CN102041045B - On-stream method of residual oil hydrogenation process - Google Patents
On-stream method of residual oil hydrogenation process Download PDFInfo
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Abstract
The invention discloses an on-stream method of a residual oil hydrogenation process, comprising the following steps of: selecting oxidation-state residual oil hydrogenation-series catalysts according to the requirement of the residual oil hydrogenation process, wherein the oxidation-state residual oil hydrogenation-series catalysts comprise a residual-oil-hydrogenation protective agent, a residual-oil-hydrogenation metal catalyst, a residual-oil-hydrogenation desulfurization catalyst and a residual-oil-hydrogenation denitrification catalyst, and the oxidation-state residual-oil-hydrogenation desulfurization catalyst and/or the oxidation-state residual-oil-hydrogenation denitrification catalyst are/is processed in an ex-situ presulfurization method; introducing a vulcanizing agent, with the amount accounting for 95-150% of the theoretically-required sulfur amount of all the oxidation-state residual-oil-hydrogenation catalysts, to the catalysts to be subjected to presulfurization; and filling the required catalyst in a reactor, heating, activating, and then switching the residual oil raw materials to carry out hydrogenation. In the method, ex-situ presulfurization is only carried out on partial catalysts required by the residual oil hydrogenation process so that the advantages of saving the production cost and reducing the catalyst loss when the advantage of an ex-situ presulfurization process is kept.
Description
Technical field
The present invention relates to a kind of start-up method of residual oil technique, particularly use the technique start-up method of the outer prevulcanized residual oil hydrocatalyst of device.
Technical background
Along with crude production rate increasess slowly and heaviness increasingly, and market improves constantly light-end products requirement, add the increasingly stringent of environmental regulation, therefore, in the world residua upgrading technology is especially paid attention to, residual oil working ability increases rapidly, and particularly fixed bed residual hydrocracking technical development is the fastest, accounts for 85.3% of world's residual hydrogenation ability.Unprecedentedly active in the research in this field both at home and abroad, there are the residual hydrocracking technology of features in Chevron, UOP, Exxon, Shell HeIFPDeng major company.
The feature of residue fixed-bed hydrogenation technique has determined that residual hydrogenation equipment is generally no more than 2 years and just needs to stop work change agent running period, residual hydrogenation equipment is as the core apparatus of refinery, when accepting the unmanageable heavy hydrocarbon in upstream, for downstream unit provides high-quality charging as heavy oil fluid catalytic cracking, its on-stream efficiency is directly connected to refinery's economic benefit and production run cost again.Residue fixed-bed device characteristic is that reactor maximizes, and its diameter can reach more than 4 meters, highly reaches tens meters, and is generally a plurality of reactor series windings.Therefore,, between residue fixed-bed dress displacer under-stream period, there is strict shutting down period planning refinery.
When the active metal component of residual oil hydrocatalyst is only converted into sulphided state, just have higher catalytic activity, so presulfiding of catalyst is extremely important concerning giving full play to catalyst performance.The method for pre-sulphuration of catalyzer can be divided into prevulcanized and the outer prevulcanized of device in device by the mode of carrying sulphur.Prevulcanized exists the high and catalyzer of facility investment and the shortcoming such as grows on-stream time in device, uses inflammable and poisonous sulfide simultaneously, and environment is easily produced to pollution.The problems such as in device, the Residual catalyst of prevulcanized also brings on-stream time long in addition, and running cost is many, dangerous height.Thereby the outer method for pre-sulphuration of device arises at the historic moment.The advantage of the outer pre-curing technology of device is: the outer pre-curing technology of (1) device improves the utilization ratio of activity of hydrocatalyst metal component, and catalyst vulcanization obtains more abundant, and then reduces the generation probability of as-reduced metal compound; (2) the outer pre-curing technology of device can be saved on-stream time greatly, makes to go into operation easier; (3) poisonous sulfide has been avoided using in the scene of going into operation of the outer pre-sulfide catalyst of device, nor special-purpose vulcanizing deice need to be installed; (4), while skimming for full scale plant catalyzer, more can embody this technology feature easily that goes into operation.But the outer method for pre-sulphuration of device exists deficiencies such as being afraid of strong collision, fearness high temperature, the storage of catalyzer and transportation is had to higher requirement simultaneously.Particularly, when loading catalyst, need nitrogen protection.The research of prevulcanized aspect outside eighties device abroad.As Xpress technology of the actiCAT technology of the EasyActive technology of EURACAT company, CRITERION company and TRICAT company etc.Domestic Fushun Petrochemical Research Institute has also successfully developed Hydrogenation Catalyst With Ex-situ Pre-sulfurization Technology, and has obtained wide range of industrial applications.
