CN102051205B - In-situ presulfurization method of hydrogenation catalyst - Google Patents
In-situ presulfurization method of hydrogenation catalyst Download PDFInfo
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Abstract
The invention discloses an in-situ presulfurization method of a hydrogenation catalyst. The method comprises the following steps: in the wetting stage of the catalyst, introducing sulfurized oil and hydrogen gas from the bottom of a reactor; when the reactor is full of the sulfurized oil, introducing the sulfurized oil and the hydrogen gas from the top of the reactor for closed cycle; and filling a vulcanizing agent into the sulfurized oil gradually to complete sulfurization. In the method provided by the invention, the mode of introducing the sulfurized oil from the bottom of the reactor into the reactor is adopted for the wetting process of the catalyst, thus the wetting of the catalyst is more sufficient and complete, and the dry area in a catalyst bed can be effectively prevented; and meanwhile, as the catalyst is fully wetted, the condition that the catalyst in the oxidation state is reduced by hydrogen gas thus the sulfurization is difficult to perform can be effectively avoided. The sulfurization method provided by the invention is simple in process and is convenient to operate, and the sulfurization effect is better than that of the conventional method, thereby being favorable for improving the activity of the catalyst.
Description
Technical field
The present invention relates to a kind of interior sulfuration of device start-up method of hydrogenation catalyst, relate to specifically a kind of interior prevulcanized start-up method of device of oxidation state hydrogenation catalyst.
Technical background
Because crude production rate increasess slowly and heaviness increasingly, and the world today constantly increases the clear gusoline demand, and quality product requires also more and more stricter.The petroleum fractions hydrogenation technique is the major technique of current production clear gusoline, and wherein the technology of preparing of hydrogenation catalyst is the key of hydrogen addition technology.The active metal component of the hydrogenation catalyst of preparation is oxidation state, and oxidized catalyst is before industrial application, and its reactive metal need be converted into sulphided state and just have higher catalytic activity.Therefore, the sulfuration of catalyzer has material impact to the performance of catalyzer, is the important process step before catalyzer is used.
Up to now, both at home and abroad most refinery still adopts prevulcanized mode in the device, and namely fresh or regenerated catalyst loads and introduces vulcanizing agent behind the reactor and vulcanize.State according to vulcanizing agent is different, and the prevulcanized mode can be divided into again wet method sulfuration and dry method sulfuration in the device.The wet method sulfuration also claims the liquid phase sulfuration.Be in the presence of hydrogen, the liquid curing agent be dissolved in form vulcanized oil in the benzoline first, then contact with hydrogenation catalyst in the input reactor and carry out vulcanization reaction.Its sulfidation is roughly, and is warmed up to first certain temperature, introduces vulcanized oil again catalyst irrigation is vulcanized, wetting stability number hour, the last persistently overheating vulcanization reaction that carries out.In this process, the uniform wet processes of hydrogenation catalyst has very important effect to the activity of its follow-up sulfuration and final catalyzer.It act as:
1, make granules of catalyst all be in wetting regime, prevent the existence in " dried district " in the beds, the existence of " doing the district " will reduce the gross activity of catalyzer;
2, the sulfur crude medium sulphide content is adsorbed on the catalyzer, prevents that active metal oxide from by hydrogen reducing, causing difficulty to sulfuration, because the vulcanization rate of metal oxide is more faster than the vulcanization rate of metal, be conducive to improve the activity of catalyzer;
3, avoid the water molecules that generates in the sulfidation on the impact of catalyzer.
And the heat and mass environment of liquid is better than gas phase, so the liquid phase sulfidation is easy to control with respect to the gas phase sulfidation.So both at home and abroad most refinery is in adopting device during the prevulcanized mode, great majority adopts the wet methods sulfuration.
