulcanization process of catalyst.
Below by embodiment, further illustrate concrete condition of the present invention.Catalyst FF-46 is that the wax oil cut fraction hydrogenation of China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute's development and production is processed catalyst.
Table 1 feedstock oil main character.
| Feedstock oil | Iran VGO |
| Density (20 ℃)/gcm -3 | 0.9135 |
| Boiling range/℃ | 350~545 |
| Sulfur content, wt% | 1.74 |
| Nitrogen content, μ gg -1 | 1535 |
| Aromatic hydrocarbons, wt% | 43.8 |
Table 2 embodiment process conditions and result of the test.
| Process conditions | Embodiment 1 | Reference example 1 | Reference example 2 | Embodiment 2 | Embodiment 3 |
| Catalyst | FF-46 | FF-46 | FF-46 | FF-46 | FF-46 |
| Vulcanization process | This method | Dry method sulfuration | Wet method sulfuration | This method | This method |
| Vulcanizing agent | ?DMDS | ?DMDS | ?DMDS | CS 2 | CS 2 |
| Pressure/MPa | 15.0 | 15.0 | 15.0 | 13.0 | 10.0 |
| Hydrogen sulfide penetrate front reactor inlet temperature/℃ | 80 | 180 | 180 | 135 | 110 |
| Introducing go into operation oil temperature/℃ | 80 | — | 80 | 120 | 50 |
| Stop going into operation oil temperature/℃ | 230 | — | 330 | 210 | 260 |
| Final curing temperature/℃ | 370 | 370 | 330 | 360 | 370 |
| Sulfuration rear catalyst activity rating condition and result | ? | ? | ? | ? | ? |
| Feedstock oil | Iran VGO | Iran VGO | Iran VGO | Iran VGO | Iran VGO |
| Reaction pressure/MPa | 15.7 | 15.7 | 15.7 | 15.7 | 15.7 |
| Volume space velocity/h -1 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Hydrogen to oil volume ratio | 1000 | 1000 | 1000 | 1000 | 1000 |
| Average reaction temperature/℃ | 385 | 389 | 388 | 385 | 385 |
| Generate oily nitrogen content/μ gg -1 | 4.8 | 8.4 | 7.3 | 5.6 | 5.0 |
By embodiment, can be found out, adopt the catalyst vulcanization method of the inventive method, can effectively bring into play the activity of catalyst, start-up process is stable simultaneously, does not produce large temperature fluctuation, is conducive to hydrogenation plant and steadily goes into operation safely.
Claims (14)
1. a start-up vulcanization method for hydrogenation plant, is characterized in that comprising the steps:
(a), when hydrogenation plant goes into operation sulfuration, the circulating air of hydrogenation plant is divided into two parts, i.e. first's circulating air and second portion circulating air; The volume ratio of first's circulating air and second portion circulating air is 1:10～10:1;
(b) more than first's circulating air is heated to through heating furnace temperature that vulcanizing agent hydrogenolysis is hydrogen sulfide, vulcanizing agent is introduced before heating furnace or after heating furnace in this part circulating air;
(c) second portion circulating air is through the heating of heating furnace only, and mixes through heating furnace first's circulating air of introducing vulcanizing agent, and mixed gas enters in reactor the hydrogenation catalyst in reactor is vulcanized;
(d) reactor is introduced the oil that goes into operation, and stops introducing the oil that goes into operation after hydrogen sulfide penetrates after reactor, is warming up to 190～270 ℃;
(e) stop introducing and go into operation after oil, dry method conditions of vulcanization is adjusted the temperature of circulating air routinely, and the injection rate of vulcanizing agent and heating rate complete the sulfidation of catalyst.
2. in accordance with the method for claim 1, it is characterized in that: in step (a), the circulating air hydrogen purity of using when hydrogenation plant goes into operation is not less than 50%.
3. in accordance with the method for claim 1, it is characterized in that: in step (a), vulcanizing agent is the conventional vulcanizing agent using of hydrogenation process, and requiring hydrogenolysis temperature is higher than 140 ℃.
4. according to the method described in claim 1 or 3, it is characterized in that: in step (a), vulcanizing agent is CS
2, DMDS, C
8h
18s
4, diethyl disulfide or dipropyl disulfide.