The vulcanization process of a CN01106022.0 catalyst for hydroprocessing of heavy oil, be characterized in solid-state inorganic sulphide to mix with Hydrodemetalation catalyst, then by adopting the means that dry method under low temperature is vulcanized with under high temperature, wet method vulcanization process combines, reduced the consumption of vulcanized oil, reduced sulfuration cost, and vulcanizing agent sulfurization rate is good, given full play to the performance of catalyzer.
US 6417134 discloses a kind of outer method for pre-sulphuration of device of hydrocarbon hydrotreating catalyst, be characterized in first by elementary sulfur, organic sulfide, organic polysulfide, containing the oil of alkene, containing the component solvent cut of alkene, at the temperature of 30～200 ℃, carry out again dip treating catalyzer, then at the temperature of 250～600 ℃, use hydrogen treat, finally use oxygen-containing gas passivation.This catalyst vulcanization method is complicated, and the raw material of use is more, and cost is higher.
CN1557556A directly adopts inorganic sulphide agent solution to process catalyzer, in vulcanizing agent, without interpolation, contain the organic compound of oxygen and unsaturated link(age), process in the introducing catalyzer of vulcanizing agent is carried out at room temperature or lower temperature, without heat, the catalyzer of sulfuration preparation is without by oxygen containing gas Passivation Treatment.When inorganic sulphide is vulcanizing agent, generally need to repeatedly vulcanize, production process is complicated.
CN1268433C adopts a kind of component containing alkene, organic polysulfide and auxiliary agent to mix, and under 90～400 ℃ of conditions, heats said mixture 0.5～8.0 hour, obtains the mixture of Containing Sulfur alkene.The hydrogenation catalyst of the impregnation mixture oxidation state of the Containing Sulfur alkene obtaining, and heat this solidliquid mixture 0.5～8.0 hour under 100～300 ℃ of conditions, obtain product and flood after 1～12 hour with hydrocarbon ils at 20～120 ℃, evaporate to dryness hydrocarbon ils makes the hydrogenation catalyst after sulfuration.The raw material type that the method is used is many, and cost is higher.
US5169819 is first at 0～50 ℃, without H
2condition under with (NH
4)
2s solution impregnating catalyst, then dry under the oxygen-containing atmosphere lower than 120 ℃, then with (the NH that contains additive
4)
2the S aqueous solution floods this catalyzer, finally drying treatment under lower than 130 ℃ of conditions.Additive is for containing sulphur compound, as thiophene, thioic acid sulfoacid, sulfo-amine, thiocyanate, thioesters, thiazole, thiocarbamide and mercaptan etc., preferably HOC
2h
4sSC
2h
4oH.The method complex disposal process, prevulcanized cost is higher.
US5397756 adopts impregnation mixture catalyzer.Mixture is by vulcanizing agent, olefin component and solvent composition.Vulcanizing agent can be elementary sulfur, can be also organic polysulfide.What this patent olefin component adopted is fatty acid triglyceride, and what solvent adopted is white oil.After catalyst soakage, need to heat-treat (higher than 100 ℃), remove portion solvent, makes elementary sulfur react with the two keys in alkene component on the other hand on the one hand.Also there is the deficiencies such as production process complexity in the method.
The catalyzer of residual hydrogenation utilization generally comprises several catalyzer gratings and uses, and the kind of residual oil hydrocatalyst generally comprises residual hydrogenation protective material, residuum hydrogenating and metal-eliminating catalyst, residuum hydrodesulfurization catalyzer and residual hydrogenation denitrification catalyst etc.When industrial application, general above-mentioned several catalyzer are used simultaneously, sometimes for the difference of raw material impurity content, can not use residual hydrogenation denitrification catalyst or not use Hydrobon catalyst.Residual oil hydrocatalyst is general, and to use no acidic or weakly acidic material be carrier, and load hydrogenation active metals component is close on forming with common Hydrobon catalyst.