USP4725571 discloses a kind of wet method sulfuration of catalyzer, and this kind method is to adopt to add two kinds of vulcanizing agents in vulcanized oil.The vulcanization process of a Chinese patent CN1362493A catalyst for hydroprocessing of heavy oil, at first solid-state inorganic sulphide and Hydrodemetalation catalyst are mixed, then by adopting the means that dry method sulfuration under the low temperature is combined with wet method vulcanization process under the high temperature, reduced the consumption of vulcanized oil, reduced the sulfuration cost, and the vulcanizing agent sulfurization rate is good, has given full play to the performance of catalyzer.One kind of CN99123716.1 filling is two/reformer of multimetallic catalyst start-up method again, comprise and use the nitrogen purging reaction unit, then at 350～420 ℃ of lower dry catalysts, pass into stock oil afterwards in reforming reactor, the control water chloride balance is until reach the operational condition of normal production.CN101003749A provides a kind of and is adopting under the existing hydrocracking catalyst condition, need not to carry out the start-up method of oxidation state hydrocracking catalyst of the prevulcanized of catalyzer.With the oxidation state hydrocracking catalyst reactor of packing into; Reach the air in the reactor line in the logical nitrogen replacement reactor, the reactive system adherence pressure is to the required pressure of hydrocracking reaction; Switch hydrogen behind the steady air current, promote again the temperature of beds after hydrogen flowing quantity is stablized to required catalyst reduction temperature, constant temperature, it is temperature required that bed temperature is adjusted to hydrocracking reaction, and hydrogen is transferred to the required flow of hydrocracking reaction; Incision reacted hydrocarbon raw material.Need not to add again vulcanizing agent the catalyzer of oxidation state is carried out prevulcanized, avoid the problem brought by prevulcanized, and the catalyzer of partial reduction has higher hydrogenation cracking activity.
In the above-mentioned hydrogenation catalyst vulcanization process, be that all oxidation state hydrogenation catalysts are seated in the reactor, vulcanizing agent is one or both, but its all to be liquid phase enter reactor from reactor head.Its main deficiency is in the hydrogenating catalyst that sulfuration is wetting may be not exclusively, vulcanize insufficient, or for guaranteeing that sulfuration fully adds two kinds of vulcanizing agents so that the processing cost increase, complicated operation.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of interior sulfuration of device start-up method of hydrogenation catalyst.
Hydrogenation catalyst sulfuration start-up method of the present invention may further comprise the steps:
(1) gets the oxidation state hydrogenation catalyst;
(2) the oxidation state hydrogenation catalyst is loaded at normal temperatures and pressures into reactor, pass into the air in the nitrogen replacement reactive system, and carry out the catalyzer drying;
(3) behind dry the end, reduce reactor batch temperature, use hydrogen exchange nitrogen, it is close to carry out hydrogen;
(4) continue to adjust reactor batch temperature, and introduce vulcanized oil from reactor bottom, carry out wetting to catalyzer;
(5) after reactive system is filled with vulcanized oil, vulcanized oil and hydrogen are changed into by the reactor head introducing, the reactive system closed cycle is progressively injected vulcanizing agent in vulcanized oil, continue to heat up and finish sulfuration;
(6) after sulfuration finishes, introduce stock oil from reactor head.
Oxidation state hydrogenation catalyst described in the step (1) is generally take the refractory porous oxide as carrier, such as the composite oxides of aluminum oxide, silicon oxide, amorphous silicon aluminium, titanium oxide, molecular sieve and several elements or mixed oxide carrier etc.The hydrogenation activity component of Hydrobon catalyst is one or more among W, Mo, Ni and the Co, is generally 3wt%～50wt% in oxide compound hydrogenation activity component concentration.Concrete hydrogenation catalyst can be selected the commercial goods as required, can by the preparation of this area general knowledge, also can be that decaying catalyst is through the regenerated catalyst after regenerating also.