5. in accordance with the method for claim 1, it is characterized in that: in step (b), the first's circulating air temperature by heating furnace by surpass the hydrogenolysis temperature of use vulcanizing agent, need to be higher than used vulcanizing agent hydrogenolysis temperature more than 10 ℃.
6. it is characterized in that in accordance with the method for claim 1: the sulfuration dosage of introducing in step (b) is that 500～6000 μ L/L determine by beds entrance hydrogen sulfide in gas phase content.
7. in accordance with the method for claim 1, it is characterized in that: in step (d), the tail oil that the boat coal that the oil that goes into operation using when hydrogenation plant goes into operation is straight run boat coal, straight-run diesel oil, hydrofinishing obtains, the diesel oil that hydrofinishing obtains, boat coal that hydrocracking obtains, diesel oil that hydrocracking obtains or hydrocracking obtain.
8. in accordance with the method for claim 1, it is characterized in that: the reactor inlet temperature that step (d) is introduced while going into operation oil is 50～150 ℃, and the oil that goes into operation is heated to relevant temperature.
9. according to right, want the method described in 1 or 8, it is characterized in that: step (d) hydrogen sulfide penetrates before reactor hydrogenation catalyst bed, and beds inlet temperature is lower than 160 ℃.
10. it is characterized in that in accordance with the method for claim 1: step (d) hydrogen sulfide is warmed up to 190～270 ℃ after penetrating reactor catalyst bed.
11. in accordance with the method for claim 1, it is characterized in that: step (e) stops introducing the sulfidation going into operation after oil and adopts this area conventional process and condition to carry out catalyst vulcanization, when keeping reactor outlet concentration of hydrogen sulfide to be 5000～30000 μ L/L, be warming up to 330～380 ℃, and at the temperature being finally raised to constant temperature at least 8 hours.
12. in accordance with the method for claim 1, it is characterized in that: hydrogenation plant is Naphtha hydrofining unit, gasoline hydrogenation device, kerosene hydrogenation device, diesel hydrotreating unit, Wax Oil Hydrogenation Unit, hydrocracking unit or residual hydrogenation equipment, hydrogenation plant uses non-precious metal catalyst.
13. in accordance with the method for claim 5, it is characterized in that: in step (b), the first's circulating air temperature by heating furnace by surpass the hydrogenolysis temperature of use vulcanizing agent, need to be higher than used vulcanizing agent hydrogenolysis temperature more than 30 ℃.
14. want the method described in 9 according to right, it is characterized in that: step (d) hydrogen sulfide penetrates before reactor hydrogenation catalyst bed, and beds inlet temperature is 80 ℃～140 ℃.
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| CN116059925A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrogenation reaction rectification process starting method and hydrogenation reaction rectification device applying same |
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| US4177136A (en) * | 1978-01-03 | 1979-12-04 | The Standard Oil Company (Ohio) | Hydrotreating process utilizing elemental sulfur for presulfiding the catalyst |
| CN101260319A (en) * | 2008-04-25 | 2008-09-10 | 江苏佳誉信实业有限公司 | Vulcanization method for hydrogenation catalyst |
| CN102051205A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | In-situ presulfurization method of hydrogenation catalyst |
| CN102049318A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Sulfidizing agent supply method for use in catalyst wet sulfidizing process |
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|---|---|---|---|---|
| JP5057315B2 (en) * | 1998-10-30 | 2012-10-24 | 日揮株式会社 | Method for producing gas turbine fuel oil |
| AUPS014702A0 (en) * | 2002-01-25 | 2002-02-14 | Ceramic Fuel Cells Limited | Desulfurisation of fuel |
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| US4177136A (en) * | 1978-01-03 | 1979-12-04 | The Standard Oil Company (Ohio) | Hydrotreating process utilizing elemental sulfur for presulfiding the catalyst |
| US4177136B1 (en) * | 1978-01-03 | 1994-05-03 | Standard Oil Co Ohio | Hydrotreating process utilizing elemental sulfur for presulfiding the catalyst |
| CN101260319A (en) * | 2008-04-25 | 2008-09-10 | 江苏佳誉信实业有限公司 | Vulcanization method for hydrogenation catalyst |
| CN102051205A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | In-situ presulfurization method of hydrogenation catalyst |
| CN102049318A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Sulfidizing agent supply method for use in catalyst wet sulfidizing process |
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