After the outer prevulcanized of residual oil hydrocatalyst device, while going into operation, adopt the operating method directly heating up.When residual oil hydrocatalyst carries out prevulcanized, the catalyzer that is generally all kinds vulcanizes respectively, because catalyst type is more, every kind of catalyzer has different character, required sulfidizing condition is also slightly different, therefore during residual oil hydrocatalyst prevulcanized, production process is comparatively complicated.Simultaneously, catalytic amount is larger, the catalytic amount that needs the outer prevulcanized of device to process is larger, the outer preprocessing process of device needs the time longer, processing cost increases, the in the situation that shorter or pre-sulfide catalyst production task being larger in the pre-sulfide catalyst supply time, may affect on time going into operation of residual hydrogenation equipment.Because the intensity of some kind catalyzer own is not high, outside device, in pre-vulcanization process, easily cause loss too high simultaneously, cause that production cost increases.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of start-up method of Residue Hydrotreating Technology, reduce the catalyst levels that needs the outer prevulcanized of device in Residue Hydrotreating Technology, the outer pre-sulfide catalyst production cycle of shortener, security in the outer pre-sulfide catalyst production process of supercharge, avoid oxidation state residual oil catalyst for demetalation because intensity is too low simultaneously, cause unnecessary loss.
The start-up method of Residue Hydrotreating Technology of the present invention comprises following content:
(1) by the requirement of Residue Hydrotreating Technology, selective oxidation state residual hydrogenation catalyst series, oxidation state residual hydrogenation catalyst series comprises residual hydrogenation protective material, residuum hydrogenating and metal-eliminating catalyst, residuum hydrodesulfurization catalyzer and residual hydrogenation denitrification catalyst, with the outer method for pre-sulphuration of device, processes oxidation state residuum hydrodesulfurization catalyzer and/or oxidation state residual hydrogenation denitrification catalyst;
(2) carrying out the amount that oxidation state residuum hydrodesulfurization catalyzer that the outer prevulcanized of device processes and/or oxidation state residual hydrogenation denitrification catalyst introduce vulcanizing agent is that all oxidation state residual oil hydrocatalyst theories need 95%～150% of sulfur content, is preferably 100%～120%;
(3) by above-mentioned prevulcanized and not the residual hydrogenation system catalyst of prevulcanized by Residue Hydrotreating Technology requirement, pack reactor into; Filling is sequentially for the engagement sequence of reaction mass and residual hydrogenation catalyst series is: residual hydrogenation protective material, residuum hydrogenating and metal-eliminating catalyst, residuum hydrodesulfurization catalyzer, residual hydrogenation denitrification catalyst;
(4) hydrogen is entered in reactor, after each reactor bed, recycle;
(5) reactor heats up, and is warming up to 200～280 ℃ of constant temperature 1h～16h, ends that go into operation after continuing to be warming up to 300～360 ℃, and switching residual oil raw material carries out hydrotreatment.
In the inventive method, each required serial oxidation state residual oil hydrocatalyst can be determined according to the needs of concrete residual hydrogenation reaction process, can select extensive stock catalyzer, as the residual hydrogenation catalyst series of Fushun Petrochemical Research Institute's development and production, the consumption of concrete kind catalyzer is determined according to the design of Residue Hydrotreating Technology.The oxidation state residual oil hydrocatalyst that carries out the outer prevulcanized processing of device is preferably all oxidation state residuum hydrodesulfurization catalyzer and oxidation state residual hydrogenation denitrification catalyst.Catalyzer packs into after reactor, with 10 ℃/h～40 ℃/h speed, heats up.Intensification start-up process adopts dry method or wet-process activation residual oil hydrocatalyst, under hydrogen recycle state, heats up.While adopting wet method, can in the time of 70 ℃～100 ℃, introduce the oil that goes into operation, device closed cycle, the oil that goes into operation, for virgin kerosene or straight-run diesel oil, can be also through hydrorefined kerosene or diesel oil etc., the oily volume space velocity that goes into operation is generally 0.5～10h
-1.When dry method, gas is closed cycle in device.When rising to 150～180 ℃, temperature starts to inject liquefied ammonia, to reduce the initial activity of residual oil hydrocatalyst.