Drying conditions described in the step (2) is: under nitrogen pressure 1.0～3.0MPa, recycle compressor full dose circulation rises to 150～300 ℃ of constant temperature with the heat-up rate of 10～30 ℃/h with reactor batch temperature.Treat the double open fire＜1L/h of putting of high score, constant temperature finishes.
After the drying described in the step (3), reactor batch temperature is down to 95～180 ℃, carries out hydrogen exchange, and it is airtight to carry out hydrogen.
Adjusting reactor batch temperature in the step (4) is 95～180 ℃, and vulcanized oil and hydrogen are introduced the reactor at the bottom of reactor.
Vulcanized oil described in the step (4) is straight-run spirit, virgin kerosene, straight-run diesel oil, refined diesel oil, refining coal wet goods.The vulcanized oil air speed is 0.5～2h
-1, hydrogen to oil volume ratio is 100～1000.
After reactor is filled with vulcanized oil described in the step (5), vulcanized oil and hydrogen changed into by reactor head enter reactor, reactive system carries out closed cycle.In vulcanized oil, progressively inject vulcanizing agent, carry out bed with 10 ℃/h～30 ℃/h and heat up, when bed temperature rises to 200 ℃～250 ℃, constant temperature sulfuration 2h～10h.After constant temperature finishes, carry out bed and heat up with 10 ℃/h～30 ℃/h again, when bed temperature rises to 280～320 ℃, constant temperature sulfuration 2～10h, sulfuration finishes.
Vulcanizing agent described in the step (5) is selected from dithiocarbonic anhydride (CS2), dimethyl disulphide (DMDS), ethanol sulphur (EM), n-butyl mercaptan (NBM), two uncles and appoints Quito sulfide (TNPS), dimethylsulphide (DMS) etc.
After sulfuration finishes described in the step (6), adjust bed to temperature of reaction, switch stock oil.
Oxidation state hydrogenation catalyst vulcanization process of the present invention has following advantage:
1, the vulcanization process of oxidation state Hydrobon catalyst provided by the invention can guarantee that higher sulfuration rate and greater catalytic agent are active.
2, since in the inventive method vulcanized oil enter reactor from reactor bottom and carry out wettingly so that the oxidation state hydrogenation catalyst is wetting more fully thoroughly, can effectively prevent the existence of " doing the district " in the beds; Hydrogenation catalyst fully wetting effectively prevents active metal oxide by hydrogen reducing simultaneously, thereby causes difficulty to sulfuration, because the vulcanization rate of metal oxide is more faster than the vulcanization rate of as-reduced metal.Thereby the inventive method is conducive to improve the activity of catalyzer, and reduces the wetting rear stable step of oxidation state hydrogenation catalyst.
3, owing to adopt reactor bottom introducing vulcanized oil when vulcanizing, like this in the vulcanized oil contained vulcanizing agent behind injecting reactor progressively, the vulcanized oil medium sulphide content of Containing Sulfur agent can fully be adsorbed on the catalyzer, so that the hydrogenation catalyst vulcanization reaction is more complete, and the vulcanization reaction process is an exothermic process, such flow pattern can better prevent localized heat release in the reaction process and the Local Dry district that causes so that hydrogenation catalyst be a moistening state sulfuration all the time.
4, adopt the vulcanization process of oxidation state Hydrobon catalyst provided by the invention, its technique is simple, simple operation, and hydrogenation catalyst can have higher catalytic activity.
Embodiment
The oxidation state Hydrobon catalyst that adopts among the embodiment among the present invention is FH-UDS (Fushun Petrochemical Research Institute's development, Hua Hua group company in Wenzhou produces).This catalyzer is take aluminum oxide as carrier, and take W-Mo-Ni-Co as active ingredient, its reactive metal counts 30% with oxide weight.The surface-area of this catalyzer is 180m
2/ g, pore volume are 0.34mL/g.The per-cent that does not wherein indicate benchmark is weight percentage.
Used stock oil character sees Table 1 in the embodiment of the invention simultaneously.
Table 1 stock oil main character
| The oil product title | Stock oil (straight bavin, urge the bavin Medium diesel oil) |
| Density (20 ℃)/gcm -3 | 0.8571 |
| The boiling range scope/℃ | 176～371 |
| Sulphur/μ g.g -1 | 16053 |
| Nitrogen/μ g.g -1 | 170 |
| Existent gum/mg. (100mL) -1 | 92 |
| Condensed-nuclei aromatics/v% | 13.6 |
| Cetane value | 47.5 |
Comparative Examples 1
Catalyzer at first will pass through industrially drying in industrial application, the used time of industrially drying is about 24 hours.This simultaneous test is selected small-sized reaction unit, so do not need this process.Catalyzer 100g packs in the mini-reactor, airtight qualified, the hydrogen dividing potential drop is adjusted into 6.0MPa and begins 20 ℃/h intensification, rising to 140 ℃ is to begin to add vulcanized oil from reactor head, carry out wettingly, closed cycle is installed after being full of vulcanized oil by system, and vulcanized oil is the virgin kerosene that contains 2wt% dithiocarbonic anhydride, condition is hydrogen to oil volume ratio 350: 1, volume space velocity 2.0h
-1, constant temperature is 3 hours simultaneously.Treat that constant temperature finishes to continue to be warming up to 210 ℃ with 20 ℃/h, constant temperature 6 hours treats that constant temperature finishes to continue to be warming up to 280 ℃ with 20 ℃/h, and constant temperature 8 hours finishes constant temperature and continues to be warming up to 320 ℃ with 20 ℃/h, constant temperature 3 hours, and constant temperature finishes, and switches stock oil by operation.Rise to 350 ℃ of runnings 48 hours after switching raw material, adopt the finished product oil sample and analyze, catalyst activity the results are shown in Table 2.
Embodiment 1
Catalyzer at first will pass through industrially drying in industrial application, the used time of industrially drying is about 24 hours.Small-sized reaction unit is selected in this test, so do not need this process.Catalyzer 100g packs in the mini-reactor, and is airtight qualified, and the hydrogen dividing potential drop is adjusted into 6.0MPa and begins 20 ℃/h and heat up, and rising to 140 ℃ is to begin to add vulcanized oil from reactor bottom, carries out wetting.After system is full of vulcanized oil, changes into from reactor head and enter vulcanized oil, the luggage of going forward side by side is put closed cycle, and vulcanized oil is the virgin kerosene that contains 2wt% dithiocarbonic anhydride, and condition is hydrogen to oil volume ratio 350: 1, volume space velocity 2.0h
-1Continuation is warming up to 220 ℃ with 20 ℃/h, and constant temperature 8 hours finishes constant temperature and continues to be warming up to 320 ℃ with 20 ℃/h, constant temperature 3 hours, and constant temperature finishes, and switches stock oil by operation.Rise to 350 ℃ of runnings 48 hours after switching raw material, adopt the finished product crude oil sample analysis, catalyst activity the results are shown in Table 2.
Embodiment 2
Catalyzer at first will pass through industrially drying in industrial application, the used time of industrially drying is about 24 hours.Small-sized reaction unit is selected in this test, so do not need this process.Catalyzer 100g packs in the mini-reactor, and is airtight qualified, and the hydrogen dividing potential drop is adjusted into 6.0MPa and begins 20 ℃/h and heat up, and rising to 140 ℃ is to begin to add vulcanized oil from reactor bottom, carries out wetting.After system is full of vulcanized oil, changes into from reactor head and enter vulcanized oil, the luggage of going forward side by side is put closed cycle, and vulcanized oil is the virgin kerosene that contains 2wt% dithiocarbonic anhydride, and condition is hydrogen to oil volume ratio 350: 1, volume space velocity 2.0h
-1Continuation is warming up to 220 ℃ with 20 ℃/h, and constant temperature 8 hours finishes constant temperature and continues to be warming up to 320 ℃ with 20 ℃/h, constant temperature 3 hours, and constant temperature finishes, and switches stock oil by operation.Rise to 350 ℃ of runnings 48 hours after switching raw material, adopt the finished product crude oil sample analysis, catalyst activity the results are shown in Table 2.