The outer method for pre-sulphuration of catalyst device can be undertaken by the existing method in this area, owing to only oxidation state residuum hydrodesulfurization catalyzer and oxidation state residual hydrogenation denitrification catalyst being carried out to prevulcanized processing, so the vulcanizing agent add-on in the catalyzer of prevulcanized processing need increase in proportion.Preferably carry out as follows presulfiding of catalyst processing.
Catalyst presulfurizing method comprises following content:
(1) get oxidation state residuum hydrodesulfurization catalyzer and/or oxidation state residual hydrogenation denitrification catalyst in oxidation state residual hydrogenation catalyst series;
(2) by oxidation state residuum hydrodesulfurization catalyzer and/or oxidation state residual hydrogenation denitrification catalyst sulfur loaded agent and organic solvent, wherein vulcanizing agent consumption is that residual hydrogenation catalyst series theory needs 95%～150% of sulfur content, is preferably 100%～120%;
(3) the oxidation state residuum hydrodesulfurization catalyzer of sulfur loaded agent and organic solvent and/or oxidation state residual hydrogenation denitrification catalyst are heat-treated.
It is that on catalyzer, contained hydrogenation metal component is converted into sulfide (Co that oxidation state residual hydrogenation catalyst series theory needs sulfur content
9s
8, MoS
2, Ni
3s
2, WS
2) time need the amount of sulphur.Vulcanizing agent can be elementary sulfur (being elemental sulfur) or sulfocompound, and sulfocompound comprises inorganic sulfocompound and sulfur-containing organic compound.Vulcanizing agent can be one or more in elementary sulfur and sulfocompound, preferred elements sulphur and (NH
4)
2s mixes use.Elementary sulfur and (NH
4)
2s mixes while using, and preferred weight ratio is 1: 0.2～1: 0.5.
Organic solvent is the organic solvent that contains unsaturated link(age), and as alkene, Vegetable oil lipoprotein etc., alkene can be selected from the petroleum fractions containing alkene, as catalytically cracked gasoline, catalytic cracking diesel oil, coker gasoline, coker gas oil etc.In organic solvent, carbonatoms is generally 5～20, is preferably 7～16, and organic solvent can be a kind of, can be also that two or more mixes use.Consumption of organic solvent is the oxidation state residuum hydrodesulfurization catalyzer processed of prevulcanized and/or the weight 1%～45% of oxidation state residual hydrogenation denitrification catalyst, preferably 5%～35%.
Before introducing organic solvent and vulcanizing agent, afterwards or can also introduce other auxiliary agent simultaneously, as oxygen-bearing organic matter, itrogenous organic substance etc.
The oxidation state residuum hydrodesulfurization catalyzer of load organic solvent and vulcanizing agent and/or oxidation state residual hydrogenation denitrification catalyst carry out heat treated, heat treated condition can, for processing 1～15 hour at 110 ℃～260 ℃, preferably be processed 2～8 hours at 120～180 ℃.Heat treated can be carried out under the conditions such as air atmosphere, oxygen-denuded air atmosphere, inert gas atmosphere, water vapour atmosphere.
The pre-sulphur method of residual oil hydrocatalyst of the present invention and work starting method for hydrogenation process tool have the following advantages:
1, the vulcanization process of oxidation state residual oil hydrocatalyst provided by the invention, can guarantee the effect utilization ratio of higher sulfuration rate and higher sulphur.
2, a kind of containing processing and the (NH of olefin liquid to oxidation state residuum hydrodesulfurization catalyzer and oxidation state residual hydrogenation denitrification catalyst owing to the invention provides
4)
2the use of S; not only can make catalyzer there is higher sulphur reservation degree; and be that pre-vulcanization process is more even; even heat release while contributing to catalyzer to go into operation; simultaneously prevulcanized rear oxidation state residuum hydrodesulfurization catalyzer and oxidation state residual hydrogenation denitrification catalyst need not protection of inert gas, the depositing, transport and load without nitrogen protection of catalyzer.
3, technique is simple, adopts cheap industrial chemicals, and equipment is simple, workable, particularly take elemental sulfur and inorganic sulfur as main, avoids contacting of people and organosulfur, reduces the damage to human body.
4, adopt oxygen oxidation state residuum hydrodesulfurization catalyzer and oxidation state residual hydrogenation denitrification catalyst to process, can effectively shorten the production cycle of sulfide type catalyst, reduced the usage quantity of the outer pretreatment catalyst of device, reduce some accident risks, can solve the short problem with needing to concentrate the supply of material of supply time requirement simultaneously.
5, due to oxidation state residual oil catalyst for demetalation and residual hydrogenation protective material intensity lower; outside device, in pre-vulcanization process, there is the too high factor of loss; the inventive method does not need the prevulcanized of oxidation state residual oil catalyst for demetalation; therefore can avoid the unnecessary loss producing in oxidation state residual oil catalyst for demetalation and protective material pre-vulcanization process, reduce production cost.
Working method when 6, adopting residual hydrogenation start-up method provided by the invention and all catalyzer carries out the outer prevulcanized of device is basic identical, and technique is simple, simple operation, and there is higher catalytic activity.
Embodiment
Further illustrate by the following examples the present invention program and effect.
Stock oil character used in the embodiment of the present invention is in Table 1.
Table 1 stock oil main character
| Stock oil | Long residuum in sand |
| Density (20 ℃), g.cm -3 | 0.9819 |
| Sulphur, quality % | 4.02 |
| Nitrogen, μ g.g -1 | 2255 |
| Carbon residue, quality % | 11.86 |
| Metal (Ni+V), μ g.g -1 | 103.1 |
In the embodiment of the present invention, used catalyst technology assessment condition is in Table 2.
Table 2 catalyst process appreciation condition
| Stock oil | Normal slag in sand |
| Catalyzer | FZC series residual oil hydrocatalyst |
| Reaction stagnation pressure, MPa | 14.0 |
| Hydrogen to oil volume ratio | 800 |
| Volume space velocity, h -1 | 0.250 |
| Temperature of reaction, ℃ | 394 |
The oxidation state residual hydrogenation catalyst series adopting in embodiment in the present invention is the FZC series residual oil hydrocatalyst of Fushun Petrochemical Research Institute's development and production.In each embodiment, residual hydrogenation protective material FZC-102 usage quantity is 50 grams; residuum hydrogenating and metal-eliminating catalyst FZC-20 usage quantity is 60 grams, and it is 100 grams with residual hydrogenation denitrification catalyst FZC-40 usage quantity that residuum hydrodesulfurization catalyzer FZC-30 usage quantity is 100 grams.
Comparative example 1
First oxidation state FZC series residual oil hydrocatalyst will pass through industrially drying in industrial application, and the industrially drying time used is about 24 hours.This simultaneous test, selects small-sized reaction unit, therefore must this process.By residual hydrogenation protective material, residuum hydrogenating and metal-eliminating catalyst, residuum hydrodesulfurization catalyzer and residual hydrogenation denitrification catalyst order, above-mentioned catalyzer is packed in mini-reactor; airtight qualified; carry out device closed cycle; be warming up to 150 ℃ and enter vulcanized oil; vulcanized oil is the virgin kerosene that contains 2wt% dithiocarbonic anhydride; rise to 250 ℃, constant temperature 18 hours.Treat that constant temperature finishes to continue to be warming up to 340 ℃, constant temperature 5 hours, is then warming up to 370 ℃, constant temperature 2 hours, and constant temperature finishes, and is adjusted to desired reaction temperature swap-in stock oil.Curing time is about 41 hours.After switching raw material, according to the technology assessment condition of table 2, turn round 48 hours, adopt finished product crude oil sample analysis, catalyst activity the results are shown in Table 3.
Comparative example 2
Oxidation state FZC series residual oil hydrocatalyst floods respectively 120g organic solvent (organic solvent is coking kerosene cut) altogether, and in organic solvent, the ratio of carbonatoms 9～12 is not less than 50%, dipping time 1 hour.(the NH of elemental sulfur 30g and 7.5g
4)
2s mixes.By the FZC series residual oil hydrocatalyst after dipping and vulcanizing agent mixing, (residual oil hydrocatalyst presses that metal content is different to be mixed with the vulcanizing agent of Optimum respectively, vulcanizing agent consumption needs sulfur content ratio to distribute in catalyzer theory), and at 170 ℃, process naturally cooling 4 hours.The pre-sulfide catalyst obtaining, prevulcanized FZC series residual oil hydrocatalyst is distributed in mini-reactor, airtight qualified, is warming up to 250 ℃, constant temperature 14 hours.Finish constant temperature and continue to be warming up to 370 ℃, by operation, switch stock oil.Curing time is about 27 hours.After switching raw material, according to the technology assessment condition of table 2, turn round 48 hours, adopt finished product crude oil sample analysis, catalyst activity the results are shown in Table 3.