Embodiment 3
Catalyzer at first will pass through industrially drying in industrial application, the used time of industrially drying is about 24 hours.Small-sized reaction unit is selected in this test, so do not need this process.Catalyzer 100g packs in the mini-reactor, and is airtight qualified, and the hydrogen dividing potential drop is adjusted into 6.0MPa and begins 20 ℃/h and heat up, and rising to 140 ℃ is to begin to add vulcanized oil from reactor bottom, carries out wetting.After system is full of vulcanized oil, changes into from reactor head and enter vulcanized oil, the luggage of going forward side by side is put closed cycle, and vulcanized oil is the virgin kerosene that contains 2wt% dithiocarbonic anhydride, and condition is hydrogen to oil volume ratio 350: 1, volume space velocity 2.0h
-1Continuation is warming up to 230 ℃ with 20 ℃/h, and constant temperature 6 hours finishes constant temperature and continues to be warming up to 320 ℃ with 20 ℃/h, constant temperature 5 hours, and constant temperature finishes, and switches stock oil by operation.Rise to 350 ℃ of runnings 48 hours after switching raw material, adopt the finished product crude oil sample analysis, catalyst activity the results are shown in Table 2.
Embodiment 4
Catalyzer at first will pass through industrially drying in industrial application, the used time of industrially drying is about 24 hours.This selects small-sized reaction unit to testing, so do not need this process.Catalyzer 100g packs in the mini-reactor, and is airtight qualified, and the hydrogen dividing potential drop is adjusted into 6.0MPa and begins 20 ℃/h and heat up, and rising to 140 ℃ is to begin to add vulcanized oil from reactor bottom, carries out wetting.After system is full of vulcanized oil, changes into from reactor head and enter vulcanized oil, the luggage of going forward side by side is put closed cycle, and vulcanized oil is the virgin kerosene that contains 2wt% dithiocarbonic anhydride, and condition is hydrogen to oil volume ratio 350: 1, volume space velocity 2.0h
-1Continuation is warming up to 230 ℃ with 20 ℃/h, and constant temperature 6 hours finishes constant temperature and continues to be warming up to 320 ℃ with 20 ℃/h, constant temperature 5 hours, and constant temperature finishes, and switches stock oil by operation.Rise to 350 ℃ of runnings 48 hours after switching raw material, adopt the finished product crude oil sample analysis, catalyst activity the results are shown in Table 2.
Embodiment 5
Catalyzer at first will pass through industrially drying in industrial application, the used time of industrially drying is about 24 hours.Small-sized reaction unit is selected in this test, so do not need this process.Catalyzer 100g packs in the mini-reactor, and is airtight qualified, and the hydrogen dividing potential drop is adjusted into 6.0MPa and begins 20 ℃/h and heat up, and rising to 140 ℃ is to begin to add vulcanized oil from reactor bottom, carries out wetting.After system is full of vulcanized oil, changes into from reactor head and enter vulcanized oil, the luggage of going forward side by side is put closed cycle, and vulcanized oil is the virgin kerosene that contains 2wt% dithiocarbonic anhydride, and condition is hydrogen to oil volume ratio 350: 1, volume space velocity 2.0h
-1Continuation is warming up to 210 ℃ with 20 ℃/h, and constant temperature 6 hours continues to be warming up to 300 ℃ with 20 ℃/h, constant temperature 5 hours, and constant temperature finishes, and switches stock oil by operation.Rise to 350 ℃ of runnings 48 hours after switching raw material, adopt the finished product crude oil sample analysis, catalyst activity the results are shown in Table 2.