Embodiment 1
FZC-30 is 100g, is immersed in 15g organic solvent (organic solvent is coking kerosene cut), and in organic solvent, the ratio of carbonatoms 9～12 is not less than 50%, dipping time 1 hour.(the NH of elemental sulfur 30g and 7.5g
4)
2s mixes.FZC-30 catalyzer after dipping is mixed with vulcanizing agent, and at 170 ℃, process 3 hours, naturally cooling.The pre-sulfide catalyst obtaining, the FZC-30 catalyzer of prevulcanized and oxidation state FZC-102 catalyzer, oxidation state FZC-20 (first contacts FZC-102 by reaction mass in being distributed into mini-reactor with oxidation state FZC-40 catalyzer, contacting FZC-20 and contacting FZC-30, finally contacting the order filling of FZC-40, other embodiment and comparative example are identical), airtight qualified, beginning heats up with 20 ℃/h, rises to 220 ℃, constant temperature 8 hours.Finish constant temperature and continue to be warming up to 360 ℃ with 20 ℃/h, by operation, switch stock oil.Curing time is about 27 hours.After switching raw material, according to the technology assessment condition of table 2, turn round 48 hours, adopt finished product crude oil sample analysis, catalyst activity the results are shown in Table 3.
Embodiment 2
FZC-40 is 100g, is immersed in 15g organic solvent (organic solvent is coking kerosene cut), and in organic solvent, the ratio of carbonatoms 9～12 is not less than 50%, dipping time 1 hour.(the NH of elemental sulfur 30g and 7.5g
4)
2s mixes.Catalyzer after dipping is mixed with vulcanizing agent, and at 170 ℃, process 3 hours, naturally cooling.The pre-sulfide catalyst obtaining, the FZC-40 catalyzer of prevulcanized and oxidation state FZC-102 catalyzer, oxidation state FZC-20 and oxidation state FZC-30 catalyzer are distributed in mini-reactor by embodiment 1 order, airtight qualified, beginning heats up with 20 ℃/h, rises to 220 ℃, constant temperature 8 hours.Finish constant temperature and continue to be warming up to 360 ℃ with 20 ℃/h, by operation, switch stock oil.Curing time is about 27 hours.After switching raw material, according to the technology assessment condition of table 2, turn round 48 hours, adopt finished product crude oil sample analysis, catalyst activity the results are shown in Table 3.
Embodiment 3
FZC-30 is 100g, is immersed in 20g organic solvent (organic solvent is coking kerosene cut), and in organic solvent, the ratio of carbonatoms 9～12 is not less than 50%, dipping time 1 hour.(the NH of elemental sulfur 26g and 13g
4)
2s mixes.Catalyzer after dipping is mixed with vulcanizing agent, and at 170 ℃, process 3 hours, naturally cooling.The pre-sulfide catalyst obtaining, the FZC-30 catalyzer of prevulcanized and oxidation state FZC-102 catalyzer, oxidation state FZC-20 and oxidation state FZC-40 catalyzer are distributed in mini-reactor by the order of embodiment 1, airtight qualified, beginning heats up with 20 ℃/h, rises to 220 ℃, constant temperature 6 hours.Finish constant temperature and continue to be warming up to 360 ℃ with 20 ℃/h, by operation, switch stock oil.Curing time is about 25 hours.After switching raw material, according to the technology assessment condition of table 2, turn round 48 hours, adopt finished product crude oil sample analysis, catalyst activity the results are shown in Table 3.
Embodiment 4
FZC-40 is 100g, is immersed in 20g organic solvent (organic solvent is coking kerosene cut), and in organic solvent, the ratio of carbonatoms 9～12 is not less than 50%, dipping time 1 hour.(the NH of elemental sulfur 26g and 13g
4)
2s mixes.Catalyzer after dipping is mixed with vulcanizing agent, and at 170 ℃, process 3 hours, naturally cooling.The pre-sulfide catalyst obtaining, the FZC-40 catalyzer of prevulcanized and oxidation state FZC-102 catalyzer, oxidation state FZC-20 and oxidation state FZC-30 catalyzer are distributed in mini-reactor by the order of embodiment 1, airtight qualified, beginning heats up with 30 ℃/h, rises to 210 ℃, constant temperature 8 hours.Finish constant temperature and continue to be warming up to 360 ℃ with 30 ℃/h, by operation, switch stock oil.Curing time is about 21 hours.After switching raw material, according to the technology assessment condition of table 2, turn round 48 hours, adopt finished product crude oil sample analysis, catalyst activity the results are shown in Table 3.
Embodiment 5
FZC-30 is 100g, and FZC-40 is that 100g is immersed in respectively 20g and 20g organic solvent (organic solvent is coking kerosene cut), and in organic solvent, the ratio of carbonatoms 9～12 is not less than 50%, dipping time 1 hour.(the NH that the vulcanizing agent that FZC-40 catalyzer is used is elemental sulfur 16g and 5g
4)
2s mixture, (the NH that the vulcanizing agent that FC-30 catalyzer is used is elemental sulfur 16g and 5g
4)
2s mixture.FZC-30 and FZC-40 after dipping are mixed with corresponding vulcanizing agent respectively, and at 180 ℃, process 3 hours, naturally cooling.The pre-sulfide catalyst obtaining, packs prevulcanized FZC-30, prevulcanized FZC-40, oxidation state FZC-102 and oxidation state FZC-20 in mini-reactor into by the order of embodiment 1, airtight qualified, starts to heat up with 20 ℃/h, rises to 230 ℃, constant temperature 6 hours.Finish constant temperature and continue to be warming up to 360 ℃ with 20 ℃/h, by operation, switch stock oil.Curing time is about 25 hours.After switching raw material, according to the technology assessment condition of table 2, turn round 48 hours, adopt finished product crude oil sample analysis, catalyst activity the results are shown in Table 3.
Embodiment 6
FZC-30 is 100g, and FZC-40 is that 100g is immersed in respectively 15g and 15g organic solvent (organic solvent is coking kerosene cut), and in organic solvent, the ratio of carbonatoms 9～12 is not less than 50%, dipping time 1 hour.(the NH that the vulcanizing agent that FZC-40 catalyzer is used is elemental sulfur 16g and 5g
4)
2s mixture, (the NH that the vulcanizing agent that FZC-30 catalyzer is used is elemental sulfur 16g and 5g
4)
2s mixture.FZC-30 and FZC-40 after dipping are mixed with corresponding vulcanizing agent respectively, and at 180 ℃, process 3 hours, naturally cooling.The pre-sulfide catalyst obtaining, packs prevulcanized FZC-30, prevulcanized FZC-40, oxidation state FZC-102 and oxidation state FZC-20 in mini-reactor into by the order of embodiment 1, airtight qualified, starts to heat up with 20 ℃/h, rises to 230 ℃, constant temperature 8 hours.Finish constant temperature and continue to be warming up to 360 ℃ with 20 ℃/h, by operation, switch stock oil.Curing time is about 27 hours.After switching raw material, according to the technology assessment condition of table 2, turn round 48 hours, adopt finished product crude oil sample analysis, catalyst activity the results are shown in Table 3.
Table 3 embodiment and comparative example go into operation and catalyst performance contrast
Result by table 3 can be found out, adopts prevulcanized provided by the invention to compare conventional oxidized catalyst curing time with start-up method and greatly shortens, suitable with existing sulphided state catalyzer time used that goes into operation, and its catalyst activity is also substantially suitable.But because the outer pretreatment catalyst amount of needs device reduces, therefore can shorten the production time of sulphided state catalyzer, reduce production costs, avoid the loss in advance outside sulphur time device outside of the weak residual hydrogenation protective material of intensity and residuum hydrogenating and metal-eliminating catalyst simultaneously.