Embodiment 6
Catalyzer at first will pass through industrially drying in industrial application, the used time of industrially drying is about 24 hours.Small-sized reaction unit is selected in this test, so do not need this process.Catalyzer 100g packs in the mini-reactor, and is airtight qualified, and the hydrogen dividing potential drop is adjusted into 6.0MPa and begins 20 ℃/h and heat up, and rising to 140 ℃ is to begin to add vulcanized oil from reactor bottom, carries out wetting.After system is full of vulcanized oil, carry out the device closed cycle, vulcanized oil is the virgin kerosene that contains 2wt% dithiocarbonic anhydride, and condition is hydrogen to oil volume ratio 350: 1, volume space velocity 2.0h
-1Continuation is warming up to 210 ℃ with 20 ℃/h, and constant temperature 6 hours finishes constant temperature and continues to be warming up to 300 ℃ with 20 ℃/h, constant temperature 5 hours, and constant temperature finishes, and switches stock oil by operation.Change into from the incoming stock oil of reactor head this moment.Rise to 350 ℃ of runnings 48 hours after switching raw material, adopt the finished product crude oil sample analysis, catalyst activity the results are shown in Table 2.
Table 2 embodiment and comparative example go into operation and the catalyst performance contrast
| The embodiment numbering | The product sulphur content, μ g/g | Product nitrogen content, μ g/g |
| Comparative Examples 1 | 361 | 37 |
| Embodiment 1 | 329 | 29 |
| Embodiment 2 | 331 | 28 |
| Embodiment 3 | 335 | 30 |
| Embodiment 4 | 322 | 28 |
| Embodiment 5 | 328 | 29 |
| Embodiment 6 | 321 | 28 |
Result by table 2 can find out, adopts sulfuration start-up method provided by the invention to compare conventional hydrogenation catalyst sulfuration start-up method and saves steady time after wetting, and its catalyst activity also is better than conventional hydrogenation catalyst sulfuration start-up method.But because the inventive method only needs existing installation is transformed, just can reach good activity of hydrocatalyst.
Claims (8)
1. vulcanize start-up method in the device of a hydrogenation catalyst, may further comprise the steps:
(1) gets the oxidation state hydrogenation catalyst, described oxidation state hydrogenation catalyst is take aluminum oxide, silicon oxide, amorphous silicon aluminium, titanium oxide, molecular sieve as carrier, the hydrogenation activity component is one or more among W, Mo, Ni and the Co, take oxide compound hydrogenation activity component concentration as 3wt%～50wt%;
(2) the oxidation state hydrogenation catalyst is loaded at normal temperatures and pressures into reactor, pass into the air in the nitrogen replacement reactive system, and carry out the catalyzer drying;
(3) behind dry the end, reduce reactor batch temperature, use hydrogen exchange nitrogen, it is airtight to carry out hydrogen;
(4) continue to adjust reactor batch temperature, and introduce vulcanized oil from reactor bottom, carry out wetting to catalyzer;
(5) after reactive system is filled with vulcanized oil, vulcanized oil and hydrogen are changed into by the reactor head introducing, the reactive system closed cycle is progressively injected vulcanizing agent in vulcanized oil, continue to heat up and finish sulfuration;
(6) after sulfuration finishes, introduce stock oil from reactor head.
2. according to start-up method claimed in claim 1, it is characterized in that, described drying conditions is: under nitrogen pressure 1.0～3.0MPa, the circulation of recycle compressor full dose, heat-up rate with 10～30 ℃/h rises to 150～300 ℃ of constant temperature with reactor batch temperature, treat the double open fire＜1L/h of putting of high score, constant temperature finishes.
3. according to start-up method claimed in claim 1, it is characterized in that, behind dry the end, reactor batch temperature is down to 95～180 ℃ in the step (3), carry out hydrogen exchange, and it is airtight to carry out hydrogen.
4. according to start-up method claimed in claim 1, it is characterized in that adjusting reactor batch temperature in the step (4) is 95～180 ℃, vulcanized oil and hydrogen are introduced the reactor from reactor bottom.