Claims (9)
1. a start-up method for Residue Hydrotreating Technology, comprising:
(1) by the requirement of Residue Hydrotreating Technology, selective oxidation state residual hydrogenation catalyst series, oxidation state residual hydrogenation catalyst series comprises residual hydrogenation protective material, residuum hydrogenating and metal-eliminating catalyst, residuum hydrodesulfurization catalyzer and residual hydrogenation denitrification catalyst, with the outer method for pre-sulphuration of device, processes oxidation state residuum hydrodesulfurization catalyzer and/or oxidation state residual hydrogenation denitrification catalyst;
(2) carrying out the amount that oxidation state residuum hydrodesulfurization catalyzer that the outer prevulcanized of device processes and/or oxidation state residual hydrogenation denitrification catalyst introduce vulcanizing agent is that all oxidation state residual oil hydrocatalyst theories need 95%～150% of sulfur content;
(3) by above-mentioned prevulcanized and not the residual hydrogenation system catalyst of prevulcanized by Residue Hydrotreating Technology requirement, pack reactor into;
(4) hydrogen is entered in reactor, after each reactor bed, recycle;
(5) reactor heats up, and is warming up to 200～280 ℃ of constant temperature 1h～16h, ends that go into operation after continuing to be warming up to 300～360 ℃, and switching residual oil raw material carries out hydrotreatment;
Step (3) catalyst loading sequentially first contacts residual hydrogenation protective material for reaction mass, then contacts residuum hydrogenating and metal-eliminating catalyst and contact residuum hydrodesulfurization catalyzer, finally contacts residual hydrogenation denitrification catalyst.
2. it is characterized in that in accordance with the method for claim 1: in step (2), carrying out the amount that oxidation state residuum hydrodesulfurization catalyzer that the outer prevulcanized of device processes and/or oxidation state residual hydrogenation denitrification catalyst introduce vulcanizing agent is that all oxidation state residual oil hydrocatalyst theories need 100%～120% of sulfur content.
3. it is characterized in that in accordance with the method for claim 1: the described reactor heat-up rate of step (5) is 10 ℃/h～40 ℃/h.
4. it is characterized in that in accordance with the method for claim 1: intensification start-up process adopts dry method or wet-process activation residual oil hydrocatalyst.
5. it is characterized in that in accordance with the method for claim 1: the outer prevulcanized of oxidation state residuum hydrodesulfurization catalyzer and/or oxidation state residual hydrogenation denitrification catalyst device is processed and comprised following content:
(1) get oxidation state residuum hydrodesulfurization catalyzer and/or oxidation state residual hydrogenation denitrification catalyst in oxidation state residual hydrogenation catalyst series;
(2), by oxidation state residuum hydrodesulfurization catalyzer and/or oxidation state residual hydrogenation denitrification catalyst sulfur loaded agent and organic solvent, wherein vulcanizing agent consumption is that residual hydrogenation catalyst series theory needs 95%～150% of sulfur content;
(3) the oxidation state residuum hydrodesulfurization catalyzer of sulfur loaded agent and organic solvent and/or oxidation state residual hydrogenation denitrification catalyst are heat-treated.
6. in accordance with the method for claim 5, it is characterized in that: vulcanizing agent is elemental sulfur or sulfocompound, and sulfocompound comprises inorganic sulfocompound and sulfur-containing organic compound.
7. according to the method described in claim 5., it is characterized in that: organic solvent is the organic solvent that contains unsaturated link(age), in organic solvent, carbonatoms is 5～20, and consumption of organic solvent is the oxidation state residuum hydrodesulfurization catalyzer of prevulcanized processing and/or the weight 1%～45% of oxidation state residual hydrogenation denitrification catalyst.
8. in accordance with the method for claim 5, it is characterized in that: before introducing organic solvent and vulcanizing agent, introduce auxiliary agent afterwards or simultaneously, auxiliary agent is oxygen-bearing organic matter or itrogenous organic substance.
9. in accordance with the method for claim 5, it is characterized in that: step (3) is heat-treated the oxidation state residuum hydrodesulfurization catalyzer of sulfur loaded agent and organic solvent and/or oxidation state residual hydrogenation denitrification catalyst, and described heat-treat condition is: at 110 ℃～260 ℃, process 1～15 hour.
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| CN103773439B (en) * | 2012-10-24 | 2015-09-30 | 中国石油化工股份有限公司 | A kind of start-up method of gasoline selective hydrodesulfurizationmodification technique |
| CN103769242B (en) * | 2012-10-26 | 2016-03-09 | 中国石油化工股份有限公司 | A kind of ex situ presulfiding method of hydrogenation catalyst |
| CN103769243B (en) * | 2012-10-26 | 2016-04-27 | 中国石油化工股份有限公司 | The ex situ presulfiding method of hydrogenation catalyst |
| CN111068794B (en) * | 2018-10-22 | 2023-02-03 | 中国石油化工股份有限公司 | External presulfurization method of hydrogenation catalyst |
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