5. according to start-up method claimed in claim 1, it is characterized in that the vulcanized oil described in the step (4) is straight-run spirit, virgin kerosene, straight-run diesel oil, refined diesel oil, kerosene raffinate, the vulcanized oil air speed is 0.5～2h
-1, hydrogen to oil volume ratio is 100～1000.
6. according to start-up method claimed in claim 1, it is characterized in that step (5) is progressively injected vulcanizing agent in vulcanized oil, carry out bed with 10 ℃/h～30 ℃/h and heat up, when bed temperature rises to 200 ℃～250 ℃, constant temperature sulfuration 2h～10h; Continuation is carried out bed with 10 ℃/h～30 ℃/h and is heated up, when bed temperature rises to 280～320 ℃, and constant temperature sulfuration 2～10h.
7. according to start-up method claimed in claim 1, it is characterized in that the vulcanizing agent described in the step (5) comprises that dithiocarbonic anhydride, dimethyl disulphide, ethanol sulphur, n-butyl mercaptan, two uncles appoint one or more in Quito sulfide and the dimethylsulphide.
8. according to start-up method claimed in claim 1, it is characterized in that described hydrogenation catalyst is the regenerated catalyst after live catalyst or the regeneration of decaying catalyst process.
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| CN102872922B (en) * | 2011-07-11 | 2015-07-22 | 中国石油化工股份有限公司 | Hydrofining catalyst vulcanization method |
| CN102407148A (en) * | 2011-10-08 | 2012-04-11 | 中国科学院山西煤炭化学研究所 | Method for activating hydrodesulfurization catalyst |
| CN103100447B (en) * | 2011-11-10 | 2014-10-15 | 中国石油化工股份有限公司 | Startup sulfuration method of hydrogenation unit |
| CN103100448B (en) * | 2011-11-10 | 2015-04-15 | 中国石油化工股份有限公司 | In-situ sulfuration method for hydrogenation catalyst |
| CN103100446B (en) * | 2011-11-10 | 2015-04-15 | 中国石油化工股份有限公司 | Startup sulfuration method of hydrogenation unit |
| CN102604664A (en) * | 2012-03-23 | 2012-07-25 | 海南朗洁新能源科技有限公司 | Method for producing high-cetane-number diesel oil on hydrogenation device by using triglyceride |
| CN103666524B (en) * | 2012-09-20 | 2015-07-29 | 中国石油化工股份有限公司 | A kind of catalytic cracking unit start-up method |
| CN103666523B (en) * | 2012-09-20 | 2015-07-01 | 中国石油化工股份有限公司 | Work starting method for catalytic cracking unit |
| CN103773454B (en) * | 2012-10-24 | 2015-11-18 | 中国石油化工股份有限公司 | A kind of catalyst vulcanization method of liquid phase circulation hydrogenation unit |
| CN105709860B (en) * | 2014-12-20 | 2018-03-16 | 中国石油化工股份有限公司 | A kind of vulcanization process of hydrogenation catalyst |
| CN105709859B (en) * | 2014-12-20 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of vulcanization process of fixed bed hydrogenation catalyst |
| CN108273450A (en) * | 2018-02-02 | 2018-07-13 | 上海英保能源化工科技有限公司 | Boiling bed hydrogenation technique and its device used |
| CN110653007B (en) * | 2018-06-29 | 2022-08-09 | 中国石油化工股份有限公司 | Hydrogenation catalyst start-up vulcanization method |
| CN111822058B (en) * | 2019-04-19 | 2023-01-10 | 中国石油化工股份有限公司 | Pre-sulfurizing process of hydrogenation catalyst |
| CN117299233B (en) * | 2023-11-29 | 2024-02-23 | 淄博市临淄恒兴化工厂有限公司 | Sulfided hydrogenation catalyst and preparation method thereof |
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